CN104831248B - The method that bigger serface copper particle film composite material is prepared without template - Google Patents
The method that bigger serface copper particle film composite material is prepared without template Download PDFInfo
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Abstract
The method that bigger serface copper particle film composite material is prepared without template, chromiumcopper film is prepared on glass basis surface, and matrix is maintained at a certain temperature so that product is made for copper particle in alloy film superficial growth in copper atom.The present invention prepares copper alloy thin films and matrix In Situ Heating technology using the double target co-depositions of magnetron sputtering, realize and prepare large-specific surface area nano Copper thin film/copper particle composite structures material without template, it can increase more than 20% than fine copper film specific surface area, Copper thin film thickness, copper particle scale in the sandwich can regulate and control in the range of micro/nano-scale, without using template, cost is low, it is green, it is easy on matrix prepare large area, high-performance nano copper particle film composite material without template.
Description
Technical field
The present invention relates to micro-, nanometer sized materials preparation fields, specifically a kind of prepared without template compares table greatly
The method of area copper particle film composite material.
Background technology
With micro-nano scientific and technical development, micron and nano thin-film, the excellent properties of particle and broad prospect of application
Gradually recognized by researcher and cause the great interest of countries in the world material scholar, physicist and chemist.When size reaches
During nanoscale, obvious quantum size effect, small-size effect, skin effect and macro quanta tunnel effect will be presented in particle,
There is broad prospect of application in fields such as catalysis, optical filtering, light absorbs, medical science, magnetizing mediums and new materials.
Need to design new nano material system, the particularly design of nano composite system and grind according to performance in recent years
Study carefully, oneself turns into current nanoscale science and technology and forward position and the focus of Condensed Matter Physics research, and the research of this respect is more emphasized by people
Wish design new system, obtain desired characteristic, therefore, nano composite system has been to be concerned by more and more people,
Wherein Nano composite granules film is exactly a kind of nano composite material with broad prospect of application, due to the performance of nano-particle,
The change of the parameters such as process conditions all has significant impact to the performance of nano compound film, therefore, can be in more bar
The regulation and control to its functional characteristic are realized under part.Copper thin film, titanium film all have good antibacterial, catalytic performance, if by nanometer
Copper thin film, copper particle and titanium film, which are grouped together, will show that more preferable antibacterial, catalysis characteristics.
After two or more material is carried out into Surface coating processing, new function can be produced, such as to ultra-fine
Particle surface is modified through row, i.e., will greatly be expanded using the structure and composition of method change particle surface physically or chemically super
Fine grain application space has broad application prospects in fields such as microelectronics, sensing, catalysis, photoelectric display, biological medicines.
Due to good combination property and cost advantage, fine copper (Cu) 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.Cu oxide mainly has cupric oxide and cuprous oxide, they as typical semi-conducting material,
Catalysis, air-sensitive, solar cell etc. are also widely used.
Due to having broad application prospects, high efficiency, the micro-nano-scale Cu films of low cost, copper particle and its compound
Material preparation technology turns into one of study hotspot of this area.The preparation method of Copper thin film mainly has magnetron sputtering method, steamed at present
The methods of plating method, plating, chemical plating, collosol and gel, electro-deposition.The preparation method of sub-micro and nanoscale Cu particles is main at present
Including：It is hydro-thermal method, reduction mantoquita method, crystal seed method, ultraviolet light, electrochemistry formated, vapour deposition, soft or hard template, anti-phase
Micelle assay.Researcher can prepare the Cu particles of different scale by these methods.Also someone uses hydrothermal reduction legal system
For Cu particles, the preparation process and technological parameter involved by the method are more, and experimental period is longer, prepared copper cluster of grains
Cluster is easier to assemble.In addition, by traditional sputtering method pure Cu particles can also be prepared, but the pure Cu particle sizes prepared by
Limitation, once particle scale more than more than ten nanometers, just occurs that particle is interconnected to form the phenomenon of film.Ground based on current
The Copper thin film of sub-micro and nanoscale can be prepared by a variety of methods in laboratory although studying carefully present situation and can be seen that people
With copper particle, but prepared copper particle be substantially free state monodisperse particles or many particle agglomerations together,
It is difficult to these particles are fixed on matrix or film surface.Although it can be grown by template in matrix or film surface
Fine copper particle, but this method and technology is complicated, and easily Cu particles are polluted during removing template is removed, thus
It is also not suitable for industrialized development demand.
In view of the foregoing it is apparent that art methods are difficult Cu be well combined in film surface growth with film
Grain, that is to say, that it is difficult to prepare Copper thin film/copper particulate composite.
The content of the invention
It is an object of the invention to provide a kind of method that no template prepares bigger serface copper particle film composite material.
The present invention for realize technical scheme that above-mentioned technical purpose uses for：Bigger serface copper membrana granulosa is prepared without template
The method of composite, copper-evanohm film is prepared on glass basis surface, and matrix is kept certain temperature so that copper atom exists
Alloy film superficial growth is that product is made in copper particle.
Described the step of copper-evanohm film is prepared on glass basis surface, is as follows：
1）It is placed in after glass basis is cleaned up on magnetron sputtering coater chip bench；
2）Place Cu targets and Cr 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, then chip bench is heated again, heating is warm to vacuum chamber
200 DEG C~330 DEG C of degree；
3）Being passed through high-purity argon gas to vacuum chamber makes the air pressure in vacuum chamber be 0.2-0.8Pa, be then also turned on Cu targets and
The power supply of Cr targets cosputtering on glass basis deposits Cu-Cr alloy firms；
4）After the completion of Cu-Cr alloy firms deposition, continue to be incubated 30-100min, so that the Cu in Cu-Cr alloy firms is former
Son is in film surface precipitation, forming core, the Cu particles for being grown to serve as different scale.
Cu content is 2-30at%, thickness 5-100nm in the Cu-Cr alloy firms.
Technical scheme is as follows：Glass basis is fixed on magnetron sputtering coater chip bench first, then
Chip bench is heated（200 DEG C~350 DEG C of heating-up temperature）, finally by the double target codeposition techniques of magnetron sputtering in glass
(PI) substrate deposit heterogeneity, the Cu-Cr alloy films of different-thickness, held for some time（30-100 minutes）, it is possible to
On glass basis surface one, step prepares Copper thin film/copper particle composite structures.Concrete technical scheme is as follows：
(1), glass basis cleans
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 then put into ultrasonic cleaning 5-15 minutes in the beaker equipped with deionized water again, will be 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 coating machine chip bench heats
Plated film uses JCP-350 magnetically controlled DC sputtering coating machines, and purity is placed respectively on the target position of coating machine
99.99at% Cu targets and purity 99.99at% Cr targets.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, is heated to start plated film after up to required temperature；
(3), a step prepares Copper thin film/copper particle composite structures
When chip bench is heated to start plated film after predetermined temperature is stable.Plated film splashes using three target position JCP-350 magnetic controls
Penetrate coating machine.Target used in plated film is purity 99.99at% Cu targets and purity 99.99at% Cr targets.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 Cu targets and Cr targets starts cosputtering Cu-Cr alloy firms, alloy firm is deposited on glass basis
Middle Cr content is by controlling the sputtering power of Cr targets to regulate and control.Cu targets and Cr sputtering power according to required growth rate and
Thin film composition adjusts sputtering power.By adjusting process parameter, Cu-2~30at.%Cr alloy films can be prepared, film thickness exists
5-100nm.Chip bench continues to be incubated 30-100 minutes after thin film deposition.Due to film, chip bench has in deposition process
Certain temperature, in-situ annealing is carried out equivalent to film, promoted the Cu atoms in alloy film in surface precipitation, forming core, growth
As the Cu particles of different scale, so as to prepare Copper thin film/copper particle composite structures by one-step method；
Beneficial effect：The present invention prepares copper alloy thin films and matrix In Situ Heating skill using the double target co-depositions of magnetron sputtering
Art, realize and prepare large-specific surface area nano Copper thin film/copper particle composite structures material without template, compare table than fine copper film
Area can increase more than 20%.Cr elements in alloy film can suppress Cu atoms and be spread to glass basis, and glass basis can press down
Made membrane residual stress discharges, and promotes Cu atoms to diffuse to the surface to form approach of the Cu particles as stress release.This method
Copper thin film thickness, copper particle scale in the sandwich of preparation can regulate and control in the range of micro/nano-scale.The present invention
Method is simple, easy to operate, without using template, cost is low, green, is easy on matrix prepare big face without template
Product, high-performance nano copper particle film composite material, it can be applied to the neck such as electronic device, catalysis, sensor, photoelectric display device
Domain.
Embodiment
With reference to specific embodiment, the invention will be further elaborated.
Embodiment 1
The method that bigger serface copper particle film composite material is prepared without template, comprises the following steps：
(1), glass basis cleans
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, then the glass after cleaning is put into the beaker equipped with deionized water again 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 coating machine chip bench heats
Place purity 99.99at% Cu targets and purity 99.99at% Cr targets 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), a step prepares a nanometer Copper thin film/copper particle composite structures
Plated film is using three target position JCP-350 magnetron sputtering coaters.When chip bench temperature stabilization is to 200 DEG C, simultaneously
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 Cu targets and Cr targets and start the cosputtering on glass basis and deposit Cu-Cr alloy firms, Cu targets and Cr sputtering
Power is respectively 100W and 30W, and two targets all sputter 2 minutes.Prepare Cu-11.6at.%Cr alloy films, film thickness 28
Nanometer.Chip bench continues insulation 30 minutes after thin film deposition, promote Cu atoms in alloy film surface precipitation, forming core,
The Cu particles of 42 nanometers of average dimension are grown to serve as, so as to which in the case where template is not used, a step has prepared nanoscale
Copper thin film/nano copper particle sandwich, than fine copper film specific surface area increase 23%.
Embodiment 2
The method that bigger serface copper particle film composite material is prepared without template, comprises the following steps：
(1), glass basis cleans
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, then the glass after cleaning is put into the beaker equipped with deionized water again 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 coating machine chip bench heats
Place purity 99.99at% Cu targets and purity 99.99at% Cr targets 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), a step prepares Copper thin film/copper particle composite structures
Plated film is using three target position JCP-350 magnetron sputtering coaters.When chip bench temperature stabilization is to 280 DEG C, simultaneously
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 Cu targets and Cr targets starts the cosputtering on glass basis and deposits Cu-Cr alloy firms, and Cu targets and Cr's splashes
It is respectively 120W and 50W to penetrate power, and two targets all sputter 4 minutes.Cu-9.7at.%Cr alloy films are prepared, film thickness is
58 nanometers.Chip bench continues insulation 45 minutes after thin film deposition, promotes the Cu atoms in alloy film to be separated out on surface, shape
Core, the Cu particles for being grown to serve as 165 nanometers of average dimension, so as to which in the case where template is not used, a step has prepared nanometer
Yardstick Copper thin film/nano copper particle sandwich, than fine copper film specific surface area increase 32%.
Embodiment 3
The method that bigger serface copper particle film composite material is prepared without template, comprises the following steps：
(1), glass basis cleans
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, then the glass after cleaning is put into the beaker equipped with deionized water again 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 coating machine chip bench heats
Place purity 99.99at% Cu targets and purity 99.99at% Cr targets 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), a step prepares Copper thin film/copper particle composite structures
Plated film is using three target position JCP-350 magnetron sputtering coaters.When chip bench temperature stabilization is to 330 DEG C, simultaneously
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 Cu targets and Cr targets and start the cosputtering on glass basis and deposit Cu-Cr alloy firms, Cu targets and Cr sputtering
Power is respectively 150W and 40W, and two targets all sputter 8 minutes.Prepare Cu-6.8at.%Cr alloy films, film thickness 91
Nanometer.Chip bench continues insulation 60 minutes after thin film deposition, promote Cu atoms in alloy film surface precipitation, forming core,
Be grown to serve as the Cu particles of 235 nanometers of average dimension, so as to be not used template in the case of, a step prepared Copper thin film/
Copper particle composite structures material, than fine copper film specific surface area increase 43%.
Claims (2)
1. the method for bigger serface copper particle film composite material is prepared without template, it is characterised in that：In glass basis surface system
Standby copper-evanohm film, and the temperature that chip bench is in 200 DEG C~330 DEG C is kept so that copper atom is grown to copper particle and is made
Product；Described the step of copper-evanohm film is prepared on glass basis surface, is as follows：
1）It is placed in after glass basis is cleaned up on magnetron sputtering coater chip bench；
2）Place Cu targets and Cr 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, then chip bench is heated again, 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 Cu targets and Cr targets
Power supply on glass basis cosputtering deposit Cu-Cr alloy firms；
4）After the completion of Cu-Cr alloy firms deposition, continue to be incubated 30-100min to chip bench, so that in Cu-Cr alloy firms
Cu atoms are in film surface precipitation, forming core, the Cu particles for being grown to serve as different scale.
2. the method that no template according to claim 1 prepares bigger serface copper particle film composite material, its feature exist
In：Cu content is 2-30at%, thickness 5-100nm in the Cu-Cr alloy firms.
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| 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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