CN117467939A - Ag-Cu-Al alloy film and preparation method thereof - Google Patents
Ag-Cu-Al alloy film and preparation method thereof Download PDFInfo
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- CN117467939A CN117467939A CN202311435761.5A CN202311435761A CN117467939A CN 117467939 A CN117467939 A CN 117467939A CN 202311435761 A CN202311435761 A CN 202311435761A CN 117467939 A CN117467939 A CN 117467939A
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 113
- 239000000956 alloy Substances 0.000 title claims abstract description 113
- 229910017767 Cu—Al Inorganic materials 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 40
- 230000008021 deposition Effects 0.000 claims abstract description 37
- 238000004544 sputter deposition Methods 0.000 claims abstract description 31
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 28
- 239000002086 nanomaterial Substances 0.000 claims abstract description 12
- 239000010408 film Substances 0.000 claims description 99
- 239000000758 substrate Substances 0.000 claims description 52
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000005530 etching Methods 0.000 claims description 16
- 239000011159 matrix material Substances 0.000 claims description 16
- 229910018565 CuAl Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000010409 thin film Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- 238000007373 indentation Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 abstract description 11
- 229910052802 copper Inorganic materials 0.000 abstract description 11
- 238000005275 alloying Methods 0.000 abstract description 7
- 229910001316 Ag alloy Inorganic materials 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005728 strengthening Methods 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 24
- 239000010949 copper Substances 0.000 description 17
- 238000001771 vacuum deposition Methods 0.000 description 14
- 229910000838 Al alloy Inorganic materials 0.000 description 9
- -1 silver-copper-aluminum Chemical compound 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000002159 nanocrystal Substances 0.000 description 8
- 239000004642 Polyimide Substances 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910016343 Al2Cu Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
- C23C14/06—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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses an Ag-Cu-Al alloy film and a preparation method thereof, wherein the content of Cu is 4-28%, the content of Al is 3-18.3% and the balance of Ag is calculated according to the atomic content percentage; the Ag-Cu-Al alloy film is prepared by adopting a magnetron sputtering co-sputtering method, the obtained film is uniform in component and compact in structure, the content of Cu and Al in the Ag-Cu-Al alloy film is regulated by controlling the deposition power in the magnetron sputtering co-sputtering method, so that the microstructure of the alloy film forms a nanocrystalline, superfine nanocrystalline or crystalline-amorphous double-phase nanostructure, the mechanical property of the Ag alloy film can be effectively improved by alloying Cu and Al, and the strengthening effect of the alloy film is improved along with the increase of the content of Cu and Al.
Description
Technical Field
The invention relates to the field of metal structural materials, in particular to an Ag-Cu-Al alloy film and a preparation method thereof.
Background
In flexible electronic devices and microelectromechanical systems, the metal thin film is an ideal interconnect structure due to its excellent mechanical-electrical properties, and the metal thin film is subjected to load and joule heat during service. Therefore, the performance requirements of strength, hardness, plasticity, wear resistance, thermal stability and conductivity are put forward for the metal film.
According to the application requirements of flexible electronic devices and micro-electromechanical system interconnection structures, the metal film is often selected from Ag elements which have multiple sliding systems, good deformation performance, high conductivity and no compact defects. However, while Ag thin films are excellent in ductility and fatigue resistance, they are relatively low in mechanical strength and hardness. Therefore, in practical applications, further strengthening or improvement of Ag thin films may be required to increase their hardness, increase their wear resistance, and meet higher mechanical strength requirements.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the Ag-Cu-Al alloy film and the preparation method thereof, the prepared silver-copper-aluminum alloy film has uniform microstructure and excellent mechanical property, and the service performance of the silver alloy film can be effectively improved by alloying copper and aluminum.
The invention is realized by the following technical scheme:
an Ag-Cu-Al alloy film, wherein the content of Cu is 4-28%, the content of Al is 3-18.3%, and the balance of Ag is calculated according to the atomic content percentage;
the Ag-Cu-Al alloy film is a microstructure with nanocrystalline, superfine nanocrystalline or crystalline-amorphous double-phase nanostructure.
Preferably, the Cu is 4-10.1%, the Al is 3-6.6% and the microstructure of the alloy film is nanocrystalline according to the atomic content percentage;
the Cu is 10.2-21.2%, the Al is 6.7-13.4%, the microstructure of the alloy film is nanocrystalline, and the nanocrystalline grain size is less than 5nm;
the Cu is 21.3-28.3%, the Al is 13.5-18.3%, and the microstructure of the alloy film is a crystal-amorphous double-phase nano structure.
Preferably, the nano indentation hardness of the Ag-Cu-Al alloy film is 2.21-5.05 GPa.
Preferably, the Ag-Cu-Al alloy film is 2.4-3.3 μm.
The preparation method of the Ag-Cu-Al alloy film comprises the following steps:
step 1, removing impurities of a matrix;
step 2, depositing an Ag-Cu-Al alloy film on a substrate by adopting a CuAl alloy target and an Ag target and combining a magnetron sputtering co-sputtering method in a vacuum environment;
and 3, cooling the substrate obtained in the step 2 to room temperature to obtain the Ag-Cu-Al alloy film.
Preferably, the method for removing the matrix impurities in the step 1 is as follows:
sequentially ultrasonically cleaning a polished substrate in acetone and absolute ethyl alcohol, and then drying;
and etching the dried matrix by adopting an acid solution to remove the silicon oxide layer, so as to obtain the impurity-removed matrix.
Preferably, the vacuum degree of the vacuum environment in the step 2 is below 4.0X10-4 Pa, and the Ag-Cu-Al alloy film is deposited under the argon atmosphere.
Preferably, in the step 2, the CuAl alloy target is sputtered by adopting a direct current power supply, and the Ag target is sputtered by adopting a radio frequency power supply.
Preferably, the sputtering power of the Ag target is 80-100W, the sputtering power of the CuAl alloy target is 15-200W, the deposition air pressure is 0.5Pa, and the deposition time is 4922-11850 s.
Preferably, the substrate is a silicon substrate.
Compared with the prior art, the invention has the following beneficial technical effects:
the silver-copper-aluminum alloy film provided by the invention has the main element of Ag, the alloy elements of Cu and Al, and three elements of metals with FCC structures, and has the advantages of multiple sliding systems, good deformation performance and high conductivity. Wherein, cu element and Ag element have positive mixing enthalpy and are almost insoluble, so Cu is precipitated at a grain boundary while being slightly dissolved in crystals; the Al element and the Ag element have negative mixing enthalpy and are mutually soluble in a large range, and intermetallic compounds Ag2Al and Ag3Al are easily formed between the Al element and the Ag element; the two alloy elements Cu and Al have negative mixing enthalpy, and intermetallic compound Al2Cu is easy to form, so that the silver-copper-aluminum alloy film has rich alloying forms and can be used for component design and structure regulation.
According to the silver-copper-aluminum alloy film, three microstructure forms of nano crystals, superfine nano crystals and crystal-amorphous double-phase nano structures are formed in the microstructure of the alloy film by controlling the atomic content of Cu-Al, and in terms of mechanical properties, the nano indentation hardness of the silver-copper-aluminum alloy film gradually increases along with the increase of the content of Cu-Al, namely, the more the content of alloy elements in the silver-copper-aluminum alloy film is, the more obvious the strengthening effect is.
The invention relates to a preparation method of an Ag-Cu-Al alloy film, which is prepared by adopting a magnetron sputtering double-target co-sputtering method. Firstly, acetone and absolute ethyl alcohol are used for cleaning impurities on the surface of a Si substrate with the growth orientation of <111>, then an oxide film on the surface of the Si substrate is removed through erosion of hydrofluoric acid aqueous solution and washing of deionized water, and sputtering deposition is carried out at room temperature after Ar+ ion etching is carried out in a vacuum environment. In order to ensure the fixed proportion of the two alloy elements, a preparation method of pure Ag targets and Cu-Al alloy targets by co-sputtering is adopted, wherein the atomic ratio of the Cu-Al alloy targets is 1:1, and the components of the silver-copper-aluminum alloy film are adjusted by setting the power of the two targets. In order to ensure the stability of the silver-copper-aluminum alloy film structure and the uniformity of the components, a substrate is rotated at a fixed rotating speed in the process of deposition technology, so that metal atoms sputtered by two targets are uniformly distributed on the substrate. And after the sputtering magnetron sputtering process is finished, naturally cooling to room temperature in the high vacuum coating cavity, and taking out the deposited substrate. And finally, the deposited silver-copper-aluminum alloy film has a flat surface, uniform and compact structure and few defects.
Drawings
FIG. 1 is an XRD pattern diagram of an Ag-Cu-Al alloy film with different components prepared by magnetron sputtering according to the invention;
FIG. 2 is a TEM plan view of Ag-Cu-Al alloy films with different components prepared by magnetron sputtering according to the invention;
FIG. 3 is a graph showing nanoindentation load-displacement curves of Ag-Cu-Al alloy films of different compositions prepared by magnetron sputtering according to the invention;
FIG. 4 shows nanoindentation hardness results of Ag-Cu-Al alloy films of different compositions prepared by magnetron sputtering according to the present invention.
Detailed Description
The invention will now be described in further detail with reference to the accompanying drawings, which illustrate but do not limit the invention.
An Ag-Cu-Al alloy film comprises, by atomic percentage, 4-28% of Cu, 3-18.3% of Al and the balance of Ag; the alloy film is prepared by a magnetron sputtering co-sputtering method, and the thickness of the alloy film is 2.4-3.3 mu m.
In the alloy film, the atomic percentage contents of Cu and Al are different, so that three microstructures of nano crystals, superfine nano crystals and crystal-amorphous double-phase nano structures are formed by the microstructure of the alloy film.
The Cu is 4-10.1%, the Al is 3-6.6%, and the microstructure of the alloy film is nanocrystalline;
the Cu is 10.2-21.2%, the Al is 6.7-13.4%, the microstructure of the alloy film is nanocrystalline, and the nanocrystalline grain size is less than 5nm;
the Cu is 21.3-28.3%, the Al is 13.5-18.3%, and the microstructure of the alloy film is a crystal-amorphous double-phase nano structure.
FIG. 1 shows XRD patterns of Ag-Cu-Al alloy films of different compositions prepared by magnetron sputtering according to the invention, illustrating the phase composition of the Ag-Cu-Al alloy films; FIG. 2 shows TEM plane photographs of Ag-Cu-Al alloy films with different components prepared by magnetron sputtering, which illustrate three microstructures of nano crystals, superfine nano crystals and crystal-amorphous double-phase nano structures of the Ag-Cu-Al alloy films; FIG. 3 shows nanoindentation load-displacement curves and nanoindentation hardness results of Ag-Cu-Al alloy films with different components prepared by magnetron sputtering according to the invention, which show that the hardness of the Ag alloy film is improved along with the alloying of Cu and Al, the nanoindentation hardness of the Ag alloy film is improved along with the increase of the atomic contents of Cu and Al, and the nanoindentation hardness value reaches the highest value of 5.05GPa when the atomic ratio components are 53% Ag,28% Cu and 19% Al.
The Ag-Cu-Al alloy film has the advantages of uniform and compact surface, uniform distribution of internal alloy elements and microstructure of nano crystals, superfine nano crystals and crystal-amorphous double-phase nano structures. The Ag-Cu-Al alloy film has excellent mechanical property and thermal stability.
The method for producing the Ag-Cu-Al alloy film is described in detail below.
The preparation method of the Ag-Cu-Al alloy film comprises the following steps:
step 1, removing impurities of a matrix;
specifically, single crystal Si substrate with single-side polished growth orientation of <111> is taken, sequentially ultrasonically cleaned in acetone and ethanol for 10 minutes and dried, and the surface roughness of the single crystal Si substrate after ultrasonic cleaning is less than 0.8nm, so that stains and dust adhesion on the surface of the Si substrate are removed, and the bonding force between a film and the substrate is improved. And then, etching the dried Si substrate by adopting hydrofluoric acid aqueous solution, and fully flushing with deionized water to remove a silicon oxide layer on the surface of the Si substrate so as to ensure the growth orientation of crystals in the sputtering deposition process.
And 2, etching the substrate in a vacuum environment.
Specifically, a monocrystalline silicon substrate is fixed on a base plate, and is mechanically and automatically carried into a magnetron sputtering vacuum coating chamber, and vacuum is pumped until the vacuum degree of the back bottom is below 4.0x10 < -4 > Pa, and etching is performed for 5min under the argon atmosphere, wherein the etching power is 200W.
Step 3, depositing an Ag-Cu-Al alloy film on the substrate by adopting a CuAl alloy target and an Ag target and combining a magnetron sputtering co-sputtering method in a vacuum environment;
wherein, the Ag target (purity 99.995 wt%) adopts a radio frequency power supply, the power is 80-100W, the CuAl alloy target (purity 99.99 wt%) adopts a direct current power supply, the atomic ratio of Cu and Al of the CuAl alloy target is 1:1, the power is 15-200W, the deposition air pressure is set to 0.5Pa, the deposition temperature is room temperature, the rotating speed of the base plate is 15r/min, the direct current power supply and the radio frequency power supply are simultaneously started to start co-sputter deposition, the deposition time is 4922-11850 s, and the thickness of the obtained Ag-Cu-Al alloy film is 2.4-3.3 mu m.
And 4, cooling the substrate obtained in the step 3 to room temperature to obtain the Ag-Cu-Al alloy film.
The sputtering atoms bombard the matrix for a long time in the deposition process, so that the Ag-Cu-Al alloy film has a certain temperature rise when the process is finished, and the matrix is cooled to room temperature in the high vacuum coating chamber after the deposition is finished.
An Ag-Cu-Al alloy film is deposited on the surface of a monocrystalline Si wafer by adopting a magnetron sputtering co-sputtering method, and the principle is as follows: ar+ ions are generated through Ar gas ionization, the surface of a cathode target is accelerated to bombard under the attraction of cathode potential, so that the target is sputtered, target atoms and secondary electrons are sputtered, the target atoms are deposited on an anode substrate under the action of an electric field and a magnetic field, the secondary electrons do circular rolling line track motion in a plasma region close to the surface of the target, the collision probability with Ar molecules is increased, and more Ar+ ions are ionized, so that higher deposition rate is realized. Compared with other preparation technologies, the technology has the outstanding advantages of high ionization rate, high deposition rate, low working temperature, autonomous regulation and control of alloy film components, and difficult generation of uneven microstructure caused by aggregation and reverse sputtering of target atoms. After the sputtering deposition process is finished, in order to prevent debonding and cracking caused by the difference of thermal expansion coefficients of the film material and the matrix, generate larger internal stress and oxidize a sample when the sample contacts air at high temperature, the sample is naturally cooled to room temperature in a high vacuum coating chamber, and finally deposited atoms are fully diffused to form Ag-Cu-Al alloy films with different components.
Example 1
Step 1, respectively and sequentially ultrasonically cleaning a single-sided polished monocrystalline silicon substrate in analytically pure acetone and absolute ethyl alcohol for 10min, and immediately drying by warm air.
And 2, fixing the monocrystalline silicon substrate on a substrate by using a polyimide adhesive tape, mechanically and automatically conveying the monocrystalline silicon substrate into a magnetron sputtering vacuum coating chamber, vacuumizing until the vacuum degree of the back bottom is below 4.0x10 < -4 > Pa, and etching for 5min in an argon atmosphere, wherein the etching power is 200W.
Step 3, adopting magnetron sputtering direct current and radio frequency power supply double-target co-sputtering to deposit an Ag-Cu-Al alloy film on the monocrystalline silicon substrate;
wherein, the Ag target (purity 99.995 wt%) adopts a radio frequency power supply, the power is 100W, the CuAl alloy target (purity 99.99 wt%) adopts a direct current power supply, the power is 15W, the deposition air pressure is set to 0.5Pa, the deposition temperature is room temperature, the rotating speed of the base plate is 15r/min, and meanwhile, the direct current power supply and the radio frequency power supply are started to carry out co-sputtering deposition, and the deposition time is 5553s.
And 4, after the deposition is finished, naturally cooling the matrix in a high vacuum deposition chamber for 3 hours to room temperature, and taking out to obtain the Ag-Cu-Al alloy film, wherein the Ag-Cu-Al alloy film comprises 93.0at% of Ag-4.0at% of Cu-3.0at% of Al and has the thickness of 2.4 mu m.
And carrying out microstructure characterization and mechanical property test on the prepared Ag-Cu-Al alloy film, wherein the microstructure is a nanocrystalline structure, and the nanoindentation hardness is 2.21+/-0.29 GPa measured by nanoindentation under the load of 1000 mu N.
Example 2
Step 1, respectively and sequentially ultrasonically cleaning a single-sided polished monocrystalline silicon substrate in analytically pure acetone and absolute ethyl alcohol for 10min, and immediately drying by warm air.
And 2, fixing the monocrystalline silicon substrate on a substrate by using a polyimide adhesive tape, mechanically and automatically conveying the monocrystalline silicon substrate into a magnetron sputtering vacuum coating chamber, vacuumizing until the vacuum degree of the back bottom is below 4.0x10 < -4 > Pa, and etching for 5min in an argon atmosphere, wherein the etching power is 200W.
Step 3, adopting magnetron sputtering direct current and radio frequency power supply double-target co-sputtering to deposit an Ag-Cu-Al alloy film on the monocrystalline silicon substrate;
wherein, the Ag target (purity 99.995 wt%) adopts a radio frequency power supply, the power is 100W, the CuAl alloy target (purity 99.99 wt%) adopts a direct current power supply, the power is 40W, the deposition air pressure is set to 0.5Pa, the deposition temperature is room temperature, the rotating speed of the base plate is 15r/min, and meanwhile, the direct current power supply and the radio frequency power supply are started to carry out co-sputtering deposition for 5400s.
And 4, after the deposition is finished, naturally cooling the substrate in a high vacuum deposition chamber for 3 hours to room temperature, and taking out to obtain the Ag-Cu-Al alloy film, wherein the Ag-Cu-Al alloy film comprises 83.1at% of Ag-10.2at% of Cu-6.7at% of Al and has the thickness of 2.5 mu m.
And carrying out microstructure characterization and mechanical property test on the prepared Ag-Cu-Al alloy film, wherein the microstructure is an ultrafine nanocrystalline structure, and the nanoindentation hardness is 3.32+/-0.27 GPa measured by nanoindentation under the load of 1000 mu N.
Example 3
Step 1, respectively and sequentially ultrasonically cleaning a single-sided polished monocrystalline silicon substrate in analytically pure acetone and absolute ethyl alcohol for 10min, and immediately drying by warm air.
And 2, fixing the monocrystalline silicon substrate on a substrate by using a polyimide adhesive tape, mechanically and automatically conveying the monocrystalline silicon substrate into a magnetron sputtering vacuum coating chamber, vacuumizing until the vacuum degree of the back bottom is below 4.0x10 < -4 > Pa, and etching for 5min in an argon atmosphere, wherein the etching power is 200W.
Step 3, adopting magnetron sputtering direct current and radio frequency power supply double-target co-sputtering to deposit an Ag-Cu-Al alloy film on the monocrystalline silicon substrate;
wherein, the Ag target (purity 99.995 wt%) adopts a radio frequency power supply, the power is 100W, the CuAl alloy target (purity 99.99 wt%) adopts a direct current power supply, the power is 82W, the deposition air pressure is set to 0.5Pa, the deposition temperature is room temperature, the rotating speed of the base plate is 15r/min, and meanwhile, the direct current power supply and the radio frequency power supply are started to carry out co-sputtering deposition for 5230s.
And 4, after the deposition is finished, naturally cooling the matrix in a high vacuum deposition chamber for 3 hours to room temperature, and taking out to obtain the Ag-Cu-Al alloy film, wherein the Ag-Cu-Al alloy film comprises 72.6at% of Ag-16.9at% of Cu-10.5at% of Al and has the thickness of 2.9 mu m.
And carrying out microstructure characterization and mechanical property test on the prepared Ag-Cu-Al alloy film, wherein the microstructure is an ultrafine nanocrystalline structure, and the nanoindentation hardness is 4.26+/-0.07 GPa when the nanoindentation is measured under the load of 1000 mu N.
Example 4
Step 1, respectively and sequentially ultrasonically cleaning a single-sided polished monocrystalline silicon substrate in analytically pure acetone and absolute ethyl alcohol for 10min, and immediately drying by warm air.
And 2, fixing the monocrystalline silicon substrate on a substrate by using a polyimide adhesive tape, mechanically and automatically conveying the monocrystalline silicon substrate into a magnetron sputtering vacuum coating chamber, vacuumizing until the vacuum degree of the back bottom is below 4.0x10 < -4 > Pa, and etching for 5min in an argon atmosphere, wherein the etching power is 200W.
Step 3, adopting magnetron sputtering direct current and radio frequency power supply double-target co-sputtering to deposit an Ag-Cu-Al alloy film on the monocrystalline silicon substrate;
wherein, the Ag target (purity 99.995 wt%) adopts a radio frequency power supply, the power 92W and the CuAl alloy target (purity 99.99 wt%) adopt a direct current power supply, the power 116W, the deposition air pressure is set to 0.5Pa, the deposition temperature is room temperature, the rotating speed of the base plate is 15r/min, and meanwhile, the direct current power supply and the radio frequency power supply are started to carry out co-sputtering deposition for 4922s.
And 4, after the deposition is finished, naturally cooling the matrix in a high vacuum deposition chamber for 3 hours to room temperature, and taking out to obtain the Ag-Cu-Al alloy film, wherein the Ag-Cu-Al alloy film comprises 65.4at% of Ag-21.2at% of Cu-13.4at% of Al and has the thickness of 3.3 mu m.
And carrying out microstructure characterization and mechanical property test on the prepared Ag-Cu-Al alloy film, wherein the microstructure is an ultrafine nanocrystalline structure, and the nanoindentation hardness is 4.67+/-0.06 GPa measured by nanoindentation under the load of 1000 mu N.
Example 5
Step 1, respectively and sequentially ultrasonically cleaning a single-sided polished monocrystalline silicon substrate in analytically pure acetone and absolute ethyl alcohol for 10min, and immediately drying by warm air.
And 2, fixing the monocrystalline silicon substrate on a substrate by using a polyimide adhesive tape, mechanically and automatically conveying the monocrystalline silicon substrate into a magnetron sputtering vacuum coating chamber, vacuumizing until the vacuum degree of the back bottom is below 4.0x10 < -4 > Pa, and etching for 5min in an argon atmosphere, wherein the etching power is 200W.
Step 3, adopting magnetron sputtering direct current and radio frequency power supply double-target co-sputtering to deposit an Ag-Cu-Al alloy film on the monocrystalline silicon substrate;
wherein, the Ag target (purity 99.995 wt%) adopts a radio frequency power supply, the power is 80W, the CuAl alloy target (purity 99.99 wt%) adopts a direct current power supply, the power is 200W, the deposition air pressure is set to 0.5Pa, the deposition temperature is room temperature, the rotating speed of the base plate is 15r/min, and meanwhile, the direct current power supply and the radio frequency power supply are started to carry out co-sputtering deposition, and the deposition time is 5000s.
And 4, after the deposition is finished, naturally cooling the matrix in a high vacuum deposition chamber for 3 hours to room temperature, and taking out to obtain the Ag-Cu-Al alloy film, wherein the Ag-Cu-Al alloy film comprises 53.4at% of Ag-28.3at% of Cu-18.3at% of Al and has the thickness of 3.3 mu m.
And carrying out microstructure characterization and mechanical property test on the prepared Ag-Cu-Al alloy film, wherein the microstructure is a crystal-amorphous double-phase nano structure, and the nano indentation hardness is 5.05+/-0.11 GPa measured by nano indentation under the load of 1000 mu N.
The invention discloses an Ag-Cu-Al alloy film and a preparation method thereof, wherein the atomic percentage of (Cu-Al) is 7% -47%, and the balance is Ag. The invention is prepared by adopting a magnetron sputtering double-target co-sputtering method, wherein the Ag target adopts a radio frequency power supply, and the CuAl alloy target adopts a direct current power supply; the invention adjusts the content of (Cu-Al) in the Ag-Cu-Al alloy film by controlling the deposition power. The obtained film has uniform components and compact structure, and the microstructure of the film presents nanocrystalline, superfine nanocrystalline and crystal-amorphous double-phase nanostructure. The mechanical property of the Ag alloy film can be effectively improved by alloying (Cu-Al), and the strengthening effect of the Ag alloy film is improved along with the increase of the content of (Cu-Al); the invention strengthens through alloying, the alloying can change the microstructure of the material at multiple angles, and the microstructure can be regulated and controlled in the aspects of grain size, twinning and stacking fault, texture orientation, element distribution, solid solution and precipitation, phase change and amorphization and the like by introducing alloy elements, thereby directly influencing a series of performances such as strength, plasticity and the like of the metal film so as to optimize the service performance of the material.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. An Ag-Cu-Al alloy film is characterized in that Cu accounts for 4-28% by atomic content, al accounts for 3-18.3% by atomic content, and the balance is Ag;
the Ag-Cu-Al alloy film is a microstructure with nanocrystalline, superfine nanocrystalline or crystalline-amorphous double-phase nanostructure.
2. The Ag-Cu-Al alloy thin film according to claim 1, wherein the Cu is 4 to 10.1%, the Al is 3 to 6.6% in terms of atomic percentage, and the microstructure of the alloy thin film is nanocrystalline;
the Cu is 10.2-21.2%, the Al is 6.7-13.4%, the microstructure of the alloy film is nanocrystalline, and the nanocrystalline grain size is less than 5nm;
the Cu is 21.3-28.3%, the Al is 13.5-18.3%, and the microstructure of the alloy film is a crystal-amorphous double-phase nano structure.
3. The Ag-Cu-Al alloy thin film according to claim 1, wherein the nano-indentation hardness of the Ag-Cu-Al alloy thin film is 2.21-5.05 GPa.
4. The Ag-Cu-Al alloy thin film according to claim 1, wherein the Ag-Cu-Al alloy thin film is 2.4 to 3.3 μm.
5. A method for producing an Ag-Cu-Al alloy thin film according to any one of claims 1 to 4, comprising the steps of:
step 1, removing impurities of a matrix;
step 2, depositing an Ag-Cu-Al alloy film on a substrate by adopting a CuAl alloy target and an Ag target and combining a magnetron sputtering co-sputtering method in a vacuum environment;
and 3, cooling the substrate obtained in the step 2 to room temperature to obtain the Ag-Cu-Al alloy film.
6. The method for preparing an Ag-Cu-Al alloy film according to claim 4, wherein the method for removing the matrix impurities in step 1 is as follows:
sequentially ultrasonically cleaning a polished substrate in acetone and absolute ethyl alcohol, and then drying;
and etching the dried matrix by adopting an acid solution to remove the silicon oxide layer, so as to obtain the impurity-removed matrix.
7. The method according to claim 5, wherein the vacuum degree of the vacuum atmosphere in the step 2 is 4.0X10-4 Pa or less, and the deposition of the Ag-Cu-Al alloy film is performed under an argon atmosphere.
8. The method for preparing an Ag-Cu-Al alloy film according to claim 5, wherein the CuAl alloy target is sputtered by a DC power supply and the Ag target is sputtered by a RF power supply in step 2.
9. The method for preparing an Ag-Cu-Al alloy film according to claim 5, wherein the sputtering power of the Ag target is 80-100W, the sputtering power of the CuAl alloy target is 15-200W, the deposition air pressure is 0.5Pa, and the deposition time is 4922-11850 s.
10. The method for producing an Ag-Cu-Al alloy film according to claim 5, wherein the substrate is a silicon substrate.
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