CN103628004B - A kind of method adopting low-temperature annealing to prepare amorphous NiW alloy firm - Google Patents
A kind of method adopting low-temperature annealing to prepare amorphous NiW alloy firm Download PDFInfo
- Publication number
- CN103628004B CN103628004B CN201310563319.0A CN201310563319A CN103628004B CN 103628004 B CN103628004 B CN 103628004B CN 201310563319 A CN201310563319 A CN 201310563319A CN 103628004 B CN103628004 B CN 103628004B
- Authority
- CN
- China
- Prior art keywords
- target
- alloy firm
- temperature annealing
- amorphous
- annealing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a kind of method adopting low-temperature annealing to prepare amorphous NiW alloy firm, it the nanometer crystalline Ni W alloy film of magnetron sputtering deposition state is placed in vacuum annealing furnace low-temperature annealing to prepare intimate complete decrystallized NiW alloy firm.The method is simple, easy, avoids the great quenching velocity needed for conventional metals non-crystalline material preparation method.The method adopts reliable vacuum annealing and two target magnetic control sputtering technology, and repeatable high, workable, cost is low, is easy to industrially realize and promote.
Description
Technical field
The invention belongs to alloy firm technical field, relate to a kind of amorphous NiW alloy firm, especially a kind of method adopting low-temperature annealing to prepare amorphous NiW alloy firm.
Background technology
Amorphous metal material, also known as metallic glass, its internal structure has unformed feature, and namely atomic arrangement does not possess long-range order, and inside does not have the crystal structure defects such as dislocation, crystal boundary.Therefore compared with crystalline material, metallic glass has the performance of many uniquenesses, as: metallic glass has the Young's modulus suitable with metal polycrystalline material, but the room temperature strength higher than metal polycrystalline material is had, and close to compressive strength, the good elasticity performance (elastic limit strain about 2%) of theoretical value, also there is good soft magnetic performance, corrosion-resistant and wear resisting property etc. simultaneously.Its achievement in research has been widely used in MEMS (micro electro mechanical system) (MEMS), nano electromechanical systems (NEMS) device, information apparatus, the research and development of the contour frontier of senser element and design.
Traditional amorphous metal material preparation is all reached by non-equilibrium treatment technology, mainly comprises: rapid solidification process (RSP), mechanical alloy, plasma treatment, vapour deposition and jet deposition etc.Its ultimate principle is " activating and quenching ", and namely first by providing large energy to material someway, make its internal structure far from equilibrium state, then rapid quenching makes its internal structure rest on metastable state.The key of this technology and difficult point obtain great quench rates (~ 10
5-10
6ks
-1).And we prepare by annealing amorphous NiW alloy firm by the nanometer crystalline Ni W alloy thin film low temperature prepared magnetron sputtering deposition.This method avoids great quenching velocity, simple, and cost is low, has enriched the preparation method of amorphous metal material.To further retrieval and the analysis of document, not yet find so far and the same or analogous report of the technology of the present invention theme.
Summary of the invention
The object of the invention is to the shortcoming overcoming above-mentioned prior art, a kind of method adopting low-temperature annealing to prepare amorphous NiW alloy firm is provided, the method, by the nanometer crystalline Ni W alloy cryogenic vacuum annealing prepared by magnetron sputtering deposition, prepares intimate complete decrystallized NiW alloy firm.
The object of the invention is to be achieved through the following technical solutions:
This employing low-temperature annealing prepares the method for amorphous NiW alloy firm, and nanometer crystalline Ni W alloy film is placed in vacuum annealing furnace, prepares amorphous NiW alloy firm by low-temperature annealing.
Above-mentioned nanometer crystalline Ni W alloy film magnetron sputtering codeposition prepares gained.
Above-mentioned nanometer crystalline Ni W alloy film and amorphous NiW alloy firm composition are Ni
77w
23.
Further, above-mentioned employing low-temperature annealing prepares the method for amorphous NiW alloy firm, specifically comprises the following steps:
1) single-sided polishing monocrystalline silicon substrate is used respectively acetone and ultrasonic 30 minutes of alcohol, dry up, put on the rotatable base bracing frame of vacuum magnetic-control sputtering equipment, prepare plated film;
2) Ni source metal target is placed in as A target on A target seat, and W source metal target is placed in as B target on B target seat, during work, first matrix rotary knob is opened, rotating speed be 1 circle/minute, then vacuum chamber, passes into Ar gas to vacuum chamber; Start codeposition, by the atom ratio regulating electric current, voltage changes sputtering power control Ni and W, regulate depositing time to control film thickness, deposit so simultaneously and prepare nanometer crystalline Ni W alloy film;
3) the nanometer crystalline Ni W alloy film prepared by magnetron sputtering deposition is placed in annealing furnace, then air pressure in stove is evacuated to 1 × 10
-3pa, regulate annealing temperature to 473K, arranging annealing time is 1 hour, and annealing terminates rear stove and is chilled to room temperature.
Further, above-mentioned steps 2) in, described vacuum chamber to air pressure is 5 × 10
-4pa, then passes into Ar gas in vacuum chamber, make air pressure be 3 × 10
-1pa.
Further, in above-mentioned steps, the purity of sputtering target material is all greater than 99.95%.
Further, step 2) in, direct current pulse power source selected by described A target, and sputtering power is 124W, and sedimentation rate is 8-10nm/min.
Further, step 2) in, direct current pulse power source selected by described B target, and sputtering power is 65W, and sedimentation rate is 1-2nm/min.
Further, during codeposition, the magnetically controlled DC sputtering voltage of A target is 325V; The magnetically controlled DC sputtering voltage of B target is 350V, and negative bias is 100V, and the distance of matrix and target is 8-10cm.
Further, in above step, by the atom ratio regulating electric current, voltage changes sputtering power control Ni and W, it is made to reach Ni
77w
23.
The present invention compared with prior art has following beneficial effect:
(1) low-temperature annealing legal system of the present invention is for the method for amorphous NiW alloy firm, simply, easy, avoids the great quenching velocity needed for traditional amorphous metal material preparation method.
(2) low-temperature annealing legal system of the present invention is for the method for amorphous NiW alloy firm, and the amorphous NiW alloy firm composition of preparation is Ni
77w
23(at.%), traditional amorphous metal material preparation method is difficult to the amorphous NiW alloy preparing this composition.
(3) the present invention adopts vacuum annealing and two target magnetic control sputtering technology, this technically reliable, and repeatable high, workable, cost is low, is easy to industrially realize and promote.
Accompanying drawing explanation
Fig. 1 is the energy spectrum analysis of magnetron sputtering deposition state nanometer crystalline Ni W alloy film and annealed state amorphous NiW alloy firm;
Fig. 2 is magnetron sputtering deposition state nanometer crystalline Ni W alloy film, and 473K anneals 30 minutes (NiW
30min) and 473K to anneal 1 hour (NiW
60min) the XRD analysis of NiW alloy firm;
Fig. 3 is magnetron sputtering deposition state nanometer crystalline Ni W alloy film, and 473K anneals 30 minutes (NiW
30min) and 473K to anneal 1 hour (NiW
60min) NiW alloy firm cross section TEM scheme and diffraction analysis;
Fig. 4 is magnetron sputtering deposition state nanometer crystalline Ni W alloy film, and 473K anneals 30 minutes (NiW
30min) and 473K to anneal 1 hour (NiW
60min) the high resolution cross section TEM of NiW alloy firm scheme;
Embodiment
The present invention adopts low-temperature annealing to prepare the method for amorphous NiW alloy firm, is nanometer crystalline Ni W alloy film is placed in vacuum annealing furnace, prepares amorphous NiW alloy firm by low-temperature annealing.Described nanometer crystalline Ni W alloy film magnetron sputtering codeposition prepares gained.Described nanometer crystalline Ni W alloy film and amorphous NiW alloy firm composition are Ni
77w
23(at.%).
The method applied in the present invention cardinal principle is: composition is Ni
77w
23(at.%) nanometer crystalline Ni W alloy, due to its metastable structure with close to Ni
4the composition of W, in low-temperature annealing process, first alloy structure main body changes Ni into
4w phase, simultaneously in the W atom enrichment of some regions, has met or exceeded the solid solubility limit that NiW amorphous phase occurs, thus has occurred amorphous phase in these regions.Along with carrying out further of annealing, the free volume delocalization of amorphous phase and the interaction with nanometer crystalline phase thereof, make alloy monolithic decrystallized.
Method of the present invention specifically comprises the following steps:
1) single-sided polishing monocrystalline silicon substrate is used respectively acetone and ultrasonic 30 minutes of alcohol, dry up, put on the rotatable base bracing frame of vacuum magnetic-control sputtering equipment, prepare plated film;
2) be placed in Ni source metal target as A target on A target seat, and be placed in W source metal target as B target on B target seat, the purity of sputtering target material is all greater than 99.95%.During work, first matrix rotary knob is opened, rotating speed be set to 1 circle/minute, then the air pressure of vacuum chamber to be evacuated to ~ 5 × 10
-4pa, the Ar gas passing into 30sccm, to vacuum chamber, makes its operating air pressure be 3 × 10
-1pa.Direct current pulse power source selected by A target, and sputtering power is 124W, and sputtering voltage is 325V, and sedimentation rate is 8-10nm/min; B target also selects direct current pulse power source, and sputtering power is 65W, and sputtering voltage is 350V, and sedimentation rate is 1-2nm/min; Negative bias is 100V, and the distance of matrix and target is 8-10cm.Deposition prepares nanometer crystalline Ni W alloy film so simultaneously, by regulating the time controlled made membrane thickness of deposition.Described matrix, during its deposition, envrionment temperature is room temperature, is about 290-300K.
3) the nanometer crystalline Ni W alloy film prepared by magnetron sputtering deposition is placed in annealing furnace, then air pressure in stove is evacuated to ~ 1 × 10
-3pa, regulate annealing temperature to 473K, arranging annealing time is 1 hour, and annealing terminates rear stove and is chilled to room temperature.
Fig. 1 is the energy spectrum analysis of magnetron sputtering deposition state nanometer crystalline Ni W alloy film and annealed state amorphous NiW alloy firm, and result shows, and before and after annealing, the composition of NiW alloy firm, without considerable change, is ~ Ni
77w
23(at.%).
Fig. 2 is magnetron sputtering deposition state nanometer crystalline Ni W alloy film, and 473K anneals 30 minutes (NiW
30min) and 473K to anneal 1 hour (NiW
60min) the XRD analysis of NiW alloy firm, result shows, along with the prolongation of annealing time, film non-crystallization degree aggravates.Magnetron sputtering deposition state NiW alloy is the fcc nanocrystalline structure of standard, namely W atom is solid-solution in the Ni matrix of fcc, its three strongest ones peak position is high-visible, i.e. (111) peak (2 θ=43.31 °), (200) peak (2 θ=50.13 °) and peak, (220) (2 θ=74.42 °); Through 30 minutes anneal, crystalline body structural transformation was the Ni of body-centered teteragonal (bct)
4w structure, its three strongest ones' peak body position changes, Ni(W) (111) peak (2 θ=43.31 °) change Ni into
4w (211) peak (2 θ=43.52 °), Ni(W) (200) peak (2 θ=50.13 °) change Ni into
4w (130) (2 θ=50.34 °), and Ni(W) there is not considerable change in (220) peak (2 θ=74.42 °), and peak weakens by force, peak width increases, and decrystallized may generation is described; Through 1 hour anneal, crystalline body structure changed non-crystal structure into, and three strongest ones peak disappears all, and only in 2 θ=43.52, there is an amorphous peak at a ° peak position place, illustrated that non-crystallization degree is more complete.
Fig. 3 is magnetron sputtering deposition state nanometer crystalline Ni W alloy film, and 473K anneals 30 minutes (NiW
30min) and 473K to anneal 1 hour (NiW
60min) NiW alloy firm cross section TEM scheme and diffraction analysis.As shown in Fig. 3 (a) He (d), magnetron sputtering deposition state NiW alloy is nanometer columnar crystal structure, membrane plane direction grain-size is about 10nm, the dozens or even hundreds of nanometer of film direction of growth grain-size, and corresponding diffraction images of choosing is bright and sharp nanocrystalline diffraction spot; After 30 minutes anneal, alloy structure main body is still nanometer column crystal, as shown in Fig. 3 (b) He (e), but has subregion decrystallized, and corresponding selected diffraction photo occurs halation; After 1 hour anneal, alloy bulk structure has been converted into shown in non-crystal structure Fig. 3 (c) He (f), and corresponding selected diffraction only exists minority crystal spot, and the overwhelming majority is amorphous halation.In figure, red arrow represents film growth direction.
Fig. 4 is magnetron sputtering deposition state nanometer crystalline Ni W alloy film, and 473K anneals 30 minutes (NiW
30min) and 473K to anneal 1 hour (NiW
60min) the high resolution cross section TEM of NiW alloy firm scheme.Fig. 4 (a) shows, and magnetron sputtering deposition state NiW alloy firm is nanocrystalline structure, and lattice crystal boundary is high-visible; And through 30 minutes anneal, crystals occurred that local is decrystallized, a-quadrant as shown in Figure 4 (b); After 1 hour anneal, alloy bulk structure is almost completely decrystallized, as shown in Figure 4 (c).
More than illustrate that method of the present invention successfully can prepare amorphous NiW alloy firm, meanwhile, because sedimentation rate is relative with annealing time fixing, writing and setting by related computer program, is convenient to realize suitability for industrialized production and popularization.
Claims (7)
1. adopt low-temperature annealing to prepare a method for amorphous NiW alloy firm, it is characterized in that, nanometer crystalline Ni W alloy film is placed in vacuum annealing furnace, prepare amorphous NiW alloy firm by low-temperature annealing; Described nanometer crystalline Ni W alloy film magnetron sputtering codeposition prepares gained; Described nanometer crystalline Ni W alloy film and amorphous NiW alloy firm composition are Ni
77w
23; Specifically comprise the following steps:
1) single-sided polishing monocrystalline silicon substrate is used respectively acetone and ultrasonic 30 minutes of alcohol, dry up, put on the rotatable base bracing frame of vacuum magnetic-control sputtering equipment, prepare plated film;
2) Ni source metal target is placed in as A target on A target seat, and W source metal target is placed in as B target on B target seat, during work, first make matrix rotate, then vacuum chamber, pass into Ar gas to vacuum chamber; Start codeposition, by the atom ratio regulating electric current, voltage changes sputtering power control Ni and W, regulate depositing time to control film thickness, deposit so simultaneously and prepare nanometer crystalline Ni W alloy film;
3) the nanometer crystalline Ni W alloy film prepared by magnetron sputtering deposition is placed in annealing furnace, then air pressure in stove is evacuated to 1 × 10
-3pa, regulate annealing temperature to 473K, arranging annealing time is 1 hour, and annealing terminates rear stove and is chilled to room temperature.
2. employing low-temperature annealing according to claim 1 prepares the method for amorphous NiW alloy firm, it is characterized in that, step 2) in, matrix rotate rotating speed be 1 circle/minute; Described vacuum chamber to air pressure is 5 × 10
-4pa, then passes into Ar gas in vacuum chamber, make air pressure be 3 × 10
-1pa.
3. employing low-temperature annealing according to claim 1 prepares the method for amorphous NiW alloy firm, it is characterized in that, the purity of sputtering target material is all greater than 99.95%.
4. employing low-temperature annealing according to claim 1 prepares the method for amorphous NiW alloy firm, it is characterized in that, step 2) in, direct current pulse power source selected by described A target, and sputtering power is 124W, and sedimentation rate is 8-10nm/min.
5. employing low-temperature annealing according to claim 1 prepares the method for amorphous NiW alloy firm, it is characterized in that, step 2) in, direct current pulse power source selected by described B target, and sputtering power is 65W, and sedimentation rate is 1-2nm/min.
6. employing low-temperature annealing according to claim 1 prepares the method for amorphous NiW alloy firm, it is characterized in that, during codeposition, the magnetically controlled DC sputtering voltage of A target is 325V; The magnetically controlled DC sputtering voltage of B target is 350V, and negative bias is 100V, and the distance of matrix and target is 8-10cm.
7. employing low-temperature annealing according to claim 1 prepares the method for amorphous NiW alloy firm, it is characterized in that, by the atom ratio regulating electric current, voltage changes sputtering power control Ni and W, makes it reach Ni
77w
23.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310563319.0A CN103628004B (en) | 2013-11-11 | 2013-11-11 | A kind of method adopting low-temperature annealing to prepare amorphous NiW alloy firm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310563319.0A CN103628004B (en) | 2013-11-11 | 2013-11-11 | A kind of method adopting low-temperature annealing to prepare amorphous NiW alloy firm |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103628004A CN103628004A (en) | 2014-03-12 |
| CN103628004B true CN103628004B (en) | 2016-02-24 |
Family
ID=50209448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310563319.0A Active CN103628004B (en) | 2013-11-11 | 2013-11-11 | A kind of method adopting low-temperature annealing to prepare amorphous NiW alloy firm |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103628004B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105039875B (en) * | 2015-08-24 | 2017-04-12 | 浙江大学 | Ni-Nb metal thin film with ultra-low roughness and preparation method of Ni-Nb metal thin film |
| CN106244999B (en) * | 2016-08-30 | 2019-02-19 | 南通壹选工业设计有限公司 | A kind of preparation method of bulk amorphous alloys |
| CN111218657B (en) * | 2020-01-03 | 2021-07-30 | 北京工业大学 | Amorphous tungsten-based high-entropy alloy thin film material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101532153A (en) * | 2009-03-13 | 2009-09-16 | 甘军 | Amorphous nano-alloy plating layer of electrodeposition nickel-based series, electroplating liquid and electroplating process |
| CN102304679A (en) * | 2011-09-28 | 2012-01-04 | 宋玉军 | Amorphous nanocrystal gradient functional material and preparation method thereof |
| CN102912295A (en) * | 2012-11-06 | 2013-02-06 | 浙江大学 | High-elasticity metal film material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5395991B2 (en) * | 2009-03-29 | 2014-01-22 | ダブリュディ・メディア・シンガポール・プライベートリミテッド | Method for manufacturing perpendicular magnetic recording medium |
-
2013
- 2013-11-11 CN CN201310563319.0A patent/CN103628004B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101532153A (en) * | 2009-03-13 | 2009-09-16 | 甘军 | Amorphous nano-alloy plating layer of electrodeposition nickel-based series, electroplating liquid and electroplating process |
| CN102304679A (en) * | 2011-09-28 | 2012-01-04 | 宋玉军 | Amorphous nanocrystal gradient functional material and preparation method thereof |
| CN102912295A (en) * | 2012-11-06 | 2013-02-06 | 浙江大学 | High-elasticity metal film material |
Non-Patent Citations (1)
| Title |
|---|
| A combinatorial study on the influence of elemental composition and heat treatment on the phase composition， microstructure and mechanical properties of Ni–W alloy thin films;C.Borgia et al;《Acta Materialia》;20101020;第59卷;第387页左栏第18行-右栏第16行、第390页左栏倒数第5-7行、第393页左栏第7-22行、表1、图2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103628004A (en) | 2014-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103215555B (en) | A kind of cosputtering legal system that adopts is for the method for amorphous-nano-crystalline composite membrane | |
| CN107354506B (en) | A method of preparing super smooth copper single crystal film | |
| CN101665905B (en) | Aluminum-induced low temperature preparation method of large grain size polysilicon film | |
| CN103628004B (en) | A kind of method adopting low-temperature annealing to prepare amorphous NiW alloy firm | |
| CN108193276B (en) | Method for preparing large-area single-orientation hexagonal boron nitride two-dimensional atomic crystal | |
| CN102243991B (en) | Method for inducing amorphous silicon film with tin to be crystallized into polycrystalline silicon film | |
| CN110273176B (en) | Method for preparing large-area copper Cu (111) single crystal | |
| CN101740358A (en) | Method for preparing P type poly-silicon thin film on glass substrate | |
| CN201358298Y (en) | Magnetron and pulsed laser codeposition apparatus | |
| CN102931055B (en) | Method for thinning multilayer graphene | |
| CN102925870A (en) | Preparation method of Zr-Cu-Ni-Al-Si metal amorphous film material | |
| CN112359421A (en) | Method for preparing layered bismuth-oxygen-selenium semiconductor film by reverse airflow method | |
| CN105925937B (en) | It is orientated the preparation method of thin magnetic film | |
| CN104674161A (en) | Method for improving spin-orbit coupling strength of Co/Pt thin film material | |
| CN107299316A (en) | A kind of method for preparing amorphous nanocrystalline coating in Zr alloy surface | |
| CN101696481B (en) | Preparation method of ultrahigh recovery stress Ti-Ni-Cu shape memory alloy thin film | |
| CN102418078A (en) | Preparation method for ultrahigh-strength nanocrystalline metal Ru film | |
| CN101202144A (en) | Method for preparing Fe-Mn-Si magnetic shape memory alloy film | |
| CN108220897B (en) | The method of magnetron sputtering low temperature preparation vanadium dioxide film | |
| CN116752095A (en) | Preparation method of gamma-phase germanium selenide nano-sheet | |
| CN102877035A (en) | Method for preparing silicon-based germanium film with low-temperature buffer layer by means of cyclic stress modulation | |
| CN102747337B (en) | Method for preparing amorphous carbon film with large area and high quality | |
| CN103374706A (en) | Method for preparing polycrystalline silicon film | |
| CN100554500C (en) | A kind of adulterated method of cobalt that in zinc-oxide nano column, realizes | |
| CN100400703C (en) | Method for preparing film material of metal hafnium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190415 Address after: No. 721 Yanhu Road, Jiangshan Town, Yinzhou District, Ningbo City, Zhejiang Province, 315000 Patentee after: Ningbo Yuntu Technology Co., Ltd. Address before: No. 28 Xianning West Road, Xianning stele area, Xi'an, Shaanxi Patentee before: Xi'an Jiaotong University |
|
| TR01 | Transfer of patent right |