CN103130494B - PbxPdO2 block material with room-temperature ferromagnetism, and preparation method thereof - Google Patents

PbxPdO2 block material with room-temperature ferromagnetism, and preparation method thereof Download PDF

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Publication number
CN103130494B
CN103130494B CN201310055113.7A CN201310055113A CN103130494B CN 103130494 B CN103130494 B CN 103130494B CN 201310055113 A CN201310055113 A CN 201310055113A CN 103130494 B CN103130494 B CN 103130494B
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pdo
powder
temperature
room
block
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CN103130494A (en
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苏海林
吴玉程
黄荣俊
黄舜渔
黄贤良
金智渊
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Hefei University of Technology
Beijing Samsung Telecommunications Technology Research Co Ltd
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Hefei University of Technology
Beijing Samsung Telecommunications Technology Research Co Ltd
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Abstract

Aiming at the technical difficulty of the inability of preparing a PbxPdO2 block material with room-temperature ferromagnetism, existed in the prior art, the invention provides a PbxPdO2 block material with room-temperature ferromagnetism and a preparation method thereof. The PbxPdO2 block material has a single-phase body-centered orthorhombic structure, and Pb ion vacancies exist in lattices. The PbxPdO2 block material preparation method provided by the invention is substantially characterized in that a raw material formula according to which a Pb content is lower than a positive distribution ratio is adopted, such that heat treatment time is prolonged. Therefore, Pb content insufficiency is caused in PbPdO2 material, and Pb ion vacancies are formed. According to the invention, room-temperature ferromagnetism can be formed in the non-doped PbxPdO2 block material, and the method is simple and feasible. Therefore, references can be provided for the development of high-temperature ferromagnetism zero forbidden band semiconductor.

Description

The Pb that contains room-temperature ferromagnetic xpdO 2block materials and preparation method
Technical field
The present invention relates to zero bandgap semiconductor field of material preparation, especially relate to the Pb that contains room-temperature ferromagnetic xpdO 2block materials and preparation method.
Background technology
Zero bandgap semiconductor is a kind of special semiconductor material, at the bottom of its top of valence band and conduction band, at fermi level place, contact, cause thus it to there is a series of advantageous characteristic, comprising: energy band structure, transport property etc. are extremely sensitive to the reaction of the ectocines such as magnetic field, electric field, pressure, temperature; There is not lowest excited energy threshold in the migration of electronics from valence band to conduction band; Electronic mobility is than the high 2-4 of a conventional semiconductors order of magnitude.For a long time, the research of zero bandgap semiconductor concentrates on the Hg base IV-VI compounds such as HgCdTe, HgTeSe, HgZnSe always.2008, Australian Wollongong Wang professor Xiaolin of university was calculated and is found PbPdO by first principle 2material has the energy band structure in zero forbidden band.2011, PbPdO 2material is confirmed in experiment as first zero bandgap semiconductor oxide compound.The special energy band structure of this material makes it in spintronics field, have good application prospect.In order to prepare single-phase PbPdO 2material, the related manufacturing processes of at present all open reports all adopts Pb content higher than PbPdO 2the composition of raw materials of positive partition ratio is to make up the loss of Pb in preparation process.Wherein, the people such as the S.W.Chen of the people such as the T.C.Ozawa of Japanese Aoyama Gakuin university and Taiwan Univ. adopts the composition of raw materials of Pb content higher than positive partition ratio 2mol.%; The people such as the K.J.Lee of Korea S Sogang university adopt the composition of raw materials of Pb content higher than positive partition ratio 10mol.%.Adopt Pb content higher than PbPdO 2though the composition of raw materials of positive partition ratio is conducive to obtain the PbPdO of positive partition ratio 2material, but there are two distinct disadvantage: the one, in experimentation, easily cause PbPdO 2in material, remain PbO dephasign; The 2nd, sufficient Pb content can cause PbPdO 2the valence state of material internal Pb ion and Pd ion all keeps 2+, thereby is difficult to introduce magnetic moment.And manufacture Pb content lower than PbPdO 2the Pb of positive partition ratio xpdO 2material, is conducive to avoid PbPdO on the one hand 2in material, there is PbO dephasign, on the other hand also can be at PbPdO 2the valence state that causes Pb room to realize Pb ion or Pd ion in material departs from 2+, thereby effectively introduces magnetic moment, contributes to realize ferromegnetism.At present, by adopting Pb content lower than PbPdO 2the composition of raw materials of positive partition ratio and prolongation heat treatment time are prepared the single-phase Pb of Pb content lower than positive partition ratio xpdO 2document or the material object of material are not reported.
The application requiring semiconductor material of spintronics has ferromegnetism in room temperature.Before 2012, both at home and abroad for PbPdO 2all researchs of material only obtained ferromegnetism under the low temperature lower than 20K.2012, Chinese invention patent application " non-impurity-doped room-temperature ferromagnetic spin zero bandgap semiconductor film and preparation method " (application publication number: CN102747349A) provided a kind of PbPdO 2the preparation method of thin-film material.The method is chosen Pb content higher than PbPdO 2the composition of raw materials of positive partition ratio 2-10mol.%, adopts even gluing method to prepare the PbPdO of positive partition ratio 2film, by film crystal grain is controlled to 17-35nm, has successfully obtained the room-temperature ferromagnetic with spin zero forbidden band characteristic.But even gluing method has two limitation: the one, the method adopts organic solvent, has certain pollution; The 2nd, the method only can be prepared two-dimensional film on small area substrate, is difficult to the synthetic wider three-dimensional block materials of range of application.Oxide compound method for calcinating can be avoided this two shortcomings, and is applicable to large-scale mass production.Adopt oxide compound method for calcinating to prepare the Pb of Pb content lower than positive partition ratio xpdO 2block materials also successfully obtains room-temperature ferromagnetic and at home and abroad have not been reported at present.
Summary of the invention
For prior art, cannot realize and manufacture the PbPdO that contains room-temperature ferromagnetic 2a difficult problem for block materials, the invention provides a kind of Pb that contains room-temperature ferromagnetic xpdO 2block materials and preparation method.
The Pb that contains room-temperature ferromagnetic provided by the present invention xpdO 2block materials, is characterized in that: block Pb xpdO 2material is single-phase body-centered orthorhombic structure; Pb xpdO 2intracell there is Pb ion room, the x value of Pb is between 0.908 to 0.980; At 300K, Pb xpdO 2still present saturation magnetization trend and hysteresis behavior.
Manufacture the Pb that contains room-temperature ferromagnetic of the present invention xpdO 2the method of block materials,, it is characterized in that carrying out as follows:
(1) plumbous oxide (PbO) powder, palladous oxide (PdO) powder and polyvinyl alcohol (PVA) powder are crossed after 100 mesh sieves respectively, (1.70-1.82): 1:0.04 takes respectively PbO powder, PdO powder and PVA powder in mass ratio;
(2) by PbO powder and PdO powder mixed grinding until evenly, then add PVA powder to continue mixed grinding until evenly;
(3) the even mixed powder by PbO powder, PdO powder, PVA powder constituent step (2) being obtained is put into the mould of preparing block materials, subsequently this mould is applied to 100kg/cm 2pressure pressurize 15 minutes, obtain and be shaped to block blank;
(4) block blank is put into heat treatment furnace, in air atmosphere or oxygen atmosphere, calcine, the heating curve of calcining is: first with the temperature rise rate of 1-15K/ minute, temperature is risen to 423K, then with the temperature rise rate of 0.5-1K/ minute, temperature is risen to 573K and is incubated 1 hour, finally with the temperature rise rate of 2-6K/ minute, temperature is risen to 953-993K and is incubated 20-30 hour again; After calcining finishes, with heat treatment furnace, naturally cool to the product that room temperature obtains and be the Pb that contains room-temperature ferromagnetic xpdO 2block materials, wherein the span of x is between 0.908 to 0.980.
Compared with the prior art, beneficial effect of the present invention is embodied in:
The present invention, by the control to proportioning raw materials and thermal treatment process, selects Pb content lower than the composition of raw materials of positive partition ratio and extends heat treatment time, at PbPdO 2in material, manufacture the deficiency of Pb content, successfully made intracell and exist the single-phase body-centered orthorhombic structure Pb in Pb ion room xpdO 2(x=0.908-0.980) block materials, and obtained ferromegnetism in room temperature.This is first at the PbPdO that there is no magnetic ion doping 2in block materials, obtain room-temperature ferromagnetic.In addition, the raw materials used solid granule that is of oxide compound method for calcinating that the present invention adopts, is convenient to transportation and stores; Processing step is succinct, extremely low to environment and operating personnel's harm, applicable to be produced in enormous quantities.
Accompanying drawing explanation
Fig. 1 is Pb in the embodiment of the present invention 1 0.980pdO 2x-ray diffraction (XRD) collection of illustrative plates of block materials.
Fig. 2 is Pb in the embodiment of the present invention 1 0.980pdO 2x-ray energy spectrum (EDS) figure of block materials.
Fig. 3 is Pb in the embodiment of the present invention 1 0.980pdO 2the magnetic hysteresis loop of block materials 2K and 300K.
Fig. 4 is Pb in the embodiment of the present invention 2 0.953pdO 2x-ray diffraction (XRD) collection of illustrative plates of block materials.
Fig. 5 is Pb in the embodiment of the present invention 2 0.953pdO 2x-ray energy spectrum (EDS) figure of block materials.
Fig. 6 is Pb in the embodiment of the present invention 2 0.953pdO 2the magnetic hysteresis loop of block materials 2K and 300K.
Fig. 7 is Pb in the embodiment of the present invention 3 0.908pdO 2x-ray diffraction (XRD) collection of illustrative plates of block materials.
Fig. 8 is Pb in the embodiment of the present invention 3 0.908pdO 2x-ray energy spectrum (EDS) figure of block materials.
Fig. 9 is Pb in the embodiment of the present invention 3 0.908pdO 2the magnetic hysteresis loop of block materials 2K and 300K.
Embodiment
Embodiment 1
PbO powder, PdO powder and PVA powder are crossed after 100 mesh sieves respectively, according to mass ratio 1.82:1:0.04, taken respectively PbO powder, PdO powder and PVA powder;
Until evenly, then add PVA powder to continue mixed grinding until evenly PbO powder and PdO powder mixed grinding;
By putting into by the even mixed powder of PbO powder, PdO powder, PVA powder constituent the mould of preparing block materials, subsequently this mould is applied to 100kg/cm 2pressure pressurize 15 minutes, obtain and be shaped to block blank;
Block blank is put into heat treatment furnace, in oxygen atmosphere, calcine, the heating curve of calcining is: first with the temperature rise rate of 15K/ minute, temperature is risen to 423K, then with the temperature rise rate of 1K/ minute, temperature is risen to 573K and is incubated 1 hour, finally with the temperature rise rate of 6K/ minute, temperature is risen to 953K and is incubated 20 hours again; After calcining finishes, with heat treatment furnace, naturally cool to room temperature, obtain Pb 0.980pdO 2block materials.
Pb in the present embodiment 0.980pdO 2the XRD figure of block materials is composed as shown in Figure 1.Visible, block materials is single-phase body-centered orthorhombic structure, and the oxide compound that has no Pb and Pd exists.Pb 0.980pdO 2the EDS of block materials schemes as shown in Figure 2.According to this figure, can calculate Pb and Pd mol ratio is 0.980:1, illustrate and in block material lattice, have Pb ion room.Pb 0.980pdO 2the magnetic hysteresis loop of block materials 2K and 300K as shown in Figure 3, wherein, deducted by the diamagnetic signal of the matrix of block materials.Visible: block materials all presents saturation magnetization trend and hysteresis behavior at 2K and 300K, illustrate that block materials contains ferromegnetism, and ferromegnetism can remain to room temperature.
Embodiment 2
PbO powder, PdO powder and PVA powder are crossed after 100 mesh sieves respectively, according to mass ratio 1.78:1:0.04, taken respectively PbO powder, PdO powder and PVA powder;
Until evenly, then add PVA powder to continue mixed grinding until evenly PbO powder and PdO powder mixed grinding;
By putting into by the even mixed powder of PbO powder, PdO powder, PVA powder constituent the mould of preparing block materials, subsequently this mould is applied to 100kg/cm 2pressure pressurize 15 minutes, obtain and be shaped to block blank;
Block blank is put into heat treatment furnace, in oxygen atmosphere, calcine, the heating curve of calcining is: first with the temperature rise rate of 5K/ minute, temperature is risen to 423K, then with the temperature rise rate of 0.75K/ minute, temperature is risen to 573K and is incubated 1 hour, finally with the temperature rise rate of 4K/ minute, temperature is risen to 973K and is incubated 24 hours again; After calcining finishes, with heat treatment furnace, naturally cool to room temperature, obtain Pb 0.953pdO 2block materials.
Pb in the present embodiment 0.953pdO 2the XRD figure of block materials is composed as shown in Figure 4.Visible, block materials is single-phase body-centered orthorhombic structure, and the oxide compound that has no Pb and Pd exists.Pb 0.953pdO 2the EDS of block materials schemes as shown in Figure 5.According to this figure, can calculate Pb and Pd mol ratio is 0.953:1, illustrate and in block material lattice, have Pb ion room.Pb 0.953pdO 2the magnetic hysteresis loop of block materials 2K and 300K as shown in Figure 6, wherein, deducted by the diamagnetic signal of the matrix of block materials.Visible: block materials all presents saturation magnetization trend and hysteresis behavior at 2K and 300K, illustrate that block materials contains ferromegnetism, and ferromegnetism can remain to room temperature.
Embodiment 3
PbO powder, PdO powder and PVA powder are crossed after 100 mesh sieves respectively, according to mass ratio 1.70:1:0.04, taken respectively PbO powder, PdO powder and PVA powder;
Until evenly, then add PVA powder to continue mixed grinding until evenly PbO powder and PdO powder mixed grinding;
By putting into by the even mixed powder of PbO powder, PdO powder, PVA powder constituent the mould of preparing block materials, subsequently this mould is applied to 100kg/cm 2pressure pressurize 15 minutes, obtain and be shaped to block blank;
Block blank is put into heat treatment furnace, in air atmosphere, calcine, the heating curve of calcining is: first with the temperature rise rate of 1.5K/ minute, temperature is risen to 423K, then with the temperature rise rate of 0.5K/ minute, temperature is risen to 573K and is incubated 1 hour, finally with the temperature rise rate of 2.85K/ minute, temperature is risen to 993K and is incubated 30 hours again; After calcining finishes, with heat treatment furnace, naturally cool to room temperature, obtain Pb 0.908pdO 2block materials.
Pb in the present embodiment 0.908pdO 2the XRD figure of block materials is composed as shown in Figure 7.Visible, block materials is single-phase body-centered orthorhombic structure, and the oxide compound that has no Pb and Pd exists.Pb 0.908pdO 2the EDS of block materials schemes as shown in Figure 8.According to this figure, can calculate Pb and Pd mol ratio is 0.908:1, illustrate and in block material lattice, have Pb ion room.Pb 0.908pdO 2the magnetic hysteresis loop of block materials 2K and 300K as shown in Figure 9, wherein, deducted by the diamagnetic signal of the matrix of block materials.Visible: block materials all presents saturation magnetization trend and hysteresis behavior at 2K and 300K, illustrate that block materials contains ferromegnetism, and ferromegnetism can remain to room temperature.

Claims (2)

1. contain the Pb of room-temperature ferromagnetic xpdO 2block materials, is characterized in that: the Pb of block shape xpdO 2for single-phase body-centered orthorhombic structure; Pb xpdO 2intracell there is Pb ion room, the x value of Pb is between 0.908 to 0.980; At 300K, Pb xpdO 2still present saturation magnetization trend and hysteresis behavior.
2. the Pb that contains room-temperature ferromagnetic as claimed in claim 1 xpdO 2the preparation method of block materials, is characterized in that carrying out as follows:
(1) PbO powder, PdO powder and PVA powder are crossed respectively to 100 mesh sieves, then according to mass ratio 1.70-1.82:1:0.04, take respectively PbO powder, PdO powder and PVA powder;
(2) by PbO powder and PdO powder mixed grinding until evenly, then add PVA powder to continue mixed grinding until evenly;
(3) the even mixed powder by PbO powder, PdO powder and PVA powder constituent step (2) being obtained is put into the mould of preparing block materials, subsequently this mould is applied to 100kg/cm 2pressure pressurize 15 minutes, obtain and be shaped to block blank;
(4) block blank is put into heat treatment furnace, in air atmosphere or oxygen atmosphere, calcine, the heating curve of calcining is: first with the temperature rise rate of 1-15K/ minute, temperature is risen to 423K, then with the temperature rise rate of 0.5-1K/ minute, temperature is risen to 573K and is incubated 1 hour, finally with the temperature rise rate of 2-6K/ minute, temperature is risen to 953-993K and is incubated 20-30 hour again; After calcining finishes, with heat treatment furnace, naturally cool to the product that room temperature obtains and be the Pb that contain room-temperature ferromagnetic of x span between 0.908 to 0.980 xpdO 2block materials.
CN201310055113.7A 2013-02-21 2013-02-21 PbxPdO2 block material with room-temperature ferromagnetism, and preparation method thereof Expired - Fee Related CN103130494B (en)

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