CN104030672B - A kind of preparation method of spinel ferrite body thin film - Google Patents
A kind of preparation method of spinel ferrite body thin film Download PDFInfo
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- CN104030672B CN104030672B CN201410255248.2A CN201410255248A CN104030672B CN 104030672 B CN104030672 B CN 104030672B CN 201410255248 A CN201410255248 A CN 201410255248A CN 104030672 B CN104030672 B CN 104030672B
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- spinel ferrite
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Abstract
The invention provides a kind of preparation method of spinel ferrite body thin film, belong to thin film technique field.First the present invention adopts electrochemical deposition method to prepare alloy firm, in strong base solution, then adopt galvanostatic method alloy film to carry out anode activation, and finally sintering obtains spinel ferrite body thin film.Sintering time required when adopting the inventive method to prepare spinel ferrite body thin film is short, and does not need when sintering to pass into oxygen, and the film obtained is columnar structure, and its saturation magnetization perpendicular to face direction is comparatively large, has better magnetic property.
Description
Technical field
The invention belongs to thin film technique field, be specifically related to a kind of preparation method of spinel ferrite body thin film.
Background technology
Ferrite is a kind of novel nonmetal magnetic material developed rapidly the forties in 20th century.Compared with metallicl magnetic material, ferrite has that resistivity is large, dielectric properties are high, has the advantages such as higher magnetic permeability and be widely used when high frequency.What be wherein most widely used is ferrospinel material, and its chemical molecular formula can use MFe
2o
4represent, in formula, M represents the divalent-metal ions such as manganese, nickel, zinc, copper, cobalt.Along with the development of science and technology, ferrite is not only increasingly extensive in field application such as communication broadcast, automatically control, computing technique and instrument, and also opens wide application space in space travel, satellite communication, information displaying and pollution plot etc.
In production technique, ferritic preparation technology is similar to general ceramic process, and easy to operate being easy to controls, and will roll into thin slice or make fine powder medium and could apply unlike metallicl magnetic material.Because ferrite performance is good, cost is low, technique simply, again can save a large amount of precious metal, become a kind of nonmetal magnetic material rising in high frequency light current field.The common method preparing ferrite film has sol-gel method, pulse laser deposition, sputtering method, electrochemical deposition method etc.Comparatively speaking, electrochemical deposition method technique is simple, with low cost, and comparatively can be easy to the thickness of control film, composition and structure, sedimentation rate regulates and controls by deposition current simultaneously, be applicable to the body material of different shape, thus receive concern and the attention of research worker.Existing electrochemical deposition technique is prepared ferrite film and is mainly first electroplated out alloy firm, then carries out sintering for a long time in oxygen atmosphere obtaining ferrite film, and sintering required time is longer, is generally more than 8 hours.Fu Ruohong (Fu Ruohong, CoFe
2o
4the preparation of film, sign and magnetic property research, University of Electronic Science and Technology's master thesis) when adopting electrochemical deposition method to prepare cobalt ferrite thin films, at 500 DEG C, sintering 8 hours under the environment of oxygen, recycling conventional annealing techniques, in 600 ~ 1200 DEG C, annealing obtains cobalt ferrite thin films.In the method, sintering time is long, easily causes film to split, and needs during sintering to continue to pass into oxygen, and add reaction cost, these all limit the widespread use of the method.
Summary of the invention
The invention provides a kind of preparation method of spinel ferrite body thin film, first the method adopts electrochemical deposition method to prepare alloy firm, then adopts anode activation technical profession alloy film, and finally sintering obtains spinel ferrite body thin film.The sintering time adopting the inventive method to prepare needed for spinel ferrite body thin film is short, and does not need when sintering to pass into oxygen, effectively reduces reaction times and cost; The film obtained is columnar structure, and its saturation magnetization perpendicular to face direction is comparatively large, has better magnetic property.
Technical scheme of the present invention is as follows:
A preparation method for spinel ferrite body thin film, comprises the following steps:
Step 1: adopt electrochemical deposition method to prepare alloy firm MFe
2;
Step 2: adopt three-electrode method alloy film to carry out anode activation: the alloy firm obtained with step 1 is working electrode, is electrolytic solution with strong base solution, and in electrolytic solution, the concentration of OH-is 1 ~ 5mol/L, adopt galvanostatic method at-200mA/cm
2~-50mA/cm
2current density under activation 10 ~ 60min, obtain activate after alloy firm;
Step 3: retort furnace put into by the alloy firm after activation step 2 obtained, sinters 3h at 400 DEG C ~ 600 DEG C temperature, then obtains described spinel ferrite body thin film with stove Temperature fall;
The chemical formula of the alloy firm that step 1 obtains is MFe
2, the chemical formula of the ferrospinel that step 3 obtains is MFe
2o
4, wherein M
2+for Co
2+, Ni
2+, Mn
2+, Zn
2+, Cu
2+, Ca
2+or Mg
2+deng.
Electrochemical deposition method described in step 1 prepares alloy firm MFe
2concrete steps be: a) prepare electrolytic solution, make M in electrolytic solution
2+with Fe
2+concentration ratio be 1:2, then PH to 3 ~ 4 are regulated with acid, b) three-electrode method plating alloy film is adopted: adopt Ni sheet, Si-Pt sheet, stainless steel substrates or Cu plate electrode to be working electrode, saturated calomel electrode is reference electrode, platinized platinum is to electrode, in-10V ~-0.4V scope, under arbitrary voltage, adopt constant voltage method to electroplate 3min, obtain MFe
2alloy firm.Wherein, step a) described in acid be HCl, H
2sO
4or HNO
3deng.
The reference electrode that three-electrode method alloy film described in step 2 carries out adopting in anode activation process is saturated calomel electrode, is platinized platinum to electrode.Highly basic described in step 2 is KOH or NaOH etc.
Beneficial effect of the present invention is:
1, the present invention before sintering alloy film carried out anode activation process, shorten the sintering time of alloy firm, and do not need when sintering to pass into oxygen, simplify step, reduce production cost.
2, the ferrospinel film adopting the inventive method to prepare has better crystal property.
3, the present invention's alloy film before sintering processes has carried out anode activation process, is conducive to the growth of column ferrospinel.Alloy firm without anode activation process forms the film of even compact after sintering, the ferrite surfaces that alloy firm after anode activation process obtains after sintering is then columnar structure, and ferrite film is comparatively large perpendicular to the saturation magnetization of face, has better magnetic property.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention 1 is composed with the XRD figure of comparative example.Wherein, the XRD figure spectrum of (a) cobalt ferrite thin films of obtaining for comparative example; The XRD figure spectrum of b cobalt ferrite thin films that () obtains for embodiment 1.
Fig. 2 is the SEM figure of the cobalt ferrite thin films section that embodiment obtains.Wherein, (a) SEM of cobalt ferrite thin films section of obtaining for comparative example; The SEM of b cobalt ferrite thin films section that () obtains for embodiment 1.
Fig. 3 is the magnetic hysteresis loop of the cobalt ferrite thin films that embodiment 1,2,3 obtains.Wherein, (a) magnetic hysteresis loop of cobalt ferrite thin films of obtaining for embodiment 1; The magnetic hysteresis loop of b cobalt ferrite thin films that () obtains for embodiment 2; The magnetic hysteresis loop of c cobalt ferrite thin films that () obtains for embodiment 3.
Embodiment
Embodiment 1
A kind of vectolite CoFe
2o
4the preparation method of film, comprises the following steps:
Step 1: the electrolytic solution of preparation 50ml, wherein CoSO
47H
2the concentration of O is 0.025mol/L, FeSO
47H
2the concentration of O is 0.05mol/L, then drips H
2sO
4regulate PH to 4; With Si-Pt sheet for working electrode, saturated calomel electrode is reference electrode, and platinized platinum is to electrode, adopts constant voltage method to electroplate 3min, obtain ferro-cobalt film CoFe under-2.1V voltage
2;
Step 2: adopt three-electrode method alloy film to carry out anode activation process: the NaOH solution of preparation 50mL1.5mol/L is as electrolytic solution, the ferro-cobalt film adopting step 1 to obtain is working electrode, saturated calomel electrode is reference electrode, and platinized platinum is to electrode, at current density, J=-90mA/cm
2lower employing galvanostatic method activation 30min, obtains the ferro-cobalt film after activating;
Step 3: the ferro-cobalt film after activation step 2 obtained is placed in retort furnace, is elevated to 550 DEG C with the speed of 5 DEG C/min from room temperature, sinters 3 hours, then obtains CoFe with stove Temperature fall at 550 DEG C
2o
4ferrite film.
The CoFe that Fig. 1 (b) obtains for embodiment 1
2o
4the X ray diffracting spectrum (XRD) of film, collection of illustrative plates display embodiment 1 has successfully prepared vectolite, the vectolite prepared with comparative example contrasts and finds, the peak of the vectolite that the peak of the vectolite that embodiment 1 obtains obtains relative to comparative example is stronger, show under identical sintering temperature, the vectolite crystal property prepared after anode activation process is better.The CoFe that Fig. 2 (b) obtains for embodiment 1
2o
4the SEM of ferrite film section, show that the film surface that embodiment 1 obtains is columnar structure, the thickness of columnar structure is 4um.The CoFe that Fig. 3 (a) obtains for embodiment 1
2o
4the magnetic hysteresis loop of film, from Fig. 3 (a), the coercive force of film is about 2.5kOe, and vertical face saturation magnetization is 80emu/cm
3.
Embodiment 2
The present embodiment and embodiment 1 be distinguished as step 2 when carrying out anode activation process, current density, J=-110mA/cm
2.
The CoFe that Fig. 3 (b) obtains for embodiment 2
2o
4the magnetic hysteresis loop of film, from Fig. 3 (b), the coercive force of film is about 2.5kOe, and vertical face saturation magnetization is 110emu/cm
3.
Embodiment 3
The present embodiment and embodiment 1 be distinguished as step 2 when carrying out anode activation process, current density, J=
-130mA/cm
2.
The CoFe that Fig. 3 (c) obtains for embodiment 3
2o
4the magnetic hysteresis loop of film, from Fig. 3 (c), the coercive force of film is about 2.5kOe, and vertical face saturation magnetization is 150emu/cm
3.
Comparative example
Vectolite CoFe
2o
4the preparation method of film, comprises the following steps:
Step 1: the electrolytic solution of preparation 50ml, wherein CoSO
47H
2the concentration of O is 0.025mol/L, FeSO
47H
2the concentration of O is 0.05mol/L, then drips H
2sO
4regulate PH to 4; With Si-Pt sheet for working electrode, saturated calomel electrode is reference electrode, and platinized platinum is to electrode, adopts constant voltage method to electroplate 3min, obtain ferro-cobalt film CoFe under-2.1V voltage
2;
Step 2: the ferro-cobalt film obtained is placed in retort furnace, is elevated to 550 DEG C with the speed of 5 DEG C/min from room temperature, sinters 3 hours, then obtains CoFe with stove Temperature fall at 550 DEG C
2o
4ferrite film.
The CoFe that Fig. 1 (a) obtains for comparative example
2o
4the X ray diffracting spectrum (XRD) of ferrite film, collection of illustrative plates display comparison embodiment has successfully prepared vectolite, but the peak of vectolite that comparative example obtains does not have the peak of the vectolite of embodiment 1 strong.The CoFe that Fig. 2 (a) obtains for comparative example
2o
4the SEM of ferrite film section, show the lumphy structure of film in densification that comparative example obtains, thickness is 3um.
In sum, the crystal property of the vectolite prepared after anode activation process is better, and obtain the film of columnar structure, its coercive force is larger with the saturation magnetization of vertical face.Further, along with the increase of activation current, the saturation magnetization of vertical face increases.
Claims (5)
1. a preparation method for spinel ferrite body thin film, comprises the following steps:
Step 1: adopt electrochemical deposition method to prepare alloy firm MFe
2;
Step 2: adopt three-electrode method alloy film to carry out anode activation: the alloy firm obtained with step 1 is working electrode, is electrolytic solution with strong base solution, OH in electrolytic solution
-concentration be 1 ~ 5mol/L, adopt galvanostatic method at-200mA/cm
2~-50mA/cm
2current density under activation 10 ~ 60min, obtain activate after alloy firm;
Step 3: retort furnace put into by the alloy firm after activation step 2 obtained, sinters 3h at 400 DEG C ~ 600 DEG C temperature, then obtains described spinel ferrite body thin film with stove Temperature fall;
The chemical formula of the alloy firm that step 1 obtains is MFe
2, the chemical formula of the ferrospinel that step 3 obtains is MFe
2o
4, wherein M
2+for Co
2+, Ni
2+, Mn
2+, Zn
2+, Cu
2+, Ca
2+, Mg
2+in one.
2. the preparation method of spinel ferrite body thin film according to claim 1, is characterized in that, the electrochemical deposition method described in step 1 prepares alloy firm MFe
2concrete steps be: a) prepare electrolytic solution, make M in electrolytic solution
2+with Fe
2+concentration ratio be 1:2, then with acid for adjusting pH to 3 ~ 4; B) three-electrode method plating alloy film is adopted: adopt Ni sheet, Si-Pt sheet, stainless steel substrates or Cu plate electrode to be working electrode, saturated calomel electrode is reference electrode, platinized platinum is to electrode, adopts constant voltage method to electroplate 3min, obtain MFe in-10V ~-0.4V scope under arbitrary voltage
2alloy firm.
3. the preparation method of spinel ferrite body thin film according to claim 2, is characterized in that, step a) described in acid be HCl, H
2sO
4, HNO
3.
4. the preparation method of spinel ferrite body thin film according to claim 1, is characterized in that, the reference electrode that the three-electrode method alloy film described in step 2 carries out adopting in anode activation process is saturated calomel electrode, is platinized platinum to electrode.
5. the preparation method of spinel ferrite body thin film according to claim 1, is characterized in that, the highly basic described in step 2 is KOH, NaOH.
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| CN107227471B (en) * | 2017-05-19 | 2018-12-21 | 上海工程技术大学 | Inert anode NiFe_2O_4 spinel composite coating and its preparation are pre-oxidized based on low oxygen pressure |
| CN109267114B (en) * | 2018-10-22 | 2020-08-21 | 中国科学院金属研究所 | Preparation method of cobalt-manganese spinel coating |
| CN113087532B (en) * | 2021-03-04 | 2022-10-14 | 电子科技大学 | Preparation method of high-performance NiZn ferrite film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230446A (en) * | 2007-10-30 | 2008-07-30 | 电子科技大学 | Preparation method lowering annealing temperature of spinel ferrite thin film material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230446A (en) * | 2007-10-30 | 2008-07-30 | 电子科技大学 | Preparation method lowering annealing temperature of spinel ferrite thin film material |
Non-Patent Citations (1)
| Title |
|---|
| Room temperature synthesis of nanocrystalline ferrite(MFe2O4,M=Cu,Co and Ni) thin films using novel electrochemical route;S.D. Sartale et al.;《Applied Surface Science》;20011231;第182卷;第367页右栏第1-2段，第369页左栏第1、3段，第371页右栏结论部分 * |
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