CN108726888A - A kind of CoFe2-xGdxO4Ferromagnetic thin film and preparation method thereof - Google Patents
A kind of CoFe2-xGdxO4Ferromagnetic thin film and preparation method thereof Download PDFInfo
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- CN108726888A CN108726888A CN201810672033.9A CN201810672033A CN108726888A CN 108726888 A CN108726888 A CN 108726888A CN 201810672033 A CN201810672033 A CN 201810672033A CN 108726888 A CN108726888 A CN 108726888A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
Abstract
A kind of CoFe of the present invention2‑xGdxO4Ferromagnetic thin film and preparation method thereof, x=0.02~0.18.Preparation method includes：Step 1, it is in molar ratio 1:(2-x):Cobalt nitrate, ferric nitrate and gadolinium nitrate are dissolved in ethylene glycol monomethyl ether by x, are stirring evenly and then adding into acetic anhydride, are continued to stir evenly, are obtained precursor liquid；Step 2, precursor liquid is spin-coated on FTO/glass substrates, obtains wet film, wet film toasts to obtain dry film after spin coating at 170~190 DEG C, anneals in air at 620~640 DEG C, obtains crystalline state CoFe2‑xGdxO4Film；Step 3, by crystalline state CoFe2‑xGdxO4Film cooling repeats step 2 until reaching preset thickness to get to CoFe to room temperature2‑xGdxO4Ferromagnetic thin film.Gd3+The incorporation of ion is mainly instead of the Fe in lattice3+Ion improves ferromagnetic property.
Description
Technical field
The invention belongs to field of functional materials, it is related to preparing CoFe on the surface of functionalization2-xGdxO4(CF2-xGxO) ferromagnetic
Property film, specially a kind of CoFe2-xGdxO4Ferromagnetic thin film and preparation method thereof.
Background technology
Nowadays the world has come into the information age, and with the development of the times, the development of information industry be unable to do without storage skill
Art.Information storing technology includes magnetic recording information storing technology, optical information storing technology, semiconductor flash memory technology.Magnetic is remembered at present
The technology of the storage of record has prodigious advantage, and has prodigious development potentiality and application prospect.Cobalt ferrite (CoFe2O4), referred to as
CFO is a kind of retentive material with Magnetostrictive Properties, has higher coercive field, moderate saturation magnetisation value, high
Insulating properties, good chemical stability, and there are higher magnetic conductivity and higher dielectric properties in high frequency, therefore special
It is not suitble to apply under high frequency and hyperfrequency.
But since it has smaller remanent magnetization, big saturation magnetization and lower stupid field of spoiling, lead to it
The rectangular degree of hysteresis loop is relatively low, limits the application of cobalt ferrite in practice, and a large amount of research at present all concentrates on replacing
CoFe2O4In Co3+Ion, but the rectangular degree of hysteresis loop is not improved.
Invention content
The purpose of the present invention is to provide a kind of CoFe2-xGdxO4Ferromagnetic thin film and preparation method thereof, this method equipment are wanted
Ask simple, experiment condition is easy to reach, and doping is easy to control, and film obtained is CoFe2-xGdxO4Ferromagnetic thin film can carry
The rectangular degree of high hysteresis loop improves CoFe2O4The ferromagnetic property of base film.
The present invention is to be achieved through the following technical solutions：
A kind of CoFe2-xGdxO4Ferromagnetic thin film, chemical formula CoFe2-xGdxO4, wherein x=0.02~0.18,
For a cube inverse spinel structure, space group Fd3m；CoFe2-xGdxO4Ferromagnetic thin film is along (311) crystal plane direction oriented growth.
Preferably, as x=0.02, remanent magnetization Mr=125.5emu/cm3, saturation magnetization Ms=
192.8emu/cm3, squareness ratio R=0.65.
A kind of CoFe2-xGdxO4The preparation method of ferromagnetic thin film, includes the following steps：
Step 1, it is in molar ratio 1:(2-x):Cobalt nitrate, ferric nitrate and gadolinium nitrate are dissolved in ethylene glycol monomethyl ether by x, stirring
Acetic anhydride is added after uniformly, continues to stir evenly, obtains the precursor liquid of ferromagnetic thin film；
Step 2, precursor liquid is spin-coated on FTO/glass substrates, obtains wet film, wet film is after spin coating at 170~190 DEG C
Under toast to obtain dry film, anneal in air at 620~640 DEG C, obtain crystalline state CoFe2-xGdxO4Film；
Step 3, by crystalline state CoFe2-xGdxO4Film cooling to room temperature, repeat step 2 until reach preset thickness to get
To CoFe2-xGdxO4Ferromagnetic thin film.
Preferably, in step 1, the total concentration of metal ion is 0.20~0.40mol/L in precursor liquid.
Preferably, in step 1, ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are (2.5~3.5) in precursor liquid:1.
Preferably, step 2 first cleans up FTO/glass substrates before carrying out, and then irradiates under ultraviolet light, makes FTO/
Glass substrate surfaces reach atomic cleanliness degree.
Preferably, the spin coating rotating speed in step 2 when spin coating is 3500~4000r/min, and spin coating time is 19~25s.
Preferably, the baking time in step 2 after spin coating is 12~16min.
Preferably, the annealing time in step 2 is 35~55min.
Compared with prior art, the present invention has technique effect beneficial below：
The CoFe of the present invention2-xGdxO4Ferromagnetic thin film is cube inverse spinel structure, space group Fd3m, Gd3+Ion
Incorporation mainly instead of the Fe in lattice3+Ion forms CoFe2-xGdxO4Structural formula makes CoFe2-xGdxO4Ferromagnetism
The structure of film is with respect to CoFe2O4Certain distortion of lattice has occurred, improves ferromagnetic property.The result shows that being remained when x=0.00
Residual magnetization Mr=120.5emu/cm3, saturation magnetization Ms=266.5emu/cm, squareness ratio R=0.45；When x=0.02
Its remanent magnetization Mr=125.5emu/cm3, saturation magnetization Ms=192.8emu/cm3, squareness ratio R=0.65.Explanation
Gd3+The rear film of ion incorporation reduces saturation magnetization, and then influence it on the basis of not changing remanent magnetization
The raising of squareness ratio improves the magnetic property of film, obtained CoFe2-xGdxO4Ferromagnetic thin film shows excellent ferromagnetism
Energy.
CF provided by the invention2-xGxThe preparation method of O ferromagnetic thin films, using sol-gel method, cobalt nitrate, ferric nitrate
It is raw material with gadolinium nitrate, using the precursor liquid that ethylene glycol monomethyl ether and acetic anhydride are prepared as solvent, then anneal with spin-coating method and layer by layer
Technique is prepared for CoFe2-xGdxO4Ferromagnetic thin film, the present invention use sol-gel technology, the side of film are prepared compared to other
Method, this method equipment requirement is simple, and experiment condition is easily achieved, of low cost, reacts and is easy to carry out, and technical process temperature is low,
Preparation process and doping are easy to control, chemical constituent controllable precise, suitable on big surface and surface in irregular shape
Prepare film, it is easy to mix to equal and quantitative some trace elements, atom or molecular level can be obtained in a short time
Uniformity, CF prepared by the present invention2-xGxO ferromagnetic thin film uniformities are preferable, show preferable ferromagnetic property.
Description of the drawings
Fig. 1 is CF prepared by 1-6 of the embodiment of the present invention2-xGxThe XRD spectrum of O ferromagnetic thin films；
Fig. 2 is CF prepared by the embodiment of the present invention 1,4 and 62-xGxThe Raman collection of illustrative plates of O ferromagnetic thin films；
Fig. 3 is that the embodiment of the present invention 1,2 prepares CF2-xGxThe hysteresis loop of O ferromagnetic thin films.
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
A kind of CoFe2-xGdxO4Ferromagnetic thin film, wherein x=0.02~0.18 is cube inverse spinel structure, space group
For Fd3m；CoFe2-xGdxO4Ferromagnetic thin film is along (311) crystal plane direction oriented growth.
The CoFe2-xGdxO4Ferromagnetic thin film, its remanent magnetization M as x=0.02r=125.5emu/cm3,
Saturation magnetization Ms=192.8emu/cm3, squareness ratio R=0.65.
The CoFe2-xGdxO4The preparation method of ferromagnetic thin film, includes the following steps：
Step 1：It is 1 in molar ratio:(2-x):Cobalt nitrate, ferric nitrate and gadolinium nitrate are dissolved in ethylene glycol monomethyl ether by x, stirring
Acetic anhydride is added after uniformly, continues to stir evenly, obtains precursor liquid；Wherein x=0.02~0.18；
Step 2：Precursor liquid is spin-coated on FTO/glass substrates, obtains wet film, wet film is after spin coating at 170~190 DEG C
Under toast to obtain dry film, anneal in air at 620~640 DEG C, obtain crystalline state CoFe2-xGdxO4Film；
Step 3：By crystalline state CoFe2-xGdxO4Film cooling to room temperature, repeat step 2 until reach required thickness to get to
CoFe2-xGdxO4Ferromagnetic thin film.
The total concentration of metal ion is 0.20~0.40mol/L in precursor liquid in the step 1.
Ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are (2.5~3.5) in the precursor liquid:1.
The step 2 first cleans up FTO/glass substrates before carrying out, and then irradiates under ultraviolet light, makes FTO/
Glass substrate surfaces reach atomic cleanliness degree.
Spin coating rotating speed in the step 2 when spin coating is 3500~4000r/min, and spin coating time is 19~25s.
Baking time in the step 2 after spin coating is 12~16min.
Annealing time in the step 2 is 35~55min.
Specific embodiment is as follows.
Embodiment 1
Step 1：FTO/glass substrates are totally sealed up for safekeeping with liquid detergent, acetone, washes of absolute alcohol in absolute ethyl alcohol respectively
In it is spare；
Step 2：Cobalt nitrate and ferric nitrate are raw material, are in molar ratio 1:2 are dissolved in ethylene glycol monomethyl ether, stir 30min, then
Acetic anhydride is added, stirs 90min, obtains the precursor liquid for the stabilization that metal ion total concentration is 0.2mol/L；Wherein ethylene glycol first
The volume ratio of ether and acetic anhydride is 3:1；
Step 3：N is used after FTO/glass substrates are washed with deionized water only2Drying, then it is clean with ultraviolet radiation instrument irradiation
Net FTO/glass substrate 40min, make FTO/glass substrate surfaces reach atomic cleanliness degree；
Step 4：Then precursor liquid is spin-coated on FTO/glass substrates, spin coating rotating speed is 4000r/min, when spin coating
Between be 20s, obtain wet film, wet film toasts 14min at 190 DEG C and obtains dry film, then the 45min that anneals in air at 640 DEG C, i.e.,
Obtain crystalline state CoFe2O4Film.
Step 5：By crystalline state CoFe2O4Film cooling to room temperature, repeat step 4 until reach preset thickness to get to
CoFe2O4(CFO) film.
Embodiment 2
CoFe2-xGdxO4Ferromagnetic thin film, wherein x=0.02, preparation method are as follows：
Step 1：FTO/glass substrates are totally sealed up for safekeeping with liquid detergent, acetone, washes of absolute alcohol in absolute ethyl alcohol respectively
In it is spare；
Step 2：Cobalt nitrate, ferric nitrate and gadolinium nitrate are raw material, are in molar ratio 1:1.98:0.02 is dissolved in ethylene glycol monomethyl ether
In, 30min is stirred, acetic anhydride is added, stirs 90min, obtains the forerunner for the stabilization that metal ion total concentration is 0.2mol/L
Liquid；Wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1；
Step 3：N is used after FTO/glass substrates are washed with deionized water only2Drying, then it is clean with ultraviolet radiation instrument irradiation
Net FTO/glass substrate 40min, make FTO/glass substrate surfaces reach atomic cleanliness degree；
Step 4：Then precursor liquid is spin-coated on FTO/glass substrates, spin coating rotating speed is 4000r/min, when spin coating
Between be 20s, obtain wet film, wet film toasts 14min at 190 DEG C and obtains dry film, then the 45min that anneals in air at 640 DEG C, i.e.,
Obtain crystalline state CoFe1.98Gd0.02O4(CFG0.02O) film；
Step 5：By crystalline state CoFe1.98Gd0.02O4Film cooling repeats step 4 until reaching preset thickness to room temperature,
Obtain CoFe1.98Gd0.02O4(CFG0.02O) ferromagnetic thin film.
Embodiment 3
CoFe2-xGdxO4Ferromagnetic thin film, wherein x=0.06, preparation method are as follows：
Step 1：FTO/glass substrates are totally sealed up for safekeeping with liquid detergent, acetone, washes of absolute alcohol in absolute ethyl alcohol respectively
In it is spare；
Step 2：Cobalt nitrate, ferric nitrate and gadolinium nitrate are raw material, are in molar ratio 1:1.94:0.06 is dissolved in ethylene glycol monomethyl ether
In, 30min is stirred, acetic anhydride is added, stirs 90min, obtains the forerunner for the stabilization that metal ion total concentration is 0.2mol/L
Liquid；Wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1；
Step 3：N is used after FTO/glass substrates are washed with deionized water only2Drying, then it is clean with ultraviolet radiation instrument irradiation
Net FTO/glass substrate 40min, make FTO/glass substrate surfaces reach atomic cleanliness degree；
Step 4：Then precursor liquid is spin-coated on FTO/glass substrates, spin coating rotating speed is 4000r/min, when spin coating
Between be 20s, obtain wet film, wet film toasts 14min at 190 DEG C and obtains dry film, then the 45min that anneals in air at 640 DEG C, i.e.,
Obtain crystalline state CoFe1.94Gd0.06O4(CFG0.06O) film；
Step 5：By crystalline state CoFe1.94Gd0.06O4Film cooling repeats step 4 until reaching preset thickness to room temperature,
Obtain CoFe1.94Gd0.06O4(CFG0.06O) ferromagnetic thin film.
Embodiment 4
CoFe2-xGdxO4Ferromagnetic thin film, wherein x=0.10, preparation method are as follows：
Step 1：FTO/glass substrates are totally sealed up for safekeeping with liquid detergent, acetone, washes of absolute alcohol in absolute ethyl alcohol respectively
In it is spare；
Step 2：Cobalt nitrate, ferric nitrate and gadolinium nitrate are raw material, are in molar ratio 1:1.90:0.10 is dissolved in ethylene glycol monomethyl ether
In, 30min is stirred, acetic anhydride is added, stirs 90min, obtains the forerunner for the stabilization that metal ion total concentration is 0.2mol/L
Liquid；Wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1；
Step 3：N is used after FTO/glass substrates are washed with deionized water only2Drying, then it is clean with ultraviolet radiation instrument irradiation
Net FTO/glass substrate 40min, make FTO/glass substrate surfaces reach atomic cleanliness degree；
Step 4：Then precursor liquid is spin-coated on FTO/glass substrates, spin coating rotating speed is 4000r/min, when spin coating
Between be 20s, obtain wet film, wet film toasts 14min at 190 DEG C and obtains dry film, then the 45min that anneals in air at 640 DEG C, i.e.,
Obtain crystalline state CoFe1.90Gd0.10O4(CFG0.10O) film；
Step 5：By crystalline state CoFe1.90Gd0.10O4Film cooling repeats step 4 until reaching preset thickness to room temperature,
Obtain CoFe1.90Gd0.10O4(CFG0.10O) ferromagnetic thin film.
Embodiment 5
CoFe2-xGdxO4Ferromagnetic thin film, wherein x=0.14, preparation method are as follows：
Step 1：FTO/glass substrates are totally sealed up for safekeeping with liquid detergent, acetone, washes of absolute alcohol in absolute ethyl alcohol respectively
In it is spare；
Step 2：Cobalt nitrate, ferric nitrate and gadolinium nitrate are raw material, are in molar ratio 1:1.86:0.14 is dissolved in ethylene glycol monomethyl ether
In, 30min is stirred, acetic anhydride is added, stirs 90min, obtains the forerunner for the stabilization that metal ion total concentration is 0.2mol/L
Liquid；Wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1；
Step 3：N is used after FTO/glass substrates are washed with deionized water only2Drying, then it is clean with ultraviolet radiation instrument irradiation
Net FTO/glass substrate 40min, make FTO/glass substrate surfaces reach atomic cleanliness degree；
Step 4：Then precursor liquid is spin-coated on FTO/glass substrates, spin coating rotating speed is 4000r/min, when spin coating
Between be 20s, obtain wet film, wet film toasts 14min at 190 DEG C and obtains dry film, then the 45min that anneals in air at 640 DEG C, i.e.,
Obtain crystalline state CoFe1.86Gd0.14O4(CFG0.14O) film；
Step 5：By crystalline state CoFe1.86Gd0.14O4Film cooling repeats step 4 until reaching preset thickness to room temperature,
Obtain CoFe1.86Gd0.14O4(CFG0.14O) ferromagnetic thin film.
Embodiment 6
CoFe2-xGdxO4Ferromagnetic thin film, wherein x=0.18, preparation method are as follows：
Step 1：FTO/glass substrates are totally sealed up for safekeeping with liquid detergent, acetone, washes of absolute alcohol in absolute ethyl alcohol respectively
In it is spare；
Step 2：Cobalt nitrate, ferric nitrate and gadolinium nitrate are raw material, are in molar ratio 1:1.82:0.18 is dissolved in ethylene glycol monomethyl ether
In, 30min is stirred, acetic anhydride is added, stirs 90min, obtains the forerunner for the stabilization that metal ion total concentration is 0.2mol/L
Liquid；Wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1；
Step 3：N is used after FTO/glass substrates are washed with deionized water only2Drying, then it is clean with ultraviolet radiation instrument irradiation
Net FTO/glass substrate 40min, make FTO/glass substrate surfaces reach atomic cleanliness degree；
Step 4：Then precursor liquid is spin-coated on FTO/glass substrates, spin coating rotating speed is 4000r/min, when spin coating
Between be 20s, obtain wet film, wet film toasts 14min at 190 DEG C and obtains dry film, then the 45min that anneals in air at 640 DEG C, i.e.,
Obtain crystalline state CoFe1.82Gd0.18O4(CFG0.18O) film；
Step 5：By crystalline state CoFe1.82Gd0.18O4Film cooling repeats step 4 until reaching preset thickness to room temperature,
Obtain CoFe1.82Gd0.18O4(CFG0.18O) ferromagnetic thin film.
Embodiment 7
CoFe2-xGdxO4Ferromagnetic thin film, wherein x=0.02, preparation method are as follows：
Step 1：FTO/glass substrates are totally sealed up for safekeeping with liquid detergent, acetone, washes of absolute alcohol in absolute ethyl alcohol respectively
In it is spare；
Step 2：Cobalt nitrate, ferric nitrate and gadolinium nitrate are raw material, are in molar ratio 1:1.98:0.02 is dissolved in ethylene glycol monomethyl ether
In, 30min is stirred, acetic anhydride is added, stirs 90min, obtains the forerunner for the stabilization that metal ion total concentration is 0.3mol/L
Liquid；Wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 2.5:1；
Step 3：N is used after FTO/glass substrates are washed with deionized water only2Drying, then it is clean with ultraviolet radiation instrument irradiation
Net FTO/glass substrate 40min, make FTO/glass substrate surfaces reach atomic cleanliness degree；
Step 4：Then precursor liquid is spin-coated on FTO/glass substrates, spin coating rotating speed is 3500r/min, when spin coating
Between be 19s, obtain wet film, wet film toasts 12min at 180 DEG C and obtains dry film, then the 35min that anneals in air at 630 DEG C, i.e.,
Obtain crystalline state CoFe1.98Gd0.02O4(CFG0.02O) film；
Step 5：By crystalline state CoFe1.98Gd0.02O4Film cooling repeats step 4 until reaching preset thickness to room temperature,
Obtain CoFe1.98Gd0.02O4(CFG0.02O) ferromagnetic thin film.
Embodiment 8
CoFe2-xGdxO4Ferromagnetic thin film, wherein x=0.02, preparation method are as follows：
Step 1：FTO/glass substrates are totally sealed up for safekeeping with liquid detergent, acetone, washes of absolute alcohol in absolute ethyl alcohol respectively
In it is spare；
Step 2：Cobalt nitrate, ferric nitrate and gadolinium nitrate are raw material, are in molar ratio 1:1.98:0.02 is dissolved in ethylene glycol monomethyl ether
In, 30min is stirred, acetic anhydride is added, stirs 90min, obtains the forerunner for the stabilization that metal ion total concentration is 0.4mol/L
Liquid；Wherein the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3.5:1；
Step 3：N is used after FTO/glass substrates are washed with deionized water only2Drying, then it is clean with ultraviolet radiation instrument irradiation
Net FTO/glass substrate 40min, make FTO/glass substrate surfaces reach atomic cleanliness degree；
Step 4：Then precursor liquid is spin-coated on FTO/glass substrates, spin coating rotating speed is 3800r/min, when spin coating
Between be 25s, obtain wet film, wet film toasts 16min at 170 DEG C and obtains dry film, then the 55min that anneals in air at 620 DEG C, i.e.,
Obtain crystalline state CoFe1.98Gd0.02O4(CFG0.02O) film；
Step 5：By crystalline state CoFe1.98Gd0.02O4Film cooling repeats step 4 until reaching preset thickness to room temperature,
Obtain CoFe1.98Gd0.02O4(CFG0.02O) ferromagnetic thin film.
CF is measured using Ranman2-xGxThe key of O ferromagnetic thin films shakes.CF is measured with SEM2-xGxO ferromagnetic thin films it is micro-
Pattern is seen, the MPMS-XL-7 type superconductive quantum interference magnetometers produced with U.S. Quantum Design, to obtain institute at room temperature
The magnetic property of ferromagnetic thin film processed.
To CF made from embodiment 1-62-xGxO ferromagnetic thin films carry out the above test, as a result as shown in Figure 1, Figure 2, Figure 3 shows.
Fig. 1 is that CF is made in 1-6 of the embodiment of the present invention2-xGxThe XRD diagram of O ferromagnetic thin films, it can be seen that collosol and gel
CoFe prepared by method2-xGdxO4Ferromagnetic thin film, wherein CoFe2-xGdxO4Ferromagnetic thin film is cubic phase, spinel structure,
Space group is Fd3m, does not have the appearance of other impurities in ferromagnetic thin film, but with Ga3+The increase of doping, CoFe2- xGdxO4The diffraction maximum of (400) crystal face of ferromagnetic thin film then gradually weakens to disappearance, and the peak broadening of its (311) crystal face, says
Gd is illustrated3+The incorporation of ion can inhibit the growth of (400) crystal face, CoFe2-xGdxO4Ferromagnetic thin film takes along (311) crystal plane direction
To growth.
Fig. 2 is the obtained CF in the embodiment of the present invention 1,4 and 62-xGxThe Raman of O ferromagnetic thin films schemes, it can be seen that colloidal sol
CoFe prepared by gel method2-xGdxO4The Raman spectrum 470cm of ferromagnetic thin film-1Peak is attributed to tetrahedral lattice vibration, and
690cm-1Peak is then derived from the vibration of octahedra lattice, and Raman spectrum are very sensitive, A to lattice structure1gPattern corresponds to Fe-O
Stretching vibration, T2gPattern corresponds to Co-O key stretching vibrations, along with Gd3+The doping A of ion1gThe vibration of pattern occurs bright
Aobvious decrease, T2gThere is faint decrease in the vibration of pattern, illustrates Gd3+The incorporation of ion does not have mainly instead of Fe
Co ions are substituted, CoFe is formd2-xGdxO4Structural formula makes CoFe2-xGdxO4The structure of ferromagnetic thin film is with respect to CoFe2O4Occur
Certain distortion of lattice.
Fig. 3 shows CF2-xGxO ferromagnetic thin films, remanent magnetization M when x=0.00r=120.5emu/cm3, it is saturated magnetic
Change intensity Ms=266.5emu/cm, squareness ratio R=0.45；Its remanent magnetization M when x=0.02r=125.5emu/cm3, satisfy
And magnetization Ms=192.8emu/cm3, squareness ratio R=0.65.Illustrate Gd3+Ion substitution Fe3+After make CoFe2-xGdxO4It is ferromagnetic
The magnetic property of property film is improved.
Above said content is that a further detailed description of the present invention in conjunction with specific preferred embodiments, is not
Whole or unique embodiment, those of ordinary skill in the art are by reading description of the invention to technical solution of the present invention
Any equivalent transformation taken is that claim of the invention is covered.
Claims (9)
1. a kind of CoFe2-xGdxO4Ferromagnetic thin film, which is characterized in that its chemical formula is CoFe2-xGdxO4, wherein x=0.02~
0.18, it is cube inverse spinel structure, space group Fd3m；CoFe2-xGdxO4Ferromagnetic thin film takes along (311) crystal plane direction
To growth.
2. CoFe according to claim 12-xGdxO4Ferromagnetic thin film, which is characterized in that as x=0.02, remanent magnetization
Intensity Mr=125.5emu/cm3, saturation magnetization Ms=192.8emu/cm3, squareness ratio R=0.65.
3. a kind of claim 1-2 any one of them CoFe2-xGdxO4The preparation method of ferromagnetic thin film, which is characterized in that packet
Include following steps：
Step 1, it is in molar ratio 1:(2-x):Cobalt nitrate, ferric nitrate and gadolinium nitrate are dissolved in ethylene glycol monomethyl ether by x, are stirred evenly
After acetic anhydride is added, continue to stir evenly, obtain the precursor liquid of ferromagnetic thin film；
Step 2, precursor liquid is spin-coated on FTO/glass substrates, obtains wet film, wet film dries after spin coating at 170~190 DEG C
Dry film is baked to obtain, anneals in air at 620~640 DEG C, obtains crystalline state CoFe2-xGdxO4Film；
Step 3, by crystalline state CoFe2-xGdxO4Film cooling to room temperature, repeat step 2 until reach preset thickness to get to
CoFe2-xGdxO4Ferromagnetic thin film.
4. CoFe according to claim 32-xGdxO4The preparation method of ferromagnetic thin film, which is characterized in that preceding in step 1
The total concentration for driving metal ion in liquid is 0.20~0.40mol/L.
5. CoFe according to claim 32-xGdxO4The preparation method of ferromagnetic thin film, which is characterized in that preceding in step 1
It is (2.5~3.5) to drive ethylene glycol monomethyl ether and the volume ratio of acetic anhydride in liquid:1.
6. CoFe according to claim 32-xGdxO4The preparation method of ferromagnetic thin film, which is characterized in that step 2 carries out
It is preceding first to clean up FTO/glass substrates, it then irradiates under ultraviolet light, so that FTO/glass substrate surfaces is reached atom clear
Cleanliness.
7. CoFe according to claim 32-xGdxO4The preparation method of ferromagnetic thin film, which is characterized in that even in step 2
Spin coating rotating speed when glue is 3500~4000r/min, and spin coating time is 19~25s.
8. CoFe according to claim 32-xGdxO4The preparation method of ferromagnetic thin film, which is characterized in that even in step 2
Baking time after glue is 12~16min.
9. CoFe according to claim 32-xGdxO4The preparation method of ferromagnetic thin film, which is characterized in that in step 2
Annealing time is 35~55min.
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