CN106756852A - A kind of preparation method of the nanocrystalline metal cobalt thin film of different phase structures - Google Patents
A kind of preparation method of the nanocrystalline metal cobalt thin film of different phase structures Download PDFInfo
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- CN106756852A CN106756852A CN201710013738.5A CN201710013738A CN106756852A CN 106756852 A CN106756852 A CN 106756852A CN 201710013738 A CN201710013738 A CN 201710013738A CN 106756852 A CN106756852 A CN 106756852A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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Abstract
A kind of preparation method of the nanocrystalline metal cobalt thin film of different phase structures, the Nanocrystalline Cobalt film of pure FCC and HCP phases and its mixed phase is prepared in particular by programmable direct current magnetron sputtering process and by controlling dutycycle and sputtering power.Shielding power supply uses programmable dc source, sputtering target material that the cobalt target of more than 99.9wt% is reached for purity, and substrate is single crystalline Si piece (100), and before the deposition, by the cleaning of Si pieces, the base vacuum of vacuum chamber is evacuated to 3 5x10‑4More than Pa, is passed through high-purity argon gas in sputtering chamber, operating pressure is set to 1.5 2Pa, and substrate temperature remains room temperature；Dutycycle is 50%, the 200W of sputtering power 150, prepares pure HCP phases film；Dutycycle is 67%, and sputtering power is 150 200W, prepares FCC and HCP mixed phase cobalt thin films；Dutycycle is 100%, and sputtering power is 150 200W, prepares pure FCC phases film.The present invention is simple to operate, reproducible, realizes working well.
Description
Technical field
The invention provides a kind of pure FCC and HCP phases and its preparation method of mixed phase nanocrystalline metal cobalt thin film, especially
It is that pure FCC and HCP phases and its mixed are prepared using programmable direct current magnetron sputtering process and by controlling dutycycle and sputtering power
Close the Nanocrystalline Cobalt film of phase.
Background technology
Cobalt is a kind of glossiness metal of silver gray, and 1495 DEG C of fusing point, 2870 DEG C of boiling point has ductility and ferromagnetism, cobalt
More stable in the air of normal temperature, during higher than 300 DEG C, cobalt starts oxidation in atmosphere.Cobalt is because with good high temperature resistant, resistance to
Burn into magnetic behavior and be widely used in the industrial circles such as Aero-Space, machine-building, electric and electronic, chemistry, ceramics, be system
Make one of important source material of high temperature alloy, hard alloy, ceramic paint, catalyst, battery.And cobalt or a kind of excessive race's magnetic
Property material, in the field such as film magnetic head, magnetic recording and Magnetic Sensor extensive application.It is anti-that there is pure cobalt ppolymorphism to change
Should, at 422 DEG C above is face-centred cubic structure, and below the temperature it is close-packed hexagonal structure.And there are some researches show nanocrystalline
Cobalt generally remains its high-temperature-phase and face-centered cubic phase in room temperature, rather than close-packed hexagonal phase.In fact, there are some researches show working as crystal grain
When size is less than 20nm, the cobalt of FCC configuration is most stable of structure；Between 20nm-40nm, HCP mixes crystallite dimension with FCC
Mutually exist；When crystallite dimension is in more than 40nm, HCP phase stable existences.
In sum, the cobalt film for preparing different phase structures directly determines that its combination property is good and bad, has an effect on it in reality
Reliability in the application of border.Conventional preparation method has electrodeposition process and magnetron sputtering method, it is necessary to add when prepared by electrodeposition process
Organic additive, configures plating solution, and comparatively laborious and can introduce foreign atom, these foreign atoms would generally influence the property of film
Energy.
The content of the invention
The present invention seeks to：A kind of magnetron sputtering method of simple programmable is provided to prepare the nanocrystalline gold of different phase structures
Belong to the preparation method of cobalt thin film, the Nanocrystalline Cobalt film of different phase compositions, energy are obtained by controlling its sputtering power and dutycycle
It is enough to obtain high-purity cobalt thin film of different phase compositions in room temperature, but some impurity elements can be introduced in electrodeposition process preparation process.This
Invention can also obtain high-purity single-phase nano crystalline cobalt except that can obtain mixed phase cobalt thin film by controlling sputtering parameter, and
And repeatability is good.
The technical scheme is that:A kind of preparation method of the nanocrystalline metal cobalt thin film of different phase structures, using can
Formula direct current magnetron sputtering process, sputtering target material reaches more than 99.9% cobalt for purity, and substrate is single crystalline Si piece (100), heavy
Before product, by Wafer Cleaning, vacuum chamber base vacuum is then evacuated to 3-5x10-4Pa, sputter gas are high-purity argon gas, sputtering pressure
It is by force 1.5-2Pa, underlayer temperature is room temperature；The growth rate of cobalt thin film is determined that is, the thickness of film is by control by sputtering power
Sputtering time control processed；Dutycycle is 50%, sputtering power 150-200W, prepares pure HCP phases film；Dutycycle is 67%, is splashed
Power is penetrated for 150-200W, FCC and HCP mixed phase cobalt thin films are prepared；Dutycycle is 100%, and sputtering power is 150-200W, system
Standby pure FCC phases film.
The sputtering target material selects diameter 60mm, the cobalt of thickness 3mm.
The flow of the high-purity argon gas is 30sccm, is 1.5-2Pa by flashboard valve regulation vacuum degree in vacuum chamber.
In order to remove cobalt target material surface oxide and spot, first to target pre-sputtering 20min, baffle plate is then opened, carried out
The deposition of cobalt thin film.
The power-supply system of the magnetic control sputtering device of use is furnished with a DSP-600-01.25HD programmable dc source, maximum
Power can reach 600W.
Characterizing method is characterized for XRD.
The experimental technique step that magnetically controlled DC sputtering prepares different Nanocrystalline Cobalt films is as follows：
A. backing material selects single crystalline Si (100) piece
B. the Nanocrystalline Cobalt of the first pure HCP phase, sputtering power 150-200W, dutycycle 50% are first prepared
C. second HCP and FCC mixed phase Nanocrystalline Cobalt, sputtering power 150-200W, dutycycle 67% are then prepared
D. the Nanocrystalline Cobalt of the third pure FCC phase, sputtering power 150-200W, dutycycle 100% are prepared
E. XRD signs are carried out to three groups of samples
The condition of high vacuum degree being had using DC sputtering can effectively prevent the oxidation of cobalt film, can guarantee that the purity of cobalt, together
When by parameter regulation, the relatively good control realized to each thing phase of Nanocrystalline Cobalt can be obtained by adjusting dutycycle
All realized at ambient temperature to the Nanocrystalline Cobalt of pure HCP phases and FCC and HCP mixed phases, and this whole process.
Compared with existing preparation method, the invention has the advantages that：
1. the present invention is capable of achieving to each phase control of metallic cobalt film, can be prepared pure HCP, pure FCC and be mixed phase structure
Nanocrystalline Cobalt film, control method is simple and convenient, and repeatability is preferably.
2. compared with electrodeposition process, electro-deposition can be introduced into the additive element in electroplate liquid when preparing, cause the pure of film
Degree is poor, and uses this method, it is only necessary to provide the target of high-purity, the thin film composition for sputtering out and target material composition basic
Sample.
3. compared with traditional magnetron sputtering, previous studies person realizes difference to the present invention by of a relatively high temperature
The preparation of the cobalt thin film of structure, is a kind of mode for wasting the energy, and comparatively laborious.This method uses programmable direct current
Source, prepares the cobalt thin film of different structure at room temperature, it is not necessary to extra to control temperature to realize the control to membrane structure, relatively
It is simple and convenient.
Brief description of the drawings
Fig. 1 dutycycles are the pulse diagram of 50% programmable dc source.
Fig. 2 dutycycles are the pulse diagram of 67% programmable dc source.
Fig. 3 dutycycles are the pulse diagram of 100% programmable dc source.
The XRD analysis figure of the Nanocrystalline Cobalt film of Fig. 4 HCP phases.
The XRD analysis figure of the Nanocrystalline Cobalt film of Fig. 5 mixed phases.
The XRD analysis figure of the Nanocrystalline Cobalt film of Fig. 6 FCC phases.
The TEM photos of the Nanocrystalline Cobalt film of Fig. 7 HCP phases：A) bright field image, b) dark field image, c) SEAD figure,
D) crystallite dimension statistical Butut.
The TEM photos of the Nanocrystalline Cobalt film of Fig. 8 mixed phases：A) bright field image, b) dark field image, c) SEAD figure,
D) crystallite dimension statistical Butut.
The TEM photos of the Nanocrystalline Cobalt film of Fig. 9 FCC phases：A) bright field image, b) dark field image, c) SEAD figure,
D) crystallite dimension statistical Butut.
Specific embodiment
The Nanocrystalline Cobalt film of different phase structures is prepared using direct current magnetron sputtering process, the equipment for using is Chinese Academy of Sciences Shen
The FJL-560a type dual chamber magnetic controls and ionic beam combined sputtering deposition system of positive scientific instrument development center Co., Ltd production, should
Equipment installs 3 magnetic control targets, and it is common permanent magnetism magnetic control target that one is, two strong magnetic targets, target diameter is all that 60mm, RF and DC are simultaneous
Hold, maximum sputtering power is 400W；One six station has the sample rotating disk of revolution function, and sample can heat also water-cooled, most
Heating-up temperature high is up to 500 degree, it is adaptable to prepare the various metals that can be sputtered, ceramics and sull.Power-supply system
Equipped with programmable dc source, the effective temperature for suppressing target.Vacuum system
Material prepares：Sputtering target material for purity 99.9% cobalt, diameter 60mm, thickness 3mm, substrate monocrystal Si (100) piece,
To improve the adhesion and surface quality of film, silicon chip is cleaned by ultrasonic 20min with acetone, alcohol respectively successively, removes surface
Dust and oil stain, this is favorably improved the quality of film.Before sputtering, first to cobalt target pre-sputtering 20min, to remove surface
Oxide and spot, improve the quality of film.
Co film preparations：Using programmable direct current magnetron sputtering process, base vacuum is evacuated to 3-5x10-4Pa, argon flow amount is
20sccm, operating pressure is 1.5-2Pa, is biased as -50V.Plastics thickness control in 2000nm, by controlling effective sputtering time
To control film thickness.Underlayer temperature keeps room temperature.Specific implementation method is divided into following three groups：A) dutycycle is 50%, sputtering
Power 150-200W, prepares pure HCP phases film；B) dutycycle is 67%, and sputtering power is 150-200W, prepares FCC and HCP and mixes
Close phase cobalt thin film；C) dutycycle is 100%, and sputtering power is 150-200W, prepares pure FCC phases film；
Structural characterization and result：
A) dutycycle is 50%, sputtering power 150-200W, understands that the film is solid matter six by carrying out XRD analysis to cobalt film
Square structure, it can be seen that crystal grain distribution is uniform from transmission plot, SEAD further proves close-packed configuration, crystal grain chi
Very little about 38nm, the hardness number measured with nano impress is 5.03GPa；
B) dutycycle is 67%, and sputtering power is 150-200W, and the film is understood by carrying out X-ray diffraction analysis to cobalt film
Be the mixed structure of HCP+FCC, from transmission image it can be seen that etc. shaft-like crystal grain distribution it is uniform, SEAD image
Diffraction ring match with the peak position of XRD, crystallite dimension is about 37nm, and the hardness number measured with nano impress is 5.88GPa；
C) dutycycle is 100%, and sputtering power is 150-200W, understands that the film is face-centred cubic structure by XRD analysis,
Can be seen that crystallite dimension is tiny and is evenly distributed from TEM image, the centroid structure diffraction ring of SEAD and cobalt is very
Good correspondence, crystallite dimension is about 25nm, and the hardness number measured with nano impress is 4.74GPa.
Using programmable direct current magnetron sputtering process, by controlling sputtering power and dutycycle, can realize well to difference
The Nanocrystalline Cobalt film of phase structure, is tested by XRD, and prepared cobalt film is pure FCC phases, and pure HCP phases, HCP and FCC mixes
Phase.The experimental repeatability is good, simple to operate.
Claims (6)
1. a kind of preparation method of the nanocrystalline metal cobalt thin film of different phase structures, using programmable direct current magnetron sputtering process, splashes
Material of shooting at the target reaches more than 99.9% cobalt for purity, and substrate is single crystalline Si piece (100), before the deposition, by Wafer Cleaning, then
Vacuum chamber base vacuum is evacuated to 3-5x10-4Pa, sputter gas are high-purity argon gas, and sputtering pressure is 1.5-2Pa, and underlayer temperature is
Room temperature；The growth rate of cobalt thin film is determined that is, the thickness of film is controlled by controlling sputtering time by sputtering power；Dutycycle is
50%, sputtering power 150-200W, prepare pure HCP phases film；Dutycycle is 67%, and sputtering power is 150-200W, prepares FCC
With HCP mixed phase cobalt thin films；Dutycycle is 100%, and sputtering power is 150-200W, prepares pure FCC phases film.
2. the preparation method of the nanocrystalline metal cobalt thin film of a kind of different phase structures according to claim 1, it is characterized in that,
The sputtering target material selects diameter 60mm, the cobalt of thickness 3mm.
3. the preparation method of the nanocrystalline metal cobalt thin film of a kind of different phase structures according to claim 1, it is characterized in that,
The flow of the high-purity argon gas is 30sccm, is 1.5-2Pa by flashboard valve regulation vacuum degree in vacuum chamber.
4. the preparation method of the nanocrystalline metal cobalt thin film of a kind of different phase structures according to claim 1, it is characterized in that,
In order to remove cobalt target material surface oxide and spot, first to target pre-sputtering 20min, baffle plate is then opened, carry out cobalt thin film
Deposition.
5. the preparation method of the Nanocrystalline Cobalt film of a kind of different phase structures according to right 1, it is characterized in that, the magnetic of use
The power-supply system for controlling sputter is furnished with a DSP-600-01.25HD programmable dc source, and peak power can reach 600W.
6. the preparation method of the Nanocrystalline Cobalt film of a kind of different phase structures according to right 1, it is characterized in that, characterizing method
For XRD is characterized.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323946A (en) * | 2008-07-15 | 2008-12-17 | 南京大学 | Preparation of nanocrystalline metal Ta film having out phase structure |
| CN102560367A (en) * | 2012-03-06 | 2012-07-11 | 广东工业大学 | Magnetic control sputtering method for growing cobalt film with pyramid appearance characteristics |
| CN103741107A (en) * | 2013-12-26 | 2014-04-23 | 北京航空航天大学 | Method for plating metal film on surface of microorganism in magnetron sputtering manner |
| CN105088157A (en) * | 2015-07-27 | 2015-11-25 | 河南科技大学 | Method for preparing composite particle membrane by wrapping copper particles with nanometer cobalt membranes |
-
2017
- 2017-01-09 CN CN201710013738.5A patent/CN106756852A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323946A (en) * | 2008-07-15 | 2008-12-17 | 南京大学 | Preparation of nanocrystalline metal Ta film having out phase structure |
| CN102560367A (en) * | 2012-03-06 | 2012-07-11 | 广东工业大学 | Magnetic control sputtering method for growing cobalt film with pyramid appearance characteristics |
| CN103741107A (en) * | 2013-12-26 | 2014-04-23 | 北京航空航天大学 | Method for plating metal film on surface of microorganism in magnetron sputtering manner |
| CN105088157A (en) * | 2015-07-27 | 2015-11-25 | 河南科技大学 | Method for preparing composite particle membrane by wrapping copper particles with nanometer cobalt membranes |
Non-Patent Citations (1)
| Title |
|---|
| 李洪涛等: "占空比对磁控溅射纯Cr镀层微观组织结构的影响", 《真空科学与技术学报》 * |
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