CN104478235A - Multiferroic Bi(0.98-x)Sr0.02RExFe0.97Mn0.03O3-CuFe2O4 composite film and preparation method thereof - Google Patents

Multiferroic Bi(0.98-x)Sr0.02RExFe0.97Mn0.03O3-CuFe2O4 composite film and preparation method thereof Download PDF

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CN104478235A
CN104478235A CN201410764963.9A CN201410764963A CN104478235A CN 104478235 A CN104478235 A CN 104478235A CN 201410764963 A CN201410764963 A CN 201410764963A CN 104478235 A CN104478235 A CN 104478235A
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CN104478235B (en
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谈国强
晏霞
任慧君
夏傲
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation

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Abstract

The invention discloses a multiferroic Bi(0.98-x)Sr0.02RExFe0.97Mn0.03O3-CuFe2O4 composite film and a preparation method thereof. The composite film comprises Bi(0.98-x)Sr0.02RExFe0.97Mn0.03O3 crystal films and CuFe2O4 crystal films which are composited together. The preparation method comprises the following steps: firstly, preparing a Bi(0.98-x)Sr0.02RExFe0.97Mn0.03O3 precursor solution and a CuFe2O4 precursor solution respectively; secondly, preparing multiple layers of CuFe2O4 films on a substrate by spin coating, and preparing multiple layers of Bi(0.98-x)Sr0.02RExFe0.97Mn0.03O3 films on the CuFe2O4 films by spin coating to obtain a target product. The equipment requirement is simple, the uniformity of the prepared film is high, the doping amount is easy to control, the ferroelectric and ferromagnetic properties of the film are improved, and the leakage current density of the film is effectively reduced.

Description

A kind of multiferroic Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4composite membrane and preparation method thereof
Technical field
The invention belongs to field of functional materials, relate to multiferroic Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4composite membrane and preparation method thereof.
Background technology
BiFeO 3be a kind of typical single-phase multiferroic perovskite material, at room temperature there is ferroelectricity (T simultaneously c~ 1103k) and ferromegnetism (T n~ 640k).Due to BiFeO 3material has magnetoelectric effect, has formed the research boom of a worldwide single-phase magnetic electric material in recent years.Along with the development of microelectronics, photoelectron and sensor technology, more and more higher to the requirement of material property, ferroelectric membranc, because of its good ferroelectric, the character such as piezoelectricity, dielectric, pyroelectricity, becomes the critical function material that can be widely used in the fields such as microtronics, photoelectronics, integrated optics and microelectromechanical systems.
But, pure phase BiFeO 3there is larger leakage current, the BiFeO that has its source in that leakage conductance exists 3middle existence is unstable, volatile Bi 3+ion, along with Bi 3+the volatilization of ion, sintering process can form Lacking oxygen in the material, and causes Fe 3+fluctuation (the Fe of ion combination valency 3+to Fe 2+ion is changed), produce certain conductance.Lacking oxygen in perovskite material also play the effect of space charge, and the increase of space charge concentration can cause farmland to produce pinning effect.And under the effect of electric field, the displacement of Lacking oxygen also forms leakage current, causes the decline of residual polarization.BiFeO 3leakage current large in material causes him cannot obtain saturated ferroelectric hysteresis loop and its weak ferromagnetism essence, thus limits the practical application of this material.
Summary of the invention
The object of the present invention is to provide a kind of multiferroic Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4composite membrane and preparation method thereof, effectively can reduce BiFeO 3leakage current, improve its ferroelectric and ferromagnetic property simultaneously.
To achieve these goals, the present invention adopts following technical scheme:
A kind of multiferroic Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4composite membrane, comprises the lower membrane and upper layer film that are combined with each other, and wherein lower membrane is CuFe 2o 4crystalline state film, upper layer film is Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3crystalline state film, RE is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, x=0 ~ 0.15.
Described Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3the crystal formation of crystalline state film is tripartite's phase, and space structure group is R3m:R, and unit cell parameters is a=b=c=3.9634, α=β=γ=89.72 °; CuFe 2o 4the crystal formation of crystalline state film is Emission in Cubic, and space structure group is Fd-3m (227).
Described x=0.03 ~ 0.15.
A kind of multiferroic Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4the preparation method of composite membrane, comprises the following steps:
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, adds diacetyl oxide again after stirring, obtains CuFe 2o 4precursor liquid, CuFe 2o 4in precursor liquid, the concentration of Cu ion is 0.15 ~ 0.25mol/L;
Step 2, is dissolved in solvent for 1.03-x:0.02:x:0.97:0.03 by Bismuth trinitrate, strontium nitrate, nitric acid RE, iron nitrate and manganous nitrate in molar ratio, obtains Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3precursor solution, Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3in precursor solution, the total concn of metal ion is 0.25 ~ 0.35mol/L, RE is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, x=0 ~ 0.15, and solvent is the mixed solution of ethylene glycol monomethyl ether and acetic anhydride;
Step 3, adopts spin-coating method spin coating CuFe on FTO/glass substrate 2o 4precursor liquid, obtains CuFe 2o 4film, CuFe 2o 4film toasts to obtain dry film after even glue at 180 ~ 210 DEG C, then anneals in atmosphere at 580 ~ 600 DEG C, obtains crystalline state CuFe 2o 4film;
Step 4, treats crystalline state CuFe 2o 4after film cooling, at crystalline state CuFe 2o 4repeating step 3 on film, until reach desired thickness, obtains CuFe 2o 4crystalline state film;
Step 5, at CuFe 2o 4spin coating Bi on crystalline state film 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3precursor solution, obtains Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3film, Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3film toasts to obtain dry film after even glue at 180 ~ 210 DEG C, then anneals in atmosphere at 540 ~ 550 DEG C, obtains crystalline state Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3film;
Step 6, treats crystalline state Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3after film cooling, at crystalline state Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3repeating step 5 on film, until reach desired thickness, obtains multiferroic Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4composite membrane.
Described CuFe 2o 4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5 ~ 3.5): 1;
In described solvent, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5 ~ 3.5): 1.
Described step 3 is first cleaned FTO/glass substrate before carrying out, then radiation treatment under ultraviolet light, makes FTO/glass substrate surface reach atomic cleanliness degree, then spin coating CuFe 2o 4precursor liquid;
Described step 5 before carrying out first to CuFe 2o 4crystalline state film carries out UV-irradiation process, makes CuFe 2o 4crystalline state film surface reaches atomic cleanliness degree, then spin coating Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3precursor solution.
Even glue rotating speed in described step 3 and step 5 is 3800 ~ 4100r/min, and spin coating time is 12 ~ 15s.
Baking time in described step 3 and step 5 after even glue is 8 ~ 12min.
In described step 3, annealing time is 7 ~ 9min; In step 5, annealing time is 8 ~ 12min.
Crystalline state CuFe 2o 4the number of plies of film is 4 ~ 8 layers, crystalline state Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3the number of plies of film is 8 ~ 12 layers.
Relative to prior art, beneficial effect of the present invention is:
1. multiferroic Bi provided by the invention 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4the preparation method of composite membrane, selects lanthanon rare earth elements RE and alkaline earth element Sr to carry out BiFeO 3a position doping, select transient metal Mn carry out BiFeO 3b position doping, because the ionic radius of rare earth elements RE is comparable to Bi 3+, the radius of Mn is less than Fe 3+, after doping, rare earth element and Mn can be melting into into lattice admittedly, and can make the approximate bismuth ferrite crystal lattices distortion in perovskite structure originally, structural aberration aggravates, simultaneously due to Sr 2+to Bi 3+further substitute, and Mn element appraising at the current rate in annealing process, the volatilization of the Bi that can effectively draw up, reduces Fe in film 2+with the content of Lacking oxygen, thus the polarizability of enhanced film under extra electric field, discharge its macroscopic magnetization simultaneously, improve ferroelectricity and the ferromegnetism of film.But due to BiFeO 3itself there is the essence of weak magnetic, so the present invention is in conjunction with CuFe 2o 4film meets with it.CuFe 2o 4have very strong magnetic, its magnetic coercive field is very little again simultaneously, is desirable matrix material.The present invention is by alkaline earth element Sr, rare earth elements RE and transition metal Mn element codoped BiFeO 3, and in conjunction with ferromagnetism CuFe 2o 4, formed and there is superior ferroelectric and ferromagnetic Bi simultaneously 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4laminated film.
2. at present for the preparation of BiFeO 3the method of film has a lot, as chemical Vapor deposition process (CVD), magnetron sputtering method (rf magnetron sputtering), deposition of metal organic method (MOD), metal-organic chemical vapor deposition equipment method (MOCVD), liquid phase deposition (LPD), molecular beam epitaxy (MBE), pulsed laser deposition (PLD), sol-gel method (Sol-Gel) etc.Compare additive method, Sol-Gel method due to equipment simple, reaction is easily carried out, temperature of reaction is lower, easy to operate, be suitable for preparing film on large surface and surface in irregular shape, easily realize the Uniform Doped on molecular level, and the advantage such as chemical composition controllable precise and be widely used for preparing ferroelectric material.Sol-gel method is adopted in the present invention, by rare earth elements RE, alkaline earth element Sr and transition metal Mn element codoped, simultaneously composite Cu Fe 2o 4film, Bi prepared by FTO substrate 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4composite membrane.Present device requires simple, and experiment condition easily reaches, and doping easily controls, by doping and CuFe 2o 4the compound of film can increase substantially the ferroelectric of film and ferromagnetic property, obtained Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4composite membrane good uniformity, has lower leakage current density and higher anti-breakdown electric field, possesses comparatively excellent ferroelectric and ferromegnetism simultaneously.
3. multiferroic Bi provided by the invention 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4composite membrane, being originally similar to doped with rare-earth elements RE, alkaline earth element Sr and transition metal Mn in the bismuth ferrite crystal lattices in perovskite structure, make bismuth ferrite crystal lattices distortion, structural aberration aggravates, and reduces Fe in film simultaneously 2+with the content of Lacking oxygen, thus the polarizability of enhanced film under extra electric field, discharge its macroscopic magnetization simultaneously, improve ferroelectric properties and the ferromagnetic property of film, reduce the leakage current density of film, and in conjunction with the CuFe of ferromagnetism, low coercive field 2o 4film, makes multiferroic Bi of the present invention 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4composite membrane has excellent ferroelectric properties and ferromagnetic property simultaneously.
Accompanying drawing explanation
Fig. 1 is Bi prepared by the present invention 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3the XRD figure of crystalline state film;
Fig. 2 is Bi prepared by the present invention 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3the Raman spectrogram of crystalline state film;
Fig. 3 is Bi prepared by the present invention 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3the SEM figure of crystalline state film;
Fig. 4 is CuFe prepared by the present invention 2o 4the XRD figure of crystalline state film.
Embodiment
Below in conjunction with accompanying drawing and the preferred embodiment of the invention, the present invention is described in further detail.
Multiferroic Bi provided by the invention 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4composite membrane, comprises the lower membrane and upper layer film that are combined with each other, and wherein lower membrane is CuFe 2o 4crystalline state film, its crystal formation is Emission in Cubic, and space structure group is Fd-3m (227); Upper layer film is Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3crystalline state film, its crystal formation is tripartite's phase, and space structure group is R3m:R, unit cell parameters is a=b=c=3.9634, α=β=γ=89.72 °, and RE is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, x=0 ~ 0.15, preferred x=0.03 ~ 0.15.
Embodiment 1
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, after stirring 30min, then adds diacetyl oxide, obtains the stable CuFe that Cu ionic concn is 0.15mol/L 2o 4precursor liquid, CuFe 2o 4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1;
Step 2, is dissolved in (x=0, Bismuth trinitrate excessive 5%) in solvent for 1.03:0.02:0.97:0.03 in molar ratio by Bismuth trinitrate, strontium nitrate, iron nitrate and manganous nitrate, the total concn obtaining metal ion is the stable Bi of 0.25mol/L 0.98sr 0.02fe 0.97mn 0.03o 3precursor solution; Solvent is volume ratio is the ethylene glycol monomethyl ether of 3:1 and the mixed solution of acetic anhydride;
Step 3, selects FTO/glass substrate to be substrate, the FTO/glass substrate of well cutting is placed in washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrate after each ultrasonic cleaning 10min, finally dry up with nitrogen.Then FTO/glass substrate is put into 60 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Again the FTO/glass substrate of cleaning is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating CuFe on FTO/glass substrate 2o 4precursor liquid, preparation CuFe 2o 4film, even glue rotating speed is 3800r/min, and spin coating time is 15s, after even cementing bundle, toasts 12min and obtain dry film at 180 DEG C of temperature, then the 9min that anneals layer by layer in air at 580 DEG C of temperature, obtains crystalline state CuFe 2o 4film;
Step 4, treats crystalline state CuFe 2o 4after film cooling, at crystalline state CuFe 2o 4repeating step 3 on film, repeats 3 times, obtains CuFe 2o 4crystalline state film;
Step 5, by CuFe 2o 4crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min, makes its surface reach atomic cleanliness degree; Again at CuFe 2o 4spin coating Bi on crystalline state film 0.98sr 0.02fe 0.97mn 0.03o 3precursor solution, even glue rotating speed is 3800r/min, and spin coating time is 15s, after the even cementing bundle of even glue, toasts 12min and obtain dry film at 180 DEG C, then the 12min that anneals layer by layer in air at 540 DEG C, obtains crystalline state Bi 0.98sr 0.02fe 0.97mn 0.03o 3film;
Step 6, treats crystalline state Bi 0.98sr 0.02fe 0.97mn 0.03o 3after film cooling, at crystalline state Bi 0.98sr 0.02fe 0.97mn 0.03o 3repeating step 5 on film, repeats 7 times, obtains multiferroic Bi 0.98sr 0.02fe 0.97mn 0.03o 3-CuFe 2o 4composite membrane.
Embodiment 2
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, after stirring 30min, then adds diacetyl oxide, obtains the stable CuFe that Cu ionic concn is 0.25mol/L 2o 4precursor liquid, CuFe 2o 4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 2.5:1;
Step 2, Bismuth trinitrate, strontium nitrate, cerous nitrate, iron nitrate and manganous nitrate are dissolved in (RE=Ce in solvent for 1:0.02:0.03:0.97:0.03 in molar ratio, x=0.03, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.35mol/L 0.95sr 0.02ce 0.03fe 0.97mn 0.03o 3precursor solution; Solvent is volume ratio is the ethylene glycol monomethyl ether of 2.5:1 and the mixed solution of acetic anhydride;
Step 3, selects FTO/glass substrate to be substrate, the FTO/glass substrate of well cutting is placed in washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrate after each ultrasonic cleaning 10min, finally dry up with nitrogen.Then FTO/glass substrate is put into 60 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Again the FTO/glass substrate of cleaning is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating CuFe on FTO/glass substrate 2o 4precursor liquid, preparation CuFe 2o 4film, even glue rotating speed is 3900r/min, and spin coating time is 14s, after even cementing bundle, toasts 11min and obtain dry film at 190 DEG C of temperature, then the 8min that anneals layer by layer in air at 590 DEG C of temperature, obtains crystalline state CuFe 2o 4film;
Step 4, treats crystalline state CuFe 2o 4after film cooling, at crystalline state CuFe 2o 4repeating step 3 on film, repeats 7 times, obtains CuFe 2o 4crystalline state film;
Step 5, by CuFe 2o 4crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min, makes its surface reach atomic cleanliness degree; Again at CuFe 2o 4spin coating Bi on crystalline state film 0.95sr 0.02ce 0.03fe 0.97mn 0.03o 3precursor solution, even glue rotating speed is 3900r/min, and spin coating time is 14s, after the even cementing bundle of even glue, toasts 11min and obtain dry film at 190 DEG C, then the 10min that anneals layer by layer in air at 545 DEG C, obtains crystalline state Bi 0.95sr 0.02ce 0.03fe 0.97mn 0.03o 3film;
Step 6, treats crystalline state Bi 0.95sr 0.02ce 0.03fe 0.97mn 0.03o 3after film cooling, at crystalline state Bi 0.95sr 0.02ce 0.03fe 0.97mn 0.03o 3repeating step 5 on film, repeats 8 times, obtains multiferroic Bi 0.95sr 0.02ce 0.03fe 0.97mn 0.03o 3-CuFe 2o 4composite membrane.
Embodiment 3
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, after stirring 30min, then adds diacetyl oxide, obtains the stable CuFe that Cu ionic concn is 0.22mol/L 2o 4precursor liquid, CuFe 2o 4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3.5:1;
Step 2, Bismuth trinitrate, strontium nitrate, neodymium nitrate, iron nitrate and manganous nitrate are dissolved in (RE=Nd in solvent for 0.98:0.02:0.05:0.97:0.03 in molar ratio, x=0.05, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.28mol/L 0.93sr 0.02nd 0.05fe 0.97mn 0.03o 3precursor solution; Solvent is volume ratio is the ethylene glycol monomethyl ether of 3.5:1 and the mixed solution of acetic anhydride;
Step 3, selects FTO/glass substrate to be substrate, the FTO/glass substrate of well cutting is placed in washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrate after each ultrasonic cleaning 10min, finally dry up with nitrogen.Then FTO/glass substrate is put into 60 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Again the FTO/glass substrate of cleaning is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating CuFe on FTO/glass substrate 2o 4precursor liquid, preparation CuFe 2o 4film, even glue rotating speed is 4100r/min, and spin coating time is 12s, after even cementing bundle, toasts 8min and obtain dry film at 210 DEG C of temperature, then the 8.5min that anneals layer by layer in air at 585 DEG C of temperature, obtains crystalline state CuFe 2o 4film;
Step 4, treats crystalline state CuFe 2o 4after film cooling, at crystalline state CuFe 2o 4repeating step 3 on film, repeats 4 times, obtains CuFe 2o 4crystalline state film;
Step 5, by CuFe 2o 4crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min, makes its surface reach atomic cleanliness degree; Again at CuFe 2o 4spin coating Bi on crystalline state film 0.93sr 0.02nd 0.05fe 0.97mn 0.03o 3precursor solution, even glue rotating speed is 4100r/min, and spin coating time is 12s, after the even cementing bundle of even glue, toasts 8min and obtain dry film at 210 DEG C, then the 11min that anneals layer by layer in air at 542 DEG C, obtains crystalline state Bi 0.93sr 0.02nd 0.05fe 0.97mn 0.03o 3film;
Step 6, treats crystalline state Bi 0.93sr 0.02nd 0.05fe 0.97mn 0.03o 3after film cooling, at crystalline state Bi 0.93sr 0.02nd 0.05fe 0.97mn 0.03o 3repeating step 5 on film, repeats 10 times, obtains multiferroic Bi 0.93sr 0.02nd 0.05fe 0.97mn 0.03o 3-CuFe 2o 4composite membrane.
Embodiment 4
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, after stirring 30min, then adds diacetyl oxide, obtains the stable CuFe that Cu ionic concn is 0.2mol/L 2o 4precursor liquid, CuFe 2o 4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1;
Step 2, Bismuth trinitrate, strontium nitrate, praseodymium nitrate, iron nitrate and manganous nitrate are dissolved in (RE=Pr in solvent for 0.88:0.02:0.15:0.97:0.03 in molar ratio, x=0.15, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.3mol/L 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3precursor solution; Solvent is volume ratio is the ethylene glycol monomethyl ether of 3:1 and the mixed solution of acetic anhydride;
Step 3, selects FTO/glass substrate to be substrate, the FTO/glass substrate of well cutting is placed in washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrate after each ultrasonic cleaning 10min, finally dry up with nitrogen.Then FTO/glass substrate is put into 60 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Again the FTO/glass substrate of cleaning is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating CuFe on FTO/glass substrate 2o 4precursor liquid, preparation CuFe 2o 4film, even glue rotating speed is 4000r/min, and spin coating time is 13s, after even cementing bundle, toasts 9min and obtain dry film at 200 DEG C of temperature, then the 7min that anneals layer by layer in air at 600 DEG C of temperature, obtains crystalline state CuFe 2o 4film;
Step 4, treats crystalline state CuFe 2o 4after film cooling, at crystalline state CuFe 2o 4repeating step 3 on film, repeats 5 times, obtains CuFe 2o 4crystalline state film;
Step 5, by CuFe 2o 4crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min, makes its surface reach atomic cleanliness degree; Again at CuFe 2o 4spin coating Bi on crystalline state film 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3precursor solution, even glue rotating speed is 4000r/min, and spin coating time is 13s, after the even cementing bundle of even glue, toasts 9min and obtain dry film at 200 DEG C, then the 8min that anneals layer by layer in air at 550 DEG C, obtains crystalline state Bi 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3film;
Step 6, treats crystalline state Bi 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3after film cooling, at crystalline state Bi 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3repeating step 5 on film, repeats 9 times, obtains multiferroic Bi 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3-CuFe 2o 4composite membrane.
XRD is adopted to test multiferroic Bi 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3-CuFe 2o 4the thing phase composite structure of composite membrane, FE-SEM tests multiferroic Bi 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3-CuFe 2o 4the pattern of composite film surface.
Get multiferroic Bi prepared by the present invention 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3-CuFe 2o 4the upper strata Bi of composite membrane 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3crystalline state film carries out XRD test, and as shown in Figure 1, Fig. 1 and PDF72-2112 standard card coincide result, as can be seen from the figure, and Bi 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3crystalline state film is the perovskite structure of distortion, does not occur dephasign, and be the R3m:R space structure group of tripartite's phase, its unit cell parameters is a=b=c=3.9634, α=β=γ=89.72 °.
Fig. 2 is Bi 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3the Raman spectrogram of crystalline state film, with pure phase BiFeO 3film is compared and is had a very large change; Three strongest ones peak in pure phase film is occur A at low frequency 1vibrations mould, and at Bi 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3in crystalline state film, A 1the peak broadening of mould and intensity obviously reduce, and this is mainly because Pr and Sr substitutes a part of Bi 3+ion, has disperseed Bi-O key to cause; Be positioned at 625cm -1place E-9 mould peak by force significantly strengthen and higher than A 1mould, this is attributable to Mn 2+ion substitution part Fe 3+ion, Bi 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3crystalline state film defines [(Fe, Mn) O by Jahn-Teller effect 6] octahedra.
Get multiferroic Bi prepared by the present invention 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3-CuFe 2o 4the upper strata Bi of composite membrane 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3crystalline state film carries out SEM test, observes its surface topography, and result as shown in Figure 3, shows the Bi that the present invention obtains 0.83sr 0.02pr 0.15fe 0.97mn 0.03o 3crystalline state film grain development is good, size uniform, surface compact, smooth.
Fig. 4 is the CuFe that the present invention obtains 2o 4the XRD figure of crystalline state film.The CuFe that can obtain pure phase is shown by Fig. 4 2o 4film, it is Fd-3m (227) the space structure group of Emission in Cubic.
Embodiment 5
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, after stirring 30min, then adds diacetyl oxide, obtains the stable CuFe that Cu ionic concn is 0.18mol/L 2o 4precursor liquid, CuFe 2o 4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 2.8:1;
Step 2, Bismuth trinitrate, strontium nitrate, samaric nitrate, iron nitrate and manganous nitrate are dissolved in (RE=Sm in solvent for 0.93:0.02:0.1:0.97:0.03 in molar ratio, x=0.1, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.32mol/L 0.88sr 0.02sm 0.1fe 0.97mn 0.03o 3precursor solution; Solvent is volume ratio is the ethylene glycol monomethyl ether of 2.8:1 and the mixed solution of acetic anhydride;
Step 3, selects FTO/glass substrate to be substrate, the FTO/glass substrate of well cutting is placed in washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrate after each ultrasonic cleaning 10min, finally dry up with nitrogen.Then FTO/glass substrate is put into 60 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Again the FTO/glass substrate of cleaning is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating CuFe on FTO/glass substrate 2o 4precursor liquid, preparation CuFe 2o 4film, even glue rotating speed is 3850r/min, and spin coating time is 14.5s, after even cementing bundle, toasts 11.5min and obtain dry film at 185 DEG C of temperature, then the 7.5min that anneals layer by layer in air at 595 DEG C of temperature, obtains crystalline state CuFe 2o 4film;
Step 4, treats crystalline state CuFe 2o 4after film cooling, at crystalline state CuFe 2o 4repeating step 3 on film, repeats 6 times, obtains CuFe 2o 4crystalline state film;
Step 5, by CuFe 2o 4crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min, makes its surface reach atomic cleanliness degree; Again at CuFe 2o 4spin coating Bi on crystalline state film 0.88sr 0.02sm 0.1fe 0.97mn 0.03o 3precursor solution, even glue rotating speed is 3850r/min, and spin coating time is 14.5s, after the even cementing bundle of even glue, toasts 11.5min and obtain dry film at 185 DEG C, then the 9min that anneals layer by layer in air at 548 DEG C, obtains crystalline state Bi 0.88sr 0.02sm 0.1fe 0.97mn 0.03o 3film;
Step 6, treats crystalline state Bi 0.88sr 0.02sm 0.1fe 0.97mn 0.03o 3after film cooling, at crystalline state Bi 0.88sr 0.02sm 0.1fe 0.97mn 0.03o 3repeating step 5 on film, repeats 12 times, obtains multiferroic Bi 0.88sr 0.02sm 0.1fe 0.97mn 0.03o 3-CuFe 2o 4composite membrane.
Embodiment 6
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, after stirring 30min, then adds diacetyl oxide, obtains the stable CuFe that Cu ionic concn is 0.17mol/L 2o 4precursor liquid, CuFe 2o 4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3.2:1;
Step 2, Bismuth trinitrate, strontium nitrate, europium nitrate, iron nitrate and manganous nitrate are dissolved in (RE=Eu in solvent for 0.95:0.02:0.08:0.97:0.03 in molar ratio, x=0.08, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.27mol/L 0.9sr 0.02eu 0.08fe 0.97mn 0.03o 3precursor solution; Solvent is volume ratio is the ethylene glycol monomethyl ether of 3.2:1 and the mixed solution of acetic anhydride;
Step 3, selects FTO/glass substrate to be substrate, the FTO/glass substrate of well cutting is placed in washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrate after each ultrasonic cleaning 10min, finally dry up with nitrogen.Then FTO/glass substrate is put into 60 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Again the FTO/glass substrate of cleaning is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating CuFe on FTO/glass substrate 2o 4precursor liquid, preparation CuFe 2o 4film, even glue rotating speed is 3950r/min, and spin coating time is 13.5s, after even cementing bundle, toasts 10min and obtain dry film at 195 DEG C of temperature, then the 8min that anneals layer by layer in air at 592 DEG C of temperature, obtains crystalline state CuFe 2o 4film;
Step 4, treats crystalline state CuFe 2o 4after film cooling, at crystalline state CuFe 2o 4repeating step 3 on film, repeats 5 times, obtains CuFe 2o 4crystalline state film;
Step 5, by CuFe 2o 4crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min, makes its surface reach atomic cleanliness degree; Again at CuFe 2o 4spin coating Bi on crystalline state film 0.9sr 0.02eu 0.08fe 0.97mn 0.03o 3precursor solution, even glue rotating speed is 3950r/min, and spin coating time is 13.5s, after the even cementing bundle of even glue, toasts 10min and obtain dry film at 195 DEG C, then the 8min that anneals layer by layer in air at 550 DEG C, obtains crystalline state Bi 0.9sr 0.02eu 0.08fe 0.97mn 0.03o 3film;
Step 6, treats crystalline state Bi 0.9sr 0.02eu 0.08fe 0.97mn 0.03o 3after film cooling, at crystalline state Bi 0.9sr 0.02eu 0.08fe 0.97mn 0.03o 3repeating step 5 on film, repeats 9 times, obtains multiferroic Bi 0.9sr 0.02eu 0.08fe 0.97mn 0.03o 3-CuFe 2o 4composite membrane.
Embodiment 7
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, after stirring 30min, then adds diacetyl oxide, obtains the stable CuFe that Cu ionic concn is 0.23mol/L 2o 4precursor liquid, CuFe 2o 4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1;
Step 2, Bismuth trinitrate, strontium nitrate, Gadolinium trinitrate, iron nitrate and manganous nitrate are dissolved in (RE=Gd in solvent for 0.91:0.02:0.12:0.97:0.03 in molar ratio, x=0.12, Bismuth trinitrate excessive 5%), the total concn obtaining metal ion is the stable Bi of 0.33mol/L 0.86sr 0.02gd 0.12fe 0.97mn 0.03o 3precursor solution; Solvent is volume ratio is the ethylene glycol monomethyl ether of 3:1 and the mixed solution of acetic anhydride;
Step 3, selects FTO/glass substrate to be substrate, the FTO/glass substrate of well cutting is placed in washing composition, acetone, ethanol ultrasonic cleaning successively, with a large amount of distilled water flushing substrate after each ultrasonic cleaning 10min, finally dry up with nitrogen.Then FTO/glass substrate is put into 60 DEG C of baking oven baking 5min, take out and leave standstill to room temperature.Again the FTO/glass substrate of cleaning is placed in ultraviolet radiation instrument and irradiates 40min, substrate surface is reached " atomic cleanliness degree ".Adopt spin-coating method spin coating CuFe on FTO/glass substrate 2o 4precursor liquid, preparation CuFe 2o 4film, even glue rotating speed is 4050r/min, and spin coating time is 12.5s, after even cementing bundle, toasts 8.5min and obtain dry film at 205 DEG C of temperature, then the 7min that anneals layer by layer in air at 598 DEG C of temperature, obtains crystalline state CuFe 2o 4film;
Step 4, treats crystalline state CuFe 2o 4after film cooling, at crystalline state CuFe 2o 4repeating step 3 on film, repeats 6 times, obtains CuFe 2o 4crystalline state film;
Step 5, by CuFe 2o 4crystalline state film is placed in ultraviolet radiation instrument and irradiates 40min, makes its surface reach atomic cleanliness degree; Again at CuFe 2o 4spin coating Bi on crystalline state film 0.86sr 0.02gd 0.12fe 0.97mn 0.03o 3precursor solution, even glue rotating speed is 4050r/min, and spin coating time is 12.5s, after the even cementing bundle of even glue, toasts 8.5min and obtain dry film at 205 DEG C, then the 10min that anneals layer by layer in air at 545 DEG C, obtains crystalline state Bi 0.86sr 0.02gd 0.12fe 0.97mn 0.03o 3film;
Step 6, treats crystalline state Bi 0.86sr 0.02gd 0.12fe 0.97mn 0.03o 3after film cooling, at crystalline state Bi 0.86sr 0.02gd 0.12fe 0.97mn 0.03o 3repeating step 5 on film, repeats 10 times, obtains multiferroic Bi 0.86sr 0.02gd 0.12fe 0.97mn 0.03o 3-CuFe 2o 4composite membrane.
RE in the nitric acid RE used in above-described embodiment also can be La, Tb, Dy, Ho, Er, Tm, Yb or Lu.
The multiferroic Bi that also can obtain in the present invention 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4au electrode prepared by composite film surface ion sputtering, then 295 DEG C are carried out electrode anneal process.Multiferroic Bi prepared by the present invention is tested again with Agilent2901A 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4the leakage current density of composite membrane, with the ferroelectric test system and test multiferroic Bi of TF2000 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4the ferroelectric properties of composite membrane, with the multiferroic Bi of superconductive quantum interference magnetic tester system testing invention preparation 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4the ferromagnetic property of composite membrane.
Present device requires simple, and experiment condition easily reaches, and the uniformity of film of preparation is better, and doping easily controls, by the suitable selection of doping, and CuFe 2o 4the interpolation of laminated magnetic film, can increase substantially the ferroelectric properties of film, reduces the leakage current density of film, improves the ferromegnetism of film simultaneously.
Above said content is in conjunction with concrete preferred implementation further description made for the present invention, it not whole or unique embodiment, the conversion of those of ordinary skill in the art by reading specification sheets of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.

Claims (10)

1. a multiferroic Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4composite membrane, is characterized in that: comprise the lower membrane and upper layer film that are combined with each other, and wherein lower membrane is CuFe 2o 4crystalline state film, upper layer film is Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3crystalline state film, RE is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, x=0 ~ 0.15.
2. multiferroic Bi according to claim 1 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4composite membrane, is characterized in that: described Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3the crystal formation of crystalline state film is tripartite's phase, and space structure group is R3m:R, and unit cell parameters is a=b=c=3.9634, α=β=γ=89.72 °; CuFe 2o 4the crystal formation of crystalline state film is Emission in Cubic, and space structure group is Fd-3m (227).
3. multiferroic Bi according to claim 1 and 2 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4composite membrane, is characterized in that: described x=0.03 ~ 0.15.
4. a multiferroic Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4the preparation method of composite membrane, is characterized in that, comprises the following steps:
Step 1, by iron nitrate and cupric nitrate in molar ratio for 1:2 is dissolved in ethylene glycol monomethyl ether, adds diacetyl oxide again after stirring, obtains CuFe 2o 4precursor liquid, CuFe 2o 4in precursor liquid, the concentration of Cu ion is 0.15 ~ 0.25mol/L;
Step 2, is dissolved in solvent for 1.03-x:0.02:x:0.97:0.03 by Bismuth trinitrate, strontium nitrate, nitric acid RE, iron nitrate and manganous nitrate in molar ratio, obtains Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3precursor solution, Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3in precursor solution, the total concn of metal ion is 0.25 ~ 0.35mol/L, RE is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, x=0 ~ 0.15, and solvent is the mixed solution of ethylene glycol monomethyl ether and acetic anhydride;
Step 3, adopts spin-coating method spin coating CuFe on FTO/glass substrate 2o 4precursor liquid, obtains CuFe 2o 4film, CuFe 2o 4film toasts to obtain dry film after even glue at 180 ~ 210 DEG C, then anneals in atmosphere at 580 ~ 600 DEG C, obtains crystalline state CuFe 2o 4film;
Step 4, treats crystalline state CuFe 2o 4after film cooling, at crystalline state CuFe 2o 4repeating step 3 on film, until reach desired thickness, obtains CuFe 2o 4crystalline state film;
Step 5, at CuFe 2o 4spin coating Bi on crystalline state film 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3precursor solution, obtains Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3film, Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3film toasts to obtain dry film after even glue at 180 ~ 210 DEG C, then anneals in atmosphere at 540 ~ 550 DEG C, obtains crystalline state Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3film;
Step 6, treats crystalline state Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3after film cooling, at crystalline state Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3repeating step 5 on film, until reach desired thickness, obtains multiferroic Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4composite membrane.
5. multiferroic Bi according to claim 4 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4the preparation method of composite membrane, is characterized in that: described CuFe 2o 4in precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5 ~ 3.5): 1;
In described solvent, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (2.5 ~ 3.5): 1.
6. multiferroic Bi according to claim 4 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4the preparation method of composite membrane, is characterized in that: described step 3 is first cleaned FTO/glass substrate before carrying out, then radiation treatment under ultraviolet light, makes FTO/glass substrate surface reach atomic cleanliness degree, then spin coating CuFe 2o 4precursor liquid;
Described step 5 before carrying out first to CuFe 2o 4crystalline state film carries out UV-irradiation process, makes CuFe 2o 4crystalline state film surface reaches atomic cleanliness degree, then spin coating Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3precursor solution.
7. multiferroic Bi according to claim 4 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4the preparation method of composite membrane, is characterized in that: the even glue rotating speed in described step 3 and step 5 is 3800 ~ 4100r/min, and spin coating time is 12 ~ 15s.
8. multiferroic Bi according to claim 4 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4the preparation method of composite membrane, is characterized in that: the baking time in described step 3 and step 5 after even glue is 8 ~ 12min.
9. multiferroic Bi according to claim 4 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4the preparation method of composite membrane, is characterized in that: in described step 3, annealing time is 7 ~ 9min; In step 5, annealing time is 8 ~ 12min.
10. multiferroic Bi according to claim 4 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3-CuFe 2o 4the preparation method of composite membrane, is characterized in that: crystalline state CuFe 2o 4the number of plies of film is 4 ~ 8 layers, crystalline state Bi 0.98-xsr 0.02rE xfe 0.97mn 0.03o 3the number of plies of film is 8 ~ 12 layers.
CN201410764963.9A 2014-12-11 2014-12-11 A kind of multiferroic Bi0.98‑xSr0.02RExFe0.97Mn0.03O3‑CuFe2O4Composite membrane and preparation method thereof Active CN104478235B (en)

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CN109336406A (en) * 2018-09-18 2019-02-15 陕西科技大学 A kind of the BGSFMC/CFGO laminated film and preparation method of symmetrical rectangular ferroelectric hysteresis loop
CN109336406B (en) * 2018-09-18 2021-08-10 陕西科技大学 BGSFMC/CFGO composite film with symmetrical rectangular hysteresis loop and preparation method thereof
CN112206781A (en) * 2020-10-22 2021-01-12 广州绿然环保新材料科技有限公司 Catalyst for purifying waste gas and preparation method thereof
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