CN104451568A - Preparing method for double-magnetism phase nanocomposite film - Google Patents

Preparing method for double-magnetism phase nanocomposite film Download PDF

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CN104451568A
CN104451568A CN201510006670.9A CN201510006670A CN104451568A CN 104451568 A CN104451568 A CN 104451568A CN 201510006670 A CN201510006670 A CN 201510006670A CN 104451568 A CN104451568 A CN 104451568A
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film
alloy nanoparticle
preparation
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nano compound
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彭栋梁
王俊宝
王来森
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Xiamen University
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Xiamen University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C23C14/08—Oxides
    • C23C14/085—Oxides of iron group metals
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Thin Magnetic Films (AREA)

Abstract

The invention relates to nanocomposite films, in particular to a preparing method for a double-magnetism phase nanocomposite film. Two Fe65Co35 targets are installed on opposite-direction target devices; an Ni0.5Zn0.5Fe2O4 target is installed on a single target, a silicon substrate is fixed to a sample rack in a deposition chamber to be vacuumized; Fe and Co atom steam is generated, Fe65Co35 particles are formed in a sputtering chamber through the gas phase Fe and Co atoms, and nano particle beams are obtained after the Fe65Co35 particles are screened through filtering area nozzles, enter the deposition chamber and are deposited on the substrate; an Ni0.5Zn0.5Fe2O4 film is prepared; the Fe65Co35 alloy nanometer particles and the Ni0.5Zn0.5Fe2O4 film are alternately deposited on the substrate through a rotating system, and the Fe65Co35 alloy nanometer particles are directly assembled to the Ni0.5Zn0.5Fe2O4 film in situ in a vacuum to form the double-magnetism phase nanocomposite film.

Description

The preparation method of a kind of pair of Magnetic Phase nano compound film
Technical field
The present invention relates to nano compound film, especially relate to the preparation method of a kind of pair of Magnetic Phase nano compound film of magnetic metal/alloy nanoparticle and conventional ferrite composite film material.
Background technology
In order to meet, people are light to electron device, small and exquisite, the user demand of high frequency (ghz band) application etc., cause its electromagnetic element towards high frequency, microminiaturization, filming, the future development such as integrated.Although existing integrated circuit fabrication process can significantly reduce treater size, still some core component such as radio frequency such as integrated inductor, noise suppressor magnetic device high frequency, microminiaturization and integrated etc. in face many difficulties.In order to solve an above difficult problem, the soft magnetic material film with high saturation and magnetic intensity, high magnetic permeability, high resonant frequency and high resistivity (effectively suppressing eddy-current loss) causes people and more and more pays close attention to.
Although soft magnetic metal thin-film material has higher saturation magnetization, its lower resistivity limits the application on high-frequency element.Ferrite as traditional high frequency soft magnetic materials, although have very high resistivity, because its saturation magnetization is low, according to Snoek theory ((μ s-1) f r=(2/3) γ 4 π M s) (J.L.SNOEK, Gyromagnetic Resonancein Ferrites, Nature, 1947,160,90), high magnetic permeability cannot be kept under GHz frequency of utilization.Therefore ferrite is can not meet the requirement of modern radio-frequency unicircuit to the development of high frequency, microminiaturization etc. as single-phase high-frequency magnetic material.At present, an important channel of improving magnetic membrane material high frequency performance to have the ferromagnetic particle of high saturation and magnetic intensity (as Fe 65co 35alloy nanoparticle) composite package to soft magnetic ferrite film (as Ni 0.5zn 0.5fe 2o 4film) in form novel (Fe 65co 35)@(Ni 0.5zn 0.5fe 2o 4) two Magnetic Phase nano compound film, this laminated film not only has the characteristic (high saturation magnetization) of ferromagnetic particle, and can keep the critical nature of conventional ferrite film (high resistivity).
But, the method of traditional cosputtering can not be used for preparing this Novel compound film, this is because the magnetic atom such as Fe, Co, Ni of sputtering out from magneticmetal (Fe, Fe-Co, Fe-Ni etc.) target of high saturation and magnetic intensity can together with the various atoms sputtered out from ferrite target, form the ferrite film of another kind of component proportions or a kind of mixed structure of complexity, and desired two Magnetic Phase nano compound films can not be obtained, and then affect its high frequency performance.
Summary of the invention
The object of the invention is to the technical barrier preparing nano compound film for existing cosputtering method, the preparation method of a kind of pair of Magnetic Phase nano compound film is provided.
The present invention includes following steps:
1) by two panels Fe 65co 35target is arranged on subtend target assembly, connects direct supply; By Ni 0.5zn 0.5fe 2o 4target is arranged on single target, connects radio-frequency power supply, to be fixed on by silicon substrate in sediment chamber on rotatable specimen holder and to vacuumize;
2) produce Fe, Co atom vapor, gas phase Fe, Co atom form Fe by the damage in collision energy with rare gas element in sputtering chamber 65co 35alloy nanoparticle, the Fe of formation 65co 35alloy nanoparticle obtains nanometer particle beam under the impact of pressure gradient after the screening of filtrating area nozzle, finally enters sediment chamber and deposits on silicon substrate;
3) Ni is prepared 0.5zn 0.5fe 2o 4film;
4) under the effect of rotational system, silicon substrate alternating deposit Fe is made 65co 35alloy nanoparticle and Ni 0.5zn 0.5fe 2o 4film, makes Fe 65co 35alloy nanoparticle in a vacuum direct in-situ is assembled into Ni 0.5zn 0.5fe 2o 4to form (Fe in film 65co 35)@(Ni 0.5zn 0.5fe 2o 4) two Magnetic Phase nano compound film.
In step 2) in, described method generation Fe, Co atom vapor producing Fe, Co atom vapor and subtend target plasma can be adopted to sputter; Described formation Fe 65co 35the method of alloy nanoparticle can sputter inert-gas condensation method by using plasma; Described Fe 65co 35the size of alloy nanoparticle can regulate described Fe by the gas flow of Ar, He and ratio 65co 35the size of alloy nanoparticle can be 4 ~ 18nm.
In step 3) in, described preparation Ni 0.5zn 0.5fe 2o 4the method that film sputters by conventional magnetron prepares Ni 0.5zn 0.5fe 2o 4film.
Fe 65co 35alloy nanoparticle and Ni 0.5zn 0.5fe 2o 4the sedimentation rate of film can be measured respectively by quartz crystal film thickness monitor and step film thickness gauge, by changing the spacing of adjustable baffle plate thus control Ni 0.5zn 0.5fe 2o 4the ratio of matrix, the thickness of laminated film is measured by step film thickness gauge, Fe in laminated film 65co 35the content of alloy nanoparticle is finally recorded by electronic probe.
The present invention by by the standby magneticmetal of plasma sputtering inert-gas condensation legal system or alloy nanoparticle in a vacuum direct in-situ be assembled in ferrite matrix, and the structure control of laminated film can be realized and composition adjustable.Instant invention overcomes ferrite fraction in the laminated film caused by traditional cosputtering method can reformed technical barrier.Laminated film prepared by the present invention both make use of the feature of magneticmetal or alloy nanoparticle high saturation and magnetic intensity, again because the magneticmetal of low-resistivity or alloy nano particle are kept apart by the soft magnetic ferrite film of high resistivity, thus make laminated film comparing under the prerequisite that single soft magnetic ferrite film saturation magnetization significantly improves, still there is the feature of high resistivity; And preparation technology is simple, stuctures and properties regulation and control are convenient, are applicable to scientific research and industrial production.
Accompanying drawing explanation
Fig. 1 is nanoparticle composite film depositing system schematic diagram provided by the present invention.This system is divided into three chambers, is respectively sputtering chamber A, filtrating area B and sediment chamber C; In Fig. 1, mark 1 is subtend target assembly; 2 is sputtering chamber nozzle; 3 is first order jet nozzle; 4 is secondary nozzle; 5 is push-pull valve; 6 is nano particle line; 7 is single target assembly; 8 is quartz crystal film thickness monitor; 9 is adjustable baffle plate; 10 is silicon substrate; 11 is specimen holder; 12 is rotational system; 13 is sediment chamber's push-pull valve; 14 is sputtering chamber push-pull valve.
Fig. 2 is Fe prepared in the embodiment of the present invention 1 65co 35the transmission electron microscope photo of alloy nanoparticle.In fig. 2, scale is 20nm.
Fig. 3 is Fe prepared in the embodiment of the present invention 1 65co 35alloy nanoparticle content is the Fe2P of the laminated film of 24.5% 3/2the XPS spectrum figure in region.In figure 3, X-coordinate is for combining energy (eV), and ordinate zou is intensity (arb.units), and curve a is original collection of illustrative plates, and curve b is matched curve, and curve c is the matching peak of metal Fe, and curve d is Fe 2+matching peak, curve e is Fe 3+matching peak.
Fig. 4 is Fe prepared in the embodiment of the present invention 1 65co 35alloy nanoparticle content is the Co2P of the laminated film of 24.5% 3/2the XPS spectrum figure in region.In the diagram, X-coordinate is for combining energy (eV), and ordinate zou is intensity (arb.units), and curve a is original collection of illustrative plates, and curve b is matched curve, and curve c is the matching peak of metal Co.
Fig. 5 is Fe prepared in the embodiment of the present invention 1 65co 35alloy nanoparticle content is the Ni2P of the laminated film of 24.5% 3/2the XPS spectrum figure in region.In Figure 5, X-coordinate is for combining energy (eV), and ordinate zou is intensity (arb.units), and curve a is original collection of illustrative plates, and curve b is matched curve, and curve c is Ni 2+matching peak.
Fig. 6 is Fe prepared in the embodiment of the present invention 1 65co 35alloy nanoparticle content is the Zn2P of the laminated film of 24.5% 3/2the XPS spectrum figure in region.In figure 6, X-coordinate is for combining energy (eV), and ordinate zou is intensity (arb.units), and curve a is original collection of illustrative plates, and curve b is Zn 2+matching peak.
Fig. 7 is different Fe in the embodiment of the present invention 1 65co 35the magnetzation curve of alloy nanoparticle content a is 51%, b be 35.4%, c be 24.5%, d be 18.5%, e to be 3.1%, f the be laminated film of 0.In the figure 7, X-coordinate is magneticstrength (Oe), and ordinate zou is the specific magnetising moment (emu/cm 3).
Fig. 8 is the resistivity of laminated film in the embodiment of the present invention 1, saturation magnetization and coercive force and Fe 65co 35the relation of alloy nanoparticle content.In fig. 8, X-coordinate is Fe 65co 35alloy nanoparticle content (%), ordinate zou is resistivity (10 9μ Ω cm), saturation magnetization (emu/cm 3) and coercive force (Oe).
Embodiment
Embodiment 1: see Fig. 1 ~ 8, novel (Fe 65co 35)@(Ni 0.5zn 0.5fe 2o 4) gas-phase synthesizing method of two Magnetic Phase nano compound film, its synthesis step is as follows:
A () is by two panels Fe 65co 35target is arranged on subtend target assembly 1, and subtend target assembly 1 meets in holding circuit the direct supply D forming steady current; By Ni 0.5zn 0.5fe 2o 4target is arranged on single target 7, and single target 7 meets the supporting radio-frequency power supply G of plasma body; Regulate the spacing of fender plate 9 in advance, cleaned silicon substrate 10 to be fixed in sediment chamber C on rotatable specimen holder 11, open mechanical pump to vacuumize, when vacuum tightness reaches about 20Pa, open sediment chamber's push-pull valve 13 and sputtering chamber push-pull valve 14, the molecular pump E opening sediment chamber and sputtering chamber continues to vacuumize, and makes each room base vacuum reach 5 × 10 -4pa;
B () adjust flux meter makes the flow of the Ar gas passing into sputtering chamber A be 300sccm, close push-pull valve 5 and sputtering chamber push-pull valve 14, open lobe pump F, at this moment sputtering chamber pressure is 98Pa, regulate specimen holder 11 position, make non-mounted substrate position alignment nozzle, open direct supply and start pre-sputtering, sputtering power is 400W, and the pre-sputtering time is 1h;
C () adjust flux meter makes the flow of the Ar gas passing into sediment chamber C be 28.3sccm, the openings of sizes of sediment chamber's push-pull valve 13 is regulated to make sediment chamber's pressure be 0.4Pa, regulate specimen holder 11 position, make non-mounted substrate position alignment list target 7, open radio-frequency power supply and start pre-sputtering, sputtering power is 100W, and the pre-sputtering time is 20min;
D () is opened push-pull valve 5, Fe between room, Co atom forming core in sputtering chamber A and is grown up, enter filtrating area B after sputtering chamber nozzle 2, then after the filtration of first order jet nozzle 3 and secondary nozzle 4, Fe 65co 35the size of alloy nanoparticle will become more homogeneous, finally form nano particle line 6 and enter sediment chamber C.Quartz crystal film thickness monitor 8 sensor is down to the shaft core position of nano particle line, utilizes molecular vibration film thickness gauge to measure Fe 65co 35alloy nanoparticle sedimentation rate.Open rotational system 12, regulate speed of rotation, make the rhythmical rotation of specimen holder, now, have the position of substrate will alternately appear on nano particle line axle center and single target shaft core position direction, alternating deposit Fe 65co 35alloy nanoparticle and Ni 0.5zn 0.5fe 2o 4film, by controlling the spacing control Ni of fender plate 9 0.5zn 0.5fe 2o 4the ratio of matrix in laminated film, controls the thickness of laminated film by controlling depositing time.
Embodiment 2: novel Fe@(Ni 0.5zn 0.5fe 2o 4) gas-phase synthesizing method of two Magnetic Phase nano compound film, adopt the step identical with embodiment 1, two panels target is changed to Fe target.
Embodiment 3: novel (Fe-Ni)@(Ni 0.5zn 0.5fe 2o 4) gas-phase synthesizing method of two Magnetic Phase nano compound film, adopt the step identical with embodiment 1, two panels target is changed to Fe-Ni alloy/C target.
Principle of work of the present invention is: by by the standby ferromagnetic metal of plasma sputtering inert-gas condensation legal system or alloy nanoparticle in a vacuum direct in-situ be assembled in ferrite matrix, regulated the ratio of nano particle and matrix by the spacing changing fender plate.
The present invention utilizes plasma sputtering inert-gas condensation method to prepare magnetic metal/alloy nano particle, the method deposited iron ferrite thin film simultaneously utilizing conventional magnetron to sputter, under the effect of automatically controlled rotational system, make magnetic nanoparticle and ferrite matrix prepare novel pair of Magnetic Phase nano compound film by assemble in situ in a vacuum, overcoming ferrite fraction in the laminated film caused by traditional cosputtering method can reformed technical barrier.This novel laminated film not only maintains the feature of ferromagnetic metal/alloy nanoparticle high saturation and magnetic intensity but also has the feature of ferrite film high resistivity, and the structure and composition of laminated film is controlled, preparation technology is simple, is applicable to scientific research and industrial production.

Claims (6)

1. a preparation method for two Magnetic Phase nano compound film, is characterized in that comprising the following steps:
1) by two panels Fe 65co 35target is arranged on subtend target assembly, connects direct supply; By Ni 0.5zn 0.5fe 2o 4target is arranged on single target, connects radio-frequency power supply, to be fixed on by silicon substrate in sediment chamber on rotatable specimen holder and to vacuumize;
2) produce Fe, Co atom vapor, gas phase Fe, Co atom form Fe by the damage in collision energy with rare gas element in sputtering chamber 65co 35alloy nanoparticle, the Fe of formation 65co 35alloy nanoparticle obtains nanometer particle beam under the impact of pressure gradient after the screening of filtrating area nozzle, finally enters sediment chamber and deposits on silicon substrate;
3) Ni is prepared 0.5zn 0.5fe 2o 4film;
4) under the effect of rotational system, silicon substrate alternating deposit Fe is made 65co 35alloy nanoparticle and Ni 0.5zn 0.5fe 2o 4film, makes Fe 65co 35alloy nanoparticle in a vacuum direct in-situ is assembled into Ni 0.5zn 0.5fe 2o 4to form (Fe in film 65co 35)@(Ni 0.5zn 0.5fe 2o 4) two Magnetic Phase nano compound film.
2. the preparation method of a kind of pair of Magnetic Phase nano compound film as claimed in claim 1, is characterized in that in step 2) in, described Fe, Co atom vapor that produces adopts the method for subtend target plasma sputtering to produce Fe, Co atom vapor.
3. the preparation method of a kind of pair of Magnetic Phase nano compound film as claimed in claim 1, is characterized in that in step 2) in, described formation Fe 65co 35the method using plasma sputtering inert-gas condensation method of alloy nanoparticle.
4. the preparation method of a kind of pair of Magnetic Phase nano compound film as claimed in claim 1, is characterized in that in step 2) in, described Fe 65co 35the size of alloy nanoparticle is regulated by the gas flow of Ar, He and ratio.
5. the preparation method of a kind of pair of Magnetic Phase nano compound film as claimed in claim 1, is characterized in that in step 2) in, described Fe 65co 35alloy nanoparticle is of a size of 4 ~ 18nm.
6. the preparation method of a kind of pair of Magnetic Phase nano compound film as claimed in claim 1, is characterized in that in step 3) in, described preparation Ni 0.5zn 0.5fe 2o 4the method that film is sputtered by conventional magnetron prepares Ni 0.5zn 0.5fe 2o 4film.
CN201510006670.9A 2015-01-07 2015-01-07 Preparing method for double-magnetism phase nanocomposite film Pending CN104451568A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105749926A (en) * 2016-02-03 2016-07-13 厦门大学 Preparation method of non-precious metal electrolysis hydrogen evolution catalyst

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101429646A (en) * 2008-12-12 2009-05-13 厦门大学 Production method for film generating in-plane uniaxial magnetic anisotropy in non-inducement magnetic field

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101429646A (en) * 2008-12-12 2009-05-13 厦门大学 Production method for film generating in-plane uniaxial magnetic anisotropy in non-inducement magnetic field

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J.B.WANG ET AL.: ""Structure and magnetic properties of Fe65Co35@Ni0.5Zn0.5Fe2O4composite thin films prepared by a novel nanocomposite technology"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105749926A (en) * 2016-02-03 2016-07-13 厦门大学 Preparation method of non-precious metal electrolysis hydrogen evolution catalyst

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Application publication date: 20150325