CN105819848A - Spinel type Col-xMnxFe2O4 ferromagnetic film and preparation method thereof - Google Patents

Spinel type Col-xMnxFe2O4 ferromagnetic film and preparation method thereof Download PDF

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CN105819848A
CN105819848A CN201610187623.3A CN201610187623A CN105819848A CN 105819848 A CN105819848 A CN 105819848A CN 201610187623 A CN201610187623 A CN 201610187623A CN 105819848 A CN105819848 A CN 105819848A
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谈国强
郑玉娟
杨玮
乐忠威
任慧君
夏傲
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Shaanxi University of Science and Technology
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Abstract

The invention provides a spinel type Col-xMnxFe2O4 ferromagnetic film and a preparation method thereof. The preparation method comprises the following steps of dissolving cobalt nitrate, manganese acetate and ferric nitrate into ethylene glycol monomethyl ether and acetic anhydride according to the mole ratio of (1-x): x: 2, wherein x ranges from 0.1 to 0.5, and conducting stirring, so that a Co1-xMnxFe2O4 precursor solution is obtained; preparing the spinel type Col-xMnxFe2O4 ferromagnetic film which is high in compactness and uniform in grain size and grows in the preferred orientation of a (311) crystal face on a substrate through a spin-coating method and a layer-by-layer annealing process. According to the spinel type Col-xMnxFe2O4 ferromagnetic film and the preparation method thereof, a sol-gel process is adopted, the equipment requirement is simple, it is easy to meet the experiment conditions, the film is suitable for large-area film formation, chemical components are precise and controllable, and ferromagnetic performance of the Col-xMnxFe2O4 ferromagnetic film can be regulated and controlled through the doping amount of the Mn element.

Description

A kind of spinel-type Co1-xMnxFe2O4Ferromagnetic 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 Co1-xMnxFe2O4Ferromagnetic thin film and preparation side thereof Method.
Background technology
Ferrite is the magnetic functional material that a class has extensive use.Wherein spinel-type Conjugate ferrite has preferable electromagnetic property And it is widely used in information storage system, spin electric device, various magnetic device and communication apparatus etc..Conjugate ferrite is thin simultaneously Film has certain application prospect in magnetic electric compound material.
The crystal structure of spinel type ferrite is face-centred cubic structure, and wherein oxonium ion makees face-centered cubic closs packing, there is four sides Position and octahedral position two class space, unit cell contains 8 molecules, and 32 oxygen atoms form 64 four sides positions altogether, and 32 Individual octahedral position.These gaps can not be all by occupied by cation, and only 8 four sides position, 16 octahedra potential energies are by oxygen Occupied by ion, it is masked as A position and B position respectively.The doping existing for metal ion and replacement just because of gap create Condition, so that spinel type ferrite is of a great variety, performance is more excellent.
At present, sol-gel process is not the most used to prepare spinel-type Co1-xMnxFe2O4The relevant report of ferromagnetic thin film.
Summary of the invention
It is an object of the invention to provide a kind of spinel-type Co1-xMnxFe2O4Ferromagnetic thin film and preparation method thereof, the method energy Enough prepare the Co with excellent ferromagnetic property1-xMnxFe2O4Crystalline film.
To achieve these goals, the present invention adopts the following technical scheme that
A kind of spinel-type Co1-xMnxFe2O4Ferromagnetic thin film, the structural formula of this ferromagnetic thin film is Co1-xMnxFe2O4, X=0.1～0.5；This ferromagnetic thin film is Emission in Cubic spinel structure, and space group is Fd-3m, and along (311) Solute Content in Grain Growth.
Described spinel-type Co0.5Mn0.5Fe2O4Saturation magnetization M of ferromagnetic thin films=93.6emu/cm3, remanent magnetization Intensity Mr=45.5emu/cm3, coercivity Hc=535Oe.
A kind of spinel-type Co1-xMnxFe2O4The preparation method of ferromagnetic thin film, comprises the following steps:
Step 1: cobalt nitrate, manganese acetate and ferric nitrate are dissolved in ethylene glycol monomethyl ether for 1-x:x:2 in molar ratio, x=0.1～0.5, Add acetic anhydride after stirring, obtain Co1-xMnxFe2O4Precursor liquid；
Step 2: use spin-coating method spin coating Co on substrate1-xMnxFe2O4Precursor liquid, obtains Co1-xMnxFe2O4Wet film, Co1-xMnxFe2O4Wet film toasts to obtain dry film after spin coating at 250～300 DEG C, anneals in atmosphere at 630～700 DEG C, To crystalline state Co1-xMnxFe2O4Thin film；
Step 3: treat crystalline state Co1-xMnxFe2O4After film cooling, in crystalline state Co1-xMnxFe2O4Step 2 is repeated, directly on thin film To reaching desired thickness, i.e. obtain spinel-type Co1-xMnxFe2O4Ferromagnetic thin film.
Described Co1-xMnxFe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (3.5～4.5): 1, Co1-xMnxFe2O4 In precursor liquid, the concentration of Fe ion is 0.3～0.5mol/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 4500～5000r/min, and spin coating time is 15～20s.
In described step 2, the baking time after spin coating is 10～15min.
Annealing time in described step 2 is 20～25min.
Described spinel-type Co1-xMnxFe2O4Ferromagnetic thin film is by 10～15 layer crystal states Co1-xMnxFe2O4Thin film is constituted.
Relative to prior art, the method have the advantages that
1. the spinel-type Co that the present invention provides1-xMnxFe2O4The preparation method of ferromagnetic thin film, selects transition elements Mn to carry out CoFe2O4A position doping.In the ferrite of spinel structure, the Net magnetic moment of the per unit that the replacement of Mn obtains is 5 μB, Therefore along with the increase of Mn doping content, will be to Co1-xMnxFe2O4The magnetic property of ferromagnetic thin film has a great impact, due to The magnetic property of Mn ion, it will change Co1-xMnxFe2O4The magnetic property of ferromagnetic thin film.
2. it is currently used for preparing CoFe2O4The 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 employing sol-gel process, because sol-gel process preparation process is simple, it is easy to control to introduce alloy and doping, product Purity is high, and utilizes the method can realize the mixing of molecular level, and therefore system uniformity is good.The present invention use colloidal sol coagulate Glue method, by transition elements Mn doping CoFe2O4, substrate is prepared spinel-type Co1-xMnxFe2O4Ferromagnetic thin film, The Co with excellent ferromagnetic property is obtained by doping1-xMnxFe2O4Crystalline film.
3. the spinel-type Co that the present invention provides1-xMnxFe2O4Ferromagnetic thin film is Emission in Cubic spinel structure, and space group is Fd-3m, along with the increase of Mn doping, Co1-xMnxFe2O4Ferromagnetic thin film grows along (311) Solute Content in Grain, and The doping of Mn can reduce Co1-xMnxFe2O4The ferromagnetic property of ferromagnetic thin film, reduces Co simultaneously1-xMnxFe2O4Ferromagnetism is thin The coercivity of film, therefore can be by the change of Co element doping amount to Co1-xMnxFe2O4The ferromagnetic property of ferromagnetic thin film enters Row regulation and control.
Accompanying drawing explanation
Fig. 1 is spinel-type Co prepared by the present invention0.5Mn0.5Fe2O4The XRD figure of ferromagnetic thin film；
Fig. 2 is spinel-type Co prepared by the present invention0.5Mn0.5Fe2O4The Raman collection of illustrative plates of ferromagnetic thin film；
Fig. 3 is spinel-type Co prepared by the present invention1-xMnxFe2O4The SEM figure of ferromagnetic thin film, wherein a is CoFe2O4 The SEM figure of thin film, b is Co0.5Mn0.5Fe2O4The SEM figure of ferromagnetic thin film；
Fig. 4 is spinel-type Co prepared by the present invention1-xMnxFe2O4The hysteresis curve figure of ferromagnetic thin film.
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: cobalt nitrate, manganese acetate and ferric nitrate are dissolved in ethylene glycol monomethyl ether (x=0.1) for 0.9:0.1:2 in molar ratio, stir After mixing 30min, add acetic anhydride, obtain the stable Co that Fe ion concentration is 0.3mol/L0.9Mn0.1Fe2O4Precursor liquid, Co0.9Mn0.1Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3.5:1；
Step 2: Si substrate is sequentially placed into ultrasonic waves for cleaning in detergent, acetone, ethanol, each ultrasonic waves for cleaning 10min Afterwards with a large amount of distilled water flushing FTO/ glass substrates, finally dry up with nitrogen.Then Si substrate is put into baking oven to be baked to be dried, Take out and stand to room temperature.Clean Si substrate is placed in ultraviolet radiation instrument irradiation 40min again, makes Si substrate surface reach " former Sub-cleannes ".Use spin-coating method spin coating Co on si substrates0.9Mn0.1Fe2O4Precursor liquid, prepares Co0.9Mn0.1Fe2O4Wet film, To Co0.9Mn0.1Fe2O4Wet film spin coating, spin coating rotating speed is 4600r/min, and spin coating time is 20s, after spin coating terminates, at 260 DEG C At a temperature of toast 15min obtain dry film, then the 25min that anneals layer by layer in air at a temperature of 650 DEG C, obtain crystalline state Co0.9Mn0.1Fe2O4 Thin film；
Step 3, treats crystalline state Co0.9Mn0.1Fe2O4After film cooling, in crystalline state Co0.9Mn0.1Fe2O4Step 2 is repeated on thin film, It is repeated 9 times, obtains spinel-type Co0.9Mn0.1Fe2O4Ferromagnetic thin film.
X-ray diffractometer and Raman spectrometer is used to measure Co0.9Mn0.1Fe2O4The thing phase composition structure of ferromagnetic thin film.With SEM test characterizes Co0.9Mn0.1Fe2O4The surface topography of ferromagnetic thin film.Test with SQUID MPMS-XL-7 Co0.9Mn0.1Fe2O4The magnetic property of ferromagnetic thin film.
Embodiment 2
Step 1: cobalt nitrate, manganese acetate and ferric nitrate are dissolved in ethylene glycol monomethyl ether (x=0.2) for 0.8:0.2:2 in molar ratio, stir After mixing 30min, add acetic anhydride, obtain the stable Co that Fe ion concentration is 0.35mol/L0.8Mn0.2Fe2O4Precursor liquid, Co0.8Mn0.2Fe2O4In 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 Co0.8Mn0.2Fe2O4Precursor liquid, prepares Co0.8Mn0.2Fe2O4Wet film, to Co0.8Mn0.2Fe2O4Wet film spin coating, spin coating rotating speed is 4700r/min, spin coating time is 19s, after spin coating terminates, toasts 14min and obtain dry film at a temperature of 270 DEG C, then 670 DEG C of temperature Anneal in the lower air of degree 24min layer by layer, obtains crystalline state Co0.8Mn0.2Fe2O4Thin film；
Step 3, treats crystalline state Co0.8Mn0.2Fe2O4After film cooling, in crystalline state Co0.8Mn0.2Fe2O4Step 2 is repeated on thin film, It is repeated 14 times, obtains spinel-type Co0.8Mn0.2Fe2O4Ferromagnetic thin film.
X-ray diffractometer and Raman spectrometer is used to measure Co0.8Mn0.2Fe2O4The thing phase composition structure of ferromagnetic thin film.With SEM test characterizes Co0.8Mn0.2Fe2O4The surface topography of ferromagnetic thin film.Test with SQUID MPMS-XL-7 Co0.8Mn0.2Fe2O4The magnetic property of ferromagnetic thin film.
Embodiment 3
Step 1: cobalt nitrate, manganese acetate and ferric nitrate are dissolved in ethylene glycol monomethyl ether (x=0.3) for 0.7:0.3:2 in molar ratio, stir After mixing 50min, add acetic anhydride, obtain the stable Co that Fe ion concentration is 0.4mol/L0.7Mn0.3Fe2O4Precursor liquid, Co0.7Mn0.3Fe2O4In 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 Co0.7Mn0.3Fe2O4Precursor liquid, prepares Co0.7Mn0.3Fe2O4Wet film, to Co0.7Mn0.3Fe2O4Wet film spin coating, spin coating rotating speed is 4800r/min, spin coating time is 17s, after spin coating terminates, toasts 12min and obtain dry film at a temperature of 280 DEG C, then 680 DEG C of temperature Anneal in the lower air of degree 22min layer by layer, obtains crystalline state Co0.7Mn0.3Fe2O4Thin film；
Step 3, treats crystalline state Co0.7Mn0.3Fe2O4After film cooling, in crystalline state Co0.7Mn0.3Fe2O4Step 2 is repeated on thin film, It is repeated 11 times, obtains spinel-type Co0.7Mn0.3Fe2O4Ferromagnetic thin film.
X-ray diffractometer and Raman spectrometer is used to measure Co0.7Mn0.3Fe2O4The thing phase composition structure of ferromagnetic thin film.With SEM test characterizes Co0.7Mn0.3Fe2O4The surface topography of ferromagnetic thin film.Test with SQUID MPMS-XL-7 Co0.7Mn0.3Fe2O4The magnetic property of ferromagnetic thin film.
Embodiment 4
Step 1: cobalt nitrate, manganese acetate and ferric nitrate are dissolved in ethylene glycol monomethyl ether (x=0.4) for 0.6:0.4:2 in molar ratio, stir After mixing 30min, add acetic anhydride, obtain the stable Co that Fe ion concentration is 0.45mol/L0.6Mn0.4Fe2O4Precursor liquid, Co0.6Mn0.4Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 4.2:1；
Step 2: FTO/ glass substrate 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 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 Co on FTO/ glass substrate0.6Mn0.4Fe2O4 Precursor liquid, prepares Co0.6Mn0.4Fe2O4Wet film, to Co0.6Mn0.4Fe2O4Wet film spin coating, spin coating rotating speed is 5000r/min, even The glue time is 16s, after spin coating terminates, toasts 11min and obtain dry film, then air middle level at a temperature of 700 DEG C at a temperature of 300 DEG C Layer annealing 21min, obtains crystalline state Co0.6Mn0.4Fe2O4Thin film；
Step 3, treats crystalline state Co0.6Mn0.4Fe2O4After film cooling, in crystalline state Co0.6Mn0.4Fe2O4Step 2 is repeated on thin film, It is repeated 10 times, obtains spinel-type Co0.6Mn0.4Fe2O4Ferromagnetic thin film.
X-ray diffractometer and Raman spectrometer is used to measure Co0.6Mn0.4Fe2O4The thing phase composition structure of ferromagnetic thin film.With SEM test characterizes Co0.6Mn0.4Fe2O4The surface topography of ferromagnetic thin film.Test with SQUID MPMS-XL-7 Co0.6Mn0.4Fe2O4The magnetic property of ferromagnetic thin film.
Embodiment 5
Step 1: cobalt nitrate, manganese acetate and ferric nitrate are dissolved in ethylene glycol monomethyl ether (x=0.5) for 0.5:0.5:2 in molar ratio, stir After mixing 30min, add acetic anhydride, obtain the stable Co that Fe ion concentration is 0.5mol/L0.5Mn0.5Fe2O4Precursor liquid, Co0.5Mn0.5Fe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 4:1；
Step 2: FTO/ glass substrate 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 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 Co on FTO/ glass substrate0.5Mn0.5Fe2O4 Precursor liquid, prepares Co0.5Mn0.5Fe2O4Wet film, to Co0.5Mn0.5Fe2O4Wet film spin coating, spin coating rotating speed is 4500r/min, even The glue time is 15s, after spin coating terminates, toasts 10min and obtain dry film, then air middle level at a temperature of 630 DEG C at a temperature of 250 DEG C Layer annealing 20min, obtains crystalline state Co0.5Mn0.5Fe2O4Thin film；
Step 3, treats crystalline state Co0.5Mn0.5Fe2O4After film cooling, in crystalline state Co0.5Mn0.5Fe2O4Step 2 is repeated on thin film, It is repeated 12 times, obtains spinel-type Co0.5Mn0.5Fe2O4Ferromagnetic thin film.
X-ray diffractometer and Raman spectrometer is used to measure Co0.5Mn0.5Fe2O4The thing phase composition structure of ferromagnetic thin film.With SEM test characterizes Co0.5Mn0.5Fe2O4The surface topography of ferromagnetic thin film.Test with SQUID MPMS-XL-7 Co0.5Mn0.5Fe2O4The magnetic property of ferromagnetic thin film, records its saturation magnetization Ms～93.6emu/cm3, remanent magnetization Mr～45.5emu/cm3, coercivity Hc～535Oe.
By spinel-type Co prepared by embodiment 1～51-xMnxFe2O4Ferromagnetic thin film carries out above test, result such as Fig. 1～4 Shown in.
Fig. 1 is the Co that the present invention prepares1-xMnxFe2O4The XRD figure of ferromagnetic thin film, wherein Pure is CoFe2O4Thin film, Being the method according to the present invention, the Mn that undopes in step 1 prepares.From figure 1 it appears that prepared by the present invention Co1-xMnxFe2O4Ferromagnetic thin film is Emission in Cubic, spinel structure, and space group is Fd-3m, does not has other miscellaneous in this thin film The appearance of matter, along with the increase of Mn doping, the diffraction maximum of (220), (400) crystal face of this thin film the most gradually weakens to disappearance, (311) The diffraction peak intensity of crystal face gradually strengthens, and illustrates that Mn doping causes Co1-xMnxFe2O4(311) Solute Content in Grain of thin film.
Fig. 2 is spinel-type Co prepared by the present invention0.5Mn0.5Fe2O4The Raman spectrum of ferromagnetic thin film.CoFe2O4Thin film has There are 5 characteristic oscillation modes (A1g+Eg+3T2g), CoFe2O4Thin film is at 690cm-1The A at place1gPattern correspondence Fe-O stretching vibration, 298、225、470、570cm-1The E at placeg+3T2gVibration mode is caused by Co ion, along with the incorporation of Mn, A1gPeak Weaken, 225cm-1There is T in place2g(1) vibration mode, shows Mn ion substitution part Co ion, Mn ion simultaneously Instead of part Fe ion, make Co0.5Mn0.5Fe2O4The structure of ferromagnetic thin film is relative to CoFe2O4There occurs certain distortion.
The spinel-type Co that as can be seen from Figure 3 prepared by the present invention1-xMnxFe2O4Ferromagnetic thin film surfacing, CoFe2O4Ferrum Thin magnetic film average grain size is about 70nm, Co0.5Mn0.5Fe2O4Ferromagnetic thin film has bigger crystal grain, the average chi of crystal grain Very little about 90nm.Wherein CoFe2O4Ferromagnetic thin film is the method according to the present invention, and the Mn that undopes in step 1 prepares.
Fig. 4 is spinel-type Co prepared by the present invention1-xMnxFe2O4The hysteresis curve of ferromagnetic thin film, wherein x=0 is CoFe2O4 Thin film, is the method according to the present invention, and the Mn that undopes in step 1 prepares；X=0.5 is that the present invention prepares Co0.5Mn0.5Fe2O4Ferromagnetic thin film.From fig. 4, it can be seen that CoFe2O4Saturation magnetization M of thin films～205emu/cm3, Remanent magnetization Mr～113emu/cm3, coercivity Hc～840Oe；And the Co that the present invention prepares0.5Mn0.5Fe2O4Ferromagnetism is thin Saturation magnetization M of films～93.6emu/cm3, remanent magnetization Mr～45.5emu/cm3, coercivity Hc～535Oe.Say The doping of bright Mn ion will reduce Co1-xMnxFe2O4The ferromagnetic property of ferromagnetic thin film, reduces its coercivity simultaneously.
Present device requires simple, and experiment condition easily reaches, the spinel-type Co of preparation1-xMnxFe2O4Ferromagnetic thin film is equal Even property is preferable, and Mn content is easily controlled, and by the suitable selection to Mn content, can improve CoFe2O4Crystalline film 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 solution of the present invention by reading description of the invention, is the claim institute of the present invention Contain.

Claims (10)

1. a spinel-type Co1-xMnxFe2O4Ferromagnetic thin film, it is characterised in that the structural formula of this ferromagnetic thin film is Co1-xMnxFe2O4, x=0.1～0.5；This ferromagnetic thin film is Emission in Cubic spinel structure, and space group is Fd-3m, and edge (311) Solute Content in Grain grows.
Spinel-type Co the most according to claim 11-xMnxFe2O4Ferromagnetic thin film, it is characterised in that: described point is brilliant Stone-type Co0.5Mn0.5Fe2O4Saturation magnetization M of ferromagnetic thin films=93.6emu/cm3, remanent magnetization Mr=45.5 emu/cm3, coercivity Hc=535Oe.
3. a spinel-type Co1-xMnxFe2O4The preparation method of ferromagnetic thin film, it is characterised in that comprise the following steps:
Step 1: cobalt nitrate, manganese acetate and ferric nitrate are dissolved in ethylene glycol monomethyl ether for 1-x:x:2 in molar ratio, x=0.1～0.5, Add acetic anhydride after stirring, obtain Co1-xMnxFe2O4Precursor liquid；
Step 2: use spin-coating method spin coating Co on substrate1-xMnxFe2O4Precursor liquid, obtains Co1-xMnxFe2O4Wet film, Co1-xMnxFe2O4Wet film toasts to obtain dry film after spin coating at 250～300 DEG C, anneals in atmosphere at 630～700 DEG C, To crystalline state Co1-xMnxFe2O4Thin film；
Step 3: treat crystalline state Co1-xMnxFe2O4After film cooling, in crystalline state Co1-xMnxFe2O4Step 2 is repeated, directly on thin film To reaching desired thickness, i.e. obtain spinel-type Co1-xMnxFe2O4Ferromagnetic thin film.
Spinel-type Co the most according to claim 31-xMnxFe2O4The preparation method of ferromagnetic thin film, it is characterised in that: Described Co1-xMnxFe2O4In precursor liquid, the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is (3.5～4.5): 1, Co1-xMnxFe2O4Before Driving the concentration of Fe ion in liquid is 0.3～0.5mol/L.
Spinel-type Co the most according to claim 31-xMnxFe2O4The preparation method of ferromagnetic thin film, it is characterised in that: 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 former Sub-cleannes.
Spinel-type Co the most according to claim 31-xMnxFe2O4The preparation method of ferromagnetic thin film, it is characterised in that: Described substrate is FTO/ glass substrate, Si substrate, SrTiO3Monocrystal chip or LaNiO3Monocrystal chip.
Spinel-type Co the most according to claim 31-xMnxFe2O4The preparation method of ferromagnetic thin film, it is characterised in that: In described step 2, spin coating rotating speed during spin coating is 4500～5000r/min, and spin coating time is 15～20s.
Spinel-type Co the most according to claim 31-xMnxFe2O4The preparation method of ferromagnetic thin film, it is characterised in that: In described step 2, the baking time after spin coating is 10～15min.
Spinel-type Co the most according to claim 31-xMnxFe2O4The preparation method of ferromagnetic thin film, it is characterised in that: Annealing time in described step 2 is 20～25min.
Spinel-type Co the most according to claim 31-xMnxFe2O4The preparation method of ferromagnetic thin film, it is characterised in that: Described spinel-type Co1-xMnxFe2O4Ferromagnetic thin film is by 10～15 layer crystal states Co1-xMnxFe2O4Thin film is constituted.
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CN106830089A (en) * 2017-02-22 2017-06-13 中国科学院兰州化学物理研究所 The synthesis of the spinel-type chromatic ceramics pigment containing cobalt element and preparing the application of solar energy light absorption coating
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
CN108793767A (en) * 2018-06-26 2018-11-13 陕西科技大学 A kind of CoFe2-xLaxO4Ferromagnetic thin film and preparation method thereof
CN109111127A (en) * 2018-09-18 2019-01-01 陕西科技大学 A kind of BLSFMC/CMFO film and preparation method thereof with resistance switch effect
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
CN112742416A (en) * 2021-01-20 2021-05-04 中国石油大学胜利学院 Spinel type composite oxide MnCo2O4Novel preparation method of
CN114014642A (en) * 2021-10-09 2022-02-08 国家能源集团科学技术研究院有限公司 Manganese-cobalt ferrite nano material and preparation method and application thereof

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CN104478234A (en) * 2014-12-11 2015-04-01 陕西科技大学 Bi0.90Er0.10Fe0.96Co0.02Mn0.02O3/Mn(1-x)CoxFe2O4 composite film and preparation method thereof

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CN106830089A (en) * 2017-02-22 2017-06-13 中国科学院兰州化学物理研究所 The synthesis of the spinel-type chromatic ceramics pigment containing cobalt element and preparing the application of solar energy light absorption coating
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
CN108793767A (en) * 2018-06-26 2018-11-13 陕西科技大学 A kind of CoFe2-xLaxO4Ferromagnetic 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
CN109111127A (en) * 2018-09-18 2019-01-01 陕西科技大学 A kind of BLSFMC/CMFO film and preparation method thereof with resistance switch effect
CN109111127B (en) * 2018-09-18 2021-06-29 陕西科技大学 BLSFMC/CMFO film with resistance switching effect 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
CN112742416A (en) * 2021-01-20 2021-05-04 中国石油大学胜利学院 Spinel type composite oxide MnCo2O4Novel preparation method of
CN114014642A (en) * 2021-10-09 2022-02-08 国家能源集团科学技术研究院有限公司 Manganese-cobalt ferrite nano material and preparation method and application thereof

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