CN102251279A - Ferromagnetic semiconductor crystal and preparation method thereof - Google Patents
Ferromagnetic semiconductor crystal and preparation method thereof Download PDFInfo
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- CN102251279A CN102251279A CN201110194363XA CN201110194363A CN102251279A CN 102251279 A CN102251279 A CN 102251279A CN 201110194363X A CN201110194363X A CN 201110194363XA CN 201110194363 A CN201110194363 A CN 201110194363A CN 102251279 A CN102251279 A CN 102251279A
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Abstract
The invention discloses a ferromagnetic semiconductor crystal and a preparation method thereof. The material of the semiconductor crystal is LiY(Zn1-xMnx)As, wherein y is more than 0.5 and less than 1.5, x is more than 0 and less than 0.5, and x and y represent the percentages of atoms. The invention further provides a high-pressure synthesizing method of the LiY(Zn1-xMnx)As crystal, which is a method for preparing LiY(Zn1-xMnx)As in the pressure scope of 0-20 GPa at a temperature of 600-1000 DEG C. The LiY(Zn1-xMnx)As semiconductor crystal prepared by the method disclosed by the invention has a ferromagnetic transition temperature of below 50K in specific components, belongs to a cubic system, has a space group of F-43 m, and has an important physical significance to research on the magnetic mechanisms of the ferromagnetic semiconductors.
Description
Technical field
The present invention relates to a kind of ferromagnetic semiconductor crystal and preparation method thereof.
Background technology
Ferromagnetic semiconductor is realized by doped magnetic ion in semi-conductor.Because the application prospect of spin electric device aspect, as far back as the nineties in 20th century ferromagnetic semiconductor system just be widely studied (Zutic, I. et al., Rev. Mod. Phys. 76,323,2004).The ferromagnetic semiconductor that is expected most is the III-V semi-conductor so far, is the semi-conductor of parent phase, wherein (Ga with III family element V group element compound promptly, Mn) (Science 281 for Ohno, H. more than the ferromagnetic transformation temperature of As system can reach 110K, 951,956,1998).Yet (Ga, Mn) character of As is subjected to the influence of manufacture craft very big, and because current carrier and magnetic moment have been introduced in the doping of Mn element simultaneously, makes its physical mechanism be difficult to be studied.
Summary of the invention
Problem at prior art exists the object of the present invention is to provide a kind of ferromagnetic semiconductor crystal Li
y(Zn
1-xMn
x) As; And provide two kinds of Li
y(Zn
1-xMn
x) preparation method of As superconductor.
For achieving the above object, ferromagnetic semiconductor crystal of the present invention, its chemical formula are Li
y(Zn
1-xMn
x) As, 0.5＜y＜1.5,0＜x＜0.5 wherein, x, y represents atom percentage content.
Further, Li
y(Zn
1-xMn
x) As crystalline ferromagnetic transformation temperature is T
c＜50K, its crystalline structure have the space symmetry group of F-43m, belong to isometric system, and Li
y(Zn
1-xMn
x) As crystalline lattice constant range is: a=5.8-6.2.
Li under the normal pressure of the present invention
y(Zn
1-xMn
x) As crystalline preparation method comprises following steps:
(1) under normal pressure, the preparation precursor samples, wherein presoma can be the mixture of Li, Zn, Mn, four kinds of simple substance of As, also can be the mixture of Li, ZnAs, MnAs compound;
(2) with the element proportioning be Li:Zn:Mn:As=y:(1-x): forerunner's powder of x:1 uniform mixing and press forming in glove box;
(3) sample of step (2) is encapsulated in vitro airtight, charges into the protective atmosphere of 0bar～0.5bar after requiring in the pipe to be evacuated; Then whole test tube is positioned in the High Temperature Furnaces Heating Apparatus, carries out at least one time thermal treatment in 600 ℃～1000 ℃ the temperature range under condition of normal pressure, heat treatment time was greater than 5 hours.
Further, normal pressure thermal treatment temp and time are preferably 750 ℃～850 ℃ and 10 hours～30 hours respectively.
Li under the high pressure of the present invention
y(Zn
1-xMn
x) As crystalline preparation method comprises following steps:
(1) under normal pressure, the preparation precursor samples, wherein presoma can be the mixture of Li, Zn, Mn, four kinds of simple substance of As, also can be the mixture of Li, ZnAs, MnAs compound;
(2) with the element proportioning be Li:Zn:Mn:As=y:(1-x): forerunner's powder of x:1 uniform mixing and press forming in glove box;
(3) sample with step (2) wraps up with goldleaf, and is encapsulated in the BN pipe, places the graphite furnace in the high pressure assembly then, carry out height and be pressed into, its mesohigh synthetic pressure is 1-20GPa, and temperature is 600-1000 ℃, soaking time obtains Li more than 0.2 hour equally
y(Zn
1-xMn
x) the As crystal.
Further, hot high pressure treatment temp and time are preferably 750 ℃～850 ℃ and 0.5 hour～1 hour respectively; It is more than 2 times that hot high pressure is handled the optimization number of times; Before High-Voltage Experimentation, at first carry out the demarcation of temperature and pressure, and control Heating temperature with the method for control heating power.
Li of the present invention
y(Zn
1-xMn
x) As crystal by adopting high-temperature pressure or High Temperature High Pressure synthetic method, all can prepare this kind Li
y(Zn
1-xMn
x) the As crystal, this kind compound has the ferromagnetic transformation temperature below the 50K under specific element proportioning, and the magnetic mechanism of research ferromagnetic semiconductor is had significant physical meaning.Semi-conductor Li (Zn, Mn) As can utilize simple solid state reaction synthetic, and current carrier wherein and magnetic moment provide by Li ion and Mn ion respectively, and this provides convenience for the ferromagnetic semiconductor Study on Mechanism.As a kind of ferromagnetic semiconductor of brand-new type, (Zn, Mn) the successful preparation of As also provides thinking for people seek the ferromagnetic semiconductor with higher ferromagnetic transformation temperature to Li.
Description of drawings
Fig. 1 is ferromagnetic semiconductor crystal Li of the present invention
y(Zn
1-xMnx) X ray diffracting spectrum of As;
Fig. 2 is ferromagnetic semiconductor crystal Li of the present invention
y(Zn
1-xMn
x) the dc magnetization rate of As and the graph of relation of temperature;
Fig. 3 is ferromagnetic semiconductor crystal Li of the present invention
y(Zn
1-xMn
x) the crystalline structure synoptic diagram of As.
Embodiment
In being filled with the argon gas glove box with 99.9% or the Zn powder of above purity, Mn powder, As powder according to the mol ratio uniform mixing of 0.9:0.1:1, and be pressed into the mixture sequin.Then according to the molar ratio weighing Li piece of Li:Zn:Mn:As=1.1:0.9:0.1:1, and the mixture sequin packed in the alumina-ceramic test tube with the Li piece; The ceramic test tube that sample then will be housed is packaged in the silica tube, and to vacuumizing in the silica tube, charges into argon gas and the sealing of 0.2Bar then in silica tube.Next 900 ℃ sintering temperature 5 hours in High Temperature Furnaces Heating Apparatus.
Take out sample at last, respectively sample is carried out the experiments of measuring of X-ray diffraction and dc magnetization rate, its result respectively as depicted in figs. 1 and 2.Its ferromagnetic transformation temperature is 50K.
Embodiment 2
Adopt solid phase reaction method under the normal pressure, with 99.9% or the Zn powder of above purity, As powder with mixed in molar ratio, the compressing tablet of 1:1, and be encapsulated in the vitreosil pipe, sintering under 900 ℃ condition is incubated 48 hours, can prepare monophasic ZnAs compound.Also obtain monophasic MnAs compound by same way.
In being filled with the argon gas glove box then according to the molar ratio weighing Li piece of Li:ZnAs:MnAs=1.5:0.8:0.2, and in the alumina-ceramic test tube of packing into together; The ceramic test tube that sample then will be housed is put into silica tube and is evacuated, and charges into argon gas and the sealing of 0.5Bar then in silica tube.Next in the temperature sintering of inherent 1000 ℃ of High Temperature Furnaces Heating Apparatus 30 hours.
Obtain Li at last
y(Zn
1-xMn
x) the As crystal.Experiment is carried out structure refinement to the X-ray spectrogram of this sample, and obtains its crystalline structure as shown in Figure 3.
Embodiment 3
Step according to embodiment 2 prepares ZnAs, MnAs presoma.
In being filled with the argon gas glove box then according to the molar ratio weighing Li piece of Li:ZnAs:MnAs=0.5:0.7:0.3, and in the alumina-ceramic test tube of packing into together; The ceramic test tube that sample then will be housed is put into silica tube and is evacuated, and charges into argon gas and the sealing of 0.2Bar then in silica tube.Next in the temperature sintering of inherent 600 ℃ of High Temperature Furnaces Heating Apparatus 10 hours.Obtain Li at last equally
y(Zn
1-xMn
x) the As crystal.
Embodiment 4
Step according to embodiment 2 prepares ZnAs, MnAs presoma.
In being filled with the argon gas glove box, Li piece, ZnAs powder, MnAs powder are packed in the goldleaf, and be pressed into the cylinder of φ 6 in advance, be encapsulated into again in the BN pipe of Φ 8 * 15mm according to the mol ratio of Li:ZnAs:MnAs=1:0.5:0.5.The BN pipe is put into graphite furnace, carry out height in the high pressure assembly of packing into and be pressed into.Sample synthesizes on the big press of cubic apparatus and carries out, and at first carries out the demarcation of temperature and pressure before the High-Voltage Experimentation, with the method control Heating temperature of control heating power.Earlier at room temperature slowly boost to 1GPa, restart heating schedule and be heated to 600 ℃, insulation is 1 hour under high-temperature and high-pressure conditions, is quenched to room temperature, and release then obtains autoclaving sample for the first time.
In being filled with the argon gas glove box, peel the goldleaf of autoclaving sample outside for the first time off, remaining sample is pulverized evenly ground and mixed of back.And then pack into goldleaf and be pressed into the cylinder of φ 6 in advance after be encapsulated in the BN pipe of Φ 8 * 15mm, carry out hot high pressure processing second time.High-pressure is 1GPa, and synthesis temperature is 600 ℃, and generated time is 1 hour.Obtain Li at last equally
y(Zn
1-xMn
x) the As crystal.
Embodiment 5
Step according to embodiment 2 prepares ZnAs, MnAs presoma.
In being filled with the argon gas glove box, Li piece, ZnAs powder, MnAs powder are packed in the goldleaf according to the mol ratio of Li:ZnAs:MnAs=1.1:0.9:0.1, and be pressed into the cylinder of φ 3 in advance, pack in the high pressure assembly, advance the enterprising horizontal high voltage of press synthetic at six or eight type secondarys then.At first carry out the demarcation of pressure before the High-Voltage Experimentation, utilize original position thermopair control Heating temperature in the experimentation.Earlier at room temperature slowly boost to 20GPa, restart heating schedule and be heated to 1000 ℃, insulation is 0.2 hour under high-temperature and high-pressure conditions, is quenched to room temperature, and release then obtains autoclaving sample for the first time.
The sample of above-mentioned autoclaving is put into glove box, peel the goldleaf of autoclaving sample outside for the first time off, remaining sample is pulverized evenly ground and mixed of back.And then pack into goldleaf and be pressed into the cylinder of φ 3 in advance after be encapsulated in the high pressure assembly of packing into, carry out hot high pressure processing second time.High-pressure is 20GPa, and synthesis temperature is 1000 ℃, and generated time is 0.2 hour.Obtain Li at last equally
y(Zn
1-xMn
x) the As crystal.
Claims (10)
1. a ferromagnetic semiconductor crystal is characterized in that, its chemical formula is Li
y(Zn
1-xMn
x) As, 0.5＜y＜1.5,0＜x＜0.5 wherein, x, y represents atom percentage content.
2. ferromagnetic semiconductor crystal as claimed in claim 1 is characterized in that, described ferromagnetic semiconductor crystal has the following ferromagnetic transformation temperature of 50K.
3. ferromagnetic semiconductor crystal as claimed in claim 1 is characterized in that, described ferromagnetic semiconductor crystalline spacer is F-43m, belongs to isometric system, and its lattice parameter variation range is: a=5.8-6.2.
4. one kind as the arbitrary described ferromagnetic semiconductor crystalline preparation method of claim 1-3, may further comprise the steps:
1) under normal pressure, prepares the precursor samples that contains Li, Zn, Mn, four kinds of elements of As;
2) with the precursor samples for preparing in the step 1) in the ratio uniform mixing of setting, under the condition of 0～20GPa, carry out an at least thermal treatment.
5. ferromagnetic semiconductor crystalline preparation method as claimed in claim 4 is characterized in that, described presoma is the mixture of Li, Zn, Mn, four kinds of simple substance of As; Or presoma is the mixture of Li, ZnAs, MnAs.
6. ferromagnetic semiconductor crystalline preparation method as claimed in claim 4 is characterized in that, the element mol ratio Li:Zn:Mn:As of described presoma=y:(1-x): x:1, wherein 0.5＜y＜1.5,0＜x＜0.5.
7. ferromagnetic semiconductor crystalline preparation method as claimed in claim 6 is characterized in that, the scope of described Li elements atomic percentage content y is 0.9＜y＜1.1, and the scope of Mn elements atomic percentage content x is 0＜x＜0.2.
8. ferromagnetic semiconductor crystalline preparation method as claimed in claim 5, it is characterized in that, ZnAs or MnAs prepare the presoma concrete steps and adopt solid phase reaction method under the normal pressure, with 99.9% or the Zn powder of above purity or Mn powder and As powder with the mol ratio of 1:1 in being filled with the glove box of argon gas, mix, grinding, compressing tablet, be sealed in then in the vitreosil pipe, sintering under 900 ℃ condition is incubated 48 hours, obtains monophasic ZnAs or MnAs compound.
9. ferromagnetic semiconductor crystalline preparation method as claimed in claim 5, it is characterized in that, step 2) precursor samples is encapsulated in vitro airtight in, charge into the protective atmosphere of 0bar～0.5bar after being evacuated in the pipe, then whole test tube is positioned in the High Temperature Furnaces Heating Apparatus, carry out at least one time thermal treatment under condition of normal pressure in 600 ℃～1000 ℃ the temperature range, heat treatment time was greater than 5 hours; Thermal treatment temp is selectable to be set at 750 ℃～850 ℃, and heat treatment time is selectable to be set at 10 hours～and 30 hours.
10. ferromagnetic semiconductor crystalline preparation method as claimed in claim 5, it is characterized in that, sample in the step (2) wraps up with goldleaf, and be encapsulated in the BN pipe, place graphite furnace then, carry out height and be pressed into, its mesohigh synthetic pressure is 1-20GPa, temperature is 600-1000oC, and soaking time is more than 0.2 hour; The hot high pressure treatment time is selectable to be set at 0.5 hour～and 1 hour.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103911660A (en) * | 2012-12-31 | 2014-07-09 | 中国科学院物理研究所 | Diluted magnetic semiconductor material and preparation method thereof |
| CN104058376A (en) * | 2013-03-21 | 2014-09-24 | 中国科学院物理研究所 | Ferromagnetic semiconductor material Li(Zn, Mn)P and preparation method thereof |
| CN105097173A (en) * | 2014-05-14 | 2015-11-25 | 中国科学院物理研究所 | A ferromagnetic semiconductor material (Sr, na) (Zn, mn)2As2and its prepn |
| CN107887098A (en) * | 2017-11-02 | 2018-04-06 | 中国科学院物理研究所 | A kind of magnetic semiconductor material and preparation method thereof |
| CN109841369A (en) * | 2017-11-24 | 2019-06-04 | 中国科学院物理研究所 | Dilute magnetic semiconductor material and preparation method thereof with giant magnetoresistance effect |
| KR20200060677A (en) * | 2018-11-21 | 2020-06-01 | 성균관대학교산학협력단 | Layered compound, nanosheet and preparing method thereof |
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| CN101407340A (en) * | 2008-11-11 | 2009-04-15 | 中国科学院物理研究所 | Iron arsenic compound high temperature superconductor crystal and preparation thereof |
| CN101608340A (en) * | 2009-01-21 | 2009-12-23 | 中国科学院物理研究所 | A kind of iron-based high-temperature superconductive crystal and preparation method thereof |
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| CN101407340A (en) * | 2008-11-11 | 2009-04-15 | 中国科学院物理研究所 | Iron arsenic compound high temperature superconductor crystal and preparation thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103911660A (en) * | 2012-12-31 | 2014-07-09 | 中国科学院物理研究所 | Diluted magnetic semiconductor material and preparation method thereof |
| CN104058376A (en) * | 2013-03-21 | 2014-09-24 | 中国科学院物理研究所 | Ferromagnetic semiconductor material Li(Zn, Mn)P and preparation method thereof |
| CN105097173A (en) * | 2014-05-14 | 2015-11-25 | 中国科学院物理研究所 | A ferromagnetic semiconductor material (Sr, na) (Zn, mn)2As2and its prepn |
| CN105097173B (en) * | 2014-05-14 | 2018-03-02 | 中国科学院物理研究所 | A kind of ferromagnetic semiconductor material (Sr, Na) (Zn, Mn)2As2And preparation method thereof |
| CN107887098A (en) * | 2017-11-02 | 2018-04-06 | 中国科学院物理研究所 | A kind of magnetic semiconductor material and preparation method thereof |
| CN107887098B (en) * | 2017-11-02 | 2020-01-07 | 中国科学院物理研究所 | Magnetic semiconductor material and preparation method thereof |
| CN109841369A (en) * | 2017-11-24 | 2019-06-04 | 中国科学院物理研究所 | Dilute magnetic semiconductor material and preparation method thereof with giant magnetoresistance effect |
| KR20200060677A (en) * | 2018-11-21 | 2020-06-01 | 성균관대학교산학협력단 | Layered compound, nanosheet and preparing method thereof |
| KR102250674B1 (en) | 2018-11-21 | 2021-05-13 | 성균관대학교 산학협력단 | Layered compound, nanosheet and preparing method thereof |
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Application publication date: 20111123 |