CN112927881B - Component gradient magnetic metal-magnetic oxide particle film and preparation method thereof - Google Patents

Component gradient magnetic metal-magnetic oxide particle film and preparation method thereof Download PDF

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CN112927881B
CN112927881B CN202110085952.8A CN202110085952A CN112927881B CN 112927881 B CN112927881 B CN 112927881B CN 202110085952 A CN202110085952 A CN 202110085952A CN 112927881 B CN112927881 B CN 112927881B
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magnetic metal
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film
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CN112927881A (en
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杨丰帆
于名讯
胡国祥
潘士兵
孙向民
孙建生
徐勤涛
连军涛
刘景�
桑晓明
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Shandong Non Metallic Material Research Institute
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
    • H01F1/342—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
    • H01F1/342—Oxides
    • H01F1/344—Ferrites, e.g. having a cubic spinel structure (X2+O)(Y23+O3), e.g. magnetite Fe3O4
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
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Abstract

The invention belongs to the technical field of electromagnetic wave protection materials, and particularly relates to a component gradient magnetic metal-magnetic oxide particle film and a preparation method thereof, wherein the particle film is composed of particle films with the volume content gradient of magnetic metal components continuously reduced from a base layer to a surface layer in the direction vertical to a substrate, and the gradient change range of the magnetic metal components is 20-99%; the magnetic metal is one or alloy of Fe, co and Ni, and can be doped with one or mixture of Si and B; the magnetic oxide is CoFe 2 O 4 、ZnFe 2 O 4 、NiFe 2 O 4 、MnFe 2 O 4 、NiCo 2 O 4 、Co 2 O 3 、Fe 3 O 4 One of (1); the preparation method adopts a magnetron co-sputtering process. The invention has continuous change of component gradient and simple manufacturing process, and the prepared granular film meets the requirements of impedance matching characteristic and electromagnetic wave attenuation characteristic.

Description

Component gradient magnetic metal-magnetic oxide particle film and preparation method thereof
Technical Field
The invention belongs to the technical field of electromagnetic wave protection materials, and particularly relates to a magnetic metal-magnetic oxide particle thin film with continuously-changed component gradients and a preparation method thereof.
Background
The electromagnetic wave absorbing material is an important material in the technical field of electromagnetic wave protection materials, traditional electromagnetic wave absorbing materials such as carbonyl iron powder, ferrite and other powder are limited by Snoek limit, magnetic permeability is difficult to further improve, and particularly, the absorbing effect in a radar low-frequency band (0.5 GHz-4 GHz) is generally poor.
The wave-absorbing material has two basic conditions for absorbing electromagnetic waves at the same time: 1) Impedance matching characteristics, i.e. the incident wave is maximally entered into the interior of the material without being reflected on its front surface. 2) The attenuation characteristic, that is, the electromagnetic wave entering the inside can be rapidly absorbed and attenuated by the material. This requires a material having both a high volume resistivity p and a large imaginary μ "permeability.
The magnetic particle film has high saturation magnetization and strong shape anisotropy, the magnetic conductivity and magnetic loss of the microwave frequency band of the magnetic particle film are 1-2 orders of magnitude higher than those of the magnetic metal microparticle absorbent, and the magnetic particle film has good attenuation characteristics and is expected to become a novel electromagnetic wave absorption material. At present, a large number of magnetic particle films and preparation methods thereof are disclosed at home and abroad, and the material systems mainly focus on magnetic metal oxides, magnetic metal nitrides, magnetic metal materials-nonmagnetic materials and magnetic metal materials/nonmagnetic materials]n, [ magnetic metal material oxide or nitride/non-magnetic material]And n is prepared by adopting a magnetron co-sputtering method or an alternate sputtering method. The magnetic film belongs to homogeneous materials and has high complex permeability, but the volume resistivity is usually only 10 -1 About 1m omega cm, the skin depth is small, and the electromagnetic wave is difficult to effectively enter the magnetic particle film. The magnetic particle film cannot satisfy the impedance matching characteristic, which has been a problem that it is applied as an electromagnetic wave absorbing material.
CN 101206945A discloses a component gradient multi-component high-frequency ferromagnetic thin film material prepared by adopting a multi-target co-sputtering technology, which adopts a ferromagnetic material as a main material target and is arranged right below a sputtered substrate; simple substances, oxides, nitrides, borides, carbides or phosphides and the like are used as dopants and are arranged at positions which are outwards deviated from the center of the substrate. During film coating, a uniform film is formed by depending on the components of the main material target, the components of the dopants formed on the dopant target are distributed in a gradient manner along a certain direction in the plane, the composite film is a single-layer film, the component gradient change is realized in the in-plane direction (the direction parallel to the substrate) of the film, and good in-plane uniaxial anisotropy is obtained. But still a film with uniform composition in the vertical direction of the film (the direction perpendicular to the substrate) and does not relate to the characteristic of impedance matching with air.
Yang et al (j.appl.phys., 111 (2012) 113909) employ co-sputtering of FeCoB magnetic metal with SiO 2 Non-magnetic medium material, feCoB-SiO 2 Compositionally graded magnetic particle multilayer films. The volume content of the ferromagnetic material of the multilayer film is reduced layer by layer in the vertical direction of the substrate, so that the volume resistivity of the film is gradually increased from the base layer to the surface layer, higher volume resistivity is obtained, and the impedance matching characteristic of the film and air is met. But SiO 2 As a non-magnetic medium material, the complex permeability is reduced to a certain extent.
CN 108000973B introduces a gradient magnetic multilayer electromagnetic wave absorption film and a preparation method thereof, the film adopts a co-sputtering method and an alternate sputtering method to prepare a gradient multilayer film composed of a magnetic particle film layer and an isolation layer, which meets the impedance matching requirement of the electromagnetic wave absorption film, but the multilayer film is not a continuous film, the volume content change of the components shows step-type gradient change, and the preparation process is relatively complex.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a component gradient magnetic metal-magnetic oxide particle film which has continuously changed component gradient and simple manufacturing process and simultaneously meets the requirements of impedance matching property and electromagnetic wave attenuation property and a preparation method thereof.
The technical scheme of the invention is as follows:
a composition gradient magnetic metal-magnetic oxide particle thin film, the particle thin film being composed of a particle thin film in which a gradient of a volume content of a magnetic metal component decreases continuously from a base layer to a face layer in a direction perpendicular to a substrate, the composition of the thin film having a general composition formula:
substrate/M a1 -D b1 -I (1-a1-b1) ……M an -D bn -I (1-an-bn) A protective layer;
wherein: m is one of Fe, co, ni, feCo, feNi and CoNi;
d is one or a mixture of B and Si in any proportion;
i is CoFe 2 O 4 、ZnFe 2 O 4 、NiFe 2 O 4 、MnFe 2 O 4 、NiCo 2 O 4 、Co 2 O 3 、Fe 3 O 4 One of (a) and (b);
an and bn are respectively the volume content of the M and D materials, the sum of an and bn is more than or equal to 20% and less than or equal to 99%, wherein an:20% -99%, bn: 0-30%, and the volume content value a1 > \8230: > an, n > 2, n is an integer;
the thickness of the film is 50nm to 1000nm (no protective layer is included).
In the invention, the volume content of the magnetic metal component in the magnetic particle film is continuously reduced in a gradient manner in the direction vertical to the substrate from the base layer to the surface layer, and the material system of the magnetic particle film is magnetic metal-magnetic oxide; the gradient change range of the volume content of the magnetic metal component from the base layer to the surface layer in the direction vertical to the substrate is 20-99 percent; the magnetic metal is one or the alloy of Fe, co and Ni ferromagnetic materials, and can be doped with one or the mixture of Si and B; the volume content of one or the alloy of Fe, co and Ni ferromagnetic materials in the magnetic metal is 20-99 percent, and the volume content of one or the mixture of Si and B adulterants is 0-30 percent.
Preferably, the substrate material is selected from one of quartz glass, monocrystalline silicon, polyimide, polyester, and polytetrafluoroethylene.
Preferably, the protective layer is CoFe 2 O 4 、ZnFe 2 O 4 、NiFe 2 O 4 、MnFe 2 O 4 、NiCo 2 O 4 、Co 2 O 3 、Fe 3 O 4 The magnetic particle film is prevented from being oxidized. Further preferably, the thickness is 2nm to 10nm.
The granular film of the present invention has the following advantages:
(1) The structural design of the magnetic metal component gradient continuous reduction type structure realizes that the volume resistivity of the film is gradually increased from the base layer to the surface layer, thereby realizing the impedance matching characteristic;
(2) According to the magnetic particle film material system, the magnetic oxide is adopted to replace the traditional non-magnetic material, the magnetic oxide has larger volume resistivity, good soft magnetic performance and higher complex permeability, the exchange coupling effect among magnetic particles is enhanced, the saturation magnetization Ms and the complex permeability are obviously improved, and the strong attenuation characteristic of electromagnetic waves is realized.
The component gradient magnetic metal-magnetic oxide particle thin film has the characteristic of continuous change of component gradient, meets the requirements of air impedance matching and strong electromagnetic wave absorption, has strong designability, is suitable for the technical field of electromagnetic protection, and is particularly suitable for novel absorption materials of radar low-frequency bands and electromagnetic compatible protection materials of electronic devices.
A method for preparing a component gradient magnetic metal-magnetic oxide particle film adopts a magnetron co-sputtering process for film coating, and comprises the steps of substrate cleaning, substrate and target material installation and film coating.
Preferably, in the coating process, the growth rate of the target can be regulated by adopting one of two modes of continuously regulating the sputtering power of the target;
the first mode is as follows: controlling the continuous gradient reduction of the growth rate of the components of the magnetic metal target material, and fixing the growth rate of the magnetic oxide target material;
the second mode is as follows: fixing the growth rate of the magnetic metal target, and controlling the continuous gradient increase of the growth rate of the components of the magnetic oxide target.
In the process of coating, two sputtering powers can be synchronously increased or reduced according to actual requirements, the sputtering power of the magnetic oxide target material is increased quickly, the sputtering power of the magnetic metal target material is increased slowly, or the sputtering power of the magnetic oxide target material is reduced slowly and the sputtering power of the magnetic metal target material is reduced quickly, so that the particle thin film with the continuously reduced volume content gradient of the magnetic metal components from the base layer to the surface layer in the direction vertical to the substrate can be obtained.
Preferably, the coating process is to sputter grow the magnetic particle film under the action of an induced magnetic field. If no magnetic field is induced, anisotropy cannot be generated, and the resonant frequency of the film is too low to reach the low-frequency band of radar.
Further preferably, the induced magnetic field strength is between 100Oe and 1000 Oe. The film anisotropy is too weak due to too low magnetic field strength.
Preferably, the substrate temperature in the coating process is between room temperature and 300 ℃, and the proper substrate temperature is favorable for film growth, but after the substrate temperature exceeds 300 ℃, the permanent magnet for generating the magnetic field loses magnetism and cannot generate an effective induction magnetic field.
Preferably, the argon pressure in the coating process is between 0.2Pa and 5 Pa.
The invention adopts the co-sputtering method when preparing the magnetic particle film, compared with the alternative sputtering method of multilayer films, the preparation process is simple, the operation is convenient, and the invention is suitable for large-scale production, and the prepared particle film has higher volume resistivity rho and larger magnetic permeability imaginary part mu'. The component gradient magnetic metal-magnetic oxide particle film has the characteristic of continuous change of component gradient, meets the requirements of air impedance matching and strong electromagnetic wave absorption, has strong designability, is suitable for the technical field of electromagnetic protection, and is particularly suitable for novel absorption materials of radar low-frequency bands and electromagnetic compatibility protection materials of electronic devices.
Drawings
FIG. 1 is a schematic diagram of the structure of a compositionally graded magnetic metal-magnetic oxide particle thin film of the present invention;
FIG. 2 is a hysteresis loop diagram showing easy axis and hard axis of a composition-gradient magnetic metal-magnetic oxide particle thin film prepared in example 1 of the present invention;
FIG. 3 is a magnetic spectrum of a composition-graded magnetic metal-magnetic oxide particle thin film prepared in example 1 of the present invention.
Detailed Description
The technical solution proposed by the present invention is further illustrated below with reference to the following examples, but is not limited thereto. Any technical method capable of achieving the purpose of the invention forms part of the technical scheme related to the invention.
Example 1
A method for preparing a composition gradient magnetic metal-magnetic oxide particle film comprises the following steps:
taking quartz glass as a substrate, sequentially adopting acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 15min, drying in a vacuum oven, observing pollutants such as dust under a microscope, and fixing on a sample holder with the induced magnetic field intensity of 1000 Oe; fe with the purity of 99.98 percent 65 Co 35 (the right subscript represents the volume content ratio, and the same expression is applied to the following examples.) A target material was mounted on a DC magnetron target gun (A target), and CoFe having a purity of 99.9% was applied 2 O 4 The target material is arranged on a radio frequency magnetic control target gun (B target);
two-stage vacuum pumping is carried out by adopting a mechanical pump and a molecular pump to 5 multiplied by 10 -5 Pa, conveying the sample holder into a sputtering chamber, wherein the base distance of the target A is 7cm, the base distance of the target B is 13cm, the substrate temperature is room temperature, and the autorotation rate of the sample table is 2r/min;
argon with the purity of 99.999 percent is filled into the sputtering chamber, the flow rate is 20sccm, and the total air pressure is kept at 0.5Pa;
setting the sputtering power of the targets A and B as 100W and 100W respectively, pre-sputtering for 10min, and removing impurities on the surfaces of the targets;
setting the sputtering power of the target A and the sputtering power of the target B to be 152W and 50W respectively, opening a substrate baffle plate and a target baffle plate after stabilizing for 1min, and carrying out co-sputtering to grow a magnetic particle film, wherein in the film coating process, the sputtering power of the target A is uniformly and gradiently decreased at the speed of reducing 1W every 10s, and the power regulation range is 152W-2W; the sputtering power of the target B is fixed at 50W; under the same sputtering condition, the sputtering power of the same target material is equal toThe growth rate is proportional, wherein the growth rates of the A targets at sputtering powers of 152W, 136W, 120W, 104W, 88W, 72W, 56W, 40W, 24W, 8W and 2W are respectively 0.95nm/s, 0.85nm/s, 0.75nm/s, 0.65nm/s, 0.55nm/s, 0.45nm/s, 0.35nm/s, 0.25nm/s, 0.15nm/s, 0.05nm/s and 0.125nm/s, the growth rate of the B targets is fixed at 0.05nm/s, the sputtering time is 1500s, the substrate baffle and the target baffle are closed, the B target baffle and the substrate baffle are opened finally, the B target sputtering time is 40s, and CoFe with the thickness of 2nm is grown 2 O 4 A protective layer for preventing the magnetic particle film from being oxidized to obtain FeCo-CoFe with continuously changed component gradient 2 O 4 The magnetic particle film has the film thickness of 802nm (without the thickness of a protective layer), the gradient change rate of FeCo components of 95-20 percent and the volume resistivity rho of 8.92m omega cm, which indicates that the film has good impedance matching characteristic;
FeCo-CoFe of which composition gradient is continuously changed and prepared as described above 2 O 4 The hysteresis loop of the magnetic particle film is shown in FIG. 2, and the curve shows that the film has a large saturation magnetization Ms of 962.3emu/cm 3 Wherein the easy axis coercive force Hce is 18.0Oe, the hard axis coercive force Hce is 6.8Oe, and the in-plane anisotropy Hk is 88.3Oe, which shows that the film has good soft magnetic property and obvious anisotropy;
FeCo-CoFe of which composition gradient is continuously changed and prepared as described above 2 O 4 As shown in FIG. 3, the magnetic spectrum of the magnetic particle film showed a natural resonance frequency fr of 2.43GHz and a real complex permeability μ' i 405.3, peak imaginary part μ ″) max 490.8 and 2.45GHz for the half-peak width Δ f, indicating that the film has good attenuation characteristics.
Example 2
A method for preparing a composition gradient magnetic metal-magnetic oxide particle film comprises the following steps:
the polyester substrate was cleaned in the same manner as in example 1, and the substrate was fixed to a sample holder having an induced magnetic field strength of 100 Oe. Fe with the purity of 99.96 percent 70 Si 15 B 15 The target material is arranged on a direct current magnetic control target gun (A target), and MnFe with the purity of 99.7 percent is added 2 O 4 The target material is arranged on a radio frequency magnetic control target gun (B target);
using mechanical pump and molecular pump to pump vacuum to 1 × 10 -5 Pa, conveying the sample holder into a sputtering chamber, wherein the target base distances are 22cm, the substrate temperature is room temperature, and the autorotation rate of the sample table is 10r/min;
argon with the purity of 99.999 percent is filled into the sputtering chamber, the flow rate is 10sccm, and the total air pressure is kept at 5Pa;
setting the sputtering power of the target A and the target B to be 320W and 10W respectively, pre-sputtering for 5min, and removing impurities on the surface of the target;
opening a substrate baffle and a target baffle, carrying out co-sputtering to grow a magnetic particle film, wherein the sputtering power of the A target is uniformly and gradiently decreased at the speed of 1W/s in the film coating process, and the power adjusting range is 320W-9W; the sputtering power of the target B is fixed at 10W; wherein, the growth rates of the A targets with sputtering power of 320W, 267W, 214W, 160W, 107W, 54W, 18W and 9W are respectively 0.18nm/s, 0.15nm/s, 0.12nm/s, 0.09nm/s, 0.06nm/s, 0.03nm/s, 0.01nm/s and 0.005nm/s, the growth rate of the B targets is fixed at 0.02nm/s, the sputtering time is 311s, the substrate baffle and the target baffle are closed; finally, opening a B target baffle and a substrate baffle, sputtering for 500s, and growing 10 nm-thick MnFe 2 O 4 A protective layer is obtained to obtain FeSiB-MnFe with continuously changed component gradient 2 O 4 The magnetic particle film has the film thickness of 237nm (without the thickness of a protective layer), the gradient change rate of FeSiB components is 90-20%, the volume resistivity rho is 10.92m omega cm, and the requirement of impedance matching characteristic is effectively met;
the saturation magnetization Ms of the film is 820.5emu/cm 3 Natural resonance frequency fr of 2.6GHz and real complex permeability μ' i Is 216, imaginary peak μ ″) max At 393, the half-peak width Δ f was 3.0GHz.
Example 3
A method for preparing a composition gradient magnetic metal-magnetic oxide particle film comprises the following steps:
the polyimide substrate was cleaned in the same manner as in example 1, and fixed to a sample holder having an induced magnetic field strength of 500 Oe. The Co target material with the purity of 99.99 percent is arranged on a direct current magnetic control target gun (A target), znFe with the purity of 99.7 percent is arranged on the direct current magnetic control target gun 2 O 4 Target mounting to radio frequencyA magnetic control target gun (B target);
two-stage vacuum pumping is carried out by adopting a mechanical pump and an ion pump to 3 multiplied by 10 -5 Pa, conveying the sample holder into a sputtering chamber, wherein the target base distance is 15cm, the substrate temperature is room temperature, and the autorotation speed of the sample table is 5r/min;
argon with the purity of 99.999 percent is filled into the sputtering chamber, the flow rate is 15sccm, and the total air pressure is kept at 0.2Pa;
setting the sputtering power of the targets A and B to be 10W and 10W respectively, pre-sputtering for 10min, and removing impurities on the surfaces of the targets;
setting the sputtering power of the target A and the target B to be 5W and 4W respectively, opening a substrate baffle and a target baffle after stabilizing for 1min, and carrying out co-sputtering to grow a magnetic particle film, wherein the sputtering power of the target A is fixed at 5W in the film coating process; the sputtering power of the target B is uniformly and gradiently increased at the speed of 1W/s, and the power adjusting range is 4W-352W; wherein the growth rate of the target A is fixed at 0.099nm/s, the growth rates of the targets B when the sputtering power is 4W, 24W, 44W, 80W, 160W, 280W and 352W are respectively 0.001nm/s, 0.006nm/s, 0.011nm/s, 0.02nm/s, 0.04nm/s, 0.07nm/s and 0.088nm/s, the sputtering time is 348s, and the substrate baffle and the target baffle are closed; finally opening the B target baffle and the substrate baffle, sputtering for 57s, and growing ZnFe with the thickness of 5nm 2 O 4 Protecting the layer to obtain Co-ZnFe with continuously changed component gradient 2 O 4 The magnetic particle film has a film thickness of 50nm (excluding the thickness of the protective layer), a gradient change rate of Co component of 99-53%, a volume resistivity of 3.02m omega cm, and a saturation magnetization Ms of 1020.3emu/cm 3 Natural resonance frequency fr of 2.1GHz and real complex permeability μ' i Is 362, peak imaginary part μ ″) max At 463, the half-peak width Δ f was 2.3GHz.
Example 4
A method for preparing a composition gradient magnetic metal-magnetic oxide particle film comprises the following steps:
the single crystal silicon was used as a substrate, and the cleaning process was the same as in example 1, and the substrate was fixed to a sample holder having an induced magnetic field strength of 300 Oe. Fe with the purity of 99.99 percent 50 Ni 50 The target material is arranged on a direct current magnetic control target gun (A target), and NiFe with the purity of 99.7 percent is added 2 O 4 Target material safetyMounting on a radio frequency magnetic control target gun (B target);
the vacuum is pumped to 1 × 10 by mechanical pump and molecular pump -5 Pa, the sample holder is sent into a sputtering chamber. The target base distances are all 10cm, the substrate temperature is 300 ℃, and the autorotation speed of the sample table is 20r/min;
argon with the purity of 99.999 percent is filled into the sputtering chamber, the flow rate is 20sccm, and the total air pressure is kept at 5Pa;
setting the sputtering power of the A target and the B target to be 15W and 7W respectively, pre-sputtering for 10min, and removing impurities on the surfaces of the targets;
opening a substrate baffle and a target baffle, carrying out co-sputtering to grow a magnetic particle film, wherein in the film coating process, the sputtering power of the target A is fixed at 15W, the sputtering power of the target B is uniformly and gradiently increased at the speed of increasing 1W every 30s, and the power adjustment range is 7-205W; wherein the growth rate of the target A is fixed to be 0.092nm/s, the growth rates of the targets B when the sputtering power of the targets B is 7W, 28W, 56W, 84W, 126W, 168W and 205W are respectively 0.005nm/s, 0.02nm/s, 0.04nm/s, 0.06nm/s, 0.09nm/s, 0.12nm/s and 0.146nm/s, the sputtering time is 5940s, and the substrate baffle and the target baffle are closed; finally, opening a B target baffle and a substrate baffle, wherein the sputtering time of the B target is 34s, and growing NiFe with the thickness of 5nm 2 O 4 And a protective layer. The FeNi-NiFe with continuously changed component gradient related by the invention is obtained 2 O 4 The magnetic particle film has a film thickness of 1001nm (excluding the protective layer), a FeNi component gradient change rate of 94.8-38.6%, a film volume resistivity rho of 3.51m omega cm, and a saturation magnetization Ms of 990.5emu/cm 3 Natural resonance frequency fr of 2.6GHz and real complex permeability μ' i Is 382, imaginary peak value μ ″) max At 406, the half-peak width Δ f was 2.5GHz.
Example 5
A method for preparing a composition gradient magnetic metal-magnetic oxide particle film comprises the following steps:
using Teflon as a substrate, the cleaning process was the same as in example 1, and the substrate was fixed to a sample holder having an induced magnetic field strength of 1000 Oe. The Fe target material with the purity of 99.99 percent is arranged on a direct current magnetron target gun (A target), and the Fe with the purity of 99.8 percent is arranged on a direct current magnetron target gun (A target) 3 O 4 The target material is arranged on a radio frequency magnetic control target gun (B target);
the vacuum is pumped to 1 × 10 by mechanical pump and molecular pump -5 And Pa or less, the sample holder is sent into the sputtering chamber. The target-substrate distances are all 12cm, the substrate temperature is 150 ℃, and the autorotation rate of the sample platform is 10r/min;
argon with the purity of 99.999 percent is filled into the sputtering chamber, the flow rate is 20sccm, and the total air pressure is kept at 1Pa;
setting the sputtering power of the targets A and B to be 16W and 12W respectively, pre-sputtering for 5min, and removing impurities on the surfaces of the targets;
opening a substrate baffle and a target baffle, carrying out co-sputtering to grow a magnetic particle film, and fixing the sputtering power of the A target at 16W in the film coating process; the sputtering power of the target B is uniformly and gradiently increased by 1W every 30s, and the power adjusting range is 12W-245W; wherein, the growth rate of the A target is fixed to be 0.01nm/s, the growth rates of the B target when the sputtering power is 12W, 24W, 48W, 96W, 180W, 210W and 245W are respectively 0.004nm/s, 0.008nm/s, 0.016nm/s, 0.032nm/s, 0.06nm/s, 0.07nm/s and 0.082nm/s, the sputtering time is 6990s, and the substrate baffle and the target baffle are closed; finally, opening a B target baffle and a substrate baffle, sputtering for 61s, and growing Fe with the thickness of 5nm 3 O 4 And a protective layer. Obtaining Fe-Fe with continuously changed component gradient related to the invention 3 O 4 The magnetic particle film has a film thickness of 1000nm (excluding the thickness of the protective layer), a gradient change rate of Fe component of 96-55%, a volume resistivity of 2.36m omega cm, and a saturation magnetization Ms of 960.3emu/cm 3 Natural resonance frequency fr of 2.2GHz and real complex permeability μ' i Is 312, peak imaginary part μ ″) max At 306, the half-peak width Δ f was 2.8GHz.
Example 6
A method for preparing a composition gradient magnetic metal-magnetic oxide particle film comprises the following steps:
the quartz glass was used as a substrate, and the cleaning process was the same as in example 1, and the quartz glass was fixed to a sample holder having an induced magnetic field strength of 200 Oe. Mixing Co with the purity of 99.99 percent 90 Ni 10 The target material is arranged on a direct current magnetic control target gun (A target), and Co with the purity of 99.9 percent is added 2 O 3 The target material is arranged on a radio frequency magnetic control target gun (B target);
using mechanical pump and molecular pump to pump vacuum to 1 × 10 -5 Pa, conveying the sample holder into a sputtering chamber, wherein the target base distances are 11cm, the substrate temperature is room temperature, and the autorotation rate of the sample table is 1r/min;
argon with the purity of 99.999 percent is filled into the sputtering chamber, the flow rate is 5sccm, and the total air pressure is kept at 0.4Pa;
setting the sputtering power of the A target and the B target to be 155W and 110W respectively, pre-sputtering for 5min, and removing impurities on the surfaces of the targets;
opening a substrate baffle and a target baffle, carrying out co-sputtering to grow a magnetic particle film, wherein the sputtering power of the A target is uniformly and gradiently decreased at the speed of 1W/s in the film coating process, and the power adjusting range is 155W-7W; b, fixing the sputtering power of the target at 110W; wherein, the growth rates of the A targets at sputtering powers of 155W, 121W, 86W, 52W, 17W and 7W are respectively 0.90nm/s, 0.70nm/s, 0.50nm/s, 0.30nm/s, 0.10nm/s and 0.04nm/s, the growth rate of the B targets is fixed at 0.10nm/s, the sputtering time is 148s, the substrate baffle plate and the target baffle plate are closed, the B target baffle plate and the substrate baffle plate are opened finally, the sputtering time is 20s, and Co with the thickness of 2nm is grown 2 O 3 And a protective layer. The CoNi-Co with continuously changed component gradient is obtained 2 O 3 The magnetic particle film has a film thickness of 85nm (excluding the thickness of the protective layer), a CoNi component gradient change rate of 90-28.9%, a volume resistivity rho of 3.2m omega cm, and a saturation magnetization Ms of 920.1emu/cm 3 Natural resonance frequency fr of 2.8GHz and real complex permeability μ' i Is 316, imaginary peak μ ″) max The peak width at half maximum Deltaf was 3.0GHz and 463.
Example 7
A method for preparing a composition gradient magnetic metal-magnetic oxide particle film comprises the following steps:
the quartz glass substrate was cleaned in the same manner as in example 1, and the substrate was fixed to a sample holder having an induced magnetic field strength of 1000 Oe. The Ni target with a purity of 99.99% was mounted on a DC magnetron target gun (A target), and NiCo with a purity of 99.99% was added 2 O 4 The target material is arranged on a radio frequency magnetic control target gun (B target);
using mechanical pump and molecular pump to pump vacuum to 2X 10 -5 Pa, feeding the sample holder into sputteringThe chamber, the A target base distance is 10cm, the B target base distance is 8cm, the substrate temperature is 200 ℃, and the autorotation speed of the sample platform is 10r/min;
argon with the purity of 99.999 percent is filled into the sputtering chamber, the flow rate is 5sccm, and the total air pressure is kept at 2Pa;
setting the sputtering power of the A target and the sputtering power of the B target to be 300W and 150W respectively, pre-sputtering for 10min, and removing impurities on the surfaces of the targets;
opening a substrate baffle and a target baffle, co-sputtering to grow a magnetic particle film, wherein the sputtering power of the target A is uniformly and gradiently decreased at the speed of 0.5W/s in the film coating process, and the power adjusting range is 300W-6W; the sputtering power of the target B is fixed at 150W; wherein, the growth rates of the A targets at sputtering power of 300W, 254W, 208W, 162W, 116W, 69W, 23W and 6W are respectively 1.30nm/s, 1.10nm/s, 0.90nm/s, 0.70nm/s, 0.50nm/s, 0.30nm/s, 0.10nm/s and 0.03nm/s, the growth rate of the B targets is fixed at 0.15nm/s, the sputtering time is 588s, and the substrate baffle and the target baffle are closed; finally opening a B target baffle and a substrate baffle, sputtering for 33s, and growing NiCo with the thickness of 5nm 2 O 4 Protecting layer to obtain Ni-NiCo with continuously changed component gradient 2 O 4 The magnetic particle film has a film thickness of 480nm (excluding the thickness of the protective layer), a gradient change rate of the Ni component of 89.7-16.7%, a volume resistivity rho of 4.2m omega cm, and a saturation magnetization Ms of 960.5emu/cm 3 Natural resonance frequency fr of 2.6GHz and real complex permeability μ' i 356, imaginary peak μ ″) max 423, the half-peak width Δ f was 3.2GHz.
Example 8
A method for preparing a composition gradient magnetic metal-magnetic oxide particle film comprises the following steps:
the single crystal silicon was used as a substrate, and the cleaning process was the same as in example 1, and the substrate was fixed to a sample holder having an induced magnetic field strength of 300 Oe. Fe with the purity of 99.99 percent 50 Ni 50 The target material is arranged on a direct current magnetic control target gun (A target), and NiFe with the purity of 99.7 percent is added 2 O 4 The target material is arranged on a radio frequency magnetic control target gun (B target);
using mechanical pump and molecular pump to pump vacuum to 1 × 10 -5 Pa, the sample holder is sent into a sputtering chamber, and the target base distances are all 10cm, the substrate temperature is 300 ℃, and the autorotation speed of the sample table is 20r/min;
argon with the purity of 99.999 percent is filled into the sputtering chamber, the flow rate is 20sccm, and the total air pressure is kept at 5Pa;
setting the sputtering power of the A target and the B target to be 15W and 7W respectively, pre-sputtering for 10min, and removing impurities on the surfaces of the targets;
opening a substrate baffle and a target baffle, carrying out co-sputtering to grow a magnetic particle film, and fixing the sputtering power of the A target at 15W in the film coating process; the sputtering power of the target B is uniformly and gradiently increased by increasing 1W every 30s, and the power adjusting range is 7W-205W; wherein the growth rate of the target A is fixed to be 0.092nm/s, the growth rates of the targets B when the sputtering power of the targets B is 7W, 28W, 56W, 84W, 126W, 168W and 205W are respectively 0.005nm/s, 0.02nm/s, 0.04nm/s, 0.06nm/s, 0.09nm/s, 0.12nm/s and 0.146nm/s, the sputtering time is 5940s, and the substrate baffle and the target baffle are closed; finally, opening a B target baffle and a substrate baffle, sputtering for 34s, and growing NiFe with the thickness of 5nm 2 O 4 Protecting the layer to obtain FeNi-NiFe with continuously changed component gradient 2 O 4 The magnetic particle film has a film thickness of 1001nm (excluding the protective layer), a FeNi component gradient change rate of 94.8-38.6%, a film volume resistivity rho of 3.51m omega cm, and a saturation magnetization Ms of 990.5emu/cm 3 Natural resonance frequency fr of 2.6GHz and real complex permeability μ' i Is 382, imaginary peak value μ ″) max At 406, the half-peak width Δ f was 2.5GHz.
The invention adopts a co-sputtering method when preparing the magnetic particle film, compared with an alternative sputtering method of a multilayer film, the preparation process is simple, the operation is convenient, the invention is suitable for large-scale production, and the prepared particle film has higher volume resistivity rho and larger magnetic conductivity imaginary part mu.

Claims (9)

1. A composition-gradient magnetic metal-magnetic oxide particle thin film, characterized in that: the particle film is composed of a particle film with the volume content gradient of magnetic metal components continuously reduced from a base layer to a surface layer in the direction vertical to a substrate, and the general formula of the composition of the film components is as follows:
substrate/M a1 -D b1 -I (1-a1-b1) ……M an -D bn -I (1-an-bn) A protective layer;
wherein: m is one of Fe, co, ni, feCo, feNi and CoNi;
d is one or a mixture of two of B and Si in any proportion;
i is CoFe 2 O 4 、ZnFe 2 O 4 、NiFe 2 O 4 、MnFe 2 O 4 、NiCo 2 O 4 、Co 2 O 3 、Fe 3 O 4 One of (1);
an and bn are volume contents of the M and D materials respectively, and an + bn is more than or equal to 20% and less than or equal to 99%, wherein an:20% -99%, bn:0 to 30 percent, and the volume content numerical value a1 is more than 8230, 8230refers to an, n is more than 2;
the thickness of the film after the protective layer is removed is 50nm to 1000nm;
the preparation method of the granular film comprises the following steps: and (3) coating by adopting a magnetron co-sputtering process.
2. A composition-graded magnetic metal-magnetic oxide particle thin film according to claim 1, wherein: the substrate material is selected from one of quartz glass, monocrystalline silicon, polyimide, polyester and polytetrafluoroethylene.
3. A composition-graded magnetic metal-magnetic oxide particle thin film according to claim 1, wherein: the protective layer is CoFe 2 O 4 、ZnFe 2 O 4 、NiFe 2 O 4 、MnFe 2 O 4 、NiCo 2 O 4 、Co 2 O 3 、Fe 3 O 4 To (3) is provided.
4. A composition-graded magnetic metal-magnetic oxide particle thin film according to claim 1, characterized in that: the thickness of the protective layer is 2 nm-10 nm.
5. The method for producing a composition-gradient magnetic metal-magnetic oxide particle thin film as claimed in any one of claims 1 to 4, wherein: coating by adopting a magnetron co-sputtering process;
in the coating process, the growth rate of the target can be regulated and controlled by adopting one of two modes of continuously regulating and controlling the sputtering power of the target;
the first mode is as follows: controlling the continuous gradient reduction of the growth rate of the components of the magnetic metal target material, and fixing the growth rate of the magnetic oxide target material;
the second mode is as follows: fixing the growth rate of the magnetic metal target, and controlling the continuous gradient increase of the growth rate of the components of the magnetic oxide target.
6. The method for producing a composition-gradient magnetic metal-magnetic oxide particle thin film according to claim 5, wherein: the magnetic particle film is sputtered and grown in the film coating process under the action of an induction magnetic field.
7. The method for producing a composition-gradient magnetic metal-magnetic oxide particle thin film according to claim 6, wherein: the induced magnetic field strength is between 100Oe and 1000Oe.
8. The method for producing a composition-gradient magnetic metal-magnetic oxide particle thin film according to claim 5, wherein: the substrate temperature is between room temperature and 300 ℃ in the coating process.
9. The method for producing a composition-gradient magnetic metal-magnetic oxide particle thin film according to claim 5, wherein: in the film coating process, the argon pressure is between 0.2Pa and 5 Pa.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104755649A (en) * 2012-09-21 2015-07-01 艾尼股份公司 Process for the production of an optically selective coating of a substrate for high temperature receiver solar devices and relative material obtained
JP2020061486A (en) * 2018-10-11 2020-04-16 信越ポリマー株式会社 Electromagnetic wave shield film, manufacturing method of the same, and print circuit board with electromagnetic wave shield film

Family Cites Families (5)

* Cited by examiner, † Cited by third party
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KR101399022B1 (en) * 2012-12-27 2014-05-27 주식회사 아모센스 Sheet for absorbing electromagnetic wave, manufacturing method thereof and electronic equipment including the same
CN104392823A (en) * 2014-12-01 2015-03-04 南京理工大学 Resonant damping enhanced FeCo-based high-frequency soft magnetic thin film and manufacturing method thereof
CN108000973B (en) * 2017-12-07 2019-08-23 山东非金属材料研究所 A kind of gradient multi-layered magnetic electromagentic wave absorption film and preparation method thereof
CN108617161A (en) * 2018-07-02 2018-10-02 白国华 A kind of ultra-thin anti-EMI filter film and preparation method thereof
CN110133029B (en) * 2019-03-29 2021-06-18 杭州电子科技大学 Method for designing grain boundary diffuser components in neodymium iron boron magnet with high flux

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104755649A (en) * 2012-09-21 2015-07-01 艾尼股份公司 Process for the production of an optically selective coating of a substrate for high temperature receiver solar devices and relative material obtained
JP2020061486A (en) * 2018-10-11 2020-04-16 信越ポリマー株式会社 Electromagnetic wave shield film, manufacturing method of the same, and print circuit board with electromagnetic wave shield film

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