阅读说明：本技术 一种抗电磁干扰的软磁颗粒膜及其制备方法 (Anti-electromagnetic interference soft magnetic particle film and preparation method thereof ) 是由 邓毕力 潘振海 王玉川 徐敏义 罗顶飞 晋立从 张朋 王波 于 2020-07-28 设计创作，主要内容包括：本发明提供一种抗电磁干扰的软磁颗粒膜及其制备方法,所述软磁颗粒膜为多层结构,为中间的双相纳米晶软磁薄膜和位于所述双相纳米晶软磁薄膜两侧的多个交叠重复结构,所述交叠重复结构包括一层纳米ZnO层和一层纳米六方氮化硼层；所述双相纳米晶软磁薄膜的结构式为((Fe<Sub>z</Sub>A<Sub>1-z</Sub>)<Sub>a</Sub>Co<Sub>b</Sub>Q<Sub>c</Sub>Ba<Sub>d</Sub>)<Sub>1-x</Sub>-(RO<Sub>2</Sub>)<Sub>x</Sub>；所述双相纳米晶软磁薄膜为bbc结构的α-(Fe<Sub>z</Sub>A<Sub>1-z</Sub>)<Sub>a</Sub>Co<Sub>b</Sub>Q<Sub>c</Sub>Ba<Sub>d</Sub>纳米金属颗粒被RO<Sub>2</Sub>绝缘介质纳米颗粒包裹结构。本发明通过添加RO<Sub>2</Sub>掺杂包裹bbc结构的α-(Fe<Sub>z</Sub>A<Sub>1-z</Sub>)<Sub>a</Sub>Co<Sub>b</Sub>Q<Sub>c</Sub>Ba<Sub>d</Sub>纳米金属,有效降低矫顽力,使软磁性能得到提高,有利于薄膜的颗粒细化。(The invention provides an anti-electromagnetic interference soft magnetic particle film and a preparation method thereof, wherein the soft magnetic particle film is of a multilayer structure and comprises a middle two-phase nano-crystalline soft magnetic film and a plurality of overlapped repeating structures positioned at two sides of the two-phase nano-crystalline soft magnetic film, and each overlapped repeating structure comprises a nano ZnO layer and a nano hexagonal boron nitride layer; the two-phase nanocrystalThe soft magnetic thin film has a structural formula of ((Fe) z A 1‑z ) a Co b Q c Ba d ) 1‑x ‑(RO 2 ) x (ii) a The biphase nanocrystalline soft magnetic film is alpha- (Fe) with bbc structure z A 1‑z ) a Co b Q c Ba d Nano metal particle is coated by RO 2 And the insulating medium nano-particle is wrapped in the structure. The invention adds RO 2 Alpha- (Fe) doped with bbc-wrapped structure z A 1‑z ) a Co b Q c Ba d The nano metal effectively reduces the coercive force, improves the soft magnetic performance and is beneficial to the grain refinement of the film.)

1. An anti-electromagnetic interference soft magnetic particle film, characterized in that the soft magnetic particle film is a multilayer structure, which is a middle dual-phase nano-crystalline soft magnetic film (1) and a plurality of overlapping repeating structures (2) positioned at the upper side and a plurality of overlapping repeating structures (2) positioned at the lower side of the dual-phase nano-crystalline soft magnetic film (1), and the one overlapping repeating structure (2) comprises a nano-ZnO layer (2-1) and a nano-hexagonal boron nitride layer (2-2);

the structural formula of the biphase nanocrystalline soft magnetic film is ((Fe)_zA_1-z)_aCo_bQ_cBa_d)_1-x-(RO₂)_xWherein a is more than or equal to 30 and less than or equal to 60, b is more than or equal to 50 and less than or equal to 70, c is more than or equal to 10 and less than or equal to 30, d is more than or equal to 0.1 and less than or equal to 0.5, x is more than or equal to 0.7 and less than or equal to 0.9, and z is more than or equal to 0.1 and less; the A element is a ferromagnetic transition metal element, the Q element is a noble metal element, and the R element is one or more of Ce, Mn, Si or Zr; the thickness of the biphase nanocrystalline soft magnetic film is 30-40 mu m, the thickness of the nanometer hexagonal boron nitride layer is 8-10 mu m, the thickness of the nanometer ZnO layer is 20-30 mu m, and the biphase nanocrystalline soft magnetic film is alpha- (Fe) with bbc structure_zA_1-z)_aCo_bQ_cBa_dNano metal particles and RO₂Insulating medium nano-particle composition, alpha- (Fe) of the bbc structure_zA_1-z)_aCo_bQ_cBa_dNano metal particles are coated with the RO₂Insulating medium nanoparticle coating, the alpha- (Fe)_zA_1-z)_aCo_bQ_cBa_dThe diameter of the nano metal particles is 2 nm-5 nm, and the RO₂The diameter of the insulating medium nano particles is 0.25 nm-0.5 nm.

2. The soft magnetic particle film against electromagnetic interference of claim 1, wherein said element a is one or more of Ni and Ti.

3. The soft magnetic particle film against electromagnetic interference of claim 1, wherein said Q element is one or more of Cu, Ag, Au or Pt.

4. The soft magnetic particle film against electromagnetic interference according to claim 1, wherein the Curie temperature Tc of said soft magnetic particle film is 260 ℃ to 280 ℃.

5. The soft magnetic particle film against electromagnetic interference according to claim 1, wherein said soft magnetic particle film has a uniaxial anisotropy field of 6.50kA/m to 8.50 kA/m.

6. The soft magnetic particle film against electromagnetic interference according to claim 1, wherein a plurality of said overlapping repeating structures (2) are located on the upper and lower sides of said middle dual-phase nano-crystalline soft magnetic film (1), said one overlapping repeating structure (2) is a layer of said nano ZnO layer (2-1) located on the upper side of a layer of said nano hexagonal boron nitride layer (2-2), said middle dual-phase nano-crystalline soft magnetic film (1) is an upper side of said nano hexagonal boron nitride layer (2-2), and said middle dual-phase nano-crystalline soft magnetic film (1) is an underside of said nano ZnO layer (2-1).

7. An anti-electromagnetic interference soft magnetic particle film according to claim 1, characterized in that said bi-phase nano-crystalline soft magnetic thin film (1) has 2-4 of said overlapping repeating structures (2) on the outer side.

8. The method for preparing an anti-electromagnetic interference soft magnetic particle film according to any one of claims 1 to 7, comprising the steps of:

1) using a glass cover glass with the thickness of 0.15-0.18 mm as a substrate, placing the substrate into a solution with an anionic surfactant as a detergent, soaking for 20-30 min, cleaning for 10-15 min by using ultrasonic waves at the ultrasonic frequency of 50-80 Hz, placing the substrate into a mixed organic solvent of absolute ethyl alcohol and acetone with the volume ratio of (2:5) - (3:5), cleaning for 10-20 min at the ultrasonic frequency of 30-45 Hz, and blow-drying the substrate in hot air at the temperature of 50-60 ℃ to obtain a clean and dry substrate sheet;

2) adopting high vacuum oblique three-target co-sputtering equipment, setting the plane of the target and the horizontal plane to form a angle of 20-30 degrees, wherein the distance between the target and the substrate is 80 mm-100mm, argon is filled, and a plurality of RO with the purity of 99.9 percent are added₂The compound solid small pieces are regularly arranged in Fe with the diameter of 70 mm-80 mm_z×aCo_bBa_dOn the annular etching region of the first sputtering target, adjusting the Fe_{z× a}Co_bBa_dThe sputtering power of the first sputtering target of (2) is 120W to 140W; the second sputtering target is a pure A element sputtering target, the sputtering power of the second sputtering target is adjusted to be 20-120W, and the content of the A element in the finally formed two-phase nanocrystalline soft magnetic film is further adjusted; the third sputtering target is a pure Q element sputtering target, the sputtering power of the third sputtering target is adjusted to be 20-120W, and the content of the Q element in the finally formed biphase nanocrystalline soft magnetic film is further adjusted to ensure that the ratio of the final Fe element, the final A element, the final Co element, the final Q element and the final Ba element is (zxa): ((1-z) × a): b: c: d; adjusting the RO₂The amount of solid small pieces of the compound to ensure that the ratio of Fe element to R element is (z × a × (1-x)): x;

3) in the sputtering process, the pressure of the sputtering argon is adjusted to be 0.5 Pa-0.6 Pa, the rotation speed of the substrate is 65 rpm-75 rpm, and the vacuum degree of the back substrate is 5.5 multiplied by 10^-5Pa～5.8×10^-5Pa; and after the sputtering is finished, obtaining the dual-phase nano-crystalline soft magnetic film, placing the nano ZnO powder and the nano hexagonal boron nitride powder in a vacuum sprayer under vacuum, and sequentially spraying the nano ZnO powder and the nano hexagonal boron nitride powder on the dual-phase nano-crystalline soft magnetic film under the pressure of 35 MPa-40 MPa to form a nano ZnO layer and a nano hexagonal boron nitride layer which are positioned at two sides of the dual-phase nano-crystalline soft magnetic film and are mutually spaced and overlapped.

9. The method for preparing a soft magnetic particle film against electromagnetic interference as claimed in claim 8, wherein the flow rate of argon gas is 30sccm to 40 sccm.

10. The method according to claim 8, wherein the purity of the target material of the sputtering target is 99.95-99.99%.

Technical Field

The invention belongs to the technical field of electromagnetic materials, and particularly relates to an anti-electromagnetic interference soft magnetic particle film and a preparation method thereof.

Background

With the development of scientific technology, communication technologies such as mobile phones and high-speed wireless local area networks have realized real-time communication between people and any people anywhere, and meanwhile, the data transmission rate of wireless communication technologies reaches the frequency band. For example, bluetooth is operating in the frequency band. Wireless mobile devices are rapidly moving towards more miniaturization and miniaturization in order to achieve higher and faster mobility of wireless systems. The rf circuit, which consists of two boards, a transmission circuit and a reception circuit, is a core component of a wireless system, and is favored in signal amplifiers, filters and modems due to its high integration. The widespread use of radio frequency circuits in mobile devices requires a large number of passive components, mainly capacitors and inductors. With the demand for miniaturization and high performance of devices, there is an increasing demand for soft magnetic thin films having high magnetic permeability, high saturation magnetization, low coercive force, and high resistivity.

The results of the study show that in order to maintain excellent high-frequency characteristics, the magnetic material is required to have a large resistivity ρ and a large saturation magnetization Ms and also to have an anisotropy field Hk of a moderate magnitude. On the other hand, high-density and wide-spectrum electromagnetic signals generated by the conventional integrated electronic device in operation fill the whole space to form a complex electromagnetic environment, so that the electronic equipment and the power supply are required to have good electromagnetic compatibility in each frequency band and in a use temperature range, and a series of challenges are brought to the anti-electromagnetic interference technology.

Disclosure of Invention

Aiming at the defects, the invention provides the anti-electromagnetic interference soft magnetic particle film which has good magnetic conductivity and high resistivity at high temperature, can be suitable for a high-frequency band and has a properly large uniaxial anisotropic field, and the preparation method thereof.

The invention provides the following technical scheme: the anti-electromagnetic interference soft magnetic particle film is characterized in that the soft magnetic particle film is of a multilayer structure and comprises a middle two-phase nano-crystalline soft magnetic film, a plurality of overlapped repeating structures positioned on the upper side of the two-phase nano-crystalline soft magnetic film and a plurality of overlapped repeating structures positioned on the lower side of the two-phase nano-crystalline soft magnetic film, wherein one overlapped repeating structure comprises a nano ZnO layer and a nano hexagonal boron nitride layer;

the structural formula of the biphase nanocrystalline soft magnetic film is ((Fe)_zA_1-z)_aCo_bQ_cBa_d)_1-x-(RO₂)_xWherein a is more than or equal to 30 and less than or equal to 60, b is more than or equal to 50 and less than or equal to 70, c is more than or equal to 10 and less than or equal to 30, d is more than or equal to 0.1 and less than or equal to 0.5, x is more than or equal to 0.7 and less than or equal to 0.9, and z is more than or equal to 0.1 and less; the A element is a ferromagnetic transition metal element, the Q element is a noble metal element, and the R element is one or more of Ce, Mn, Si or Zr; the thickness of the biphase nanocrystalline soft magnetic film is 30-40 mu m, the thickness of the nanometer hexagonal boron nitride layer is 8-10 mu m, the thickness of the nanometer ZnO layer is 20-30 mu m, and the biphase nanocrystalline soft magnetic film is alpha- (Fe) with bbc structure_zA_1-z)_aCo_bQ_cBa_dNano metal particles and RO₂Insulating medium sodiumRice grain composition, alpha- (Fe) of the bbc structure_zA_1-z)_aCo_bQ_cBa_dNano metal particles are coated with the RO₂Insulating medium nanoparticle coating, the alpha- (Fe)_zA_1-z)_aCo_bQ_cBa_dThe diameter of the nano metal particles is 2 nm-5 nm, and the RO₂The diameter of the insulating medium nano particles is 0.25 nm-0.5 nm.

Further, the element A is one or more of Ni and Ti.

Further, the Q element is one or more of Cu, Ag, Au or Pt.

Further, the Curie temperature Tc of the soft magnetic particle film is 260 to 280 ℃.

Further, the uniaxial anisotropy field of the soft magnetic particle film is 6.50kA/m to 8.50 kA/m.

Further, a plurality of said overlapping repeating structures are located on the upper and lower sides of said middle two-phase nano-crystalline soft magnetic thin film, said one overlapping repeating structure is a layer of said nano ZnO layer located on the upper side of a layer of said nano hexagonal boron nitride layer, said upper side of said middle two-phase nano-crystalline soft magnetic thin film is said nano hexagonal boron nitride layer, and said lower side of said middle two-phase nano-crystalline soft magnetic thin film is said nano ZnO layer.

Furthermore, one side of the outer side of the double-phase nano-crystalline soft magnetic film is provided with 2-4 overlapped repeating structures.

The invention also provides a preparation method of the anti-electromagnetic interference soft magnetic particle film, which comprises the following steps:

1) using a glass cover glass with the thickness of 0.15-0.18 mm as a substrate, placing the substrate into a solution with an anionic surfactant as a detergent, soaking for 20-30 min, cleaning for 10-15 min by using ultrasonic waves at the ultrasonic frequency of 50-80 Hz, placing the substrate into a mixed organic solvent of absolute ethyl alcohol and acetone with the volume ratio of (2:5) - (3:5), cleaning for 10-20 min at the ultrasonic frequency of 30-45 Hz, and blow-drying the substrate in hot air at the temperature of 50-60 ℃ to obtain a clean and dry substrate sheet;

2) adopting high vacuum oblique three-target co-sputtering equipment, setting the plane of the target and the horizontal plane to form a angle of 20-30 degrees, setting the distance between the target and the substrate to be 80-100 mm, filling argon gas, and subjecting a plurality of RO with the purity of 99.9 percent₂The compound solid small pieces are regularly arranged in Fe with the diameter of 70 mm-80 mm_z×aCo_bBa_dOn the annular etching region of the first sputtering target, adjusting the Fe_z×aCo_bBa_dThe sputtering power of the first sputtering target of (2) is 120W to 140W; the second sputtering target is a pure A element sputtering target, the sputtering power of the second sputtering target is adjusted to be 20-120W, and the content of the A element in the finally formed two-phase nanocrystalline soft magnetic film is further adjusted; the third sputtering target is a pure Q element sputtering target, the sputtering power of the third sputtering target is adjusted to be 20-120W, and the content of the Q element in the finally formed biphase nanocrystalline soft magnetic film is further adjusted to ensure that the ratio of the final Fe element, the final A element, the final Co element, the final Q element and the final Ba element is (zxa): ((1-z) × a): b: c: d; adjusting the RO₂The amount of solid small pieces of the compound to ensure that the ratio of Fe element to R element is (z × a × (1-x)): x;

3) in the sputtering process, the pressure of the sputtering argon is adjusted to be 0.5 Pa-0.6 Pa, the rotation speed of the substrate is 65 rpm-75 rpm, and the vacuum degree of the back substrate is 5.5 multiplied by 10^-5Pa～5.8×10^-5Pa; and after the sputtering is finished, obtaining the dual-phase nano-crystalline soft magnetic film, placing the nano ZnO powder and the nano hexagonal boron nitride powder in a vacuum sprayer under vacuum, and sequentially spraying the nano ZnO powder and the nano hexagonal boron nitride powder on the dual-phase nano-crystalline soft magnetic film under the pressure of 35 MPa-40 MPa to form a nano ZnO layer and a nano hexagonal boron nitride layer which are positioned at two sides of the dual-phase nano-crystalline soft magnetic film and are mutually spaced and overlapped.

Further, the flow rate of the argon gas is 30sccm to 40 sccm.

Further, the purity of the target material of the sputtering target is 99.95-99.99%.

The invention has the beneficial effects that:

1) due to the soft magnetic material Fe_z×aCo_bBa_dPrepared by a sputtering method, is doped with A element and Q element, and can utilize the substrate layers of the A element and the Q element to further prepareIncrease of Fe_z×aCo_bBa_dThe soft magnetic property of the soft magnetic material is realized, the element A partially replaces the element Fe, and the formed Fe-Ni alloy or Fe-Ti alloy can improve the distance temperature of the amorphous nanocrystalline dual-phase soft magnetic film and improve the stability in a high-temperature environment.

2) And by adding RO₂Alpha- (Fe) doped with bbc-wrapped structure_zA_1-z)_aCo_bQ_cBa_dThe nano metal effectively reduces the coercive force, improves the soft magnetic performance, is beneficial to the grain refinement of the film, thereby generating exchange coupling among grains and averagely changing the magnetocrystalline anisotropy into smaller effective anisotropy; at the same time, the coercive force can be reduced to mu₀M_sAnd if the resistance is more than 2.5T, the resistivity is improved, the eddy current loss is effectively reduced, and the cut-off frequency of the film is improved.

3) The non-metal M element is added to promote the precursor Fe_z×aCo_bBa_dThe final double-phase nano-crystalline soft magnetic film can form a better nano-crystalline phase by adding a ferromagnetic transition metal element-A, so that the alpha- (Fe) with the bbc structure is formed_zA_1-z)_aCo_bQ_cBa_dNano metal particles are coated with the RO₂The insulating medium nano particles are wrapped, so that the final soft magnetic particle film has a disordered three-dimensional microstructure, the higher amorphous crystallization temperature is ensured, and the soft magnetic particle film can have higher stability at high temperature.

4) The symmetrical nanometer ZnO layer and the nanometer hexagonal boron nitride layer which are mutually overlapped at intervals are formed on the two sides of the middle double-phase nanometer crystal soft magnetic film, a certain electromagnetic shielding effect can be improved through the nanometer hexagonal boron nitride layer, higher resistivity is guaranteed through the nanometer ZnO layer, and then the effects of high resistivity and high electromagnetic shielding are achieved simultaneously.

Drawings

The invention will be described in more detail hereinafter on the basis of embodiments and with reference to the accompanying drawings. Wherein:

FIG. 1 is a schematic view of a structure of a soft magnetic particle film provided in example 1 of the present invention;

FIG. 2 is a schematic view of the structure of a soft magnetic particle film provided in example 2 of the present invention;

fig. 3 is a schematic view of the structure of a soft magnetic particle film provided in embodiment 3 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The preparation of the soft magnetic particle film is carried out by adopting JGP450 type high vacuum three-target co-sputtering deposition coating equipment sold by Shenyang New blue sky vacuum technology Limited company.