CN1204571C - Nano composite rare earth permanent magnet film material and its preparation method - Google Patents
Nano composite rare earth permanent magnet film material and its preparation method Download PDFInfo
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- CN1204571C CN1204571C CN 01133311 CN01133311A CN1204571C CN 1204571 C CN1204571 C CN 1204571C CN 01133311 CN01133311 CN 01133311 CN 01133311 A CN01133311 A CN 01133311A CN 1204571 C CN1204571 C CN 1204571C
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- 238000002360 preparation method Methods 0.000 title description 9
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Abstract
The present invention relates to a nanometer composite rare earth permanent magnet thin film material which is orderly composed of a substrate, a buffer layer, a hard magnetic phase and soft magnetic phase sandwich and a protective layer. The present invention is characterized in that the substrate is made of ceramic glass, glass or Si; the buffer layer is made of one of Ti, Cr, Ta, Mo, Nb or V, and the thickness of the buffer layer is from 0 to 100 nm. The hard magnetic phase and soft magnetic sandwich respectively comprises the hard magnetic phase R (Fe, T, B) z and soft magnetic phase, wherein R stands for rare earth elements, z is equal to the number from 2 to 8 and T stands for alloy elements, wherein the atomic percentage of the alloy elements is 0 to 60%, the atomic percentage of B is 0.6 to 20% and residual parts are balanced by Fe. The thickness of the hard magnetic phase is from 1 to 500 nm. The soft magnetic phase is Fe, Co or FeCo alloy, and the thickness of the soft magnetic phase is from 0 to 50 nm. Numbers of hard magnetic phase layers and soft magnetic phase layers are respectively between 1 to 200 layers.
Description
Technical field:
The present invention relates to permanent magnetic material, a kind of nano composite rare earth permanent magnet film material and technology of preparing thereof are provided especially.
Background technology:
Permanent magnetic thin film and permanent magnetic material have many purposes: as the mutual conversion of magnetic recording, signal of telecommunication magnetic signal, magnetic storage memory storage, magneto etc.The patent that relates to this respect has many.Provide a kind of magnetoresistive multilayered film as U.S. Pat 6172589, the body-centered cubic crystal structure that magnetic thin film is made up of Fe, Fe-Ni, Fe-Co or Fe-Ni-Co and contain alloying element Si, V, Cr, Nb,, Mo, Ta, W etc.U.S. Pat 5585985 relates to magnetoresistive film, contains Co-Pt magnetic film and Ni-Zn ferrite.US5434826 provides a kind of magnetoresistive multilayered film, and the alloy that film is made up of Co, Cr, Pt and B is used for the magnetic storage memory disc.It is a kind of by the compound multilayer film of forming of soft magnetism, Hard Magnetic and nonmagnetic substance that US6111782 provides, and the thickness of film is 0.1-2nm (nanometer), and its main component is Fe, Ni and Co, and magnetic energy product is not high.These magnetic films or multi-layered magnetic film do not contain rare earth, and magnetic energy product is low, are unsuitable for preparing micromachine.Patent US4601875 then relates to the sintered rare-earth permanent magnetic made from powder metallurgy process, also is unsuitable for preparing micromachine.For many devices such as miniature magnetoes, then need permanent magnetic thin film.Patent US4596646, EP0660338, JP7272929, JP6224038, JP60038804, JP60015910, JP60140803, JP61256707 relates to the preparation method of permanent magnetic thin film, and wherein patent EP0660338 contains rare earth Pr-Co alloy, but does not relate to nano composite rare earth permanent magnet film material and preparation method thereof.Patent JP4125907, JP2000234137, JP2000182814, US6261385, JP2000348919, JP10261515 relate to nano composite permanent magnetic material and magnetic, and wherein patent US6261385 contains rare earth, but does not all relate to thin-film material.
The technology contents of invention:
The object of the present invention is to provide a kind of nano composite rare earth permanent magnet film material and preparation method thereof, it has high energy product, high-coercive force, high-curie temperature and stability.
The invention provides a kind of nano composite rare earth permanent magnet film material, it is characterized in that: this thin-film material is by substrate, resilient coating, Hard Magnetic phase and soft magnetism intersects lamination and protective layer is formed successively; Main process is as follows:
1. alloy melting
Being higher than 99.5% rare earth element and metal Fe and other alloying element and B with purity is raw material, press composition R (Fe, T, B) z, wherein R is one or more of rare earth element, z=2～8, T is alloying element Co and Nb, and the atomic percent of Co is 0.1～57%, and the atomic percent of Nb is 3%, the atomic percent of B is 0.6～20%, and rest parts is carried out balance by Fe and carried out proportioning.Raw material after the proportioning after vacuumizing in employing arc melting or the induction melting furnace, is smelted into alloy cast ingot under argon shield.
2. target is made
Cast alloy is broken into particle less than 1 millimeter, is under the protection of medium then with alcohol, adopt ball mill with the alloying pellet ball milling to powder less than 500 microns.Being pressed into diameter with 50～100 tons of press is that thickness is 1 millimeter-10 millimeters garden sheet, is being higher than 2 * 10
-5Under the vacuum condition of Pa, be heated to 900～1200 ℃, be incubated 0.5-4 hour, be cooled to room temperature then.The surface promptly can be used as the alloy target material that magnetron sputtering is used through after the polishing.
3. thin film sputtering;
The preparation of magnetic thin film adopts magnetron sputtering to prepare membrane equipment, wherein alloys target (as the Hard Magnetic phase), simple metal M target (as Fe, Co, FeCo alloy) and be used for resilient coating M
1With protective layer M
2Metallic target (M wherein
1, M
2Comprise Ti, Al, W, V, Cr, Mo, Nb, Ta, Zr etc.) be installed in the rifle that is used for magnetron sputtering respectively.The vacuum of system is evacuated to 2 * 10
-5More than the Pa, the power of direct current rifle all adopts 10～100 watts, and the power of radio frequency rifle adopts 20～160 watts.Adopt weight method to demarcate the sputter rate of every kind of material.
Carry out sputter according to following structure,
Substrate/M
1(d
M1)/[R (Fe, T, B) z (d
Alloy) M (d
M)] * n/M
2(d
M2)
Wherein (B) z, R are one or more of rare earth element to Hard Magnetic phase R for Fe, T, z=2～8, T is alloying element Co and Nb, and the atomic percent of Co is 0.1～57%, and the atomic percent of Nb is 3%, the atomic percent of B is 0.6～20%, and rest parts is carried out balance, thickness d by Fe
AlloyBe 1～500nm
Wherein soft magnetism phase M is
M is Fe, Co, FeCo alloy, its thickness d
MBe 1.5～200nm
It is 1～200 that Hard Magnetic phase and soft magnetism overlap mutually number of repetition n
Described resilient coating and protective layer are respectively M
1And M
2(Ti, Al, W, V, Cr, Mo, Nb, Ta, Zr etc.), thickness d
M1And d
M2Be respectively 0.5～100nm.
Described substrate is glass-ceramic, glass or Si;
4. the measurement of annealing and the structural analysis of anticorrosion technology and performance.
Film after the sputter is being higher than 2 * 10
-5400～750 ℃ of annealing 5sec～2h under the vacuum condition of Pa.With the phase structure of X one x ray diffractometer x observation film sample, with the magnetic property of SQUID (superconducting quantum interference device (SQUID)) MEASUREMENTS OF THIN.
Rare-earth element R described in the present invention can be among Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Dy, Tb, Ho, Er, Tm, the Yb at least a.Be preferably at least a of Nd, Dy.
Hard Magnetic described in the present invention preferably has 2: 14: 1 phase structure mutually; The number of plies of described Hard Magnetic phase layer and soft magnetism phase layer is preferably respectively between 1～100 layer; Described Hard Magnetic phase layer thickness is preferably 5～200nm.
The present invention also provides the preparation method of above-mentioned nano composite rare earth permanent magnet film material, it is characterized in that: the mode that adopts sputter, comprise that alloy melting, target are made, the thin film sputtering several steps, carry out annealing in process behind the thin film sputtering, annealing temperature is 400～750 ℃, and annealing time is 5S～2h..
The present invention at first utilizes the sputtering technology of existing preparation thin-film material, layer and soft magnetism be mutually layer mutually to obtain being in amorphous Hard Magnetic, through after the further vacuum heat, soft magnetism phase in the film and Hard Magnetic layer phase counterdiffusion mutually, crystal grain is evenly distributed after the crystallization, by regulate annealing temperature and time control soft magnetism mutually with Hard Magnetic crystallite dimension mutually, it is compound to make that rare earth permanent-magnetic material and transition metal soft magnetic material carry out magnetic on nanoscale, thereby has obtained to have the permanent magnetic material film of high energy product and high Curie temperature stability.Below by embodiment in detail the present invention is described in detail.
Description of drawings:
Fig. 1 is the x-ray diffraction pattern of above-mentioned film Si (substrate)/Ti (10nm)/NdDyFeCoNbB (300nm)/Ti (10nm), wherein (a) for the deposition after, (b) 750 ℃ annealing 30min after.
Fig. 2 is the magnetic hysteresis loop under the room temperature of above-mentioned film Si (substrate)/Ti (10nm)/NdDyFeCoNbB (300nm)/parallel film surface measurement of Ti (10nm).
Fig. 3 is the x-ray diffraction pattern of multilayer film glass-ceramic (substrate)/Ti (10nm)/[NdDyFeCoNbB (20nm) Fe (2nm)] * 20/Ti (10nm).
Fig. 4 is the magnetic hysteresis loop of multilayer film glass-ceramic (substrate)/Ti (10nm)/[NdDyFeCoNbB (20nm) Fe (2nm)] * 20/Ti (10nm) behind different temperatures annealing 30min.
Fig. 5 is the x-ray diffraction pattern of multilayer film glass-ceramic (substrate)/Ti (10nm)/[NdDyFeCoNbB (20nm) Fe (xnm)] * 20/Ti (10nm) behind 575 ℃ of annealing 30min.
Fig. 6 is the demagnetization curve of multilayer film glass-ceramic (substrate)/Ti (10nm)/[NdDyFeCoNbB (20nm) Fe (xnm)] * 20/Ti (10nm) behind 575 ℃ of annealing 30min.
Fig. 7 is the transmission electron microscope photo (TEM) of the viewed in plan of multilayer film glass-ceramic (substrate)/Ti (10nm)/[NdDyFeCoNbB (20nm) Fe (3nm)] * 20/Ti (10nm) behind 575 ℃ of annealing 30min.
Fig. 8 is the magnetic hysteresis loop of multilayer film Si (substrate)/Ti (20nm)/[NdDyFeCoNbB (15nm) Co (xnm)] * 20/Ti (20nm) behind 625 ℃ of annealing 5min.
Fig. 9 is multilayer film Si (substrate)/Ti (20nm)/[NdDyFeCoNbB (15nm) Fe
65Co
35(ynm)] * x-ray diffraction pattern of 20/Ti (20nm) behind 625 ℃ of annealing 1min.
Figure 10 is multilayer film Si (substrate)/Ti (20nm)/[NdDyFeCoNbB (15nm) Fe
65Co
35(ynm)] * 20/Ti (20nm); Magnetic hysteresis loop behind 625 ℃ of annealing 1min.
Figure 11 is multilayer film Si (substrate)/Ti (20nm)/[A (15nm) Fe
65Co
35(6nm)] * 20/Ti (20nm) is at the transmission electron microscope photo (TEM) of the viewed in plan of 625 ℃ of annealing behind the 1min.
Embodiment:
The film preparation process of following embodiment comprise Hard Magnetic phase constituent, Hard Magnetic mutually and soft magnetism mutually layer thickness and the difference of the number of times of overlapping, annealing conditions etc. will in specific embodiment, provide.The same section of film preparation process is described below:
The purity of all material all is higher than 99.5%, and the alloys target (as the Hard Magnetic phase) and the simple metal M target (as Fe, Co, FeCo alloy) that oneself prepare are installed on the direct current rifle of magnetron sputtering, are used for resilient coating M
1With protective layer M
2Metallic target (M wherein
1, M
2Comprise Ti, Al, W, V, Cr, Mo, Nb, Ta, Zr etc.) be installed on the radio frequency rifle of magnetron sputtering.The vacuum of system is evacuated to 2 * 10
-5More than the Pa, the pressure when beginning sputter behind the logical high-purity argon gas is 5mTorr.Demarcate the sputter rate of different targets by weight method.Film after the sputter is being higher than 2 * 10
-7Anneal under the vacuum condition of Torr, with the phase structure of x-ray diffractometer observation film sample, with the nanostructure of transmission electron microscope observation film, with the magnetic property of SQUID (superconducting quantum interference device (SQUID)) MEASUREMENTS OF THIN.
Embodiment 1: a kind of individual layer rare earth permanent magnet film
The process of sputter is: Si (substrate)/Ti (10nm)/NdDyFeCoNbB (300nm)/Ti (10nm).
Wherein the concrete composition of NdDyFeCoNbB is:
(Nd
0.9Dy
0.1)(Fe
0.77Co
0.12Nb
0.03B
0.08)
5.5
Accompanying drawing 1 is the x-ray diffraction pattern of above-mentioned film Si (substrate)/Ti (10nm)/NdDyFeCoNbB (300nm)/Ti (10nm), wherein (a) for the deposition after, (b) 750 ℃ annealing 30min after.
As can be seen from Figure 1, the film before the annealing presents tangible amorphous state, and annealing back Hard Magnetic principal phase is Nd
2Fe
14B-type phase (being labeled as ◆), simultaneous minor N dO
2(being labeled as zero) (is labeled as ■) mutually with rich Nd.
Embodiment 2: a kind of multilayer rare earth permanent magnet film
The composition of Hard Magnetic phase is identical with embodiment 1 in the following structure.
Accompanying drawing 3 is the x-ray diffraction pattern of multilayer film glass-ceramic (substrate)/Ti (10nm)/[NdDyFeCoNbB (20nm) Fe (2nm)] * 20/Ti (10nm).Symbol among the figure ◆, zero, and ■ represent Nd successively
2Fe
14B, NdO
2, glass-ceramic and rich Nd diffraction maximum mutually.Annealing temperature is followed successively by 500,550,575,600 and 650 ℃ from top to bottom.
Embodiment 3: a kind of multilayer rare earth permanent magnet film
The composition of Hard Magnetic phase is identical with embodiment 1 in the following structure.
Accompanying drawing 5 is the x-ray diffraction pattern of multilayer film glass-ceramic (substrate)/Ti (10nm)/[NdDyFeCoNbB (20nm) Fe (xnm)] * 20/Ti (10nm) behind 575 ℃ of annealing 30min.Symbol among the figure ◆, zero, and ■ represent Nd successively
2Fe
14B, NdO
2, glass-ceramic and rich Nd diffraction maximum mutually.As seen from the figure, along with the increase of Fe content in film, the diffraction maximum of α-Fe also increases thereupon among the figure.
Accompanying drawing 6 is the demagnetization curve of multilayer film glass-ceramic (substrate)/Ti (10nm)/[NdDyFeCoNbB (20nm) Fe (xnm)] * 20/Ti (10nm) behind 575 ℃ of annealing 30min.As can be seen from the figure, along with the increase of Fe content, the coercive force of film reduces to 4.5kOe by 9.3kOe, and when the thickness of Fe was 3nm, its maximum magnetic energy product had surpassed 24MGOe.
Accompanying drawing 7 is the transmission electron microscope photo (TEM) of the viewed in plan of multilayer film glass-ceramic (substrate)/Ti (10nm)/[NdDyFeCoNbB (20nm) Fe (3nm)] * 20/Ti (10nm) behind 575 ℃ of annealing 30min.Determine that by electron diffraction pattern Hard Magnetic is Nd mutually in the film
2Fe
14B-type phase.The crystallite dimension of Hard Magnetic phase is approximately 40nm, and the soft magnetism that contains Fe then is continuous distribution mutually.
Embodiment 4: soft magnetism contains the multilayer rare earth permanent magnet film of Co mutually
The composition of Hard Magnetic phase is identical with embodiment 1 in the following structure.
Accompanying drawing 8 is the magnetic hysteresis loop of multilayer film Si (substrate)/Ti (20nm)/[NdDyFeCoNbB (15nm) Co (xnm)] * 20/Ti (20nm) behind 625 ℃ of annealing 5min.By among the figure as can be known, the HCJ of monofilm is 17.2kOe when x=0, its remanent magnetism is 33emu/cc.In multilayer film, along with the increase of the thickness of Co, remanent magnetism is greatly enhanced, and coercive force reduces seldom.When 4≤x≤8, compare with the result of monofilm, because the existence of Hard Magnetic phase interlayer soft magnetism phase Co causes remanent magnetism to increase 270emu/cc, coercive force has reduced 4kOe.As seen, the Hard Magnetic soft magnetic phase as well as exists magnetic couplings to cause the remanent magnetism enhancement effect mutually.
Embodiment 5: soft magnetism contains the multilayer rare earth permanent magnet film of FeCo alloy mutually
The composition of Hard Magnetic phase is identical with embodiment 1 in the following structure.
Accompanying drawing 9 is multilayer film Si (substrate)/Ti (20nm)/[NdDyFeCoNbB (15nm) Fe
65Co
35(ynm)] * x-ray diffraction pattern of 20/Ti (20nm) behind 625 ℃ of annealing 1min.Symbol among the figure ◆, zero and ■ represent Nd successively
2Fe
14B, NdO
2With rich Nd diffraction maximum mutually.Compare with the result of monofilm, except the Nd of random orientation
2Fe
14The B-type mutually outside, a large amount of α-Fe (Co) and minor N dO have also appearred
2With rich Nd mutually, and along with the increase of FeCo thickness, rich Nd reduces mutually in the film.
Accompanying drawing 10 is multilayer film Si (substrate)/Ti (20nm)/[NdDyFeCoNbB (15nm) Fe
65Co
35(ynm)] * magnetic hysteresis loop of 20/Ti (20nm) behind 625 ℃ of annealing 1min.As can be seen from the figure, when the thickness of FeCo layer is 2nm, because Hard Magnetic has played leading role in film, so its magnetic performance is similar with the result of monofilm.When the thickness of FeCo layer was 10nm, its remanent magnetism had reached 692emu/cc.The remanence ratio of all films has all surpassed 0.65, therefore, exists tangible remanent magnetism enhancement effect.
Accompanying drawing 11 is multilayer film Si (substrate)/Ti (20nm)/[A (15nm) Fe
65Co
35(6nm)] * 20/Ti (20nm) is at the transmission electron microscope photo (TEM) of the viewed in plan of 625 ℃ of annealing behind the 1min.Find two types crystal grain among the figure, wherein relatively little (being designated as A) is defined as Nd by electron diffraction pattern
2Fe
14B-type phase.In addition, α-Fe (Co) soft magnetism phase of being confirmed as cube of big relatively irregular crystal grain (being designated as B).
Embodiment 6: the multilayer rare earth permanent magnet film that contains Pr
The process of sputter is: Si (substrate)/Ti (30nm)/[PrDyFeCoNbB (18nm) Fe (xnm)] * 20/Ti (30nm).
Wherein the concrete composition of PrDyFeCoNbB is:
(Pr
0.9Dy
0.1)(Fe
0.77Co
0.12Nb
0.03B
0.08)
5.5
Behind 600 ℃ of annealing of above-mentioned film 5min, the Hard Magnetic in the film is mutually for to have 2: 14: 1 phases of tetragonal, and soft magnetism is α-Fe mutually.Its magnetic property such as following table:
| Fe thickness x (nm) | Coercive force iH c(kOe) | |
Maximum magnetic energy product |
| ?(BH) max(MGOe) | |||
| ?0 | ?12.8 | ?3.4 | ?2.7 |
| ?1.5 | ?17.0 | ?6.0 | ?7.6 |
| ?3 | ?12.5 | ?7.0 | ?10.6 |
| ?6 | ?8.5 | ?7.7 | ?8.7 |
| ?9 | ?3.5 | ?11.1 | ?11.4 |
Embodiment 7: Hard Magnetic is the multilayer rare earth permanent magnet film of NdDyFeB mutually
The process of sputter is: glass-ceramic (substrate)/Ti (30nm)/[NdDyFeB (15nm) Fe (xnm)] * 20/Ti (30nm).
Wherein the concrete composition of NdDyFeCoNbB is:
(Nd
0.9Dy
0.1)
14.1Fe
80B
5.9
Behind 625 ℃ of annealing of above-mentioned film 1min, the Hard Magnetic in the film is mutually for to have 2: 14: 1 phases of tetragonal, and soft magnetism is α-Fe mutually.Its magnetic property such as following table:
| Fe thickness x (nm) | Coercive force iH c(kOe) | |
Maximum magnetic energy product (BH) max(MGOe) |
| ?0 | ?17.5 | ?6.4 | ?8.8 |
| ?2.5 | ?10.3 | ?7.7 | ?11.3 |
| ?5 | ?6.5 | ?6.4 | ?5.6 |
| ?7.5 | ?4.4 | ?7.7 | ?6.2 |
| ?10 | ?3.5 | ?7.6 | ?5 |
Claims (6)
1, a kind of nano composite rare earth permanent magnet film material is made of successively substrate, resilient coating, Hard Magnetic phase and the crossing lamination of soft magnetism and protective layer, it is characterized in that:
Described substrate is pottery, glass-ceramic, glass or Si;
Described resilient coating is a kind of among Ti, Cr, Ta, Mo, Nb or the V, and thickness is 0.5～100mm;
Described Hard Magnetic intersects lamination with soft magnetism mutually and is respectively: Hard Magnetic is R (Fe mutually, T, B) z, wherein R is a rare earth element, z=2～8, T is alloying element Co and Nb, the atomic percent of Co is 0.1～57%, and the atomic percent of Nb is 3%, and the atomic percent of B is 0.6～20%, rest parts is carried out balance by Fe, and thickness is 1～500nm; Soft magnetism is Fe, Co or FeCo alloy mutually, and thickness is 1.5-50nm; The number of plies of Hard Magnetic phase layer and soft magnetism phase layer is respectively between 1～200 layer.
2, according to the described nano composite rare earth permanent magnet film material of claim 1, it is characterized in that: described rare-earth element R is at least a among Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Dy, Tb, Ho, Er, Tm, the Yb.
3, according to the described nano composite rare earth permanent magnet film material of claim 2, it is characterized in that: described rare-earth element R is at least a among Nd, Pr, the Dy.
4, by the described nano composite rare earth permanent magnet film material of claim 1, it is characterized in that: described Hard Magnetic has 2: 14: 1 phase structure mutually.
5, by the described nano composite rare earth permanent magnet film material of claim 1, it is characterized in that: the number of plies of described Hard Magnetic phase layer and soft magnetism phase layer is respectively between 1～100 layer.
6, by the described nano composite rare earth permanent magnet film material of claim 1, it is characterized in that: described Hard Magnetic phase layer thickness is 10～100nm.
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| CN1062545C (en) * | 1997-04-23 | 2001-02-28 | 黄俊夫 | Efficient organic fertilizer and producing method thereof |
| CN101552070B (en) * | 2008-12-31 | 2012-04-18 | 浙江师范大学 | Magnetic sensitive material with high sensitivity |
| CN102446626A (en) * | 2011-11-24 | 2012-05-09 | 安徽大学 | Method for preparing SmCo5 film by using element targets |
| CN107190242A (en) * | 2017-05-12 | 2017-09-22 | 华侨大学 | A kind of preparation method with a wide range of adjustable coercivity nano thickness rare-earth transition alloy firm |
| CN112133512B (en) * | 2020-08-24 | 2024-04-19 | 宁波晨洋磁材科技有限公司 | Rare earth iron-based permanent magnet material, preparation method and vacuum hot press |
| CN113444942B (en) * | 2021-06-28 | 2022-03-18 | 包头稀土研究院 | Ferromanganese-based magnetic composite material and design method and manufacturing method thereof |
| CN114999801B (en) * | 2022-05-26 | 2023-07-21 | 中国科学院金属研究所 | Method for improving coercive force of NdFeB-based permanent magnetic thick film |
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