CN102956814B - Lanthanum strontium copper manganese sulfur oxygen diluted magnetic semiconductor material and preparation method thereof - Google Patents
Lanthanum strontium copper manganese sulfur oxygen diluted magnetic semiconductor material and preparation method thereof Download PDFInfo
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- CN102956814B CN102956814B CN201210475152.8A CN201210475152A CN102956814B CN 102956814 B CN102956814 B CN 102956814B CN 201210475152 A CN201210475152 A CN 201210475152A CN 102956814 B CN102956814 B CN 102956814B
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- magnetic semiconductor
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- lanthanum strontium
- copper manganese
- strontium copper
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Abstract
The invention discloses a lanthanum strontium copper manganese sulfur oxygen diluted magnetic semiconductor material of which the chemical formula is La1-xSrxCu1-yMnySO. The invention also discloses a preparation method of the lanthanum strontium copper manganese sulfur oxygen diluted magnetic semiconductor material. The preparation method comprises the following steps of: mixing raw materials; sufficiently grinding under the argon shield; subsequently stamping under certain pressure intensity; sealing an obtained tablet into a vacuum container; putting the container in a tubular furnace to be heated up; and further calcining in constant temperature so as to obtain the lanthanum strontium copper manganese sulfur oxygen diluted magnetic semiconductor material. According to the preparation method, a magnetic moment is introduced by using a method that Cu+ is replaced by Mn2+, subsequently the La is partially replaced by Sr so as to introduce a cavity type carrier, and through such doping, the electrical conductivity and the magnetism of the semiconductor can be controlled well, a diluted magnetic semiconductor in a ZrCuSiAs type structure with higher Curie temperature is obtained, the diluted magnetic semiconductor has very high ferromagnetic transformation temperature, the Curie temperature TC is increased to 199K, and the diluted magnetic semiconductor is free of toxic elements such as As.
Description
Technical field
The present invention relates to dilute magnetic semiconductor material and preparation field thereof, relate in particular to a kind of lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor material with higher ferromagnetic transformation temperature and preparation method thereof.
Background technology
Dilute magnetic semiconductor (Diluted Magnetic Semiconductors, DMS) refer to artificially a small amount of magnetic atom is mixed in non magnetic semi-conducting material, thereby the magnetic semiconductor material obtaining, can prepare based on this and integrate magnetic, optical, electrical novel semi-conductor electronic device.Due to the application potential in spintronics field, dilute magnetic semiconductor has obtained the concern [T.Dietl of a lot of researchers, A ten-year perspective on dilute magnetic semiconductors and oxides.Nature Materials9,965-974 (2010) .].(Ga, Mn) As, (In, Mn) As, (Ga, Mn) N is typical III-V family dilute magnetic semiconductor, with the alternative Ga of Mn or In, only can obtain metastable compound, can only utilize molecular beam epitaxy technique to grow the film with certain Mn doping content.
Recently, a phosphorus family dilute magnetic semiconductor block materials Li (Zn, Mn) As is found [Z.Deng etal., Nature Communications.2:422 (2011)], and its ferromagnetic transformation temperature (is also Curie temperature, is expressed as T
c) be only 50K, arsenic element possibility contaminated environment wherein, is also unfavorable for large-scale application.Acquisition has higher ferromagnetic transformation temperature and eco-friendly dilute magnetic semiconductor material, is to make demands before exploitation one of its application.
Non-magnetic semiconductor LaCuSO is by oxidation LaCuS at first
2mode obtain, and provided its lattice structure [M.Palazzi, Acad.Sci., Paris, C.R.1981,292,789].Utilizing the LaCuOS that solid reaction process obtains is p-type semiconductor [Y.Takano.; K.Yahagi.; K.Sekizawa.Physica A.1995,206 & 207,764].LaCuOS is the semiconductor of wide energy gap, and its energy gap reaches 3.1eV[Shin-ichiro Inoue, Kazushige Ueda, Hideo Hosono and NoriakiHamada, Phys.Rev.B64,245211 (2001)].It has identical ZrCuSiAs structure with iron-based superconductor parent LaFeAsO.As transparent p-shaped material, LaCuSO is very important for the transparent p-n junction on basis to realizing semi-conducting material, in field of optoelectronic devices, is a very attractive candidate materials.If introduce ferromagnetic order by the doping of the magnetic ions such as Mn in the p-of wide energy gap type oxide semiconductor LaCuSO, will be a huge promotion to its practical application.
Summary of the invention
In prior art, the ferromagnetic transformation temperature of dilute magnetic semiconductor (Curie temperature) is lower, and may cause the problem of environmental pollution, the invention provides a kind of have more high-curie temperature and eco-friendly dilute magnetic semiconductor material.
A lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor material, chemical formula general formula is:
La
1-xsr
xcu
1-ymn
ysO, x=0～0.1 wherein, y=0.05～0.1.
When adulterating magnetic atom a small amount of in non magnetic semi-conducting material, the magnetic that made originally non-magnetic material production.The present invention introduces magnetic ion Mn in non magnetic semi-conducting material LaCuSO
2+substitute a part of Cu
+thereby, introduced magnetic moment, make non magnetic semi-conducting material be transformed into dilute magnetic semiconductor material, optionally introduced Sr simultaneously
2+part La in replacement lattice
3+position, so just introduced cavity type charge carrier, the Sr atom of doping is more, the concentration in hole is just higher, electric conductivity is just stronger.The hole that Sr doping is introduced has also strengthened Mn
2+rKKY between ion magnetic moment interacts, and is conducive to improve ferromagnetic transformation temperature.Make so non magnetic semi-conducting material originally be converted into dilute magnetic semiconductor material, electric conductivity also increases simultaneously.
Due to Mn
2+concentration higher, the magnetic moment in material is more, Sr content is larger, the electric conductivity of material is better.Within the scope of certain Sr doping content, Sr content is larger, and the interaction between magnetic moment is also stronger, and Curie temperature is just higher.But in this material, the solid solubility of Sr has certain limitation.Therefore, as preferably, described chemical formula consists of: La
1-xsr
xcu
1-ymn
ysO, x=0.05～0.1 wherein, y=0.05～0.1.
The present invention also provides the preparation method of described lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor material, first raw material is mixed in proportion to condition of high voltage lower sheeting after abundant reaction, then by compressing tablet calcining after vacuum high-temperature is processed, finally obtain described lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor material.
A preparation method for lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor material, comprises the steps:
(1) by raw material La
2o
3, SrS, La, Cu, S and Mn fully mix in proportion, under argon shield, grinds, then under the pressure of 450～550MPa, carry out punching press and obtain compressing tablet;
(2) described compressing tablet is sealed in vacuum tank, vacuum tank is placed in tube furnace and is heated up, then calcining at constant temperature, obtains described lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor material.
As preferably, described milling time is 20～40min; Make reactant particle thin as far as possible, mix, accelerated the carrying out of solid phase reaction.
As preferably, described vacuum tank is vitreosil pipe; Vacuum degree in described vitreosil pipe is better than 0.1Pa.Under vacuum condition, between reactant, be not subject to the impact of the gas such as oxygen in air, reduced to a certain extent the generation of the impurity such as oxide.
Described Elevated Temperature Conditions is: through 1800～2200min, be warmed up to 1223 ± 50K.
Described calcining at constant temperature condition is: under 1223 ± 50K, calcine 1800～2200min.Through calcination process, can make crystal formation change, finally obtain the single-phase polycrystalline block with block form stable existence, i.e. described lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor material.
The present invention adopts Mn
2+substitute Cu
+method introduce magnetic moment, then with Sr, partly substitute La and introduce cavity type charge carrier, by above doping, can well control this semi-conductive conductivity and magnetic, obtained the dilute magnetic semiconductor of the ZrCuSiAs type structure that ferromagnetic transformation temperature (Curie temperature) is higher, this dilute magnetic semiconductor material has very high ferromagnetic transformation temperature, Curie temperature T
cbring up to 199K, and do not contain the hypertoxic elements such as As.The lanthanum strontium copper manganese sulphur oxygen that the present invention obtains, as a kind of new dilute magnetic semiconductor material, has broad application prospects in fields such as spintronics, quantum calculation, transparent semiconductor, luminescent materials.
Accompanying drawing explanation
Fig. 1 is lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor material La of the present invention
1-xsr
xcu
1-ymn
ythe lattice structure schematic diagram of SO;
Fig. 2 is La of the present invention
1-xsr
xcu
1-ymn
ysO (x=0.05,0.075,0.1, room temperature x-ray diffractogram of powder spectrum y=0.075); Its illustration has been shown lattice constant a, the c variation with Sr doping x;
Fig. 3 is La of the present invention
1-xsr
xcu
1-ymn
ysO (x=0.05,0.075,0.1, the temperature variant curve of resistivity y=0.075);
Fig. 4 is La of the present invention
1-xsr
xcu
1-ymn
ythe temperature variant curve of magnetic susceptibility of SO (x=0.05, y=0.075); When its illustration is T=2K, magnetization M is with the variation of magnetic field H;
Fig. 5 is La of the present invention
1-xsr
xcu
1-ymn
ythe temperature variant curve of magnetic susceptibility of SO (x=0.05, y=0.1), its illustration be this sample when T=2K magnetization M with the variation of magnetic field intensity H.
Embodiment
Embodiment 1
1) by La
2o
3, the raw material such as SrS, La, Cu, S and Mn powder is according to element mol ratios such as La, Sr, Cu, Mn, S, O 0.95: 0.05: 0.925: fully mix at 0.075: 1: 1, in Ar gas protective atmosphere, grind, then under the pressure of about 500MPa, carry out punching press and obtain compressing tablet;
2) above-mentioned compressing tablet is sealed in evacuated quartz ampoule, then puts into tube furnace and through 2000 minutes, be warmed up to 1223K, then, 1223K calcining 2000 minutes, then cool to room temperature, obtains polycrystalline bulk, and its lattice structure as shown in Figure 1.
From Fig. 2, can learn, utilizing the sample principal phase that above process obtains is the La with tetragonal (ZrCuSiAs type)
0.95sr
0.05cu
0.925mnn
0.075sO compound (principal phase>=99%).Except a small amount of *,
srS, (La, Sr) MnO that # indicates
3, MnS dephasign outer (dephasign content is less than 1%), all X-ray diffraction peaks can both carry out indexing, the cell parameter of sample is:
As can be seen from Figure 3, the magnitude that its resistivity is tens of ohmcms at normal temperatures, along with temperature reduces, resistivity declines rapidly, reaches at low temperatures hundreds of ohmcm, is typical semiconductor behavior.Along with the increase of Sr doping, resistivity reduces gradually.
From Fig. 4, can learn, synthetic lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor material has good ferromagnetic property: its ferromagnetic transformation temperature T
creached 180K, the highest ferromagnetic transformation temperature that has surpassed the dilute magnetic semiconductor block materials of openly having reported at present, and can find out from its illustration, when H=5kOe, saturation magnetic moment has reached 0.79 μ B/Mn, illustrates that lanthanum strontium copper manganese sulphur oxygen has huge application advantage as a kind of novel dilute magnetic semiconductor material.
Embodiment 2
1) by La
2o
3, the raw material such as SrS, La, Cu, S and Mn powder is according to element mol ratios such as La, Sr, Cu, Mn, S, O 0.95: 0.05: 0.9: fully mix at 0.1: 1: 1, in Ar gas protective atmosphere, grind, then under the pressure of about 500MPa, carry out punching press and obtain compressing tablet;
2) above-mentioned compressing tablet is sealed in evacuated quartz ampoule, then puts into tube furnace and through 2000 minutes, be warmed up to 1273K, then, 1273K calcining 2000 minutes, then cool to room temperature, obtains polycrystalline bulk, and its lattice structure as shown in Figure 1.
The sample principal phase obtaining by above process is the lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor La with tetragonal
0.95sr
0.05cu
0.9mn
0.1sO.From Fig. 5, can learn the La of synthesized
0.95sr
0.05cu
0.9mn
0.1sO dilute magnetic semiconductor material has good ferromagnetic property: its ferromagnetic transformation temperature T
creached 157K, and can find out from its illustration, when H=5kOe, saturation magnetic moment has reached 1.06 μ
b/ Mn, illustrates that lanthanum strontium copper manganese sulphur oxygen, as a kind of novel dilute magnetic semiconductor material, has advantage in practical application.
Embodiment 3-7
Table 1 is La
1-xsr
xcu
1-ymn
yraw material proportioning, calcining heat, ferromagnetic transformation temperature and the cell parameter of SO (x=0～0.1, y=0.05～0.1) sample.
Table 1
Wherein, the sample La that embodiment 6 obtains
0.9sr
0.1cu
0.925mn
0.075in SO, contain a small amount of other ferromagnetic dephasign, thus the ferromagnetic transformation temperature of its principal phase be difficult to accurately determine, be about 210K.
Claims (6)
1. a lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor material, is characterized in that, chemical formula consists of: La
1-xsr
xcu
1-ymn
ysO, x=0～0.1 wherein, y=0.05～0.1.
2. lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor material according to claim 1, is characterized in that, chemical formula consists of: La
1-xsr
xcu
1-ymn
ysO, x=0.05～0.1 wherein, y=0.05～0.1.
3. the preparation method of lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor material according to claim 1 and 2, is characterized in that, comprises the steps:
(1) by raw material La
2o
3, SrS, La, Cu, S and Mn fully mix in proportion, under argon shield, grinds, then under the pressure of 450～550MPa, carry out punching press and obtain compressing tablet;
(2) described compressing tablet is sealed in vacuum tank, vacuum tank is placed in tube furnace and is heated up, then calcining at constant temperature, obtains described lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor material;
Described Elevated Temperature Conditions is: through 1800～2200min, be warmed up to 1173～1273K;
Described calcining at constant temperature condition is: under 1173～1273K, calcine 1800～2200min.
4. the preparation method of lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor material according to claim 3, is characterized in that, described milling time is 20～40min.
5. the preparation method of lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor material according to claim 3, is characterized in that, described vacuum tank is vitreosil pipe.
6. the preparation method of lanthanum strontium copper manganese sulphur oxygen dilute magnetic semiconductor material according to claim 3, is characterized in that, the vacuum degree in described vitreosil pipe is better than 0.1Pa.
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