CN104818464B - The method that large-specific surface area nano Argent grain film composite material is prepared without template - Google Patents
The method that large-specific surface area nano Argent grain film composite material is prepared without template Download PDFInfo
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Abstract
The method that large-specific surface area nano Argent grain film composite material is prepared without template, prepares silver-colored zircaloy film, and matrix is kept uniform temperature so that silver atoms are the i.e. prepared product of Argent grain in alloy film superficial growth on glass basis surface first.The present invention prepares silver alloy film and matrix In Situ Heating technology using the double target co-depositions of magnetron sputtering, realize and prepare large-specific surface area nano Ag films/Argent grain sandwich without template, Ag films thickness, Argent grain yardstick in the sandwich can regulate and control in the range of micro/nano-scale, template need not be used, low cost, environmental protection, it is easy on glass basis prepare large area, high-performance nano Argent grain film composite material without template, more than 20% can be increased than fine silver film specific surface area.
Description
Technical field
The present invention relates to micro-, nanometer sized materials preparation fields, specifically a kind of preparation without template compares table greatly
The method of area nanometer Argent grain film composite material.
Background technology
With the development of micro-nano science and technology, micron and nanoscale film, the excellent properties of particle and wide application
Prospect is gradually cognitive by researcher and causes the great interest of countries in the world materials scholar, physicist and chemist.Work as size
When reaching nanoscale, particle will be presented obvious quantum size effect, small-size effect, skin effect and macroscopic quantum tunneling effect
Should, there is broad prospect of application in fields such as catalysis, optical filtering, light absorbs, medical science, magnetizing mediums and new materials.
Due to good combination property and cost advantage, fine silver (Ag) and its alloy material are increasingly subject to the attention of people,
Microelectronic component, interconnecting lead, conducting resinl, electrically-conducting paint, lubrication and electricity are had been widely used for as the important raw material of industry
The industrial circles such as pole material.The oxide of Ag mainly has silver oxide and argentous oxide, they as typical semi-conducting material,
The aspects such as catalysis, air-sensitive, solar cell are also widely used.
New nano material system, the particularly design of nano composite system are designed according to performance need in recent years and is ground
Study carefully, oneself turns into forward position and the focus of current nanoscale science and technology and Condensed Matter Physics research.Therefore, nano composite system is increasingly
Paid close attention to by people, wherein Nano composite granules film is exactly that a class has the nano composite material of broad prospect of application, due to
Performance of the change of the parameters such as performance, the process conditions of nano-particle all to nano compound film has significant impact, therefore,
The regulation and control to its functional characteristic can be realized under conditions of more.
The practical application of nano particle is often assembled to form the nanometer particle film of ad hoc structure, table with thin-film material
Reveal the properties not available for individual particle particle.Ag films have good catalytic performance, if by nano silver film
It is grouped together with Argent grain and will show that more preferable catalysis characteristics.Two or more material is carried out into Surface coating
After treatment, new function can be produced, for example, ultra-fine grain surface be changed by modified using method physically or chemically
The structure and composition of particle surface will greatly expand the application space of ultra-fine grain, show in microelectronics, sensing, catalysis, photoelectricity
Show, the field such as biological medicine has broad application prospects.
Due to having broad application prospects, high efficiency, the micro-nano-scale Ag films of low cost, Argent grain and its compound
Material preparation technology turns into one of study hotspot of this area.The preparation method of current Ag films mainly has magnetron sputtering method, steams
The methods such as plating method, plating, chemical plating, collosol and gel, electro-deposition.The preparation method of current sub-micro and nanoscale Ag particles is main
Including：It is hydro-thermal method, reduction silver salt method, crystal seed method, ultraviolet light, electrochemistry formated, vapour deposition, soft or hard template, anti-phase
Micelle assay.Be can be seen that based on current present Research, although people can prepare Asia in laboratory by various methods
Micro-, nanoscale Ag films and Argent grain, but prepared Argent grain be substantially free state monodisperse particles or
Many particle agglomerations together, it is difficult to these particles are fixed on into matrix or film surface.Although can be by template
Matrix or film surface growth fine silver granules, but this method and technology is complicated, and during removing template is removed easily
Ag particles are polluted, thus is also not suitable for industrialized development demand.
In view of the foregoing it is apparent that art methods are difficult Ag be well combined with film in film surface growth
Grain, that is to say, that it is difficult to prepare Ag films/Argent grain sandwich.
The content of the invention
It is an object of the invention to provide a kind of method that large-specific surface area nano Argent grain film composite material is prepared without template,
The method is to prepare bigger serface Argent grain film composite material without template on glass basis surface.
The present invention for realize technical scheme that above-mentioned technical purpose uses for：Large-specific surface area nano silver is prepared without template
The method of granulosa composite, prepares silver-zircaloy film, and make matrix keep uniform temperature to promote on glass basis surface first
Silver atoms are grown to Argent grain and product are obtained.
It is described as follows the step of glass basis surface prepares silver-zircaloy film：
1）By glass basis（Medical glass slide）It is placed in after cleaning up on magnetron sputtering coater chip bench；
2）Place Ag targets and Zr targets respectively on the target position of coating machine, be then shut off vacuum chamber, open mechanical pump and divide
Sub- pump makes vacuum reach 0.0001-0.0005Pa vacuum chamber, and chip bench is heated again then, heating temperature
200 DEG C~330 DEG C of degree；
3）Being passed through high-purity argon gas to vacuum chamber makes air pressure in vacuum chamber for 0.2-0.8Pa, be then also turned on Ag targets and
The power supply of Zr targets cosputtering deposition Ag-Zr alloy firms on glass basis；
4）After the completion of Ag-Zr alloy firms deposition, continue to be incubated 30-100min, so that the Ag in Ag-Zr alloy firms is former
Son is in film surface precipitation, forming core, the Ag particles for being grown to serve as different scale.
The content of Ag is 2-30at% in the Ag-Zr alloy firms, and thickness is 5-100nm.
Technical scheme is as follows：Glass basis is fixed on magnetron sputtering coater chip bench first, then
Chip bench is heated（200 DEG C~330 DEG C of heating-up temperature）, followed by the double target codeposition techniques of magnetron sputtering in glass
(PI) nanometer Ag-Zr alloy films of substrate deposit heterogeneity, different-thickness, held for some time（30-100 minutes）, just
Ag films/Argent grain sandwich can be prepared on glass basis surface；
Concrete operations are as follows：
(1), glass basis cleaning
Glass basis is inserted in the beaker equipped with absolute ethyl alcohol, the beaker is put into supersonic wave cleaning machine and is cleaned by ultrasonic
10-30 minutes, the glass after cleaning is put into the beaker equipped with deionized water again then and is cleaned by ultrasonic 5-15 minutes, will cleaned
Good glass basis is dried up with nitrogen, and then glass basis is fixed on magnetron sputtering coater chip bench；
(2), target prepares and the heating of coating machine chip bench
Plated film uses JCP-350 magnetically controlled DC sputtering coating machines, and purity is placed respectively on the target position of coating machine
The Ag targets of 99.99at% and the Zr targets of purity 99.99at%.By the vacuum chamber of coating machine after target and glass basis are placed
Close, and open mechanical pump, molecular pump to vacuum chamber, vacuum is reached 0.0001-0.0005Pa, then to substrate
Platform is heated, 200 DEG C~330 DEG C of heating-up temperature, and plated film is started after being heated to the temperature needed for；
(3) Ag films/Argent grain composite construction, is prepared
Start plated film after chip bench is heated to predetermined temperature stabilization.Plated film uses three target position JCP-350 magnetic controls and splashes
Penetrate coating machine.Target used by plated film is the Ag targets of purity 99.99at% and the Zr targets of purity 99.99at%.Work as vacuum degree in vacuum chamber
After reaching 0.0001-0.0005Pa, being passed through high-purity argon gas to vacuum chamber makes the air pressure in vacuum chamber reach between 0.2-0.8Pa.
Then the power supply for being also turned on Ag targets and Zr targets starts cosputtering Ag-Zr alloy firms, alloy firm is deposited on glass basis
The content of middle Zr is regulated and controled by controlling the sputtering power of Zr targets.Growth rate required for of the sputtering power of Ag targets and Zr and
Thin film composition is adjusted.By adjusting process parameter, Ag-5~30at.%Zr alloy films can be prepared, film thickness 5-100nm it
Between.Thin film deposition finishes meron platform and continues to be incubated 30-100 minutes.Due to film, chip bench is always maintained in deposition process
Uniform temperature, in-situ annealing has been carried out equivalent to film, promotes the Ag atoms in alloy film in surface precipitation, forming core, growth
Ag particles as different scale.So as to prepare Ag films/Argent grain sandwich by one-step method；
Beneficial effect：The present invention prepares silver alloy film and matrix In Situ Heating skill using the double target co-depositions of magnetron sputtering
Art, realizes and prepares high-performance, large-specific surface area nano Ag films/Argent grain sandwich without template.This side
Ag films thickness, Argent grain yardstick in sandwich prepared by method can regulate and control in the range of micro/nano-scale.Alloy
Zr elements in film can suppress Ag atoms and be spread to glass basis, and glass basis can suppress film residual stress release, promote
Ag atoms are made to diffuse to the surface to form approach of the Ag particles as Stress Release.The inventive method is simple, easy to operate, without adopting
With template, low cost, environmental protection, it is easy to prepare large area, high-performance nano Argent grain film without template on matrix and answer
Condensation material, more than 20% can be increased than fine silver film specific surface area.The high-performance silver prepared using magnetron sputtering codeposition technique
Granulosa sandwich can be applied to the fields such as electronic device, catalysis, sensor, photoelectric display device.
Specific embodiment
With reference to specific embodiment, the invention will be further elaborated.
Embodiment 1
The method that large-specific surface area nano Argent grain film composite material is prepared without template, comprises the following steps：
(1), glass basis cleaning
Glass basis is inserted in the beaker equipped with absolute ethyl alcohol, the beaker is put into supersonic wave cleaning machine and is cleaned by ultrasonic
10 minutes, the glass after cleaning is put into the beaker equipped with deionized water again then and is cleaned by ultrasonic 5 minutes, by cleaned glass
Glass matrix is dried up with nitrogen, and then glass basis is fixed on magnetron sputtering coater chip bench.
(2), target prepares and the heating of coating machine chip bench
Place the Ag targets of purity 99.99at% and the Zr targets of purity 99.99at% respectively on the target position of coating machine.By target
Material and glass basis close the vacuum chamber of coating machine after placing, and open mechanical pump, molecular pump to vacuum chamber,
Vacuum is reached 0.0005Pa, then chip bench is heated, 200 DEG C of heating-up temperature, keeping temperature stabilization.
(3) Ag films/Argent grain composite construction, is prepared
Plated film uses three target position JCP-350 magnetron sputtering coaters.When chip bench temperature stabilization to 200 DEG C, while
After vacuum degree in vacuum chamber reaches 0.0005Pa, being passed through high-purity argon gas to vacuum chamber makes vacuum room pressure reach 0.2Pa.Then it is same
When connect the power supply of Ag targets and Zr targets and start cosputtering deposition Ag-Zr alloy firms, the sputtering of Ag targets and Zr on glass basis
Power is respectively 100W and 30W, and two targets are all sputtered 2 minutes.Ag-12.3at.%Zr alloy films are prepared, film thickness is 28
Nanometer.Thin film deposition finishes meron platform and continues to be incubated 30 minutes, promote Ag atoms in alloy film surface precipitation, forming core,
It is grown to serve as the Ag particles of 36 nanometers of average dimension.So as in the case where template is not used, a step has prepared nanoscale
Ag films/nano-Ag particles sandwich, than fine silver film specific surface area increase 21%.
Embodiment 2
The method that large-specific surface area nano Argent grain film composite material is prepared without template, comprises the following steps：
(1), glass basis cleaning
Glass basis is inserted in the beaker equipped with absolute ethyl alcohol, the beaker is put into supersonic wave cleaning machine and is cleaned by ultrasonic
10 minutes, the glass after cleaning is put into the beaker equipped with deionized water again then and is cleaned by ultrasonic 10 minutes, will be cleaned
Glass basis is dried up with nitrogen, and then glass basis is fixed on magnetron sputtering coater chip bench.
(2), target prepares and the heating of coating machine chip bench
Place the Ag targets of purity 99.99at% and the Zr targets of purity 99.99at% respectively on the target position of coating machine.By target
Material and glass basis close the vacuum chamber of coating machine after placing, and open mechanical pump, molecular pump to vacuum chamber,
Vacuum is reached 0.0003Pa, then chip bench is heated, 280 DEG C of heating-up temperature, keeping temperature stabilization.
(3) Ag films/Argent grain composite construction, is prepared
Plated film uses three target position JCP-350 magnetron sputtering coaters.When chip bench temperature stabilization to 280 DEG C, while
After vacuum degree in vacuum chamber reaches 0.0003Pa, being passed through high-purity argon gas to vacuum chamber makes vacuum room pressure reach 0.35Pa.Then
The power supply for being also turned on Ag targets and Zr targets starts the cosputtering deposition Ag-Zr alloy firms on glass basis, and Ag targets and Zr's splashes
Power respectively 120W and 50W is penetrated, two targets are all sputtered 5 minutes.Ag-10.9at.%Zr alloy films are prepared, film thickness is
65 nanometers.Thin film deposition finishes meron platform and continues to be incubated 45 minutes, promotes the Ag atoms in alloy film in surface precipitation, shape
Core, the Ag particles for being grown to serve as 125 nanometers of average dimension.So as in the case where template is not used, a step has prepared nanometer
Yardstick Ag films/nano-Ag particles sandwich, than fine silver film specific surface area increase 28%.
Embodiment 3
The method that large-specific surface area nano Argent grain film composite material is prepared without template, comprises the following steps：
(1), glass basis cleaning
Glass basis is inserted in the beaker equipped with absolute ethyl alcohol, the beaker is put into supersonic wave cleaning machine and is cleaned by ultrasonic
15 minutes, the glass after cleaning is put into the beaker equipped with deionized water again then and is cleaned by ultrasonic 15 minutes, will be cleaned
Glass basis is dried up with nitrogen, and then glass basis is fixed on magnetron sputtering coater chip bench.
(2), target prepares and the heating of coating machine chip bench
Place the Ag targets of purity 99.99at% and the Zr targets of purity 99.99at% respectively on the target position of coating machine.By target
Material and glass basis close the vacuum chamber of coating machine after placing, and open mechanical pump, molecular pump to vacuum chamber,
Vacuum is reached 0.0001Pa, then chip bench is heated, 330 DEG C of heating-up temperature, keeping temperature stabilization.
(3) Ag films/Argent grain composite construction, is prepared
Plated film uses three target position JCP-350 magnetron sputtering coaters.When chip bench temperature stabilization to 330 DEG C, while
After vacuum degree in vacuum chamber reaches 0.0001Pa, being passed through high-purity argon gas to vacuum chamber makes vacuum room pressure reach 0.8Pa.Then it is same
When connect the power supply of Ag targets and Zr targets and start cosputtering deposition Ag-Zr alloy firms, the sputtering of Ag targets and Zr on glass basis
Power is respectively 140W and 40W, and two targets are all sputtered 8 minutes.Ag-8.1at.%Zr alloy films are prepared, film thickness is 90
Nanometer.Thin film deposition finishes meron platform and continues to be incubated 60 minutes, promote Ag atoms in alloy film surface precipitation, forming core,
It is grown to serve as the Ag particles of 230 nanometers of average dimension.So as to be not used template in the case of, a step prepared Ag films/
Argent grain sandwich, than fine silver film specific surface area increase 41%.
Claims (2)
1. the method that large-specific surface area nano Argent grain film composite material is prepared without template, it is characterised in that：First in glass base
Body surface face prepares silver-zircaloy film, and keeps the temperature so that silver atoms are grown to Argent grain and product is obtained；It is described in glass
The step of matrix surface prepares silver-zircaloy film is as follows：
1）It is placed in after glass basis is cleaned up on magnetron sputtering coater chip bench；
2）Place Ag targets and Zr targets respectively on the target position of coating machine, be then shut off vacuum chamber, open mechanical pump and molecular pump
To vacuum chamber, vacuum is reached 0.0001-0.0005Pa, chip bench is heated again then, heating-up temperature 200
DEG C~330 DEG C；
3）Being passed through high-purity argon gas to vacuum chamber makes the air pressure in vacuum chamber be 0.2-0.8Pa, is then also turned on Ag targets and Zr targets
Power supply on glass basis cosputtering deposition Ag-Zr alloy firms；
4）After the completion of Ag-Zr alloy firms deposition, continue to be incubated 30-100min to chip bench, so that in Ag-Zr alloy firms
Ag atoms are in film surface precipitation, forming core, the Ag particles for being grown to serve as different scale.
2. the method that large-specific surface area nano Argent grain film composite material is prepared without template according to claim 1, it is special
Levy and be：The content of Ag is 2-30at% in the Ag-Zr alloy firms, and thickness is 5-100nm.
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| CN109898057B (en) * | 2019-03-25 | 2020-12-29 | 中国科学院物理研究所 | Metallic glass film with surface Raman enhancement effect, preparation method and application thereof |
| CN110965024B (en) * | 2019-10-29 | 2020-11-20 | 南京航空航天大学 | Biomedical material and preparation method 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 |
| CN102660733B (en) * | 2012-05-09 | 2013-11-27 | 复旦大学 | Silver nanoparticle film with mixed valent state, preparation method thereof and application thereof |
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