CN111223762A - PbZrO with self-polarization behavior3/Al2O3Heterostructure composite thin film and preparation method thereof - Google Patents

PbZrO with self-polarization behavior3/Al2O3Heterostructure composite thin film and preparation method thereof Download PDF

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CN111223762A
CN111223762A CN202010041869.6A CN202010041869A CN111223762A CN 111223762 A CN111223762 A CN 111223762A CN 202010041869 A CN202010041869 A CN 202010041869A CN 111223762 A CN111223762 A CN 111223762A
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张天栋
迟庆国
张昌海
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Harbin University of Science and Technology
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Abstract

The invention relates to a PbZrO with self-polarization behavior3/Al2O3A heterostructure composite film and a preparation method thereof belong to the field of inorganic functional electronic materials. In order to solve the problems that the existing antiferroelectric preparation process is complex and the improvement effect on residual polarization is not obvious, the invention provides a PbZrO with self-polarization behavior3/Al2O3A heterostructure composite thin film comprising PbZrO3Top film of thin film and Al2O3The bottom film is composed of a film, and the top film and the bottom film are compounded through crystallization treatment. The invention adopts antiferroelectric PbZrO with different Fermi energy levels3And alumina Al2O3To construct PbZrO3/Al2O3The heterostructure composite film realizes ferroelectric self polarization, and the residual polarization intensity is increased to 42.5 mu C/cm2. Meanwhile, the insulating property of the composite film is improved, and the fatigue resistance is enhanced, so that the composite film can be applied to a nonvolatile random access memory.

Description

PbZrO with self-polarization behavior3/Al2O3Heterostructure composite thin film and preparation method thereof
Technical Field
The invention belongs to the field of inorganic functional electronic materials, and particularly relates to PbZrO with self-polarization behavior3/Al2O3HeterostructureA composite film and a preparation method thereof.
Background
With the rapid development of electronic information technology, the demand for electronic information materials is increasing, and especially related research on information storage materials such as ferroelectric medium storage materials, magnetic storage materials, semiconductor dynamic storage materials, optical storage materials and the like has become a hot problem in the development of scientific research. In the last 60 years, the polarization characteristic of ferroelectric materials is firstly proposed to realize non-volatile random access memory, and the storage mode has the characteristics of low power and high storage speed. Among them, lead zirconate titanate-PZT is typically used, and has been widely studied because of its excellent ferroelectric properties such as higher remanent polarization strength. The biggest problem of ferroelectric PZT thin films is poor fatigue resistance, mainly represented by 10 f, in view of the slaving performance of memory cells6The polarization strength of the secondary electric field is seriously deteriorated.
Research has found that antiferroelectric generally has excellent fatigue resistance and breakdown strength, and at the same time, has been widely focused due to its polarization process accompanied by field induced phase transition. Antiferroelectric bodies, e.g. lead zirconate PbZrO3And are also commonly used as capacitors for energy storage and conversion. Despite antiferroelectric PbZrO3The ferroelectric random access memory has high fatigue resistance and excellent fatigue resistance, but the residual polarization strength value is almost zero due to the antiferroelectricity, so that the application of the ferroelectric random access memory in the field of ferroelectric random access memory is limited. Therefore, how to increase the remanent polarization of antiferroelectric becomes a key issue in determining whether it can be used as a random access memory.
Currently, there are very few studies on ferroelectric self-polarization of antiferroelectric. Research shows that a self-established electric field is constructed by preparing top and bottom electrodes with different work functions on the surface of an antiferroelectric sample so as to bias a polarization curve and induce non-zero residual polarization strength, and although the method has a novel design concept, the method has a complex process and does not have a remarkable residual polarization improvement effect.
Disclosure of Invention
In order to solve the problems that the existing antiferroelectric preparation process is complex and the improvement effect on residual polarization is not obvious, the invention provides a PbZrO with self-polarization behavior3/Al2O3A heterostructure composite thin film and a method for preparing the same.
The technical scheme of the invention is as follows:
PbZrO with self-polarization behavior3/Al2O3A heterostructure composite thin film comprising PbZrO3Top film of thin film and Al2O3The bottom film is composed of a film, and the top film and the bottom film are compounded through crystallization treatment.
Further, the PbZrO3The thickness of the film is 150-400 nm, and the Al is2O3The thickness of the film is 10 to 200 nm.
Further, the PbZrO3/Al2O3The heterostructure composite film has ferroelectric polarization characteristic, and the remanent polarization intensity value is 5-42.5 mu C/cm2。
PbZrO with self-polarization behavior3/Al2O3Method for preparing heterostructure composite thin film, respectively preparing Al2O3Precursor solution and PbZrO3Precursor solution using Al by spin coating2O3Preparation of Al from precursor solution2O3Film of the obtained Al2O3Pre-burning the film at a certain temperature to obtain Al2O3Continuously spin-coating PbZrO on the film3Preparation of PbZrO from precursor solution3Film and obtaining PbZrO3/Al2O3Composite film of the obtained PbZrO3/Al2O3The composite film is presintered at a certain temperature and then crystallized to obtain crystallized PbZrO3/Al2O3The heterostructure composite thin film.
Further, said Al2O3The preparation method of the precursor solution comprises the following steps: mixing ethylene glycol monomethyl ether and glacial acetic acid according to a volume ratio of 4:1 to prepare a solvent, dissolving aluminum isopropoxide in the solvent according to a molar volume ratio of 0.01-0.05 mol:1L,stirring for 30-60 min at 60-80 ℃ to obtain a clear solution A, aging and standing for 24h to obtain Al2O3And (3) precursor solution.
Further, the PbZrO3The preparation method of the precursor solution comprises the following steps: dissolving lead acetate in ethylene glycol monomethyl ether according to a molar volume ratio of 0.2-0.4 mol:1L, stirring at 60-80 ℃ for 30-60 min to obtain a clear solution B, dropwise adding zirconium isopropoxide with the same molar amount as that of the lead acetate into the clear solution B cooled to room temperature, stirring for 30-60 min, aging and standing for 24h to obtain PbZrO3And (3) precursor solution.
Further, the rotating speed of the spin coating is 3000-4000 r/min, the spin coating time is 10-15 s, and the Al is2O3The thickness of the film is 10-200 nm, and the PbZrO is3The thickness of the film is 150 to 400 nm.
Furthermore, the pre-sintering temperature is 350-400 ℃, and the pre-sintering time is 3-5 min.
Further, the crystallization treatment is to make PbZrO3/Al2O3The composite film is heated to 700 ℃ for 30s and is kept warm for 5 min.
Further, the PbZrO3/Al2O3The heterostructure composite film has ferroelectric polarization characteristic, and the residual polarization intensity value is as high as 5-42.5 mu C/cm2。
The invention has the beneficial effects that:
the invention firstly provides a design idea of realizing ferroelectric self-polarization of the antiferroelectric by utilizing a self-established electric field at a heterojunction interface. By selecting antiferroelectric PbZrO with different Fermi energy levels3And alumina Al2O3To construct PbZrO3/Al2O3The heterostructure composite thin film. Self-establishing electric field E formed at heterostructure interfaceinLead to PbZrO3The film layer is subjected to field phase transition, and ferroelectric self-polarization is realized. At the same time, PbZrO3The film self-polarization process is accompanied by Al2O3The film layer carriers are largely consumed, and therefore, the insulating property of the composite film is improved, and the fatigue resistance is further enhanced. PbZrO 23/Al2O3Antiferroelectric PbZrO in heterostructure composite thin films3The self-polarization of the film layer increases the residual polarization intensity to 42.5 μ C/cm2Exhibits ferroelectric polarization characteristics. Therefore, the invention provides PbZrO3/Al2O3The heterostructure composite film can be applied to the fields of ferroelectric random access memory and non-volatile random access memory.
Drawings
FIG. 1 shows PbZrO prepared in example 13/Al2O3The horizontal coordinate of the ferroelectric hysteresis loop of the heterostructure composite film is voltage V, and the vertical coordinate is polarization intensity mu C/cm2；
FIG. 2 shows PbZrO prepared in example 13/Al2O3The voltage-capacitance curve of the heterostructure composite film has the abscissa of voltage V and the ordinate of capacitance F;
FIG. 3 shows PbZrO prepared in example 13/Al2O3The voltage-current density curve of the heterostructure composite film has the abscissa of voltage V and the ordinate of current density A/cm2；
FIG. 4 shows PbZrO prepared in comparative example 13/Al2O3The horizontal coordinate of the ferroelectric hysteresis loop of the heterostructure composite film is voltage V, and the vertical coordinate is polarization intensity mu C/cm2；
FIG. 5 shows PbZrO prepared in comparative example 13/Al2O3The voltage-capacitance curve of the heterostructure composite film has the abscissa of voltage V and the ordinate of capacitance F;
FIG. 6 shows PbZrO prepared in comparative example 13/Al2O3The voltage-current density curve of the heterostructure composite film has the abscissa of voltage V and the ordinate of current density A/cm2。
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1
This example provides a PbZrO with self-polarizing behavior3/Al2O3The preparation method of the heterostructure composite film comprises the following steps:
step one, preparing Al2O3Precursor solution:
mixing ethylene glycol monomethyl ether and glacial acetic acid according to a volume ratio of 4:1 to prepare a solvent, and mixing aluminum isopropoxide according to a molar volume ratio of 0.05mol: dissolving 1L of the above solution in the solvent, stirring at 60 deg.C for 30min to obtain clear solution A, aging, and standing for 24 hr to obtain Al2O3Precursor solution;
step two, preparing PbZrO3Precursor solution:
lead acetate is added into the mixture according to the molar volume ratio of 0.4mol: dissolving 1L of the mixed solution in ethylene glycol monomethyl ether, stirring the mixed solution for 30min at the temperature of 60 ℃ to obtain a clear solution B, dropwise adding zirconium isopropoxide with the molar weight equal to that of lead acetate into the clear solution B cooled to room temperature, stirring the solution for 30min, and aging and standing the solution for 24h to obtain PbZrO3Precursor solution;
step three, spin coating to prepare a composite film:
Pt/Ti/SiO with area of 10mm x 10mm by using spin coater2Al is prepared on Si substrate by adopting spin-coating method2O3Film to Pt/Ti/SiO2Dripping 4 drops of Al prepared in the first step on a Si substrate2O3Spin-coating the precursor solution for 15s at the rotation speed of 4000r/min to obtain Al with the thickness of 30nm2O3A film; mixing the obtained Al2O3Placing the film on a flat plate furnace at 375 ℃ and presintering for 3 min;
pre-sintered Al2O3After cooling, the film is placed on a spin coater and is coated with Al2O34 drops of PbZrO prepared in the second step are dripped on the film3Spin-coating the precursor solution for 15s at the rotation speed of 4000r/min to obtain PbZrO with the thickness of 220nm3A film; with PbZrO3The film is a top film and is made of Al2O3PbZrO prepared by using film as basement membrane3/Al2O3Compounding a film; the obtained PbZrO3/Al2O3The composite film is placed at 375 DEG CPre-burning for 3min on a flat plate furnace;
step four, preparing crystallized PbZrO3/Al2O3Heterostructure composite thin films:
the PbZrO obtained in the third step3/Al2O3Placing the composite film in a rapid thermal treatment furnace, rapidly heating to 700 ℃ for 30s, and keeping the temperature for 5min to obtain crystallized PbZrO3/Al2O3The heterostructure composite thin film.
PbZrO3/Al2O3Antiferroelectric PbZrO in heterostructure composite thin films3The self-polarization of the film layer increases the residual polarization intensity to 42.5 μ C/cm2。
Example 2
This example provides a PbZrO with self-polarizing behavior3/Al2O3The preparation method of the heterostructure composite film comprises the following steps:
step one, preparing Al2O3Precursor solution:
mixing ethylene glycol monomethyl ether and glacial acetic acid according to a volume ratio of 4:1 to prepare a solvent, and mixing aluminum isopropoxide according to a molar volume ratio of 0.01 mol: dissolving 1L of the above solution in the solvent, stirring at 65 deg.C for 40min to obtain clear solution A, aging, and standing for 24 hr to obtain Al2O3Precursor solution;
step two, preparing PbZrO3Precursor solution:
lead acetate is added into the mixture according to the molar volume ratio of 0.2 mol: dissolving 1L of the mixed solution in ethylene glycol monomethyl ether, stirring the mixed solution at 65 ℃ for 40min to obtain a clear solution B, dropwise adding zirconium isopropoxide with the molar weight equal to that of lead acetate into the clear solution B cooled to room temperature, stirring the solution for 30min, and aging and standing the solution for 24h to obtain PbZrO3Precursor solution;
step three, spin coating to prepare a composite film:
Pt/Ti/SiO with area of 10mm x 10mm by using spin coater2Al is prepared on Si substrate by adopting spin-coating method2O3Film to Pt/Ti/SiO2Dripping 4 drops of Al prepared in the first step on a Si substrate2O3The precursor solution is spin-coated at the rotating speed of 3000r/min15s, obtaining Al with the thickness of 10nm2O3A film; mixing the obtained Al2O3Placing the film on a flat plate furnace at 375 ℃ and presintering for 3 min;
pre-sintered Al2O3After cooling, the film is placed on a spin coater and is coated with Al2O34 drops of PbZrO prepared in the second step are dripped on the film3Spin-coating the precursor solution for 15s at the rotation speed of 4000r/min to obtain PbZrO with the thickness of 200nm3A film; with PbZrO3The film is a top film and is made of Al2O3PbZrO prepared by using film as basement membrane3/Al2O3Compounding a film; the obtained PbZrO3/Al2O3Placing the composite film on a flat plate furnace at 375 ℃ and presintering for 3 min;
step four, preparing crystallized PbZrO3/Al2O3Heterostructure composite thin films:
the PbZrO obtained in the third step3/Al2O3Placing the composite film in a rapid thermal treatment furnace, rapidly heating to 700 ℃ for 30s, and keeping the temperature for 5min to obtain crystallized PbZrO3/Al2O3The heterostructure composite thin film.
PbZrO3/Al2O3Antiferroelectric PbZrO in heterostructure composite thin films3The self-polarization of the film layer increases the residual polarization intensity to 10 μ C/cm2。
Example 3
This example provides a PbZrO with self-polarizing behavior3/Al2O3The preparation method of the heterostructure composite film comprises the following steps:
step one, preparing Al2O3Precursor solution:
mixing ethylene glycol monomethyl ether and glacial acetic acid according to a volume ratio of 4:1 to prepare a solvent, and mixing aluminum isopropoxide according to a molar volume ratio of 0.02 mol: dissolving 1L in the solvent, stirring at 70 deg.C for 45min to obtain clear solution A, aging, and standing for 24 hr to obtain Al2O3Precursor solution;
step two, preparing PbZrO3Precursor solution:
lead acetate is added into the mixture according to the molar volume ratio of 0.3 mol: dissolving 1L of the mixed solution in ethylene glycol monomethyl ether, stirring the mixed solution at 70 ℃ for 45min to obtain a clear solution B, dropwise adding zirconium isopropoxide with the molar weight equal to that of lead acetate into the clear solution B cooled to room temperature, stirring the solution B for 30min, and aging and standing the solution for 24h to obtain PbZrO3Precursor solution;
step three, spin coating to prepare a composite film:
Pt/Ti/SiO with area of 10mm x 10mm by using spin coater2Al is prepared on Si substrate by adopting spin-coating method2O3Film to Pt/Ti/SiO2Dripping 4 drops of Al prepared in the first step on a Si substrate2O3Spinning the precursor solution for 15s at the rotation speed of 4000r/min to obtain Al with the thickness of 40nm2O3A film; mixing the obtained Al2O3Placing the film on a flat plate furnace at 375 ℃ and presintering for 3 min;
pre-sintered Al2O3After cooling, the film is placed on a spin coater and is coated with Al2O34 drops of PbZrO prepared in the second step are dripped on the film3The precursor solution is spin-coated for 15s under the condition that the rotating speed is 4000r/min to prepare PbZrO with the thickness of 300nm3A film; with PbZrO3The film is a top film and is made of Al2O3PbZrO prepared by using film as basement membrane3/Al2O3Compounding a film; the obtained PbZrO3/Al2O3Placing the composite film on a flat plate furnace at 375 ℃ and presintering for 3 min;
step four, preparing crystallized PbZrO3/Al2O3Heterostructure composite thin films:
the PbZrO obtained in the third step3/Al2O3Placing the composite film in a rapid thermal treatment furnace, rapidly heating to 700 ℃ for 30s, and keeping the temperature for 5min to obtain crystallized PbZrO3/Al2O3The heterostructure composite thin film.
PbZrO3/Al2O3Antiferroelectric PbZrO in heterostructure composite thin films3The self-polarization of the film layer increases the residual polarization intensity to 42.5 μ C/cm2。
Example 4
This example provides a PbZrO with self-polarizing behavior3/Al2O3The preparation method of the heterostructure composite film comprises the following steps:
step one, preparing Al2O3Precursor solution:
mixing ethylene glycol monomethyl ether and glacial acetic acid according to a volume ratio of 4:1 to prepare a solvent, and mixing aluminum isopropoxide according to a molar volume ratio of 0.03 mol: dissolving 1L in the solvent, stirring at 75 deg.C for 50min to obtain clear solution A, aging, and standing for 24 hr to obtain Al2O3Precursor solution;
step two, preparing PbZrO3Precursor solution:
lead acetate is added into the mixture according to the molar volume ratio of 0.3 mol: dissolving 1L of the mixed solution in ethylene glycol monomethyl ether, stirring the mixed solution for 50min at the temperature of 75 ℃ to obtain a clear solution B, dropwise adding zirconium isopropoxide with the molar weight equal to that of lead acetate into the clear solution B cooled to room temperature, stirring the solution B for 30min, and aging and standing the solution B for 24h to obtain PbZrO3Precursor solution;
step three, spin coating to prepare a composite film:
Pt/Ti/SiO with area of 10mm x 10mm by using spin coater2Al is prepared on Si substrate by adopting spin-coating method2O3Film to Pt/Ti/SiO2Dripping 4 drops of Al prepared in the first step on a Si substrate2O3Spin-coating the precursor solution for 15s at the rotation speed of 4000r/min to obtain Al with the thickness of 60nm2O3A film; mixing the obtained Al2O3Placing the film on a flat plate furnace at 375 ℃ and presintering for 3 min;
pre-sintered Al2O3After cooling, the film is placed on a spin coater and is coated with Al2O34 drops of PbZrO prepared in the second step are dripped on the film3The precursor solution is spin-coated for 15s under the condition that the rotating speed is 4000r/min to prepare PbZrO with the thickness of 350nm3A film; with PbZrO3The film is a top film and is made of Al2O3PbZrO prepared by using film as basement membrane3/Al2O3Compounding a film; the obtained PbZrO3/Al2O3CompoundingPlacing the film on a flat plate furnace at 375 ℃ and presintering for 3 min;
step four, preparing crystallized PbZrO3/Al2O3Heterostructure composite thin films:
the PbZrO obtained in the third step3/Al2O3Placing the composite film in a rapid thermal treatment furnace, rapidly heating to 700 ℃ for 30s, and keeping the temperature for 5min to obtain crystallized PbZrO3/Al2O3The heterostructure composite thin film.
PbZrO3/Al2O3Antiferroelectric PbZrO in heterostructure composite thin films3The self-polarization of the film layer increases the residual polarization intensity to 40 μ C/cm2。
Example 5
This example provides a PbZrO with self-polarizing behavior3/Al2O3The preparation method of the heterostructure composite film comprises the following steps:
step one, preparing Al2O3Precursor solution:
mixing ethylene glycol monomethyl ether and glacial acetic acid according to a volume ratio of 4:1 to prepare a solvent, and mixing aluminum isopropoxide according to a molar volume ratio of 0.05mol: dissolving 1L in the solvent, stirring at 80 deg.C for 60min to obtain clear solution A, aging, and standing for 24 hr to obtain Al2O3Precursor solution;
step two, preparing PbZrO3Precursor solution:
lead acetate is added into the mixture according to the molar volume ratio of 0.4mol: dissolving 1L of the mixed solution in ethylene glycol monomethyl ether, stirring the mixed solution at the temperature of 80 ℃ for 60min to obtain a clear solution B, dropwise adding zirconium isopropoxide with the molar weight equal to that of lead acetate into the clear solution B cooled to room temperature, stirring the solution B for 30min, and aging and standing the solution B for 24h to obtain PbZrO3Precursor solution;
step three, spin coating to prepare a composite film:
Pt/Ti/SiO with area of 10mm x 10mm by using spin coater2Al is prepared on Si substrate by adopting spin-coating method2O3Film to Pt/Ti/SiO2Dripping 4 drops of Al prepared in the first step on a Si substrate2O3Precursor solution at 4000r/minSpin coating for 15s under the condition to obtain Al with the thickness of 100nm2O3A film; mixing the obtained Al2O3Placing the film on a flat plate furnace at 375 ℃ and presintering for 3 min;
pre-sintered Al2O3After cooling, the film is placed on a spin coater and is coated with Al2O34 drops of PbZrO prepared in the second step are dripped on the film3The precursor solution is spin-coated for 15s under the condition that the rotating speed is 4000r/min to prepare PbZrO with the thickness of 400nm3A film; with PbZrO3The film is a top film and is made of Al2O3PbZrO prepared by using film as basement membrane3/Al2O3Compounding a film; the obtained PbZrO3/Al2O3Placing the composite film on a flat plate furnace at 375 ℃ and presintering for 3 min;
step four, preparing crystallized PbZrO3/Al2O3Heterostructure composite thin films:
the PbZrO obtained in the third step3/Al2O3Placing the composite film in a rapid thermal treatment furnace, rapidly heating to 700 ℃ for 30s, and keeping the temperature for 5min to obtain crystallized PbZrO3/Al2O3The heterostructure composite thin film.
PbZrO3/Al2O3Antiferroelectric PbZrO in heterostructure composite thin films3The self-polarization of the film layer increases the residual polarization intensity to 30 μ C/cm2。
Comparative example 1
This comparative example provides a pure antiferroelectric PbZrO3The preparation method of the film comprises the following steps:
step one, preparing PbZrO3Precursor solution:
lead acetate is added into the mixture according to the molar volume ratio of 0.4mol: dissolving 1L of the mixed solution in ethylene glycol monomethyl ether, stirring the mixed solution for 30min at the temperature of 60 ℃ to obtain a clear solution B, dropwise adding zirconium isopropoxide with the molar weight equal to that of lead acetate into the clear solution B cooled to room temperature, stirring the solution for 30min, and aging and standing the solution for 24h to obtain PbZrO3Precursor solution;
step two, preparing PbZrO by spin coating3Film formation:
by usingThe spin coater is arranged on the Pt/Ti/SiO with the area of 10mm multiplied by 10mm2Preparation of PbZrO on Si substrate by spin coating method3Film to Pt/Ti/SiO2Dropping 4 drops of PbZrO prepared in the first step on a Si substrate3Spin-coating the precursor solution for 15s at the rotation speed of 4000r/min to obtain PbZrO with the thickness of 220nm3A film; the obtained PbZrO3Placing the film on a flat plate furnace at 375 ℃ and presintering for 3 min;
step three, preparing crystallized PbZrO3Film formation:
the PbZrO obtained in the second step3The film is placed in a rapid thermal treatment furnace, the temperature is rapidly raised to 700 ℃ for 30s and is kept for 5min, and the crystallized pure antiferroelectric PbZrO is obtained3A film.
FIG. 1 shows PbZrO prepared in example 13/Al2O3The horizontal coordinate of the ferroelectric hysteresis loop of the heterostructure composite film is voltage V, and the vertical coordinate is polarization intensity mu C/cm2(ii) a FIG. 4 shows PbZrO prepared in comparative example 13/Al2O3The horizontal coordinate of the ferroelectric hysteresis loop of the heterostructure composite film is voltage V, and the vertical coordinate is polarization intensity mu C/cm2(ii) a As can be seen by comparing FIG. 1 with FIG. 4, PbZrO3/Al2O3The heterostructure composite film shows good ferroelectric polarization characteristic and has higher residual polarization intensity of 42.5 mu C/cm2And PbZrO in FIG. 43The residual polarization intensity of the antiferroelectric film is only 5 mu C/cm2And exhibits dual hysteresis-line antiferroelectric polarization characteristics. Description of introduction of Al2O3After film formation, PbZrO3The antiferroelectric polarization characteristic of the thin film disappears and is converted into a ferroelectric polarization characteristic due to Al2O3Film layer and PbZrO3The Fermi level of the films is different, so that a self-establishing electric field is formed at the interface, and PbZrO is under the action of the self-establishing electric field3The antiferroelectric film undergoes field-induced phase transition to exhibit ferroelectric polarization characteristics. It was also found that PbZrO in FIG. 13/Al2O3The voltage which can be borne by the heterostructure composite film is as high as 75V and is far greater than that of PbZrO in figure 4315V of antiferroelectric film, mainly due to the introduction of Al2O3After the film, it has a low relative dielectric constant, Al2O3The partial pressure of the film obviously improves the insulating strength of the composite film, and on the other hand, the self-built electric field formed at the interface needs to consume Al2O3The carriers in the thin film also contribute to the improvement of the dielectric strength of itself.
FIG. 2 shows PbZrO prepared in example 13/Al2O3The voltage-capacitance curve of the heterostructure composite film has the abscissa of voltage V and the ordinate of capacitance F; FIG. 5 shows PbZrO prepared in comparative example 13/Al2O3The voltage-capacitance curve of the heterostructure composite film has the abscissa of voltage V and the ordinate of capacitance F; as can be seen by comparing FIG. 2 with FIG. 5, PbZrO3/Al2O3The heterostructure composite films exhibited "single butterfly" polarization characteristics, while PbZrO in FIG. 53The antiferroelectric film has a double butterfly curve polarization characteristic. Description of introduction of Al2O3After film formation, PbZrO3The antiferroelectric polarization characteristic of the thin film disappears and is transformed into a ferroelectric polarization characteristic. At the same time, it was found that PbZrO3/Al2O3The capacitance peak values in the voltage-capacitance curve of the heterostructure composite thin film are not symmetrically distributed along the vertical axis of the voltage zero point, but are biased to the negative polarity voltage side, which shows that a self-established electric field exists. And PbZrO3The voltage-capacitance curve of the antiferroelectric film has four typical capacitance peak values, which respectively correspond to capacitance changes caused by the antiferroelectric phase to the ferroelectric phase in the polarization process and the ferroelectric phase to the antiferroelectric phase in the depolarization process.
FIG. 3 shows PbZrO prepared in example 13/Al2O3The voltage-current density curve of the heterostructure composite film has the abscissa of voltage V and the ordinate of current density A/cm2(ii) a FIG. 6 shows PbZrO prepared in comparative example 13/Al2O3The voltage-current density curve of the heterostructure composite film has the abscissa of voltage V and the ordinate of current density A/cm2(ii) a As can be seen by comparing FIG. 3 with FIG. 6, PbZrO3/Al2O3The heterostructure composite film shows a certain rectification effectThat is, under negative polarity bias, the current density is three times that under positive polarity bias. And PbZrO in FIG. 63The antiferroelectric film shows four typical current peaks, which respectively correspond to the current density changes caused by the antiferroelectric phase to the ferroelectric phase in the polarization process and the ferroelectric phase to the antiferroelectric phase in the depolarization process.
Through experimental structural characterization and electrical property test, the antiferroelectric PbZrO in the composite film is found3The antiferroelectricity of the film disappears, the ferroelectric polarization characteristic is shown, and the heterostructure realizes antiferroelectric PbZrO3Ferroelectric self-polarization of the thin film.

Claims (10)

1. PbZrO with self-polarization behavior3/Al2O3The heterostructure composite thin film is characterized by comprising PbZrO 23Top film of thin film and Al2O3The bottom film is composed of a film, and the top film and the bottom film are compounded through crystallization treatment.
2. PbZrO according to claim 1 having self-polarization behavior3/Al2O3Heterostructure composite thin film, characterized in that the PbZrO 23The thickness of the film is 150-400 nm, and the Al is2O3The thickness of the film is 10 to 200 nm.
3. PbZrO according to claim 1 or 2 having self-polarization behavior3/Al2O3Heterostructure composite thin film, characterized in that the PbZrO 23/Al2O3The heterostructure composite film has ferroelectric polarization characteristic, and the remanent polarization intensity value is 5-42.5 mu C/cm2。
4. PbZrO with self-polarization behavior3/Al2O3A method for preparing a heterostructure composite thin film is characterized in that Al is prepared respectively2O3Precursor solution and PbZrO3Precursor solution using Al by spin coating2O3Preparation of Al from precursor solution2O3Film of the obtained Al2O3Pre-burning the film at a certain temperature to obtain Al2O3Continuously spin-coating PbZrO on the film3Preparation of PbZrO from precursor solution3Film and obtaining PbZrO3/Al2O3Composite film of the obtained PbZrO3/Al2O3The composite film is presintered at a certain temperature and then crystallized to obtain crystallized PbZrO3/Al2O3The heterostructure composite thin film.
5. PbZrO according to claim 4 having self-poling behaviour3/Al2O3A method for preparing a heterostructure composite thin film, characterized in that the Al is2O3The preparation method of the precursor solution comprises the following steps: mixing ethylene glycol monomethyl ether and glacial acetic acid according to a volume ratio of 4:1 to prepare a solvent, dissolving aluminum isopropoxide in the solvent according to a molar volume ratio of 0.01-0.05 mol:1L, stirring at 60-80 ℃ for 30-60 min to obtain a clear solution A, aging and standing for 24h to obtain Al2O3And (3) precursor solution.
6. PbZrO according to claim 4 or 5 having self-polarization behavior3/Al2O3A method for preparing a heterostructure composite thin film, characterized in that the PbZrO is3The preparation method of the precursor solution comprises the following steps: dissolving lead acetate in ethylene glycol monomethyl ether according to a molar volume ratio of 0.2-0.4 mol:1L, stirring at 60-80 ℃ for 30-60 min to obtain a clear solution B, dropwise adding zirconium isopropoxide with the same molar amount as that of the lead acetate into the clear solution B cooled to room temperature, stirring for 30-60 min, aging and standing for 24h to obtain PbZrO3And (3) precursor solution.
7. PbZrO according to claim 6 having self-poling behaviour3/Al2O3The preparation method of the heterostructure composite film is characterized in that the rotating speed of the spin coating is 3000-4000 r/min, the spin coating time is 10-15 s, and the method comprises the following stepsAl mentioned above2O3The thickness of the film is 10-200 nm, and the PbZrO is3The thickness of the film is 150 to 400 nm.
8. PbZrO according to claim 7 having self-polarization behavior3/Al2O3The preparation method of the heterostructure composite film is characterized in that the pre-sintering temperature is 350-400 ℃, and the pre-sintering time is 3-5 min.
9. PbZrO according to claim 8 having self-poling behaviour3/Al2O3The preparation method of the heterostructure composite film is characterized in that the crystallization treatment is to lead PbZrO to be mixed3/Al2O3The composite film is heated to 700 ℃ for 30s and is kept warm for 5 min.
10. PbZrO according to claim 9 having self-poling behaviour3/Al2O3A method for preparing a heterostructure composite thin film, characterized in that the PbZrO is3/Al2O3The heterostructure composite film has ferroelectric polarization characteristic, and the remanent polarization intensity value is 5-42.5 mu C/cm2。
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