CN106431382B - Method for preparing ferrite epitaxial film with room-temperature wide-frequency large-magnetic capacitance effect - Google Patents
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Abstract
The invention relates to a method for preparing a ferrite epitaxial film with a room-temperature broadband large-magnetic capacitance effect, which comprises the following steps of: (1) preparation by AFe12‑xMxO19A ferrite having a composition represented by formula (I), wherein A is at least one of Ba or Sr, M is at least one of Sc, Mg or Cr, and x is the content of M: x is more than 0 and less than or equal to 4; (2) bombarding ferrite by using pulse laser under a vacuum background, depositing the bombarded ferrite material on a substrate, and growing a ferrite epitaxial film on the substrate, wherein the substrate is a single crystal Si substrate, a Si/Pt substrate or a single crystal Al substrate2O3Substrate and single crystal SrTiO3One of the substrates; (3) cooling the ferrite epitaxial film after the ferrite epitaxial film grows; (4) and carrying out post annealing treatment on the ferrite epitaxial film. The ferrite epitaxial film prepared by the invention has the room-temperature broadband large-magnetic capacitance effect, and overcomes the defects of weak room-temperature magnetic capacitance effect and narrow frequency range of the existing single-phase magnetic capacitance film material.
Description
Technical Field
The invention relates to a magnetic capacitance film material, in particular to a method for preparing a ferrite epitaxial film with room-temperature broadband large-magnetic capacitance effect.
Background
The magnetic capacitance effect (Magnetocapacitance effect) refers to a phenomenon that capacitance or dielectric constant of a material changes under an external magnetic field. Materials with a magnetic capacitance effect may have important applications in electromagnetic devices such as magnetic field detectors, intelligent filters, and magnetic field controllers.
Materials having a magnetic capacitance effect can be classified into two types, a single-phase material and a composite material. Of these, single phase materials were the first to be discovered, but to date, the vast majority of single phase materials (e.g., BiMnO)3Etc.) can be more obvious only under the condition of being far lower than room temperature (about 100K), and the requirements of practical application can not be met. Thus people turn their eyes to magnetoelectric composite materials.
At present, there are two ways of compounding materials, namely particle compounding and layer compounding. The granular composite magnetic capacitance material is formed by mixing piezoelectric phase grains and magnetostrictive phase grains, and can have a magnetic capacitance effect at room temperature as shown in fig. 1, but the magnetic capacitance effect is generally weaker (less than 4%). The laminated composite material is formed by bonding multiple layers of single-phase materials, namely a piezoelectric phase and a magnetostrictive phase, and can have a larger magnetic capacitance effect as shown in fig. 2, but the magnetic capacitance effect of the laminated composite material is attenuated quickly along with the increase of the frequency of an electric field. Under the condition of high frequency (1MHz and above), the magnetic capacitance effect of the composite material is weak; meanwhile, the laminated composite material has certain limitation on the miniaturization of devices due to the bonding process.
With the development of miniaturization of devices, thin film materials having a large magnetic capacitance effect at room temperature are becoming more and more important. For the composite film material, the magnetic capacitance effect attenuates rapidly with the increase of the electric field frequency, and is difficult to be applied to the high-frequency condition. Therefore, the development of single-phase epitaxial thin film materials with the characteristics of large magnetic capacitance effect at room temperature and wide frequency is very important for the development of micro magnetic capacitance devices.
Most of the single-phase magnetic capacitance thin film materials reported at present have weak room temperature magnetic capacitance effect. The reported single-phase thin film material with large magnetic capacitance effect at room temperature mainly comprises BiFeO3、SnO2And Cr2O3Etc., but the large magnetic capacitance effects of these thin film materials can only occur in the low frequency range. Therefore, at present, few single-phase thin film materials having the characteristics of room temperature large magnetic capacitance effect and wide frequency band are available, and no single-phase epitaxial thin film material having the characteristics is reported.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a method for preparing a ferrite epitaxial film having a wide-band and large-magnetic capacitance effect at room temperature.
The method for preparing the ferrite epitaxial film with the room-temperature wide-frequency large-magnetic capacitance effect comprises the following steps of:
(1) preparation by AFe12-xMxO19Showing composition ofFerrite, wherein A is at least one of Ba element or Sr element, M is at least one of Sc element, Mg element or Cr element, x is the content of M: x is more than 0 and less than or equal to 4;
(2) bombarding ferrite by using pulse laser under a vacuum background, depositing the bombarded ferrite material on a substrate, and growing a ferrite epitaxial film on the substrate, wherein the substrate is a single crystal Si substrate, a Si/Pt substrate or a single crystal Al substrate2O3Substrate and single crystal SrTiO3One of the substrates;
(3) cooling the ferrite epitaxial film after the ferrite epitaxial film grows;
(4) and carrying out post annealing treatment on the ferrite epitaxial film.
Further, the preparation steps of the ferrite are as follows:
(11) with high purity BaCO3、SrCO3、Fe2O3，Sc2O3MgO and/or Cr2O3The powder medicine is taken as a raw material and is proportioned according to the atomic molar ratio in the molecular formula of the ferrite;
(12) mixing the raw materials, and adding absolute alcohol for ball milling;
(13) taking out after ball milling, drying, grinding, and presintering in air or flowing oxygen atmosphere;
(14) taking out the pre-sintered sample, grinding the sample into powder, then dripping PET bonding glue into the powder, and grinding the powder again until the sample has no caking phenomenon and has no obvious bonding with the mortar wall;
(15) pouring the powder into a mould, and carrying out pressurization treatment;
(16) taking out the molded sample after decompression, observing whether the sample has cracks, grinding the sample into powder again if the cracks exist, and pressing the powder again until no cracks exist;
(17) sintering in flowing oxygen atmosphere to obtain the ferrite;
(18) and grinding the sintered and molded sample to be smooth, wiping the sample with alcohol, and storing the sample as a target for preparing a film.
Further, the raw materials in the step (12) are mixed and then placed in a ball milling tank, ball milling beads are placed in the ball milling tank, absolute alcohol is added to the position of two thirds of the height of the ball milling tank, the ball milling tank is placed in a ball mill for ball milling, the rotating speed of the ball mill is 200R/min to 300R/min, and the ball milling time is 10 to 20 hours.
Further, the pre-sintering treatment in the step (13) is carried out according to a temperature gradient, wherein the temperature rise rate is 2 ℃/min, the pre-sintering temperature is 800 ℃ to 1000 ℃, the pre-sintering time is 10 hours to 16 hours, and the temperature reduction rate is 1 ℃/min to 3 ℃/min.
Further, the step (13) is carried out at 70 ℃ to 100 ℃ for drying for 30 minutes to 50 minutes.
Further, the sintering temperature of the sintering treatment in the step (17) is 1050 ℃ to 1300 ℃, the sintering time is 10 hours to 16 hours, the cooling rate is 1 ℃/min to 3 ℃/min, and the temperature is changed in different temperature intervals.
Further, in the step (15), a hydraulic jack is used for pressurizing, the pressure is 5MPa to 10MPa, and the pressure is kept for 8min to 10 min.
Further, in the step (2), the temperature of the substrate is 600 ℃ to 950 ℃ during the growth of the ferrite epitaxial film, and the rotation rate of the substrate is 3R/min to 5R/min; the distance between the substrate and the ferrite is 10cm to 20 cm; the rotation rate of the ferrite is 3R/min to 5R/min; the power of the pulse laser is 1mJ/cm2To 20mJ/cm2The frequency is 2Hz to 10 Hz; the atmosphere of the growing of the ferrite epitaxial film is flowing oxygen, the oxygen pressure is 3Pa to 30Pa, and the flowing speed is 10sccm to 30 sccm.
Further, the cooling rate of the step (3) is 10 ℃/min to 30 ℃/min, the cooling atmosphere is oxygen, and the oxygen pressure is 1kPa to 1 MPa.
Further, the post-annealing temperature in the step (4) is 900 ℃ to 1200 ℃, the temperature rising rate is 3 ℃/min to 5 ℃/min, and the temperature reduction rate is 1 ℃/min to 3 ℃/min; the post-annealing atmosphere is flowing oxygen, the oxygen pressure is 3Pa to 30Pa, and the flow rate is 10sccm to 30 sccm.
By the scheme, the invention at least has the following advantages:
1. molecular formula of AFe12-xMxO19The ferrite epitaxial film has a remarkable magnetic capacitance effect within 1kHz to 2MHz, the magnetic capacitance effect still presents a certain increasing trend within 2MHz, and the magnetic capacitance effect also presents a remarkable magnetic capacitance effect within a frequency range higher than 2MHz, so that the ferrite epitaxial film prepared by the invention has a room-temperature broadband magnetic capacitance effect, and simultaneously has a remarkable magnetic capacitance effect within a partial frequency range (100kHz to 1MHz), thereby overcoming the defects of weak room-temperature magnetic capacitance effect and narrow frequency range of the existing single-phase magnetic capacitance film material;
2. the magnetic capacitance effect of the ferrite epitaxial film sample prepared by the invention is increased along with the increase of the magnetic field at 1MHz, the capacitance change is up to 10% at the maximum magnetic field of 5T, and meanwhile, the magnetic capacitance is approximately linearly increased along with the magnetic field at the low magnetic field part (H < 2.5T);
3. the preparation method is simple and easy to operate.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a schematic representation of a prior art particulate composite material;
FIG. 2 is a schematic representation of a prior art layered composite;
FIG. 3 is a room temperature X-ray diffraction pattern of an epitaxial film sample prepared in accordance with the present invention;
FIG. 4 is a resistivity test pattern at different temperatures for epitaxial thin film samples prepared according to the present invention;
FIG. 5 is a spectrum of magnetic capacitance (C%) measurements of epitaxial film samples prepared in accordance with the present invention at a temperature of 300K, a magnetic field magnitude of 2.5T, and a scanning frequency range of 1kHz to 2 MHz;
FIG. 6 is a graph of the variation of magnetic capacitance (C%) with magnetic field and temperature for the epitaxial film samples prepared according to the present invention, wherein the temperature is 300K, the test frequency is 1MHz, and the magnetic field variation range is-5T to 5T.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The ferrite epitaxial thin film material has the following molecular formula: AFe12-xMxO19Wherein A is at least one of Ba element or Sr element, M is at least one of Sc element, Mg element or Cr element, and x is the content of M: x is more than 0 and less than or equal to 4.
The specific preparation method of the ferrite epitaxial film comprises the following steps:
(1) preparation by AFe12-xMxO19A ferrite having a composition represented by formula (I), wherein A is at least one of Ba or Sr, M is at least one of Sc, Mg or Cr, and x is the content of M: x is more than 0 and less than or equal to 4;
(2) preparing ferrite epitaxial film by pulse Laser Deposition (Pulsed Laser Deposition) with background vacuum degree of 2 × 10-4Pa；
(3) The substrate for film growth is single crystal Si substrate, Si/Pt substrate, single crystal Al2O3Substrate and single crystal SrTiO3One of the substrates, the temperature of the substrate during the film growth is 600 ℃ to 950 ℃, the rotation rate of the substrate is 3R/min to 5R/min, and the distance between the substrate and the ferrite is 10cm to 20 cm;
(4) the rotation rate of the ferrite is 3R/min to 5R/min during the growth of the film, and the power of the pulse laser is 1mJ/cm2To 20mJ/cm2The frequency is 2Hz to 10 Hz;
(5) the atmosphere of the film during growth is flowing oxygen, the oxygen pressure is 3Pa to 30Pa, and the flow rate is 10sccm to 30 sccm;
(6) the cooling rate is 10 ℃/min to 30 ℃/min after the film grows, the cooling atmosphere is oxygen, and the oxygen pressure is 1kPa to 1 MPa;
(7) the post-annealing temperature of the film was: 900 to 1200 ℃, the temperature rising rate is 3 to 5 ℃/min, the temperature reduction rate is 1 to 3 ℃/min, the back annealing atmosphere is flowing oxygen, the oxygen pressure is 3 to 30Pa, and the flowing rate is 10 to 30 sccm.
The specific preparation method of the ferrite in the step (1) is as follows:
(11) the invention uses high-purity BaCO3、SrCO3、Fe2O3，Sc2O3MgO and/or Cr2O3The powder medicine is taken as a raw material (the purity of the raw material is 99.99 percent) and is prepared according to the atomic mol ratio in the molecular formula; for example, when x is 1.6, the molar ratio of each component is BaCO3：SrCO3：Fe2O3：Sc2O3：MgO：Cr2O3＝80：20：520：78：3：1；
(12) Manually mixing the weighed medicines, placing the mixture into a ball milling tank, placing ball milling beads, adding absolute alcohol to the position with two thirds height of the ball milling tank, placing the ball milling tank into a ball mill for ball milling, wherein the rotating speed of the ball mill is 200R/min to 300R/min, and the ball milling time is 10 to 20 hours;
(13) after the ball milling is finished, taking out the medicine in the ball milling tank, placing the medicine in the mortar, and placing the medicine in a dryer for drying, wherein the temperature of the dryer is set to be 70-100 ℃, and the drying time is 30-50 minutes;
(14) grinding the dried medicine, placing the ground medicine into a crucible, placing the crucible into a tubular furnace to perform presintering treatment in the air or flowing oxygen atmosphere, and heating according to a certain temperature gradient, wherein the heating rate is 2 ℃/min, the presintering temperature is 800 ℃ to 1000 ℃, the presintering time is 10 hours to 16 hours, and the cooling rate is 1 ℃/min to 3 ℃/min;
(15) after the pre-sintering is finished, taking out the sample, and manually grinding the sample in a cleaned mortar for at least 20 to 40 minutes;
(16) 3 to 5 drops of PET bonding glue are dripped into the ground pre-sintered medicine powder, and the pre-sintered medicine powder is ground again until no caking phenomenon is seen and no obvious bonding is formed between the pre-sintered medicine powder and the mortar wall;
(17) pouring the powder into a mould, pressurizing by using a hydraulic jack, selecting proper pressure according to the size of a sample and the difference of the mould, and keeping the pressure for about 10 min;
(18) taking out the molded sample after decompression, observing whether the sample has cracks or not, and if the samples have cracks, grinding the samples into powder again and pressing the powder again until the cracks do not exist;
(19) placing the formed sample into a clean crucible, placing the crucible into a tubular furnace to carry out sintering treatment in a flowing oxygen atmosphere, raising the temperature according to a certain temperature gradient, wherein the temperature raising rate is 2 ℃/min, the sintering temperature is 1050-1300 ℃, the sintering time is 10-16 hours, the temperature lowering rate is 1-3 ℃/min, and the temperature is changed in different temperature intervals;
(20) and taking out the molded sample after sintering, carefully grinding the edge and the surface of the target by using sand paper, polishing the surface to be as smooth as possible, wiping the surface with alcohol after polishing, and storing the polished surface to be used as the target for preparing the film.
The material microstructure, room temperature resistance and room temperature magnetic capacitance effect of the prepared ferrite epitaxial film sample (epitaxial film with the length of 5mm, the width of 5mm and the thickness of 150 nm) are tested.
1. The result of the characterization test (X-ray diffraction, abbreviated as XRD) of the material microstructure shows that the X-ray diffraction (XRD) peak and the P-containing phase of the ferrite epitaxial thin film sample prepared by the invention can be seen from figure 363The hexaferrites are uniform in/mmc crystal symmetry and all film peaks are (00l), the surface film is an epitaxial film with C-axis out-of-plane orientation.
2. Results of resistance measurement, it can be seen from FIG. 4 that the resistivity of the ferrite epitaxial thin film sample prepared by the present invention is about 1.7X 10 at about 300K at room temperature8Ω · cm, has a higher resistivity, while the resistivity of the film sample decreases slightly with increasing temperature.
3. Magnetic capacitance test results, it can be seen from fig. 5 that the ferrite epitaxial thin film samples prepared by the present invention exhibited significant magnetic capacitance effects over the entire test frequency range (1kHz to 2 MHz). The data results show that the magnetic capacitance effect of the sample still shows a certain increasing trend at 2MHz, and thus will show a significant magnetic capacitance effect also in the frequency range higher than 2 MHz. Therefore, the ferrite epitaxial thin film has a wide-band magnetic capacitance effect at room temperature, while the magnetic capacitance effect is particularly significant in a partial frequency range (100kHz to 1 MHz). As can be seen from FIG. 6, the magnetic capacitance effect of the ferrite epitaxial thin film sample prepared by the invention increases with the increase of the magnetic field at 1MHz, and the capacitance change is as high as 10% at the maximum magnetic field of 5T; meanwhile, the magnetic capacitance increases approximately linearly with the magnetic field in the low magnetic field part (H < 2.5T).
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A method for preparing a ferrite epitaxial film with a room-temperature broadband large-magnetic capacitance effect is characterized by comprising the following steps of:
(1) preparation by AFe12-xMxO19A ferrite having a composition represented by formula (I), wherein A is at least one of Ba or Sr, M is at least one of Sc, Mg or Cr, and x is the content of M: x is more than 0 and less than or equal to 4;
(2) bombarding ferrite by using pulse laser under a vacuum background, depositing the bombarded ferrite material on a substrate, and growing a ferrite epitaxial film on the substrate, wherein the substrate is a single crystal Si substrate, a Si/Pt substrate or a single crystal Al substrate2O3Substrate and single crystal SrTiO3One of the substrates; the temperature of the substrate is 600 ℃ to 950 ℃ when the ferrite epitaxial film grows, and the rotation rate of the substrate is 3R/min to 5R/min; the distance between the substrate and the ferrite is 10cm to 20 cm; the rotation rate of the ferrite is 3R/min to 5R/min; the power of the pulse laser is 1mJ/cm2To 20mJ/cm2The frequency is 2Hz to 10 Hz; the atmosphere of the growing ferrite epitaxial film is flowing oxygen, the oxygen pressure is 3Pa to 30Pa, and the flowing speed is 10sccm to 30 sccm;
(3) cooling the ferrite epitaxial film after the ferrite epitaxial film grows; the cooling rate is 10 ℃/min to 30 ℃/min, the cooling atmosphere is oxygen, and the oxygen pressure is 1kPa to 1 MPa;
(4) carrying out post annealing treatment on the ferrite epitaxial film; the annealing temperature is 900 ℃ to 1200 ℃, the heating rate is 3 ℃/min to 5 ℃/min, and the cooling rate is 1 ℃/min to 3 ℃/min; the post-annealing atmosphere is flowing oxygen, the oxygen pressure is 3Pa to 30Pa, and the flow rate is 10sccm to 30 sccm;
the preparation steps of the ferrite are as follows:
(11) with a purity of 99.99% BaCO3、SrCO3、Fe2O3，Sc2O3MgO and/or Cr2O3The powder medicine is taken as a raw material and is proportioned according to the atomic molar ratio in the molecular formula of the ferrite;
(12) mixing the raw materials, and adding absolute alcohol for ball milling;
(13) taking out after ball milling, drying, grinding, and presintering in air or flowing oxygen atmosphere; the pre-sintering treatment is carried out according to the temperature gradient, the temperature rising rate is 2 ℃/min, the pre-sintering temperature is 800 ℃ to 1000 ℃, the pre-sintering time is 10 hours to 16 hours, and the temperature reduction rate is 1 ℃/min to 3 ℃/min;
(14) taking out the pre-sintered sample, grinding the sample into powder, then dripping PET bonding glue into the powder, and grinding the powder again until the sample has no caking phenomenon and has no obvious bonding with the mortar wall;
(15) pouring the powder into a mould, and carrying out pressurization treatment;
(16) taking out the molded sample after decompression, observing whether the sample has cracks, grinding the sample into powder again if the cracks exist, and pressing the powder again until no cracks exist;
(17) sintering in flowing oxygen atmosphere to obtain the ferrite;
(18) and grinding the sintered and molded sample to be smooth, wiping the sample with alcohol, and storing the sample as a target for preparing a film.
2. The method of claim 1, wherein: and (3) mixing the raw materials in the step (12), placing the mixture into a ball milling tank, placing ball milling beads, adding absolute alcohol to the position of two thirds of the height of the ball milling tank, placing the ball milling tank into a ball mill for ball milling, wherein the rotating speed of the ball mill is 200-300R/min, and the ball milling time is 10-20 hours.
3. The method of claim 1, wherein: and (3) drying at 70-100 ℃ for 30-50 minutes.
4. The method of claim 1, wherein: the sintering temperature of the sintering treatment in the step (17) is 1050-1300 ℃, the sintering time is 10-16 hours, the cooling rate is 1-3 ℃/min, and the temperature is changed in different temperature intervals.
5. The method of claim 1, wherein: and (5) pressurizing by using a hydraulic jack in the step (15), wherein the pressure is 5MPa to 10MPa, and keeping for 8min to 10 min.
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