CN1169745C - Zinc ferrite material with giant magnetic resistance effect and its prepn - Google Patents
Zinc ferrite material with giant magnetic resistance effect and its prepn Download PDFInfo
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- CN1169745C CN1169745C CNB011373067A CN01137306A CN1169745C CN 1169745 C CN1169745 C CN 1169745C CN B011373067 A CNB011373067 A CN B011373067A CN 01137306 A CN01137306 A CN 01137306A CN 1169745 C CN1169745 C CN 1169745C
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- zinc ferrite
- gel
- preparation
- zno
- giant magnetoresistance
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- 239000000463 material Substances 0.000 title claims abstract description 28
- 230000000694 effects Effects 0.000 title claims abstract description 24
- 229910001308 Zinc ferrite Inorganic materials 0.000 title claims abstract description 15
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 230000005291 magnetic effect Effects 0.000 title abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000005294 ferromagnetic effect Effects 0.000 claims description 6
- 229910000859 α-Fe Inorganic materials 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 239000002114 nanocomposite Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000137 annealing Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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Abstract
The present invention relates to a zinc ferrite material with giant magnetic resistance effect and a preparation method thereof. The method of the present invention is a method for preparing a material having giant magnetic resistance effect and formed by using Zn and Fe as basic raw materials, and the material is ZnxFe3-xo4, wherein X ranges from 0.05 to 0.95. The preparation method adopts a sol-gel method to prepare a polycrystal ZnxFe3-xO4 material, and the method has the manufacture steps: ZnO and Fe (NO3) 3 form sol in nitric acid, citric acid is added, the sol is heated and water is dried by evaporation to form gel, and after being cooled, the gel is annealed 3 to 5 hours at the temperature of 400 DEG C to 600 DEG C; sinters are ground into fine powder, and then the fine powder is pressed into blocks by pressure; the blocks are annealed 0.5 to 4 hours at the temperature of 1300 DEG C to 1500 DEG C; finally, the product of ZnxFe3-xO4 is obtained, wherein x ranges from 0.05 to 0.95, and the proportioning by mole number of ZnO and Fe (NO3) 3 of the raw materials is 1: 2 to 1: 60.
Description
One, technical field
The present invention is a kind of giant magnetoresistance effect material and preparation method thereof, especially a kind of preparation methods of the giant magnetoresistance effect that constitutes with Zn ferrite.
Two, background technology
Giant magnetoresistance effect (Giant Magnetoresistance Effect, be called for short the GMR effect), the resistivity that is meant material is subjected to the variation of material magnetized state and presents the phenomenon of remarkable change, and it is that Fert working group by France found in the Fe/Cr multilayer film in 1988.Because its very attractive practical prospect once finding just to have caused the very big concern of scientific and technological circle and the huge sum of money input of industrial community, has formed a very big industry since more than ten years, started the revolution of material circle.Giant magnetic resistor material can be used for the electronics technology field of forefront, and as the playback head and the non-volatile RAM (MRAM) of hard disk, the former drops into application already, thereby the storage density of hard disk has been improved tens of times quickly.Because giant magnetoresistance effect is big, easily make device miniaturization simultaneously, cheap also can be used for many conditional electronic industrial circles, as the transmitter of numerically-controlled machine, measuring vehicle speed, non-contact switch, rotary encoder etc.
At present, people have found giant magnetoresistance effect in the material of a lot of series, as multilayer film, membrana granulosa, tunnel junction, perovskite compound etc.But, the problem that some existence are all arranged on preparation or performance in each material: the giant magnetoresistance effect in the multilayer film is bigger, and maximum can reach 187% (Cu/Co series, room temperature), but initial magnetic field sensitivity is not too high, saturation magnetic field is higher, and after adopting spin valve structure, initial magnetic field sensitivity can improve, can drop into application, but owing to adopt the high vacuum sputter, preparation is difficulty relatively, and the heavy industrialization cost is very high; It is simple that the membrana granulosa preparation shows relatively slightly, but effect is lower, is about 15% (Co/Ag series, room temperature), and initial magnetic field sensitivity is lower, and saturation magnetic field is very high, and the industrialization cost is relatively also higher; The giant magnetoresistance effect of tunnel junction is bigger, reaches as high as about 100%, and magnetic field sensitivity is also higher, and saturation magnetic field is lower, but preparation is very difficult, also is in laboratory stage at present basically; The giant magnetoresistance effect of perovskite compound is extremely high, reaches as high as 10
7%, but initial magnetic field sensitivity is very low, and required saturation magnetic field is difficult to drop in the real practicality up to several teslas.
Therefore, a kind of effect sensitivity is being sought but the simple giant magnetic resistor material of technology by scientific and technological circle at present.
Three, summary of the invention
(1) goal of the invention
The purpose of this invention is to provide a kind of have higher giant magnetoresistance effect and higher magnetic field sensitivity, preparation technology is simple, cost is low, practical has Zinc ferrite material of giant magnetoresistance effect and preparation method thereof.
(2) technical scheme
A kind of Zinc ferrite material with giant magnetoresistance effect is characterized in that having composite structure, and size is the Zn of 200-800 nanometer
xFe
3-xO
4Crystal grain is by the α-Fe of 5-10 nanometer thickness
2O
3Layer parcel and isolating, 0.05≤X≤0.95 wherein, thus form many partial sandwich structures, to form by ferromagnetic zinc ferrite layer/insulation layer/ferromagnetic zinc ferrite layer, this is similar to the structure of tunnel junction.
Preparation method of the present invention adopts colloidal sol-preparing gel polycrystalline Zn
xFe
3-xO
4Material, raw-material ZnO and Fe (NO
3)
3Proportioning by mole number be calculated as 1: 2～1: 60.The step of its making is:
A. with ZnO and Fe (NO
3)
3In nitric acid, form colloidal sol,
B. add citric acid, above colloidal sol heating the water evaporate to dryness, formed gel,
C. annealed 3-5 hour at 400 ℃-600 ℃ in above gel cooling back,
D. above sinter is worn into fine powder, depresses to bulk at pressure then,
E. under 1300 ℃ of-1500 ℃ of temperature, annealed 0.5-4 hour,
Obtain Zn at last
xFe
3-xO
4With α-Fe
2O
3Nano composite structure product, wherein 0.05≤X≤0.95.
(3) technique effect
Polycrystalline Zn ferrite with method preparation of the present invention is a kind of composite structure, is made up of ferromagnetic zinc ferrite layer/insulation layer/ferromagnetic zinc ferrite layer, and this is similar to the structure of tunnel junction.And the semi-metal that wherein zinc ferrite layer had has further increased giant magnetoresistance effect.
Material character: the material of preparation gained has very big giant magnetoresistance effect, when x=0.41, reaches maximum value, the room-temperature magnetoresistance value is 158% (assigning 1380% at 4.2K), and magnetic field sensitivity is big (0.02%/Oe), and saturation magnetic field has a good application prospect less than 5000Oe.
Therefore, material of the present invention has very big giant magnetoresistance character, and has higher magnetic field sensitivity and lower saturation magnetic field, and in addition, material preparation of the present invention is simple, cost is low, is easy to suitability for industrialized production, and practicality is stronger.
Four, description of drawings
Fig. 1 is the magneto-resistor curve of the Zinc ferrite material (x=0.41) of the compound sandwich structure that is prepared into of the present invention.
Fig. 2 is the change curve of material magnetoelectricity resistance of the present invention along with composition x.
Five, specific embodiments
Get x=0.33, x=0.41, x=0.72, x=0.8 respectively, produce the material of four kinds of different components, in order to prepare the material of these four kinds of different components, we are 3.5: 26.5 in molar ratio, 4.5: 25.5; 8: 22; The ZnO of 9: 22 amount proportioning and Fe (NO
3)
3In nitric acid, form colloidal sol, add citric acid, above colloidal sol heating the water evaporate to dryness, is formed gel.After the cooling, gel was annealed 4 hours down at 500 ℃, sinter is ground to form fine powder, at 1000Kg/cm
2Pressure depress to piece, at last under 1400 ℃ of temperature annealing 2.5 hours.
After preparation was finished, we had carried out the test of relevant rerum natura to it: to x=0.33,0.41,0.72 and 0.8 have an as above Zn of structure
xFe
3-xO
4Polycrystalline, Curie temperature is respectively 307K, 318K, 334K and 343K.The magneto-resistor of four kinds of samples is respectively 34% (x=0.33), 158% (x=0.41), 53% (x=0.7), and 48% (x=0.8), their saturation magnetic field is all lower, less than 5000 oersteds.The magnetic field sensitivity height can reach 0.03% to the x=0.41 sample.
Claims (2)
1, a kind of Zinc ferrite material with giant magnetoresistance effect is characterized in that having composite structure, and size is the Zn of 200-800 nanometer
xFe
3-xO
4Crystal grain is by the α-Fe of 5-10 nanometer thickness
2O
3Layer parcel and isolating, 0.05≤X≤0.95 wherein, thus form many partial sandwich structures, to form by ferromagnetic zinc ferrite layer/insulation layer/ferromagnetic zinc ferrite layer, this is similar to the structure of tunnel junction.
2, a kind of preparation method with Zinc ferrite material of giant magnetoresistance effect is characterized in that adopting so-gel to prepare polycrystalline Zn
xFe
3-xO
4Material, raw-material ZnO and Fe (NO
3)
3Proportioning by mole number be calculated as 1: 2～step of its making in 1: 60 is:
A. with ZnO and Fe (NO
3)
3In nitric acid, form colloidal sol,
B. add citric acid, above colloidal sol heating the water evaporate to dryness, formed gel,
C. annealed 3-5 hour at 400-600 ℃ in above gel cooling back,
D. above sinter is worn into fine powder, depresses to bulk at pressure then,
E. at 1300-1500 ℃ of sintering temperature 0.5-4 hour,
Obtain Zn at last
xFe
3-xO
4With α-Fe
2O
3Nano composite structure product, wherein 0.05≤X≤0.95.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011373067A CN1169745C (en) | 2001-11-27 | 2001-11-27 | Zinc ferrite material with giant magnetic resistance effect and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011373067A CN1169745C (en) | 2001-11-27 | 2001-11-27 | Zinc ferrite material with giant magnetic resistance effect and its prepn |
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| Publication Number | Publication Date |
|---|---|
| CN1347855A CN1347855A (en) | 2002-05-08 |
| CN1169745C true CN1169745C (en) | 2004-10-06 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344573C (en) * | 2005-04-14 | 2007-10-24 | 中国科学院理化技术研究所 | Preparation method of nano spinel type ferrite powder |
| CN100413806C (en) * | 2006-03-31 | 2008-08-27 | 刘仁臣 | Preparation method of ferrite permanent magnetic material |
| CN101501851B (en) * | 2006-12-28 | 2010-11-17 | 松下电器产业株式会社 | Resistance variable element and resistance variable storage device |
| CN102531562B (en) * | 2012-01-14 | 2013-05-08 | 中北大学 | Method for preparing soft magnetic mesoporous nickel-zinc ferrite microspheres |
| CN102745982B (en) * | 2012-07-26 | 2013-09-11 | 张宇 | Method for preparing nanometer arsenic trioxide (ATO)/nanometer ferrite composite wave absorbing material |
| KR102063651B1 (en) * | 2016-03-28 | 2020-01-08 | 주식회사 엘지화학 | Mehtod of prepararing zinc ferrite catalysts |
| CN106587975A (en) * | 2016-12-28 | 2017-04-26 | 中国建筑材料科学研究总院 | Zinc ferrite material and preparation method thereof |
| CN108123028B (en) * | 2017-12-25 | 2020-03-20 | 中国科学院物理研究所 | Giant magnetoresistance device, magneton field effect transistor, and magneton tunnel junction |
-
2001
- 2001-11-27 CN CNB011373067A patent/CN1169745C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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