CN104844162A - High-temperature ferrimagnetic semiconductor CaCu3Fe2Os2O12 and preparation method thereof - Google Patents
High-temperature ferrimagnetic semiconductor CaCu3Fe2Os2O12 and preparation method thereof Download PDFInfo
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- CN104844162A CN104844162A CN201510163120.8A CN201510163120A CN104844162A CN 104844162 A CN104844162 A CN 104844162A CN 201510163120 A CN201510163120 A CN 201510163120A CN 104844162 A CN104844162 A CN 104844162A
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Abstract
The invention discloses a novel high-temperature ferrimagnetic semiconductor. The chemical formula of the high-temperature ferrimagnetic semiconductor is CaCu3Fe2Os2O12, the high-temperature ferrimagnetic semiconductor has high-temperature ferrimagnetism, and the Curie temperature of the high-temperature ferrimagnetic semiconductor approaches 600K. The invention also discloses a preparation method of the high-temperature ferrimagnetic semiconductor. The method comprises the following steps: uniformly mixing CaO, Fe2O3, CuO, Os and an oxygen source to obtain a mixture; grinding; filling a gold or platinum capsule with the mixture, and sealing; carrying out high temperature and high pressure treatment on the obtained gold or platinum capsule in a high pressure device; annealing or quenching; cooling, and releasing the pressure; taking out the obtained reaction product from the gold or platinum capsule, and fully grinding; and cleaning. The high-temperature ferrimagnetic semiconductor CaCu3Fe2Os2O12 has high Curie temperature and wide semiconductor energy gap, and has potential application values in future spintronic devices.
Description
Technical field
The present invention relates to materials synthesis field, be specifically related to a kind of high temperature Ferrimagnetic semi-conductor CaCu with high temperature ferrimagnetism
3fe
2os
2o
12and preparation method thereof.
Background technology
The present age and future are the societies of information dominant force, and the process of information, transmission and storage will require unprecedented scale and speed.The semiconductor material of large-scale integrated circuit and high frequency device plays important role in information processing and transmission, and in this kind of technology, they make use of the electric charge attribute of electronics all greatly; And information storage (as tape, CD, hard disk etc.) in information technology has been come by magneticsubstance, they mainly make use of the spin attribute of electronics.But people are be separate development substantially for elementary charge and the investigation and application of spin attribute.And if can utilize simultaneously electronics electric charge and spin attribute, brand-new looks will be brought to information technology undoubtedly.
Summary of the invention
In view of this, the present invention proposes a kind of semi-conductor CaCu with high temperature ferrimagnetism
3fe
2os
2o
12and preparation method thereof.
First aspect, the present invention proposes a kind of semi-conductor with high temperature ferrimagnetism, and its chemical formula is CaCu
3fe
2os
2o
12, there is high Curie temperature (close to 600K), wide semiconductor energy gap (about 0.92eV).
Second aspect, the present invention proposes one and prepares described high temperature Ferrimagnetic semi-conductor CaCu
3fe
2os
2o
12method, comprising: by CaO, Fe
2o
3, CuO, Os, oxygen source Homogeneous phase mixing, obtain mixture; Grinding; Mixture is filled in gold or platinum capsule and seals; Gold or platinum capsule are placed in high-tension unit high temperature high pressure process; Annealing or quench treatment; First release after cooling; Reaction product is taken out from gold or platinum capsule, fully grinds; Cleaning.
Preferably, described cleaning is for using the cleaning of non-acid with strong oxidizing property.
Preferably, described non-acid with strong oxidizing property is dilute hydrochloric acid or dust technology.
Preferably, described oxygen source is for being selected from KClO
3, KClO
4, NaClO
3, NaClO
4, Na
2o
2, Ag
2o
2one in powder.
Preferably, described high-tension unit is that six-plane piercer or 6-8 type secondary advance press.
Preferably, the pressure of described high temperature high pressure process is 6-10GPa, and temperature is greater than 1000 DEG C.
The present invention proposes high temperature Ferrimagnetic semi-conductor CaCu
3fe
2os
2o
12, there is high Ferrimagnetic transition temperature and wide semiconductor energy gap, in the advanced electronics in future, have potential application.
Accompanying drawing explanation
By referring to the description of accompanying drawing to the embodiment of the present invention, above-mentioned and other objects, features and advantages of the present invention will be more clear, in the accompanying drawings:
Fig. 1 is CaCu prepared by embodiment 1
3fe
2os
2o
12xRD figure spectrum;
Fig. 2 is CaCu prepared by embodiment 1
3fe
2os
2o
12the susceptibility obtained by ZFC-FC measurement varies with temperature curve;
Fig. 3 is CaCu prepared by embodiment 1
3fe
2os
2o
12the specific magnetising moment with change of magnetic field strength curve;
Fig. 4 is CaCu prepared by embodiment 1
3fe
2os
2o
12photoelectric current survey sheet; And
Fig. 5 is CaCu
3fe
2os
2o
12energy band diagram.
Embodiment
Based on embodiment, present invention is described below, but the present invention is not restricted to these embodiments.In hereafter details of the present invention being described, detailedly describe some specific detail sections.Do not have the description of these detail sections can understand the present invention completely for a person skilled in the art yet.In order to avoid obscuring essence of the present invention, known method, process, flow process, element and circuit do not describe in detail.Unless the context clearly requires otherwise, similar words such as " comprising ", " comprising " otherwise in whole specification sheets and claims should be interpreted as the implication that comprises instead of exclusive or exhaustive implication; That is, be the implication of " including but not limited to ".
The present invention proposes a kind of high temperature Ferrimagnetic semi-conductor CaCu with high temperature ferrimagnetism
3fe
2os
2o
12.
As a preferred embodiment of the present invention, the high temperature Ferrimagnetic semi-conductor CaCu that the present invention proposes
3fe
2os
2o
12can be prepared by the step of embodiment 1, but the present invention is not restricted to these embodiments.
Embodiment 1:
Purity is greater than CaO, Fe of 99.9%
2o
3, CuO, Os, KClO
4be mixed to get mixture according to the ratio uniform of mol ratio 1:1:3:2:k, wherein k is greater than 1.Abundant grinding mixture in the glove box being full of nitrogen.Be filled in by mixture in gold or platinum capsule and seal, wherein the wall thickness of gold or platinum capsule is 1-2mm.Gold or platinum capsule are placed in six-plane piercer, are 6-10GPa at pressure, and temperature makes the raw material in gold or platinum capsule fully be obtained by reacting reaction product under being greater than the condition of 1000 DEG C.Annealing or quench treatment.First release after cooling.Reaction product is taken out from gold or platinum capsule, again grinds.Use non-acid with strong oxidizing property to clean and obtain CaCu
3fe
2os
2o
12.In the reaction, KClO
4as oxygen source, for providing O atom.Non-acid with strong oxidizing property cleaning is for removing the KCl be mingled with in reaction product, and non-acid with strong oxidizing property refers to that the hydrogen ion that the ionization in acid goes out plays oxygenizement, and reduzate is hydrogen, and in a preferred embodiment, non-acid with strong oxidizing property is dilute hydrochloric acid or dust technology.
Fig. 1 is CaCu prepared by embodiment 1
3fe
2os
2o
12xRD figure spectrum, by position and the intensity of each diffraction peak, CaCu prepared by embodiment 1 can be drawn
3fe
2os
2o
12for the perovskite structure of Emission in Cubic, belong to Pn-3 spacer, lattice parameter is about
Fig. 2 is CaCu prepared by embodiment 1
3fe
2os
2o
12obtain susceptibility by ZFC-FC measurement and vary with temperature curve, wherein, in the measuring process of ZFC (Zero Field Colling), first the situation borehole cooling in magnetic field is not added, the susceptibility of the measure sample that then heats up under externally-applied magnetic field H, in the measuring process of FC (Field Colling), first at externally-applied magnetic field H borehole cooling, the susceptibility of the measure sample that then heats up under externally-applied magnetic field H.As shown in Figure 2, CaCu
3fe
2os
2o
12there is very strong Ferrimagnetic character and higher Curie temperature (close to 600K).
Fig. 3 is CaCu prepared by embodiment 1
3fe
2os
2o
12the specific magnetising moment with change of magnetic field strength curve, specific magnetising moment test is when to be presented at temperature be 2K, and the saturation magnetization of sample is about 5 μ
b/ f.u., illustrates CaCu
3fe
2os
2o
12there is higher saturation magnetization.
Fig. 4 is CaCu prepared by embodiment 1
3fe
2os
2o
12photoelectric measuring spirogram, the display of photoelectric measurement result is after the photon energy of incident light is greater than 0.92eV, and photo-signal increases rapidly, and CaCu is described
3fe
2os
2o
12be semi-conductor, there is the semiconductor energy gap being about 0.92ev.
Fig. 5 is the CaCu obtained by Theoretical Calculation
3fe
2os
2o
12energy band diagram.As shown in Figure 5, CaCu
3fe
2os
2o
12have the energy band structure of semi-conductor, the semiconductor energy gap certainly spinning up electronics is about 1.8eV, and the energy gap of the downward electronics that spins is 1.0eV, shows CaCu
3fe
2os
2o
12it is a kind of Ferrimagnetic semiconductor material of broad-band gap.It is worthy of note in addition, this compound is dominated (with the serious hydridization of 2p electronics of oxygen) by the 5d electronics of Os near the electronic state of Fermi surface, illustrate that thus having can based on CaCu by the energy gap of regulation and control to the Os position adjustable semi-conductor such as (such as chemical doping), carrier concentration and type etc.
3fe
2os
2o
12manufacture the magnetic p-n junction with practical value.
The present invention proposes high temperature Ferrimagnetic semi-conductor CaCu
3fe
2os
2o
12, there is high Ferrimagnetic transition temperature and wide semiconductor energy gap, electric charge at room temperature and the spin attribute of its electronics can be utilized simultaneously in the advanced electronics in future, there is excellent application prospect.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, to those skilled in the art, the present invention can have various change and change.All do within spirit of the present invention and principle any amendment, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. a high temperature Ferrimagnetic semi-conductor, its chemical formula is CaCu
3fe
2os
2o
12.
2. prepare a Ferrimagnetic method for semiconductor according to claim 1, comprising:
By CaO, Fe
2o
3, CuO, Os, oxygen source Homogeneous phase mixing, obtain mixture;
Grinding;
Mixture is filled in gold or platinum capsule and seals;
Gold or platinum capsule are placed in high-tension unit high temperature high pressure process;
Annealing or quench treatment;
First release after cooling;
Reaction product is taken out from gold or platinum capsule, fully grinds;
Cleaning.
3. the preparation method of high temperature Ferrimagnetic semi-conductor according to claim 2, wherein, described cleaning is for using the cleaning of non-acid with strong oxidizing property.
4. the preparation method of high temperature Ferrimagnetic semi-conductor according to claim 3, wherein, described non-acid with strong oxidizing property is dilute hydrochloric acid or dust technology.
5. the preparation method of high temperature Ferrimagnetic semi-conductor according to claim 2, wherein, described oxygen source is for being selected from KClO
3, KClO
4, NaClO
3, NaClO
4, Na
2o
2, Ag
2o
2one in powder.
6. the preparation method of high temperature Ferrimagnetic semi-conductor according to claim 2, wherein, described high-tension unit is that six-plane piercer or 6-8 type secondary advance press.
7. the preparation method of high temperature Ferrimagnetic semi-conductor according to claim 2, wherein, the pressure of described high temperature high pressure process is 6-10GPa, and temperature is greater than 1000 DEG C.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107162068A (en) * | 2017-04-18 | 2017-09-15 | 中国科学院物理研究所 | Ferrimagnetism semimetal NaCu3Fe2Os2O12And preparation method thereof |
CN109166686A (en) * | 2018-11-05 | 2019-01-08 | 中国科学院物理研究所 | A kind of ferrimagnetism semiconductor LaCu3Fe2Os2O12And preparation method thereof |
CN114162856A (en) * | 2021-12-07 | 2022-03-11 | 贵州民族大学 | Method for synthesizing iron-doped titanium oxide at high temperature and high pressure |
CN115074747A (en) * | 2021-03-12 | 2022-09-20 | 中国科学院物理研究所 | Quadruple perovskite oxide, preparation method and application thereof, and method for electrolyzing water |
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CN104108924A (en) * | 2014-05-19 | 2014-10-22 | 华北水利水电大学 | Material having ferrimagnetism and preparation method thereof |
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CN104108924A (en) * | 2014-05-19 | 2014-10-22 | 华北水利水电大学 | Material having ferrimagnetism and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
IKUYA YAMADA ET AL.: ""A Perovskite Containing Quadrivalent Iron as a Charge-Disproportionated Ferrimagnet"", 《ANGEW. CHEM. INT. ED.》 * |
MICHAEL W. LUFASO: "《PEROVSKITE SYNTHESIS AND ANALYSIS USING STRUCTURE PREDICTION DIAGNOSTIC SOFTWARE》", 31 December 2002, THE OHIO STATE UNIVERSITY DISSERTATION * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107162068A (en) * | 2017-04-18 | 2017-09-15 | 中国科学院物理研究所 | Ferrimagnetism semimetal NaCu3Fe2Os2O12And preparation method thereof |
CN107162068B (en) * | 2017-04-18 | 2019-07-30 | 中国科学院物理研究所 | Ferrimagnetism semimetal NaCu3Fe2Os2O12And preparation method thereof |
CN109166686A (en) * | 2018-11-05 | 2019-01-08 | 中国科学院物理研究所 | A kind of ferrimagnetism semiconductor LaCu3Fe2Os2O12And preparation method thereof |
CN115074747A (en) * | 2021-03-12 | 2022-09-20 | 中国科学院物理研究所 | Quadruple perovskite oxide, preparation method and application thereof, and method for electrolyzing water |
CN115074747B (en) * | 2021-03-12 | 2023-08-08 | 中国科学院物理研究所 | Quadruple perovskite oxide, preparation method and application thereof, and method for electrolyzing water |
CN114162856A (en) * | 2021-12-07 | 2022-03-11 | 贵州民族大学 | Method for synthesizing iron-doped titanium oxide at high temperature and high pressure |
CN114162856B (en) * | 2021-12-07 | 2023-12-05 | 贵州民族大学 | Method for doping titanium oxide by using Cheng Tie under high temperature and high pressure |
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