CN111676456A - Self-assembled Ba (Hf, Ti) O3:HfO2Nano composite lead-free epitaxial single-layer film and preparation method thereof - Google Patents

Self-assembled Ba (Hf, Ti) O3:HfO2Nano composite lead-free epitaxial single-layer film and preparation method thereof Download PDF

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CN111676456A
CN111676456A CN202010501023.6A CN202010501023A CN111676456A CN 111676456 A CN111676456 A CN 111676456A CN 202010501023 A CN202010501023 A CN 202010501023A CN 111676456 A CN111676456 A CN 111676456A
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CN111676456B (en
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刘明
段婷枝
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Xian Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/02—Epitaxial-layer growth
    • C30B23/025—Epitaxial-layer growth characterised by the substrate
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C30B29/32—Titanates; Germanates; Molybdates; Tungstates

Abstract

The invention discloses a self-assembly Ba (Hf, Ti) O3:HfO2A nano-composite lead-free epitaxial single-layer film is prepared from Nb, SrTiO3Substrate, BaHfxTi1‑xO3A layer and an upper electrode, wherein BaHfxTi1‑xO3The layer is arranged on Nb SrTiO3The upper electrode is arranged on the upper surface of the substrate and is arranged at BaHfxTi1‑xO3Upper surface of layer, wherein x is not less than 0.44, BaHfxTi1‑xO3Layer thickness of 40 a0 nm. The preparation method comprises the following steps: at Nb, SrTiO3Preparation of BaHf on the upper surface of substratexTi1‑ xO3Layer of BaHfxTi1‑xO3The upper surface of the layer is provided with an upper electrode. The thin film of the invention can improve the breakdown field intensity and the energy storage density, and simultaneously, the energy efficiency of the thin film is maintained at a higher state, and the thin film has a new structure.

Description

Self-assembled Ba (Hf, Ti) O3:HfO2Nano composite lead-free epitaxial single-layer film and preparation method thereof
Technical Field
The invention relates to the field of energy storage thin film materials, in particular to self-assembled Ba (Hf, Ti) O3:HfO2Nano meterA composite lead-free epitaxial single-layer film and a preparation method thereof.
Background
The energy problem is one of the problems facing the world at present, and with the increasingly prominent and serious energy crisis problem, the demand of people for new energy is more urgent, so the storage technology and the research and development problem of the new energy become one of the problems of close attention of people. Common energy storage devices at present include fuel cells, lithium ion batteries, super capacitors and the like. Although fuel cells have high energy conversion efficiency and a wide fuel selection range, their power density is relatively low and needs to be improved. The lithium ion battery has the defects that the lithium ion battery cannot discharge large current and needs to be controlled by a protection circuit in the operation process although the energy density is high. Although the super capacitor has high power density and short charging time, the super capacitor has low energy density and short endurance mileage. Compared with the bulk material, the thin film capacitor has better voltage resistance, so the energy storage density is better. The main characteristics of the thin film capacitor are as follows: no polarity, high insulation resistance, excellent frequency characteristics and low dielectric loss. Based on the above advantages, the thin film capacitor is widely used in the field of analog circuits. Therefore, in the field of energy storage materials, thin film memory has become one of the hot researches.
The parameters related to the performance of the film material include dielectric constant, breakdown field strength, energy storage density, energy storage efficiency and the like, and meanwhile, the temperature stability is closely related to the performance of the film material. Therefore, the energy storage characteristic of the film material is improved, and the design requirements of people can be met only when the film material has the advantages of high dielectric constant, strong breakdown field, high energy storage density, high energy storage efficiency, high temperature and high pressure resistance and the like. Because the factors influencing the performance of the film are more and have a restriction relationship with each other, different manufacturing processes, different substrate buffer layers and different growth conditions all influence the performance of the film. Therefore, how to increase the breakdown field strength and the energy storage density while maintaining the energy efficiency of the thin film memory at a higher state is a problem to be solved by those skilled in the art.
Disclosure of Invention
To solve the problems in the prior art, the present invention provides a self-assembled Ba (Hf, Ti) O3:HfO2The invention relates to a nano composite lead-free epitaxial single-layer film and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
self-assembled Ba (Hf, Ti) O3:HfO2The nano composite lead-free epitaxial single-layer film comprises Nb and SrTiO3Substrate, BaHfxTi1-xO3A layer and an upper electrode, wherein BaHfxTi1-xO3The layer is arranged on Nb SrTiO3The upper electrode is arranged on the upper surface of the substrate and is arranged at BaHfxTi1-xO3The upper surface of the layer, wherein x is more than or equal to 0.44.
Preferably, BaHfxTi1-xO3The layer thickness was 400 nm.
Preferably, Nb is SrTiO3The substrate is (001) oriented single crystal Nb SrTiO3A substrate.
Self-assembled Ba (Hf, Ti) O3:HfO2The preparation method of the nano composite lead-free epitaxial single-layer film comprises the following steps:
at Nb, SrTiO3Preparation of BaHf on the upper surface of substratexTi1-xO3Layer of BaHfxTi1-xO3Preparing an upper electrode on the upper surface of the layer, wherein x is more than or equal to 0.44.
Preferably, BaHfxTi1-xO3The layer thickness was 400 nm.
Preferably, in Nb SrTiO3Preparation of BaHf on the upper surface of the substrate by magnetron sputteringxTi1-xO3Layer, magnetron sputtering adopts BaHfxTi1-xO3A ceramic target material.
Preferably, during magnetron sputtering, a deposition cavity of the magnetron sputtering system is firstly vacuumized, so that the vacuum degree in the deposition cavity is not less than 10-5mbar; then introducing argon and oxygen into the deposition chamberAccording to the mixed gas with the volume ratio of 1/1, the air pressure in the deposition chamber is 200 mbar; then the temperature of the deposition chamber is raised to 850 ℃, and then Nb, SrTiO3Baking the substrate for 10min to remove Nb, SrTiO3Attachment to a substrate surface; then the deposition cavity is vacuumized to ensure that the vacuum degree of the deposition cavity is not less than 10-5mbar; introducing the mixed gas into the deposition cavity to ensure that the required growth pressure in the deposition cavity is 0.2 mbar;
after the air pressure in the deposition cavity is stabilized, adjusting BaHfxTi1-xO3Position and growth time of the ceramic target material in Nb SrTiO3The growth of an epitaxial film with a preset thickness is realized on the substrate, and the sputtering power is 100W;
after the growth is finished, introducing the mixed gas into the deposition cavity to enable the air pressure of the deposition cavity to reach 200mbar, and annealing for 15min under the air pressure; and after the annealing is finished, cooling to room temperature to obtain the self-assembled nano composite lead-free epitaxial single-layer film.
Preferably, in a magnetron sputtering system, the target distance is 55mm, pre-sputtering is firstly carried out for 10-12 h through mixed gas at room temperature, and impurities on the surface of the target are removed, wherein the mixed gas is mixed gas of argon and oxygen, and the volume ratio of the argon to the oxygen is 1/1; then carrying out magnetron sputtering.
Preferably, BaHfxTi1-xO3The ceramic target material adopts BaCO with the purity level of 4-5N3Powder, HfO2Powder and TiO2Preparing powder; wherein, by BaCO3Powder, HfO2Powder and TiO2Powder preparation of BaHfxTi1-xO3When the ceramic target is used, the sintering temperature is 100-200 ℃ lower than the phase forming temperature of each system.
Preferably, Nb is SrTiO3The substrate is (001) oriented single crystal Nb SrTiO3A substrate.
Compared with the prior art, the invention has the following beneficial technical effects:
the self-assembled Ba (Hf, Ti) O of the invention3:HfO2In the nano composite lead-free epitaxial single-layer film, the doping amount of Hf element is controlled to be largeAt 0.44 or less, HfO can be present2The precipitated phases are generated and a two-phase composite structure appears in the film, which is shaped like a "wave". According to the test, the precipitated phase is HfO2The composite structure can effectively inhibit breakdown, and can maintain higher energy efficiency while obtaining the maximum breakdown field strength and excellent energy storage density. The energy storage film is a new structure in the existing energy storage film, and the structure can greatly improve the breakdown field strength and the energy storage density of the doped energy storage film and ensure that the doped energy storage film maintains a better state under the condition of high temperature. In addition, the material of the invention does not contain lead, and belongs to an environment-friendly material.
The preparation method disclosed by the invention is simple in process and good in operability, the prepared film has a novel two-phase composite structure, and compared with other films with the concentration lower than that of the sample, the breakdown field strength and the energy storage density of the film are obviously improved, the energy efficiency is high, and the thermal stability is excellent.
Drawings
FIG. 1 shows self-assembly of Ba (Hf, Ti) O in example 1 of the present invention3:HfO2And (3) a transmission electron microscope photograph of the section of the nano composite lead-free epitaxial single-layer film.
FIG. 2 shows self-assembly of Ba (Hf, Ti) O in example 1 of the present invention3:HfO2And (3) a transmission electron microscope photo of partial amplification of the nano composite lead-free epitaxial single-layer film.
Fig. 3 is an X-ray energy spectrum of the Ba atom in fig. 2.
FIG. 4 is an X-ray energy spectrum of the Hf atoms in FIG. 2.
FIG. 5 is an X-ray energy spectrum of the Ti atom in FIG. 2.
FIG. 6 shows self-assembly of Ba (Hf, Ti) O in example 1 of the present invention3:HfO2Breakdown field intensity diagram of the nano composite lead-free epitaxial single-layer film.
FIG. 7 shows the self-assembly of Ba (Hf, Ti) O in example 1 of the present invention at room temperature3:HfO2And (3) an energy storage density and energy efficiency diagram of the nano composite lead-free epitaxial single-layer film.
FIG. 8 shows self-assembly of Ba (Hf, Ti) O in example 1 of the present invention3:HfO2The energy storage density and energy efficiency of the nano composite lead-free epitaxial single-layer film are in the range of-100 ℃ to 250 ℃.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
The self-assembled Ba (Hf, Ti) O of the invention3:HfO2The preparation method of the nano composite lead-free epitaxial single-layer film comprises the following steps:
(1) firstly, according to the chemical formula BaHf for preparing the thin filmxTi1-xO3According to BaHfxTi1-xO3According to the component requirements, respectively weighing corresponding amount of 4-5N-grade BaCO3High purity powder, HfO2High purity powder and TiO2High-purity powder, ball-milling, presintering, granulating, molding and sintering the mixture of the three high-purity powders, and preparing the BaHf powder by adopting the traditional solid-phase ceramic preparation processxTi1-xO3A ceramic target material. In the process of preparing the ceramic target, the sintering temperature is 100-200 ℃ lower than the system phase forming temperature.
(2) The prepared BaHfxTi1-xO3The ceramic target material is firstly polished by sand paper and then is installed in a magnetron sputtering system after the surface of the ceramic target material is cleaned by an air gun, the target distance is set to be 55mm, and the ceramic target material is arranged in argon/oxygen (Ar/O)2) Under the room-temperature sputtering environment with the mixed gas of 1/1, firstly, pre-sputtering for 10-12 h to remove impurities on the surface of the target.
(3) Selecting (001) oriented single crystal Nb SrTiO3The substrate (Nb: STO substrate) is subjected to film deposition by first depositing Nb: SrTiO3The substrate is cut to the desired size, 2.5 × 5 × 0.5.5 mm, by a wire saw3And then soaking the Nb: STO substrate into acetone, carrying out vibration cleaning for 3-5 min by using ultrasonic cleaning equipment, cleaning off redundant paraffin adhered to the surface during linear cutting, soaking the Nb: STO substrate into alcohol, carrying out vibration cleaning for 3-5 min by using ultrasonic cleaning equipment, and cleaning off residual acetone. And (3) blowing the cleaned Nb-STO substrate by using nitrogen, and immediately placing the Nb-STO substrate into a deposition cavity of a magnetron sputtering system.
(4) Pumping the air pressure in the deposition chamber to a higher vacuum degree by using a multistage air pumping system formed by combining a mechanical pump and a molecular pump, wherein the vacuum degree is not less than 10-5mbar; then introducing argon/oxygen mixed gas required by film growth into the deposition chamber, wherein Ar/O in the mixed gas2The volume ratio is 1:1, and the air pressure in the cavity is 200 mbar; then, the Nb STO substrate is baked for 10min at 850 ℃ under the pressure of 200mbar, and the attachments on the surface of the Nb STO substrate are removed; then the deposition cavity is vacuumized to ensure that the vacuum degree is not less than 10-5mbar; finally, argon/oxygen mixed gas is slowly introduced, and a mass flow meter is adjusted to the required growth pressure of 0.2 mbar.
(5) After the air pressure is stable, adjusting the position of the target material to ensure that the target material is positioned right above the Nb STO substrate; and adjusting the growth time to realize the growth of the epitaxial film on the Nb: STO substrate.
(6) After the growth is finished, introducing mixed gas to enable the air pressure of the deposition cavity to reach 200mbar, and annealing the sample for 15min under the air pressure; and after the annealing is finished, taking out the sample after the temperature is reduced to the room temperature. Thus, the self-assembled Ba (Hf, Ti) O of the present invention was obtained3:HfO2A nano composite lead-free epitaxial single-layer film.
Example 1
Self-assembled Ba (Hf, Ti) O of this example3:HfO2The preparation method of the nano composite lead-free epitaxial single-layer film comprises the following steps:
(1) firstly, according to the chemical formula BaHf for preparing the thin film0.5Ti0.5O3According to BaHf0.5Ti0.5O3According to the component requirements, respectively weighing corresponding amount of 4-5N-grade BaCO3High purity powder, HfO2High purity powder and TiO2High-purity powder, ball-milling, presintering, granulating, molding and sintering the mixture of the three high-purity powders, and preparing the BaHf powder by adopting the traditional solid-phase ceramic preparation process0.5Ti0.5O3A ceramic target material. In the process of preparing the ceramic target, the sintering temperature is 100-200 ℃ lower than the system phase forming temperature. BaHf (BaHf)0.5Ti0.5O3In the ceramic target material, x is 0.5 which is an experimental value and is adjusted according to the prepared filmAfter SEM spectral analysis testing, the final actual range identified was 0.48-0.54, which in the following expressions is BaHf0.5Ti0.5O3。
(2) The prepared BaHf0.5Ti0.5O3The ceramic target material is firstly polished by sand paper and then is installed in a magnetron sputtering system after the surface of the ceramic target material is cleaned by an air gun, the target distance is set to be 55mm, and the ceramic target material is arranged in argon/oxygen (Ar/O)2) Under the room temperature sputtering environment with the mixed gas of 1/1, firstly, pre-sputtering for 10-12 h, and removing BaHf0.5Ti0.5O3Impurities on the surface of the ceramic target material.
(3) Selecting (001) oriented single crystal Nb SrTiO3The substrate (i.e., Nb: STO substrate) was subjected to film deposition by first cutting the Nb: STO substrate to the desired size, i.e., 2.5 × 5 × 0.5.5 mm, using a wire saw3And then soaking the Nb: STO substrate into acetone, carrying out vibration cleaning for 3-5 min by using ultrasonic cleaning equipment, cleaning off redundant paraffin adhered to the surface during linear cutting, soaking the Nb: STO substrate into alcohol, carrying out vibration cleaning for 3-5 min by using ultrasonic cleaning equipment, and cleaning off residual acetone. And (3) blowing the cleaned Nb-STO substrate by using nitrogen, and immediately placing the Nb-STO substrate into a deposition cavity of a magnetron sputtering system.
(4) Pumping the air pressure in the deposition chamber to a higher vacuum degree by using a multistage air pumping system formed by combining a mechanical pump and a molecular pump, wherein the vacuum degree is not less than 10-5mbar; then introducing argon/oxygen mixed gas required by film growth into the deposition chamber, wherein Ar/O in the mixed gas2The volume ratio is 1:1, and the air pressure in the cavity is 200 mbar; then, the Nb STO substrate is baked for 10min at 850 ℃ under the pressure of 200mbar, and the attachments on the surface of the Nb STO substrate are removed; then the deposition cavity is vacuumized to ensure that the vacuum degree is not less than 10-5mbar; finally, argon/oxygen mixed gas is slowly introduced, and a mass flow meter is adjusted to the required growth pressure of 0.2 mbar.
(5) After the air pressure is stable, adjusting the position of the target material to enable the target material to be positioned right above the substrate; and adjusting the growth time to realize the growth of the epitaxial film on the Nb: STO substrate.
(6) After the growth is finished, introducing mixed gas to enable the air pressure of the deposition cavity to reach 200mbar, and annealing the sample for 15min under the air pressure; and after the annealing is finished, taking out the sample after the temperature is reduced to the room temperature. Thus obtaining the self-assembly nanometer composite lead-free epitaxial single-layer film with the thickness of 400nm (the final practical range is 386.1-429.8 nm).
After the self-assembled nano composite lead-free epitaxial single-layer film of the embodiment is prepared, the self-assembled nano composite lead-free epitaxial single-layer film is firstly subjected to structural test, during the test, a sample growing on a conductive Nb: STO substrate is partially polished, a 100-mesh square platinized gold electrode is selected, and then electron microscope test and electrical property test are carried out.
The test results show that the self-assembled Ba (Hf, Ti) O prepared in this example3:HfO2The nano composite lead-free epitaxial single-layer film has a new structure, the breakdown field strength is as high as 8.71MV/cm, and the energy storage density is 87.05J/cm3And its energy efficiency is maintained at a high level.
The film sample of the embodiment still has excellent energy storage characteristics within the temperature range of-100 ℃ to 250 ℃. At 250 ℃, under the electric field of 4.5MV/cm, the energy storage density is 30.59J/cm3And the energy storage efficiency reaches 80.82%.
The self-assembled Ba (Hf, Ti) O obtained in this example3:HfO2The properties of the nano composite lead-free epitaxial single-layer film are as follows:
the "water wave" structure of this single-layer film can be clearly seen from fig. 1 and 2; fig. 3, 4 and 5 perform X-ray spectral analysis of the different elements of fig. 2. Fig. 3 corresponds to the L layer of Ba element of the single layer film, fig. 4 corresponds to the M layer of Hf element of the single layer film, and fig. 5 corresponds to the K layer of Ti element of the single layer film. The lighter parts in fig. 3 are the parts with more Ba elements, corresponding to the darker parts in fig. 4; the lighter parts in fig. 4 are the parts with a higher Hf element content, corresponding to the darker parts in fig. 3; in fig. 5, the lighter portions are portions having a high Ti element content, and the darker portions are portions having a low Ti element content, i.e., having a high Hf element content, and correspond to fig. 3 and 4.
FIG. 6 shows the self-assembled Ba (Hf, Ti) O of this embodiment3:HfO2The breakdown field strength of the nano composite lead-free epitaxial single-layer film is calculated through Weibull distribution and is 8.71 MV/cm.
FIG. 7 shows the self-assembled Ba (Hf, Ti) O of this embodiment3:HfO2And (3) a relation graph of the energy storage density and the energy efficiency change of the nano composite lead-free epitaxial single-layer film. As can be seen from the figure, the energy storage density reached 87.5J/cm while the energy efficiency was kept high3。
FIG. 8 shows the self-assembled Ba (Hf, Ti) O of this embodiment3:HfO2The energy storage density of the nano composite lead-free epitaxial single-layer film is in a relation of the energy efficiency changing with the temperature from-100 ℃ to 250 ℃ under the condition that an external electric field is 4.5 MV/cm. It can be seen that the self-assembled Ba (Hf, Ti) O of the present example is present in the temperature range of-100 deg.C to 250 deg.C3:HfO2The energy storage density of the nano composite lead-free epitaxial single-layer film reaches 30.59J/cm3Meanwhile, the energy efficiency is kept between 80.8 and 93.1 percent. In summary, the self-assembled Ba (Hf, Ti) O prepared in this example3:HfO2The nano composite lead-free epitaxial single-layer film can keep excellent energy storage characteristics at high temperature.
The BHTO system lead-free epitaxial single-layer energy storage film provided by the invention is a BHTO single-layer film obtained on a substrate by bombarding a target material with plasma by adopting a radio frequency magnetron sputtering technology. The method comprises the steps of firstly, respectively synthesizing BHTO ceramic target materials with different components by adopting high-purity powder and a traditional ceramic solid-phase preparation process, and then, realizing epitaxial growth of a film on a substrate by bombarding the target materials by plasmas under the high-temperature and high-oxygen pressure environment by utilizing a radio frequency magnetron sputtering technology. Under the same thickness, the concentration of the doped components in the film is adjusted to enable the film to have a new structure, the breakdown field strength of the film is improved, and the energy storage density of the film is increased.
In the present invention, BaHfxTi1-xO3The thickness of the layer is 400nm because the optimal value is obtained in the range of the thickness which can be tested by the equipment, and according to the relation between the thickness and the breakdown field intensity of the energy storage density, the energy storage density is higher when the thickness is thickerThe degree and breakdown will be improved. BaHf (BaHf)xTi1-xO3The layer thickness may be from tens of nanometers to several micrometers depending on the actual requirements.
The self-assembly nano composite lead-free epitaxial single-layer film of the BHTO system has the advantages of the following aspects:
(1) the doping technology is adopted to improve the performance of the film, and element doping can improve the maximum polarization intensity or breakdown field intensity. The doped Hf element with a certain concentration grows a new structure in the aspect of structure, greatly improves the breakdown field strength and the energy storage density, and maintains the energy efficiency at a higher level.
(2) The material of the invention does not contain lead, and belongs to an environment-friendly material.

Claims (10)

1. Self-assembled Ba (Hf, Ti) O3:HfO2The nano composite lead-free epitaxial single-layer film is characterized by comprising Nb and SrTiO3Substrate, BaHfxTi1-xO3A layer and an upper electrode, wherein BaHfxTi1-xO3The layer is arranged on Nb SrTiO3The upper electrode is arranged on the upper surface of the substrate and is arranged at BaHfxTi1-xO3The upper surface of the layer, x is more than or equal to 0.44.
2. A self-assembled Ba (Hf, Ti) O according to claim 13:HfO2The nano composite lead-free epitaxial single-layer film is characterized in that Nb is SrTiO3The substrate is (001) oriented single crystal Nb SrTiO3A substrate.
3. A self-assembled Ba (Hf, Ti) O according to claim 13:HfO2The nano composite lead-free epitaxial single-layer film is characterized in that BaHfxTi1-xO3The layer thickness is 50-450 nm.
4. Self-assembled Ba (Hf, Ti) O3:HfO2The preparation method of the nano composite lead-free epitaxial single-layer film is characterized by comprising the following stepsThe process is as follows:
at Nb, SrTiO3Preparation of BaHf on the upper surface of substratexTi1-xO3Layer of BaHfxTi1-xO3Preparing an upper electrode on the upper surface of the layer, wherein x is more than or equal to 0.44.
5. A self-assembled Ba (Hf, Ti) O according to claim 43:HfO2The preparation method of the nano composite lead-free epitaxial single-layer film is characterized in that the BaHfxTi1-xO3The layer thickness is 50-450 nm.
6. A self-assembled Ba (Hf, Ti) O according to claim 53:HfO2The preparation method of the nano composite lead-free epitaxial single-layer film is characterized in that the Nb is SrTiO3Preparation of BaHf on the upper surface of the substrate by magnetron sputteringxTi1-xO3Layer, magnetron sputtering adopts BaHfxTi1-xO3A ceramic target material.
7. A self-assembled Ba (Hf, Ti) O according to claim 63:HfO2The preparation method of the nano composite lead-free epitaxial single-layer film is characterized in that during magnetron sputtering, a deposition cavity of a magnetron sputtering system is firstly vacuumized to ensure that the vacuum degree in the deposition cavity is not less than 10-5mbar; introducing mixed gas formed by mixing argon and oxygen according to the volume ratio of 1/1 into the deposition chamber, wherein the air pressure in the deposition chamber is 200 mbar; then the temperature of the deposition chamber is raised to 850 ℃, and then Nb, SrTiO3Baking the substrate for 10min to remove Nb, SrTiO3Attachment to a substrate surface; then the deposition cavity is vacuumized to ensure that the vacuum degree of the deposition cavity is not less than 10-5mbar; introducing the mixed gas into the deposition cavity to ensure that the required growth pressure in the deposition cavity is 0.2 mbar;
after the air pressure in the deposition cavity is stabilized, adjusting BaHfxTi1-xO3Position and growth time of the ceramic target material in Nb SrTiO3The growth of an epitaxial film with a preset thickness is realized on the substrate, and the sputtering power is 100W;
after the growth is finished, introducing the mixed gas into the deposition cavity to enable the air pressure of the deposition cavity to reach 200mbar, and annealing for 15min under the air pressure; and after the annealing is finished, cooling to room temperature to obtain the self-assembled nano composite lead-free epitaxial single-layer film.
8. A self-assembled Ba (Hf, Ti) O according to claim 63:HfO2The preparation method of the nano composite lead-free epitaxial single-layer film is characterized in that in a magnetron sputtering system, the target distance is 55mm, pre-sputtering is firstly carried out for 10-12 h through mixed gas at room temperature, and impurities on the surface of a target material are removed, wherein the mixed gas is mixed gas of argon and oxygen, and the volume ratio of the argon to the oxygen is 1/1; then carrying out magnetron sputtering.
9. A self-assembled Ba (Hf, Ti) O according to claim 63:HfO2The preparation method of the nano composite lead-free epitaxial single-layer film is characterized in that the BaHfxTi1-xO3The ceramic target material adopts BaCO with the purity level of 4-5N3Powder, HfO2Powder and TiO2Preparing powder; wherein, by BaCO3Powder, HfO2Powder and TiO2Powder preparation of BaHfxTi1-xO3When the ceramic target is used, the sintering temperature is 100-200 ℃ lower than the phase forming temperature of each system.
10. A self-assembled Ba (Hf, Ti) O according to any one of claims 5 to 93:HfO2The preparation method of the nano composite lead-free epitaxial single-layer film is characterized in that Nb is SrTiO3The substrate is (001) oriented single crystal Nb SrTiO3A substrate.
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