CN1324720C - Perovskite rare earth manganese oxide giant magnetic resistance material, preparing process and its use - Google Patents
Perovskite rare earth manganese oxide giant magnetic resistance material, preparing process and its use Download PDFInfo
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- CN1324720C CN1324720C CNB011418532A CN01141853A CN1324720C CN 1324720 C CN1324720 C CN 1324720C CN B011418532 A CNB011418532 A CN B011418532A CN 01141853 A CN01141853 A CN 01141853A CN 1324720 C CN1324720 C CN 1324720C
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Abstract
The present invention relates to an oxide giant magnetoresistance material of perovskite type rare earth manganese, a preparing process and an application thereof, which belongs to the technical field of material manufacture, sensing and magnetic storage. The chemical formula of the giant magnetoresistance material of the present invention is RE1-xTxDO3+/-y, wherein RE=La, Nd, Sm, Pr, Ce, Eu and ER, T=Ca, Sr, Ba, Pb and K, and D=Mn, Fe, Cr and Ni. Corresponding oxides and carbonates are uniformly mixed and are shaped by pressing in a stoichiometric ratio, and the mixture is sintered for 3 to 10 hours at the temperature of 800 to 1000 DEG C and then is sintered for10 to 50 hours at the temperature of 1300 DEG C to 1600 DEG C. The giant magnetoresistance material is finally prepared through subsequent heat treatment. The process has the advantages of simple operation, good repeatability, high efficiency and low cost; the process is good for industrialization popularization. The oxide giant magnetoresistance material overcomes the defect that the ordinary oxide giant magnetoresistance material indicates the giant magnetoresistance effect only at low temperature; the oxide giant magnetoresistance material has the magnetoresistance change rate of 62% when the temperature is near to room temperature. The present invention is suitable for preparing a high-performance sensor, magnetic storage equipment, etc.
Description
Technical field
The present invention relates to a kind of technology for preparing perovskite rare earth manganese oxide giant magnetic resistance material and products thereof purposes.Belong to made, sensing and magnetic storage technical field.
Background technology
Giant magnetoresistance (GMR, giant magnetoresistance) material is meant that resistance can a significantly reduced class functional material under the effect of outside magnetic field.People are GMR=[ρ (O)-ρ (H) with the size that the relative change rate of resistivity weighs giant magnetoresistance effect usually]/ρ (H), ρ (O), ρ (H) are respectively the resistivity under null field and the magnetic field H.This specific character has great application value in sensing and magnetic storage technical field, therefore the wide application prospect of GMR material impels the U.S., Japan and other countries to throw huge fund in the research of GMR, all achievement is striking about the basic research of giant magnetoresistance effect and application study, a large amount of papers are arranged at Nature, deliver on the famous magazine such as Science.
Ubiquity magneto-resistance effect in metal and the alloy, but magnetic field can only make resistance that small variation takes place.Ferromagnetic metal Fe, Co, Ni and alloy thereof have stronger magneto-resistance effect, reach 1～3%.The late nineteen eighties, the negative magneto-resistor up to 50% has been found in (Phys.Rev.Lett.61,2472 (1988)) such as baibich of Brazil in [Fe/Cr] multilayer film, caused people's great attention immediately, is referred to as giant magnetoresistance effect.From then on opened the prelude of giant magnetoresistance effect research.1993, people such as Helmolt (Phys.Rev.Lett 71,2331 (1993)) were at La
2/3Ba
1/3MnO
3In observe the giant magnetoresistance effect phenomenon, cause huge repercussion, because this result is pushed into oxide material with the research of giant magnetoresistance by metal, alloy sample.RE with perovskite structure
1-xT
xMnO
3There is antiferromagnetic-ferromagnetic transformation in (RE represents trivalent rare earth element, and T represents divalence alternative dopings element) compound with the variation of doping content.Under the outside magnetic field effect, the manganese ion spin is tended to parallel, and the raising of ferromagnetic ordering causes the reduction of resistivity.Nineteen ninety-five, G.Q.Gong (Appl.Phys.Lett., 67,1783 (1995)) has reported in LaCaMnO body material and has had especially big giant magnetoresistance effect, and when temperature 57K, external magnetic field 8T, magnetoresistive ratio reaches 10
8%.But huge GMR need low temperature (＜200K) and very big outfield (being generally 5-8T) just can show, limited the application of perovskite rare earth manganese oxide giant magnetic resistance material.Can improve serviceability temperature (being Curie temperature) and reduce the outfield be the key that perovskite rare earth manganese oxide giant magnetic resistance material is developed to Applied Materials.
Chinese patent (publication number CN 1259500A) has been reported a kind of oxide giant magnet electric resistance material, but magneto-resistance effect only just can embody when low temperature 5K.
Chinese patent (publication number CN 1221988A) has been reported a kind of method for preparing giant magnet resistance film of decomposing based on metallorganic, but the preparation of body material or target is not related to.
United States Patent (USP) (publication number 5939354) has been reported the oxide of a kind of Ce of containing, is used for doing catalyst.
Summary of the invention
Purpose of the present invention is exactly to solve the existing low excessively deficiency of oxide giant magnet electric resistance material serviceability temperature, and a kind of technology for preparing the room temperature oxide giant magnet electric resistance material is provided.
Another object of the present invention provides a kind of purposes of prepared room temperature oxide giant magnet electric resistance material, and this material will be widely used in sensing, magnetic storage field.
For achieving the above object, the present invention takes following technical scheme:
The technology of preparation perovskite rare earth manganese oxide giant magnetic resistance material comprises the steps:
(1) with rare earth oxide La
2O
3, Nd
2O
3, Ce
2O
3, Pr
2O
3, Sm
2O
3, Eu
2O
3, Er
2O
3Deng in one or more combination, carbonate SrCO
3, CaCO
3, BaCO
3, PbCO
3, K
2CO
3Deng in one or more combination and oxide M nO
2, Fe
2O
3, Ni
2O
3, Cr
2O
3Deng in one or more combination according to molecular formula RE
1-xT
xDO
3 ± yThe atom proportion ingredient, 0＜x＜1 wherein, 0≤y＜3, RE is one or more the combination among rare-earth elements La, Nd, Ce, Pr, Sm, Eu, the Er etc., T is one or more the combination among alkaline earth or alkali metal Sr, Ca, Ba, Pb, K etc., and D is one or more the combination among magnesium-yttrium-transition metal Mn, Fe, Ni, the Cr etc.;
(2) confected materials is carried out ball milling;
(3) powder behind the ball milling at first is shaped under forcing press, waits static pressure then;
(4) with the material that suppresses sintering in stove at first, sintering temperature is that 800～1000 ℃, sintering time are 3～10 hours, again sintering behind the broken ball milling, 3～5 times repeatedly, sintering in high temperature furnace then, sintering temperature is that 1300 ℃～1600 ℃, sintering time are 10～50 hours, with obtaining highdensity bulk after the stove cooling;
(5) with the heat treatment under oxygen atmosphere of highdensity bulk, oxygen pressure is 1Pa～1MPa, and treatment temperature is 300 ℃～1000 ℃, and temperature retention time is 1～100 hour, with the stove cooling, prepares final product then.
In above-mentioned chemical formula, the optimum value 0.3 of X, the optimum value of Y are 0.
Generate single-phase perofskite type oxide giant magnetic resistor material of the present invention by the solid phase reaction sintering, this material is under the effect of externally-applied magnetic field, and resistivity significantly descends.Near Curie temperature, resistivity reaches maximum; Below Curie temperature, resistivity increases with the rising of temperature, belongs to the metal mold conduction; When being higher than Curie temperature, resistivity descends with the rising of temperature, belongs to the semi-conductor type conduction.
In technology of the present invention, in the above-mentioned steps (2), the ball milling time is 10～120 minutes, and its particle mean size is 2～10 μ m.
In technology of the present invention, in the above-mentioned steps (3), the pressure when being shaped under forcing press is 0.5～5MPa, and the pressure of static pressure is 10～50MPa.
In technology of the present invention, in the above-mentioned steps (4), the relative density of high density bulk is 85～99.5%.
Perovskite rare earth manganese oxide giant magnetic resistance material of the present invention can be widely used in sensing, the magnetic storage field, and the prepared calcium titanium type rare earth manganese oxide giant magnetic resistance material of technology of the present invention is used to prepare transducer, read and write of hard disc in computer magnetic head or memory device.
The new technology major advantage of preparation perovskite rare earth manganese oxide giant magnetic resistance material provided by the invention is:
1, the prices of raw and semifnished materials are cheap, and can prepare the sample with different Curie temperature by the relative amount of adjusting each composition.
2, by the adjusting process parameter, can prepare near Curie temperature still has considerable magneto-resistance effect room temperature sample.
3, process equipment is simple, good reproducibility, and the efficient height, cost is low, helps Industry Promotion.
Description of drawings
Fig. 1 is the (La of the present invention's preparation
xNd
1-x)
0.7Sr
0.3MnO
3Oxide giant magnet electric resistance sample X-ray diffractogram, all samples are single-phase perovskite structure.
Fig. 2 is the (La of the present invention's preparation
xNd
1-x)
0.7Sr
0.3MnO
3The oxide giant magnet electric resistance sample, Curie temperature rises to 346K with the increase of La content by 215K.This explanation La replaces the raising that Nd helps Curie temperature.
Fig. 3, Fig. 4 are the (La of the present invention's preparation
0.4Nd
06)
0.7Sr
0.3MnO
3The sem photograph of oxide giant magnet electric resistance sample under different sintering conditions.Crystal grain is about 1～3 μ m among Fig. 3.Crystal grain is arranged closely among Fig. 4, and hole is less each other.
Fig. 5, Fig. 6 are the (La of the present invention's preparation
0.4Nd
06)
0.7Sr
0.3MnO
3The magnetoresistive ratio of oxide giant magnet electric resistance sample under different sintering conditions.
Embodiment
To help to understand the present invention by following embodiment, but not limit content of the present invention.
Embodiment 1
In the present embodiment, with La
2O
3, Nd
2O
3, SrCO
3, MnO
2According to molecular formula (La
0.4Nd
06)
0.7Sr
0.3MnO
3Atom proportioning accurate dosing.Carried out ball milling then 30 minutes, its particle mean size is 4 μ m..Powder behind the ball milling at first is shaped under forcing press, and pressure is 1MPa; Wait static pressure then, its pressure is 30MPa.
With the material that suppresses sintering in Muffle furnace at first, sintering temperature is that 1000 ℃, sintering time are 5 hours, sintering again behind the broken ball milling, and 3 times repeatedly is 8 hours at 1300 ℃ of following sintering times then, with making sample after the stove cooling.Its sem photograph as shown in Figure 3.The magnetoresistive ratio of this sample in whole measurement warm area with the rising of temperature or be declined to become linear change.As shown in Figure 5, outside magnetic field 5T effect down, 41% when magnetoresistive ratio 76% during from 15K drops to 300K represented by the curve M R5 among Fig. 5.During external magnetic field 2T, 17% when magnetoresistive ratio 30% during from 15K drops to 300K represented by the curve M R2 among Fig. 5.The linear change rate of magneto-resistor has crucial meaning for the high performance device of preparation.
In the present embodiment, except that handle changed into 16 hours at 1300 ℃ of following sintering times in 8 hours, other process conditions are all with embodiment 1.Its sem photograph as shown in Figure 4.Different with sample described in the embodiment 1 is, this sample is near Curie temperature 276K, and magnetoresistive ratio reaches maximum.As shown in Figure 6, during the 5T of outfield, the magnetoresistive ratio maximum is 62%, is represented by the curve M R5 among Fig. 6.During the 2T of outfield, the magnetoresistive ratio maximum is 23.5%, is represented by the curve M R2 among Fig. 6.This explanation can change the fine structure pattern of sample by adjusting preparation technology parameter, thereby can prepare the giant magnetic resistor material with different magnetoresistance characteristics as required.
Embodiment 3
In the present embodiment, with La
2O
3, Nd
2O
3, SrCO
3, MnO
2According to molecular formula (La
X 'Nd
1-x ')
0.7Sr
0.3MnO
3And x ' is respectively 0,0.2,0.4,0.6,0.8,1.0 atom proportioning and accurately is made into six kinds of material, makes six kinds of samples by the technology of embodiment 2.As shown in Figure 1, by seeing on the X-ray diffractogram, these six kinds of samples are single-phase perovskite structure, free from admixture.As shown in Figure 2, can illustrate, in the scope of chemical formula of the present invention and x, the desired value of y, improve La content, reduce Nd content simultaneously, then help the raising of Curie temperature by this embodiment.
Oxide giant magnet electric resistance material of the present invention has overcome the ordinary oxide giant magnetic resistor material and has had only the deficiency that just shows giant magnetoresistance effect at low temperatures, near room temperature, have 62% magnetoresistive ratio, be fit to the high performance transducer of preparation, magnetic storage apparatus etc.
Claims (4)
1, a kind of technology for preparing perovskite rare earth manganese oxide giant magnetic resistance material is characterized in that, this technology comprises the steps:
(1) with rare earth oxide La
2O
3, Nd
2O
3, Ce
2O
3, Pr
2O
3, Sm
2O
3, Eu
2O
3, Er
2O
3In one or more combination, carbonate SrCO
3, CaCO
3, BaCO
3, PbCO
3, K
2CO
3In one or more combination and oxide M nO
2, Fe
2O
3, Ni
2O
3, Cr
2O
3In one or more combination according to molecular formula RE
1-xT
xDO
3 ± yThe atom proportion ingredient, 0＜x＜1 wherein, 0≤y＜3, RE is one or more the combination among rare-earth elements La, Nd, Ce, Pr, Sm, Eu, the Er, T is one or more the combination among alkaline earth or alkali metal Sr, Ca, Ba, Pb, the K, and D is one or more the combination among magnesium-yttrium-transition metal Mn, Fe, Ni, the Cr;
(2) confected materials is carried out ball milling;
(3) powder behind the ball milling at first is shaped under forcing press, waits static pressure then;
(4) with the material that suppresses sintering in stove at first, sintering temperature is that 800～1000 ℃, sintering time are 3～10 hours, again sintering behind the ball milling, 3～5 times repeatedly, sintering in high temperature furnace then, sintering temperature is that 1300 ℃～1600 ℃, sintering time are 10～50 hours, with obtaining highdensity bulk after the stove cooling;
(5) with the heat treatment under oxygen atmosphere of highdensity bulk, oxygen pressure is 1Pa～1MPa, and treatment temperature is 300 ℃～1000 ℃, and temperature retention time is 1～100 hour, with the stove cooling, prepares final product then.
2, the technology of preparation perovskite rare earth manganese oxide giant magnetic resistance material according to claim 1 is characterized in that: in above-mentioned steps (2), the ball milling time is 10～120 minutes, and its particle mean size is 2～10 μ m.
3, the technology of preparation perovskite rare earth manganese oxide giant magnetic resistance material according to claim 1 and 2 is characterized in that: in above-mentioned steps (3), the pressure when being shaped under forcing press is 0.5～5MPa, and the pressure of static pressure is 10～50MPa.
4, the application of the prepared perovskite rare earth manganese oxide giant magnetic resistance material of the described technology of a kind of claim 1, it is characterized in that: described calcium titanium type rare earth manganese oxide giant magnetic resistance material is used to prepare transducer, read and write of hard disc in computer magnetic head or memory device.
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| CN1324720C true CN1324720C (en) | 2007-07-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600191A (en) * | 2013-10-31 | 2015-05-06 | 中国科学院物理研究所 | Heterostructure material with positive field resistance effect, preparation method and purpose thereof |
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| BRPI0915629A2 (en) * | 2008-07-08 | 2016-05-17 | Univ Denmark Tech Dtu | magnetocaloric cooler |
| RU2454370C1 (en) * | 2010-11-16 | 2012-06-27 | Федеральное государственное бюджетное учреждение науки Институт физики им. Л.В. Киренского Сибирского отделения Российской академии наук (ИФ СО РАН) | Magnetic, tellurium-containing manganese chalcogenide with giant magnetoresistance |
| CN102154700A (en) * | 2011-05-17 | 2011-08-17 | 中国科学院物理研究所 | Perovskite chromium oxide crystal and preparation method thereof |
| CN104091885A (en) * | 2014-07-25 | 2014-10-08 | 哈尔滨理工大学 | Method for preparing rare-earth-element-doped lanthanum-strontium-manganese-oxygen-system manganite magnetic resistance materials |
| CN106431402B (en) * | 2016-09-30 | 2020-09-04 | 杭州电子科技大学 | Perovskite structure manganese oxide based super giant magnetoresistance material and preparation method thereof |
| CN106910821A (en) * | 2017-01-13 | 2017-06-30 | 河北师范大学 | A kind of Double Perovskite manganese-salt phosphating with vertical exchange bias effect and preparation method thereof |
| CN116120065A (en) * | 2022-12-02 | 2023-05-16 | 安徽大学 | Magnetic material with magnetization reversal phenomenon and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05234800A (en) * | 1992-02-21 | 1993-09-10 | Casio Comput Co Ltd | Magnetic semiconductor oxide thin film and manufacture thereof |
| JPH10163510A (en) * | 1996-12-04 | 1998-06-19 | Mitsubishi Electric Corp | Infrared-detecting element |
| JPH1186236A (en) * | 1997-09-05 | 1999-03-30 | Toshiba Corp | Magnetic element, magnetic memory and magneto-optic element |
| JP2000012920A (en) * | 1998-06-24 | 2000-01-14 | Matsushita Electric Ind Co Ltd | Magnetoresistance tunnel junction element |
-
2001
- 2001-09-20 CN CNB011418532A patent/CN1324720C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05234800A (en) * | 1992-02-21 | 1993-09-10 | Casio Comput Co Ltd | Magnetic semiconductor oxide thin film and manufacture thereof |
| JPH10163510A (en) * | 1996-12-04 | 1998-06-19 | Mitsubishi Electric Corp | Infrared-detecting element |
| JPH1186236A (en) * | 1997-09-05 | 1999-03-30 | Toshiba Corp | Magnetic element, magnetic memory and magneto-optic element |
| JP2000012920A (en) * | 1998-06-24 | 2000-01-14 | Matsushita Electric Ind Co Ltd | Magnetoresistance tunnel junction element |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600191A (en) * | 2013-10-31 | 2015-05-06 | 中国科学院物理研究所 | Heterostructure material with positive field resistance effect, preparation method and purpose thereof |
| CN104600191B (en) * | 2013-10-31 | 2017-11-21 | 中国科学院物理研究所 | Heterogeneous structure material of inhibition effect and its production and use is sent a telegraph with positive field |
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| CN1409416A (en) | 2003-04-09 |
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