CN109487220A - A kind of antiferroelectric laminated film of nickel oxide-lead zirconates and preparation method thereof - Google Patents
A kind of antiferroelectric laminated film of nickel oxide-lead zirconates and preparation method thereof Download PDFInfo
- Publication number
- CN109487220A CN109487220A CN201811432139.8A CN201811432139A CN109487220A CN 109487220 A CN109487220 A CN 109487220A CN 201811432139 A CN201811432139 A CN 201811432139A CN 109487220 A CN109487220 A CN 109487220A
- Authority
- CN
- China
- Prior art keywords
- nickel oxide
- antiferroelectric
- lead
- lead zirconates
- film material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
-
- 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
- C23C14/088—Oxides of the type ABO3 with A representing alkali, alkaline earth metal or Pb and B representing a refractory or rare earth metal
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Semiconductor Memories (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
The present invention provides a kind of antiferroelectric laminated films of nickel oxide-lead zirconates and preparation method thereof, the antiferroelectric composite film material of nickel oxide-lead zirconates includes zirconic acid thin film lead and nickel oxide, the nickel oxide is in nanometer rod structure and is distributed in the lead zirconates, and the volume of the nickel oxide is the 1 ~ 20% of the composite film material；The antiferroelectric composite film material of nickel oxide-lead zirconates is using made from pulsed laser deposition.The preparation process of composite film material of the present invention is simple, diameter, distribution, the thickness controllable precise of nickel oxide nano column, gained nickel oxide-antiferroelectric laminated film of lead zirconates has both good energy storage density, ferroelectric properties and dielectric properties, effectively increase the comprehensive performance of composite film material, and production cost is low, has a extensive future.
Description
Technical field
The present invention relates to a kind of reverse ferroelectric film membrane materials, and it is antiferroelectric multiple to concretely relate to a kind of nickel oxide-lead zirconates
Close film and preparation method thereof.
Background technique
In recent years, as global metadata demand increases year by year, energy storage material becomes grinding for field of functional materials with device
Study carefully hot spot.Dielectric energy storage material with high energy storage density and high reliability has not in fields such as high energy pulse power technologies
Alternative application.Currently, commercial electric energy storage and energy transport equipment mainly include fuel cell, common batteries, electrification
Learn capacitor and dielectric capacitor etc..Although traditional fuel cell energy density is higher, due to its internal carrier
Movement slowly, causes its power density very low, to limit application of the fuel cell in high-power component.Dielectric capacitance
Although device has quite high power density, there is important application in numerous areas, its energy storage density compares tradition
Energy storage device is much smaller, thus how to improve energy density critical issue that be it urgently to be resolved in energy storage device application it
One.
In recent years the study found that some antiferroelectric materials with double ferroelectric hysteresis loop features are keeping height as dielectric
While power density, the energy storage density of dielectric substance can also be effectively improved, for the wide using opening of antiferroelectric
Prospect: on the one hand, the non-linear relation of polarization intensity and electric field strength when using an antiferroelectric ferroelectric phase transition can make storage
It can capacitor and voltage regulating element；On the other hand, make energy converter etc. using the bulk effect of an antiferroelectric ferroelectric phase transition, red
Outer detection, parameter amplification, high pressure generation etc. also have a possibility that application.
Dipole of the antiferroelectric materials in certain temperature range in adjacent ions on line is in arranged anti-parallel, macroscopically certainly
Sending out polarization intensity is zero, the material of no ferroelectric hysteresis loop.They are a kind of reversed polarity crystal, are changed by the opposite antiferroelectric phase of para-electric
When, two adjacent cells of high-temperature-phase generate antiparallel electric dipole and become sublattice, and the two constitutes a volume and increases
One times of new structure cell, also, the ferroelectric state free energy of its free energy and the crystal is very close in extra electric field and thermal stress induction
Under, antiferroelectric phase will be to ferroelectricity phase transition, so that double ferroelectric hysteresis loops can be observed.Its application principle is as follows: antiferroelectric ceramics exists
Under sufficiently large electric field strength effect, the ferroelectric phase of temporary stable state can be changed into the antiferroelectric phase of stable state, this is a storage electricity
The process of energy；When electric field strength is reduced or cancels electric field, the ferroelectric phase of temporary stable state becomes the antiferroelectric phase of stable state again, this is
The process of one release electric energy.High-power storage capacitor is prepared using this process of storage electric energy and release electric energy
Device can use this process also to make non-linear element.Meanwhile the transition process of antiferroelectric phase and ferroelectric phase is necessarily adjoint
There is the variation of volume, in other words, when phase transformation will cause the variation of element linear size, this process can facilitate electric energy and machinery again
Conversion between energy can make antiferroelectric energy converter using the conversion between this energy.Utilize anti-ferroelectric thin film used manufactured height
Pressure, high power energy-storage capacitor have many advantages, such as it is small in size, it is light-weight high with energy storage density, play it in modern high technology
Increasingly important role and become the hot spot studied both at home and abroad.
Typical antiferroelectric material includes lead zirconates (PbZrO3), rubidium nitrate (RbNO3), ammonium dihydrogen phosphate
(NH4H2PO4), ammonium sulfate (NH4)2SO4), ammonium hydrogen sulfate (NH4HSO4), sodium niobate (NaNbO3), hafnium lead plumbate (PbHfO3), acid iodide
Ammonium (NH4IO3), tungstic acid (WO3) and deuterated salt etc., wherein the lead zirconates based antiferroelectric material with perovskite structure is
One kind is widely used, studies antiferroelectric energy-accumulating medium material that is more, most having development potentiality.However, research achievement table now
Bright, the anti-ferroelectric thin film used iron electric polarization of pure lead zirconates is smaller and energy storage density is lower, is not able to satisfy the requirement of practical application.Cause
This, how to further increase the anti-ferroelectric thin film used energy storage density of lead zirconates is to realize it in the member electricity such as capacitor or energy converter
Widely applied top priority in sub- device.
Summary of the invention
An object of the present invention is to provide a kind of antiferroelectric composite film material of nickel oxide-lead zirconates, existing to solve
Zirconic acid lead material iron electric polarization is smaller and the lower problem of energy storage density.
The second object of the present invention is to provide a kind of preparation method of antiferroelectric laminated film of nickel oxide-lead zirconates, to adopt
Ferroelectricity and the excellent antiferroelectric composite film material of energy-storage property is prepared with cost-effective method.
An object of the present invention is achieved in that
A kind of antiferroelectric composite film material of nickel oxide-lead zirconates comprising lead zirconates and nickel oxide, the nickel oxide are in nanometer
It rod structure and is distributed in the zirconic acid thin film lead, the volume of the nickel oxide accounts for the 1 ~ 20% of the composite film material.
The composite film material with a thickness of 130 ~ 160 nm.
The iron electric polarization intensity of the composite film material is 36 μ C/cm2~91 μC/cm2。
The energy storage intensity of the composite film material is 7.5 J/cm3~25 J/cm3。
The dielectric constant of the composite film material is 275 ~ 1175.
The second object of the present invention is to what is be achieved:
A kind of preparation method of the antiferroelectric composite film material of nickel oxide-lead zirconates comprising following steps:
(a) prepare nickel oxide target and lead zirconates target, the nickel oxide target and the lead zirconates target are respectively placed at
It is spare in the settling chamber of pulse laser depositing device；
(b) to Nb:SrTiO3Substrate is cleaned, is pre-processed, its surface topography TiO is made2Step, it is dry, it is placed on
In the settling chamber of pulse laser depositing device；
(c) the lead zirconates target is first bombarded with laser 1 ~ 7 second using pulsed laser deposition, deposits zirconic acid on the substrate
Thin film lead, then nickel oxide target 10 ~ 20 seconds described in laser bombardment, the deposited oxide nickel on the zirconic acid thin film lead；
(d) it repeats step (c) 30 ~ 60 times, the antiferroelectric laminated film of nickel oxide-lead zirconates can be obtained.
In step (a), the nickel oxide target and lead zirconates target are commercially available, and the preparation of solid state powder sintering process can also be used
It obtains.
The method that nickel oxide target is prepared using solid state powder sintering process are as follows: by nickel oxide powder compression moulding, then exist
800 °C of sintering 30h, can be obtained the nickel oxide target of pure phase.
The method that lead zirconates target is prepared using solid state powder sintering process are as follows: by lead oxide and Zirconium powder according to mole
Than Pb: Zr=1: 1 mixing, after compression moulding, burning is buried under 1350 °C 30 hours, the lead zirconates target of pure phase can be obtained.
In step (b), to Nb:SrTiO3Substrate carries out pretreated method are as follows: respectively that substrate is molten in acetone and alcohol
Each 20 min of ultrasonic cleaning in liquid, and by the Nb:SrTiO after being dried with nitrogen3The pH value that substrate is put into dilute HF acid is 4
It is impregnated 30 seconds in fluorination ammonia spirit, taking-up, which is put into tubular annealing furnace, calcines 120min, and obtaining surface topography is TiO2Step
Substrate.Preferably, the TiO2The width of step is 100 ~ 200 nm.
It is TiO by surface topography in step (b)2The substrate of step is placed in the settling chamber of pulse laser depositing device,
750 °C are warming up to, 30 min is kept the temperature, is made annealing treatment.
In step (c), when being deposited using pulsed laser deposition, laser energy is 1.5 J/cm2, target and substrate
The distance between be 4 cm；Depositing temperature is 650 DEG C, and partial pressure of oxygen is 0.1 Torr.
In step (c), the time with laser bombardment nickel oxide target is preferably 10 ~ 15 seconds, preferably 10 seconds, 15 seconds or 20
Second, more preferable 10 seconds.
In step (d), it is preferable that by the preparation-obtained antiferroelectric laminated film of nickel oxide-lead zirconates in an atmosphere
Then pressure, 30 min of in-situ annealing are cooled to room temperature with the rate of 2 °C/min.
The antiferroelectric laminated film of nickel oxide-lead zirconates is made using pulsed laser deposition in the present invention, and wherein nickel oxide is in
Nanometer column structure, is evenly distributed in zirconic acid thin film lead, and the diameter of nickel oxide nano column, distribution, thickness controllable precise, institute
It obtains the antiferroelectric laminated film of nickel oxide-lead zirconates and has both good energy storage density, ferroelectric properties and dielectric properties, effectively increase
The comprehensive performance of composite film material, the highest energy storage density and maximum saturation polarization intensity of laminated film are up to 25 J/cm3With
90 μC/cm2, zirconic acid thin film lead is compared, energy storage density and saturated polarization improve 3 times.
Composite film material preparation process of the present invention is simple, and method economical and effective, production cost is low, and gained is antiferroelectric compound
Thin-film material can be used for making high power pulsed ion beams energy-storage capacitor, supercapacitor, straightline capacitor, current source, micro electronmechanical set
It is standby and its mutually switch etc. fields, it is industrialized and functionization is of great significance, is had a extensive future.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the antiferroelectric composite film material of nickel oxide-lead zirconates.
Fig. 2 is the atomic force microscope of the antiferroelectric composite film material of nickel oxide-lead zirconates prepared by embodiment 1 ~ 5
Figure.
Fig. 3 is 2 institute of the antiferroelectric composite film material of nickel oxide-lead zirconates prepared by embodiment 1,3,5,7 and comparative example
The X-ray diffractogram of lead zirconates thin-film material is prepared, wherein P-1, P-2, P-3, P-4, P-5, P-6 and P-7 respectively indicate oxidation
The composite film material that the percent by volume of nickel is 1%, 3%, 5%, 10%, 13%, 15%, 20%, P-0 are indicated prepared by comparative example 2
Pure zirconic acid thin film lead.
Fig. 4 is the low power transmission electron microscopy of the antiferroelectric composite film material of nickel oxide-lead zirconates prepared by embodiment 4
Mirror photo.
Fig. 5 is the high power transmission electron microscopy of the antiferroelectric composite film material of nickel oxide-lead zirconates prepared by embodiment 4
Mirror photo.
Fig. 6 ~ 12 are that the antiferroelectric composite film material of nickel oxide-lead zirconates prepared by embodiment 1 ~ 6 and comparative example 2 are made
The polarization intensity of standby zirconic acid thin film lead and the relational graph of voltage.
Figure 13 is that the antiferroelectric composite film material of nickel oxide-lead zirconates prepared by embodiment 1 ~ 6 and comparative example 2 are made
The calculated energy storage density of iron electric polarization of standby zirconic acid thin film lead with nickel oxide percent by volume trend chart.
Figure 14 is that the antiferroelectric composite film material of nickel oxide-lead zirconates prepared by embodiment 1 ~ 7 and comparative example 1,2 are made
The dielectric properties datagram of standby nickel oxide and zirconic acid thin film lead.
Specific embodiment
Below with reference to embodiment, the present invention is further elaborated, and following embodiments are only as explanation, not with any
Mode limits the present invention.
Lead oxide (PbO) used, zirconium oxide (ZrO in embodiment2) and the purity of nickel oxide (NiO) material powder be
99.99%, agents useful for same is that analysis is pure or chemical pure and commercially available or pass through side well known within the skill of those ordinarily skilled
Method preparation.Following embodiments realize the purpose of the present invention.
Embodiment 1
As shown in Figure 1, a kind of antiferroelectric composite film material of nickel oxide-lead zirconates, a kind of nickel oxide-lead zirconates are antiferroelectric compound
Thin-film material comprising be grown in Nb:SrTiO3(001) the zirconic acid thin film lead and nickel oxide film on monocrystal substrate, wherein
The percent by volume of NiO is 1%, PbZrO3Percent by volume be 99%.
The preparation method of the antiferroelectric composite film material includes the following steps:
Lead zirconates target is prepared using solid state powder sintering process: by zirconium oxide and lead oxide powder according to molar ratio Pb: Zr=
1: 1 mixing after compression moulding, buries burning 30 hours in 1200 °C of Muffle furnaces, obtains the lead zirconates target of pure phase.
Nickel oxide target is prepared using solid state powder sintering process: nickel oxide powder is put into crucible respectively 500
DEG C, 600 DEG C, be sintered at 700 DEG C and 800 DEG C, sintering 20 hours, are sintered 30 hours at 800 DEG C after compression moulding, obtain every time
To the nickel oxide target of pure phase.
Prepared lead zirconates target and nickel oxide target are respectively placed in the settling chamber of pulse laser depositing device,
It is spare.
To Nb:SrTiO3(001) monocrystal substrate (being abbreviated as Nb:STO (001)) is surpassed in alcohol and acetone respectively
Sound wave clean 20 min, after being dried with nitrogen, dilute HF acid pH value be 4 fluorination ammonia spirit in impregnates 30 seconds, taking-up
It is put into tubular annealing furnace and calcines 120 min, obtain TiO2Then gained substrate is placed in pulse and swashed by the substrate of surface topography
In the settling chamber of light deposition equipment, 750 °C are warming up to, 30 min is kept the temperature, is made annealing treatment.
Depositing temperature is set as 600 ~ 700 °C, preferably 650 DEG C, laser energy is 1.5 J/cm2, between target and substrate
Distance be 4 cm, partial pressure of oxygen be 0.1 Torr.It is first bombarded with laser lead zirconates target 7 seconds, one is sporadically deposited on substrate
Layer zirconic acid thin film lead；Then it uses laser bombardment nickel oxide target 10 seconds, the gap for not growing zirconic acid thin film lead on substrate is raw
Long one layer of nickel oxide film.It repeats aforementioned laser to bombard process 30 times, lead zirconates and nickel oxide be all during each laser bombardment
Epitaxial growth on film before each leisure, moves in circles and nickel oxide-lead zirconates nanometer column laminated film can be obtained.
Finally, at one atm, 30 min of in-situ annealing, and be cooled to room temperature with the rate of 2 °C/min
Obtaining percent by volume shared by NiO is 1%, with a thickness of nickel oxide-antiferroelectric laminated film of lead zirconates nanometer column of 160 nm,
Its structural schematic diagram is as shown in Figure 1, atomic force surface topography is as shown in Figure 2.
Gained sample is tested for the property using X-ray diffraction, transmission electron microscope, gained X-ray diffraction spectrogram
As shown in figure 3, transmitted electron spectrogram, as shown in Fig. 4 ~ 5, iron polarization and energy storage density data are as shown in Fig. 6 and 13, dielectric properties
Characterize data is as shown in figure 14.From figure 3, it can be seen that nickel oxide-antiferroelectric laminated film of lead zirconates nanometer column is along (001)
The crystal orientation epitaxial growth in face.From Fig. 4 ~ 5 as can be seen that the film is a nanometer column structure, the boundary of nickel oxide and lead zirconates
Face is high-visible.Meanwhile from Fig. 7,13 ~ 14 as can be seen that the gained antiferroelectric laminated film iron of nickel oxide-lead zirconates nanometer column
Electric polarization and energy storage density increased.
Embodiment 2
A kind of antiferroelectric composite film material of nickel oxide-lead zirconates comprising Nb:SrTiO3(001) monocrystal substrate, lead zirconates are thin
Film and nickel oxide film, wherein the percent by volume of NiO is 3%, PbZrO3Percent by volume be 97%.
The preparation method of the antiferroelectric composite film material of this nanometer of column is substantially the same manner as Example 1, unlike, with swash
Light first bombards lead zirconates target 6 seconds, and lead zirconates film is deposited on substrate；Then it uses laser bombardment nickel oxide target 10 seconds,
Deposited oxide nickel film on zirconic acid thin film lead.It repeats aforementioned laser and bombards process 35 times, at one atm, in-situ annealing 30
Then min is cooled to room temperature with the rate of 2 °C/min, it is 3%, with a thickness of 155 nm that percent by volume shared by NiO, which can be obtained,
The antiferroelectric laminated film of nickel oxide-lead zirconates.Gained nickel oxide-lead zirconates antiferroelectric laminated film iron electric polarization and energy storage
Density increased.
Embodiment 3
A kind of antiferroelectric composite film material of nickel oxide-lead zirconates comprising Nb:SrTiO3(001) monocrystal substrate, lead zirconates are thin
Film and nickel oxide film, wherein the percent by volume of NiO is 5%, PbZrO3Percent by volume be 95%.
The preparation method of the antiferroelectric composite film material of this nanometer of column is substantially the same manner as Example 1, unlike, with swash
Light first bombards lead zirconates target 5 seconds, and lead zirconates film is deposited on substrate；Then it uses laser bombardment nickel oxide target 10 seconds,
Deposited oxide nickel film on zirconic acid thin film lead.It repeats aforementioned laser and bombards process 40 times, at one atm, in-situ annealing 30
Then min is cooled to room temperature with the rate of 2 °C/min, it is 5%, with a thickness of 150 nm that percent by volume shared by NiO, which can be obtained,
Nickel oxide-antiferroelectric laminated film of lead zirconates nanometer column of energy storage density enhancing.
Gained sample is tested for the property, from the X-ray diffraction spectrogram (Fig. 3) of gained sample as can be seen that gained oxygen
Change the antiferroelectric laminated film sample of nickel-lead zirconates nanometer column along the crystal orientation epitaxial growth in (001) face, and with embodiment 1
It compares, with the increase of nickel oxide content, diffraction maximum is significantly deviated towards more high angle；Gained nickel oxide-lead zirconates is antiferroelectric
The iron electric polarization performance data and energy storage density data of laminated film are respectively as shown in Fig. 9 and 13, it can be seen from the figure that ferroelectricity
Performance is greatly improved, energy storage density is higher；Gained nickel oxide-lead zirconates antiferroelectric laminated film dielectric properties characterize number
According to as shown in figure 14, dielectric constant compared to properties of sample obtained by Examples 1 and 2 be improved significantly.
Embodiment 4
A kind of antiferroelectric composite film material of nickel oxide-lead zirconates comprising Nb:SrTiO3(001) monocrystal substrate, lead zirconates are thin
Film and nickel oxide film, wherein the percent by volume of NiO is 10%, PbZrO3Percent by volume be 90%.
The preparation method of the antiferroelectric composite film material of this nanometer of column is substantially the same manner as Example 1, unlike, with swash
Light first bombards lead zirconates target 4 seconds, and lead zirconates film is deposited on substrate；Then it uses laser bombardment nickel oxide target 10 seconds,
Deposited oxide nickel film on zirconic acid thin film lead.It repeats aforementioned laser and bombards process 45 times, at one atm, in-situ annealing 30
Then min is cooled to room temperature with the rate of 2 °C/min, it is 10%, with a thickness of 145 that percent by volume shared by NiO, which can be obtained,
The antiferroelectric laminated film of nickel oxide-lead zirconates of nm energy storage density enhancing.
The antiferroelectric laminated film of gained is tested for the property, it can from the X-ray diffraction spectrogram (Fig. 3) of gained sample
Out, compared with embodiment 1 and 3, with the increase of nickel oxide content, diffraction maximum is deviated towards more high angle；Gained is antiferroelectric multiple
The transmission electron microscope data of film are closed as shown in Fig. 4 ~ 5, nickel oxide exists in the form of nano-pillar in zirconic acid thin film lead, with oxygen
Change the increase of nickel content, the quantity and diameter of nickel oxide nano column increase with it；Gained nickel oxide-anti-the iron of lead zirconates nanometer column
The iron electric polarization performance data and energy storage density data of electric laminated film respectively as shown in Figure 10 and 13, it can be seen from the figure that
Its iron electric polarization and energy storage density can be improved；Gained nickel oxide-lead zirconates antiferroelectric laminated film dielectric properties characterization
Data are as shown in figure 14, dielectric constant compared to embodiment 1,2 and 3 gained properties of sample be improved significantly.
Embodiment 5
A kind of antiferroelectric composite film material of nickel oxide-lead zirconates comprising Nb:SrTiO3(001) monocrystal substrate, lead zirconates are thin
Film and nickel oxide film, wherein the percent by volume of NiO is 13%, PbZrO3Percent by volume be 87%.
The preparation method of the antiferroelectric composite film material of this nanometer of column is substantially the same manner as Example 1, unlike, with swash
Light first bombards lead zirconates target 3 seconds, and lead zirconates film is deposited on substrate；Then it uses laser bombardment nickel oxide target 10 seconds,
Deposited oxide nickel film on zirconic acid thin film lead.It repeats aforementioned laser and bombards process 45 times, at one atm, in-situ annealing 30
Then min is cooled to room temperature with the rate of 2 °C/min, it is 13%, with a thickness of 140 that percent by volume shared by NiO, which can be obtained,
Nickel oxide-antiferroelectric laminated film of lead zirconates nanometer column of nm energy storage density enhancing.
Gained sample is tested for the property, from the X-ray diffraction spectrogram (Fig. 3) of gained sample as can be seen that gained oxygen
Change the antiferroelectric laminated film sample of nickel-lead zirconates nanometer column along the crystal orientation epitaxial growth in (001) face, with embodiment 1 and 3
It compares, with the increase of nickel oxide content, diffraction maximum is deviated towards more high angle；Gained nickel oxide-lead zirconates nanometer column is anti-
Iron electric polarization performance data and energy storage density the data difference of ferro-electricity compound film as shown in figures 11 and 13, can from figure
Out, iron electric polarization performance is declined compared to embodiment 4；Gained nickel oxide-lead zirconates antiferroelectric laminated film dielectric
Performance characterization data is as shown in figure 14, and the dielectric constant of gained laminated film sample is gradually reduced, but performance is still better than pure
Zirconic acid thin film lead.
Embodiment 6
A kind of antiferroelectric composite film material of nickel oxide-lead zirconates comprising Nb:SrTiO3(001) monocrystal substrate, lead zirconates are thin
Film and nickel oxide film, wherein the percent by volume of NiO is 15%, PbZrO3Percent by volume be 85%.
The preparation method of the antiferroelectric composite film material of this nanometer of column is substantially the same manner as Example 1, unlike, with swash
Light first bombards lead zirconates target 2 seconds, and lead zirconates film is deposited on substrate；Then it uses laser bombardment nickel oxide target 10 seconds,
Deposited oxide nickel film on zirconic acid thin film lead.It repeats aforementioned laser and bombards process 50 times, at one atm, in-situ annealing 30
Then min is cooled to room temperature with the rate of 2 °C/min, it is 15%, with a thickness of 135 that percent by volume shared by NiO, which can be obtained,
Nickel oxide-antiferroelectric laminated film of lead zirconates nanometer column of nm energy storage density enhancing.
Gained sample is tested for the property, from the X-ray diffraction spectrogram (Fig. 3) of gained sample as can be seen that and implementing
Example 1 ~ 5 is compared, and with the increase of nickel oxide content, diffraction maximum is deviated towards more high angle；Gained nickel oxide-lead zirconates nano-pillar
Iron electric polarization performance data and energy storage density the data difference of the antiferroelectric laminated film of shape are as shown in Figures 12 and 13, can be with from figure
Find out, under the antiferroelectric laminated film iron electric polarization performance of gained nickel oxide-lead zirconates nanometer column is significant compared to embodiment 1 ~ 5
Drop；Gained nickel oxide-lead zirconates antiferroelectric laminated film dielectric properties characterize data is as shown in figure 14, gained laminated film sample
The dielectric constant of product reduces.
Embodiment 7
A kind of antiferroelectric composite film material of nickel oxide-lead zirconates comprising Nb:SrTiO3(001) monocrystal substrate, lead zirconates are thin
Film and nickel oxide film, wherein the percent by volume of NiO is 20%, PbZrO3Percent by volume be 80%.
The preparation method of the antiferroelectric composite film material of this nanometer of column is substantially the same manner as Example 1, unlike, with swash
Light first bombards lead zirconates target 1 second, and lead zirconates film is deposited on substrate；Then it uses laser bombardment nickel oxide target 10 seconds,
Deposited oxide nickel film on zirconic acid thin film lead.It repeats aforementioned laser and bombards process 60 times, at one atm, in-situ annealing 30
Then min is cooled to room temperature with the rate of 2 °C/min, it is 20%, with a thickness of 130 that percent by volume shared by NiO, which can be obtained,
Nickel oxide-antiferroelectric laminated film of lead zirconates nanometer column of nm energy storage density enhancing.
Gained sample is tested for the property, from the X-ray diffraction spectrogram (Fig. 3) of gained sample as can be seen that gained oxygen
Change the antiferroelectric laminated film sample of nickel-lead zirconates nanometer column along the crystal orientation epitaxial growth in (001) face, with embodiment 1 ~ 6
It compares, with the increase of nickel oxide content, diffraction maximum is significantly deviated towards more high angle；Gained nickel oxide-lead zirconates nano-pillar
The antiferroelectric laminated film dielectric properties characterize data of shape is as shown in figure 14, it can be seen from the figure that with nickel oxide volume ratio
Increase, dielectric properties are promoted in low-frequency range compared to pure zirconic acid thin film lead, but high band is then remarkably decreased, property
It can be deteriorated.
Comparative example 1
By Nb:SrTiO3(001) substrate is respectively in acetone and dehydrated alcohol (content 99.7%), deionized water (conductivity 0.1
Us/cm 20 min of microwave ultrasound in)；After being dried with nitrogen, impregnated 30 seconds in the fluorination ammonia spirit of dilute HF acid, taking-up is put
Enter and calcine 120 min in tubular annealing furnace, obtains TiO2The substrate of surface topography；By treated, substrate is placed in pulse laser
In the settling chamber of depositing device, heated under vacuum keeps the temperature 30 minutes to 750 °C and anneals；Set nickel oxide target and substrate it
Between distance be 4cm, adjust the energy of pulse laser and the position of focus lamp, it is ensured that energy density of the laser bombardment on target
For 1.5 J/cm2, under conditions of depositing temperature is 650 °C, partial pressure of oxygen is 0.1 Torr, in Nb:SrTiO3 (001) substrate
Upper deposition obtains the pure nickel film (NiO) with a thickness of 150 nm.
The dielectric properties of gained nickel oxide film (NiO) are characterized, as shown in figure 14, it can be seen from the figure that institute
The dielectric properties of nickel oxide film are obtained with the increase of frequency, is gradually reduced, falls below the 480 of high frequency from the 1175 of low frequency.
Comparative example 2
By Nb:SrTiO3(001) substrate is respectively in acetone and dehydrated alcohol (volume content 99.7%), deionized water (conductivity
For 20 min of microwave ultrasound in 0.1 us/cm)；After being dried with nitrogen, impregnated 30 seconds in the fluorination ammonia spirit of dilute HF acid,
Taking-up, which is put into tubular annealing furnace, calcines 120 min, obtains TiO2The substrate of surface topography；By treated, substrate is placed in arteries and veins
In the settling chamber of impulse light deposition equipment, heated under vacuum keeps the temperature 30 minutes to 750 °C and anneals；Set lead zirconates target with
The distance between substrate is 4 cm, adjusts the energy of pulse laser and the position of focus lamp, it is ensured that laser bombardment is on target
Energy density is 1.5 J/cm2, under conditions of depositing temperature is 650 °C, partial pressure of oxygen is 0.1 Torr, in Nb:SrTiO3
(001) it sinks on substrate and obtains the pure zirconic acid thin film lead (PZO) with a thickness of 150 nm.
Iron electric polarization and energy storage density performance characterization, data such as Fig. 6 and 13 institute are carried out to gained zirconic acid thin film lead (PZO)
Show；Its dielectric properties is characterized, data are as shown in figure 14.
As can be seen from Figure 13, the energy storage density of pure lead zirconates thin-film material is 7.5 J/cm3, more excellent to receive with this comparison
The energy storage density that the antiferroelectric laminated film sample of meter Zhu Zhuan (NiO percent by volume is 5%) calculates it according to iron electric polarization is reachable
25 J/cm3；The saturated polarization of pure lead zirconates thin-film material is 36 μ C/cm2, with this comparison, more excellent nanometer column is antiferroelectric
Saturated polarization in laminated film sample (NiO percent by volume is 5%) is up to 91 μ C/cm2.It follows that nickel oxide-
The ferroelectric properties of lead zirconates nanometer column composite antiferroelectric thin-film material can be regulated and controled by controlling the content of NiO, and pure
Zirconic acid thin film lead compare, iron electric polarization and energy storage density all improve 3 times or so, and performance significantly increases.
Figure 14 is it is found that nickel oxide prepared by embodiment 1 ~ 7-lead zirconates nanometer column composite antiferroelectric thin-film material and right
Pure nickel prepared by ratio 1,2, lead zirconates the film sample relative dielectric constant in 100 kHZ is respectively 438,510,589,
740,572,532,430,373 and 1020.The relative dielectric constant of pure barium titanate thin-film material is 373, in contrast to this, more excellent oxygen
The relative dielectric constant for changing Ni-Ti acid barium nanometer column laminated film (NiO percent by volume be 10%) is improved by about one time,
Dielectric properties significantly improve.
The preparation process and feature of above-described embodiment and comparative example only to illustrate the invention, its object is to allow be familiar with this
The personage of technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.All
According to equivalent change or modification made by spirit of the invention, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of antiferroelectric composite film material of nickel oxide-lead zirconates comprising zirconic acid thin film lead and nickel oxide, the nickel oxide
In nanometer rod structure and be distributed in the zirconic acid thin film lead, the volume of the nickel oxide account for the composite film material 1 ~
20%。
2. the antiferroelectric composite film material of nickel oxide-lead zirconates according to claim 1, which is characterized in that described compound
Thin-film material with a thickness of 130 ~ 160nm.
3. a kind of preparation method of the antiferroelectric composite film material of nickel oxide-lead zirconates described in claim 1, feature exist
In including the following steps:
(a) prepare nickel oxide target and lead zirconates target, the nickel oxide target and the lead zirconates target are respectively placed at
It is spare in the settling chamber of pulse laser depositing device；
(b) to Nb:SrTiO3Substrate is cleaned, is pre-processed, its surface topography TiO is made2Step, it is dry, it is placed on arteries and veins
In the settling chamber of impulse light deposition equipment；
(c) the lead zirconates target is first bombarded with laser 1 ~ 7 second using pulsed laser deposition, deposits zirconic acid on the substrate
Thin film lead, then nickel oxide target 10 ~ 20 seconds described in laser bombardment, the deposited oxide nickel on the zirconic acid thin film lead；
(d) it repeats step (c) 30 ~ 60 times, the antiferroelectric laminated film of nickel oxide-lead zirconates can be obtained.
4. the preparation method of the antiferroelectric composite film material of nickel oxide-lead zirconates according to claim 3, feature exist
In in step (b), to Nb:SrTiO3Substrate carries out pretreated method are as follows: respectively surpasses substrate in acetone and alcoholic solution
Sound wave cleans each 20 min, and by the Nb:SrTiO after being dried with nitrogen3Substrate is put into the ammonium fluoride that the pH value of dilute HF acid is 4
It is impregnated 30 seconds in aqueous solution, taking-up, which is put into tubular annealing furnace, calcines 120min, and obtaining surface topography is TiO2The substrate of step.
5. the preparation method of the antiferroelectric composite film material of nickel oxide-lead zirconates according to claim 3, feature exist
In, in step (b), by surface topography be TiO2The substrate of step is placed in the settling chamber of pulse laser depositing device, heating
To 750 °C, 30 minutes are kept the temperature, is made annealing treatment.
6. the preparation method of the antiferroelectric composite film material of nickel oxide-lead zirconates according to claim 3, feature exist
In in step (c), when being deposited using pulsed laser deposition, laser energy is 1.5 J/cm2, between target and substrate
Distance be 4 cm；Depositing temperature is 650 DEG C, and partial pressure of oxygen is 0.1 Torr.
7. the preparation method of the antiferroelectric composite film material of nickel oxide-lead zirconates according to claim 3, feature exist
In in step (d), it is preferable that at one atm by the preparation-obtained antiferroelectric laminated film of nickel oxide-lead zirconates,
30 min of in-situ annealing, is then cooled to room temperature with the rate of 2 °C/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811432139.8A CN109487220B (en) | 2018-11-28 | 2018-11-28 | Nickel oxide-lead zirconate antiferroelectric composite film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811432139.8A CN109487220B (en) | 2018-11-28 | 2018-11-28 | Nickel oxide-lead zirconate antiferroelectric composite film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109487220A true CN109487220A (en) | 2019-03-19 |
| CN109487220B CN109487220B (en) | 2020-12-29 |
Family
ID=65697970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811432139.8A Active CN109487220B (en) | 2018-11-28 | 2018-11-28 | Nickel oxide-lead zirconate antiferroelectric composite film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109487220B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113314342A (en) * | 2021-04-15 | 2021-08-27 | 华南师范大学 | Method for improving energy storage density of dielectric film capacitor and dielectric film capacitor |
| CN114592237A (en) * | 2022-03-11 | 2022-06-07 | 淮北师范大学 | Preparation method of epitaxial film |
| CN115747726A (en) * | 2022-11-24 | 2023-03-07 | 中国科学院深圳先进技术研究院 | High-flux component gradient antiferroelectric-based thin film material and preparation method thereof |
| CN115747726B (en) * | 2022-11-24 | 2024-05-31 | 中国科学院深圳先进技术研究院 | High flux component gradient antiferroelectric base film material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004988B (en) * | 2013-02-26 | 2016-06-15 | 中国科学院金属研究所 | A kind of lanthanum strontium manganese oxygen-nickel oxide nano composite film material and preparation method thereof |
| CN105986227A (en) * | 2015-02-16 | 2016-10-05 | 中国科学院金属研究所 | LCMO-NiO nanocomposite film material and preparation method thereof |
| CN107604310A (en) * | 2017-08-02 | 2018-01-19 | 河北大学 | A kind of nickel oxide barium titanate nano composite ferroelectric film material and preparation method and application |
-
2018
- 2018-11-28 CN CN201811432139.8A patent/CN109487220B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004988B (en) * | 2013-02-26 | 2016-06-15 | 中国科学院金属研究所 | A kind of lanthanum strontium manganese oxygen-nickel oxide nano composite film material and preparation method thereof |
| CN105986227A (en) * | 2015-02-16 | 2016-10-05 | 中国科学院金属研究所 | LCMO-NiO nanocomposite film material and preparation method thereof |
| CN107604310A (en) * | 2017-08-02 | 2018-01-19 | 河北大学 | A kind of nickel oxide barium titanate nano composite ferroelectric film material and preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 周国香等: "锆酸铅的反铁电相对称性研究", 《人工晶体学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113314342A (en) * | 2021-04-15 | 2021-08-27 | 华南师范大学 | Method for improving energy storage density of dielectric film capacitor and dielectric film capacitor |
| CN113314342B (en) * | 2021-04-15 | 2022-08-05 | 华南师范大学 | Method for improving energy storage density of dielectric film capacitor and dielectric film capacitor |
| CN114592237A (en) * | 2022-03-11 | 2022-06-07 | 淮北师范大学 | Preparation method of epitaxial film |
| CN115747726A (en) * | 2022-11-24 | 2023-03-07 | 中国科学院深圳先进技术研究院 | High-flux component gradient antiferroelectric-based thin film material and preparation method thereof |
| CN115747726B (en) * | 2022-11-24 | 2024-05-31 | 中国科学院深圳先进技术研究院 | High flux component gradient antiferroelectric base film material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109487220B (en) | 2020-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Review of lead-free Bi-based dielectric ceramics for energy-storage applications | |
| CN101665915B (en) | Method for preparing bismuth ferric film material | |
| Luo et al. | Growth and characterization of lead-free piezoelectric BaZr0. 2Ti0. 8O3–Ba0. 7Ca0. 3TiO3 thin films on Si substrates | |
| Chen et al. | Significant enhancement of energy storage density and polarization in self-assembled PbZrO 3: NiO nano-columnar composite films | |
| CN107604310B (en) | A kind of nickel oxide-barium titanate nano composite ferroelectric film material and the preparation method and application thereof | |
| CN109487220A (en) | A kind of antiferroelectric laminated film of nickel oxide-lead zirconates and preparation method thereof | |
| Sun et al. | Composition-driven inverse-to-conventional transformation of electrocaloric effect and large energy storage density in strontium modified Ba (Zr 0.1 Ti 0.9) O 3 thin films | |
| Abbas et al. | High energy storage efficiency and thermal stability of A‐site‐deficient and 110‐textured BaTiO3–BiScO3 thin films | |
| CN110527952A (en) | A kind of barium titanate/nickel acid lanthanum ferroelectric superlattice material and preparation method thereof | |
| Gao et al. | Softening of antiferroelectric order in a novel PbZrO3-based solid solution for energy storage | |
| Craciun et al. | Pulsed laser deposition: fundamentals, applications, and perspectives | |
| CN106591781A (en) | Improvement method for interface dead layer of ultrathin lanthanum-strontium-manganese oxide film | |
| CN110863184B (en) | Wide-working-temperature lead-free epitaxial film and preparation method thereof | |
| CN110937925A (en) | Bismuth ferrite-based thin film with high polarization strength and large strain characteristic and preparation method thereof | |
| Guo et al. | Epitaxial growth of bronze phase titanium dioxide by molecular beam epitaxy | |
| CN109797367A (en) | A kind of lead zirconate titanate/nickel oxide ferroelectric superlattice material and preparation method thereof | |
| CN106854748A (en) | A kind of lead zirconate titanate/barium titanate ferroelectric superlattice material and preparation method thereof | |
| CN110643948A (en) | Strontium titanate/ruthenate strontium ferroelectric superlattice thin film material and preparation method thereof | |
| CN102719793A (en) | Lead strontium titanate ferroelectric thin film with high tuning rate and preparation method thereof | |
| Yazawa et al. | Composition dependence of crystal structure and electrical properties for epitaxial films of Bi (Zn1/2Ti1/2) O3–BiFeO3 solid solution system | |
| Zhou et al. | Structure and ferroelectric properties of ferroelectromagnetic YMnO3 thin films prepared by pulsed laser depositon | |
| KR20150042011A (en) | Preparation method of a film comprising nanowires, the film comprising nanowires and a thin film battery conprsing the same | |
| JP4465461B2 (en) | Method for producing perovskite oxide epitaxial thin films | |
| Yu et al. | Preparation, structure, and properties of 0.3 Pb (Zn1/3Nb2/3) O3-0.7 PbTiO3 thin films on LaNiO3/YSZ/Si substrates | |
| CN107794497B (en) | Preparation method of A-phase or B-phase vanadium dioxide film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |