CN109306414A - Silver alloy target, film and preparation method thereof - Google Patents
Silver alloy target, film and preparation method thereof Download PDFInfo
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- CN109306414A CN109306414A CN201811240415.0A CN201811240415A CN109306414A CN 109306414 A CN109306414 A CN 109306414A CN 201811240415 A CN201811240415 A CN 201811240415A CN 109306414 A CN109306414 A CN 109306414A
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- silver alloy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
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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
- C23C14/02—Pretreatment of the material to be coated
-
- 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
Abstract
The present invention provides silver alloy target, film and preparation method thereof, which is configured to AgxInyMzQnWherein the ratio of indium is 8%≤y≤40% (atomic ratio), M is at least one of tin, gold, platinum, palladium, niobium, rhodium, ruthenium element, 0≤z≤8% (atomic ratio), Q is at least one of rare earth element element, 0≤n≤3% (atomic ratio), and content x >=60% (atomic ratio) of silver.The silver alloy target can be by magnetron sputtering, ion sputtering plating, vacuum evaporation or electron beam evaporation be made with excellent heat resistance, adhesive force, electric conductivity, corrosion resistance and sulfuration resistant silver alloy film, be suitable for the fields such as reflective electrode film, liquid crystal display, optical recording medium, Organic Light Emitting Diode and electrochromism.
Description
Technical field
The present invention relates to high conductivity, high reflectance and corrosion resistant silver alloy, the sputtering target material containing the composition of alloy
And silver alloy film and preparation method thereof.The silver alloy film be suitable for reflective electrode film, liquid crystal display, optical recording medium and
The fields such as Organic Light Emitting Diode, further, the silver alloy film apply also for reflection-type or Transreflective electrochromism group
Part.
Background technique
The film that pure silver spattering target is formed, due to high conductivity and the characteristic of high reflectance, especially suitable for reflecting electrode
The fields such as film, liquid crystal display, optical recording medium, Organic Light Emitting Diode and electrochromism.
But fine silver haves the shortcomings that oxidizable, sulfidation-resistance is poor, oxidation and vulcanization make its corrosion, make Ag films reflectivity
And conductivity reduces, and the adhesive force of film and substrate is made to be deteriorated.To which examination recently has carried out much remaining pure about one side
The original high conductivity of high reflectance of silver, improves its corrosion resistance test by adding alloying element on one side.Moreover, carrying out this
While the film of sample improves, also target used in formation silver alloy film is studied, for example, Japanese Patent Laid-Open
The silver that the aluminium of ruthenium and 0.1~10 atom % that 0.5~10 atom % is added in silver is disclosed in flat 11-134715 bulletin closes
Gold discloses the silver alloy of the palladium of addition 0.4~4.9 in silver in Japanese Patent Laid-Open 2000-109943 bulletin, in Japan
A kind of following sputtering target is disclosed as electronic component-use metal material in open patent 2001-192752 bulletin, with
Silver is main component, and in order to improve weatherability and palladium containing 0.1~3 weight %, further for inhibiting to cause due to palladium
Resistivity increase and what slave aluminium, gold, platinum, copper, tantalum, chromium, titanium, nickel, cobalt etc. containing 0.1~3 weight % range were constituted
At least one element selected in group.The corrosion resistance of these silver alloy is good, is also able to maintain reflectivity under use environment, fits
Cooperation is that (details about these prior arts refers to Japanese Patent Laid-Open 11-134715 bulletin and day in reflecting layer
This patent special open 2000-109943 bulletin).But above silver alloy, its conductivity can be bright with the extension of use time
Aobvious decline, so people are badly in need of developing a kind of high reflection, high conductivity and corrosion-resistant material.
Gentex Corp of the U.S. application No. is the patent of invention of 201310509360.X provide one kind based on silver
Ingredient is wanted, containing the precious metal materials such as gold, palladium, rhodium, osmium, and bullion content is up to 7% or more, with high costs.The present invention
Its phosphide element that joined larger proportion compared with above-mentioned patent, corrosion resistance, reflectivity and electric conductivity do not reduce, compared with
The addition of large scale phosphide element greatly reduces the cost of silver alloy film in the case where guaranteeing that performance is constant.
In addition, Taiwan Patent bulletin No. 385263 cases of I provide a kind of reflective electrode film of organic light-emitting diode element
It is formed and uses AI alloy target, the content of the indium of the AI alloy target is 0.1~1.5 mass %, and the AI alloy target
Crystal grain average grain diameter be 150~400um.Though the AI alloy target can be used for making by adding the phosphide element of low ratio
The electrode of OLED, but the problem of the AI alloy target is easy to happen electric arc paradoxical discharge and splash in sputter coating process,
Cause the fineness of obtained AI alloy film insufficient.Biyadi Co Ltd application No. is 201110175989.6
Patent of invention provide one kind using silver as main component, the palladium containing 2~4 weight %, the scandium of 0.3~1 weight %, 0.2~
The lanthanum of 0.5 weight % or the silver alloy reflective of ytterbium, the silver alloy reflective are applied to electrochromism field, but not due to it
Electrochemical corrosion resistant silver alloy reflective cannot directly be contacted with electrochromic material, it is also necessary to be plated again on silver alloy reflective
Transparency conducting layer processed just can apply to electrochromism field, and the method preparation flow is complicated, and with high costs.
Therefore the prior art has not yet to see a kind of silver alloy target suitable for vacuum coating, also there are no a kind of silver alloy
One can be made via technique for vacuum coating while there is satisfactory electrical conductivity, good anti-oxidant sulfuration resistant, good adhesion, high reflection
The silver alloy film of the performances such as rate and high-fineness.Thus, adding rare earth element into silver alloy target is necessary, rare earth
The electronic structure of element is different from other elements, in their atomic electrons layer, there is one layer of internal layer not filled up by electronics
With 4f electronic shell.Due to the presence of unsaturated electronic shell, make rare earth element that there is unique characteristic.Add a small amount of rare earth element
It can strong influence materials microstructure and performance.Rare earth can refine the crystal grain of casting alloy, less or elimination column crystal, expand
The effects of isometric crystalline region.When rare earth element be added to silver and its alloy in, the light-liquid interfacial tension of silver alloy can be made to reduce, it is critical
Nucleus radius reduces, and nucleation is easy, nucleus refinement.Rare earth element can hinder growing up for silver alloy crystal grain in annealing process, dilute
The presence of earth elements increases the quantity of fault, effectively hinders recrystal grain seam and grows up, moves back cold-rolling deformation, recrystallization
Crystal grain obviously refines after fire.Therefore, the silver alloy film that the target preparation of rare earth element is added in silver alloy can be certain
Inhibit the phenomenon that film generates structure Relaxation and crystallization under external condition.Rare earth element in silver alloy target or film in addition to having
Except having inhibition to crystallize, another important function is that the metallic element in metallic element or promotion alloy in same alloy generates gold
Belong to part compound, these effects will improve the performances such as plasticity, corrosion resistance, the intensity of silver alloy target or film.
Summary of the invention
Technical problem to be solved by the present invention lies in providing a kind of preparation method of silver alloy target, and apply the target
The high conductivity of preparation, corrosion resistance silver alloy film, suitable for reflective electrode film, liquid crystal display, optical recording medium and have
The fields such as machine light emitting diode, further, the silver alloy film apply also for reflection-type or Transreflective electrochromic window assemblies.
To achieve the goals above, present invention employs following technical solutions:
Silver alloy sputtering target material of the invention: silver alloy is configured to AgxInyMzQn, wherein ratio 8%≤y≤40% of indium
(atomic ratio), M are at least one of tin, gold, platinum, palladium, niobium, rhodium, ruthenium element, and 0≤z≤8% (atomic ratio), Q is rare earth member
At least one of element element, 0≤n≤3% (atomic ratio), and content x >=60% (atomic ratio) of silver.Preferably, described
Rare earth element is that at least one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium and scandium are first
Element.
Preferably, the rare earth element containing 0.01~3 atom % in the silver alloy sputtering target material.
Also, the manufacturing method of silver alloy sputtering target material successively implements hot-rolled process, bosher to melting and casting ingot casting
Sequence, cold rolling process, heat treatment procedure, machining operation and manufacture silver alloy sputtering target, the melting and casting ingot casting have such as
It is lower at being grouped as: the indium containing 8~40 atom %, the tin, gold, platinum, palladium, niobium, rhodium, ruthenium or 0~3 also containing 0~8 atom % are former
At least one of sub- % rare earth element element, and the content of silver is not less than 60 atom %.
When above-mentioned silver alloy target contains the indium of total 8~20 atom %, indium is the element for being solid-solution in silver.
When above-mentioned silver alloy target contains the indium of total 20~40 atom %, the indium of 20 atom % is solid-solution in silver
Element, the indium of 20~40 atom % are present in target in the form of Ag3In and Ag2In.
Including being coated with, the plating is made as one of magnetron sputtering, ion sputtering plating, vacuum evaporation and electron beam evaporation
?.
It is coated with before silver alloy and is made with one or more kinds of laminations of silica, nickel, chromium, iron, aluminum oxide, titanium or aluminium
For the transition zone of silver alloy film and substrate, transition zone with a thickness of 5~50nm.
The silver alloy film with a thickness of 1~200nm.
Compared with the prior art, the advantages of the present invention are as follows:
One or more of suitable indium and tin, gold, platinum, palladium, niobium, rhodium, ruthenium or rare earth element are added in silver alloy
Improve silver alloy performance so that invention silver alloy target be applied to silver alloy film have excellent electric conductivity, corrosion resistance,
Adjustable reflectivity is guaranteeing performance not so that film service life is substantially improved, and is added to the phosphide element of larger proportion
The use ratio that precious metal element is reduced in the case where change, significantly reduces cost, is applicable to reflective electrode film, liquid crystal
The fields such as display, optical recording medium, Organic Light Emitting Diode and electrochromic window assemblies.
Detailed description of the invention
Fig. 1 is the silver alloy target of embodiment 1 through the anti-of the visible light wave range of film initial state made by sputter coating
Penetrate rate figure；
Fig. 2 is that the silver alloy target surface of film after heat resistance is tested made by the sputter coating of embodiment 1 is swept
Retouch formula electron microscope picture；
Fig. 3 is the silver alloy target surface scan of film after salt spray test made by the sputter coating of embodiment 1
Formula electron microscope picture；
Fig. 4 is that the silver alloy target surface of film after heat resistance is tested made by the sputter coating of comparative example 1 is swept
Retouch formula electron microscope picture；
Fig. 5 is the silver alloy target surface scan of film after salt spray test made by the sputter coating of comparative example 1
Formula electron microscope picture；
Fig. 6 is the structural schematic diagram of coating in silver alloy film preparation process of the invention.
In figure: I substrate, II transition zone, III silver alloy film.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.
Composition for verifying silver alloy target of the invention is thin via silver alloy obtained by sputter coating process for it
The reflectivity of film, electric conductivity, the influence of adhesive force, sulfuration resistant performance etc., following cited embodiment 1 to 8 and comparative example 1 to
4 silver alloy target and obtained silver alloy film generally through obtained by identical processing step, the difference is that,
The ingredient and thickness of the type of each ingredient and its alloy and the coat of metal in the silver alloy target of previous example and reference examples, each reality
The preparation method for applying example and reference examples is as described below.
Embodiment 1 to 8, comparative example 1 to 4: silver alloy target, film and preparation method thereof
The preparation method of silver alloy target:
According to ratio shown in table 1, using the silver of 99.99 weight % of purity or more, indium, purity: the tin of 99.9 weight %,
Gold, platinum, palladium, niobium, rhodium, ruthenium or rare earth element add the indium of 8~40 atom % as raw material in the molten liquid of silver, addition
At least one of tin, gold, platinum, palladium, niobium, rhodium, ruthenium or 0~3 atom % rare earth element of total 0~8 atom % element, and
The content of silver is not less than 60 atom %.
Also, above melting/casting preferably carries out in vacuum or the atmosphere of inert gas replacement, to reduce ingot casting
In oxygen or nonmetallic inclusion content.In order to make homogenization of composition, smelting furnace is preferably induction heater.Also, with rectangular
Mold cast obtain rectangular solid ingot be it is effective and preferred.
Rectangular-shape ingot casting heating to obtaining, after being hot-rolled down to regulation plate thickness, quenching imposes cold rolling, heat treatment.
Specifically, the rolling rate of every a time in smart hot rolling is 10~40%, rate of straining is 2~15/sec, and
Temperature after passage is 400~900 DEG C.Hot rolling includes the smart hot rolling of a time or more.Total rolling rate of hot rolling entirety is for example set
It is 30% or more.The final smart hot rolling is subjected to a time to multi-pass as needed.
The more preferable range of smart hot rolling be the rolling rate of every a time be 20~35%, rate of straining 6~12% ,/sec,
And the rolling temperature after passage is 500~700 DEG C, and the smart hot rolling of three passages or more is preferably implemented.
After this hot rolling.It is quenched from 400~900 DEG C of temperature with the cooling velocity of 50-1200 DEG C/min.
Method as quenching carries out water leaching in 1~2 minute.
Then, the average value of the rolling rate of every a time in all rolling passes is 10~40% or so, is owned
Rate of straining average value in rolling pass carries out cold rolling under conditions of being 2~15/sec, until target plate thickness.Plate after cold rolling
Material temperature is 180 DEG C or less.
It is kept for 0.5~4 hour in heat treatment after cold rolling with 300~600 DEG C.The obtained milled sheet is passed through into roll-type
After straightener etc. is corrected, required size is completed in a manner of electro-discharge machining, Milling Process etc..
The preparation method of silver alloy film:
The silver alloy target of embodiment 1 to 8, comparative example 1 to 4 is placed in magnetron sputtering cavity, using sheet glass as substrate
I, using one or more kinds of laminations of silica, nickel, chromium, iron, aluminum oxide, titanium or aluminium as transition zone II, by magnetic control
After sputtering equipment base vacuum is evacuated to 5 × 10-4Pa, the argon gas for being passed through 30SCCM makes the intracorporal pressure of magnetron sputtering chamber
0.4Pa sets Dc source power as 1200W, prepares silver alloy film III to carry out magnetron sputtering, is used for reflectivity, sulfur resistive
The test such as change.
Test example 1: reflectance test
Using absolute reflectance of the wavelength of each alloy firm of spectrophotometric determination silver at 550nm, it the results are shown in Table 2.
Test example 2: sulfuration resistant test
During each silver alloy film is placed in the Na2S solution containing 0.02wt%, observes each silver alloy film and connect with sulfur vapor
It touches and the situation of blackening, time needed for recording each silver alloy film blackening, the results are shown in Table 2.
Test example 3: heat resistance test
By each silver alloy film as in argon atmosphere, with 300 DEG C of annealing 30min, finally shown with scanning electron
Micro mirror observes the configuration of surface that each silver alloy film is handled after annealing, the results are shown in Table 2.
Test example 4: adhesive force test
As a child as in the hot and humid environment that temperature is 85 DEG C and humidity is 85% 48 by each silver alloy film, with 3M
Company Scotch600 type adhesive tape carries out adhesive force test.The surface that the adhesive tape is affixed on each silver alloy super model is removed this again
Adhesive tape, checks whether each silver alloy film separates with substrate, if sample does not fall off phenomenon, then the sample silver alloy film with
Adhesive force is good for substrate, the results are shown in Table 2.
Test example 5: the square resistance of film
The square resistance that each silver alloy film initial state is tested using four probe sheet resistance instrument, the results are shown in Table 2.
Test example 6: electrochemical reduction potential test
Using electrochemical workstation, three-electrode system, electrolyte is 0.1M tetrabutyl ammonium tetrafluoroborate/GBL, reference electrode
It for AgCl/Ag, is tested using cyclic voltammetry, checks its electrochemical reduction current potential.
Test example 7: salt spray test
Using 5% sodium chloride salt aqueous solution, solution pH value tune is in neutral range (6~7) as solution by spraying.Examination
Testing temperature is 35 DEG C, and the sedimentation rate of salt fog sprays sample for 24 hours in 2ml/80cm2.h, tests its reflectivity after the completion, the results are shown in Table
2。
1 silver alloy target elements of table composition
2 silver alloy film correlated performance test result of table
It is coated on a glass substrate using the silver alloy target of 1 element of embodiment composition through certain coating process, respectively
It is coated with the silver alloy film of different film thickness, tests reflectivity, transmitance and the square resistance of each silver alloy film, as a result such as table 3:
3 different-thickness silver alloy film correlated performance test result of table
Industrial availability
In traditional its device architecture of reflective electrochromic field are as follows: glass/transparency conducting layer/electrochromic material/
Transparency conducting layer/glass/transition zone/reflecting layer/protective layer.As described above, silver alloy film of the invention have high reflectance,
The advantages of preferable electric conductivity and corrosion resistance, can simplify traditional reflective electrochromic device structure are as follows: glass/transparent
Conductive layer/electrochromic material/transition zone/silver alloy film/glass, preparation flow is simple, and cost is relatively low, and silver alloy
Film conductivity is much higher than conventional transparent conductive layer, is much better than using the reflective electrochromic device performance of this silver alloy film
Traditional reflective electrochromic device.In addition, silver alloy film also includes the film with translucency in the present invention, therefore,
It can be used for semi-transparent semi-reflective electrochromic device.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. silver alloy target sputtering target material, it is characterised in that: silver alloy is configured to AgxInyMzQn, wherein 8%≤y of ratio of indium≤
40% (atomic ratio), M are at least one of tin, gold, platinum, palladium, niobium, rhodium, ruthenium element, 0≤z≤8% (atomic ratio), and silver
Content x >=60% (atomic ratio).
2. silver alloy target sputtering target material according to claim 1, which is characterized in that the composition is AgxInyMzQnSilver
Q in alloy is rare-earth elements of lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium
At least one of Er, thulium Tm, ytterbium Yb, lutetium Lu, yttrium Y and scandium Sc element, and 0≤n≤3% (atomic ratio).
3. the manufacturing method of silver alloy sputtering target material successively implements hot-rolled process, cooling process, cold rolling to melting and casting ingot casting
Process, heat treatment procedure, machining operation and manufacture silver alloy sputtering target, the melting and casting ingot casting have as follows at grouping
At the indium containing 8~40 atom %, tin, gold, platinum, palladium, niobium, rhodium, ruthenium and 0~3 atom % also containing 0~8 atom %
At least one of rare earth element element, and the content of silver is not less than 60 atom %.
4. the manufacturing method of silver alloy sputtering target material according to claim 3, it is characterised in that: contain total 8~20
When the indium of atom %, indium is the element for being solid-solution in silver.
5. according to the manufacturing method of silver alloy sputtering target material described in claims 3-4 any one, it is characterised in that: contain
When the indium of total 20~40 atom %, the indium of 20 atom % is the element for being solid-solution in silver, and the indium of 20~40 atom % is with Ag3In
It is present in target with the form of Ag2In.
6. silver alloy film, which is characterized in that formed using silver alloy described in claim 1-5 any one.
7. the preparation method of silver alloy film, it is characterised in that: including being coated with, the plating is made as magnetron sputtering, ion sputtering
One of plating, vacuum evaporation and electron beam evaporation.
8. according to the preparation method of silver alloy film described in 7 any one of claims, it is characterised in that: glass be base
Piece, using one or more kinds of laminations of silica, titanium dioxide, nickel, chromium, zinc oxide, aluminum oxide, titanium or aluminium as silver
The transition zone of alloy firm and substrate, thickness range are 5~50nm.
9. the preparation method of silver alloy film according to claim 7, it is characterised in that: the thickness of the silver alloy film
Degree is 10~200nm.
10. the preparation method of silver alloy film according to claim 7, it is characterised in that: the silver alloy film is
Electric conductivity and the good reflectance coating of corrosion resistance or transflective film.
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| CN110076474A (en) * | 2019-04-30 | 2019-08-02 | 温州宏丰合金有限公司 | A kind of hard alloy cladding welding material and preparation method thereof |
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| CN112725675A (en) * | 2020-12-23 | 2021-04-30 | 苏州希镝瑞新材料科技有限公司 | Method for manufacturing dysprosium/terbium target |
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| CN115044877A (en) * | 2022-06-29 | 2022-09-13 | 烟台招金励福贵金属股份有限公司 | Preparation method of silver-based ternary alloy target |
| CN115466926A (en) * | 2021-09-07 | 2022-12-13 | 惠州市拓普金属材料有限公司 | Silver alloy target material and preparation method and application thereof |
| CN115976478A (en) * | 2022-12-13 | 2023-04-18 | 江苏迪纳科精细材料股份有限公司 | Silver sulfide resistant alloy target material and preparation method thereof |
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