CN105332057B - Using one-step method direct growth magnetoelectric material Mn4Nb2O9The method of monocrystalline - Google Patents

Using one-step method direct growth magnetoelectric material Mn4Nb2O9The method of monocrystalline Download PDF

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Publication number
CN105332057B
CN105332057B CN201510659844.1A CN201510659844A CN105332057B CN 105332057 B CN105332057 B CN 105332057B CN 201510659844 A CN201510659844 A CN 201510659844A CN 105332057 B CN105332057 B CN 105332057B
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monocrystalline
rod
charge bar
seed crystal
stove
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CN105332057A (en
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曹义明
曹世勋
向茂林
康保娟
张金仓
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C30B29/30—Niobates; Vanadates; Tantalates
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention discloses one kind to use one-step method direct growth magnetoelectric material Mn4Nb2O9The method of monocrystalline, its step are：Initial feed uses MnCO of the purity for more than 3N3With Nb2O5In molar ratio 4:1 prepares the i.e. upper rod of charge bar and lower rod；Be placed in high temperature furnace 900 DEG C, 12 h are sintered under Ar gas shieldeds, be down to room temperature naturally with stove；Obtained charge bar grows monocrystalline in optics floating region stove.The characteristics of this method is no matter that the single-crystal surface finish, consistency, uniformity of gained are all highly desirable；Mn of the present invention4Nb2O9That obtained during charge bar pre-synthesis is MnNb2O6And Mn3O4Mixed phase, grown using the charge bar and seed crystal of the mixed phase under Ar gas shieldeds, a step has directly obtained the Mn of pure phase4Nb2O9Monocrystalline.Obtained large size single crystal will provide technical foundation for follow-up basic research and device application.

Description

Using one-step method direct growth magnetoelectric material Mn4Nb2O9The method of monocrystalline
Technical field
The present invention relates to a kind of preparation method of crystalline material, there is magnetic and ferroelectric simultaneously more particularly to a kind of The preparation method of crystalline material, the extraordinary magneto-electric functional material technology of preparing applied to devices such as sensor or acoustic wave transducers are led Domain.
Background technology
In recent years, multi-ferroic material is widely used with ferroelectric material in modern science and technology.Ferromagnetic material (ferromagnetics) there are Spontaneous Magnetic Moments, and it can change and overturn with externally-applied magnetic field, switching function be realized, so as to real Existing information storage.Hyundai electronicses industry, including computer etc., widely use magnetic storage technology.Ferroelectric material has spontaneous electrode Change, this electric polarization can change and overturn with extra electric field, realize switching function.Many ferroelectrics are also ferroelastics simultaneously (ferroelastics), its electropolarized change is generally along with the change of shape or lattice constant, therefore is widely used in passing Sensor or acoustic wave transducer etc..Further, compared with the memory being widely used at present, the ferroelectricity based on ferroelectric material Random-access memory (ferroelectric random access memory, FeRAM) has non-volatile and read fast The advantages that fast is spent, thus there is huge applications prospect.With the progress of science and technology, the requirement to device miniaturization is increasingly Height, this is just needed to develop while has the new material of two or more function, and multiple functions can be realized simultaneously to develop New device.It will inevitably be interacted because various physical effects coexist in a system, between them, so as to The mutual regulation and control between difference in functionality may be realized, the multifunction device to develop new provides chance.In view of magnetic and ferroelectricity Can the extensive use in modern science and technology, people expect being combined together magnetic and ferroelectricity naturally, and acquisition has simultaneously The reading and control of magnetic and ferroelectric material, it is possible to break through the bottleneck of current spintronics --- spin states, have Prestige develops new antetype device based on this.One most prominent example of multiferroic possible application is：Magnetic recording reading speed Write soon slowly, ferroelectricity record reads complexity and write soon；If the use of multiferroic is recording medium, it is possible to realize simultaneously The read-write process of superelevation speed.
Nanjing University Y. Fang in 2015 et al. report Mn first4Nb2O9Adjusted at polycrystalline Ne＆1＆el temperature along with magnetic field The polarization of control, implies Mn4Nb2O9It is magnetoelectric material, but there is presently no on Mn4Nb2O9The report of monocrystalline.
The content of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind Using one-step method direct growth magnetoelectric material Mn4Nb2O9The method of monocrystalline, large scale is directly prepared using the step of floating zone method one Mn4Nb2O9Monocrystalline, preparation process is corrosion-free, pollution-free, and growing efficiency is high, and process repeatability is good, prepared Crystal perfection is good, and crystal mass is high, and satisfaction prepares the special type function material demand of magnetoelectronic devices.
Purpose is created to reach foregoing invention, using following technical proposals：
One kind uses one-step method direct growth magnetoelectric material Mn4Nb2O9The method of monocrystalline, comprises the following steps：
1. preparation and the pre-synthesis technique of polycrystalline rod：
A. MnCO of the purity for more than 3N is used3And Nb2O5As initial feed, and by MnCO3With Nb2O5In molar ratio For 4:1 ratio is matched, and after the compound by above-mentioned proportioning components is ground and is sufficiently mixed, compound is put In in high temperature furnaces, under Ar gas shielded atmospheric conditions and 12 h are sintered at a temperature of 900 DEG C, are then down to room temperature naturally with stove, Obtain pre-sintered raw material for standby；
B. the pre-sintered raw material prepared in the step a is ground to obtain, then the polycrystalline feed powder after grinding is put Enter in mould, the isostatic pressing under 50-200 MPa pressure, prepared composition MnNb2O6And Mn3O4Mixed phase raw material Rod；
2. one-step method monocrystalline growing process：
A. a raw material charge bar is fixed on the seat stand of lower section seed rod as seed crystal rod, by an other fuel rod It is suspended on the hook of square stock bar and is used as charge bar, then adjust the relative position between seed crystal rod and charge bar, ensures seed crystal Rod and charge bar are coaxially disposed；
B. floating zone method is used, starts rotary system, it is 10 ~ 30 rpm to control rotating speed, and control air draught flow exists Between 2-6 L/min, after automatic power per liter to 45%, continue to use manual power per liter, after charge bar fusing uniformly, start pair Splicing rod and seed crystal rod, after stable after melting zone, crystalline material is grown with 5 mm/h velocity-stabilization, growth crystalline material terminates Afterwards, room temperature is slowly dropped to, the Mn of final obtained pure phase4Nb2O9Monocrystalline；It is preferred that finally the diameter of obtained pure phase is not less than 7mm and length Large scale Mn of the degree not less than 35mm4Nb2O9Monocrystal material.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
1. the present invention combines floating zone method using pre-sintering, large-sized magnetic of pure phase has been directly obtained by a step Electric material Mn4Nb2O9Monocrystalline, the single-crystal surface finish of gained is good, consistency is high and uniformity is good；
2. the present invention obtains MnNb during pre-sintering2O6And Mn3O4Mixed phase, using the mixed phase charge bar and Seed crystal grows under Ar gas shieldeds, and a step can directly obtain the Mn of pure phase4Nb2O9Monocrystalline, it is not necessary to pass through monophase materialses material Material prepares monocrystal material, and technique is easily achieved, and the cost of raw material is low.
Brief description of the drawings
Fig. 1 is that the preferred embodiment of the present invention prepares magnetoelectric material Mn4Nb2O9The floating zone method grower principle of monocrystalline Figure.
Embodiment
Details are as follows for the preferred embodiments of the present invention：
In the present embodiment, one-step method direct growth magnetoelectric material Mn is used referring to Fig. 1, one kind4Nb2O9The method of monocrystalline, Comprise the following steps：
1. preparation and the pre-synthesis technique of polycrystalline rod：
A. MnCO of the purity for more than 3N is used3And Nb2O5As initial feed, and by MnCO3With Nb2O5In molar ratio For 4:1 ratio is matched, and after the compound by above-mentioned proportioning components is ground and is sufficiently mixed, compound is put In in high temperature furnaces, under Ar gas shielded atmospheric conditions and 12 h are sintered at a temperature of 900 DEG C, are then down to room temperature naturally with stove, Obtain pre-sintered raw material for standby；
B. the pre-sintered raw material prepared in the step a is ground to obtain, then the polycrystalline feed powder after grinding is put Enter in mould, the isostatic pressing under 50-200 MPa pressure, prepare the mm of diameter 8, the mm of length about 50 fuel rod 1 respectively With the mm of diameter 5mm, length about 30 seed crystal rod 2, confirm through XRD, the fuel rod 1 and seed crystal rod 2 are MnNb2O6And Mn3O4 Mixed phase, rather than single-phase Mn4Nb2O9Polycrystalline material, that is, obtain rod and lower rod；
2. one-step method monocrystalline growing process：
A. the seed crystal rod 2 of a 30 mm length is fixed on the seat stand of lower section seed rod as lower rod, by 50 mm Long fuel rod 1, which is suspended on the hook of square stock bar, is used as upper rod, then adjusts the phase between seed crystal rod 2 and fuel rod 1 To position, ensure that seed crystal rod 2 and fuel rod 1 are coaxially disposed；
B. floating zone method is used, optics floating region stove is set, as shown in figure 1, optics floating region stove mainly there are three part structures Into：Heating system 3, Machinery Control System and atmosphere control system, heating system are halogen iodine-tungsten lamp or xenon lamp, its heating-up temperature 2200 DEG C and 2800 DEG C are up to respectively；Start rotary system, it is 10 ~ 30 rpm to control rotating speed, controls air draught flow Between 2-6 L/min, after automatic power per liter to 45%, continue to use manual power per liter, after charge bar fusing uniformly, start Charge bar and seed crystal rod are docked, after stable after melting zone 4, crystalline material is grown with 5 mm/h velocity-stabilization, grows crystalline material knot Shu Hou, room temperature is slowly dropped to, the large scale Mn that finally a diameter of 7mm of obtained pure phase and length are 35mm4Nb2O9Monocrystal material.
In the present embodiment, referring to Fig. 1, Mn is directly successfully prepared using the step of floating zone method one4Nb2O9Monocrystalline, gained Though single-crystal surface finish, consistency, uniformity it is all highly desirable.The present embodiment Mn4Nb2O9In charge bar sintering process To can not be monophase materialses, but MnNb2O6And Mn3O4Mixed phase, using the charge bar and seed crystal of the mixed phase in Ar gas Protection is lower to be grown, and a step has directly obtained the Mn of pure phase4Nb2O9Monocrystalline.The present embodiment prepares Mn4Nb2O9The advantage of single-crystal techniques It is corrosion-free, pollution-free, crystal perfection is good, is of high quality, and growing efficiency is high, favorable repeatability.
The embodiment of the present invention is illustrated above in conjunction with accompanying drawing, but the invention is not restricted to above-described embodiment, can be with A variety of changes are made according to the purpose of the innovation and creation of the present invention, under all Spirit Essence and principle according to technical solution of the present invention Change, modification, replacement, combination or the simplification made, should be equivalent substitute mode, as long as meeting the goal of the invention of the present invention, One-step method direct growth magnetoelectric material Mn is used without departing from the present invention4Nb2O9The technical principle and invention structure of the method for monocrystalline Think, belong to protection scope of the present invention.

Claims (2)

1. one kind uses one-step method direct growth magnetoelectric material Mn4Nb2O9The method of monocrystalline, it is characterised in that including following step Suddenly：
1. preparation and the pre-synthesis technique of polycrystalline rod：
A. MnCO of the purity for more than 3N is used3And Nb2O5As initial feed, and by MnCO3With Nb2O5It is 4 in molar ratio:1 Ratio matched, after the compound by above-mentioned proportioning components is ground and is sufficiently mixed, compound is placed in height In warm stove, under Ar gas shielded atmospheric conditions and 12 h are sintered at a temperature of 900 DEG C, then room temperature is down to naturally with stove, obtains Pre-sintered raw material for standby；
B. the pre-sintered raw material prepared in the step a is ground, then the polycrystalline feed powder after grinding is put into mould In, the isostatic pressing under 50-200 MPa pressure, prepared composition MnNb2O6And Mn3O4Mixed phase fuel rod；
2. one-step method monocrystalline growing process：
A. a raw material charge bar is fixed on the seat stand of lower section seed rod as seed crystal rod, an other fuel rod is hung Up expect be used as charge bar on the hook of bar, then adjust the relative position between seed crystal rod and charge bar, ensure seed crystal rod with Charge bar is coaxially disposed；
B. floating zone method is used, starts rotary system, it is 10 ~ 30 rpm to control rotating speed, and control air draught flow is in 2-6 Between L/min, after automatic power per liter to 45%, continue to use manual power per liter, after charge bar fusing uniformly, start to splicing Rod and seed crystal rod, after stable after melting zone, crystalline material is grown with 5 mm/h velocity-stabilization, after growth crystalline material terminates, delayed Slowly room temperature is down to, the Mn of final obtained pure phase4Nb2O9Monocrystalline.
2. one-step method direct growth magnetoelectric material Mn is used according to claim 14Nb2O9The method of monocrystalline, its feature exist In：The step 2. in, the Mn of final obtained pure phase4Nb2O9The diameter of monocrystalline is not less than 35mm not less than 7mm and length.
CN201510659844.1A 2015-10-14 2015-10-14 Using one-step method direct growth magnetoelectric material Mn4Nb2O9The method of monocrystalline Expired - Fee Related CN105332057B (en)

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CN102358954A (en) * 2011-10-12 2012-02-22 北京工业大学 Method for growing CaxBa1-xNb2O6 series crystals
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