CN101891469B - Method for regulating and controlling magnetic property and ferroelectric property of multiferroic material Bi2NiTiO6 - Google Patents
Method for regulating and controlling magnetic property and ferroelectric property of multiferroic material Bi2NiTiO6 Download PDFInfo
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- CN101891469B CN101891469B CN2010101648155A CN201010164815A CN101891469B CN 101891469 B CN101891469 B CN 101891469B CN 2010101648155 A CN2010101648155 A CN 2010101648155A CN 201010164815 A CN201010164815 A CN 201010164815A CN 101891469 B CN101891469 B CN 101891469B
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Abstract
The invention discloses a method for regulating and controlling magnetic property and ferroelectric property of a multiferroic material Bi2NiTiO6. The method mainly comprises the following steps of: annealing the multiferroic material Bi2NiTiO6; and realizing the change of valence states of Ni ions and Ti ions and the change of an electronic spin arrangement mode by controlling the annealing temperature so as to regulate a magnetic torque, an action form and the strength of the ferroelectric property. The multiferroic material Bi2NiTiO6 is annealed, so that the influence of electron transfer on the magnetic property and the electric property can be researched, and a mutual action mechanism of the multiferroic material can be understood deeply.
Description
Technical field
The present invention relates to a kind of magnetic property of uhligite multi-iron material and the regulate and control method of ferroelectric properties.
Background technology
For Bi is ABO
3Type uhligite multi-ferroic material, the Bi ion 6s of A position
2Lone-pair electron distort lattice, provide to produce polar power.And the B position generally is single or a plurality of metals ions that magnetic can be provided.Between the ion of B position whether interaction is arranged, or interactional type decided is in the type whether magnetic order or magnetic order are arranged of material.Interactional power then determines the temperature range that the magnetic order degree exists.For magneto-electric coupled, because Bi is ABO
3The ferroelectric properties of type uhligite multi-ferroic material is because 6s
2Lone-pair electron provide, can magnetic order (electricity in order) be regulated and control and add magnetic field (electric field), thereby causes the variation of lattice, and then to electricity in order (magnetic order) regulate and control, reach the regulation and control of magnetic () to electricity (magnetic) performance.For valence state between the metals ion of B position is the system that electric charge can shift between ion; Between the ion of B position the transfer of electric charge can influence between them interactional type with change electron spinning on each ion situation of arranging; Thereby determine the type or the complicated mixed magnetic attitude structure of its magnetic, and then regulate and control its electrical property.Through studying the influence of transfer transport, deeply understand the interaction mechanism of multi-iron material to magnetic and electrical property to multi-iron material Bi2NiTi06 anneal.The further investigation of this mechanism can provide theoretical direction to magneto-electric coupled material devices key for design technology.
Summary of the invention
It is a kind of through anneal, to multi-iron material Bi that the present invention provides
2NiTiO
6The method of magnetic property and ferroelectric properties regulation and control.
For realizing above-mentioned purpose, multi-iron material Bi of the present invention
2NiTiO
6The regulate and control method of magnetic property and ferroelectric properties is specially: to multi-iron material Bi
2NiTiO
6Carry out anneal,, realize Ni ion and the variation of Ti ionic valence state and the variation of electron spinning arrangement mode, adjust magnetic moment size and action mode and ferroelectric properties intensity through the control annealing temperature.
Further, said annealing temperature is 150 ℃-550 ℃.
Further, the time of said anneal is 3-20 hour.
Further, said anneal is carried out under air, nitrogen, oxygen or inert gas atmosphere.
Further, along with the change of said annealing temperature, said multi-iron material Bi
2NiTiO
6Magnetic moment, resistivity and maximum polarization follow change.
The magnetic property of multi-iron material Bi2NiTiO6 of the present invention and the regulate and control method of ferroelectric properties through studying the influence of transfer transport to magnetic and electrical property to multi-iron material Bi2NiTiO6 anneal, are deeply understood the interaction mechanism of multi-iron material.
Description of drawings
Fig. 1 is a Bi2NiTiO6 material of the present invention, through the neutron collection of illustrative plates of neutron measurement and software match;
Fig. 2 is Bi2NiTiO6 material XRD figure spectrum of the present invention and software match collection of illustrative plates;
Specific inductivity and loss that Fig. 3 records through heating and cooling for Bi2NiTiO6 material of the present invention;
Effective magnetic moment that Fig. 4 obtains for the Curie's weiss match of Bi2NiTiO6 material paramagnetic of the present invention zone and Curie's weiss temperature are with the variation relation of annealing temperature;
The susceptibility that Fig. 5 records after different aftertreatments for Bi2NiTiO6 material of the present invention is with variation of temperature;
The respective change that Fig. 6 changes along with annealing temperature for resistivity in the Bi2NiTiO6 material of the present invention;
Fig. 7 is the maximum polarization and the variation of coercive field along with different post-processing temperatures of Bi2NiTiO6 material room temperature of the present invention.
Embodiment
Single phase multi-iron material among the present invention is Bi
2NiTiO
6, this material is monophasic orthohormbic structure Pn2
1A structure, wherein Bi ionic 6S
2Lone-pair electron are that this material presents ferroelectric source, interaction type and intensity between the transfer impact magnetic ion of Ni ion and Ti ionic variation of valence and electronics between.
The regulatable multi-iron material Bi of performance
2NiTiO
6, its structure is confirmed to be specially:
1) with high pressure synthetic Bi
2NiTiO
6Polycrystalline ceramics grinds to form particle at micron powder, obtains the variation relation figure of diffraction intensity along with diffraction angle through the x optical diffraction, and is as shown in Figure 2;
2) with high pressure synthetic Bi
2NiTiO
6Polycrystalline carries out neutron diffraction, obtains the variation relation figure of diffraction intensity along with diffraction angle, and is as shown in Figure 1;
3) collection of illustrative plates being carried out structure through analysis software Fullprof and GSAS demarcates;
4) the non-centrosymmetrical Pn2 of the final crystal space crowd who demarcates for allowing iron electric polarization to exist
1A.
As shown in Figure 3, this multi-iron material Bi
2NiTiO
6Dielectric properties are measured near find 513K, to take place obvious heat stagnation one-level ferroelectric phase transition.An antiferromagnetic phase transformation takes place near being illustrated in 60K in Magnetic Measurement, and low temperature is an antiferromagnetic interactional spin glass.Through being handled, the aerial after annealing of sample finds that sample is very responsive to treatment condition.We are pressed into Bi to height respectively
2NiTiO
6Sample was 150 ℃, 300 ℃, 450 ℃, 550 ℃ annealing 3-20 hour, and annealing atmosphere has air, oxygen, hydrogen, nitrogen etc. respectively.Through performance is relatively found performance change for annealing atmosphere and annealing time (3-20 hour) and insensitive, and mainly is influenced by annealing temperature.Comparison for ease, Bi among the present invention
2NiTiO
6The sample annealing conditions is respectively in air 150 ℃, 300 ℃, 450 ℃, 550 ℃ annealing 16 hours.Annealing can change Bi
2NiTiO
6The variation of the variation of Ni and Ti ionic valence state and spin arrangement mode in the ceramics sample.
Fig. 4 and Fig. 5 provide susceptibility and the variation relation of effective magnetic moment along with annealing temperature, as can be seen from the figure, and for unannealed sample, Bi
2NiTiO
6Sample is with Ni
2+And Ti
4+Be main valence state, the effective magnetic moment of the paramagnetic that provides is 2.83 μ B; When annealing temperature was 300 ℃, valence state was with Ni
3+And Ti
3+Be main, the effective magnetic moment maximum of paramagnetic that this moment is corresponding is 4.24 μ B; Further annealing, valence state is still with Ni when annealing temperature is 550 ℃
3+And Ti
3+Be main, but the spin arrangement mode changes, this moment, corresponding effective magnetic moment was 2.45 μ B.And the variation of spin arrangement mode must cause Bi
2NiTiO
6The resistance change of ceramics sample.
That Fig. 6 provides is Bi
2NiTiO
6The respective change that resistivity changes along with annealing temperature in the ceramics sample.As can be seen from the figure the great variety of 5 one magnitude takes place along with the rising of annealing temperature descends rapidly in resistivity.The resistivity minimum is about 10 when annealing temperature is 300 ℃
6Ω cm.Further the resistance annealing rate changes to the direction that increases.If the variation of resistivity causes merely owing to annealing produces the oxygen room, resistivity should reduce along with the annealing temperature dullness that raises.But the non-monotone variation of experimental data.Therefore the variation of change in resistance and spin arrangement mode is closely connected and is in the same place.
As can be seen from Figure 7 along with the variation of 1 one magnitude has also taken place the annealing temperature ferroelectric maximum polarization that raises, when annealing temperature arrives 300 ℃, it is maximum that maximum polarization reaches, and is 8 μ C/cm
2Further the annealing maximum polarization changes to the direction that reduces.Corresponding variation also takes place with the variation of annealing temperature in corresponding coercive field, this variation corresponding Bi
2NiTiO
6The variation of the effective magnetic moment of the paramagnetic variation of arrangement mode of just spinning in the ceramics sample.And magnetic property changes and the variation of ferroelectric properties is one to one, and is together interrelated, at Bi
2NiTiO
6Successfully ferroelectric properties is regulated and control in the system through magnetic property.In order further to get rid of the influence of oxygen room for ferroelectric properties, we are with Bi
2NiTiO
6Ceramics sample was annealed 16 hours in differing temps (100-600 ℃) in oxygen with in the nitrogen respectively, afterwards its ferroelectricity was measured.No matter find is in oxygen or at the sample of AN, unannealed relatively its ferroelectric properties of sample is also obviously strengthened.Through testing the ferroelectric variation of further confirmation is to contact directly with the arrangement mode variation of magnetic just of spinning to be in the same place.Annealing temperature of the present invention is not limited to listed temperature in the embodiment, under other annealing temperature the influence of the magnetic property of ferroelectric material and ferroelectric properties is seldom done to endure at this and states.
It is to be noted and any distortion of making according to embodiment of the present invention all do not break away from the scope that spirit of the present invention and claim are put down in writing.
Claims (3)
1. multi-iron material Bi
2NiTiO
6The regulate and control method of magnetic property and ferroelectric properties is specially: to multi-iron material Bi
2NiTiO
6Carry out anneal, through the control annealing temperature, magnetic moment size and action mode and ferroelectric properties intensity are adjusted in the variation of realization Ni ion and Ti ionic valence state and the variation of electron spinning arrangement mode; Said annealing temperature is 150 ℃-550 ℃, along with the change of said annealing temperature, and said multi-iron material Bi
2NiTiO
6Magnetic moment, resistivity and maximum polarization follow change.
2. multi-iron material Bi as claimed in claim 1
2NiTiO
6The control methods of magnetic property and ferroelectric properties is characterized in that, the time of said anneal is 3-20 hour.
3. multi-iron material Bi as claimed in claim 1
2NiTiO
6The control methods of magnetic property and ferroelectric properties is characterized in that, said anneal is carried out under air, nitrogen, oxygen or inert gas atmosphere.
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CN104591721B (en) * | 2015-02-06 | 2017-05-17 | 武汉理工大学 | Single-phase multiferroic M-type lead ferrite ceramic material and preparation method thereof |
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