CN105845316A - Spinel type Zn<1-x>Ni<x>Fe<2>O<4> paramagnetic and ferromagnetic thin film and preparation method therefor - Google Patents

Spinel type Zn<1-x>Ni<x>Fe<2>O<4> paramagnetic and ferromagnetic thin film and preparation method therefor Download PDF

Info

Publication number
CN105845316A
CN105845316A CN201610187622.9A CN201610187622A CN105845316A CN 105845316 A CN105845316 A CN 105845316A CN 201610187622 A CN201610187622 A CN 201610187622A CN 105845316 A CN105845316 A CN 105845316A
Authority
CN
China
Prior art keywords
thin film
spinel
paramagnetism
type
ferromagnetic
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.)
Pending
Application number
CN201610187622.9A
Other languages
Chinese (zh)
Inventor
谈国强
杨玮
耶维
乐忠威
任慧君
夏傲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN201610187622.9A priority Critical patent/CN105845316A/en
Publication of CN105845316A publication Critical patent/CN105845316A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F10/00—Thin magnetic films, e.g. of one-domain structure
    • H01F10/08—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers
    • H01F10/10—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition
    • H01F10/18—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition being compounds
    • H01F10/20—Ferrites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/265—Compositions containing one or more ferrites of the group comprising manganese or zinc and one or more ferrites of the group comprising nickel, copper or cobalt
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62222—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic coatings
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/624—Sol-gel processing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
    • H01F41/22—Heat treatment; Thermal decomposition; Chemical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
    • H01F41/24—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates from liquids
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/762—Cubic symmetry, e.g. beta-SiC
    • C04B2235/763—Spinel structure AB2O4

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Thin Magnetic Films (AREA)

Abstract

The invention provides a spinel type Zn<1-x>Ni<x>Fe<2>O<4> paramagnetic and ferromagnetic thin film and a preparation method therefor. The preparation method comprises the steps of dissolving zinc nitrate, nickel acetate and ferric nitrate into ethylene glycol methyl ether and acetic anhydride at a molar ratio, and stirring the mixture to obtain a uniform precursor liquid; and preparing the high-density and uniform-grain-size paramagnetic and ferromagnetic Zn<1-x>Ni<x>Fe<2>O<4> thin film on a substrate by a spin-coating method and a layer-by-layer annealing process, wherein x is equal to 0.1-0.7; when x is equal to 0.1, the thin film shows the super-paramagnetic property; and when x is equal to 0.3-0.7, the thin film shows the ferromagnetic property. The preparation method adopts a sol-gel process and has low equipment requirement, so that the thin film is suitable for being manufactured on large and irregular surfaces; the chemical components are controllable; and in addition, the paramagnetic and ferromagnetic properties of the thin film can be regulated and controlled by changing the doping amounts of elements.

Description

A kind of spinel-type Zn1-xNixFe2O4Paramagnetism and ferromagnetic thin film and preparation method thereof
Technical field
The invention belongs to field of functional materials, be specifically related to a kind of spinel-type Zn1-xNixFe2O4Paramagnetism and ferromagnetic thin film and Its preparation method.
Background technology
Ferrite is the most outstanding a kind of semi-conducting material, is also a kind of very important magnetic material simultaneously, is widely used in Ferrofluid, magnetic medicine transmission, magnetic high density data storage；Its bulk also has excellent soft magnetism.
Such as nanometer Zn Fe2O4It is a kind of important soft magnetic materials, shows many novel characteristics at aspects such as light, heat, electricity, magnetic, In recent years by the common concern of people, the research and development further to this class ferrite utilizes tool to be of great significance.
Spinelle belongs to ionic compound, and formula is A(2+)B2 (3+)O4, belong to cubic system, Fd-3M space group, be morphologically Cube crystal formation, and cleavage.O2-In face-centered cubic tightly packed in the structure shown here, at O2-Gap in there will be metal ion edge Embedding wherein.Have in 8 molecular distribution structure cell in spinel structure crystal, 64 tetrahedrons and 16 octahedrons wherein by 16 oxonium ion compositions, metal ion only occupies 8 tetrahedrons (A position) therein and 16 octahedrons (B position).Wherein A-O, B-O is stronger ionic bond, and electrostatic bond intensity is equal, causes spinelle to have certain property, as material is hard Degree is big, stable chemical performance, fusing point advantages of higher.
But ZnFe2O4The ferromagnetic property of thin film is the most weak, it is impossible to meet actual ferromagnetism application.Therefore, how research improves ZnFe2O4The ferromagnetic property of thin film is significant.
Summary of the invention
It is an object of the invention to provide a kind of spinel-type Zn1-xNixFe2O4Paramagnetism and ferromagnetic thin film and preparation method thereof, By doping ferromagnetism Ni2+Ion, it is possible to obtain the Zn with excellent ferromagnetic property1-xNixFe2O4Crystalline film.
To achieve these goals, the present invention adopts the following technical scheme that
A kind of spinel-type Zn1-xNixFe2O4Paramagnetism and ferromagnetic thin film, the structural formula of this thin film is Zn1-xNixFe2O4, X=0.1～0.7；This thin film is the spinel structure of Emission in Cubic, and space group is Fd-3m (227)；This thin film performance as x=0.1 For superparamagnetic characteristic, as x=0.3～0.7, this thin film shows as ferromagnetic characteristic.
As x=0.1, saturation magnetization Ms=10 of this thin film～11emu/cm3；As x=0.3～0.7, this thin film saturated Magnetization M s=156～246emu/cm3, remanent magnetization Mr=4～62emu/cm3。
A kind of spinel-type Zn1-xNixFe2O4Paramagnetism and the preparation method of ferromagnetic thin film, comprise the following steps:
Step 1: zinc nitrate, nickel acetate and ferric nitrate are dissolved in ethylene glycol monomethyl ether for 1-x:x:2 in molar ratio, x=0.1～0.7, Add acetic anhydride after stirring, obtain Zn1-xNixFe2O4Precursor liquid；
Step 2: use spin-coating method spin coating Zn on substrate1-xNixFe2O4Precursor liquid, obtains Zn1-xNixFe2O4Wet film, Zn1-xNixFe2O4Wet film toasts to obtain dry film after spin coating at 250～300 DEG C, anneals in atmosphere at 650～750 DEG C, To crystalline state Zn1-xNixFe2O4Thin film；
Step 3: treat crystalline state Zn1-xNixFe2O4After film cooling, in crystalline state Zn1-xNixFe2O4Step 2 is repeated on thin film, until Reach desired thickness, i.e. obtain spinel-type Zn1-xNixFe2O4Paramagnetism and ferromagnetic thin film.
Described Zn1-xNixFe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (3.5～4.5): 1, Zn1-xNixFe2O4 In precursor liquid, the concentration of Fe ion is 0.1～0.3mol/L.
Substrate surface, before carrying out, is first cleaned up by described step 2, the most under ultraviolet light treatment with irradiation, makes substrate surface reach To atomic cleanliness degree.
Described substrate is FTO/ glass substrate, Si substrate, SrTiO3Monocrystal chip or LaNiO3Monocrystal chip.
In described step 2, spin coating rotating speed during spin coating is 4200～4500r/min, and spin coating time is 7～10s.
In described step 2, the baking time after spin coating is 10～15min.
Annealing time in described step 2 is 25～30min.
Described spinel-type Zn1-xNixFe2O4Paramagnetism and ferromagnetic thin film are by 10～15 layer crystal states Zn1-xNixFe2O4Thin film structure Become.
Relative to prior art, the method have the advantages that
1. the spinel-type Zn that the present invention provides1-xNixFe2O4Paramagnetism and the preparation method of ferromagnetic thin film, select transition metal Ni carries out ZnFe2O4A position doping, owing to Ni is to have ferromagnetic metallic element, along with the increase of Ni doping content, The spinel-type Zn prepared1-xNixFe2O4The saturation magnetization of paramagnetism and ferromagnetic thin film increases, and improves ZnFe2O4Thin film Ferromagnetic property.Its reason is, on the one hand, this is because Ni ion changes the structure of thin film and changes Fe-O-Fe Angle, on the other hand, the Ferrimagnetic coupling between magnetic Ni and Fe ion can increase saturation magnetization.
2. it is currently used for preparing ZnFe2O4The method of thin film is a lot, such as mechanochemical synthesis, chemical coprecipitation, colloidal sol-solidifying Glue method (Sol-Gel), hydro-thermal method, predecessor solid reaction process etc..Comparing additive method, Sol-Gel method is simple due to equipment, Reaction is easily carried out, and reaction temperature is relatively low, easily operates, and suitably prepares thin film, easily on big surface and surface in irregular shape Realize the Uniform Doped on molecular level, and the advantage such as chemical constituent controllable precise and be widely used for preparing ferroelectric material.This Bright middle employing sol-gal process, because not having mechanical mixture in sol-gel process preparation process, is not easily introduced impurity, product purity Height, and utilize the method can realize the mixing of molecular level, therefore system uniformity is good.The present invention passes through transition elements Ni Doping ZnFe2O4, substrate is prepared Zn1-xNixFe2O4Paramagnetism and ferromagnetic thin film, can obtain high saturated by doping The intensity of magnetization.
3. the spinel-type Zn that the present invention provides1-xNixFe2O4Paramagnetism and ferromagnetic thin film, show as superparamagnetic when x=0.1 Characteristic, shows as ferromagnetic characteristic when x=0.3～0.7, can be by the change of Ni element doping amount to Zn1-xNixFe2O4Thin film Paramagnetism and ferromagnetism regulate and control.
Accompanying drawing explanation
Fig. 1 is Zn prepared by the present invention1-xNixFe2O4The XRD figure of thin film；Wherein (b) is the partial enlarged drawing of (a)；
Fig. 2 is Zn prepared by the present invention0.5Ni0.5Fe2O4The Raman collection of illustrative plates of thin film；
Fig. 3 is Zn prepared by the present invention0.5Ni0.5Fe2O4The SEM figure of thin film；
Fig. 4 is Zn prepared by the present invention1-xNixFe2O4The hysteresis curve figure of thin film；
Fig. 5 is Zn prepared by the present invention1-xNixFe2O4Saturation magnetization Ms of thin film and the relation curve of doping x of Ni.
Detailed description of the invention
Below in conjunction with the present invention preferably embodiment and accompanying drawing, the present invention is described in further details.
Embodiment 1
Step 1, is dissolved in ethylene glycol monomethyl ether (x=0.1) for 0.9:0.1:2 in molar ratio by zinc nitrate, nickel acetate and ferric nitrate, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.3mol/L0.9Ni0.1Fe2O4Precursor liquid, Zn0.9Ni0.1Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 4:1；
Step 2, is sequentially placed into ultrasonic waves for cleaning in detergent, acetone, ethanol, each ultrasonic waves for cleaning by FTO/ glass substrate With a large amount of distilled water flushing FTO/ glass substrates after 10min, finally dry up with nitrogen.Then FTO/ glass substrate is put into baking oven It is baked to be dried, takes out and stand to room temperature.Clean FTO/ glass substrate is placed in ultraviolet radiation instrument irradiation 40min again, FTO/ glass substrate surface is made to reach " atomic cleanliness degree ".Use spin-coating method spin coating Zn on FTO/ glass substrate0.9Ni0.1Fe2O4 Precursor liquid, prepares Zn0.9Ni0.1Fe2O4Wet film, to Zn0.9Ni0.1Fe2O4Wet film spin coating, spin coating rotating speed is 4300r/min, spin coating Time is 8s, after spin coating terminates, toasts 12min and obtains dry film, then move back layer by layer in air at a temperature of 700 DEG C at a temperature of 280 DEG C Fire 28min, obtains crystalline state Zn0.9Ni0.1Fe2O4Thin film；
Step 3, treats crystalline state Zn0.9Ni0.1Fe2O4After film cooling, in crystalline state Zn0.9Ni0.1Fe2O4Step 2, weight is repeated on thin film Multiple 12 times, obtain spinel-type Zn0.9Ni0.1Fe2O4Paramagnetism and ferromagnetic thin film.
Use XRD determining spinel-type Zn0.9Ni0.1Fe2O4The thing phase composition structure of paramagnetism and ferromagnetic thin film.Use SQUID MPMS-XL-7 tests spinel-type Zn0.9Ni0.1Fe2O4It is superparamagnetic behavior under paramagnetism and ferromagnetic thin film room temperature, records it Saturation magnetization Ms=10～11emu/cm3.And according to the method for the present invention, the ZnFe that the Ni that undopes in step 1 prepares2O4 Saturation magnetization Ms=7 of thin film～8emu/cm3。
Embodiment 2
Step 1, is dissolved in ethylene glycol monomethyl ether (x=0.3) for 0.7:0.3:2 in molar ratio by zinc nitrate, nickel acetate and ferric nitrate, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.3mol/L0.7Ni0.3Fe2O4Precursor liquid, Zn0.7Ni0.3Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 4:1；
Step 2, is sequentially placed into ultrasonic waves for cleaning in detergent, acetone, ethanol, each ultrasonic waves for cleaning by FTO/ glass substrate With a large amount of distilled water flushing FTO/ glass substrates after 10min, finally dry up with nitrogen.Then FTO/ glass substrate is put into baking oven It is baked to be dried, takes out and stand to room temperature.Clean FTO/ glass substrate is placed in ultraviolet radiation instrument irradiation 40min again, FTO/ glass substrate surface is made to reach " atomic cleanliness degree ".Use spin-coating method spin coating Zn on FTO/ glass substrate0.7Ni0.3Fe2O4 Precursor liquid, prepares Zn0.7Ni0.3Fe2O4Wet film, to Zn0.7Ni0.3Fe2O4Wet film spin coating, spin coating rotating speed is 4300r/min, spin coating Time is 8s, after spin coating terminates, toasts 12min and obtains dry film, then move back layer by layer in air at a temperature of 700 DEG C at a temperature of 280 DEG C Fire 28min, obtains crystalline state Zn0.7Ni0.3Fe2O4Thin film；
Step 3, treats crystalline state Zn0.7Ni0.3Fe2O4After film cooling, in crystalline state Zn0.7Ni0.3Fe2O4Step 2, weight is repeated on thin film Multiple 12 times, obtain spinel-type Zn0.7Ni0.3Fe2O4Paramagnetism and ferromagnetic thin film.
Use XRD determining spinel-type Zn0.7Ni0.3Fe2O4The thing phase composition structure of paramagnetism and ferromagnetic thin film.Use SQUID MPMS-XL-7 tests spinel-type Zn0.7Ni0.3Fe2O4Ferromagnetic property under paramagnetism and ferromagnetic thin film room temperature, records it and remains Residual magnetization Mr=4～6emu/cm3, saturation magnetization Ms=156～158emu/cm3。
Embodiment 3
Step 1, is dissolved in ethylene glycol monomethyl ether (x=0.5) for 0.5:0.5:2 in molar ratio by zinc nitrate, nickel acetate and ferric nitrate, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.3mol/L0.5Ni0.5Fe2O4Precursor liquid, Zn0.5Ni0.5Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 4:1；
Step 2, is sequentially placed into ultrasonic waves for cleaning in detergent, acetone, ethanol, each ultrasonic waves for cleaning by FTO/ glass substrate With a large amount of distilled water flushing FTO/ glass substrates after 10min, finally dry up with nitrogen.Then FTO/ glass substrate is put into baking oven It is baked to be dried, takes out and stand to room temperature.Clean FTO/ glass substrate is placed in ultraviolet radiation instrument irradiation 40min again, FTO/ glass substrate surface is made to reach " atomic cleanliness degree ".Use spin-coating method spin coating Zn on FTO/ glass substrate0.5Ni0.5Fe2O4 Precursor liquid, prepares Zn0.5Ni0.5Fe2O4Wet film, to Zn0.5Ni0.5Fe2O4Wet film spin coating, spin coating rotating speed is 4300r/min, spin coating Time is 8s, after spin coating terminates, toasts 12min and obtains dry film, then move back layer by layer in air at a temperature of 700 DEG C at a temperature of 280 DEG C Fire 28min, obtains crystalline state Zn0.5Ni0.5Fe2O4Thin film；
Step 3, treats crystalline state Zn0.5Ni0.5Fe2O4After film cooling, in crystalline state Zn0.5Ni0.5Fe2O4Step 2, weight is repeated on thin film Multiple 12 times, obtain spinel-type Zn0.5Ni0.5Fe2O4Paramagnetism and ferromagnetic thin film.
Use XRD determining spinel-type Zn0.5Ni0.5Fe2O4The thing phase composition structure of paramagnetism and ferromagnetic thin film.Use Raman Spectroscopic assay spinel-type Zn0.5Ni0.5Fe2O4The relative position of paramagnetism and the eigen vibration mould of ferromagnetic thin film, thus analyze knot The change of structure.Spinel-type Zn is measured with FE-SEM0.5Ni0.5Fe2O4Paramagnetism and the microscopic appearance of ferromagnetic thin film.Use SQUID MPMS-XL-7 tests spinel-type Zn0.5Ni0.5Fe2O4Ferromagnetic property under paramagnetism and ferromagnetic thin film room temperature, records it and remains Residual magnetization Mr=40～45emu/cm3, saturation magnetization Ms=244～246emu/cm3。
Embodiment 4
Step 1, is dissolved in ethylene glycol monomethyl ether (x=0.7) for 0.3:0.7:2 in molar ratio by zinc nitrate, nickel acetate and ferric nitrate, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.3mol/L0.3Ni0.7Fe2O4Precursor liquid, Zn0.3Ni0.7Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 4:1；
Step 2, is sequentially placed into ultrasonic waves for cleaning in detergent, acetone, ethanol, each ultrasonic waves for cleaning by FTO/ glass substrate With a large amount of distilled water flushing FTO/ glass substrates after 10min, finally dry up with nitrogen.Then FTO/ glass substrate is put into baking oven It is baked to be dried, takes out and stand to room temperature.Clean FTO/ glass substrate is placed in ultraviolet radiation instrument irradiation 40min again, FTO/ glass substrate surface is made to reach " atomic cleanliness degree ".Use spin-coating method spin coating Zn on FTO/ glass substrate0.3Ni0.7Fe2O4 Precursor liquid, prepares Zn0.3Ni0.7Fe2O4Wet film, to Zn0.3Ni0.7Fe2O4Wet film spin coating, spin coating rotating speed is 4300r/min, spin coating Time is 8s, after spin coating terminates, toasts 12min and obtains dry film, then move back layer by layer in air at a temperature of 700 DEG C at a temperature of 280 DEG C Fire 28min, obtains crystalline state Zn0.3Ni0.7Fe2O4Thin film；
Step 3, treats crystalline state Zn0.3Ni0.7Fe2O4After film cooling, in crystalline state Zn0.3Ni0.7Fe2O4Step 2, weight is repeated on thin film Multiple 12 times, obtain spinel-type Zn0.3Ni0.7Fe2O4Paramagnetism and ferromagnetic thin film；
Use XRD determining spinel-type Zn0.3Ni0.7Fe2O4The thing phase composition structure of paramagnetism and ferromagnetic thin film.Use SQUID MPMS-XL-7 tests spinel-type Zn0.3Ni0.7Fe2O4Ferromagnetic property under paramagnetism and ferromagnetic thin film room temperature, records it and remains Residual magnetization Mr=60～62emu/cm3, saturation magnetization Ms=224～226emu/cm3。
Embodiment 5
Step 1, is dissolved in ethylene glycol monomethyl ether (x=0.2) for 0.8:0.2:2 in molar ratio by zinc nitrate, nickel acetate and ferric nitrate, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.1mol/L0.8Ni0.2Fe2O4Precursor liquid, Zn0.8Ni0.2Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3.5:1；
Step 2, is sequentially placed into ultrasonic waves for cleaning in detergent, acetone, ethanol, each ultrasonic waves for cleaning 10min by Si substrate Afterwards with a large amount of distilled water flushing Si substrates, finally dry up with nitrogen.Then Si substrate is put into baking oven to be baked to be dried, take out quiet Put to room temperature.Clean Si substrate is placed in ultraviolet radiation instrument irradiation 40min again, makes Si substrate surface reach " atomic cleanliness Degree ".Use spin-coating method spin coating Zn on si substrates0.8Ni0.2Fe2O4Precursor liquid, prepares Zn0.8Ni0.2Fe2O4Wet film, right Zn0.8Ni0.2Fe2O4Wet film spin coating, spin coating rotating speed is 4200r/min, and spin coating time is 10s, after spin coating terminates, 250 DEG C of temperature The lower baking 15min of degree obtains dry film, then the 27min that anneals layer by layer in air at a temperature of 680 DEG C, obtains crystalline state Zn0.8Ni0.2Fe2O4 Thin film；
Step 3, treats crystalline state Zn0.8Ni0.2Fe2O4After film cooling, in crystalline state Zn0.8Ni0.2Fe2O4Step 2, weight is repeated on thin film Multiple 9 times, obtain spinel-type Zn0.8Ni0.2Fe2O4Paramagnetism and ferromagnetic thin film.
Embodiment 6
Step 1, is dissolved in ethylene glycol monomethyl ether (x=0.4) for 0.6:0.4:2 in molar ratio by zinc nitrate, nickel acetate and ferric nitrate, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.2mol/L0.6Ni0.4Fe2O4Precursor liquid, Zn0.6Ni0.4Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 4.5:1；
Step 2, by SrTiO3Monocrystal chip is sequentially placed into ultrasonic waves for cleaning in detergent, acetone, ethanol, each ultrasonic waves for cleaning With a large amount of distilled water flushing SrTiO after 10min3Monocrystal chip, finally dries up with nitrogen.Then by SrTiO3Monocrystal chip is put into Baking oven is baked to be dried, and takes out and stands to room temperature.Again by clean SrTiO3Monocrystal chip is placed in ultraviolet radiation instrument irradiation 40min, makes SrTiO3Monocrystal chip surface reaches " atomic cleanliness degree ".Use spin-coating method at SrTiO3Spin coating on monocrystal chip Zn0.6Ni0.4Fe2O4Precursor liquid, prepares Zn0.6Ni0.4Fe2O4Wet film, to Zn0.6Ni0.4Fe2O4Wet film spin coating, spin coating rotating speed is 4400r/min, spin coating time is 9s, after spin coating terminates, toasts 10min and obtain dry film at a temperature of 300 DEG C, then 650 DEG C of temperature Anneal in lower air 30min layer by layer, obtains crystalline state Zn0.6Ni0.4Fe2O4Thin film；
Step 3, treats crystalline state Zn0.6Ni0.4Fe2O4After film cooling, in crystalline state Zn0.6Ni0.4Fe2O4Step 2, weight is repeated on thin film Multiple 14 times, obtain spinel-type Zn0.6Ni0.4Fe2O4Paramagnetism and ferromagnetic thin film.
Embodiment 7
Step 1, is dissolved in ethylene glycol monomethyl ether (x=0.6) for 0.4:0.6:2 in molar ratio by zinc nitrate, nickel acetate and ferric nitrate, stirs After mixing 30min, add acetic anhydride, obtain the stable Zn that Fe ion concentration is 0.25mol/L0.4Ni0.6Fe2O4Precursor liquid, Zn0.4Ni0.6Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3.8:1；
Step 2, by LaNiO3Monocrystal chip is sequentially placed into ultrasonic waves for cleaning in detergent, acetone, ethanol, and each ultrasound wave is clear Wash after 10min with a large amount of distilled water flushing LaNiO3Monocrystal chip, finally dries up with nitrogen.Then by LaNiO3Monocrystal chip Put into baking oven to be baked to be dried, take out and stand to room temperature.Again by clean LaNiO3Monocrystal chip is placed in ultraviolet radiation instrument photograph Penetrate 40min, make LaNiO3Monocrystal chip surface reaches " atomic cleanliness degree ".Use spin-coating method at LaNiO3Spin coating on monocrystal chip Zn0.4Ni0.6Fe2O4Precursor liquid, prepares Zn0.4Ni0.6Fe2O4Wet film, to Zn0.4Ni0.6Fe2O4Wet film spin coating, spin coating rotating speed is 4500r/min, spin coating time is 7s, after spin coating terminates, toasts 13min and obtain dry film at a temperature of 270 DEG C, then 750 DEG C of temperature Anneal in lower air 25min layer by layer, obtains crystalline state Zn0.4Ni0.6Fe2O4Thin film；
Step 3, treats crystalline state Zn0.4Ni0.6Fe2O4After film cooling, in crystalline state Zn0.4Ni0.6Fe2O4Step 2, weight is repeated on thin film Multiple 11 times, obtain spinel-type Zn0.4Ni0.6Fe2O4Paramagnetism and ferromagnetic thin film.
Spinel-type Zn prepared by the present invention1-xNixFe2O4Paramagnetism and ferromagnetic thin film carry out performance test, embodiment 1～4 The spinel-type Zn prepared1-xNixFe2O4The result of paramagnetism and ferromagnetic thin film is as shown in Fig. 1～5.
Fig. 1 is the spinel-type Zn that the present invention prepares1-xNixFe2O4Paramagnetism and the XRD figure of ferromagnetic thin film, wherein Pure For ZnFe2O4Thin film, is the method according to the present invention, and the Ni that undopes in step 1 prepares.As can be known from Fig. 1, this The spinel-type Zn of bright preparation1-xNixFe2O4Paramagnetism and ferromagnetic thin film are Emission in Cubic, spinel structure, and space group is Fd-3m (227), spinel-type Zn1-xNixFe2O4Paramagnetism and ferromagnetic thin film do not have the appearance of other impurity.
Fig. 2 the most further demonstrates simultaneously, spinel-type Zn1-xNixFe2O4Paramagnetism and ferromagnetic thin film are along with Ni content Increasing, structure does not change.
Spinel-type Zn as can be seen from Figure 30.5Ni0.5Fe2O4Paramagnetism and ferromagnetic thin film surfacing, crystallite dimension is at 500nm Left and right.
Fig. 4 is spinel-type Zn prepared by the present invention1-xNixFe2O4Paramagnetism and the hysteresis curve of ferromagnetic thin film, wherein Pure For ZnFe2O4Thin film, is the method according to the present invention, and the Ni that undopes in step 1 prepares.Fig. 5 is prepared by the present invention Spinel-type Zn1-xNixFe2O4Saturation magnetization Ms of paramagnetism and ferromagnetic thin film and the relation curve of doping x of Ni, Wherein x=0 is ZnFe2O4Thin film.As can be seen from Figure 4 and Figure 5, ZnFe2O4Saturation magnetization Ms=7 of thin film～8 emu/cm3, spinel-type Zn0.9Ni0.1Fe2O4Paramagnetism and saturation magnetization Ms=10 of ferromagnetic thin film～11emu/cm3, That is as x=0～0.1, spinel-type Zn1-xNixFe2O4Paramagnetism and ferromagnetic thin film show as superparamagnetic characteristic.Along with The increase of Ni content, spinel-type Zn1-xNixFe2O4The ferromagnetic property of paramagnetism and ferromagnetic thin film strengthens, as x=0.3～0.7 Time, spinel-type Zn1-xNixFe2O4Paramagnetism and ferromagnetic thin film show as ferromagnetic characteristic, wherein spinel-type Zn0.7Ni0.3Fe2O4 Paramagnetism and remanent magnetization Mr=4 of ferromagnetic thin film～6emu/cm3, saturation magnetization Ms=156～158emu/cm3； Spinel-type Zn0.5Ni0.5Fe2O4The saturation magnetization of paramagnetism and ferromagnetic thin film is maximum, itself Ms=244～246emu/cm3, Remanent magnetization Mr=40～45emu/cm3；Spinel-type Zn0.3Ni0.7Fe2O4The remanent magnetization of paramagnetism and ferromagnetic thin film is strong Degree Mr=60～62emu/cm3, saturation magnetization Ms=224～226emu/cm3。
Present device requires simple, and experiment condition easily reaches, the spinel-type Zn of preparation1-xNixFe2O4Paramagnetism and ferromagnetism Uniformity of film is preferable, and Ni content is easily controlled, by the suitable selection of Ni content, it is possible to increase substantially Zn1-xNixFe2O4 The paramagnetic of crystalline film and ferromagnetic property.
The foregoing is only one embodiment of the present invention, be not all of or unique embodiment, those of ordinary skill in the art The conversion of any equivalence taked technical scheme by reading the description of the present invention, the right being the present invention is wanted Ask and contained.

Claims (10)

1. a spinel-type Zn1-xNixFe2O4Paramagnetism and ferromagnetic thin film, it is characterised in that: the structural formula of this thin film is Zn1-xNixFe2O4, x=0.1～0.7；This thin film is the spinel structure of Emission in Cubic, and space group is Fd-3m (227)；Work as x=0.1 Time this thin film show as superparamagnetic characteristic, as x=0.3～0.7, this thin film shows as ferromagnetic characteristic.
Spinel-type Zn the most according to claim 11-xNixFe2O4Paramagnetism and ferromagnetic thin film, it is characterised in that: when During x=0.1, saturation magnetization Ms=10 of this thin film～11emu/cm3；As x=0.3～0.7, the saturated magnetization of this thin film is strong Degree Ms=156～246emu/cm3, remanent magnetization Mr=4～62emu/cm3。
3. a spinel-type Zn1-xNixFe2O4Paramagnetism and the preparation method of ferromagnetic thin film, it is characterised in that include following Step:
Step 1: zinc nitrate, nickel acetate and ferric nitrate are dissolved in ethylene glycol monomethyl ether for 1-x:x:2 in molar ratio, x=0.1～0.7, Add acetic anhydride after stirring, obtain Zn1-xNixFe2O4Precursor liquid；
Step 2: use spin-coating method spin coating Zn on substrate1-xNixFe2O4Precursor liquid, obtains Zn1-xNixFe2O4Wet film, Zn1-xNixFe2O4Wet film toasts to obtain dry film after spin coating at 250～300 DEG C, anneals in atmosphere at 650～750 DEG C, To crystalline state Zn1-xNixFe2O4Thin film；
Step 3: treat crystalline state Zn1-xNixFe2O4After film cooling, in crystalline state Zn1-xNixFe2O4Step 2 is repeated on thin film, until Reach desired thickness, i.e. obtain spinel-type Zn1-xNixFe2O4Paramagnetism and ferromagnetic thin film.
Spinel-type Zn the most according to claim 31-xNixFe2O4Paramagnetism and the preparation method of ferromagnetic thin film, it is special Levy and be: described Zn1-xNixFe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (3.5～4.5): 1, Zn1-xNixFe2O4In precursor liquid, the concentration of Fe ion is 0.1～0.3mol/L.
Spinel-type Zn the most according to claim 31-xNixFe2O4Paramagnetism and the preparation method of ferromagnetic thin film, it is special Levy and be: substrate surface, before carrying out, is first cleaned up by described step 2, the most under ultraviolet light treatment with irradiation, make substrate table Face reaches atomic cleanliness degree.
Spinel-type Zn the most according to claim 31-xNixFe2O4Paramagnetism and the preparation method of ferromagnetic thin film, it is special Levy and be: described substrate is FTO/ glass substrate, Si substrate, SrTiO3Monocrystal chip or LaNiO3Monocrystal chip.
Spinel-type Zn the most according to claim 31-xNixFe2O4Paramagnetism and the preparation method of ferromagnetic thin film, it is special Levy and be: in described step 2, spin coating rotating speed during spin coating is 4200～4500r/min, and spin coating time is 7～10s.
Spinel-type Zn the most according to claim 31-xNixFe2O4Paramagnetism and the preparation method of ferromagnetic thin film, it is special Levy and be: in described step 2, the baking time after spin coating is 10～15min.
Spinel-type Zn the most according to claim 31-xNixFe2O4Paramagnetism and the preparation method of ferromagnetic thin film, it is special Levy and be: the annealing time in described step 2 is 25～30min.
Spinel-type Zn the most according to claim 31-xNixFe2O4Paramagnetism and the preparation method of ferromagnetic thin film, its It is characterised by: described spinel-type Zn1-xNixFe2O4Paramagnetism and ferromagnetic thin film are by 10～15 layer crystal states Zn1-xNixFe2O4 Thin film is constituted.
CN201610187622.9A 2016-03-29 2016-03-29 Spinel type Zn<1-x>Ni<x>Fe<2>O<4> paramagnetic and ferromagnetic thin film and preparation method therefor Pending CN105845316A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610187622.9A CN105845316A (en) 2016-03-29 2016-03-29 Spinel type Zn<1-x>Ni<x>Fe<2>O<4> paramagnetic and ferromagnetic thin film and preparation method therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610187622.9A CN105845316A (en) 2016-03-29 2016-03-29 Spinel type Zn<1-x>Ni<x>Fe<2>O<4> paramagnetic and ferromagnetic thin film and preparation method therefor

Publications (1)

Publication Number Publication Date
CN105845316A true CN105845316A (en) 2016-08-10

Family

ID=56584031

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610187622.9A Pending CN105845316A (en) 2016-03-29 2016-03-29 Spinel type Zn<1-x>Ni<x>Fe<2>O<4> paramagnetic and ferromagnetic thin film and preparation method therefor

Country Status (1)

Country Link
CN (1) CN105845316A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108726888A (en) * 2018-06-26 2018-11-02 陕西科技大学 A kind of CoFe2-xGdxO4Ferromagnetic thin film and preparation method thereof
CN112340787A (en) * 2020-11-09 2021-02-09 东北大学秦皇岛分校 Single-phase spinel type high-entropy oxide, preparation method and application

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101244931A (en) * 2008-03-19 2008-08-20 北京化工大学 Method for manufacturing silicon base body stephanoporate ferrite thin film with hydrotalcite forerunner method
CN101577178A (en) * 2009-03-23 2009-11-11 兰州大学 Preparation method of ferrite magnetic film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101244931A (en) * 2008-03-19 2008-08-20 北京化工大学 Method for manufacturing silicon base body stephanoporate ferrite thin film with hydrotalcite forerunner method
CN101577178A (en) * 2009-03-23 2009-11-11 兰州大学 Preparation method of ferrite magnetic film

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
FENG LIU ET AL.: "NiCuZn ferrite thin films grown by a sol–gel method and rapid thermal annealing", 《JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS》 *
M. ATIF ET AL.: "Sol–gel synthesis of nanocrystalline Zn1-xNiXFe2O4 ceramics and its structural, magnetic and dielectric properties", 《J SOL-GEL SCI TECHNOL》 *
MRUGESH DESAI ET AL.: "Anomalous variation of coercivity with annealing in nanocrystalline NiZn ferrite films", 《JOURNAL OF APPLIED PHYSICS》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108726888A (en) * 2018-06-26 2018-11-02 陕西科技大学 A kind of CoFe2-xGdxO4Ferromagnetic thin film and preparation method thereof
CN108726888B (en) * 2018-06-26 2021-08-17 陕西科技大学 CoFe2-xGdxO4Ferromagnetic thin film and preparation method thereof
CN112340787A (en) * 2020-11-09 2021-02-09 东北大学秦皇岛分校 Single-phase spinel type high-entropy oxide, preparation method and application
CN112340787B (en) * 2020-11-09 2023-01-24 东北大学秦皇岛分校 Single-phase spinel type high-entropy oxide, preparation method and application

Similar Documents

Publication Publication Date Title
CN105819848B (en) A kind of spinel-type Co1-xMnxFe2O4Ferromagnetic thin film and preparation method thereof
CN105837196A (en) Bi0.92-xHo0.08AExFe0.97Mn0.03O3-Zn1-yNiyFe2O4 ferromagnetic composite film and preparation method thereof
CN104538140B (en) Multiferroic Bi1-xRExFe0.97-yMn0.03TMyO3/CoFe2O4 composite film and preparation method thereof
CN105271798B (en) A kind of high-ferromagnetic can be with the Bi of ferroelectric properties0.9Er0.1Fe1‑xCoxO3Film and preparation method thereof
CN105845316A (en) Spinel type Zn&lt;1-x&gt;Ni&lt;x&gt;Fe&lt;2&gt;O&lt;4&gt; paramagnetic and ferromagnetic thin film and preparation method therefor
CN104476832B (en) A kind of laminated BiFe0.97-xmn0.03tMxo3/ CoFe2o4multiferroic composite membrane and preparation method thereof
CN105632756B (en) A kind of spinel-type Tetragonal CuFe2O4 ferromagnetic thin films and preparation method thereof
CN105859152B (en) A kind of high magnetism Bi0.96Sr0.04FeO3Base/CoFe2O4Laminated film and preparation method thereof
CN105906221B (en) A kind of multiferroic Bi0.83Pr0.15Sr0.02Fe0.97-xMn0.03CuxO3-CuFe2O4Composite membrane and preparation method thereof
CN104478229B (en) A kind of Bi1-xrExfe0.96co0.02mn0.02o3ferroelectric thin film and preparation method thereof
CN104478228B (en) A kind of Bi0.85‑xPr0.15AExFe0.97Mn0.03O3Ferroelectric thin film and preparation method thereof
CN107082576B (en) HoSrMnNi codoped bismuth ferrite multiferroic film and preparation method thereof
CN105859273B (en) A kind of 2-2 type BiFeO3-CuFe2O4 laminated film and preparation method thereof
CN107245704B (en) A kind of HoSrMnNi/HoSrMnZn is co-doped with bismuth ferrite superlattice film and preparation method thereof
CN107098395B (en) A kind of HoSrMnZn is co-doped with tripartite&#39;s bismuth ferrite superlattice film and preparation method thereof
Duan et al. Annealing heating rate dependence of microstructure and multiferroic properties in Bi4Ti2. 9Fe0. 1O12/CoFe2O4 layered magnetoelectric composite films prepared by chemical solution deposition method
CN107162437B (en) A kind of HoSrMnZn is co-doped with bismuth ferrite superlattice film and preparation method thereof
CN103601249B (en) A kind of high remnant polarization and high-k BiFe 0.96-ymn 0.04cr yo 3ferroelectric membranc and preparation method thereof
CN107082578B (en) A kind of HoSrMnNi is co-doped with tripartite&#39;s bismuth ferrite superlattice film and preparation method thereof
CN107032632B (en) A kind of HoSrMnNi is co-doped with bismuth ferrite superlattice film and preparation method thereof
CN107140849B (en) A kind of LaSrMnCo/GdSrMnCo is co-doped with bismuth ferrite superlattice film and preparation method thereof
CN107021649B (en) A kind of LaSrMnCo is co-doped with bismuth ferrite superlattice film and preparation method thereof
CN105845436A (en) SrFeO2.5 magnetic thin film and preparation method therefor
CN107082577B (en) A kind of HoSrMnZn is co-doped with bismuth ferrite/Mn and mixes zinc ferrite laminated film and preparation method thereof
CN105837199B (en) A kind of Bi0.96Sr0.04Fe0.98-xMnxCo0.02O3More iron thin films and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20160810