CN114525014A - Preparation method of ferrite-based magnetic antenna substrate - Google Patents
Preparation method of ferrite-based magnetic antenna substrate Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
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Abstract
The invention discloses a preparation method of a ferrite-based magnetic antenna substrate, which comprises the following steps of firstly, carrying out ALD treatment on a ferrite raw material; and then compounding the ferrite powder and the polymer to obtain the antenna substrate. According to the method, a proper low-loss deposition layer material is selected, the surface of the ferrite powder is processed through the ALD technology, the thickness of the deposition layer is controlled, and the magneto-dielectric loss of the substrate is reduced on the premise that the magnetic conductivity is not influenced.
Description
Technical Field
The invention belongs to the technical field of antenna substrate preparation, and particularly relates to a preparation method of a ferrite-based magnetic antenna substrate.
Background
The miniaturization (compactness) design of antennas based on conventional non-magnetic dielectric substrates tends to be contradictory to the broadband requirements of the antennas. In order to solve the problem, researchers mainly optimize the physical structure of the antenna at present to obtain a certain degree of improvement effect. According to the electromagnetic theory, the size of the antenna is integral multiple of a quarter of the medium wavelength, so that the physical size of the antenna can be obviously reduced by improving the medium permeability by using the magnetic material as the antenna substrate. Meanwhile, the bandwidth of the antenna can be understood as the impedance matching problem between the medium and the air, and as the magnetic permeability is increased and approaches to the relative dielectric constant, the wave impedance in the medium is gradually matched with the air wave impedance, so that the bandwidth is expanded. In conclusion, the magnetic medium material containing magnetic permeability can expand the bandwidth while reducing the size of the antenna, and can be compatible with the traditional antenna structure design, so that the material has better application prospect.
Ferrite materials have the characteristic of high magnetic permeability, but the traditional ferrite materials have low cut-off frequency and large loss, and are often applied to the design of antennas under kHz and MHz. For higher GHz frequency, although hexagonal ferrite or spinel Ni-Zn ferrite and the like have higher magnetic permeability and higher cut-off frequency and are suitable for device design of radio frequency and microwave frequency bands, the magnetic dielectric loss is also introduced, and even if the magnetic dielectric loss is made into a composite material with polymer, the loss tangent is still higher (>0.05), which exceeds the loss (<0.001) of a typical commercial polymer antenna substrate by more than one order of magnitude. The antenna designed by using the material is often low in efficiency, and the gain is affected, so that the requirement of practical application cannot be met. Therefore, loss control and loss reduction processing of magnetic materials are key issues in the current research of magnetic antenna dielectric substrates.
In order to reduce the loss of the magnetic medium, an Atomic Layer Deposition (ALD) method is adopted to deposit a layer of low-loss medium with controllable thickness on the surface of the ferrite material layer by layer, so as to achieve the beneficial effect of reducing the overall loss of the composite material, thereby improving the comprehensive performance of the antenna, particularly obtaining the gain of the antenna and improving the efficiency of the antenna, and promoting the practicability of the magnetic substrate.
Disclosure of Invention
The invention aims to provide a preparation method of a ferrite-based magnetic antenna substrate, which is used for obtaining a substrate with low magnetic dielectric loss.
The technical scheme adopted by the invention is that the preparation method of the ferrite-based magnetic antenna substrate is implemented according to the following steps:
and 2, carrying out composite processing on the ferrite powder obtained in the step 1 and a polymer to obtain the antenna substrate.
The present invention is also characterized in that,
in the step 1, the method specifically comprises the following steps:
step 1.1, putting a ferrite powder raw material into atomic deposition equipment, vacuumizing until the pressure of a chamber is less than 5.3Pa, simultaneously heating to a preset temperature, and preserving heat for 30min, wherein the preset temperature is 50-200 ℃;
step 1.2, heating and gasifying the precursor substance to form precursor gas, and respectively introducing the precursor gas and oxygen source gas into atomic deposition equipment to carry out atomic deposition reaction;
step 1.3, after the step 2, introducing inert gas into atomic deposition equipment for purging; the purging time is 10-300 seconds, the residue of the cleaning reaction is remained, and the powder is collected for later use.
In the step 1.1, the ferrite raw material is any one of M-type hexaferrite, Y-type hexaferrite, Z-type hexaferrite and spinel-type ferrite.
In step 1.2, the precursor is Al (CH)3)3、C8H24N4Ti、TiCl4、SiH4、Zn(C2H5)2Any one of the above; the heating temperature of the precursor substance is 50-100 ℃.
In step 1.2, the introduction time of the precursor gas is 1-100 seconds, and the introduction time of the oxygen source is 1-200 seconds.
In the step 2, the mass ratio of the ferrite powder to the polymer is 1-6: 4-9; the polymer is any one of epoxy resin, PVDF, rubber, HDPE and POE.
The invention has the beneficial effects that: according to the method, a proper low-loss deposition layer material is selected, the surface of the ferrite powder is processed through the ALD technology, the thickness of the deposition layer is controlled, and the magneto-dielectric loss of the substrate is reduced on the premise that the magnetic conductivity is not influenced.
Drawings
FIG. 1 is a schematic diagram of the deposition of ALD in the process of the present invention;
FIG. 2 is an electron micrograph of an NZO powder material before and after ALD surface treatment and an X-ray diffraction spectrum of the powder after ALD treatment in example 1 of the present invention;
FIG. 3 is a hysteresis loop of an ALD surface treated NZO powder material in example 1 of the present invention;
FIG. 4 is the relative permittivity and permeability measured for the NZO/rubber composite material in example 1 of the present invention;
FIG. 5 shows that NiZn ferrite is coated with Al in example 1 of the present invention2O3Microstrip patch antenna designed on rubber-compounded substrate and S of antenna manufactured by substrate without ALD treatment11Comparing parameters;
FIG. 6 is a NiZn ferrite clad with Al in example 1 of the present invention2O3Comparing the antenna radiation efficiency with a microstrip patch antenna designed on a rubber composite substrate and an antenna directional pattern manufactured by a substrate which is not processed by ALD (atomic layer deposition);
FIG. 7 shows that Z-type hexaferrite is coated with TiO in example 2 of the present invention2Microstrip patch antenna made with epoxy substrate and simulation S of substrates not treated with ALD11A parameter;
FIG. 8 shows example 2 of the present invention in which Z-type hexaferrite is coated with TiO2A microstrip patch antenna made of an epoxy resin substrate and a radiation pattern of a central frequency point of the substrate which is not subjected to ALD treatment;
FIG. 9 is the central frequency radiation pattern of the microstrip patch antenna made of the substrate made of PVDF and M-type hexaferrite coated with ZnO and the substrate without ALD treatment in example 3 of the present invention;
fig. 10 shows the central frequency radiation patterns of the microstrip patch antenna made of the substrate made of PVDF and M-type hexaferrite coated with ZnO and the substrate without ALD treatment in example 3 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a preparation method of a ferrite-based magnetic antenna substrate, which is implemented according to the following steps:
step 1.1, putting a ferrite raw material into atomic deposition equipment, vacuumizing until the pressure of a chamber is less than 5.3Pa, simultaneously heating to a preset temperature and preserving heat for 30 min;
the preset temperature is 50-200 ℃;
the ferrite raw material is any one of M-type hexagonal ferrite, Y-type hexagonal ferrite, Z-type hexagonal ferrite and spinel type ferrite;
the general formula of the M-type hexaferrite is Ba (CoTi)xFe12-2xO19，0<x≤3；
The general formula of the Y-shaped hexaferrite is Ba2Co2Fe12O12；
The general formula of the Z-type hexaferrite is Ba3Co2Fe24O41；
The spinel type ferrite has a general formula of NixZnyCozCu1-x-y-zFe2O4，0<x, y, z are less than or equal to 1 and 0<x+y+z≤1)；
Step 1.2, heating and gasifying the precursor substance to form precursor gas, and respectively introducing the precursor gas and oxygen source gas into atomic deposition equipment to carry out atomic deposition reaction;
the precursor is trimethyl aluminum Al (CH)3)3Tetra (dimethylamino) titanium C8H24N4Ti、TiCl4、SiH4Diethyl zinc Zn (C)2H5)2Any one of(ii) a The heating temperature of the precursor substance is 50-100 ℃;
oxygen source substance is O2、O3Or water vapor; wherein the liquid oxygen source needs to be heated and gasified;
the introducing time of the precursor gas is 1-100 seconds, the thickness of a reaction deposition layer is determined, and the introducing time of an oxygen source is 1-200 seconds, so that the full reaction is ensured;
step 1.3, after the step 2, introducing inert gas into atomic deposition equipment for purging; purging for 10-300 seconds, cleaning reaction residues, and collecting powder for later use;
the mass ratio of the ferrite powder to the polymer is 1-6: 4-9;
the polymer is specifically any one of epoxy resin, PVDF, rubber, HDPE and POE;
when the polymer is made of thermosetting molding materials such as epoxy resin or rubber, the antenna substrate is prepared by adopting a casting body process, which specifically comprises the following steps: fully mixing and stirring ferrite powder, polymer and curing agent uniformly at room temperature, vacuumizing to remove bubbles, injecting into a forming die, and heating, curing and forming at the curing temperature of the material;
when the polymer is selected from thermoplastic forming polymers such as PVDF, HDPE or POE, the antenna substrate is prepared by adopting a hot press forming process, which specifically comprises the following steps: completely softening ferrite powder and polymer at the softening temperature of the material, fully mixing and stirring uniformly, vacuumizing to remove bubbles, extruding and molding, and naturally cooling and hardening at room temperature.
The existing magnetic composite antenna substrate material is mainly formed by directly compounding and processing ferrite powder and polymer. In the application process, the antenna processed by the substrate material generally has the obvious defects of small gain and low efficiency, and the application research of the magnetic antenna is severely limited. The main reason for this is that the magneto-dielectric loss of ferrite ceramics is usually much higher than that of the dielectric material of the conventional non-magnetic antenna substrate. For example, the polytetrafluoroethylene glass cloth plate (F4B-2) isA commercial antenna substrate having a dielectric constant (2.65), a loss tangent (C:) in the microwave range<0.001) with no magnetic losses of the material. And Z-type hexaferrite Ba3Co2Fe24O41Is a typical microwave ferrite material with a dielectric constant (15), a loss tangent (C:) in the microwave range>0.05) and at the same time the permeability (9) of the material, the magnetic loss tangent (c: (a)>0.1), the comprehensive magnetic dielectric loss is 1-2 orders of magnitude higher than that of the F4B-2 polymer antenna substrate, and the antenna performance is seriously influenced.
Studies have shown that the dielectric loss of ferrites is mainly due to the leakage conduction loss of the material (i.e. the material conductivity is higher), while the magnetic loss is mainly due to the eddy current loss, which is also associated with high conductivity. Therefore, the reduction of the conductivity is the key to the suppression of the ferrite magneto-dielectric loss.
The deposition principle of ALD in the method of the invention is shown in figure 1, and a layer of Al is deposited on the prepared ferrite principle2O3、TiO2ZnO or SiO2And the like, thereby reducing the loss caused by the original ferrite; meanwhile, the advantage of controllable thickness of the deposited layer is utilized, the deposited layer is controlled as much as possible, and the adverse effect of the nonmagnetic deposited layer material on the magnetic permeability of the composite material is reduced.
In the method, the atomic layer deposition method is adopted to coat the surface of the ferrite powder, and the method has the advantages that:
(1) uniformly coating a high-resistivity dielectric layer such as Al on the surface of each ferrite micron powder2O3And the physical isolation layer is formed among the ferrite powder bodies, so that the leakage conduction loss and the eddy current loss are effectively inhibited, and the magnetic dielectric loss of the composite material is reduced;
(2) compared with other powder coating methods such as wet chemical coating and the like, the method can effectively prevent the ferrite powder from agglomerating, form a high-quality deposition layer with uniform thickness, compact structure and no holes, and increase the growth thickness of the deposition layer (about 1nm/s) by taking the atomic scale as a step length in the method, so that the thickness of the coating layer is accurate and controllable, compact coating can be realized by the minimum coating thickness to obtain a loss reduction effect, and the negative effects of reducing the magnetic permeability of the composite material and the like caused by overlarge thickness of the non-magnetic coating layer are avoided.
Example 1
The invention relates to a preparation method of a ferrite-based magnetic antenna substrate, which is implemented according to the following steps:
step 1.1, putting a ferrite raw material into atomic deposition equipment, vacuumizing until the pressure of a chamber is less than 5.3Pa, simultaneously heating to a preset temperature and preserving heat for 30 min;
the preset temperature is 150 ℃; the ferrite raw material is spinel type ferrite; the spinel type ferrite has a general formula of NixZnyCozCu1-x-y-zFe2O4，0<x, y, z are less than or equal to 1 and 0<x + y + z ≦ 1), in this embodiment, x ═ y ═ 0.5, and z ═ 0, i.e., the ferrite formulation is Ni0.5Zn0.5Fe2O4(abbreviated as: NZO);
step 1.2, heating and gasifying the precursor substance to form precursor gas, and respectively introducing the precursor gas and oxygen source gas into atomic deposition equipment to carry out atomic deposition reaction;
the precursor is trimethyl aluminum Al (CH)3)3(ii) a The heating temperature of the precursor substance is 100 ℃;
the oxygen source substance is water vapor;
the introducing time of the precursor gas is 10 seconds, and the introducing time of the oxygen source is 10 seconds;
step 1.3, after the step 2, introducing inert gas into atomic deposition equipment for purging; the purging time is 50 seconds, the reaction residue is cleaned, and after the reaction residue is cleaned, the powder is collected to obtain the NZO @ Al2O3A ferrite powder sample of shell structure; the microstructure and crystal structure of the powder are shown in FIG. 2, and comparing FIGS. 2(A) and (B), it can be seen that after ALD treatment, the surface of the ferrite powder particles is uniformly coated with a layer of Al2O3And the thickness of the dielectric layer is about 5 nm. As can be seen from the XRD test result in FIG. 2(C), the powder crystal phase is NiZn ferrite crystal phase with cubic spinel structure, and cannot be detected by XRDCoating layer Al2O3The crystal phase structure of (B) shows Al2O3The coating thickness is very small. The hysteresis loop test in fig. 3 shows that the coated powder is a soft magnetic ferrite material with obvious magnetism, and the saturation magnetization of the coated powder is consistent with that of the uncoated powder, which indicates that the non-magnetic coating layer obtained by the ALD process is very thin and has no influence on the ferrite magnetism.
And 2, carrying out composite processing on the sample obtained in the step 1 and a polymer to obtain the antenna substrate.
And (4) measuring the size of the poured dielectric substrate after the rubber is solidified. In the examples, a magnetic medium substrate of a NZO/rubber composite material was fabricated, circular, 50mm in diameter and 4mm in height. Fig. 4 shows the electromagnetic parameters of the composite substrate material in the range of 2-8GHz, for example, it can be seen that the relative permittivity at 5GHz frequency is 3.8, the loss is 0.02, the permeability is 1.4, and the loss is 0.1. According to the electromagnetic parameter spectrum data test result, the antenna design can be carried out on the substrate. A circular microstrip patch antenna is exemplified, where the parameters d is 50mm, l is 8mm, p is 31.5mm, and h is 4 mm. The antenna adopts a back SMA interface, the feed front surface is a radiation patch, the diameter is p, and the back surface is the ground. And (3) simulating the antenna by using simulation software HFSS, and manufacturing an antenna object for testing. The test results are shown in fig. 5 and 6. FIG. 5 is S of the antenna11Parameter comparison chart, the working frequency band of the antenna without ALD treatment is 2.16GHz-2.45GHz, and the bandwidth is 12.7% (290MHz), but the bandwidth is mainly from loss and can not be really radiated. The antenna designed by the substrate processed by ALD has obvious improvement on the antenna efficiency. Fig. 6 is a gain comparison of an antenna compared to the efficiency of the antenna. The maximum gain obtained for the antenna without ALD treatment in the simulation was 1.2dBi, while it was 2.9dBi after ALD treatment.
Example 2
The invention relates to a preparation method of a ferrite-based magnetic antenna substrate, which is implemented according to the following steps:
step 1.1, putting a ferrite raw material into atomic deposition equipment, vacuumizing until the pressure of a chamber is less than 5.3Pa, simultaneously heating to a preset temperature and preserving heat for 30 min;
the preset temperature is 170 ℃;
the ferrite raw material is Z-shaped hexaferrite; the general formula of the Z-type hexaferrite is Ba3Co2Fe24O41；
Step 1.2, heating and gasifying the precursor substance to form precursor gas, and respectively introducing the precursor gas and oxygen source gas into atomic deposition equipment to carry out atomic deposition reaction;
the precursor is tetra (dimethylamino) titanium C8H24N4Ti; the heating temperature of the precursor substance is 50 ℃;
the oxygen source substance is O3(ii) a Wherein the liquid oxygen source needs to be heated and gasified;
the introducing time of the precursor gas is 100 seconds, and the introducing time of the oxygen source is 20 seconds;
step 1.3, after the step 2, introducing inert gas into atomic deposition equipment for purging; the purging time is 300 seconds, the residue of the cleaning reaction is remained, and after the completion, the powder is collected to obtain the Z-shaped hexaferrite @ TiO2Ferrite powder samples of shell structure.
for a medium substrate to be cast, it is necessary to measure the size of the medium substrate after the rubber is solidified. In the example, a magnetic dielectric substrate of a Z-type ferrite/epoxy composite material was fabricated, square, circular with a diameter of 50mm and a height of 4 mm. Relative permittivity of 11, loss of 0.002, permeability of 1.8, and loss of 0.08. An antenna is designed on the substrate. The present invention is exemplified by a circular microstrip patch antenna. Where the parameter d is 50mm, l is 6.2mm, p is 31.5mm, and h is 4 mm. The antenna adopts a back SMA interface, the feed front surface is a radiation patch, the diameter is p, and the back surface is the ground. Simulation of the antenna was performed using the simulation software HFSS. The test results are shown in fig. 7 and 8. FIG. 7 is S of the test specimen antenna11The simulation chart of the parameters has the working frequency band of 1.14GHz-1.2GHz and the bandwidth of 5% (60 MHz).Fig. 8 is a gain pattern of the antenna center frequency point. Compared with the antenna designed by the substrate which is not subjected to ALD treatment, the bandwidth of the antenna is reduced within a certain normal range due to the reduction of loss, but the gain of the antenna is obviously improved.
Example 3
The invention relates to a preparation method of a ferrite-based magnetic antenna substrate, which is implemented according to the following steps:
step 1.1, putting a ferrite raw material into atomic deposition equipment, vacuumizing until the pressure of a chamber is less than 5.3Pa, simultaneously heating to a preset temperature and preserving heat for 30 min;
the preset temperature is 250 ℃;
the ferrite raw material is M-type hexagonal ferrite; the general formula of the M-type hexaferrite is Ba (CoTi)xFe12-2xO19，0<x≤3；
Step 1.2, heating and gasifying the precursor substance to form precursor gas, and respectively introducing the precursor gas and oxygen source gas into atomic deposition equipment to carry out atomic deposition reaction;
the precursor is diethyl zinc Zn (C)2H5)2(ii) a The heating temperature of the precursor substance is 100 ℃;
the oxygen source substance is water vapor; the introducing time of the precursor gas is 50 seconds, and the introducing time of the oxygen source is 50 seconds;
step 1.3, after the step 2, introducing inert gas into atomic deposition equipment for purging; the purging time is 200 seconds, the reaction residue is cleaned, and after the reaction residue is cleaned, the powder is collected to obtain a ferrite powder sample with the M-type hexagonal ferrite @ ZnO shell structure.
and (4) measuring the size of the poured dielectric substrate after the rubber is solidified. In the example, a magnetic medium substrate of an M-type ferrite/epoxy resin composite material is manufactured, wherein the magnetic medium substrate is square, and the circle has the diameter of 50mm and the height of 4 mm. Relative dielectric constant of 10, loss of 0001, permeability 2, loss 0.1. An antenna is designed on the substrate, and a circular microstrip patch antenna is taken as an example. Where the parameter d is 50mm, l is 5.5mm, p is 31.5mm, and h is 4 mm. The antenna adopts a back SMA interface to feed, the front surface is a radiation patch, the diameter is p, and the back surface is the ground. Simulation of the antenna was performed using the simulation software HFSS. The test results are shown in fig. 9 and 10. FIG. 9 is S of the test specimen antenna11The simulation chart of the parameters has the working frequency band of 1.19GHz-1.23GHz and the bandwidth of 3.8% (46 MHz). Fig. 10 is a gain pattern at the center frequency of the antenna. Compared with the antenna designed by the substrate which is not subjected to ALD processing, the loss is reduced, the bandwidth of the antenna is normally reduced to a certain extent, and the gain of the antenna is obviously improved.
Claims (6)
1. A preparation method of a ferrite-based magnetic antenna substrate is characterized by comprising the following steps:
step 1, carrying out ALD treatment on a ferrite raw material;
and 2, carrying out composite processing on the ferrite powder obtained in the step 1 and a polymer to obtain the antenna substrate.
2. The method for preparing a ferrite-based magnetic antenna substrate according to claim 1, wherein the step 1 specifically comprises:
step 1.1, putting a ferrite raw material into atomic deposition equipment, vacuumizing until the pressure of a chamber is less than 5.3Pa, simultaneously heating to a preset temperature, and preserving heat for 30min, wherein the preset temperature is 50-200 ℃;
step 1.2, heating and gasifying the precursor substance to form precursor gas, and respectively introducing the precursor gas and oxygen source gas into atomic deposition equipment to carry out atomic deposition reaction;
step 1.3, after the step 2, introducing inert gas into atomic deposition equipment for purging; the purging time is 10-300 seconds, the residue of the cleaning reaction is remained, and the powder is collected for later use.
3. The method for preparing a ferrite-based magnetic antenna substrate as claimed in claim 2, wherein in step 1.1, the ferrite material is any one of M-type hexaferrite, Y-type hexaferrite, Z-type hexaferrite, and spinel-type ferrite.
4. The method for manufacturing a ferrite-based magnetic antenna substrate as claimed in claim 2, wherein the precursor in step 1.2 is Al (CH)3)3、C8H24N4Ti、TiCl4、SiH4、SiCl4、Zn(C2H5)2Any one of the above; the heating temperature of the precursor substance is 50-100 ℃.
5. The method according to claim 2, wherein in step 1.2, the precursor gas is introduced for 1-100 seconds, and the oxygen source is introduced for 1-200 seconds.
6. The method for preparing the ferrite-based magnetic antenna substrate as claimed in claim 1, wherein in the step 2, the mass ratio of ferrite powder to polymer is 1-6: 4-9; the polymer is any one of epoxy resin, PVDF, rubber, HDPE and POE.
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| CN113337808A (en) * | 2021-05-10 | 2021-09-03 | 西安交通大学 | Method for strengthening inner and outer surfaces of voltage reduction element with complex structure |
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| US20100215897A1 (en) * | 2007-11-05 | 2010-08-26 | Weimer Alan W | Metal ferrite spinel energy storage devices and methods for making and using same |
| CN112466589A (en) * | 2020-10-21 | 2021-03-09 | 广东省科学院材料与加工研究所 | CVD (chemical vapor deposition) coated iron-silicon alloy powder and iron-silicon magnetic powder core and preparation method thereof |
| CN113096907A (en) * | 2021-03-10 | 2021-07-09 | 广东省科学院材料与加工研究所 | Metal magnetic powder core and preparation method thereof |
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