CN109841369B - Diluted magnetic semiconductor material with giant magnetoresistance effect and preparation method thereof - Google Patents
Diluted magnetic semiconductor material with giant magnetoresistance effect and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a diluted magnetic semiconductor material with giant magnetoresistance effect and its preparation method, and application of said diluted magnetic semiconductor materialSemiconductor electronic devices made of magnetic semiconductor materials and electronic apparatuses including the semiconductor electronic devices. According to one embodiment, there is provided a diluted magnetic semiconductor material with giant magnetoresistance effect, which has a chemical formula of Na1+x(Zn1‑yMny) Sb, wherein x and y are atomic percent, x is more than or equal to 0 and less than or equal to 0.2, and y is more than or equal to 0.05 and less than or equal to 0.5.
Description
Technical Field
The present invention relates generally to the field of magnetics, and more particularly, to a diluted magnetic semiconductor material with giant magnetoresistance effect and a method for preparing the same.
Background
Diluted magnetic semiconductor materials have gained much attention due to their potential applications in the field of spintronic devices. Diluted magnetic semiconductors are generally obtained by introducing small amounts of magnetic ions into the semiconductor. Typically based on group III-V semiconductors, e.g. made of Mn2+Substituted for Ga3+(Ga, Mn) As and (Ga, Mn) N. Due to the non-equivalent substitution, very limited chemical solubility is caused, and the carriers and spins cannot be separately regulated (see document h. ohno, et al, Science 281,951-956(1998)), so that the curie temperature cannot be effectively increased at all times, and therefore cannot be put into practical use. Recently, BaZn based on II-II-V group semiconductor2As2Diluted magnetic semiconductor (Ba, K) (Zn, Mn)2As2Was successfully prepared (see document K.ZHao et al, Nature Communications 4:1442(2013) DOI:10.1038/ncomms 2447). In this system, the charge carriers can be controlled by doping with the element K and the spin can be controlled by Mn2+Substituted Zn2+The amount of the doped material is regulated, so that the doping mechanism separation of charges and spins is realized. The ferromagnetic transition temperature of 230K is higher than that of about 200K in (Ga, Mn) As. Thus (Ba, K) (Zn, Mn)2As2The magnetic committee of the world's well-known institute of electrical and electronics engineers (eels) is known as a milestone material for the development of diluted magnetic semiconductors (see the documents IEEE Transactions on Magnetics, Roadmap for experimental materials for sports devices Applications,51,1 (2016)).
The giant magnetoresistance effect has been developed since its discovery, and hard magnetic disks developed with the giant magnetoresistance effect have small and sensitive data read heads. This allows the size of the magnetic material required to store a single byte of data to be greatly reduced, thereby allowing the storage capacity of the disk to be greatly increased. However, the conventional giant magnetoresistance effect is obtained from a ferromagnetic material having a spontaneous magnetization, the magnetic moment of which may have an influence on surrounding circuit elements.
Disclosure of Invention
Therefore, one aspect of the present invention is to provide a diluted magnetic semiconductor material with giant magnetoresistance effect, which has a chemical formula of Na1+x(Zn1-yMny) Sb, wherein x and y represent atomic content percentage, x is more than or equal to 0 and less than or equal to 0.2, and y is more than or equal to 0.05 and less than or equal to 0.5. The crystal structure of the material is a tetragonal system, the space group is P4/nmm, and the variation range of the lattice parameter is
The material is also a diluted magnetic semiconductor with separated spin and charge doping mechanisms, the adjustment and control of the magnetic resistance of the diluted magnetic semiconductor material are realized through the respective injection of charges and spins, and the negative magnetic resistance of all samples reaches over 90% under the conditions of 2T external field and 2K. In addition, the material has the advantage that the material enters the spin glass state at a low temperature, and the spin glass material does not generate spontaneous polarization, so that the magnetic moment of the material does not influence surrounding electronic elements, and the material has better compatibility. Therefore, the Na (Zn, Mn) Sb material is a giant magnetoresistance effect diluted magnetic semiconductor material with great application potential.
In another aspect of the present invention, there is provided a method for preparing the diluted magnetic semiconductor material, including: preparing a precursor material, wherein the precursor material is a mixture comprising four elements of Na, Zn, Mn and Sb, and the atomic ratio of the four elements is Na, Zn, Mn, Sb (1+ x) to (1-y) y: 1; and carrying out heat treatment on the precursor material under an inert atmosphere. The precursor may include Na3A mixture of Sb, Zn, Mn and Sb. Before the heat treatment, the method may further include: grinding the precursor into powder to uniformly mix the various elements; and pressing the powder into a block. The heat treatment may be performed two or more times, and the grinding and pressing steps may be performed on the precursor material between adjacent heat treatments. The heat treatment is carried out under normal pressure or high pressure, the high pressure is in the range of 1-20GPa, the heating temperature of the normal pressure heat treatment is 400-1000 ℃, the heating time is 4-30 hours, the heating temperature of the high pressure heat treatment is 500-1200 ℃, and the heating time is 0.5-6 hours. After performing the heat treatment, the method may further include: cooling at a rate of 1-5 ℃/hr.
Still another aspect of the present invention also provides a semiconductor electronic device including a semiconductor layer made of the diluted magnetic semiconductor material described above.
Still another aspect of the present invention also provides an electronic apparatus including a semiconductor electronic device including a semiconductor layer made of the diluted magnetic semiconductor material described above.
The above and other advantages and features of the present invention will become apparent from the following description of exemplary embodiments, which is to be read in connection with the accompanying drawings.
Drawings
Some exemplary embodiments of the invention will be described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 11.1(Zn0.85Mn0.15) An X-ray diffraction pattern of Sb;
FIG. 2 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 11.1(Zn0.85Mn0.15) The resistivity of Sb is plotted against the magnetic field;
FIG. 3 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 11.1(Zn0.85Mn0.15) Sb is a relation curve of a real part and an imaginary part of alternating-current magnetic susceptibility and temperature under different frequencies;
FIG. 4 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 21.1(Zn0.75Mn0.25) An X-ray diffraction pattern of Sb;
FIG. 5 shows a schematic diagram of a system according to an embodiment2 the diluted magnetic semiconductor material Na prepared by the method1.1(Zn0.75Mn0.25) The resistivity of Sb is plotted against the magnetic field;
FIG. 6 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 21.1(Zn0.75Mn0.25) Sb is a relation curve of a real part and an imaginary part of alternating-current magnetic susceptibility and temperature under different frequencies;
FIG. 7 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 31.075(Zn0.85Mn0.15) An X-ray diffraction pattern of Sb;
FIG. 8 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 31.075(Zn0.85Mn0.15) The resistivity of Sb is plotted against the magnetic field;
FIG. 9 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 31.075(Zn0.85Mn0.15) Sb is a relation curve of a real part and an imaginary part of alternating-current magnetic susceptibility and temperature under different frequencies;
FIG. 10 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 41.15(Zn0.85Mn0.15) An X-ray diffraction pattern of Sb;
FIG. 11 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 41.15(Zn0.85Mn0.15) The resistivity of Sb is plotted against the magnetic field;
FIG. 12 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 41.15(Zn0.85Mn0.15) Sb is a relation curve of a real part and an imaginary part of alternating-current magnetic susceptibility and temperature under different frequencies;
FIG. 13 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 51.05(Zn0.65Mn0.35) An X-ray diffraction pattern of Sb;
FIG. 14 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 51.05(Zn0.65Mn0.35) The resistivity of Sb is plotted against the magnetic field;
FIG. 15 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 51.05(Zn0.65Mn0.35) Sb is a relation curve of a real part and an imaginary part of alternating-current magnetic susceptibility and temperature under different frequencies;
FIG. 16 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 61.2(Zn0.55Mn0.45) An X-ray diffraction pattern of Sb;
FIG. 17 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 61.2(Zn0.55Mn0.45) The resistivity of Sb is plotted against the magnetic field; and
FIG. 18 shows a diluted magnetic semiconductor material Na prepared according to the method provided in example 61.2(Zn0.55Mn0.45) Sb is a relation curve of a real part and an imaginary part of alternating-current magnetic susceptibility and temperature under different frequencies.
Detailed Description
The invention provides a diluted magnetic semiconductor material with giant magnetoresistance effect, and the chemical formula is Na1+x(Zn1-yMny) Sb, wherein x and y represent atomic content percentage, x is more than or equal to 0 and less than or equal to 0.2, and y is more than or equal to 0.05 and less than or equal to 0.5. The crystal structure of the material is a tetragonal system, the space group is P4/nmm, and the variation range of the lattice parameter is
The material is also a diluted magnetic semiconductor with separated spin and charge doping mechanisms, the adjustment and control of the magnetic resistance of the diluted magnetic semiconductor material are realized through the respective injection of charges and spins, and the negative magnetic resistance of all samples reaches over 90% under the conditions of 2T external field and 2K. Furthermore, one advantage of this material is that it enters the spin-glassy state at low temperatures, whereas the spin-glassy material does not produce spontaneous polarization, so that its magnetic moment does not affect the surrounding electronic components. Therefore, the Na (Zn, Mn) Sb material is a giant magnetoresistance effect diluted magnetic semiconductor material with great application potential.
The diluted magnetic semiconductor material with giant magnetoresistance effect can be prepared by a heat treatment method, and specifically comprises the following steps.
First, a precursor material is prepared, which may be a mixture including four elements of Na, Zn, Mn, Sb, and may include Na, for example3A mixture of Sb, Zn, Mn and Sb particles, wherein the ratio of the elements Na: Zn: Mn: Sb: 1+ x: 1-y: 1, and x and y satisfy the above-mentioned ranges.
Next, in order to uniformly mix the various elements, the precursor material particles may be ground into powder in a glove box so that the various elements are sufficiently uniformly mixed. Furthermore, the precursor material powder may also be compressed into a bulk material, for example in the form of a tablet. By the compacting process, the interaction between the various elements during the subsequent heat treatment can be facilitated.
The precursor material in bulk form can then be heat treated. The heat treatment may be carried out under normal pressure or under high pressure. Compared with normal pressure heat treatment, the high pressure heat treatment has the advantages of short treatment time, good sample compactness, less crystal boundary and higher quality.
The heat treatment under normal pressure is first described below. And packaging the precursor block obtained by pressing in a closed quartz tube, vacuumizing the tube, and introducing a certain amount of inert gas, such as argon. Preferably, the precursor block can be packaged in a closed container, such as a niobium tube, that is resistant to alkali corrosion and high temperatures.
Then, the closed quartz tube or the closed container is placed in a high-temperature furnace, and at least one heat treatment is carried out at the temperature of 400-1000 ℃ under normal pressure, wherein the heat treatment time range is 4-30 hours. Preferably, the heat treatment may be performed at a temperature ranging from 400 to 600 ℃ for 5 to 10 hours. Then, the temperature is reduced to 300 ℃ or lower at a rate of 1 to 5 ℃/hour, preferably to 200 ℃ or lower at a rate of 1 to 2 ℃/hour, and then the mixture is naturally cooled to normal temperature.
The precursor material may also be subjected to two or more of the aforementioned heat treatments. Between adjacent heat treatments, the precursor material may be subjected to the aforementioned grinding and pressing steps to promote uniform mixing and full reaction of the various elements, improving the quality of the material produced.
If the heat treatment is performed at high pressure, the precursor block can be wrapped with gold foil and enclosed within a BN (boron nitride) tube that can compress the gold foil wrapped precursor block from each face (typically 6 faces). Then, the BN tube is placed in a graphite furnace, the graphite furnace containing the BN tube is placed in a pyrophyllite material container, pressure is applied to the pyrophyllite container through a high-pressure device, the pressure is transmitted to the precursor block through the graphite material and the BN tube, and the pressure can be 1-20 GPa. Under the pressure, the precursor block can be heated by a graphite furnace, the heating temperature can be 500-1200 ℃, and the heating time is 0.5-6 hours, preferably 2-3 hours. Then, the temperature is reduced to 300 ℃ or lower at a rate of 1 to 5 ℃/hour, preferably to 200 ℃ or lower at a rate of 1 to 2 ℃/hour, and then the mixture is naturally cooled to normal temperature. Also, the high pressure heat treatment may be performed two or more times, and between the adjacent high pressure heat treatments, the aforementioned grinding and pressing steps may be performed to promote uniform mixing and sufficient reaction of various elements, improving the quality of the prepared material. Compared with normal pressure heat treatment, the high pressure heat treatment has the advantages of short treatment time, good sample compactness, less crystal boundary and higher quality.
Example 1
The sample preparation method comprises the following steps: 1) pressing Na in a glove box filled with argon1.1(Zn0.85Mn0.15) Sb ratio, 2.099 g Na3Uniformly mixing Sb powder, 1.668 g of Zn powder, 0.247 g of Mn powder and 2.314 g of Sb powder, grinding the mixture into powder in an agate pot, pressing the powder into blocks, and filling the blocks into an alumina ceramic test tube; 2) sealing the ceramic test tube filled with the sample in a quartz tube in inert gas atmosphere; 3) the quartz tube is placed in a muffle furnace to be sintered for 5 hours at the temperature of 500 ℃, and the diluted magnetic semiconductor material Na can be obtained after sintering1.1(Zn0.85Mn0.15) And (5) Sb. The XRD results for this sample are shown in FIG. 1, with all diffraction peaks belonging to the sample itself, indicating that sample Na was prepared according to this example1.1(Zn0.85Mn0.15) The Sb mass is high.
Giant magnetoresistance effect measurement: and placing the sintered long strip sample with the length of about 4mm, the width of 2mm and the thickness of about 1.5mm into a comprehensive physical property measurement system PPMS, and measuring the giant magnetoresistance by using a four-probe method. The fixed temperature is 2K, and the resistance value of the sample is measured along with the change of the magnetic field in the change range of the external field from 7T to minus 7T. Fig. 2 shows the measurement results of the magnetic resistance, and it can be seen that the resistance of the sample rapidly decreases with an increase in the magnetic field, and exhibits a giant magnetic resistance of about-88% under the condition of an external field 2T at a temperature of 2K, and a further increase in the magnetic resistance of about-95% under the condition of an external field 5T at a temperature of 2K.
Measurement of alternating-current magnetic susceptibility: and (3) placing the sample in PPMS (point-to-point magnetic field) with zero magnetic field, and measuring the change of the real part and the imaginary part of the magnetic susceptibility of the sample with the temperature under different frequencies of 633Hz, 3633Hz and 6633Hz, wherein the temperature range is 2K-40K. The measurement result is shown in fig. 3, under the condition of zero magnetic field and the same frequency, the peak of the imaginary part curve of the magnetic susceptibility is positioned at the left side of the peak of the real part curve; and as the frequency applied to the sample increases, the peak of the sample susceptibility curve moves toward the high temperature region, corresponding to the spin glass transition temperature of the sample increasing as the frequency applied increases. Tf of the sample at 633Hz was-12.1K, when the frequency increased to 3633Hz, Tf became 13K, and when the frequency was 6633Hz, Tf of the corresponding sample was-13.4K. From the test results of the alternating magnetic susceptibility, the sample has a distinct spin glass property, in this case a spin glassy state.
Example 2
The present embodiment provides a method for preparing a semiconductor material with giant magnetoresistance, including:
1) pressing Na in a glove box filled with argon1.1(Zn0.75Mn0.25) Sb ratio, 2.099 g Na3Uniformly mixing Sb powder, 1.570 g of Zn powder, 0.330 g of Mn powder and 2.314 g of Sb powder, grinding the mixture into powder, pressing the powder into blocks, and filling the blocks into an alumina ceramic test tube; 2) sealing the ceramic test tube filled with the sample in a quartz tube in inert gas atmosphere; 3) the quartz tube is placed in a muffle furnace to be sintered for 10 hours at the temperature of 700 ℃, and the diluted magnetic semiconductor material Na can be obtained after sintering1.1(Zn0.75Mn0.25)Sb。
The XRD results for this sample are shown in FIG. 4, with all diffraction peaks belonging to the sample itself, indicating that sample Na was prepared according to this example1.1(Zn0.75Mn0.25) The Sb mass is high.
Giant magnetoresistance effect measurement: and placing the sintered long strip sample with the length of about 3.9mm, the width of 1.8mm and the thickness of about 1.2mm into a comprehensive physical property measurement system PPMS, and measuring the giant magnetoresistance by using a four-probe method. The fixed temperature is 2K, and the resistance value of the sample is measured along with the change of the magnetic field in the change range of the external field from 7T to minus 7T. The magneto-resistance measurement of this sample at 2K is shown in fig. 5. It can be seen that the resistance of the sample rapidly decreases with the increase of the magnetic field, and the sample shows giant magnetoresistance property of about-95% under the conditions of 2T external field and 2K temperature; and about-99.83% at an external field of 5T, exhibiting giant magnetoresistance properties.
Measurement of alternating-current magnetic susceptibility: and (3) placing the sample in PPMS (point-to-point magnetic field) with zero magnetic field, and measuring the change of the real part and the imaginary part of the magnetic susceptibility of the sample with the temperature under different frequencies of 633Hz, 3633Hz and 6633Hz, wherein the temperature range is 2K-40K. The measurement result is shown in fig. 6, under the condition of zero magnetic field and the same frequency, the peak of the imaginary part curve of the magnetic susceptibility is positioned at the left side of the peak of the real part curve; and as the frequency applied to the sample increases, the peak of the sample susceptibility curve moves toward the high temperature region, corresponding to the spin glass transition temperature of the sample increasing as the frequency applied increases. Tf for the sample at 633Hz was 13.08K, and Tf for the corresponding sample when the frequency was increased to 6633Hz was 13.76K. From the test results of the alternating magnetic susceptibility, the sample has a distinct spin glass property, in this case a spin glassy state.
Example 3
The present embodiment provides a method for preparing a semiconductor material with giant magnetoresistance, including:
1) pressing Na in a glove box filled with argon1.075(Zn0.85Mn0.15) Sb ratio, 2.0508 g Na3Sb powder, 1.668 g of Zn powder, 0.2472 g of Mn powder and 2.3497 g of Sb powder are uniformly mixed, ground into powder, pressed into blocks and filled into alumina ceramic test tubes(ii) a 2) Sealing the ceramic test tube filled with the sample in a quartz tube in inert gas atmosphere; 3) the quartz tube is placed in a muffle furnace to be sintered for 15 hours at the temperature of 1000 ℃, and the diluted magnetic semiconductor material Na can be obtained after sintering1.075(Zn0.85Mn0.15)Sb。
The XRD results for this sample are shown in FIG. 7, with all diffraction peaks belonging to the sample itself, indicating that sample Na was prepared according to this example1.075(Zn0.85Mn0.15) The Sb mass is high.
Giant magnetoresistance effect measurement: the sintered long strip sample with the length of about 3.5mm, the width of 1.5mm and the thickness of about 1.2mm is put into a comprehensive physical property measurement system PPMS, and the giant magnetoresistance is measured by a four-probe method. The fixed temperature is 2K, and the resistance value of the sample is measured along with the change of the magnetic field in the change range of the external field from 7T to minus 7T. The measurement result of the magnetic resistance is shown in fig. 8, and it can be observed that the resistance of the sample rapidly decreases with the increase of the magnetic field, and the sample exhibits a giant magnetic resistance of about-80% under the conditions of an external field of 2T and a temperature of 2K; the giant magnetoresistance is about-90% under the conditions of 5T external field and 2K temperature.
Measurement of alternating-current magnetic susceptibility: and (3) placing the sample in PPMS (point-to-point magnetic field) with zero magnetic field, and measuring the change of the real part and the imaginary part of the magnetic susceptibility of the sample with the temperature under different frequencies of 633Hz, 3633Hz and 6633Hz, wherein the temperature range is 2K-40K. The measurement result is shown in fig. 9, under the condition of zero magnetic field and the same frequency, the peak of the imaginary part curve of the magnetic susceptibility is positioned at the left side of the peak of the real part curve; and as the frequency applied to the sample increases, the peak of the sample susceptibility curve moves toward the high temperature region, corresponding to the spin glass transition temperature of the sample increasing as the frequency applied increases. Tf of the sample at 633Hz was 13.01K, and Tf of the corresponding sample when the frequency was increased to 6633Hz was 13.1K. From the test results of the alternating magnetic susceptibility, the sample has a distinct spin glass property, in this case a spin glassy state.
Example 4
The present embodiment provides a method for preparing a semiconductor material with giant magnetoresistance, including:
1) in a glove box filled with argonAccording to Na1.15(Zn0.85Mn0.15) Sb ratio, 2.1939 g Na3Uniformly mixing Sb powder, 1.668 g of Zn powder, 0.2472 g of Mn powder and 2.2533 g of Sb powder, grinding the mixture into powder, pressing the powder into blocks, and filling the blocks into an alumina ceramic test tube; 2) sealing the ceramic test tube filled with the sample in a quartz tube in inert gas atmosphere; 3) the quartz tube is placed in a muffle furnace to be sintered for 20 hours at the temperature of 400 ℃, and the diluted magnetic semiconductor material Na can be obtained after sintering1.15(Zn0.85Mn0.15)Sb。
The X-ray diffraction pattern of the sample is shown in fig. 10, and it can be seen from fig. 10 that corresponding diffraction indexes can be found in all diffraction peaks of the sample, which illustrates that the method provided by this embodiment prepares the diluted magnetic semiconductor material Na with high purity1.15(Zn0.85Mn0.15)Sb。
Giant magnetoresistance effect measurement: and placing the sintered long strip sample with the length of about 4.5mm, the width of 1.7mm and the thickness of about 1.5mm into a comprehensive physical property measurement system PPMS, and measuring the giant magnetoresistance by using a four-probe method. The fixed temperature is 2K, and the resistance value of the sample is measured along with the change of the magnetic field in the change range of the external field from 7T to minus 7T. The measurement result of the magnetic resistance is shown in fig. 11, and it can be observed that the magnetic field has a great influence on the resistance of the sample, and the giant magnetic resistance is about-90% under the conditions of an external field of 2T and a temperature of 2K; under the conditions of 5T external field and 2K temperature, the giant magnetoresistance reaches about-95%.
Measurement of alternating-current magnetic susceptibility: and (3) placing the sample in PPMS (point-to-point magnetic field) with zero magnetic field, and measuring the change of the real part and the imaginary part of the magnetic susceptibility of the sample with the temperature under different frequencies of 633Hz, 3633Hz and 6633Hz, wherein the temperature range is 2K-40K. The measurement result is shown in fig. 12, under the same frequency and zero magnetic field, the peak of the imaginary part curve of the magnetic susceptibility is positioned at the left side of the peak of the real part curve; and as the frequency applied to the sample increases, the peak of the sample susceptibility curve moves toward the high temperature region, corresponding to the spin glass transition temperature of the sample increasing as the frequency applied increases. Tf for the sample at 633Hz was 12.7K, and Tf for the corresponding sample when the frequency was increased to 6633Hz was 13.9K. From the test results of the alternating magnetic susceptibility, the sample has a distinct spin glass property, in this case a spin glassy state.
Example 5
The embodiment provides a preparation method of a diluted magnetic semiconductor material, which comprises the following steps:
1) pressing Na in a glove box filled with argon1.05(Zn0.65Mn0.35) Sb ratio, 2.003 g Na3Uniformly mixing Sb powder, 1.2755 g of Zn powder, 0.5669 g of Mn powder and 2.3751 g of Sb powder, grinding into powder, pressing the powder into blocks, wrapping the blocks with gold foil, and filling the blocks into a high-pressure assembly part; 2) placing the high-pressure assembly part into a high-pressure device, performing high-pressure sintering in an argon environment, wherein the sintering procedure is to slowly increase the pressure to 1GPa at room temperature, then start a heating procedure to heat to 600 ℃, keep the temperature for 1 hour at the high-temperature high-pressure condition, then reduce the temperature to room temperature, and then release the pressure to obtain Na1.05(Zn0.65Mn0.35) And (5) Sb. By high-pressure sintering in an inert gas environment, a sample with high density and few crystal boundaries can be rapidly prepared.
The X-ray diffraction pattern of the sample is shown in fig. 13, and it can be seen from fig. 13 that corresponding diffraction indexes can be found for all diffraction peaks of the sample, which illustrates that the method provided by this embodiment prepares the diluted magnetic semiconductor material Na with high purity1.05(Zn0.65Mn0.35)Sb。
Giant magnetoresistance effect measurement: grinding the prepared sample into a strip with the length of about 2.2mm, the width of 1.1mm and the thickness of about 0.8mm, putting the strip into a comprehensive physical property measurement system PPMS, and measuring the giant magnetoresistance by using a four-probe method. The fixed temperature is 2K, and the resistance value of the sample is measured along with the change of the magnetic field in the change range of the external field from 7T to minus 7T. The measurement result of the magnetic resistance is shown in fig. 14, and it can be observed that the magnetic field has a great influence on the resistance of the sample, and the giant magnetic resistance is about-92% under the conditions of an external field 2T and a temperature 2K; the giant magnetoresistance reaches about-97% at an external field of 5T and a temperature of 2K.
Measurement of alternating-current magnetic susceptibility: and (3) placing the sample in PPMS (point-to-point magnetic field) with zero magnetic field, and measuring the change of the real part and the imaginary part of the magnetic susceptibility of the sample with the temperature under different frequencies of 633Hz, 3633Hz and 6633Hz, wherein the temperature range is 2K-40K. The measurement result is shown in fig. 15, under the same frequency and zero magnetic field, the peak of the imaginary part curve of the magnetic susceptibility is positioned at the left side of the peak of the real part curve; and as the frequency applied to the sample increases, the peak of the sample susceptibility curve moves toward the high temperature region, corresponding to the spin glass transition temperature of the sample increasing as the frequency applied increases. The Tf for the sample at 633Hz was 13.0K, and the Tf for the corresponding sample increased to about 13.6K when the frequency increased to 6633 Hz. From the test results of the alternating magnetic susceptibility, the sample has a distinct spin glass property, in this case a spin glassy state.
Example 6
The embodiment provides a preparation method of a diluted magnetic semiconductor material, which comprises the following steps:
1) pressing Na in a glove box filled with argon1.2(Zn0.55Mn0.45) Sb ratio, 2.0985 g Na3Sb powder, 1.0793 g Zn powder, 0.7417 g Mn powder, and 2.3142 g Sb powder were mixed uniformly and the mixture was charged into a high pressure assembly; 2) placing the high-pressure assembly part into a high-pressure device, performing high-pressure sintering in an argon environment, wherein the sintering procedure is to slowly increase the pressure to 15GPa at room temperature, then start a heating procedure to heat to 1100 ℃, keep the temperature for 0.5 hour at the high-temperature high-pressure condition, then reduce the temperature to room temperature, and then release the pressure to obtain Na1.1(Zn0.65Mn0.35) And (5) Sb. By high-pressure sintering in an inert gas environment, a sample with high density and few crystal boundaries can be rapidly prepared.
The X-ray diffraction pattern of the sample is shown in fig. 17, and it can be seen from fig. 17 that corresponding diffraction indexes can be found in all diffraction peaks of the sample, which illustrates that the method provided by this embodiment prepares the diluted magnetic semiconductor material Na with high purity1.2(Zn0.55Mn0.45)Sb。
Giant magnetoresistance effect measurement: the prepared strip sample with the length of about 2.1mm, the width of 1.1mm and the thickness of about 0.8mm is put into a comprehensive physical property measurement system PPMS, and the giant magnetoresistance is measured by a four-probe method. The fixed temperature is 2K, and the resistance value of the sample is measured along with the change of the magnetic field in the change range of the external field from 7T to minus 7T. The measurement result of the magnetic resistance is shown in fig. 16, and it can be observed that the magnetic field has a great influence on the resistance of the sample, and the giant magnetic resistance is about-91% under the conditions of an external field of 2T and a temperature of 2K; the giant magnetoresistance reaches about-94% at an external field of 5T and a temperature of 2K.
Measurement of alternating-current magnetic susceptibility: and (3) placing the sample in PPMS (point-to-point magnetic field) with zero magnetic field, and measuring the change of the real part and the imaginary part of the magnetic susceptibility of the sample with the temperature under different frequencies of 633Hz, 3633Hz and 6633Hz, wherein the temperature range is 2K-40K. The measurement result is shown in fig. 18, under the same frequency and zero magnetic field, the peak of the imaginary part curve of the magnetic susceptibility is positioned at the left side of the peak of the real part curve; and as the frequency applied to the sample increases, the peak of the sample susceptibility curve moves toward the high temperature region, corresponding to the spin glass transition temperature of the sample increasing as the frequency applied increases. Tf for the sample at 633Hz was 13.48K, and Tf for the corresponding sample when the frequency was increased to 6633Hz was 15.35K. From the test results of the alternating magnetic susceptibility, the sample has a distinct spin glass property, in this case a spin glassy state.
In summary, the above embodiments successfully synthesize the diluted magnetic semiconductor material with giant magnetoresistance according to the present invention by using a solid phase reaction method under normal pressure (about one atmosphere) or high pressure (higher than one atmosphere), Na1+x(Zn1-yMny) Sb, wherein x and y represent atomic content percentage, x is more than or equal to 0 and less than or equal to 0.2, and y is more than or equal to 0.05 and less than or equal to 0.5. The ratios of the various substances in the precursors used in the methods provided in the above embodiments are merely exemplary, and are not intended to limit the scope of the present application, and one skilled in the art can easily synthesize Na according to the needs1+x(Zn1-yMny) The weight ratio of various substances in the precursor is determined according to the specific values of x and y in Sb, and the content of various substances is enough to prepare the diluted magnetic semiconductor material Na1+x(Zn1-yMny) The proportion of various elements in Sb is only needed.
According to other embodiments of the present invention, the container for holding the precursor is not limited to the alumina ceramic test tube, niobium tube, etc. used in the above embodiments, but may be other corrosion-resistant containers, such as BN tube, etc.
According to other embodiments of the present invention, the manner of containing the precursor during sintering is not limited to the manner provided in the above embodiments, and the precursor can be sintered in an environment isolated from oxygen, for example, under protection of an inert gas, or under a vacuum environment.
According to other embodiments of the invention, atmospheric sintering forms the diluted magnetic semiconductor material Na1+x(Zn1-yMny) The temperature of Sb is preferably 400 to 1000 ℃ and more preferably 500 ℃ and the sintering time is preferably 5 hours.
According to other embodiments of the invention, wherein the high pressure sintering forms a diluted magnetic semiconductor material Na1+x(Zn1-yMny) The temperature of Sb is preferably 500 to 1200 ℃, more preferably 700 ℃, the sintering time is preferably 0.5 hour or more, more preferably 0.5 to 1 hour, and particularly preferably 1 hour, and the sintering pressure is higher than one atmosphere, preferably 1GPa to 20GPa, and more preferably 5 GPa.
According to other embodiments of the present invention, wherein the sintering process under normal pressure and high pressure may include two or more times of sintering, the precursor may be subjected to grinding and pressing again between sintering.
The diluted magnetic semiconductor material can be used for preparing various semiconductor electronic devices, such as semiconductor layers in the semiconductor electronic devices, and the semiconductor electronic devices can be used in various electronic equipment. Semiconductor electronic devices that can be fabricated using diluted magnetic semiconductor materials have been discussed in the prior art and are not described in detail herein.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A diluted magnetic semiconductor material with giant magnetoresistance effect has chemical formula of Na1+x(Zn1-yMny) Sb, wherein x and y are atomic percent, x is more than or equal to 0 and less than or equal to 0.2, y is more than or equal to 0.05 and less than or equal to 0.5,
wherein the diluted magnetic semiconductor material belongs to a tetragonal system with a space group of P4/nmm, and the variation range of the lattice parameter of the diluted magnetic semiconductor material is
2. A method of preparing the diluted magnetic semiconductor material of claim 1, comprising:
preparing a precursor material, wherein the precursor material is a mixture comprising four elements of Na, Zn, Mn and Sb, and the atomic ratio of the four elements is Na, Zn, Mn, Sb (1+ x) to (1-y) y: 1; and
and carrying out heat treatment on the precursor material.
3. The method of claim 2, wherein the precursor material comprises Na3A mixture of Sb, Zn, Mn and Sb.
4. The method of claim 2, wherein prior to performing the heat treatment, the method further comprises:
grinding the precursor material into powder to uniformly mix the various elements; and
pressing the powder into a block.
5. The method of claim 4, wherein the heat treatment is performed two or more times and the grinding and pressing steps are performed on the precursor material between adjacent heat treatments.
6. The method according to claim 2, wherein the heat treatment is carried out under normal pressure or high pressure, the high pressure being in the range of 1-20GPa, the heating temperature of the normal pressure heat treatment being 400-1000 ℃ and the heating time being 4-30 hours, the heating temperature of the high pressure heat treatment being 500-1200 ℃ and the heating time being 0.5-6 hours.
7. A semiconductor electronic device comprising a semiconductor layer made of the diluted magnetic semiconductor material of claim 1.
8. An electronic device comprising a semiconductor layer made of the diluted magnetic semiconductor material of claim 1.
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