CN110459377A - A kind of ferromagnetic material and preparation method thereof with huge Negative magnetoresistance effect - Google Patents
A kind of ferromagnetic material and preparation method thereof with huge Negative magnetoresistance effect Download PDFInfo
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Abstract
The present invention provides a kind of ferromagnetic material and preparation method thereof with huge Negative magnetoresistance effect, belongs to ferromagnetic material technical field.Its chemical general formula is Liy(Cd1‑xMnx) P, wherein 0.6 < y < 1.4,0 < x < 0.4, x, y indicate atom percentage content.It belongs to the cubic system that space group is F-43m, and lattice parameter variation range isA kind of ferromagnetic material with huge Negative magnetoresistance effect provided by the invention has wider carrier adjustable range, and with the giant magnetoresistance effect that can be adjusted, solves the problems, such as that carrier concentration in the prior art is adjusted and is difficult to coexist with huge Negative magnetoresistance effect.
Description
Technical field
The present invention relates to ferromagnetic material technical fields, more particularly to a kind of ferromagnetic material with huge Negative magnetoresistance effect
And preparation method thereof.
Background technique
Magnetoelectric effect refers to that material is changed by the magnetic property that external electric field induces or the electrical property of external magnetic field induction changes.Magnetic
Inhibition effect refers to the variation of resistivity of material under external magnetic field, can also range magnetoelectric effect.Giant magnetoresistance effect usually may be used
To observe in the alternate composite construction of magnetic material and non-magnetic material, for example people have found in siderochrome multilayer film for the first time
50% giant magnetoresistance, the giant magnetoresistance effect in monophase materials are actually rare.Report that more monophase materials there are bialternative series
(La, Ca) MnO3, semimetal TaAs2Deng.Have also discovered the biggish material of some magnetoresistances in magnetic semiconductor, such as through
(Ga, the Mn) As of allusion quotation has 30% or so negative magnetoresistance.Ferromagnetic semiconductor Li (Zn, the Mn) As reported recently is considered arranged side by side
With traditional III-V, the new class ferromagnetic semiconductor material of II-VI.But ferromagnetic semiconductor Li (Zn, Mn) As contains toxic member
Plain As, is unfavorable for large-scale application.Then it is successfully developed, but ferromagnetic is partly led without containing Li (Zn, the Mn) P of toxic element
The energy gap of body Li (Zn, Mn) P is wide, its carrier concentration is made to be difficult to adjust.
Summary of the invention
It is an object of the present invention to provide a kind of ferromagnetic material with huge Negative magnetoresistance effect, above-mentioned technology is overcome
Defect solves the problems, such as that carrier concentration in the prior art is adjusted and huge Negative magnetoresistance effect is difficult to coexist.
Particularly, the present invention provides a kind of ferromagnetic material with huge Negative magnetoresistance effect, chemical general formula Liy
(Cd1-xMnx) P, wherein 0.6 < y < 1.4,0 < x < 0.4, x, y indicate atom percentage content.
Optionally, belong to the cubic system that space group is F-43m, lattice parameter variation range is
Optionally, ferromagnetic material is ferrimagnetic state, highest Curie temperature 30K at low temperature；It is infused respectively by charge and spin
Enter to realize the regulation to the magnetic resistance of the ferromagnetic material.
Optionally, for the ferromagnetic material under conditions of outfield 7T and 5K, maximum negative magnetoresistance is greater than 80%.
The present invention also provides a kind of atmospheric preparation method of ferromagnetic material with huge Negative magnetoresistance effect, including it is following
Step:
S1 prepares precursor samples, and presoma is the mixture of tetra- kinds of substances of Li, Cd, Mn, P；
Element is matched and uniformly mixes and suppress in glove box for the presoma of Li:Cd:Mn:P=y:1-x:x:1 by S2
Forming, obtains S2 sample；
S2 sample is encapsulated in closed container by S3, requires to be filled with after being evacuated in the closed container a certain amount of
Inert gas；
The closed container is placed in high temperature furnace by S4, within the temperature range of 600 DEG C under atmospheric pressure~900 DEG C into
At least one time heat treatment of row, heat treatment time range are greater than 4 hours.
Optionally, in S1, the presoma is the mixture of Li source material, Cd source material, Mn source material, P source material；
The Li source material, Cd source material, Mn source material, P source material can be simple substance or compound respectively；Optionally, before described
Drive body is Li3P, the mixture of Zn, Mn, P.
Optionally, in S3, the closed container is closed, alkali corrosion resistance and pipe resistant to high temperature；The pipe is quartz
Pipe, aluminium oxide ceramics test tube, BN pipe or niobium pipe；
Optionally, in S4, the heat treatment number is that twice, the temperature of the heat treatment is 800 DEG C, the heat treatment
Time be 10 hours.
The present invention also provides a kind of high pressure method for preparing of ferromagnetic material with huge Negative magnetoresistance effect, including it is following
Step:
S11 prepares precursor samples, and presoma is the mixing of tetra- kinds of substances of Li, Cd, Mn, P；
Element is matched and uniformly mixes and suppress in glove box for the presoma of Li:Cd:Mn:P=y:1-x:x:1 by S12
Forming, obtains S12 sample；
S12 sample is wrapped up with goldleaf, and is encapsulated in BN pipe, the graphite furnace being subsequently placed in high pressure assembly by S13
In, place into progress high voltage driving IC synthesis in high-pressure installation.
Optionally, in S11, the presoma is the mixing of Li source material, Cd source material, Mn source material, P source material
Object；The Li source material, Cd source material, Mn source material, P source material can be simple substance or compound respectively；Optionally, described
Presoma is Li3P, the mixture of Zn, Mn, P.
Optionally, in S13, the pressure of the high voltage driving IC synthesis is 1-20GPa, and temperature is 550 DEG C -950 DEG C,
Soaking time is greater than 30min；
Optionally, the number of the high voltage driving IC synthesis is 2 times；
Optionally, the pressure of the high voltage driving IC synthesis is 5GPa, and temperature is 800 DEG C, and soaking time is 1 hour.
A kind of ferromagnetic material with huge Negative magnetoresistance effect provided by the invention, chemical general formula Liy(Cd1-xMnx)
P, wherein 0.6 < y < 1.4,0 < x < 0.4, x, y indicate atom percentage content.Crystal structure is cubic system, space group F-
The variation range of 43m, crystal parameters is Enter ferrimagnetic state (highest Curie temperature under low temperature
30K).It is injected separately into the regulation realized to this material magnetic resistance by charge and spin, under conditions of the outfield 7T and 5K, most
Big negative magnetoresistance has reached 80% or more.
A kind of ferromagnetic material Li with huge Negative magnetoresistance effect provided by the inventiony(Cd1-xMnx) P, there is wider load
Sub- adjustable range is flowed, and with the giant magnetoresistance effect that can be adjusted.
A kind of preparation method of ferromagnetic material with huge Negative magnetoresistance effect provided by the invention, can be easier to prepare
High-purity, the ferromagnetic material Li with giant magnetoresistance property outy(Cd1-xMnx)P。
According to the following detailed description of specific embodiments of the present invention in conjunction with the accompanying drawings, those skilled in the art will be brighter
The above and other objects, advantages and features of the present invention.
Detailed description of the invention
Some specific embodiments of the present invention is described in detail by way of example and not limitation with reference to the accompanying drawings hereinafter.
Identical appended drawing reference denotes same or similar part or part in attached drawing.It should be appreciated by those skilled in the art that these
What attached drawing was not necessarily drawn to scale.In attached drawing:
Fig. 1 is a kind of crystal structure schematic diagram of ferromagnetic material with huge Negative magnetoresistance effect provided by the invention；
Fig. 2 is Li in embodiment 10.6Cd0.9Mn0.1The X ray diffracting spectrum of P；
Fig. 3 is Li in embodiment 10.6Cd0.9Mn0.1The curve graph that the DC magnetic susceptibility of P varies with temperature；
Fig. 4 is Li in embodiment 10.6Cd0.9Mn0.1The negative magnetoresistance of P at different temperatures；
Fig. 5 is Li in embodiment 21.4Cd0.6Mn0.4The X ray diffracting spectrum of P；
Fig. 6 is Li in embodiment 21.4Cd0.6Mn0.4The curve graph that the DC magnetic susceptibility of P varies with temperature；
Fig. 7 is Li in embodiment 21.4Cd0.6Mn0.4The negative magnetoresistance of P at different temperatures；
Fig. 8 is Li in embodiment 31.1Cd0.9Mn0.1The X ray diffracting spectrum of P；
Fig. 9 is Li in embodiment 31.1Cd0.9Mn0.1The curve graph that the DC magnetic susceptibility of P varies with temperature；
Figure 10 is Li in embodiment 31.1Cd0.9Mn0.1The negative magnetoresistance of P at different temperatures；
Figure 11 is Li in embodiment 40.7Cd0.8Mn0.2The X ray diffracting spectrum of P；
Figure 12 is Li in embodiment 40.7Cd0.8Mn0.2The curve graph that the DC magnetic susceptibility of P varies with temperature；
Figure 13 is Li in embodiment 40.7Cd0.8Mn0.2The negative magnetoresistance of P at different temperatures；
Figure 14 is Li in embodiment 51.3Cd0.6Mn0.4The X ray diffracting spectrum of P；
Figure 15 is Li in embodiment 51.3Cd0.6Mn0.4The curve graph that the DC magnetic susceptibility of P varies with temperature；
Figure 16 is Li in embodiment 51.3Cd0.6Mn0.4The negative magnetoresistance of P at different temperatures；
Figure 17 is Li in embodiment 61.05Cd0.7Mn0.3The X ray diffracting spectrum of P；
Figure 18 is Li in embodiment 61.05Cd0.7Mn0.3The curve graph that the DC magnetic susceptibility of P varies with temperature；
Figure 19 is Li in embodiment 61.05Cd0.7Mn0.3The negative magnetoresistance of P at different temperatures；
Figure 20 is a kind of stream of the atmospheric preparation method of ferromagnetic material with huge Negative magnetoresistance effect provided by the invention
Journey schematic diagram；
Figure 21 is a kind of stream of the high pressure method for preparing of ferromagnetic material with huge Negative magnetoresistance effect provided by the invention
Journey schematic diagram.
Specific embodiment
The present inventor is had found: ferromagnetic half by furtheing investigate to ferromagnetic semiconductor material in the prior art
Conductor Li (Zn, Mn) As contains toxic element As, is unfavorable for large-scale application；The carrier of ferromagnetic semiconductor Li (Zn, Mn) P is dense
It is to cause the energy gap of Li (Zn, Mn) P wide since the electronegativity of P element is higher compared with As element that degree, which is difficult to the reason of adjusting,.And also
Have found influence of the carrier concentration to Negative magnetoresistance effect, i.e., too low or too high carrier is all unfavorable for the production of negative magnetoresistance
It is raw.Therefore, it is based on this discovery, inventor substitutes Zn with Cd, the energy gap of material effectively reduced, to obtain broader carrier
Adjustable range, the carrier by adulterating Li (Cd, Mn) P can achieve 1019cm-3, the highest carrier than Li (Zn, Mn) P is dense
2 orders of magnitude are spent big.Moreover, also with considerable Negative magnetoresistance effect (highest is greater than 80%), Li (Zn, Mn) P of ratio
With all big 2 times or more of Li (Zn, Mn) As (both rear is respectively 30% and 16%).
Fig. 1 is a kind of crystal structure schematic diagram of ferromagnetic material with huge Negative magnetoresistance effect provided by the invention.Such as
Shown in Fig. 1, a kind of ferromagnetic material with huge Negative magnetoresistance effect provided by the invention, chemical general formula Liy(Cd1-xMnx)
P, wherein 0.6 < y < 1.4,0 < x < 0.4, x, y indicate atom percentage content.It belongs to the cubic system that space group is F-43m,
Lattice parameter variation range isFerromagnetic material Liy(Cd1-xMnx) P is ferrimagnetic state at low temperature, most it is in
In temperature be 30K；The regulation to realize the magnetic resistance to the ferromagnetic material is injected separately by charge and spin.Ferromagnetic material
Liy(Cd1-xMnx) for P under conditions of the outfield 7T and 5K, maximum negative magnetoresistance is greater than 80%.
A kind of ferromagnetic material Li with huge Negative magnetoresistance effect provided by the inventiony(Cd1-xMnx) P, compared with (La, Ca)
MnO3, TaAs2Equal giant magnetic resistances, a big advantage of ferromagnetic material Li of the invention (Cd, Mn) P are there is lattice therewith
The semiconductor material LiCdP matched, by building (while there is ferromagnetism and giant magnetoresistance effect) Li (Cd, Mn) P with partly lead
The hetero-junctions of body LiCdP can be developed spinning LED (spin-LED), magnetic tunnel-junction, a variety of function such as exchange biased device
It can device.
A kind of ferromagnetic material Li with huge Negative magnetoresistance effect provided by the inventiony(Cd1-xMnx) P, there is wider load
Sub- adjustable range is flowed, and with the giant magnetoresistance effect that can be adjusted.
Figure 20 is a kind of stream of the atmospheric preparation method of ferromagnetic material with huge Negative magnetoresistance effect provided by the invention
Journey schematic diagram.As shown in figure 20, the present invention also provides a kind of preparations of the normal pressure of ferromagnetic material with huge Negative magnetoresistance effect
Method generally may comprise steps of:
S1 prepares precursor samples, and presoma is the mixture of tetra- kinds of substances of Li, Cd, Mn, P；
Element is matched and uniformly mixes and suppress in glove box for the presoma of Li:Cd:Mn:P=y:1-x:x:1 by S2
Forming, obtains S2 sample；
S2 sample is encapsulated in closed container by S3, requires to be filled with after being evacuated in the closed container a certain amount of
Inert gas；
The closed container is placed in high temperature furnace by S4, within the temperature range of 600 DEG C under atmospheric pressure~900 DEG C into
At least one time heat treatment of row, heat treatment time range are greater than 4 hours.
Specifically, in S1, presoma is the mixture of Li source material, Cd source material, Mn source material, P source material.The source Li
Material, Cd source material, Mn source material, P source material can be simple substance respectively, be also possible to compound.Compound such as Li3P、CdP、
MnP.In a specific embodiment, presoma Li3P, the mixture of Zn, Mn, P.
In S3, closed container is closed, alkali corrosion resistance and pipe resistant to high temperature；Closed container can be quartz ampoule, oxygen
Change any one in aluminium ceramics test tube, BN pipe or niobium pipe.Since precursor is needed during the sintering process in the ring being isolated with oxygen
It is sintered under border, therefore it needs closed, alkali corrosion resistance and container resistant to high temperature.Wherein, the Sheng of presoma during the sintering process
Dress mode is not limited to above-mentioned provided mode, it is only necessary to meet presoma and need to be isolated with oxygen during the sintering process.
In S4, heat treatment number can be it is secondary, be also possible to repeatedly.In a specific embodiment, at heat
Managing number is that twice, the temperature of heat treatment is 800 DEG C, and the time of heat treatment is 10 hours.
Figure 21 is a kind of stream of the high pressure method for preparing of ferromagnetic material with huge Negative magnetoresistance effect provided by the invention
Journey schematic diagram.As shown in figure 21, the present invention also provides a kind of preparations of the high pressure of ferromagnetic material with huge Negative magnetoresistance effect
Method generally may comprise steps of:
S11 prepares precursor samples, and presoma is the mixing of tetra- kinds of substances of Li, Cd, Mn, P；
Element is matched and uniformly mixes and suppress in glove box for the presoma of Li:Cd:Mn:P=y:1-x:x:1 by S12
Forming, obtains S12 sample；
S12 sample is wrapped up with goldleaf, and is encapsulated in BN pipe, the graphite furnace being subsequently placed in high pressure assembly by S13
In, place into progress high voltage driving IC synthesis in high-pressure installation.
Specifically, in S11, presoma is the mixture of Li source material, Cd source material, Mn source material, P source material.Li
Source material, Cd source material, Mn source material, P source material can be simple substance respectively, be also possible to compound.Compound such as Li3P、
CdP,MnP.In a specific embodiment, presoma Li3P, the mixture of Zn, Mn, P.
In S13, the pressure of high voltage driving IC synthesis is 1-20GPa, and temperature is 550 DEG C -950 DEG C, and soaking time is big
In 30min.
Heat treatment number can be it is secondary, be also possible to repeatedly.In a specific embodiment, high voltage driving IC closes
At number be 2 times.
In a specific embodiment, the pressure of high voltage driving IC synthesis is 5GPa, and temperature is 800 DEG C, when heat preservation
Between be 1 hour.
A kind of preparation method of ferromagnetic material with huge Negative magnetoresistance effect provided by the invention, can be easier to prepare
High-purity, the ferromagnetic material Li with giant magnetoresistance property outy(Cd1-xMnx)P.And compare atmospheric preparation method, high pressure method for preparing
The advantages of preparation, is that short preparation period, sample good compactness, crystal boundary are few.
It is described in detail below with reference to more specific some embodiments.
Embodiment 1
1) in inert gas filled glove box by high-purity Li block, Cd powder, Mn powder, P powder according to predetermined ratio
(Li0.6Cd0.9Mn0.1P, quality are respectively 0.21 gram of Li block, 5.06 grams of Cd powder, 0.27 gram of Mn powder, 1.55 grams of P powder) uniformly mixing,
And it fills this blend into aluminium oxide ceramics test tube；
2) by the ceramic test tube Vacuum Package equipped with sample in quartz ampoule；
3) quartz ampoule is placed in high temperature furnace at a temperature of 600 DEG C and is sintered 20 hours, obtained after the completion of sintering
Li0.6Cd0.9Mn0.1P。
The X ray diffracting spectrum for the sample that the method for the present embodiment obtains is as shown in Fig. 2, all diffraction maximums can look for
To the corresponding indices of diffraction, it is good to illustrate that method provided in this embodiment has prepared high-purity, crystallinity
Li0.6Cd0.9Mn0.1P.The DC magnetic susceptibility of sample and relation curve such as Fig. 3 of temperature, ferromagnetic transformation temperature are the temperature of 20K and 5K
Under degree, the resistance of sample and the relation curve such as Fig. 4 in magnetic field, maximum negative magnetoresistance are 61%.
Embodiment 2
1) in inert gas filled glove box by high-purity Li block, Cd powder, Mn powder, P powder according to predetermined ratio
(Li1.4Cd0.6Mn0.4P, quality are respectively 0.49 gram of Li block, 3.37 grams of Cd powder, 1.10 grams of Mn powder, 1.55 grams of P powder) uniformly mixing,
And it fills this blend into aluminium oxide ceramics test tube；
2) by the ceramic test tube Vacuum Package equipped with sample in quartz ampoule, and a certain amount of inertia is filled with into quartz ampoule
Gas；
3) quartz ampoule is placed in high temperature furnace at a temperature of 900 DEG C and is sintered 5 hours, obtained after the completion of sintering
Li1.4Cd0.6Mn0.4P。
The X ray diffracting spectrum for the sample that the method for the present embodiment obtains is as shown in figure 5, all diffraction maximums can look for
To the corresponding indices of diffraction, illustrate the Li of method preparation provided in this embodiment1.4Cd0.6Mn0.4P purity is high, crystallinity are good.
The DC magnetic susceptibility of sample and the relation curve of temperature as shown in fig. 6, ferromagnetic transformation temperature be 25K and 5K at a temperature of, sample
Resistance and magnetic field relation curve such as Fig. 7, maximum negative magnetoresistance be 65%.
Embodiment 3
1) in inert gas filled glove box by high-purity Li3P, P, Cd, Mn, CdP, MnP according to predetermined ratio
(Li1.1Cd0.9Mn0.1P, quality are respectively 1.14 grams of Li3P, and 0.25 gram of P, 3.03 grams of Cd, 0.16 gram of Mn, 3.87 grams of CdP,
0.26 gram of MnP) uniformly mixing, niobium pipe is filled this blend into, and by the niobium seal of tube under the protection of inert gas；
2) by niobium pipe Vacuum Package in quartz ampoule；
3) quartz ampoule is placed in high temperature furnace at a temperature of 800 DEG C and is sintered 20 hours；
4) sample will be obtained after the completion of being sintered and grinds mixing and tabletting under the protection of inert gas, fills this blend into niobium
Guan Zhong, and by the niobium seal of tube under the protection of inert gas；
5) by niobium pipe Vacuum Package in quartz ampoule；
6) quartz ampoule is placed in high temperature furnace at a temperature of 800 DEG C and is sintered 20 hours, obtain Li1.1Cd0.9Mn0.1P。
The X ray diffracting spectrum of sample provided in this embodiment is as shown in figure 8, all diffraction maximums can find correspondence
The indices of diffraction, illustrate the Li of method provided in this embodiment preparation1.1Cd0.9Mn0.1P purity is high, crystallinity are good.Sample
DC magnetic susceptibility and the relation curve of temperature as shown in figure 9, ferromagnetic transformation temperature be 30K and 5K at a temperature of, the resistance of sample
With the relation curve such as Figure 10 in magnetic field, maximum negative magnetoresistance is 84%.
Embodiment 4
1) in inert gas filled glove box by high-purity Li block, Cd powder, Mn powder, P powder according to predetermined ratio
(Li0.7Cd0.8Mn0.2P, quality are respectively 0.029 gram of Li block, 0.540 gram of Cd powder, 0.066 gram of Mn powder, 0.186 gram of P powder) uniformly
Mixing is packed into high pressure assembly；
2) high pressure assembly is put into interior carry out high-pressure sinter in high-pressure installation.Sintering procedure is slowly to boost at room temperature
1GPa restarts heating schedule and is heated to 550 DEG C, is down to room temperature after keeping the temperature 2 hours under high-temperature and high-pressure conditions, then release,
Obtain Li0.7Cd0.8Mn0.2P。
The X ray diffracting spectrum for the sample that the method for the present embodiment obtains is as shown in figure 11, and all diffraction maximums are ok
The corresponding indices of diffraction are found, illustrate the Li of method preparation provided in this embodiment0.7Cd0.8Mn0.2P purity is high, crystallinity are good
It is good.The DC magnetic susceptibility of sample and the relation curve of temperature are as shown in figure 12, at a temperature of ferromagnetic transformation temperature is 13K and 5K,
The resistance of sample and the relation curve such as Figure 13 in magnetic field, maximum negative magnetoresistance are 72%.
Embodiment 5
1) in inert gas filled glove box by high-purity Li3P, P, Cd, Mn, CdP, MnP according to predetermined ratio
(Li1.3Cd0.6Mn0.4P, quality are respectively 0.145 gram of Li3P, and 0.025 gram of P, 0.202 gram of Cd, 0.099 gram of Mn, CdP
0.258 gram, 0.052 gram of MnP) uniformly mixing, it is packed into high pressure assembly；
2) high pressure assembly is put into interior carry out high-pressure synthesis in high-pressure installation.Sintering procedure is slowly to boost at room temperature
15GPa restarts heating schedule and is heated to 950 DEG C, is down to room temperature after keeping the temperature 0.1 hour under high-temperature and high-pressure conditions, then unloads
Pressure, obtains Li1.3Cd0.6Mn0.4P。
The X ray diffracting spectrum for the sample that the method for the present embodiment obtains is as shown in figure 14, and all diffraction maximums are ok
The corresponding indices of diffraction are found, illustrate the Li of method preparation provided in this embodiment1.3Cd0.6Mn0.4P purity is high, crystallinity are good
It is good.The DC magnetic susceptibility of sample and the relation curve of temperature are as shown in figure 15, at a temperature of ferromagnetic transformation temperature is 8K and 5K, sample
The resistance of product and the relation curve such as Figure 16 in magnetic field, maximum negative magnetoresistance are 47%.
Embodiment 6
1) in inert gas filled glove box by high-purity Li3P, P, Cd, Mn, CdP, MnP according to predetermined ratio
(Li1.05Cd0.7Mn0.3P, quality are respectively 0.109 gram of Li3P, and 0.028 gram of P, 0.236 gram of Cd, 0.049 gram of Mn, CdP
0.301 gram, 0.077 gram of MnP) uniformly mixing, it is packed into high pressure assembly；
2) high pressure assembly is put into interior carry out high-pressure synthesis in high-pressure installation.Sintering procedure is slowly boosting at room temperature
To 5GPa, restart heating schedule and be heated to 800 DEG C, is down to room temperature after keeping the temperature 1 hour under high-temperature and high-pressure conditions, then unloads
Pressure；
3) sample will be obtained and grind mixing under the protection of inert gas, be again loaded into high pressure assembly；
4) high pressure assembly is put into interior carry out high-pressure synthesis in high-pressure installation.Sintering procedure is slowly boosting at room temperature
To 5GPa, restart heating schedule and be heated to 800 DEG C, is down to room temperature after keeping the temperature 1 hour under high-temperature and high-pressure conditions, then unloads
Pressure, obtains Li1.05Cd0.7Mn0.3P。
The X ray diffracting spectrum for the sample that the method for the present embodiment obtains is as shown in figure 17, and all diffraction maximums are ok
The corresponding indices of diffraction are found, illustrate the Li of method preparation provided in this embodiment1.05Cd0.7Mn0.3P purity is high, crystallinity are good
It is good.The DC magnetic susceptibility of sample and the relation curve of temperature are as shown in figure 18, and ferromagnetic transformation temperature is the temperature of 12.5K and 5K
Under, the resistance of sample and the relation curve such as Figure 19 in magnetic field, maximum negative magnetoresistance are 50%.
Above-mentioned each embodiment utilizes the solid phase reaction under normal pressure (atmospheric pressure) or high pressure (being higher than an atmospheric pressure)
Method has successfully synthesized ferromagnetic material Li according to the present inventiony(Cd1-xMnx) P, 0.6 < y < 1.4,0 < x < 0.4.Wherein above-mentioned each reality
The ratio for applying the various substances in precursor employed in the method for example offer is exemplary only, it is not intended that limits this Shen
Protection scope please, those skilled in the art can be easily according to the Li of required synthesisy(Cd1-xMnx) specific x and y value in P
And determine the ratio of the weight of various substances in precursor.
So far, although those skilled in the art will appreciate that present invention has been shown and described in detail herein multiple shows
Example property embodiment still without departing from the spirit and scope of the present invention, still can according to the present disclosure directly
Determine or deduce out many other variations or modifications consistent with the principles of the invention.Therefore, the scope of the present invention is understood that and recognizes
It is set to and covers all such other variations or modifications.
Claims (10)
1. a kind of ferromagnetic material with huge Negative magnetoresistance effect, which is characterized in that its chemical general formula is Liy(Cd1-xMnx) P,
In, 0.6 < y < 1.4,0 < x < 0.4, x, y indicate atom percentage content.
2. ferromagnetic material according to claim 1, which is characterized in that it belongs to the cubic system that space group is F-43m, brilliant
Lattice parameter variation range is
3. ferromagnetic material according to claim 1, which is characterized in that ferromagnetic material is ferrimagnetic state at low temperature, is most in
In temperature 30K；The regulation to realize the magnetic resistance to the ferromagnetic material is injected separately by charge and spin.
4. ferromagnetic material according to claim 3, which is characterized in that the ferromagnetic material is in the outfield 7T and the condition of 5K
Under, maximum negative magnetoresistance is greater than 80%.
5. a kind of atmospheric preparation method of the ferromagnetic material with huge Negative magnetoresistance effect, which comprises the following steps:
S1 prepares precursor samples, and presoma is the mixture of tetra- kinds of substances of Li, Cd, Mn, P；
Element is matched presoma uniformly mixing and compression moulding in glove box for Li:Cd:Mn:P=y:1-x:x:1 by S2,
Obtain S2 sample；
S2 sample is encapsulated in closed container by S3, requires to be filled with a certain amount of inertia after being evacuated in the closed container
Gas；
The closed container is placed in high temperature furnace by S4, carried out within the temperature range of 600 DEG C under atmospheric pressure~900 DEG C to
Few heat treatment, heat treatment time range are greater than 4 hours.
6. atmospheric preparation method according to claim 5, which is characterized in that in S1, the presoma be Li source material,
Cd source material, Mn source material, P source material mixture；The Li source material, Cd source material, Mn source material, P source material can be with
It is simple substance or compound respectively；Optionally, the presoma is Li3P, the mixture of Zn, Mn, P.
7. atmospheric preparation method according to claim 5, which is characterized in that in S3, the closed container be it is closed,
Alkali corrosion resistance and pipe resistant to high temperature；The pipe is quartz ampoule, aluminium oxide ceramics test tube, BN pipe or niobium pipe；
Optionally, in S4, the heat treatment number is that twice, the temperature of the heat treatment is 800 DEG C, the heat treatment when
Between be 10 hours.
8. a kind of high pressure method for preparing of the ferromagnetic material with huge Negative magnetoresistance effect, which comprises the following steps:
S11 prepares precursor samples, and presoma is the mixing of tetra- kinds of substances of Li, Cd, Mn, P；
Element is matched and uniformly mixes and be pressed into glove box for the presoma of Li:Cd:Mn:P=y:1-x:x:1 by S12
Shape obtains S12 sample；
S12 sample is wrapped up with goldleaf, and is encapsulated in BN pipe by S13, is subsequently placed in the graphite furnace in high pressure assembly, then
It is put into progress high voltage driving IC synthesis in high-pressure installation.
9. high pressure method for preparing according to claim 8, which is characterized in that in S11, the presoma is the source Li material
The mixture of material, Cd source material, Mn source material, P source material；The Li source material, Cd source material, Mn source material, P source material can
To be simple substance or compound respectively；Optionally, the presoma is Li3P, the mixture of Zn, Mn, P.
10. high pressure method for preparing according to claim 8, which is characterized in that in S13, the high voltage driving IC synthesis
Pressure be 1-20GPa, temperature be 550 DEG C -950 DEG C, soaking time be greater than 30min；
Optionally, the number of the high voltage driving IC synthesis is 2 times；
Optionally, the pressure of the high voltage driving IC synthesis is 5GPa, and temperature is 800 DEG C, and soaking time is 1 hour.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113481420A (en) * | 2021-07-12 | 2021-10-08 | 河南工业大学 | Ferromagnetic metal material and preparation method and application thereof |
| CN114446625A (en) * | 2020-11-02 | 2022-05-06 | 浙江东阳东磁稀土有限公司 | Sintering preparation method for improving intrinsic coercivity of neodymium iron boron magnet |
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| 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 |
| CN105084330A (en) * | 2014-05-14 | 2015-11-25 | 中国科学院物理研究所 | Ferromagnetic semiconductor material Li (Cd, Mn) P and preparation method thereof |
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| GB1035594A (en) * | 1964-05-15 | 1966-07-13 | Centre Nat Rech Scient | Ferromagnetic materials and their process of manufacture |
| 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 |
| CN105084330A (en) * | 2014-05-14 | 2015-11-25 | 中国科学院物理研究所 | Ferromagnetic semiconductor material Li (Cd, Mn) P and preparation method thereof |
Cited By (3)
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| CN114446625A (en) * | 2020-11-02 | 2022-05-06 | 浙江东阳东磁稀土有限公司 | Sintering preparation method for improving intrinsic coercivity of neodymium iron boron magnet |
| CN113481420A (en) * | 2021-07-12 | 2021-10-08 | 河南工业大学 | Ferromagnetic metal material and preparation method and application thereof |
| CN113481420B (en) * | 2021-07-12 | 2022-03-08 | 河南工业大学 | Ferromagnetic metal material and preparation method and application thereof |
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Application publication date: 20191115 |