CN102976746B - Preparation method of ferroferric oxide and lanthanum-doped bismuth titanate composite magnetoelectric film - Google Patents

Preparation method of ferroferric oxide and lanthanum-doped bismuth titanate composite magnetoelectric film Download PDF

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CN102976746B
CN102976746B CN201210532448.9A CN201210532448A CN102976746B CN 102976746 B CN102976746 B CN 102976746B CN 201210532448 A CN201210532448 A CN 201210532448A CN 102976746 B CN102976746 B CN 102976746B
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CN102976746A (en
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吴秀梅
翟亚
孙弘扬
欧慧灵
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Southeast University
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Abstract

The invention relates to a preparation method of a ferroferric oxide and lanthanum-doped bismuth titanate composite magnetoelectric film, which is characterized in that a ferroelectric lanthanum-doped bismuth titanate film and a ferromagnetic ferroferric oxide film are effectively synthesized, thus preparing the multiferroic magnetoelectric composite film material. The preparation method comprises the following specific steps: 1, preparing Fe2O3 and Bi3.25La0.75Ti3O12 (BLT) target materials; and 2, using a pulse laser sputtering deposition system to prepare the Fe3O4/BLT multiferroic magnetoelectric composite film on a Pt/Ti/SiO2/Si substrate. The Fe3O4/BLT multiferroic magnetoelectric composite film material fills up the blank of compounding Fe3O4 and BLT into the multiferroic magnetoelectric composite material and widens the research range of the magnetoelectric composite film material.

Description

Z 250 and bismuth titanates are mixed the preparation method of lanthanum compound magnetoelectric film
Technical field
The present invention is a kind of by by having, ferroelectric film bismuth titanates is mixed lanthanum and to have the film Z 250 of ferrimagnetism effectively synthetic, thereby prepare the preparation method of multiferroic magnetoelectric composite film material, belong to technical field prepared by multiferroic magnetoelectric composite film material.
Background technology
Multi-ferroic material is because it not only has single iron (as ferroelectricity, ferromegnetism and ferroelasticity), and because the coupling synergy between different iron can produce new magnetoelectric effect, the technology such as the novel information stores processor in development based on ferroelectric-integrated effect of magnetic and magnetoelectricity device provide huge potential application potential.Wherein, magnetoelectric composite film material is owing to having good microelectronic technique compatibility characteristics and good performance, make the research of magnetoelectric composite film material become one of focus of numerous investigators' concerns, but because the research of magnetoelectric composite film material is started late, also exist and much have physical problem to be solved, such as based on to material property, the understanding of physics law etc., find more effective ferroelectric/ferromagnetic composite film material, the matching degree of bi-material and matrix material growth technique, need to drop into more concern, pay more effort, to meet the requirement of new device to composite film material.
In the research of existing thin-film material, Z 250 (Fe 3o 4) be a kind of magneticsubstance with spinel structure, because making again it, its special electronic structure belongs to a kind of semimetallic material that is called, and the theoretical value 1 of the Fermi surface electron energy state spin-polarized degree of semi-metallic, can obtain large giant magnetoresistance effect, Fe 3o 4this special structure and performance cause that people pay attention to widely.The bismuth titanates with laminated perovskite structure is mixed lanthanum (as Bi 3.25la 0.75ti 3o 12) ferroelectric membranc, due to have larger residual polarization, preferably fatigue resistance, lower premium propertiess such as preparation temperature, be one of ferroelectric material of widely paying close attention to.
Up to the present, due to the difficulty of the preparation technology who tests, oxidizing condition etc., by Fe 3o 4and Bi 3.25la 0.75ti 3o 12(BLT) Fe being composited 3o 4/ Bi 3.25la 0.75ti 3o 12(Fe 3o 4/ BLT) magnetoelectric composite film material, yet there are no relevant report.
Summary of the invention
Technical problem: the object of this invention is to provide a kind of Z 250 and bismuth titanates and mix the preparation method that lanthanum is combined into Magnetoelectric film, this Fe 3o 4/ Bi 3.25la 0.75ti 3o 12multiferroic magnetoelectric composite film material, has filled up Fe 3o 4with Bi 3.25la 0.75ti 3o 12be combined into the blank of multiferroic magnetic electric compound material, expanded the research range of magnetoelectric composite film material.Meanwhile, be Fe 3o 4/ Bi 3.25la 0.75ti 3o 12the further research of the performance such as ferroelectric, ferromagnetic and magneto-electric coupled of magnetoelectric composite film, has established experiment preparation basis.
Technical scheme: Z 250 of the present invention and bismuth titanates are mixed the preparation method of lanthanum compound magnetoelectric film, specifically comprise the following steps:
Step 1:Bi 3.25la 0.75ti 3o1 2 (bLT) preparation of target
A). batching: reactant feed is Bi 2o 3, La 2o 3, TiO 2; Three kinds of starting material are pressed the mixed in molar ratio of (13.5-14.5): 3:24,
B). the reactant feed of mixing is put into agate tank and add acetone to put into ball grinder, add agate ball, be sealingly fastened on ball mill, Ball-milling Time is more than 15h, and milling time is longer, and BLT powder is thinner, and effect is better;
C). with powder compressing machine, ground reactant feed compressing tablet is shaped, diameter 10-20mm;
D). pre-burning: the block that compressing tablet is shaped is put in box-type furnace, is warming up to 750-850 ℃, insulation 4-6h, and then be rapidly heated to 850-950 ℃, insulation 3-5h, naturally cooling is down to room temperature, makes it tentatively to become phase;
E). sintering: the target of again process step d) being processed, at 1000-1100 ℃, is incubated 1.5-2.5h, is more slowly down to room temperature;
Step 2:Fe 2o 3the preparation of target
The Fe that is α by cell configuration 2o 3powder grinds, then uses powder compressing machine compressing tablet, and being pressed into diameter is 10-20mm, and then sintering forms, and sintering temperature is 800-1000 ℃, insulation 16-24h;
Step 3: preparation Fe 3o 4/ BLT magnetoelectric composite film material
Adopt Gas Sensor Films Deposited by Pulsed Laser Deposition system at Pt/Ti/SiO 2on/Si substrate, prepare Fe 3o 4/ BLT multiferroic magnetoelectric composite film.
Beneficial effect: successfully prepared Fe by present method 3o 4/ Bi 3.25la 0.75ti 3o 12(Fe 3o 4/ BLT) multiferroic magnetoelectric composite film material, Z 250 (Fe 3o 4) be a kind of magneticsubstance with spinel structure, because making again it, its special electronic structure belongs to a kind of semimetallic material that is called, and the theoretical value 1 of the Fermi surface electron energy state spin-polarized degree of semi-metallic, can obtain large giant magnetoresistance effect.BLT is one of ferroelectric thin-flim materials of widely paying close attention to, has larger residual polarization, preferably fatigue resistance, lower premium propertiess such as preparation temperature.
Up to the present, due to the difficulty of the preparation technology who tests, oxidizing condition etc., by Fe 3o 4the Fe being composited with BLT 3o 4/ BLT magnetoelectric composite film material, yet there are no relevant report.
The present invention has successfully prepared Fe 3o 4/ BLT multiferroic magnetoelectric composite film material, has filled up Fe 3o 4be combined into the blank of multiferroic magnetic electric compound material, the research range that has expanded magnetoelectric composite film material with BLT.Meanwhile, be Fe 3o 4the further research of the performance such as ferroelectric, ferromagnetic and magneto-electric coupled of/BLT magnetoelectric composite film, has established experiment preparation basis.
Accompanying drawing explanation
Fig. 1 is the schema of preparation process of the present invention.
Fig. 2 is multiferroic magnetoelectric composite film F e3O 4the X-ray diffractogram of/BLT.
Embodiment
Z 250 of the present invention and bismuth titanates are mixed the preparation method of lanthanum compound magnetoelectric film, it is characterized in that the method comprises the following steps:
One. preparation Fe 2o 3and Bi 3.25la 0.75t i3o 12(BLT) target
1.Bi 3.25la 0.75ti 3o1 2(BLT) preparation of target
A) batching: reactant feed is Bi 2o 3, La 2o 3, TiO2; Three kinds of starting material are pressed the mixed in molar ratio of 13:3:24, due to the volatility of Bi, and generally will be with excessive Bi in experiment 2o 3compensate the loss of Bi, so added the Bi2O3 of 5-20% in raw material.
B) raw material of mixing is put into agate tank and add acetone to put into ball grinder, add agate ball, be sealingly fastened on ball mill, Ball-milling Time is more than 15h, and milling time is longer, and BLT powder is thinner, and effect is better.
C) with powder compressing machine, ground raw material compressing tablet is shaped, diameter 10-20mm.
D) pre-burning: the fast body that compressing tablet is shaped is put in box-type furnace, is warming up to 750-850 ℃, insulation 4-6h, and then be rapidly heated to 850-950 ℃, insulation 3-5h, naturally cooling is down to room temperature, makes it tentatively to become phase.
E) sintering: target, at 1000-1100 ℃, is incubated to 1.5-2.5h, is more slowly down to room temperature.
2.Fe 2o 3the preparation of target
The Fe that is α by cell configuration 2o 3powder grinds, then uses powder compressing machine compressing tablet, and being pressed into diameter is 10-20mm, and then sintering forms.Sintering temperature is 800-1000 ℃, insulation 16-24h left and right.
Two. preparation Fe 3o 4/ BLT magnetoelectric composite film material
Instrument is the PLD-300 Gas Sensor Films Deposited by Pulsed Laser Deposition system that adopts Shenyang Scientific Instrument Research & Mfg. Center Co., Ltd., C.A.S to produce, the light source that this system adopts is the KrF excimer laser of the relevant company of the U.S., model C OMPex Pro205, wavelength 248nm, pulse width 20ns.The substrate of experiment use is Pt/Ti/SiO 2/ Si.
Before experiment, prepare:
A) start laser apparatus, laser apparatus enters self check state.
B) to the venting of PLD cavity, when chamber internal gas pressure is identical with ambient pressure, open chamber door.By Fe 2o 3target,
BLT target is separately fixed on target platform, substrate Pt/Ti/SiO 2/ Si is fixed on chip bench, closes chamber door and purging valve.
The preparation process of step 1.BLT film:
A) target position is adjusted to BLT target.Then start cooling circulating water system.Open PLD system main-control power switch processed, open vacuumometer power switch.
B) open the other valve of taking out pipeline of cavity, start mechanical pump, allow mechanical pump to cavity forvacuum.
C) when vacuum arrives 5-6pa, close the other valve of taking out pipeline of mechanical pump, start molecular pump and vacuumize.
D) open temperature controller switch, set underlayer temperature 590-610 ℃, regulate heating current, start substrate to heat.After, limit heating edge vacuumizes.
E) in chamber, vacuum tightness reaches 1 * 10 -3-2 * 10 -3during Pa, reduce the slide valve of molecular pump, open oxygen valve, make oxygen pressure in chamber reach 18-22Pa.Now, the self check of laser apparatus finishes, and the operating mode of laser apparatus is set to wait can pattern.The energy of laser pulse is made as 230-250mJ, frequency 5-6Hz, sputter umber of pulse 350-3500.
F) regulate light path, pre-proof product 2-3min, formal plated film then, a sputter 350-3500 pulse.
G) after deposition finishes, temperature is adjusted to 690-750 ℃, insulation 30-60min.
Step 2.Fe 3o 4/ BLT method for manufacturing thin film:
The BLT film of preparation is without taking-up, and Fe then grows on BLT film 3o 4film.Experimental procedure is: a) close oxygen valve, after temperature controller temperature is set is 590-710 ℃, be evacuated to 8 * 10 -4pa-2 * 10 -3pa.b) target position is adjusted to Fe 2o 3target, it is 295-305mJ that pulse energy is set, frequency 9-10Hz, umber of pulse 2500-15000.
C) regulate light path, pre-proof product 2-3min, formal plated film then, a sputter 2500-15000 pulse.
D) after deposition finishes, insulation 1-5min.
E) under vacuum condition, disconnect heating power supply, stop heating.
While f) being down to room temperature, close slide valve, stop molecular pump, by cavity venting, take out sample and target.
By step 1 and step 2, just at Pt/Ti/SiO 2on/Si substrate, prepared Fe 3o 4/ BLT multiferroic magnetoelectric composite film.

Claims (1)

1. Z 250 and bismuth titanates are mixed a preparation method for lanthanum compound magnetoelectric film, it is characterized in that the method comprises the following steps:
Step 1:Bi 3.25la 0.75ti 3o 12(BLT) preparation of target
A). batching: reactant feed is Bi 2o 3, La 2o 3, TiO 2; Three kinds of starting material are by the mixed in molar ratio of (13.5-14.5): 3:24;
B). the reactant feed of mixing is put into agate tank and add acetone to put into ball grinder, add agate ball, be sealingly fastened on ball mill, Ball-milling Time is more than 15h, and milling time is longer, and BLT powder is thinner, and effect is better;
C). with powder compressing machine, ground reactant feed compressing tablet is shaped, diameter 10-20mm;
D). pre-burning: the block that compressing tablet is shaped is put in box-type furnace, is warming up to 750-850 ℃, insulation 4-6h, and then be rapidly heated to 850-950 ℃, insulation 3-5h, naturally cooling is down to room temperature, makes it tentatively to become phase;
E). sintering: again will be through steps d) target processed is at 1000-1100 ℃, insulation 1.5-2.5h, be more slowly down to room temperature;
Step 2:Fe 2o 3the preparation of target
The Fe that is α by cell configuration 2o 3powder grinds, then uses powder compressing machine compressing tablet, and being pressed into diameter is 10-20mm, and then sintering forms, and sintering temperature is 800-1000 ℃, insulation 16-24h;
Step 3: preparation Fe 3o 4/ BLT magnetoelectric composite film material
Adopt Gas Sensor Films Deposited by Pulsed Laser Deposition system at Pt/Ti/SiO 2on/Si substrate, prepare Fe 3o 4/ BLT multiferroic magnetoelectric composite film, specifically comprises:
One), before experiment, prepare:
A) start laser apparatus, laser apparatus enters self check state;
B) to the venting of PLD cavity, when chamber internal gas pressure is identical with ambient pressure, open chamber door, by Fe 2o 3target, BLT target are separately fixed on target platform, substrate Pt/Ti/SiO 2/ Si is fixed on chip bench, closes chamber door and purging valve;
Two), preparation BLT film:
A) target position is adjusted to BLT target, then starts cooling circulating water system, open PLD system main-control power switch processed, open vacuumometer power switch;
B) open the other valve of taking out pipeline of cavity, start mechanical pump, allow mechanical pump to cavity forvacuum;
C) when vacuum arrives 5-6Pa, close the other valve of taking out pipeline of mechanical pump, start molecular pump and vacuumize;
D) open temperature controller switch, set underlayer temperature 590-610 ℃, regulate heating current, start substrate heating, after, limit heating edge vacuumizes;
E) in chamber, vacuum tightness reaches 1 * 10 -3-2 * 10 -3during Pa, reduce the slide valve of molecular pump, open oxygen valve, make oxygen pressure in chamber reach 18-22Pa, now, the self check of laser apparatus finishes, and the operating mode of laser apparatus is set to wait energy pattern, the energy of laser pulse is made as 230-250mJ, frequency 5-6Hz, sputter umber of pulse 350-3500;
F) regulate light path, pre-proof product 2-3min, formal plated film then, a sputter 350-3500 pulse;
G) after deposition finishes, temperature is adjusted to 690-750 ℃, insulation 30-60min;
Three), preparation Fe 3o 4/ BLT film:
The BLT film of preparation is without taking-up, and Fe then grows on BLT film 3o 4film, experimental procedure is:
A) close oxygen valve, after temperature controller temperature is set is 590-710 ℃, be evacuated to 8 * 10 -4pa-2 * 10 -3pa;
B) target position is adjusted to Fe 2o 3target, it is 295-305mJ that pulse energy is set, frequency 9-10Hz, umber of pulse 2500-15000;
C) regulate light path, pre-proof product 2-3min, formal plated film then, a sputter 2500-15000 pulse;
D) after deposition finishes, insulation 1-5min;
E) under vacuum condition, disconnect heating power supply, stop heating;
While f) being down to room temperature, close slide valve, stop molecular pump, by cavity venting, take out sample and target;
By step 1, step 2 and step 3, just at Pt/Ti/SiO 2on/Si substrate, prepared Fe 3o 4/ BLT multiferroic magnetoelectric composite film.
CN201210532448.9A 2012-12-11 2012-12-11 Preparation method of ferroferric oxide and lanthanum-doped bismuth titanate composite magnetoelectric film Expired - Fee Related CN102976746B (en)

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CN104446449B (en) * 2014-11-26 2017-07-14 陕西科技大学 A kind of preparation method of BIT Fe multiferroic ferroelectric bulk ceramics
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