CN117661118A - Al with high magnetocrystalline anisotropy: YIG single crystal material and preparation method thereof - Google Patents
Al with high magnetocrystalline anisotropy: YIG single crystal material and preparation method thereof Download PDFInfo
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- CN117661118A CN117661118A CN202311537523.5A CN202311537523A CN117661118A CN 117661118 A CN117661118 A CN 117661118A CN 202311537523 A CN202311537523 A CN 202311537523A CN 117661118 A CN117661118 A CN 117661118A
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- 239000013078 crystal Substances 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002223 garnet Substances 0.000 claims abstract description 7
- 230000004907 flux Effects 0.000 claims abstract 3
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000010583 slow cooling Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000005415 magnetization Effects 0.000 abstract description 12
- 230000005350 ferromagnetic resonance Effects 0.000 description 10
- 230000005291 magnetic effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 3
- 238000013461 design Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000002902 ferrimagnetic material Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001172 neodymium magnet Inorganic materials 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an Al with high magnetocrystalline anisotropy: YIG single crystal material and preparation method thereof, belonging to ferrite single crystal material technical field, the preparation method of the invention adopts PbO-PbF 2 ‑B 2 O 3 Growth of garnet Y in flux system 3 Fe x5‑ Al x O 12 Single crystal, Y prepared by the method 3 Fe x5‑ Al x O 12 The magnetocrystalline anisotropy of the ferrite single crystal material is obviously higher than that of Ga-doped YIG single crystal material, can reach more than 100 and Oe, has good element doping concentration distribution uniformity and high saturation magnetization consistency, and can be applied to a permanent magnet bias type miniaturized broadband filter.
Description
Technical Field
The invention relates to the technical field of ferrite single crystal materials, in particular to an Al with high magnetocrystalline anisotropy: YIG single crystal material and its preparation method are provided.
Background
The garnet type YIG ferrite single crystal material is a ferrimagnetic material, has the characteristics of excellent saturation magnetization uniformity, narrow ferromagnetic resonance line width, weak magnetocrystalline anisotropy field and the like, is an excellent gyromagnetic material, and is widely applied to various magnetic tuning microwave devices with low frequency, high Q value and low insertion loss.
Currently, in order to achieve miniaturization of microwave devices, a permanent magnet bias is adopted to replace a soft magnetic excitation coil to provide a bias magnetic field for YIG ferrite single crystal materials. However, a general permanent magnetic material, such as NdFeB, has a large temperature coefficient, that is, the bias magnetic field provided by the material decreases with increasing temperature, so that the operating frequency of the microwave device has obvious temperature drift, and the device performance is obviously reduced. One of the methods for remedying the defect is to offset the temperature drift caused by the bias magnetic field by using the temperature drift caused by the magnetocrystalline anisotropy field of the ferrite single crystal material. The specific principle is as follows, along the [ 10 ] direction of the ferrite single crystal pellet, the ferromagnetic resonance frequency is as follows:
wherein, gamma is gyromagnetic ratio, H 0 Biasing provided for permanent magnet materialMagnetic field, H a Is the magnetocrystalline anisotropy field of ferrite single crystal material. The frequency drift coefficient with temperature is:
therefore, in order to reduce the frequency drift of the device, the temperature coefficient of the magnetocrystalline anisotropy field of the ferrite single crystal material needs to be increasedTo counteract the change of the bias magnetic field of the permanent magnet>Make the difference->Close to 0. Therefore, in order to meet the demand of high-performance miniaturized permanent magnet bias type ferrite microwave devices, ferrite single crystal materials with high magnetocrystalline anisotropy fields are required to be prepared. However, the anisotropic fields of the conventional pure YIG and Ga-doped YIG single crystal materials are smaller and generally smaller than 50Oe, so that the related requirements, especially the application requirements of a miniaturized permanent magnet bias type ferrite microwave device, cannot be met.
Disclosure of Invention
Aiming at the problem that the conventional YIG and Ga-doped YIG single crystal material cannot meet the requirements of miniaturized permanent magnet bias type ferrite microwave devices, the invention provides garnet type Al with high magnetocrystalline anisotropy: method for growing YIG ferrite single crystal material by improving raw material formula and using proper amount of Al 3+ Ion doping improves the magnetocrystalline anisotropy field.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
high anisotropic Al: the preparation method of the YIG single crystal material comprises the following steps:
(1) According to crystal formula Y 3 Fe 5-x Al x O 12 Calculate the high purity raw material (purity>99.99％)Y 2 O 3 、Al 2 O 3 、Fe 2 O 3 Solute and PbO, pbF 2 、B 2 O 3 The mass proportion of the fluxing agent is respectively and accurately weighed and evenly mixed with the raw materials;
(2) Filling the mixed powder obtained in the step (1) into a container, compacting the powder, and sealing the container;
(3) Placing the sealed container in the step (2) in a molten salt furnace vertically for slow cooling growth;
(4) And (3) after the growth is finished, taking out the crystal in the container in the step (3), and removing the fluxing agent to obtain the garnet type Al-doped YIG ferrite single crystal.
As a preferable embodiment, in the step (1), the solute molar quantity ratio is Y 2 O 3 ：Al 2 O 3 ：Fe 2 O 3 =1: 0.36 to 0.42 x:0.48 to 0.52 x (5-x), wherein x is the amount of Al in the formula, 0<x<1。
In a preferred embodiment, in the step (1), the fluxing agents PbO and PbF are 2 、B 2 O 3 The molar ratio of (2) is 7-8: 10 to 11:1, the mol ratio of the fluxing agent to the solute is 1.6-1.7: 1.
in the preferred embodiment, in the step (1), the mixing mode is ball milling.
As a preferable technical scheme, the ball milling time is 4-6 hours.
In the preferred technical scheme, in the step (2), the container is a platinum crucible.
In the step (3), as a preferable technical scheme, the slow cooling growth process is as follows: raising the temperature to 1300-1350 ℃ at a heating rate of 100-120 ℃/h, preserving heat for 10-12 h, quickly lowering the temperature to 1200 ℃ at a cooling rate of 5-10 ℃/h, and slowly lowering the temperature to the growth stop temperature of 1000 ℃ at a cooling rate of 0.5-1.0 ℃/h.
As a preferable technical solution, in the step (4), the method for removing the fluxing agent is as follows: boiling in nitric acid and glacial acetic acid mixed acid solution until the fluxing agent is completely removed.
The invention is prepared by proper amount of Al 3+ The YIG crystal is doped, the formula of the fluxing agent is improved, and the growth process is realized, so that the high-quality garnet type Al with uniform saturation magnetization and high magnetic crystal anisotropy is realized: the preparation of YIG ferrite single crystal material has important significance for the development of miniaturized permanent magnet bias type magnetic tuning microwave devices.
Compared with the prior art, the invention has the advantages that: al prepared by the method of the invention: YIG ferrite single crystal material, compared with YIG and Ga: the YIG single crystal magnetocrystalline anisotropic field is obviously improved, and the material has the advantages of uniform saturation magnetization distribution and small ferromagnetic resonance linewidth of garnet single crystal materials, and can be used in miniaturized permanent magnet bias type low-loss microwave devices.
Drawings
Fig. 1 is Al prepared in example 1: YIG ferrite single crystal appearance photographs;
fig. 2 shows Al prepared in example 1: YIG ferrite spherical harmonic oscillator photographs;
fig. 3 is Al of example 1: XRD pattern of YIG ferrite single crystal;
fig. 4 shows Al prepared in example 1: EDS test results of YIG ferrite single crystal;
fig. 5 shows Al prepared in example 1: room temperature hysteresis loop of YIG ferrite single crystal along [ 10 ], [ 11 ] 0] direction and calculated magnetocrystalline anisotropic field;
fig. 6 shows Al prepared in example 1: ferromagnetic resonance linewidth of YIG ferrite single crystal.
Detailed Description
The invention will be further described with reference to the accompanying drawings.
Example 1:
high magnetocrystalline anisotropy Al: the growth method of YIG ferrite single crystal material comprises the following steps:
weighing the required Y according to the formula 2 O 3 (weight 142 g), al 2 O 3 (weight 11 g), fe 2 O 3 (weight 230 g), B 2 O 3 (weight 13 g), pbF 2 (weight 484 g), pbO (weight 320 g), and ball-milling for 4 hours by using a ball mill to uniformly mix the materials; the ball-milled feedstock was then placed into platinumThe crucible is covered and sealed by a platinum crucible cover after being ground and compacted forcefully by a pestle; setting a process curve: heating to 1300 ℃ at a heating rate of 100 ℃/h, preserving heat for 10h, rapidly cooling to 1200 ℃ at a cooling rate of 10 ℃/h, and slowly cooling to a growth cut-off temperature of 1000 ℃ at a cooling rate of 0.5 ℃/h; cooling to room temperature along with the furnace, and after the growth is finished, performing acid boiling on the crystal by using a mixed solution of nitric acid (300 ml), glacial acetic acid (200 ml) and water (500 ml) to remove residual fluxing agent;
the morphology photo diagram of the obtained bulk single crystal is shown in figure 1, the crystal size can reach the order of centimeters, and the maximum linear dimension is 2.5cm. To characterize the physicochemical properties of the obtained single crystal, XRD and EDS were used to test and analyze the crystal structure and composition, respectively, the test results are shown in FIG. 3 and FIG. 4, which show that the chemical composition of the obtained single crystal is Y 3 Fe 4.56 Al 0.44 O 12 The method meets the expected design; the obtained single crystal is processed in batch, polished and spherical harmonic oscillator, as shown in figure 2, the saturation magnetization 4 pi Ms of the test sample ball according to GB/T9633-2012, gyromagnetic Material Performance measurement method for microwave frequency application, is 1000 Gs+ -20 Gs (as shown in figure 5), the ferromagnetic resonance linewidth DeltaH at 5GHz is lower than 0.8Oe (as shown in figure 6), and the saturation magnetization is according to [ 10 ] in figure 5]Direction and [ 1.0]Area surrounded by the directional magnetization curve ([ 10]Direction and [ 1.0]The difference between the magnetization work in the direction) can calculate the magnetocrystalline anisotropy field H of the single crystal sample a 122Oe, the magnetocrystalline anisotropy field is obviously higher than that of Ga prepared by the traditional cosolvent method: YIG single crystal.
Example 2
In this example, as compared with example 1, only "Al 2 O 3 (weight 7 g), fe 2 O 3 (weight 234 g) ", the rest was the same as in example 1, and the chemical composition of the obtained single crystal was Y 3 Fe 4.72 Al 0.28 O 12 。
Example 3
In this example, as compared with example 1, only "Al 2 O 3 (weight 19.5 g), fe 2 O 3 (weight 226 g) ", the rest was the same as in example 1, and the chemical composition of the obtained single crystal was Y 3 Fe 4.22 Al 0.78 O 12 。
Comparative example 1
In this comparative example, as compared with example 1, only "Al 2 O 3 (weight 0 g), fe 2 O 3 (weight 241 g) ", the rest was the same as in example 1, and the chemical composition of the obtained single crystal was Y 3 Fe 5 O 12 (i.e., without Al substitution).
Comparative example 2
In this comparative example, as compared with example 1, only "Al 2 O 3 (weight 25 g), fe 2 O 3 (weight 216 g) ", the rest was the same as in example 1, and the chemical composition of the single crystal obtained was Y 3 Fe 4 Al 1 O 12 (x＝1)。
XRD tests were performed on the single crystal materials grown in the foregoing examples 1, 2, and 3, and the test results are shown in fig. 3, in which the increase in the Al doping amount causes Al: the XRD diffraction peak position of YIG single crystal material slightly shifts right because Al ions replace part of Fe ions to make lattice constant smaller and unit cell volume smaller. Three kinds of Al are tested by a vibrating magnetometer and a ferromagnetic resonance method respectively: YIG single crystal material, as well as comparative example 1 and comparative example 2, with saturation magnetization of 4pi Ms, magnetocrystalline anisotropy field Ha, and ferromagnetic resonance linewidth ΔH, each material was tested for 3 single crystal pellets, and the test results are shown in Table 1, indicating Al prepared by the formulation design and growth process of the present invention: YIG ferrite single crystal material with saturation magnetization intensity covering 400-1300 Gs, ferromagnetic resonance line width lower than 0.8Oe, and magnetocrystalline anisotropy field higher than 100Oe. For comparative example 2, when the Al amount x=1, the single crystal Y was obtained 3 Fe 4 Al 1 O 12 The theoretical value of saturation magnetization is 0, and no practical application exists in a microwave device, so that magnetocrystalline anisotropy field and ferromagnetic resonance line width are not tested any more.
TABLE 1 results of testing saturation magnetization and ferromagnetic resonance linewidth of single crystal materials grown in examples
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (9)
1. Al with high magnetocrystalline anisotropy: the preparation method of the YIG single crystal material is characterized by comprising the following steps:
(1) According to crystal formula Y 3 Fe x5- Al x O 12 Calculating the raw material solute Y 2 O 3 、Al 2 O 3 、Fe 2 O 3 Fluxing agent PbO, pbF 2 、B 2 O 3 Respectively and accurately weighing and uniformly mixing the raw materials;
(2) Filling the mixed powder obtained in the step (1) into a container, compacting the powder, and sealing the container;
(3) Placing the sealed container in the step (2) in a molten salt furnace for slow cooling growth;
(4) And (3) after the growth is finished, taking out the crystal in the container in the step (3), and removing the fluxing agent to obtain the garnet type Al-doped YIG ferrite single crystal.
2. The method according to claim 1, characterized in that: in the step (1), the solute molar quantity ratio is Y 2 O 3 ：Al 2 O 3 ：Fe 2 O 3 =1：0.36~0.42×x：0.48~0.52×(5-x) Wherein, the method comprises the steps of, wherein,xis the quantity of Al in the molecular formula, 0<x<1。
3. The method according to claim 1, wherein in step (1), the fluxes PbO, pbF are selected from the group consisting of 2 、B 2 O 3 The molar ratio of (2) is 7-8: 10-11: 1, the molar ratio of the total amount of the fluxing agent to the total amount of the solute is 1.6-1.7: 1.
4. The method of claim 1, wherein in step (1), the mixing is ball milling.
5. The method of claim 4, wherein the ball milling time is 4-6 hours.
6. The method of claim 1, wherein in step (2), the container is a platinum crucible.
7. The method according to claim 1, characterized in that: in the step (3), the slow cooling growth process is as follows: and (3) heating to 1300-1350 ℃ at a heating rate of 100-120 ℃/h, preserving heat for 10-12 h, rapidly cooling to 1200 ℃ at a cooling rate of 5-10 ℃/h, and slowly cooling to the growth stop temperature of 1000 ℃ at a cooling rate of 0.5-1.0 ℃/h.
8. The method of claim 1, wherein in step (4), the flux is removed by: boiling in nitric acid and glacial acetic acid mixed acid solution until the fluxing agent is completely removed.
9. The high magnetocrystalline anisotropy Al prepared by the method of any one of claims 1 to 8: YIG single crystal material.
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