CN109234678B - Copper-doped barium titanate/nickel zinc ferrite multiphase film material and preparation method thereof - Google Patents

Copper-doped barium titanate/nickel zinc ferrite multiphase film material and preparation method thereof Download PDF

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CN109234678B
CN109234678B CN201810866019.2A CN201810866019A CN109234678B CN 109234678 B CN109234678 B CN 109234678B CN 201810866019 A CN201810866019 A CN 201810866019A CN 109234678 B CN109234678 B CN 109234678B
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zinc ferrite
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杜丕一
月扬宇
顾健
王宗荣
马宁
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Zhejiang University ZJU
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Abstract

The invention discloses a copper-doped barium titanate/nickel zinc ferrite complex phase film material and a preparation method thereof. The film copper-doped nickel-zinc ferrite phase and the barium titanate phase are uniformly and densely distributed, wherein the nickel-zinc ferrite phase grows along the (111) crystal face orientation. The film is prepared by a radio frequency magnetron sputtering method, synchronously introducing copper doped ions through a copper cover with a window additionally arranged outside a sputtering source target material to obtain an amorphous deposition film, and then performing heat treatment in an air atmosphere. Compared with the undoped barium titanate/nickel zinc ferrite complex phase film, the preparation method can obtain the ferroelectric and ferromagnetic two-phase composite film with the ferromagnetic phase having the (111) oriented growth characteristic in the complex phase system. The ferroelectric and ferromagnetic two-phase composite film with the ferromagnetic phase (111) oriented growth is beneficial to realizing high-performance magnetic and electric coupling, and has simpler preparation process and low cost.

Description

Copper-doped barium titanate/nickel zinc ferrite multiphase film material and preparation method thereof
Technical Field
The invention belongs to the technical field of multi-iron complex phase film materials, and particularly relates to a copper-doped barium titanate/nickel zinc ferrite complex phase film material and a preparation method thereof, wherein the material is a copper-doped barium titanate/nickel zinc ferrite complex phase film which grows in a (111) orientation mode and is prepared from a nickel zinc ferrite phase by a magnetron sputtering method.
Background
The development trend of electronic devices in the digital network era is small, light, thin and high performance, and the rapid development of these high-technology electronic devices also puts higher demands on new materials. With the rapid development of electronic information industries represented by large-scale integrated circuits, thin film materials increasingly show important and critical roles.
Barium titanate (BaTiO) of perovskite structure3BTO for short) has a number of important properties as the most important class of ferroelectric materials in modern industry: dielectric property, piezoelectric property, pyroelectric property, etc., and can realize electric energyAnd the electric energy, the mechanical energy, the electric energy, the heat energy and the electric energy are mutually converted. Spinel-structured nickel-zinc ferrite (Ni)0.5Zn0.5Fe2O4NZFO for short) is a traditional ferrimagnetic material, has the characteristics of large magnetostriction coefficient, high resistivity, low eddy current loss at high frequency and the like, and is widely applied to devices such as magnetic sensors, magnetic storage devices, high-frequency devices, transformers and the like at present.
For example, barium titanate, nickel zinc ferrite BTO and NZFO are compounded together, if the two materials respectively have the electrical and magnetostrictive properties, the electromagnetic coupling is expected to be realized through the magnetic and electrical composite material, and a magnetoelectric coupling effect is generated, and the magnetoelectric coupling effect can provide a new direction for the design of a novel electromagnetic device, for example, the material polarization can be controlled by applying an external magnetic field to the composite magnetic/electrical film, or the material magnetic polarization can be controlled by applying an external electric field to the composite magnetic/electrical film. Therefore, the composite magnetic/electric thin film is expected to be applied to aspects of multi-state memories, electromagnetic sensors and the like on a large scale.
In fact, in the composite magnetic/electric film, to realize efficient magnetoelectric coupling, such as applying an external electric field to realize control over the magnetic polarization of a material, the key is to solve the problem that a ferromagnetic phase can be acted by force fields with different magnitudes from a ferroelectric phase in different directions, so that the ferromagnetic phase is subjected to non-uniform stress, and thus effective change of magnetic dipole moment is realized through lattice distortion so that the magnetic performance of the ferromagnetic phase is obviously changed. Therefore, the existing research on the complex phase thin film is generally prepared into a 1-3 structure or a 2-2 structure to ensure that the ferromagnetic phase is acted by the force field from the ferroelectric phase and generate an anisotropic action effect so as to realize effective magnetoelectric coupling. However, the conventional 1-3 or 2-2 structure complex phase thin film has a very complicated preparation process and structure, which is not favorable for the practical application of the complex phase thin film.
According to the prior art, one of the most mature preparation processes of the complex phase film at present and the processes capable of well butting with the existing semiconductor process is the magnetron sputtering preparation method. The ferroelectric phase and ferromagnetic phase complex phase film can be prepared and obtained by the method through the simplest and most convenient and direct process. As most of the film is a two-phase uniformly distributed structure, namely a 0-0 structure complex phase film. Therefore, if the problem of electric and magnetic coupling between two phases with uniform distribution can be solved, the method obviously has important theoretical significance and practical value for the application of the film. Therefore, dumpdet et al designed a BTO/NZFO complex phase thin film (ZL201510500941.6) with (100) orientation on a (111) orientation single crystal silicon substrate, which is most commonly used in semiconductor processing, using magnetron sputtering. The film is expected to grow through the (100) orientation of the ferromagnetic phase, so that the ferromagnetic phase is subjected to an acting force field only in the direction vertical to the (100) crystal plane, namely, the anisotropic force field, and an effective magnetoelectric coupling effect is obtained. The (100) orientation of the ferromagnetic phase in such a film is actually achieved by lattice-induced growth of the crystalline phase of NZFO by the monocrystalline silicon substrate, through good similarity between the lattice structures on the Si (111) and NZFO (800) crystal planes.
However, according to the analysis of the NZFO structure and the easy magnetization direction, the change of the magnetic dipole generated before and after the (100) oriented NZFO crystal phase is affected by the ferroelectric phase under the above-mentioned anisotropic force field is not the maximum, i.e. the coupling efficiency obtained here is not the best. According to the analysis of the magnetic physical principle, when the NZFO crystal phase is in (111) orientation, the coupling effect generated by the NZFO crystal phase in the same situation is better. It can be seen that if (111) oriented growth of NZFO can be realized in such a complex-phase thin film, it will have more important practical significance for the application of such a complex-phase magnetoelectric thin film in the aspect of magnetoelectric coupling performance.
However, since the matching situation between the (800) crystal plane structure and the Si (111) crystal plane structure in the (111) crystal plane direction of the NZFO crystal phase (100) crystal plane direction does not appear obviously, how to solve the problem of growing the (111) oriented NZFO crystal phase on the Si single crystal substrate will become the key to obtain such ferroelectric and ferromagnetic complex phase thin films with efficient coupling characteristics.
Therefore, to deposit a relevant thin film with specific structural properties, it is critical to solve the problem of matching the NZFO lattice with the Si lattice. The crystal structures of NZFO and single crystal Si are analyzed in detail,the (111) crystal face structure of Si and the (222) crystal face structure of NZFO are distributed in a hexagonal close-packed lattice; further, Si is known to have a lattice parameter of
Figure BDA0001750956240000021
And NZFO has a lattice parameter of
Figure BDA0001750956240000022
Much larger than the Si substrate. However, considering the lattice distance between the atoms of the Si (111) plane and the NZFO (222) plane, the distance between the atoms is twice as large as that of the NZFO (222) plane
Figure BDA0001750956240000023
Three times as long as the interatomic distance on the Si (111) crystal plane
Figure BDA0001750956240000024
It can be seen that the atomic arrangement distribution, regularity and interatomic distance on this crystal plane are substantially the same, but the parameter of NZFO (222) is slightly larger than that of Si (111), but the difference is only 2.9%, that is, it is possible to achieve induction matching of these two structures in this crystal plane direction by analyzing the structural parameters, and it is expected that (111) oriented growth of the NZFO crystal phase can be achieved by Si (111) substrate induction. However, if the aim of inducing the NZFO to grow in an orientation manner along the (111) crystal face direction on the Si (111) substrate by inducing the larger lattice parameter on the crystal face of the NZFO crystal phase (222) through the smaller lattice parameter on the crystal face of the Si substrate (111) is achieved, the capability of enabling the NZFO crystal lattice to have proper distortion and be well matched with the crystal lattice of the Si substrate needs to be solved, and the BTO/NZFO complex phase film with NZFO growing in the (111) orientation manner is formed. Based on research and analysis of existing NZFO materials, it is known that Cu ion doping may be an ion that facilitates the growth of NZFO on Si (111) substrates in the (111) crystal plane orientation (j. mater. res.,1994,9: 2425-. Considering that the distortion characteristic of the NZFO is adjusted by controlling the B lattice point of the doped Cu entering the NZFO crystal phase, the distortion capability of the NZFO is promoted to be improved when the lattice parameter in the (111) crystal plane direction is expanded and the lattice parameter in the (111) crystal plane direction is contracted, the good matching between the (222) crystal plane parameter forming the NZFO and the Si (111) crystal plane parameter is strived for, namely, the Si (1) crystal plane parameter is realized11) The crystal planes produce induced oriented growth in the (111) crystal plane direction for NZFO.
Therefore, the scheme provides a radio frequency magnetron sputtering method, a metal Cu cover with a window is added to the outer side of a multiphase ceramic (BTO/NZFO) sputtering target material to serve as a Cu metal source, a single radio frequency sputtering technology is directly utilized to introduce copper ions while a ceramic film is sputtered by utilizing a radio frequency technology while the BTO/NZFO is sputtered, the sputtering degree of the multiphase ceramic (BTO/NZFO) target material and the introduction degree of the Cu ions are controlled by controlling the size of the window of the copper cover, and the NZFO crystal phase is deposited on a (111) oriented monocrystalline silicon substrate to obtain the BTO/NZFO multiphase film with the (111) orientation through induced orientation growth, wherein the sputtering schematic diagram is shown in figure 1.
Further, considering the control characteristics of the magnetron sputtering deposition process on the formation, orientation and the like of the film, another key problem for depositing and forming the BTO/NZFO complex-phase film with NZFO being (111) orientation growth is how to avoid the direct control effect of the glow deposition process on the formation, orientation and the like of the crystal phase and the interference effect of the second phase structure on the formation of the crystal phase orientation. The design of the scheme is that firstly the sputtering deposition is controlled at room temperature, firstly an amorphous phase basement membrane is obtained, thereby eliminating the direct control and influence effect of high energy on the orientation of the film crystalline phase during the deposition, and achieving the purpose of freely forming the related crystalline phase during the temperature rise. The method comprises the following steps of regulating and controlling the crystalline phase formation activation energy of a system through a specific heat treatment process, controlling to fully form an NZFO crystalline phase at a lower temperature by utilizing the temperature difference of different crystalline phases generated by the lower temperature of the NZFO crystalline phase and the higher temperature of the BTO crystalline phase, and forming the NZFO crystalline phase in an amorphous phase system by utilizing the characteristic that the BTO cannot form a second phase crystal at the lower temperature, so that the influence on the formation and the oriented growth of the NZFO crystalline phase due to the existence of the second phase crystal lattice is completely avoided; secondly, the influence of the surface energy on the oriented growth of the film is considered at the same time, and particularly, if the crystal plane with the lowest surface energy is in the surface direction in the film in an amorphous base phase, namely in an environment in which the crystal phase can grow freely, the crystal plane with the lowest surface energy is the (111) plane in the NZFO crystal phase, so that the NZFO crystal phase is expected to realize the (111) oriented growth in such a system.
In addition, the Cu doping can affect the magnetism of the nickel-zinc ferrite (J.Magn.,2013,18:391-394, Fuel,2017,191:463-471, J.Magn.Magn.Mater.,2016,401:918-924), so that the barium titanate/nickel-zinc ferrite complex phase film with excellent NZFO phase (111) oriented growth and magnetic performance can be successfully prepared only by controlling the doping amount of Cu and adjusting the nickel-zinc ferrite to obtain excellent magnetic performance on the premise of achieving good (111) matching characteristic, and the problem of preparing the complex phase film with high magnetic and electric coupling characteristics by using the traditional magnetron sputtering method is expected to be finally solved.
Disclosure of Invention
The invention aims to solve the problem that the ferromagnetic and ferroelectric phases in a composite magnetic and electric thin film prepared by the simplest magnetron sputtering method are mostly polycrystalline bodies which are uniformly and densely distributed, and the ferromagnetic phase in the composite magnetic and electric thin film needs to be formed in a (111) orientation manner in order to effectively and more efficiently generate a magnetic electric coupling effect in the system, and provides a ferroelectric/ferromagnetic (barium titanate/nickel zinc ferrite) complex phase thin film which is doped with a ferromagnetic phase and grows in the (111) orientation manner and a preparation method thereof. The nickel-zinc ferrite crystal phase (111) in the film grows in an oriented mode, and the film is prepared by depositing at room temperature through a radio frequency magnetron sputtering method and performing post-heat treatment. The preparation process of the magnetic and electric coupling complex phase film material is matched with the traditional semiconductor process, and the preparation is relatively simple and the cost is low.
The copper-doped barium titanate/nickel zinc ferrite thin film material is formed by compounding barium titanate and Cu-doped nickel zinc ferrite and can be expressed as Cu-doped xBaTiO3-(1-x)Ni0.5Zn0.5Fe2O4Wherein x is 0.2-0.8, and Cu is doped into the nickel-zinc ferrite to replace Ni, and the proportion of Cu in the lattice position of Ni is 20-30%; the film is grown on a Si (111) substrate, and the nickel zinc ferrite crystal phase grows along the (111) plane orientation.
The two-phase crystal grains are uniformly and compactly distributed, and the size of the crystal grains is 30-70 nm.
The method for preparing the copper-doped barium titanate/nickel zinc ferrite complex phase thin film material adopts a radio frequency magnetron sputtering method, takes xBTO- (1-x) NZFO and x as 0.2-0.8 as a target material, and adds a copper outer cover with a window at the lower end outside the target material, wherein the diameter of the target material is 56mm, the diameter of the window of the copper outer cover is 45mm, and the distance between the lower end of the copper outer cover and the target material is 16mm, and the copper-doped barium titanate/nickel zinc ferrite complex phase thin film is prepared on a (111) Si substrate by deposition.
The method specifically comprises the following steps:
a. preliminarily cleaning a single crystal Si (111) substrate in deionized water, soaking in hydrofluoric acid for 10-30 min, then putting in acetone for ultrasonic treatment for 10-15 min, then performing ultrasonic treatment in absolute ethyl alcohol for 10-15 min, and finally drying by using nitrogen to obtain the single crystal Si (111) substrate for sputtering;
b. the specific technological parameters of sputtering are as follows: b, using an xBTO- (1-x) NZFO target material, and performing sputtering on the single crystal Si (111) substrate treated in the step a, wherein the total sputtering pressure is 0.6Pa, the flow rates of argon and oxygen are respectively 15sccm and 10sccm, the sputtering power is 180W, the substrate temperature is room temperature, and the sputtering time is 100-260min, so as to obtain an amorphous xBTO- (1-x) NZFO film layer containing Cu on the single crystal Si (111) substrate, wherein the Cu doping amount is 0.2-0.3 of the Cu/(Cu + Ni) molar ratio;
c. c, carrying out heat treatment on the amorphous film containing Cu deposited on the single crystal Si (111) substrate and obtained in the step b in a muffle furnace under the air atmosphere, heating the amorphous film to 600-700 ℃ from room temperature at the speed of 5 ℃/min, and preserving the heat for 2 hours; and then heating to 900-960 ℃ at the speed of 10-15 ℃/min, preserving the heat for 2h, then cooling to room temperature along with the furnace, and obtaining the copper-doped barium titanate/nickel zinc ferrite multiphase film material on the single crystal Si (111) substrate, wherein the nickel zinc ferrite crystal phase grows along the (111) plane in an oriented manner. In the heat treatment process, a barium titanate/nickel zinc ferrite complex phase film with a ferromagnetic phase NZFO as (111) oriented growth is finally obtained by inducing the formation of the NZFO in an amorphous matrix phase by a Si (111) substrate at 600-700 ℃, particularly by combining the matched modulation of the NZFO lattice parameter introduced by Cu doping, wherein 20-30% of the Ni position is replaced by copper ions.
Compared with the prior art, the invention has the beneficial effects that:
a. the complex phase film successfully realizes the oriented growth of the nickel-zinc ferrite crystal phase along the (111) plane in a ferroelectric and ferromagnetic complex phase system by doping a certain amount of Cu element.
b. The film provides the possibility of utilizing a ferroelectric/ferromagnetic complex phase system to realize high-efficiency magnetoelectric coupling and performance regulation.
c. The preparation process of the ferroelectric/ferromagnetic complex phase film is relatively simple, sputtering deposition is carried out on a single crystal Si (111) substrate at room temperature, and then a proper post-heat treatment process is assisted, so that the ferroelectric/ferromagnetic complex phase film has no harsh experimental environment requirements and low cost.
Drawings
FIG. 1 is a schematic diagram of a sputtering source (target and copper shield) for Cu-doped xBTO- (1-x) NZFO thin films;
FIG. 2 is an XRD spectrum of a Cu doped 0.5BTO-0.5NZFO film prepared in example 1;
FIG. 3, XRD spectrum of Cu doped 0.2BTO-0.8NZFO film prepared in example 2;
FIG. 4, XRD spectrum of Cu doped 0.4BTO-0.6NZFO film prepared in example 3;
FIG. 5, XRD spectrum of Cu doped 0.6BTO-0.4NZFO film prepared in example 4;
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of protection of the present invention.
The copper-doped barium titanate/nickel zinc ferrite thin film material can be expressed as Cu-doped xBTO- (1-x) NZFO (x is 0.2-0.8), wherein a nickel zinc ferrite crystal phase grows along a (111) plane in an oriented mode. As shown in fig. 1 (unit is mm in the figure), the film is prepared by a radio frequency magnetron sputtering method, xBTO- (1-x) NZFO, x is 0.2-0.8 as a target material, a copper outer cover with a window at the lower end is additionally arranged on the outer side of the target material, the diameter of the target material is 56mm, the diameter of the window of the copper outer cover is 45mm, the distance between the lower end of the copper outer cover and the target material is 16mm, and the film is prepared by firstly cleaning a single crystal Si (111) substrate by deionized water, hydrofluoric acid, deionized water, acetone and absolute ethyl alcohol in sequence. Then bombarding the xBTO- (1-x) NZFO target and the Cu cover simultaneously by using a radio frequency magnetron sputtering method, and depositing an amorphous film on the single crystal Si (111) substrate. The technological parameters are as follows: the sputtering target is xBTO- (1-x) NZFO (x is 0.2-0.8), the total sputtering pressure is 0.6Pa, the flow rates of argon and oxygen are respectively 15sccm and 10sccm, the sputtering power is 180W, the substrate temperature is room temperature, and the sputtering time is 100-260 min. Then carrying out heat treatment on the amorphous film in an air atmosphere, heating the amorphous film from room temperature to 600-700 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 h; then heating to 900-. According to the method, a Si (111) substrate induces NZFO in an amorphous base phase at 600-700 ℃, and particularly, the matching modulation of NZFO lattice parameters introduced by Cu doping is combined, so that the barium titanate/nickel zinc ferrite complex phase film with a ferromagnetic phase NZFO oriented to (111) growth is finally obtained, wherein 20-30% of Ni positions are replaced by copper ions.
And (3) carrying out phase structure and morphology test on the prepared film by using XRD, TEM and SEM to determine the structural formation of the (111) oriented NZFO phase. The amount of Cu in the film is 0.2 to 0.3 in terms of Cu/(Cu + Ni) atomic ratio as measured by ICP.
The invention is further illustrated by the following specific examples:
example 1:
a. preliminarily cleaning the single crystal Si (111) substrate with deionized water, soaking in hydrofluoric acid for 10min, adding acetone, performing ultrasonic treatment for 10min, adding absolute ethyl alcohol, performing ultrasonic treatment for 10min, and finally drying with nitrogen to obtain the single crystal Si (111) substrate for sputtering.
b. The 0.5BTO-0.5NZFO target material and the Cu cover with the molar ratio of 5:5 are arranged on a target position of a radio frequency magnetron sputtering instrument, and a single crystal Si (111) substrate is arranged on a sputtering platform, and the sputtering platform rotates at a low speed. Vacuumizing the sputtering cavity, then introducing argon and oxygen, wherein the flow rates of the argon and the oxygen are respectively 15sccm and 10sccm, and controlling the total pressure of the mixed gas to be 0.6 Pa. And starting a radio frequency power source, adjusting the power to 180W, and performing sputtering deposition at room temperature for 220min to obtain a uniform and compact amorphous film.
c. Putting the uniform compact amorphous film deposited on the single crystal Si (111) substrate into a muffle furnace, heating from room temperature to 650 ℃ at the speed of 5 ℃/min in the air atmosphere, preserving heat for 2h, heating to 920 ℃ at the speed of 10 ℃/min, preserving heat for 2h, and then cooling to room temperature along with the furnace to obtain the Cu-doped 0.5BTO-0.5NZFO film.
FIG. 2 is an XRD spectrum of the Cu doped 0.5BTO-0.5NZFO film obtained in this example. It can be seen that the nickel zinc ferrite crystal phase grows along the (111) plane orientation.
Example 2:
a. preliminarily cleaning the single crystal Si (111) substrate with deionized water, soaking in hydrofluoric acid for 30min, adding acetone, performing ultrasonic treatment for 10min, adding absolute ethyl alcohol, performing ultrasonic treatment for 10min, and finally drying with nitrogen to obtain the single crystal Si (111) substrate for sputtering.
b. The 0.2BTO-0.8NZFO target material and the Cu cover with the molar ratio of 2:8 are arranged on a target position of a radio frequency magnetron sputtering instrument, and a single crystal Si (111) substrate is arranged on a sputtering platform, and the sputtering platform rotates at a low speed. Vacuumizing the sputtering cavity, then introducing argon and oxygen, wherein the flow rates of the argon and the oxygen are respectively 15sccm and 10sccm, and controlling the total pressure of the mixed gas to be 0.6 Pa. And starting a radio frequency power source, adjusting the power to 180W, and performing sputtering deposition at room temperature for 220min to obtain a uniform and compact amorphous film.
c. Putting the uniform compact amorphous film deposited on the single crystal Si (111) substrate into a muffle furnace, heating the uniform compact amorphous film from room temperature to 600 ℃ at the speed of 5 ℃/min, and preserving the heat for 2 h; and then heating to 960 ℃ at the speed of 15 ℃/min, preserving the heat for 2h, and then cooling to room temperature along with the furnace to obtain the Cu-doped 0.2BTO-0.8NZFO film.
FIG. 3 is the XRD spectrum of the Cu doped 0.2BTO-0.8NZFO film obtained in this example. It can be seen that the nickel zinc ferrite crystal phase grows along the (111) plane orientation.
Example 3:
a. preliminarily cleaning the single crystal Si (111) substrate with deionized water, soaking in hydrofluoric acid for 15min, adding acetone, performing ultrasound for 15min, adding absolute ethyl alcohol, performing ultrasound for 15min, and finally drying with nitrogen to obtain the single crystal Si (111) substrate for sputtering.
b. The 0.4BTO-0.6NZFO target material with the molar ratio of 4:6 and the Cu cover are arranged on a target position of a radio frequency magnetron sputtering instrument, and a single crystal Si (111) substrate is placed on a sputtering platform, and the sputtering platform rotates at a low speed. Vacuumizing the sputtering cavity, then introducing argon and oxygen, wherein the flow rates of the argon and the oxygen are respectively 15sccm and 10sccm, and controlling the total pressure of the mixed gas to be 0.6 Pa. And starting a radio frequency power source, adjusting the power to 180W, and performing sputtering deposition at room temperature for 260min to obtain a uniform and compact amorphous film.
c. Putting the uniform compact amorphous film deposited on the single crystal Si (111) substrate into a muffle furnace, heating from room temperature to 650 ℃ at the speed of 5 ℃/min, and preserving heat for 2 h; and then heating to 920 ℃ at the speed of 10 ℃/min, preserving the heat for 2h, and then cooling to room temperature along with the furnace to obtain the Cu-doped 0.4BTO-0.6NZFO film.
FIG. 4 is the XRD spectrum of the Cu doped 0.4BTO-0.6NZFO film obtained in this example. It can be seen that the nickel zinc ferrite crystal phase grows along the (111) plane orientation.
Example 4:
a. primarily cleaning the monocrystalline Si (111) substrate with deionized water, soaking in hydrofluoric acid for 20min, adding acetone, performing ultrasound for 10min, adding absolute ethyl alcohol, performing ultrasound for 15min, and finally drying with nitrogen to obtain the sputtering monocrystalline Si (111) substrate.
b. The 0.6BTO-0.4NZFO target material with the molar ratio of 6:4 and the Cu cover are arranged on a target position of a radio frequency magnetron sputtering instrument, and a single crystal Si (111) substrate is placed on a sputtering platform, and the sputtering platform rotates at a low speed. Vacuumizing the sputtering cavity, then introducing argon and oxygen, wherein the flow rates of the argon and the oxygen are respectively 15sccm and 10sccm, and controlling the total pressure of the mixed gas to be 0.6 Pa. And starting a radio frequency power source, adjusting the power to 180W, and performing sputtering deposition at room temperature for 120min to obtain a uniform and compact amorphous film.
c. Putting the uniform compact amorphous film deposited on the single crystal Si (111) substrate into a muffle furnace, heating the uniform compact amorphous film from room temperature to 600 ℃ at the speed of 5 ℃/min, and preserving the heat for 2 h; and then heating to 960 ℃ at the speed of 15 ℃/min, preserving the heat for 2h, and then cooling to room temperature along with the furnace to obtain the Cu-doped 0.6BTO-0.4NZFO film.
FIG. 5 is an XRD spectrum of the Cu doped 0.6BTO-0.4NZFO thin film obtained in this example. It can be seen that the nickel zinc ferrite crystal phase grows along the (111) plane orientation.

Claims (4)

1. The copper-doped barium titanate/nickel zinc ferrite multiphase film material is characterized in that the film is formed by compounding barium titanate and copper-doped nickel zinc ferrite and is expressed as Cu-doped xBaTiO3-(1-x) Ni0.5Zn0.5Fe2O4Wherein x = 0.2-0.8, and Cu is doped into the nickel-zinc ferrite to replace Ni, and the proportion of Cu in the lattice position of Ni is 20-30%; the film is grown on a Si (111) substrate, and the nickel zinc ferrite crystal phase grows along the (111) plane orientation.
2. The copper-doped barium titanate/nickel zinc ferrite complex-phase thin film material of claim 1, wherein the two-phase crystal grains are uniformly and densely distributed, and the size of the crystal grains is 30-70 nm.
3. The method for preparing the copper-doped barium titanate/nickel zinc ferrite complex phase thin film material as claimed in claim 1 is characterized in that a radio frequency magnetron sputtering method is adopted, xBTO- (1-x) NZFO and x = 0.2-0.8 are taken as targets, a copper outer cover with a window at the lower end is additionally arranged on the outer side of the target, the diameter of the target is 56mm, the diameter of the window of the copper outer cover is 45mm, the distance between the lower end of the copper outer cover and the target is 16mm, and the copper-doped barium titanate/nickel zinc ferrite complex phase thin film is prepared on a Si (111) substrate in a deposition mode.
4. The preparation method of the copper-doped barium titanate/nickel zinc ferrite complex phase thin film material according to claim 3, which is characterized by comprising the following steps:
a. preliminarily cleaning a single crystal Si (111) substrate in deionized water, soaking in hydrofluoric acid for 10-30 min, then putting in acetone for ultrasonic treatment for 10-15 min, then performing ultrasonic treatment in absolute ethyl alcohol for 10-15 min, and finally drying by using nitrogen to obtain the single crystal Si (111) substrate for sputtering;
b. the specific technological parameters of sputtering are as follows: b, using an xBTO- (1-x) NZFO target material, and performing sputtering on the single crystal Si (111) substrate treated in the step a, wherein the total sputtering pressure is 0.6Pa, the flow rates of argon and oxygen are respectively 15sccm and 10sccm, the sputtering power is 180W, the substrate temperature is room temperature, and the sputtering time is 100-260min, so as to obtain an amorphous xBTO- (1-x) NZFO film layer containing Cu on the single crystal Si (111) substrate, wherein the Cu doping amount is 0.2-0.3 of the Cu/(Cu + Ni) molar ratio;
c. c, carrying out heat treatment on the amorphous film containing Cu deposited on the single crystal Si (111) substrate and obtained in the step b in a muffle furnace under the air atmosphere, heating the amorphous film to 600-700 ℃ from room temperature at the speed of 5 ℃/min, and preserving the heat for 2 hours; and then heating to 900-960 ℃ at the speed of 10-15 ℃/min, preserving the heat for 2h, then cooling to room temperature along with the furnace, and obtaining the copper-doped barium titanate/nickel zinc ferrite multiphase film material on the single crystal Si (111) substrate, wherein the nickel zinc ferrite crystal phase grows along the (111) plane in an oriented manner.
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