CN105819848B - A kind of spinel-type Co1-xMnxFe2O4Ferromagnetic thin film and preparation method thereof - Google Patents

A kind of spinel-type Co1-xMnxFe2O4Ferromagnetic thin film and preparation method thereof Download PDF

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CN105819848B
CN105819848B CN201610187623.3A CN201610187623A CN105819848B CN 105819848 B CN105819848 B CN 105819848B CN 201610187623 A CN201610187623 A CN 201610187623A CN 105819848 B CN105819848 B CN 105819848B
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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 present invention provides a kind of spinel-type Co1‑xMnxFe2O4Ferromagnetic thin film and preparation method thereof, comprising the following steps: by cobalt nitrate, manganese acetate and ferric nitrate be in molar ratio that 1-x:x:2 (x=0.1~0.5) is dissolved in ethylene glycol monomethyl ether and acetic anhydride, stir to get Co1‑xMnxFe2O4Precursor liquid, the technique with spin-coating method and successively annealed prepare the spinel-type Co of edge (311) the Solute Content in Grain growth of the high even grain size of consistency on substrate1‑ xMnxFe2O4Ferromagnetic thin film.The present invention uses sol gel process, and equipment requirement is simple, and experiment condition is easy to reach, suitable large area film forming, and chemical constituent controllable precise, and can be by Mn element doping amount to Co1‑xMnxFe2O4The ferromagnetic property of ferromagnetic thin film is regulated and controled.

Description

A kind of spinel-type Co1-xMnxFe2O4Ferromagnetic thin film and preparation method thereof
Technical field
The invention belongs to field of functional materials, and in particular to a kind of spinel-type Co1-xMnxFe2O4Ferromagnetic thin film and its Preparation method.
Background technique
Ferrite is a kind of magnetic functional material with extensive use.Wherein spinel-type Conjugate ferrite has preferable Electromagnetic property and be widely used in information storage system, spin electric device, various magnetic devices and communication apparatus etc..Simultaneously Cobalt ferrite thin films have 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, deposits At four sides, position and two class gap of octahedral position, unit cell contain 8 molecules, and 32 oxygen atoms form 64 tetrahedrons altogether Position, 32 octahedral positions.These gaps cannot be all occupied by cation, only 8 four sides positions, 16 octahedral positions Can be occupied by oxonium ion, mark is A and B respectively.Just because of the doping and substitution for existing for metal ion in gap It creates condition, to keep spinel type ferrite many kinds of, performance is more excellent.
Currently, preparing spinel-type Co using sol-gel method not yet1-xMnxFe2O4The related report of ferromagnetic thin film Road.
Summary of the invention
The purpose of the present invention is to provide a kind of spinel-type Co1-xMnxFe2O4Ferromagnetic thin film and preparation method thereof, should Method can prepare the Co with excellent ferromagnetic property1-xMnxFe2O4Crystalline film.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of spinel-type Co1-xMnxFe2O4Ferromagnetic thin film, the structural formula of the ferromagnetic thin film are Co1-xMnxFe2O4, X=0.1~0.5；The ferromagnetic thin film be cubic phase spinel structure, space group Fd-3m, and along (311) crystal face preferentially Oriented growth.
The spinel-type Co0.5Mn0.5Fe2O4The saturation magnetization M of ferromagnetic thin films=93.6emu/cm3, remain Residual magnetization Mr=45.5emu/cm3, coercivity Hc=535Oe.
A kind of spinel-type Co1-xMnxFe2O4The preparation method of ferromagnetic thin film, comprising the following steps:
Step 1: it is in molar ratio that 1-x:x:2 is dissolved in ethylene glycol monomethyl ether by cobalt nitrate, manganese acetate and ferric nitrate, x=0.1 ~0.5, acetic anhydride is added after mixing evenly, obtains Co1-xMnxFe2O4Precursor liquid；
Step 2: using 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 air at 630~700 DEG C, Obtain crystalline state Co1-xMnxFe2O4Film；
Step 3: to crystalline state Co1-xMnxFe2O4After film cooling, in crystalline state Co1-xMnxFe2O4Step 2 is repeated on film, directly To reaching required thickness to get to spinel-type Co1-xMnxFe2O4Ferromagnetic thin film.
The Co1-xMnxFe2O4Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are (3.5~4.5) in precursor liquid: 1, Co1-xMnxFe2O4The concentration of Fe ion is 0.3~0.5mol/L in precursor liquid.
The step 2 first cleans up substrate surface before progress, then treatment with irradiation under ultraviolet light, makes substrate Surface reaches atomic cleanliness degree.
The substrate is FTO/ glass substrate, Si substrate, SrTiO3Monocrystal chip or LaNiO3Monocrystal chip.
Spin coating revolving speed in the step 2 when spin coating is 4500~5000r/min, and spin coating time is 15~20s.
Baking time in the step 2 after spin coating is 10~15min.
Annealing time in the step 2 is 20~25min.
The spinel-type Co1-xMnxFe2O4Ferromagnetic thin film is by 10~15 layer crystal state Co1-xMnxFe2O4Film is constituted.
Compared with the existing technology, the invention has the following advantages:
1. spinel-type Co provided by the invention1-xMnxFe2O4The preparation method of ferromagnetic thin film selects transition elements Mn Carry out CoFe2O4The position A doping.In the ferrite of spinel structure, the Net magnetic moment for the per unit that the substitution of Mn obtains is 5 μB, therefore with the increase of Mn doping content, it will be to Co1-xMnxFe2O4The magnetic property of ferromagnetic thin film has a great impact, by In the magnetic property of Mn ion, it will change Co1-xMnxFe2O4The magnetic property of ferromagnetic thin film.
2. currently used for preparing CoFe2O4There are many method of film, such as mechanochemical synthesis, chemical coprecipitation, molten Glue-gel method (Sol-Gel), hydro-thermal method, predecessor solid reaction process etc..Compared to other methods, Sol-Gel method is due to equipment Simply, reaction is easy to carry out, and reaction temperature is lower, easy to operate, is suitable for preparing on big surface and surface in irregular shape Film, easily realize molecular level on Uniform Doped and chemical constituent controllable precise the advantages that and be widely used for preparing iron Electric material.The present invention uses sol-gel method because sol-gel method preparation process is simple, easily controllable introducing dopant and Its doping, product purity is high, and the mixing of molecular level may be implemented using the method, therefore system uniformity is good.This Sol-gal process is used in invention, and CoFe is adulterated by transition elements Mn2O4, spinel-type Co is prepared on substrate1-xMnxFe2O4 Ferromagnetic thin film obtains the Co with excellent ferromagnetic property by doping1-xMnxFe2O4Crystalline film.
3. spinel-type Co provided by the invention1-xMnxFe2O4Ferromagnetic thin film is cubic phase spinel structure, spatial point Group is Fd-3m, with the increase of Mn doping, Co1-xMnxFe2O4Ferromagnetic thin film is grown along (311) Solute Content in Grain, and And the doping of Mn can reduce Co1-xMnxFe2O4The ferromagnetic property of ferromagnetic thin film, while reducing Co1-xMnxFe2O4Ferromagnetism The coercivity of film, therefore can be by the variation of Co element doping amount to Co1-xMnxFe2O4The ferromagnetic property of ferromagnetic thin film Regulated and controled.
Detailed description of the invention
Fig. 1 is spinel-type Co prepared by the present invention0.5Mn0.5Fe2O4The XRD diagram of ferromagnetic thin film；
Fig. 2 is spinel-type Co prepared by the present invention0.5Mn0.5Fe2O4The Raman map of ferromagnetic thin film；
Fig. 3 is spinel-type Co prepared by the present invention1-xMnxFe2O4The SEM of ferromagnetic thin film schemes, and wherein a is CoFe2O4It is thin The SEM of film schemes, b Co0.5Mn0.5Fe2O4The SEM of ferromagnetic thin film schemes；
Fig. 4 is spinel-type Co prepared by the present invention1-xMnxFe2O4The hysteresis loop figure of ferromagnetic thin film.
Specific embodiment
The present invention is described in further details below with reference to the present invention preferably embodiment and attached drawing.
Embodiment 1
Step 1: by cobalt nitrate, manganese acetate and ferric nitrate are that 0.9:0.1:2 is dissolved in ethylene glycol monomethyl ether (x=in molar ratio 0.1) after, stirring 30min, acetic anhydride is added, obtains the stable Co that Fe ion concentration is 0.3mol/L0.9Mn0.1Fe2O4Before Drive liquid, Co0.9Mn0.1Fe2O4Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are 3.5:1 in precursor liquid；
Step 2: Si substrate is sequentially placed into detergent, acetone, ultrasonic cleaning in ethyl alcohol, each ultrasonic cleaning With a large amount of distilled water flushing FTO/ glass substrates after 10min, finally with being dried with nitrogen.Then Si substrate is put into baking oven baking To drying, takes out and stand to room temperature.Clean Si substrate is placed in ultraviolet radiation instrument again and irradiates 40min, makes Si substrate table Face reaches " atomic cleanliness degree ".Using spin-coating method spin coating Co on si substrates0.9Mn0.1Fe2O4Precursor liquid, preparation Co0.9Mn0.1Fe2O4Wet film, to Co0.9Mn0.1Fe2O4Wet film spin coating, spin coating revolving speed be 4600r/min, spin coating time 20s, it is even After glue, 15min is toasted at a temperature of 260 DEG C and obtains dry film, then the 25min that anneals layer by layer in air at a temperature of 650 DEG C, is obtained Crystalline state Co0.9Mn0.1Fe2O4Film；
Step 3, to crystalline state Co0.9Mn0.1Fe2O4After film cooling, in crystalline state Co0.9Mn0.1Fe2O4Step is repeated on film 2, it is repeated 9 times, obtains spinel-type Co0.9Mn0.1Fe2O4Ferromagnetic thin film.
Co is measured using x-ray diffractometer and Raman spectrometer0.9Mn0.1Fe2O4The object phase composition structure of ferromagnetic thin film. Characterization Co is tested with SEM0.9Mn0.1Fe2O4The surface topography of ferromagnetic thin film.It is tested with SQUID MPMS-XL-7 Co0.9Mn0.1Fe2O4The magnetic property of ferromagnetic thin film.
Embodiment 2
Step 1: by cobalt nitrate, manganese acetate and ferric nitrate are that 0.8:0.2:2 is dissolved in ethylene glycol monomethyl ether (x=in molar ratio 0.2) after, stirring 30min, acetic anhydride is added, obtains the stable Co that Fe ion concentration is 0.35mol/L0.8Mn0.2Fe2O4Before Drive liquid, Co0.8Mn0.2Fe2O4Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are 4.5:1 in precursor liquid；
Step 2: by SrTiO3Monocrystal chip is sequentially placed into detergent, acetone, ultrasonic cleaning in ethyl alcohol, each ultrasonic wave With a large amount of distilled water flushing SrTiO after cleaning 10min3Monocrystal chip, finally with being dried with nitrogen.Then by SrTiO3Monocrystal chip It is put into baking oven and is baked to drying, take out and stand to room temperature.Again by clean SrTiO3Monocrystal chip is placed in ultraviolet radiation instrument 40min is irradiated, SrTiO is made3Monocrystal chip surface reaches " atomic cleanliness degree ".Using spin-coating method in SrTiO3It is revolved on monocrystal chip Apply Co0.8Mn0.2Fe2O4Precursor liquid prepares Co0.8Mn0.2Fe2O4Wet film, to Co0.8Mn0.2Fe2O4Wet film spin coating, spin coating revolving speed are 4700r/min, spin coating time 19s after spin coating, toast 14min at a temperature of 270 DEG C and obtain dry film, then in 670 DEG C of temperature Anneal 24min layer by layer in lower air, obtains crystalline state Co0.8Mn0.2Fe2O4Film；
Step 3, to crystalline state Co0.8Mn0.2Fe2O4After film cooling, in crystalline state Co0.8Mn0.2Fe2O4Step is repeated on film 2, it is repeated 14 times, obtains spinel-type Co0.8Mn0.2Fe2O4Ferromagnetic thin film.
Co is measured using x-ray diffractometer and Raman spectrometer0.8Mn0.2Fe2O4The object phase composition structure of ferromagnetic thin film. Characterization Co is tested with SEM0.8Mn0.2Fe2O4The surface topography of ferromagnetic thin film.It is tested with SQUID MPMS-XL-7 Co0.8Mn0.2Fe2O4The magnetic property of ferromagnetic thin film.
Embodiment 3
Step 1: by cobalt nitrate, manganese acetate and ferric nitrate are that 0.7:0.3:2 is dissolved in ethylene glycol monomethyl ether (x=in molar ratio 0.3) after, stirring 50min, acetic anhydride is added, obtains the stable Co that Fe ion concentration is 0.4mol/L0.7Mn0.3Fe2O4Before Drive liquid, Co0.7Mn0.3Fe2O4Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are 3.8:1 in precursor liquid；
Step 2: by LaNiO3Monocrystal chip is sequentially placed into detergent, acetone, ultrasonic cleaning in ethyl alcohol, each ultrasonic wave With a large amount of distilled water flushing LaNiO after cleaning 10min3Monocrystal chip, finally with being dried with nitrogen.Then by LaNiO3Monocrystal chip It is put into baking oven and is baked to drying, take out and stand to room temperature.Again by clean LaNiO3Monocrystal chip is placed in ultraviolet radiation instrument 40min is irradiated, LaNiO is made3Monocrystal chip surface reaches " atomic cleanliness degree ".Using spin-coating method in LaNiO3It is revolved on monocrystal chip Apply Co0.7Mn0.3Fe2O4Precursor liquid prepares Co0.7Mn0.3Fe2O4Wet film, to Co0.7Mn0.3Fe2O4Wet film spin coating, spin coating revolving speed are 4800r/min, spin coating time 17s after spin coating, toast 12min at a temperature of 280 DEG C and obtain dry film, then in 680 DEG C of temperature Anneal 22min layer by layer in lower air, obtains crystalline state Co0.7Mn0.3Fe2O4Film；
Step 3, to crystalline state Co0.7Mn0.3Fe2O4After film cooling, in crystalline state Co0.7Mn0.3Fe2O4Step is repeated on film 2, it is repeated 11 times, obtains spinel-type Co0.7Mn0.3Fe2O4Ferromagnetic thin film.
Co is measured using x-ray diffractometer and Raman spectrometer0.7Mn0.3Fe2O4The object phase composition structure of ferromagnetic thin film. Characterization Co is tested with SEM0.7Mn0.3Fe2O4The surface topography of ferromagnetic thin film.It is tested with SQUID MPMS-XL-7 Co0.7Mn0.3Fe2O4The magnetic property of ferromagnetic thin film.
Embodiment 4
Step 1: by cobalt nitrate, manganese acetate and ferric nitrate are that 0.6:0.4:2 is dissolved in ethylene glycol monomethyl ether (x=in molar ratio 0.4) after, stirring 30min, acetic anhydride is added, obtains the stable Co that Fe ion concentration is 0.45mol/L0.6Mn0.4Fe2O4Before Drive liquid, Co0.6Mn0.4Fe2O4Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are 4.2:1 in precursor liquid；
Step 2: FTO/ glass substrate being sequentially placed into detergent, acetone, ultrasonic cleaning in ethyl alcohol, each ultrasonic wave is clear It washes after 10min with a large amount of distilled water flushing FTO/ glass substrates, finally with being dried with nitrogen.Then FTO/ glass substrate is put into Baking oven is baked to drying, takes out and stands to room temperature.Clean FTO/ glass substrate is placed in ultraviolet radiation instrument again and is irradiated 40min makes FTO/ glass substrate surface reach " atomic cleanliness degree ".Using spin-coating method spin coating in FTO/ glass substrate Co0.6Mn0.4Fe2O4Precursor liquid prepares Co0.6Mn0.4Fe2O4Wet film, to Co0.6Mn0.4Fe2O4Wet film spin coating, spin coating revolving speed are 5000r/min, spin coating time 16s after spin coating, toast 11min at a temperature of 300 DEG C and obtain dry film, then in 700 DEG C of temperature Anneal 21min layer by layer in lower air, obtains crystalline state Co0.6Mn0.4Fe2O4Film；
Step 3, to crystalline state Co0.6Mn0.4Fe2O4After film cooling, in crystalline state Co0.6Mn0.4Fe2O4Step is repeated on film 2, it is repeated 10 times, obtains spinel-type Co0.6Mn0.4Fe2O4Ferromagnetic thin film.
Co is measured using x-ray diffractometer and Raman spectrometer0.6Mn0.4Fe2O4The object phase composition structure of ferromagnetic thin film. Characterization Co is tested with SEM0.6Mn0.4Fe2O4The surface topography of ferromagnetic thin film.It is tested with SQUID MPMS-XL-7 Co0.6Mn0.4Fe2O4The magnetic property of ferromagnetic thin film.
Embodiment 5
Step 1: by cobalt nitrate, manganese acetate and ferric nitrate are that 0.5:0.5:2 is dissolved in ethylene glycol monomethyl ether (x=in molar ratio 0.5) after, stirring 30min, acetic anhydride is added, obtains the stable Co that Fe ion concentration is 0.5mol/L0.5Mn0.5Fe2O4Before Drive liquid, Co0.5Mn0.5Fe2O4Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are 4:1 in precursor liquid；
Step 2: FTO/ glass substrate being sequentially placed into detergent, acetone, ultrasonic cleaning in ethyl alcohol, each ultrasonic wave is clear It washes after 10min with a large amount of distilled water flushing FTO/ glass substrates, finally with being dried with nitrogen.Then FTO/ glass substrate is put into Baking oven is baked to drying, takes out and stands to room temperature.Clean FTO/ glass substrate is placed in ultraviolet radiation instrument again and is irradiated 40min makes FTO/ glass substrate surface reach " atomic cleanliness degree ".Using spin-coating method spin coating in FTO/ glass substrate Co0.5Mn0.5Fe2O4Precursor liquid prepares Co0.5Mn0.5Fe2O4Wet film, to Co0.5Mn0.5Fe2O4Wet film spin coating, spin coating revolving speed are 4500r/min, spin coating time 15s after spin coating, toast 10min at a temperature of 250 DEG C and obtain dry film, then in 630 DEG C of temperature Anneal 20min layer by layer in lower air, obtains crystalline state Co0.5Mn0.5Fe2O4Film；
Step 3, to crystalline state Co0.5Mn0.5Fe2O4After film cooling, in crystalline state Co0.5Mn0.5Fe2O4Step is repeated on film 2, it is repeated 12 times, obtains spinel-type Co0.5Mn0.5Fe2O4Ferromagnetic thin film.
Co is measured using x-ray diffractometer and Raman spectrometer0.5Mn0.5Fe2O4The object phase composition structure of ferromagnetic thin film. Characterization Co is tested with SEM0.5Mn0.5Fe2O4The surface topography of ferromagnetic thin film.It is tested with SQUID MPMS-XL-7 Co0.5Mn0.5Fe2O4The magnetic property of ferromagnetic thin film measures its saturation magnetization Ms~93.6emu/cm3, remanent magnetization Mr~45.5emu/cm3, coercivity Hc~535Oe.
Pass through the spinel-type Co prepared to Examples 1 to 51-xMnxFe2O4Ferromagnetic thin film carries out the above test, as a result As shown in Fig. 1~4.
Fig. 1 is Co produced by the present invention1-xMnxFe2O4The XRD diagram of ferromagnetic thin film, wherein Pure is CoFe2O4Film is The method according to the invention is undoped in step 1 made from Mn.From figure 1 it appears that Co prepared by the present invention1- xMnxFe2O4Ferromagnetic thin film is cubic phase, spinel structure, space group Fd-3m, does not have other impurities in the film Occur, with the increase of Mn doping, (220) of the film, the diffraction maximum of (400) crystal face then gradually weaken to disappearance, (311) The diffraction peak intensity of crystal face gradually increases, and illustrates that Mn doping leads to Co1-xMnxFe2O4(311) Solute Content in Grain of film.
Fig. 2 is spinel-type Co prepared by the present invention0.5Mn0.5Fe2O4The Raman spectrum of ferromagnetic thin film.CoFe2O4It is thin Film has 5 characteristic oscillation modes (A1g+Eg+3T2g), CoFe2O4Film is in 690cm-1The A at place1gMode corresponds to the flexible vibration of Fe-O It is dynamic, 298,225,470,570cm-1The E at placeg+3T2gVibration mode is as caused by Co ion, with the incorporation of Mn, A1gPeak hair Raw reduction, 225cm-1There is T in place2g(1) vibration mode shows Mn ion substitution part Co ion, while Mn ion substitution Part Fe ion, makes Co0.5Mn0.5Fe2O4The structure of ferromagnetic thin film is with respect to CoFe2O4Certain distortion has occurred.
Spinel-type Co prepared by the present invention as can be seen from Figure 31-xMnxFe2O4Ferromagnetic thin film surfacing, CoFe2O4 Ferromagnetic thin film average grain size is about 70nm, Co0.5Mn0.5Fe2O4Ferromagnetic thin film has biggish crystal grain, and crystal grain is average Size is about 90nm.Wherein CoFe2O4Ferromagnetic thin film is the method according to the invention, is undoped made from Mn in step 1.
Fig. 4 is spinel-type Co prepared by the present invention1-xMnxFe2O4The hysteresis loop of ferromagnetic thin film, wherein x=0 be CoFe2O4Film, is the method according to the invention, is undoped made from Mn in step 1；X=0.5 is produced by the present invention Co0.5Mn0.5Fe2O4Ferromagnetic thin film.From fig. 4, it can be seen that CoFe2O4The saturation magnetization M of films~205emu/cm3, Remanent magnetization Mr~113emu/cm3, coercivity Hc~840Oe；And Co produced by the present invention0.5Mn0.5Fe2O4Ferromagnetism is thin The saturation magnetization M of films~93.6emu/cm3, remanent magnetization Mr~45.5emu/cm3, coercivity Hc~535Oe.It says The doping of bright Mn ion will reduce Co1-xMnxFe2O4The ferromagnetic property of ferromagnetic thin film, while reducing its coercivity.
Present device requires simply, and experiment condition is easy to reach, the spinel-type Co of preparation1-xMnxFe2O4Ferromagnetism is thin Film uniformity is preferable, and Mn content is easy to control, and by the appropriate selection to Mn content, will improve CoFe2O4Crystalline film Ferromagnetic property.
The foregoing is merely one embodiment of the present invention, it is not all of or unique embodiment, this field is common Any equivalent transformation that technical staff takes technical solution of the present invention by reading description of the invention, is the present invention Claim covered.

Claims (10)

1. a kind of spinel-type Co1-xMnxFe2O4The preparation method of ferromagnetic thin film, which comprises the following steps:
Step 1: it is in molar ratio that 1-x:x:2 is dissolved in ethylene glycol monomethyl ether by cobalt nitrate, manganese acetate and ferric nitrate, x=0.1~ 0.5, acetic anhydride is added after mixing evenly, obtains Co1-xMnxFe2O4Precursor liquid；
Step 2: using 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, obtains in air at 630~700 DEG C To crystalline state Co1-xMnxFe2O4Film；
Step 3: to crystalline state Co1-xMnxFe2O4After film cooling, in crystalline state Co1-xMnxFe2O4Step 2 is repeated on film, until reaching To required thickness to get arrive spinel-type Co1-xMnxFe2O4Ferromagnetic thin film.
2. spinel-type Co according to claim 11-xMnxFe2O4The preparation method of ferromagnetic thin film, it is characterised in that: The Co1-xMnxFe2O4Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are (3.5~4.5) in precursor liquid: 1, Co1-xMnxFe2O4 The concentration of Fe ion is 0.3~0.5mol/L in precursor liquid.
3. spinel-type Co according to claim 11-xMnxFe2O4The preparation method of ferromagnetic thin film, it is characterised in that: The step 2 first cleans up substrate surface before progress, then treatment with irradiation under ultraviolet light, reaches substrate surface Atomic cleanliness degree.
4. spinel-type Co according to claim 11-xMnxFe2O4The preparation method of ferromagnetic thin film, it is characterised in that: The substrate is FTO/ glass substrate, Si substrate, SrTiO3Monocrystal chip or LaNiO3Monocrystal chip.
5. spinel-type Co according to claim 11-xMnxFe2O4The preparation method of ferromagnetic thin film, it is characterised in that: Spin coating revolving speed in the step 2 when spin coating is 4500~5000r/min, and spin coating time is 15~20s.
6. spinel-type Co according to claim 11-xMnxFe2O4The preparation method of ferromagnetic thin film, it is characterised in that: Baking time in the step 2 after spin coating is 10~15min.
7. spinel-type Co according to claim 11-xMnxFe2O4The preparation method of ferromagnetic thin film, it is characterised in that: Annealing time in the step 2 is 20~25min.
8. spinel-type Co according to claim 11-xMnxFe2O4The preparation method of ferromagnetic thin film, it is characterised in that: The spinel-type Co1-xMnxFe2O4Ferromagnetic thin film is by 10~15 layer crystal state Co1-xMnxFe2O4Film is constituted.
9. a kind of spinel-type Co that the described in any item methods of claim 1-8 are prepared1-xMnxFe2O4Ferromagnetic thin film, It is characterized in that, the structural formula of the ferromagnetic thin film is Co1-xMnxFe2O4, x=0.1~0.5；The ferromagnetic thin film is cubic phase Spinel structure, space group Fd-3m, and grown along (311) Solute Content in Grain.
10. spinel-type Co according to claim 91-xMnxFe2O4Ferromagnetic thin film, it is characterised in that: the point is brilliant Stone-type Co0.5Mn0.5Fe2O4The saturation magnetization M of ferromagnetic thin films=93.6emu/cm3, remanent magnetization Mr= 45.5emu/cm3, coercivity Hc=535Oe.
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