CN102925870A - Preparation method of Zr-Cu-Ni-Al-Si metal amorphous film material - Google Patents
Preparation method of Zr-Cu-Ni-Al-Si metal amorphous film material Download PDFInfo
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- CN102925870A CN102925870A CN2012104192815A CN201210419281A CN102925870A CN 102925870 A CN102925870 A CN 102925870A CN 2012104192815 A CN2012104192815 A CN 2012104192815A CN 201210419281 A CN201210419281 A CN 201210419281A CN 102925870 A CN102925870 A CN 102925870A
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Abstract
The invention discloses a preparation method of a Zr-Cu-Ni-Al-Si metal amorphous film material. The preparation method adopts a magnetron sputtering technology. The Zr-Cu-Ni-Al-Si metal amorphous film material obtained by the preparation method has a fully-amorphous structure and has a controllable size distribution and a controllable deposition rate. The preparation method can realize preparation of the Zr-Cu-Ni-Al-Si metal amorphous film material having a compact structure and high surface quality, can control an amorphous film deposition rate by a change of film parameters, and provides an approach for preparation of an amorphous film material having a fully-amorphous structure and a controllable size. The preparation method can realize preparation of the Zr-Cu-Ni-Al-Si metal amorphous film material which has a clear amorphous structure and is compact and flat, can keep a stable amorphous structure by control thereby changing a film size, and provides an approach for preparation of an amorphous film material having a controllable size. The preparation method has simple processes and a low cost and can be popularized and industrialized easily.
Description
Technical field
The invention belongs to the metallic film material technical field, relate to a kind of preparation of non-crystal structure metallic film material, especially a kind of method that adopts magnetron sputtering technique to prepare Zr Base Metal noncrystal membrane.
Background technology
The glass that is comprised of metallic bond is called metallic glass.Be different from the glass that is comprised of other keys, it is the most difficult in all glass that metallic bond non-directional causes the preparation of metallic glass.Different from crystalline material, metallic glass has unordered, the short range order of long-range, does not have crystal boundary, does not have the special immanent structures such as crystal structure defects such as dislocation.So it has a lot of outstanding performances, such as: near the compressive strength of theoretical value, good elasticity performance (elastic limit strain about 2%), good soft magnetic performance, corrosion resistance nature and wear resisting property etc.
The sixties in last century, the people such as Klement have found metallic glass for the first time by the Au-Si alloy being carried out the rapid quenching experiment.From that time, seeking different element set merging keeps non-crystal structure once becoming one of study hotspot of metallic glass under lower critical cooling velocity.Along with the development of non-crystal technique, metal glass material has all been obtained breakthrough progress in all many-sides such as glass forming ability that increase sample size, exploitation new alloy system, raising metallic glass.The development of metallic glass develops into the bulk-metallic glass that present size can surpass 1mm gradually by early stage band shape, filament, pulverous fritter, thin sheet of metal glass.The preparation method of block metal glass has been tending towards ripe substantially at present, mainly comprises directional solidification method, induction heating copper mold teeming practice, arc melting copper mold casting etc.
With respect to traditional crystalline state microelectromechanical systems (MEMS) material, metallic glass has a lot of advantages, and for example: high strength does not have crystal boundary to cause it to have good corrosion resistance, good thermostability etc.In addition, its good hot workability makes the possibility that is processed into of the various complicated shapes of device.These are so that metallic glass has good application prospect in high-new Application Areass such as MEMS device, information apparatus, senser elements.Because the requirement of the continuous miniaturization of MEMS device, lightness development, the size of device constantly reduces, and it is complicated that shape constantly is tending towards, and the conventional blocks metallic glass can't satisfy the requirement of device miniaturization development based on the preparation method of quick cooling.How to make the metallic glass thin-film material cast aside the method for quick cooling, and obtain continuous, stable non-crystal structure and have controlled distribution of sizes to remain further to be studied.
The Zr base noncrystal alloy is with its good tensile property (1800MPa) at present, high microhardness (HV500-600), and extraordinary glass forming ability, with plastic forming ability (supercooled liquid is the about 100K of temperature range mutually), be considered to have good application prospect.It is controlled that the present invention is intended to propose a kind of novel size, fully the Zr Base Metal thin film technology method of the even structure densification of amorphous.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of preparation method of ZrCuNiAlSi amorphous metal thin-film material is provided, and the method adopts magnetron sputtering technique, and the metallic film of preparation has completely non-crystal structure, and distribution of sizes, sedimentation rate is controlled.The membrane structure of this technique preparation is fine and close, and surface quality is high, can be easy to control by changing the plated film parameter sedimentation rate of noncrystal membrane, thereby is the complete non-crystal structure of preparation, and the controlled Amorphous Films of size provides possibility.Simultaneously, the method is simple to operate, and cost is lower, is easy in industrial realization and popularization.
The objective of the invention is to solve by the following technical programs:
The preparation method of this ZrCuNiAlSi amorphous metal thin-film material may further comprise the steps:
1) the single-sided polishing monocrystalline silicon substrate is used respectively acetone and alcohol ultrasonic cleaning 15 ~ 30 minutes, after hair dryer dries up, put on the superhigh vacuum magnetron sputtering equipment chip bench, prepare plated film;
2) will be placed in by the quinary alloy target that Zr, Al, Cu, Ni, Si form on the target seat, the sputtering raste of the power control target by power supply in adjusting, sputtering power is 30W ~ 80W, the sedimentation rate of film is 2nm/min ~ 4nm/min; Adopt high-purity Ar as ionization of gas, gas velocity is 6.3sccm;
3) during the silicon chip sputtering sedimentation, adopt direct current pulse power source, in the sputter procedure, biasing adopts the intermittently every deposition 5 ~ 10min of depositional mode, suspends sputter 15min film is cooled off fully; Simultaneously chip bench is rotated, guarantees that noncrystal membrane is evenly fine and close, finally reach required thicknesses of layers size.
Further, above-mentioned steps 2) in, the atomicity percentage composition of the Zr of described quinary alloy target, Al, Cu, Ni, Si is respectively: 61%, 7.5%, 17.5%, 10%, 4%; The quinary alloy target is formed according to the atomic percent compacting at the pure element powder more than 99.999% by each purity.
Above-mentioned steps 2) in, the purity of described high-purity Ar is 99.99%.
The present invention has following beneficial effect:
The metallic film of the present invention preparation, non-crystal structure is distinct, and the rete densification is smooth, and it is constant to be easy to control non-crystal structure, and film dimensions is changed, thereby provides possibility for the controlled amorphous metal thin-film material of preparation size.And the method is simple to operate, and cost is lower, is easy in industrial realization and popularization.
Description of drawings
Fig. 1 is for intermittently depositing ZrCuNiAlSi amorphous metal thin-membrane section scanning electron microscope microtexture synoptic diagram.
Fig. 2 is for intermittently depositing ZrCuNiAlSi amorphous metal film surface scanning electron microscope microtexture synoptic diagram.
Fig. 3 is for intermittently depositing ZrCuNiAlSi amorphous metal film surface atomic force microscopy mirror microstructure synoptic diagram.
Fig. 4 intermittently deposits different thicknesses of layers ZrCuNiAlSi amorphous metal film X-ray diffraction analysis synoptic diagram.
Fig. 5 is for intermittently depositing ZrCuNiAlSi amorphous metal film cross section transmission electron microscope microtexture synoptic diagram.
Embodiment
The invention provides a kind of magnetron sputtering technique that utilizes, simultaneously in conjunction with the batch-plating technology, prepare the method for novel ZrCuNiAlSi amorphous metal thin-film material.The method may further comprise the steps
1) the single-sided polishing monocrystalline silicon substrate is used respectively acetone and alcohol ultrasonic cleaning 15 ~ 30 minutes, after hair dryer dries up, put on the superhigh vacuum magnetron sputtering equipment chip bench, prepare plated film.
2) with Zr
61Al
7.5Cu
17.5Ni
10Si
4(at%) be placed on the target seat as target (target is the quinary alloy target that forms according to the atomic percent compacting at the pure element powder more than 99.999% by various purity), control the sputtering raste of target by the power of power supply in adjusting, sputtering power is generally 30W ~ 80W, can suitably control film deposition rate, through test of many times, the sedimentation rate of film is approximately 2nm/min ~ 4nm/min.In addition, sputtering power is difficult for too high, and when power surpassed 100W, the film non-crystal structure can be destroyed; Adopt high-purity Ar (purity 99.99%) as main ionization of gas, gas velocity is 6.3sccm, guarantees effective glow discharging process.
3) during the silicon chip sputtering sedimentation, adopt direct current pulse power source, chip bench does not adopt heating or cooling way.In the sputter procedure, biasing does not adopt the intermittently every deposition 5 ~ 10min of depositional mode, suspends sputter 15min film is cooled off fully, if adopt successive sedimentation plated film mode, thereby the destruction that the plated film overlong time can cause film temperature to raise and may cause non-crystal structure.Simultaneously chip bench is rotated, guarantees that noncrystal membrane is evenly fine and close, finally reach required thicknesses of layers size.
Below in conjunction with specific embodiments and the drawings the present invention is done and to describe in further detail:
Present embodiment adopts Zr
61Al
7.5Cu
17.5Ni
10Si
4(at%) the quinary alloy target is as sputtering target material, and preparation has the Zr based film material of complete non-crystal structure.The specific embodiment of ZrCuNiAlSi amorphous metal film is as follows:
1) with diamond blade the monocrystalline silicon piece of single-sided polishing is cut into desired size, then with the respectively ultrasonic cleaning 20 minutes of acetone and raw spirit, after hair dryer dries up, put on the superhigh vacuum magnetron sputtering equipment chip bench.
2) according to Zr
61Al
7.5Cu
17.5Ni
10Si
4(at%) atomic percent uses purity to be placed on the target seat at the quinary alloy target gained quinary alloy target that the compacting of the pure element powder more than 99.999% forms, and closes the sputter hatch door, vacuumizes.
3) reach 3 * 10 when the base vacuum degree
-7During mba, open the argon bottle valve, the adjusting argon flow amount is 6.3sccm, opens pulse dc power, and regulating power is 30W, prepares sputter.
4) deposition process parameters: DC-pulse source power: 100W, substrate bias does not add, the rotation of additional substrate platform, depositing temperature: room temperature.Under this parameter, every deposition 5min, powered-down suspends plated film 15min, and after the deposit film cooling, repeated deposition and time-out process are until required coating film thickness.
Fig. 1 is for intermittently depositing ZrCuNiAlSi amorphous metal thin-membrane section scanning electron microscope microtexture synoptic diagram.Associativity is good between film and the base material, and thickness is about 2 μ m, and rete is fine and close, grows into film surface from substrate always.Fig. 2 has shown its surface scan Electronic Speculum structure iron, and as seen, the smooth densification of film surface does not have obvious crackle, and the defectives such as particle exist, and the film surface quality is high.Fig. 3 is the microanalysis of ZrCuNiAlSi film surface atomic power.As we can see from the figure, film surface is comprised of the microscopic particles of some row, and in conjunction with good, and the particle degree of fluctuating reaches Nano grade, only up to 7.78nm, its surperficial r.m.s. roughness value Rms reaches 1.010nm in the zone of 1.00 μ m * 1.00 μ m.
Fig. 4 intermittently deposits, and prepares different thicknesses of layers ZrCuNiAlSi amorphous metal film X-ray diffraction analysis synoptic diagram.The structural analysis of the ZrAlNiCuSi film of different thickness being carried out by XRD, can see 300nm, wide diffuse scattering peak (it is generally acknowledged that " steamed bun peak " halfwidth is exactly non-crystalline state greater than 3 degree) appears in 1mm and 2mm film near 2 θ=37 °, do not observe the diffraction peak that characterizes the crystal phase and occur, this shows that prepared film sample is non-crystal structure.Fig. 5 is ZrCuNiAlSi amorphous metal film cross section transmission electron microscope microtexture synoptic diagram, can see that therefrom atomic arrangement presents obvious labyrinth-like pattern, the phenomenon of local crystallization do not occur.Its selected area electron diffraction figure is shown as the wide and diffraction corona of disperse of center spot and one, and does not have diffractional lattice or the diffraction ring that characterizes the crystal phase.The complete amorphous structure of the film that further accurate Characterization is prepared.
More than these, illustrate that method of the present invention can prepare the higher novel ZrCuNiAlSi amorphous metal thin-film material of quality.Simultaneously, because pitch time is relative with sedimentation rate fixing, by the writing and setting of related computer program, be convenient to realize suitability for industrialized production and popularization.
Claims (3)
1. the preparation method of a ZrCuNiAlSi amorphous metal thin-film material is characterized in that, may further comprise the steps:
1) the single-sided polishing monocrystalline silicon substrate is used respectively acetone and alcohol ultrasonic cleaning 15 ~ 30 minutes, after hair dryer dries up, put on the superhigh vacuum magnetron sputtering equipment chip bench, prepare plated film;
2) will be placed in by the quinary alloy target that Zr, Al, Cu, Ni, Si form on the target seat, the sputtering raste of the power control target by power supply in adjusting, sputtering power is 30W ~ 80W, the sedimentation rate of film is 2nm/min ~ 4nm/min; Adopt high-purity Ar as ionization of gas, gas velocity is 6.3sccm;
3) during the silicon chip sputtering sedimentation, adopt direct current pulse power source, in the sputter procedure, biasing adopts the intermittently every deposition 5 ~ 10min of depositional mode, suspends sputter 15min film is cooled off fully; Simultaneously chip bench is rotated, guarantees that noncrystal membrane is evenly fine and close, finally reach required thicknesses of layers size.
2. the preparation method of ZrCuNiAlSi amorphous metal thin-film material according to claim 1 is characterized in that, the atomicity percentage composition of the Zr of described quinary alloy target, Al, Cu, Ni, Si is respectively: 61%, 7.5%, 17.5%, 10%, 4%; The quinary alloy target is formed according to the atomic percent compacting at the pure element powder more than 99.999% by each purity.
3. the preparation method of ZrCuNiAlSi amorphous metal thin-film material according to claim 1 is characterized in that step 2) in, the purity of high-purity Ar is 99.99%.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103215555A (en) * | 2013-04-11 | 2013-07-24 | 西安交通大学 | Method for preparing noncrystalline-nanocrystalline composite membrane by adopting co-sputtering method |
| CN104233207A (en) * | 2014-09-04 | 2014-12-24 | 兰州空间技术物理研究所 | Method for enhancing atomic oxygen attack resistance of paint film |
| CN104480443A (en) * | 2014-12-08 | 2015-04-01 | 中国人民解放军装甲兵工程学院 | Hard and tough nano composite ZrAlCuN coating and preparation method thereof |
| CN107130210A (en) * | 2017-05-03 | 2017-09-05 | 中国建筑材料科学研究总院 | Surface is coated with chalcogenide glass of infrared DLC protecting film and preparation method thereof |
| CN107829074A (en) * | 2017-10-31 | 2018-03-23 | 桂林电子科技大学 | A kind of non-crystaline amorphous metal reflective mirror and preparation method thereof |
| CN108588646A (en) * | 2018-04-12 | 2018-09-28 | 西安交通大学 | A method of preparing the amorphous/amorphous nano-multilayer film of plasticity raising |
| CN109811309A (en) * | 2019-01-25 | 2019-05-28 | 广东工业大学 | A kind of high-purity Bulk Nanocrystalline Metals and its preparation method and application based on PVD technique |
| CN110724921A (en) * | 2019-10-12 | 2020-01-24 | 华中科技大学 | Intermittent magnetron sputtering method for improving disorder of amorphous material |
| CN115537764A (en) * | 2022-10-14 | 2022-12-30 | 哈尔滨工业大学 | Diamond and metal connecting method, welding joint and microwave window |
| CN116043141A (en) * | 2022-10-29 | 2023-05-02 | 烟台大学 | Preparation method of Zr-based ultra-stable metallic glass |
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Cited By (14)
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| CN103215555A (en) * | 2013-04-11 | 2013-07-24 | 西安交通大学 | Method for preparing noncrystalline-nanocrystalline composite membrane by adopting co-sputtering method |
| CN103215555B (en) * | 2013-04-11 | 2015-08-26 | 西安交通大学 | A kind of cosputtering legal system that adopts is for the method for amorphous-nano-crystalline composite membrane |
| CN104233207A (en) * | 2014-09-04 | 2014-12-24 | 兰州空间技术物理研究所 | Method for enhancing atomic oxygen attack resistance of paint film |
| CN104480443A (en) * | 2014-12-08 | 2015-04-01 | 中国人民解放军装甲兵工程学院 | Hard and tough nano composite ZrAlCuN coating and preparation method thereof |
| CN104480443B (en) * | 2014-12-08 | 2017-06-13 | 中国人民解放军装甲兵工程学院 | A kind of hard tough nano combined ZrAlCuN coatings and preparation method thereof |
| CN107130210A (en) * | 2017-05-03 | 2017-09-05 | 中国建筑材料科学研究总院 | Surface is coated with chalcogenide glass of infrared DLC protecting film and preparation method thereof |
| CN107829074A (en) * | 2017-10-31 | 2018-03-23 | 桂林电子科技大学 | A kind of non-crystaline amorphous metal reflective mirror and preparation method thereof |
| CN107829074B (en) * | 2017-10-31 | 2020-09-08 | 桂林电子科技大学 | Amorphous alloy reflector and preparation method thereof |
| CN108588646A (en) * | 2018-04-12 | 2018-09-28 | 西安交通大学 | A method of preparing the amorphous/amorphous nano-multilayer film of plasticity raising |
| CN109811309A (en) * | 2019-01-25 | 2019-05-28 | 广东工业大学 | A kind of high-purity Bulk Nanocrystalline Metals and its preparation method and application based on PVD technique |
| CN110724921A (en) * | 2019-10-12 | 2020-01-24 | 华中科技大学 | Intermittent magnetron sputtering method for improving disorder of amorphous material |
| CN115537764A (en) * | 2022-10-14 | 2022-12-30 | 哈尔滨工业大学 | Diamond and metal connecting method, welding joint and microwave window |
| CN115537764B (en) * | 2022-10-14 | 2024-04-02 | 哈尔滨工业大学 | Diamond and metal connecting method, welded joint and microwave window |
| CN116043141A (en) * | 2022-10-29 | 2023-05-02 | 烟台大学 | Preparation method of Zr-based ultra-stable metallic glass |
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Application publication date: 20130213 |