CN108624852A - A kind of ferrozirconium amorphous multilayer film of high-curie temperature and preparation method thereof - Google Patents

A kind of ferrozirconium amorphous multilayer film of high-curie temperature and preparation method thereof Download PDF

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CN108624852A
CN108624852A CN201710153336.5A CN201710153336A CN108624852A CN 108624852 A CN108624852 A CN 108624852A CN 201710153336 A CN201710153336 A CN 201710153336A CN 108624852 A CN108624852 A CN 108624852A
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amorphous
multilayer film
curie temperature
ferrozirconium
thickness
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CN108624852B (en
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孙铭
吴斌
冯涛
彭国
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/001—Amorphous alloys with Cu as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/02—Amorphous alloys with iron as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thin Magnetic Films (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses ferrozirconium amorphous multilayer films of a kind of high-curie temperature and preparation method thereof.Amorphous multilayer film is Fe75Zr25/Cu64Zr36Material, thickness in monolayer 10nm, totally 50 layers.Non-crystaline amorphous metal of the present invention also has higher Curie temperature while with FeZr single thin film material advantages, is higher than room temperature 300K, be the top performance that current FeZr amorphous system reaches, it can be achieved that FeZr systems extensive use.

Description

A kind of ferrozirconium amorphous multilayer film of high-curie temperature and preparation method thereof
Technical field
The invention belongs to amorphous alloy field, more particularly to a kind of Curie temperature is higher than room temperature, has preferable application Fe-based amorphous multilayer film alloy and preparation method thereof.
Background technology
Amorphous alloy is a kind of with shortrange order, the alloy material of longrange disorder structure.Atom in amorphous is nothing Sequence arrangement, and there is no the vacancy in amorphous metal, dislocation, crystal boundaries and the defects of fault.The unique design feature of amorphous, Bring unique performance, such as very high catalyzing activation, outstanding biocompatibility, excellent soft magnetism, high intensity, High rigidity etc..
Amorphous multi-layer film material has more complicated interfacial structure, this has change, the raising of performance important Effect.The excellent magnetics of amorphous multi-layer film material, mechanics and photoelectric properties, are applied in multiple fields.Than Such as, Fe/Cr nano-multilayer films show giant magnetoresistance effect in external magnetic field, it will are that area information storage is very promising Material.
It is as soft magnetic materials field that amorphous alloy material, which is developed at most,.Non-crystalline material is unordered because its interior atoms Arrangement, and crystal boundary, Section 2 particle is not present to the pinning effect of domain wall, coercivity is lower, magnetic conductivity higher.FeZr amorphous Alloy material, the superconductivity having by its own, ferromagnetism, spin glass, anti-ferromagnetism become the hot spot of current research. But the Curie temperature of tradition FeZr non-crystaline amorphous metals is relatively low, about 200K, is less than room temperature, limits it in miniature device and room Application under temperature, in order to solve these problems, a kind of FeZr systems non-crystaline amorphous metal with high-curie temperature of exploitation just seem outstanding It is important.
Invention content
The purpose of the present invention is analyzing in view of the above technology and there are problems, a kind of ferrozirconium amorphous of high-curie temperature is provided Multilayer film and preparation method thereof.
Realize that the technical solution of the object of the invention is：A kind of ferrozirconium amorphous multilayer film of high-curie temperature, ingredient are Fe75Zr25/Cu64Zr36, the thickness of each monofilm is 10nm, and the number of plies is 50 layers.
The Fe75Zr25/Cu64Zr36The Curie temperature of amorphous multilayer film is more than 300K.
Above-mentioned multi-layer film material preparation method is as follows：
(1) Fe has been selected75Zr25、Cu64Zr36Alloys target selects clean Si (111) single-chips as substrate base, high-purity Argon gas is working gas, dry gas of the nitrogen as chamber；
(2) when sputtering, forvacuum to 1*10-4Pa is hereinafter, be passed through argon gas so that pressure reaches 0.5Pa, target as sputter work( Rate is 30W, and the growth thickness for controlling each monofilm is 10nm, and the growth number of plies is 50 layers.
Further, in step (2), by controlling Fe75Zr25The sputtering time of alloys target is 400s, Cu64Zr36Alloys target Sputtering time be 150s, the growth thickness that cycle-index is 25 times to control each monofilm is 10nm, growth the number of plies be 50 Layer.
Compared with prior art, advantages of the present invention：
There is non-crystaline amorphous metal made from the method excellent soft magnet performance, Curie temperature to be higher than through the invention 300K, and the Curie temperature for the FeZr non-crystaline amorphous metal systems reported at present is in 200K or so.
Description of the drawings
Fig. 1 is the Fe that embodiment 1 obtains75Zr25/Cu64Zr36Multilayer film actual (real) thickness section SEM figures.
Fig. 2 is the Fe that embodiment 1 obtains75Zr25/Cu64Zr36The practical XRD diagram of multilayer film.
Fig. 3 is the Fe that embodiment 1 obtains75Zr25/Cu64Zr36The ZFC-FC curves of multilayer film.
Fig. 4 is the Fe that embodiment 1 obtains75Zr25/Cu64Zr36The M-H curves of multilayer film are (at a temperature of a is 4K
M-H curves, b are the M-H curves at a temperature of 300K).
Specific implementation mode
The present invention is described in further detail below in conjunction with attached drawing and example.
Embodiment 1
The example prepares Fe using magnetron sputtering method75Zr25/Cu64Zr36X-ray diffractometer is used in combination in amorphous multilayer film, scanning Electronic Speculum carries out structural characterization, and comprehensive physical property measuring system carries out Magnetic Test.
(1) Fe has been selected75Zr25Alloys target, Cu64Zr36Alloys target, a diameter of 50mm of thickness 3mm, target.It selects For clean Si (111) single-chips as substrate base, high-purity argon gas is working gas, dry gas of the nitrogen as chamber.
(2) when sputtering, forvacuum to 1*10-4Pa is hereinafter, be passed through argon gas so that pressure reaches 0.5Pa.Target as sputter work( Rate is 30W, prepares the Fe of single layer respectively75Zr25Film, Cu64Zr36Film is used in combination SEM to observe section thickness, when 2 hours plated films Between, Fe75Zr25Film thickness is 180nm, Cu64Zr36Film thickness is 480nm, obtains the growth rate of film.
(3) Fe of 10nm thickness in monolayer is prepared75Zr25/Cu64Zr36Multilayer film is programmed using computer control system, is realized Control to each target switch time and cycle-index, design parameter such as table 1.
1 coating process parameter of table
Using the non crystalline structure of XRD characterization film, test result such as Fig. 1 is only existed in the XRD spectrum of sample one wide Diffusing scattering peak, preferable non crystalline structure.And the thickness and ingredient of film, test result such as Fig. 2 and table are measured using SEM-EDS 2, discovery is prepared for that ingredient is more uniform, thickness very close to multi-layer film material.
2 Fe of table75Zr25/Cu64Zr36The component ratio of multilayer film
FeZr/CuZr Fe (at%) Cu (at%) Zr (at%) Ta (at%) Fe:Cu(at)
10nm 41 28 30 1 1.5:1
(4) magnetism of multilayer film is measured with comprehensive physical property measuring system, the test result of ZFC-FC curves is as schemed The test result of 3, M-H curves such as Fig. 4.It was found that the Curie temperature of multi-layer film material is apparently higher than 300K, magnetic is saturated at a temperature of 4K Change intensity is 0.75 μB, saturation intensity is 0.58 μ at a temperature of 300KB。
Comparing embodiment 1
The example prepares Fe using magnetron sputtering method75Zr25Amorphous monofilm, is used in combination X-ray diffractometer, scanning electron microscope into Row structural characterization, comprehensive physical property measuring system carry out Magnetic Test.
(1) Fe has been selected75Zr25Alloys target, a diameter of 50mm of thickness 3mm, target select clean Si (111) single For chip as substrate base, high-purity argon gas is working gas, dry gas of the nitrogen as chamber.
(2) when sputtering, forvacuum to 1*10-4Pa is hereinafter, be passed through argon gas so that pressure reaches 0.5Pa.Target as sputter work( Rate is 30W, prepares the Fe that thickness in monolayer is 250nm75Zr25Film.
(3) as a result the structure that sample is characterized with X-ray diffraction method shows that one is only existed in the XRD spectrum of sample is wide Diffusing scattering peak, preferable non crystalline structure.And the thickness and ingredient of film are measured using SEM-EDS, it is found that sample composition is more equal Even, thickness is about 250nm.
(4) magnetism of multilayer film is measured with comprehensive physical property measuring system, including M-H, ZFC-FC curve.As a result it shows Show Fe75Zr25The saturation magnetization of amorphous monofilm is close with multilayer film, but Curie temperature is less than room in 200K or so Temperature.
Comparing embodiment 2
Document Finite-size effects in amorphous Fe90Zr10/ are used in comparing embodiment 2 Al75Zr25 multilayers, P.T.Korelis et.al, PHYSICAL REVIEW B, in 85,214430 (2012) Fe90Zr10/Al75Zr25 amorphous multi-layer film materials, equally analyze Curie temperature and saturation magnetization, find the multilayer film The Curie temperature of material is below 200K.

Claims (4)

1. a kind of ferrozirconium amorphous multilayer film of high-curie temperature, which is characterized in that its ingredient is Fe75Zr25/Cu64Zr36, Mei Yidan The thickness of tunic is 10nm, and the number of plies is 50 layers.
2. ferrozirconium amorphous multilayer film as described in claim 1, which is characterized in that the Fe75Zr25/Cu64Zr36Amorphous multilayer The Curie temperature of film is more than 300K.
3. the preparation method of ferrozirconium amorphous multilayer film as claimed in claim 1 or 2, which is characterized in that steps are as follows：
(1) Fe has been selected75Zr25、Cu64Zr36Alloys target selects clean Si (111) single-chips as substrate base, high-purity argon gas For working gas, dry gas of the nitrogen as chamber；
(2) when sputtering, forvacuum to 1*10-4Pa is hereinafter, be passed through argon gas so that pressure reaches 0.5Pa, and target as sputter power is 30W, the growth thickness for controlling each monofilm are 10nm, and the growth number of plies is 50 layers.
4. method as claimed in claim 3, which is characterized in that in step (2), by controlling Fe75Zr25When the sputtering of alloys target Between be 400s, Cu64Zr36The sputtering time of alloys target is 150s, cycle-index is 25 times thick to control the growth of each monofilm Degree is 10nm, and the growth number of plies is 50 layers.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109930122A (en) * 2019-03-28 2019-06-25 西安交通大学 A method of it is heterogeneous to prepare homogeneity amorphous multilayer membrane change non crystalline structure
CN114147191A (en) * 2021-10-27 2022-03-08 宁波雄海稀土速凝技术有限公司 Casting and strip throwing process of ferrozirconium cast sheet

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001220656A (en) * 2000-01-07 2001-08-14 Korea Electrotechnology Research Inst Ion-zirconium-boron-silver soft magnetic material and method for deposition of thin film
CN1614070A (en) * 2004-09-23 2005-05-11 同济大学 Preparation for block amorphous nanometer crystal double-phase composite soft magnetic alloy
CN101104907A (en) * 2007-06-29 2008-01-16 北京航空航天大学 Nano-crystal soft-magnetic Fe44Co(43-x)Zr7B5Al(1+x) with high curie temperature
US20100265028A1 (en) * 2006-02-21 2010-10-21 Carnegie Mellon Univesity Soft magnetic alloy and uses thereof
CN106298141A (en) * 2016-10-11 2017-01-04 东南大学 A kind of Fe-based nanocrystalline magnetically soft alloy material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001220656A (en) * 2000-01-07 2001-08-14 Korea Electrotechnology Research Inst Ion-zirconium-boron-silver soft magnetic material and method for deposition of thin film
CN1614070A (en) * 2004-09-23 2005-05-11 同济大学 Preparation for block amorphous nanometer crystal double-phase composite soft magnetic alloy
US20100265028A1 (en) * 2006-02-21 2010-10-21 Carnegie Mellon Univesity Soft magnetic alloy and uses thereof
CN101104907A (en) * 2007-06-29 2008-01-16 北京航空航天大学 Nano-crystal soft-magnetic Fe44Co(43-x)Zr7B5Al(1+x) with high curie temperature
CN106298141A (en) * 2016-10-11 2017-01-04 东南大学 A kind of Fe-based nanocrystalline magnetically soft alloy material and preparation method thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
MARTINA AHLBERG ET AL.: "Reversed interface effects in amorphous FeZr/AlZr multilayers", 《PHYSICAL REVIEW B》 *
P.GORRIA ET AL.: "Crystallisation and polymorphic transformations in Fe–Zr", 《PHYSICA B》 *
PARMANAND SHARMA ET AL.: "Magnetic behavior of cosputtered Fe-Zr amorphous thin films exhibiting perpendicular", 《PHYSICAL REVIEW B》 *
PEDRO GORRIA ET AL.: "Crystallization of Fe75Zr25 metallic glass: a two-step process involving metastable bcc-Fe and polymorphic transformation", 《PHYSICA STATUS SOLIDI-RAPID RESEARCH LETTERS》 *
R.PIZARRO ET AL.: "Synthesis and characterisation of amorphous Fe75Zr25", 《JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109930122A (en) * 2019-03-28 2019-06-25 西安交通大学 A method of it is heterogeneous to prepare homogeneity amorphous multilayer membrane change non crystalline structure
CN109930122B (en) * 2019-03-28 2020-06-19 西安交通大学 Method for preparing homogeneous amorphous multilayer film to change heterogeneity of amorphous structure
CN114147191A (en) * 2021-10-27 2022-03-08 宁波雄海稀土速凝技术有限公司 Casting and strip throwing process of ferrozirconium cast sheet
CN114147191B (en) * 2021-10-27 2023-02-07 宁波雄海稀土速凝技术有限公司 Casting and strip throwing process of ferrozirconium cast sheet

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