CN100443609C - Silver alloy, sputtering target material thereof, and thin film thereof - Google Patents
Silver alloy, sputtering target material thereof, and thin film thereof Download PDFInfo
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- CN100443609C CN100443609C CNB2004800277184A CN200480027718A CN100443609C CN 100443609 C CN100443609 C CN 100443609C CN B2004800277184 A CNB2004800277184 A CN B2004800277184A CN 200480027718 A CN200480027718 A CN 200480027718A CN 100443609 C CN100443609 C CN 100443609C
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- 229910001316 Ag alloy Inorganic materials 0.000 title claims abstract description 231
- 239000013077 target material Substances 0.000 title claims description 50
- 238000005477 sputtering target Methods 0.000 title claims description 42
- 239000010409 thin film Substances 0.000 title description 2
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 35
- 229910052802 copper Inorganic materials 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims description 40
- 239000011248 coating agent Substances 0.000 claims description 39
- 239000012528 membrane Substances 0.000 claims description 29
- 238000009826 distribution Methods 0.000 claims description 14
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 5
- 229910017821 Cu—Ge Inorganic materials 0.000 abstract description 22
- 238000010438 heat treatment Methods 0.000 abstract description 18
- 238000005987 sulfurization reaction Methods 0.000 abstract description 11
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 9
- 238000004383 yellowing Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000006866 deterioration Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 121
- 230000000052 comparative effect Effects 0.000 description 98
- 238000002310 reflectometry Methods 0.000 description 54
- 239000010949 copper Substances 0.000 description 40
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 25
- 239000000758 substrate Substances 0.000 description 19
- 238000004544 sputter deposition Methods 0.000 description 18
- 230000003746 surface roughness Effects 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 17
- 239000010944 silver (metal) Substances 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 14
- 229910052709 silver Inorganic materials 0.000 description 14
- 239000004411 aluminium Substances 0.000 description 12
- 238000012545 processing Methods 0.000 description 11
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- 230000000694 effects Effects 0.000 description 9
- 239000004332 silver Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 229910002668 Pd-Cu Inorganic materials 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
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- 230000015572 biosynthetic process Effects 0.000 description 5
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- 238000002425 crystallisation Methods 0.000 description 3
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- 239000010946 fine silver Substances 0.000 description 3
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 150000001398 aluminium Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
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- 239000011521 glass Substances 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
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- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- -1 ITO Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
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Abstract
An Ag-Pd-Cu-Ge silver alloy is disclosed which enables to form a reflective electrode film which has such two characteristics at the same time that decrease in the reflectance due to thermal deterioration is extremely small and yellowing due to sulfuration hardly occurs even after the heating step during production of color liquid crystal displays. The silver alloy is characterized by having a chemical composition composed of at least 4 elements wherein Ag is mainly contained, and 0.10-2.89 wt% of Pd, 0.10-2.89 wt% of Cu and 0.01-1.50 wt% of Ge are also contained such that the total content of Pd, Cu and Ge is 0.21-3.00 wt%.
Description
Technical field
The present invention relates to the silver alloys of thermotolerance sulfidation-resistance excellence, contain the sputter target material that this silver alloys is formed, this silver alloy film and silver alloys slurry.And this silver alloy film is suitable for the purposes of reflectance coating, reflective electrode film, electrode film or the distribution etc. of indicating meters such as liquid-crystal display or LED electronic units such as (photodiodes).Further, this silver alloy film also is suitable for the reflectance coating and the slim semi-permeable membranes of CD media, the perhaps purposes of the reflectance coating of the illuminace components such as projection lamp of headlight, projector, and can become the electromagnetic wave shielding protective membrane.
Background technology
In the manufacturing of colour liquid crystal display device, in the heating process of in the assembling of colour filter etc. etc., carrying out,, therefore require reflective electrode film to have the thermotolerance that can tolerate this heating owing to be heated to about 250 ℃.Up to the present, use Al (aluminium) always or with aluminium as the alloy of principal constituent as reflective electrode film, but silver alloys is discussed as the high-reflectivity of expectation and the reflecting electrode mould material of low resistance rate.
For example, the applicant disclose about be applicable to reflective electrode film and the reflection distribution electrode film silver alloys Ag (silver)-Pd (palladium)-Cu (copper) be silver alloys.(for example with reference to patent documentation 1～3.)
Patent documentation 1: the spy opens 2000-109943 communique, claim 4
Patent documentation 2: the spy opens 2001-192752 communique, claim 1
Patent documentation 3: the spy opens 2001-226765 communique, claim 2
So the reflectance coating without the optical record mediums such as CD-ROM of heating process when making as colour liquid crystal display device has that to make Ag-Pd be the disclosure of the Invention (for example with reference to patent documentation 4) that silver alloys contains Ge (germanium).At this, Ge has the effect of the weathering resistance of silver alloys, particularly, has the effect that prevents that reflectivity that the long-time use because of reflectance coating causes from reducing.
Patent documentation 4: the spy opens 2003-193155 communique, claim 1
Summary of the invention
Even the object of the present invention is to provide a kind of process being the above-mentioned heating process of colour liquid crystal display device manufacturing process about 250 ℃ heating process as an example, the Ag-Pd-Cu-Ge that also can form the reflective electrode film with following 2 characteristics is a silver alloys.Described 2 characteristics are few for the reflectivity that causes because of thermal degradation when reduces, and the yellowing that causes because of sulfuration is difficult to take place.
The object of the present invention is to provide as Ag-Pd-Cu-Ge is the silver alloy sputtering target material of silver alloys form, silver alloy film and silver alloys slurry.
The objective of the invention is to by making Ag-Pd-Cu-Ge is that silver alloy filmization is used as reflectance coating, distribution, electrode or reflecting electrode, in addition, the present invention also aims to provide possess and contain the reflectance coating that Ag-Pd-Cu-Ge is a silver alloys, the self-luminous display that pass semi-permeable membranes, distribution, electrode or reflecting electrode are arranged, flat-panel monitor.In the purposes of indicating meter, because that Ag-Pd-Cu-Ge is the reflectivity of silver alloy film is low, sulfuration is few, therefore can improve brightness.Have again, the present invention also aims to, be accompanied by the raising of weathering resistance, with silver alloy film of the present invention as the reflectance coating of CD media and slim semi-permeable membranes, headlight or projector reflectance coating, perhaps as reflectance coating, distribution, electrode or the reflecting electrode of electronic units such as LED with illuminace components such as lamps.In addition, the present invention also aims to silver alloy film of the present invention as the electromagnetic wave shielding protective membrane.
The inventor is in order to develop all excellent silver alloys of thermotolerance and sulfidation-resistance, studied intensively the composition of silver alloys, found that: owing in the Ag-Pd alloy, have Cu and Ge simultaneously, therefore the synergy by Cu and Ge can obtain excellent thermotolerance, and can obtain sulfidation-resistance by the effect of Ge.Thereby finished the present invention.Promptly, silver alloys of the present invention is characterised in that: have the composition that contains at least 4 kinds of elements, wherein, with Ag is principal constituent, setting Pd content is that 0.10～2.89wt%, Cu content are 0.10～2.89wt%, Ge content is 0.01～1.50wt%, and the total content of setting Pd, Cu and Ge is 0.21～3.00wt%.At this, in silver alloys of the present invention, preferably have the composition that only contains 4 kinds of elements, and Ag content is 97.00～99.79wt%.The content ratio of further preferred Cu and Ge is that Cu content/Ge content is (1/20)～(20/1).
Silver alloy sputtering target material of the present invention is characterized in that, is to form with the silver alloys of above-mentioned composition.
Silver alloy film of the present invention is characterized in that, is to form with above-mentioned silver alloys.
Silver alloys of the present invention or silver alloy film comprise following situation, and the reflection of light rate of having carried out 1 hour 550nm after the heat treated in air under 250 ℃ is 90% or higher.
Silver alloys of the present invention or silver alloy film comprise following situation, and the reflection of light rate that at room temperature is exposed to the 550nm after 48 hours in the hydrogen sulfide atmosphere of 100ppm is 75% or higher.
Silver alloys of the present invention or silver alloy film comprise following situation, and the reflection of light rate that is exposed to the 550nm after 200 hours in 85 ℃, the hot and humid atmosphere of 90RH% is 88% or higher.
Silver alloy film of the present invention also is included as reflectance coating or slim semi-permeable membranes or the pass semi-permeable membranes is arranged or form the electrode of pattern or the situation of distribution.These reflectance coatings or slim semi-permeable membranes or the pass semi-permeable membranes is arranged or form the situation of the electrode of pattern or the formation portion material that distribution is included as self-luminous display or flat-panel monitor or be the situation of quartzy vibrator with electrode.Above-mentioned reflectance coating, distribution, electrode or reflecting electrode also are included as the situation of the formation portion material of electronic units such as LED.Silver alloy film of the present invention also is included as the situation of the electromagnetic wave shielding protective membrane of reflection electromagnetic wave well.
The invention still further relates to the self-luminous display and the flat-panel monitor that possess reflectance coating of the present invention or the pass semi-permeable membranes is arranged.The invention still further relates to the headlight that possesses reflectance coating of the present invention or projector mirror with illuminace components such as lamps.The invention still further relates to either party CD media at least that possesses reflectance coating of the present invention or slim semi-permeable membranes.At this, self-luminous display comprises OLED display, inorganic EL indicating meter, SED (SurfaceConductionElectronEmitterDisplay or surface conductance type electron emission display device) and FED (field-emitter display).Flat-panel monitor comprises liquid-crystal display, PDP (plasma display), TFT (Thin Film Transistor) and C-STN (Color Super Twisted Nematic).As CD media, DVD-R, DVE-RW, DVD-RAM, HD-DVD, BD-R, BD-RE or BD-ROM are for example arranged.As the mode example of preceding lamp part, the reflectance coating in the configuration of the rear of luminescent part is arranged.As the mode example of projector, the speculum that has projection to use.The mirror of lamp part comprises tamper (light detects (pick up) and uses mirror, optical communication mirror).
Silver alloys of the present invention is brought into play excellent thermotolerance by the synergy of Cu and Ge, and brings into play excellent sulfidation-resistance by the existence of Ge.The result has excellent thermotolerance and sulfidation-resistance concurrently.Therefore, during as reflective electrode film, for example in the manufacturing process of the manufacturing process of flat-panel monitors such as colour liquid crystal display device or organic EL, self-luminous displays such as inorganic EL, LED, even through heating process, the yellowing that the reflectivity that causes because of thermal degradation when reduces seldom and is difficult to take place cause because of sulfuration.And, because weathering resistance is improved, silver alloy film of the present invention can be used as reflectance coating and the formation portion material of electronic units such as slim semi-permeable membranes, LED or the reflectance coating of illuminace components such as headlight or projector lamp of CD media.Can also be with silver alloy film of the present invention as the electromagnetic wave shielding protective membrane.Silver alloys of the present invention can also be as the silver alloys slurry.
Description of drawings
[Fig. 1] is the sketch chart of a kind of mode of the expression mold that injects silver alloys, the situation on expression heated mold top.
[Fig. 2] is the sketch chart of the 2nd kind of mode of the expression mold that injects silver alloys, the situation of expression cooling mold bottom.
[Fig. 3] represents for chilled ingot the sketch chart of a kind of mode of the tangent line of feeding head portion (a-a ' line).
[Fig. 4] is the afm image after the silver alloy film film forming, (a) expression embodiment 1, (b) expression comparative example 1, (c) expression comparative example 3, (d) expression comparative example 5.
[Fig. 5] is the comparison diagram of the reflection spectrum of expression embodiment 1 and comparative example 1,3,5.
[Fig. 6] is the afm image of silver alloy film after 250 ℃ of following 1 hour heat treated, (a) expression embodiment 2, (b) expression comparative example 2, (c) expression comparative example 4, (d) expression comparative example 6.
[Fig. 7] is the comparison diagram of the reflection spectrum of expression embodiment 2 and comparative example 2,4,6.
[Fig. 8] is the afm image after Ag-Pd-Cu-Ge 250 ℃ of following 1 hour heat treated that to be silver alloy film cause because of the Ge content, (a) expression embodiment 3, (b) expression embodiment 4, (c) expression embodiment 5, (d) expression comparative example 4.
[Fig. 9] is the comparison diagram of the reflection spectrum of expression embodiment 3 and comparative example 4.
[Figure 10] is that Ag-Pd-Cu-Ge is the afm image of the hot and humid processing that causes because of the Ge content of silver alloy film (85 ℃, 90%RH, after 30 minutes), (a) expression embodiment 6, (b) expression embodiment 7, (c) expression embodiment 8, (d) expression comparative example 7.
[Figure 11] is the comparison diagram of the reflection spectrum of expression embodiment 14, comparative example 11, reference example 1.
[Figure 12] is the comparison diagram of the reflection spectrum of expression embodiment 15, comparative example 12, comparative example 13, reference example 2.
Embodiment
Embodiment is shown below, the present invention is described in detail, but be not limited to these records for explanation of the present invention.
The described silver alloys of present embodiment is a principal constituent with Ag, has the composition of at least 4 kinds of elements that contain Ag, Pd, Cu and Ge.Though the described silver alloys of present embodiment is principal constituent with Ag, as the reflecting electrode mould material time, with Al or Al alloy phase ratio, the high-reflectivity and the low-resistivity of expectation reflective electrode film.The described silver alloys of present embodiment is with the basis that consists of of 4 kinds of elements containing Ag-Pd-Cu-Ge system, and the Ag content in the preferred silver alloys is 97.00～99.79wt%.The reason of silver alloys as the composition that contains at least 4 kinds of elements is in addition, although it basic composition is Ag-Pd-Cu-Ge system, also can suitably add the 5th kind of element in reaching the scope of effect of the present invention.
In the described silver alloys of present embodiment, Pd content is made as 0.10～2.89wt%, be preferably 0.5～2.0wt%.If add Pd, just can in the grain circle of Ag, disperse equably to fill Pd, thereby improve the no weathering resistance under high temperature and high humidity (how wet) environment that Ag possesses; If Pd contains quantity not sufficient 0.10wt%, will be difficult to produce the effect of improving of weathering resistance.On the other hand, essential from the interpolation of these 2 kinds of elements of Cu, Ge if Pd content surpasses 2.89wt%, Ag content reduces as a result, thereby can be observed original reflectivity reduction.
In the described silver alloys of present embodiment, Cu content is made as 0.10～2.89wt%, be preferably 0.20～2.0wt%.Merely only add Pd in Ag, if through for example 250 ℃ of following heating processes of about 1 hour, then comparative example is described as described later, can see the growth of the surfaceness that causes because of cohesion and the generation of projection significantly.Therefore, Pd content is controlled in the above-mentioned scope, in silver alloys, also contains the Cu of 0.10～2.89wt% as the third element.If Cu contains quantity not sufficient 0.10wt%, will be difficult to produce the effect of improving that suppresses projection.On the other hand, essential from the interpolation of these 2 kinds of elements of Pd, Ge if Cu content surpasses 2.89wt%, Ag content reduces as a result, thereby can be observed original reflectivity reduction.
In the described silver alloys of present embodiment, Ge content is set at 0.01～1.50wt%, be preferably 0.05～1.0wt%.At simple Ag-Pd-Cu is in the silver alloys, if through for example 250 ℃ of following heating processes of about 1 hour, then comparative example is described as described later, and the growth of the surfaceness that causes because of cohesion and the generation of projection all can produce, thereby causes the reduction of reflectivity.And then, promote sulfuration by heating, owing to do not improved fully, therefore be accompanied by Ag-Pd-Cu and be the yellowing that the sulfuration of silver alloys will produce reflective electrode film for sulfuration, also can cause the brightness of colour liquid crystal display device to reduce.Therefore, in order to improve sulfidation-resistance, and, in silver alloys, contain the Ge of 0.01～1.50wt% as the 4th kind of element in order to improve the thermotolerance of bringing because of the synergy of Cu and Ge.If Ge contains quantity not sufficient 0.01wt%, just be difficult to produce the raising of thermotolerance and sulfidation-resistance.On the other hand, essential from the interpolation of these 2 kinds of elements of Pd, Cu if Ge content surpasses 1.50wt%, Ag content reduces as a result, thereby can see that original reflectivity reduces, weathering resistance reduces and resistivity increases.
In the described silver alloys of present embodiment, preferably the total content with Pd, Cu and Ge is made as 0.21～3.00wt%.If the total of Pd, Cu and Ge contains quantity not sufficient 0.21wt%,, thereby can not obtain weathering resistance, thermotolerance, sulfidation-resistance then because the content of Pd, Cu and Ge is few.On the other hand,, then can not obtain silver-colored original reflectivity, and can see that resistivity increases if the total content of Pd, Cu and Ge surpasses 3.00wt%.
And then in the described silver alloys of present embodiment, the content ratio of Cu and Ge is that Cu content/Ge content is preferably set to (1/20)～(20/1).As the explanation among the embodiment, by in Ag-Pd, adding Cu and Ge, can obtain by add Cu or add that Ge is unavailable, the growth of columnar-shaped particle after the heat treated suppresses and sulfuration suppresses.This can by and deposit Cu and Ge realizes.Therefore, brought into play,, preferably Cu content/Ge content has been set in the scope of (1/20)～(20/1) in order fully to suppress the growth of the columnar-shaped particle after the heat treated because of Cu and Ge are in the silver alloys and deposit the effect of bringing at Ag-Pd-Cu-Ge.
The described silver alloys of present embodiment can be made the silver alloy sputtering target material that is used to make silver alloy film and the form of silver alloys slurry.Also have purposes such as jewelry material.
Described silver alloys of present embodiment or silver alloy film, by being made as above-mentioned composition, the reflection of light rate of having carried out 1 hour 550nm after the heat treated in air under 250 ℃ preferably reaches 90% or higher.And the reflection of light rate that at room temperature is exposed to the 550nm after 48 hours in the hydrogen sulfide atmosphere of 100ppm preferably reaches 75% or higher.And the reflection of light rate that is exposed to the 550nm after 200 hours in 85 ℃, the hot and humid atmosphere of 90RH% preferably reaches 88% or higher.
Then, in the described silver alloys of present embodiment, the method for making the silver alloy sputtering target material is described.
Carry out the weighing of Ag, Pd, the various feed metals of Cu, Ge (gold), and drop in the crucible.At this moment, crucible selects oxygen containing ratio such as carbonaceous crucible few.Perhaps also can use alumina crucible, magnesia crucible.When selecting carbonaceous crucible, because can ratio-frequency heating, therefore there is the carbonaceous crucible of various base metals to put into high-frequency melting furnace input, vacuumize.The pressure of this moment is made as 1.33Pa or littler.Then, make formation Ar atmosphere (1.33 * 10 in the working chamber
4～8.0 * 10
4Pa), melting begins.Smelting temperature is made as 1050～1400 ℃.At this moment, it is that 0.10～2.89wt%, Cu are 0.10～2.89wt% that Ag is made as 97.00～99.79wt%, Pd, Ge content is made as 0.01～1.50wt%, the total content of Pd, Cu and Ge is made as 0.21～3.00wt%, and the content ratio that forms Cu and Ge is the composition of Cu content/Ge content for (1/20)～(20/1), carries out fusion.
After the molten state stabilization, inject melts, make ingot to mold.For the kind of mold, except the few carbonaceous mold of oxygen containing ratio, can also use cast iron casting mould, aluminum oxide mold.In order to make internal gas be easy to be discharged into the external world,, perhaps heat top as shown in Figure 1 or cool off the bottom as shown in Figure 2 for mold.In Fig. 1, when heated mold top, carry out resistance-type heating or because of the heating due to the radio-frequency coil.Behind the cool to room temperature, as shown in Figure 3, cut the top (feeding head portion) of ingot by a-a ' line.
At 600～900 ℃ of following thermal treatment ingots, carry out heat forged, calendering.In the process of rolling, anneal.Annealing is 2 times or carries out more for a long time with in the terminal stage in products thickness.In order to obtain fine and uniform crystal grain, annealing temperature is made as 300～700 ℃.Annealing is preferably carried out in a vacuum or under the inert gas atmosphere.Then, carry out bending correction with pressing machine, straightener.
Cutting surface or periphery are made component shape in rotating disk or milling machine etc.All surfaces that also can abrasive article.The adjustment sheet surface roughness finally can be made the sputter target material of Ag alloy of the present invention.
As mentioned above, when the sputter target material of the silver alloys of making present embodiment, both made when carrying out fusion Ag being added Pd, Cu, Ge, and can be suitable for the easy method that in the past adopted, price still is that method for making all has very big advantage.
Manufacture method to the described silver alloy film of present embodiment describes.The described silver alloy film of present embodiment can adopt above-mentioned silver alloy sputtering target material and obtain by sputtering film-forming.And, 4 kinds of elements are divided into a plurality of targets, carry out sputter simultaneously, control the discharge capacity of various elements, also can carry out film forming by the composition that forms the described silver alloys of present embodiment.
In addition, when the described silver alloy film of present embodiment is carried out film forming, also bonding coat can be set suitably between substrate and film.In this case, as the promotion adherent ground film of various glass substrates, preferred Si, Ta, Ti, Mo, Cr, Al, ITO, ZnO, SiO
2, TiO
2, Ta
2O
5, ZrO
2
The described 4 yuan of prime system silver alloys of present embodiment, wherein, resistivity is identical with 3 elements (Ag-Pd-Cu).
The described silver alloy film of present embodiment, because weathering resistance, thermotolerance, sulfidation-resistance excellence, therefore has following purposes: reflective electrode film, the reflectance coating of (1) self-luminous display and flat-panel monitor etc. or the pass semi-permeable membranes is arranged, (2) distribution, (3) reflectance coating of CD media and slim semi-permeable membranes, (4) electromagnetic shielding film, reflectance coating, distribution or the electrode film of electronic units such as (5) LED, (6) mirror of illuminace component such as headlight or projector lamp, (7) building glass etc.Silver alloy film of the present invention also is included as the situation of slim semi-permeable membranes.Semi-permeable membranes is except being 1～50nm can obtain when thin at thickness, even can also surpass the pass semi-permeable membranes that has that is formed with light hole that 50nm also makes a part of incident light see through and obtain by making thickness.Slim semi-permeable membranes is mainly used in CD media, and the pass semi-permeable membranes that has that forms light hole is mainly used in self-luminous display or flat-panel monitor or reflecting electrode.In addition, CD media comprises either party situation at least with reflectance coating or slim semi-permeable membranes.And, even the described silver alloy film of present embodiment as electronic unit, also can widespread use.For example, as circuit block, can be as the electrode of resistor or electrical condenser etc., perhaps as the contact of switch etc., perhaps be used as the distribution of network of communication element, strainer, safety fuse, thermistor, vibrator resonator, varistor, printed-wiring board (PWB) etc., perhaps as the electrode of source element etc., perhaps as the distribution of power source circuit parts etc., perhaps as the electrode of unicircuit, IC etc.Can also be as light parts, transmitter, display unit, I/O (I/O) and widespread use.The contact that for example can be used as the reflectance coating, input input element etc. of light parts etc. uses.
Embodiment
(embodiment 1)
Make 98.7Ag-0.8Pd-0.3Cu-0.2Ge with the method shown in the embodiment and (be meant Ag content: 98.7wt%, Pd content: 0.8wt%, Cu content: 0.3wt%, Ge content: 0.2wt%.The composition of below representing silver alloys with this labelling method.) the silver alloy sputtering target material.Adopt this silver alloy sputtering target material, have on the quartz glass substrate of smooth-flat-surface the silver alloy reflective that forms above-mentioned composition with sputtering method, with this as embodiment 1.Thickness is 200nm.Film forming AFM (atomic force microscope, Atomic Force Microscope, SII society system, the model SPA300HV) image of film shown in Fig. 4 (a).At this moment, carry out surface roughness analysis, Ra (nm) is 1.410, and RMS (nm) is 1.785, and P-V (nm) is 14.07.Further use spectrophotometer (society of Shimadzu Seisakusho Ltd. system, model UV-3100PC) to measure the reflectivity of the silver alloy film of embodiment 1.The wavelength region of using is made as 400～800nm.The results are shown in Fig. 5.
(embodiment 2)
Silver alloy film to embodiment 1 in air, under 250 ℃ has carried out 1 hour heat treated.With this as embodiment 2.For the silver alloy film of embodiment 2, also carry out AFM in the same manner and observe with embodiment 1, afm image is shown among Fig. 6 (a).At this moment, carry out surface roughness analysis, Ra (nm) is 1.693, and RMS (nm) is 2.203, and P-V (nm) is 24.55.And then, measured the reflectivity of the silver alloy film of embodiment 2 in the same manner with embodiment 1.The results are shown among Fig. 7.
(comparative example 1)
Make the silver alloy sputtering target material of 99.2Ag-0.8Pd with the method shown in the embodiment.Adopt this silver alloy sputtering target material, have on the quartz glass substrate of smooth-flat-surface the silver alloy reflective that forms above-mentioned composition with sputtering method, with this as a comparative example 1.Thickness is 200nm.With embodiment 1 in the same manner film forming the afm image of film be shown among Fig. 4 (b).At this moment, carry out surface roughness analysis, Ra (nm) is 6.265, and RMS (nm) is 8.447, and P-V (nm) is 64.31.Further measured the reflectivity of the silver alloy film of comparative example 1.The results are shown among Fig. 5.
(comparative example 2)
Silver alloy film to comparative example 1 in air, under 250 ℃ has carried out 1 hour heat treated.With this as a comparative example 2.For the silver alloy film of comparative example 2, also carry out AFM in the same manner and observe with embodiment 1, afm image is shown among Fig. 6 (b).At this moment, carry out surface roughness analysis, Ra (nm) is 6.265, and RMS (nm) is 8.447, and P-V (nm) is 64.31.And then, measured the reflectivity of the silver alloy film of comparative example 2 in the same manner with embodiment 1.The results are shown among Fig. 7.
(comparative example 3)
Make the silver alloy sputtering target material of 98.9Ag-0.8Pd-0.3Cu with the method shown in the embodiment.Adopt this silver alloy sputtering target material, have on the quartz glass substrate of smooth-flat-surface the silver alloy reflective that forms above-mentioned composition with sputtering method, with this as a comparative example 3.Thickness is 200nm.With embodiment 1 in the same manner film forming the afm image of film be shown among Fig. 4 (c).At this moment, carry out surface roughness analysis, Ra (nm) is 1.533, and RMS (nm) is 1.977, and P-V (nm) is 16.98.Further measured the reflectivity of the silver alloy film of comparative example 3.The results are shown among Fig. 5.
(comparative example 4)
Silver alloy film to comparative example 3 in air, under 250 ℃ carries out 1 hour heat treated.With this as a comparative example 4.For the silver alloy film of comparative example 4, also carry out AFM in the same manner and observe with embodiment 1, afm image is shown among Fig. 6 (c).At this moment, carry out surface roughness analysis, Ra (nm) is 2.034, and RMS (nm) is 2.850, and P-V (nm) is 35.85.And then, measured the reflectivity of the silver alloy film of comparative example 4 in the same manner with embodiment 1.The results are shown among Fig. 7.
(comparative example 5)
Make the silver alloy sputtering target material of 99.0Ag-0.8Pd-0.2Ge with the method shown in the embodiment.Adopt this silver alloy sputtering target material, have on the quartz glass substrate of smooth-flat-surface the silver alloy reflective that forms above-mentioned composition with sputtering method, with this as a comparative example 5.Thickness is 200nm.With embodiment 1 in the same manner film forming the afm image of film be shown among Fig. 4 (d).At this moment, carry out surface roughness analysis, Ra (nm) is 1.794, and RMS (nm) is 2.280, and P-V (nm) is 21.16.Further measured the reflectivity of the silver alloy film of comparative example 5.The results are shown among Fig. 5.
(comparative example 6)
Silver alloy film to comparative example 5 in air, under 250 ℃ carries out 1 hour heat treated.With this as a comparative example 6.For the silver alloy film of comparative example 6, identical with embodiment 1, also carry out AFM and observe, afm image is shown among Fig. 6 (d).At this moment, carry out surface roughness analysis, Ra (nm) is 8.794, and RMS (nm) is 11.80, and P-V (nm) is 83.98.And then, measured the reflectivity of the silver alloy film of comparative example 6 in the same manner with embodiment 1.The results are shown among Fig. 7.
By comparing embodiment 1 and 2 and comparative example 1～6, can estimate the thermotolerance of silver alloys.At first, with reference to Fig. 4, the comparison of the microtexture of the afm image of the reflectance coating of having estimated based on film forming with embodiment 1 and comparative example 1,3,5.For the crystal grain size of silver alloy film, be that the comparative example 1 of 2 yuan of prime systems is obviously big.3 remaining examples, any example is all little, carries out surface roughness analysis, attenuates by the order of comparative example 5, comparative example 3, embodiment 1.On the other hand, if pass through the reflectivity of Fig. 5 comparing embodiment 1 and comparative example 1,3,5, the difference of (embodiment 1) that (comparative example 1) that reflectivity is the highest and reflectivity are minimum is about 1～2% at most.Reflectivity has the high more just high more trend of silver content in the silver alloys.
Then, with reference to Fig. 6, estimate comparison based on the microtexture of the afm image of the reflectance coating after the heat treated with embodiment 2 and comparative example 2,4,6.For the crystal grain size of silver alloy film, comparative example 6 and comparative example 2 are obviously big, can see the grain growth through heat treated.Can see grain growth slightly in the comparative example 4, particularly only some particle highland becomes to grow up to column.The hi-lite of the afm image of Fig. 6 (b) is the particle that high column is grown up.On the other hand, embodiment 2 does not almost see the grain growth.Can see the result of surface roughness analysis and the correlationship of using the grain growth degree of estimating with afm image.On the other hand, the reflectivity of comparing embodiment 2 and comparative example 2,4,6.If comparative example 2,4,6 and for the comparative example 1,3,5 before the thermal treatment compares respectively, reflectivity for example when 400nm, reduces about 21～25% significantly.On the other hand, if comparing embodiment 2 and embodiment 1, the reflectivity that is caused by heat treated is reduced to about 7%.Therefore, if embodiment 2 compares with comparative example 2,4,6, reflectivity has improved 13～17% when 400nm.
By the comparison of embodiment 1,2 and comparative example 1～6, understand following situation.If in Ag-Pd system, add Cu or Ge or Cu-Ge, even can realize the minuteness particleization of film in either case.Then, the interpolation of Cu can suppress to grow up because of the grain that heating causes, but does not reach the growth that suppresses local big column crystallization of growing up.On the other hand, the interpolation of Ge can cause the grain growth that causes because of heating.Yet, add Cu-Ge and can all suppress to grow up and the growth of column crystallization because of the grain that heating causes.With add Ge and can cause that grain grows up comparatively speaking, add simultaneously Cu and Ge then grain grow up and the growth of column crystallization all is inhibited.Though this reason is uncertain, compare with either party situation of adding Cu and Ge, by in silver alloys, being contained jointly, think to obtain the inhibition effect that above-mentioned grain is grown up.And then, when comparison diagram 5 and Fig. 7,, think because of the growth of the surfaceness that has suppressed reflectance coating and the generation of projection even why embodiment 2 also still keeps high-reflectivity through heat treated.And if visual observations embodiment 2 and comparative example 2,4,6, comparative example 2,4,6 vulcanizes a little and yellowing is relative therewith, does not have painted in embodiment 2.Therefore think that in embodiment 2, except the generation of the growth that suppresses surfaceness and projection, Ag-Pd-Cu-Ge is that silver alloys can not vulcanize through after the heat treated yet, has therefore kept high-reflectivity.Think that this mainly adds the effect of Ge.
Then, be that silver alloys has carried out because of the thermotolerance that the Ge content causes, the evaluation of reflectivity for Ag-Pd-Cu-Ge.
(embodiment 3)
Make the silver alloy sputtering target material of 98.4Ag-0.8Pd-0.3Cu-0.5Ge with the method shown in the embodiment.Adopt this silver alloy sputtering target material, have the silver alloy reflective that forms above-mentioned composition on the quartz glass substrate of smooth-flat-surface with sputtering method.Thickness is 200nm.In air, under 250 ℃, this silver alloy film is carried out 1 hour heat treated.With this as embodiment 3.Silver alloy film to embodiment 3 also carries out the AFM observation in the same manner with embodiment 1, and afm image is shown among Fig. 8 (a).At this moment, carry out surface roughness analysis, Ra (nm) is 1.727, and RMS (nm) is 2.314, and P-V (nm) is 28.06.And then, measured the reflectivity of the silver alloy film of embodiment 3 in the same manner with embodiment 1.The results are shown among Fig. 9.
(embodiment 4)
Make the silver alloy sputtering target material of 97.9Ag-0.8Pd-0.3Cu-1.0Ge with the method shown in the embodiment.Adopt this silver alloy sputtering target material, have the silver alloy reflective that forms above-mentioned composition on the quartz glass substrate of smooth-flat-surface with sputtering method.Thickness is 200nm.In air, under 250 ℃, this silver alloy film is carried out 1 hour heat treated.With this as embodiment 4.Silver alloy film to embodiment 4 also carries out the AFM observation in the same manner with embodiment 1, and afm image is shown among Fig. 8 (b).At this moment, carry out surface roughness analysis, Ra (nm) is 1.252, and RMS (nm) is 1.656, and P-V (nm) is 22.75.
(embodiment 5)
Make the silver alloy sputtering target material of 97.4Ag-0.8Pd-0.3Cu-1.5Ge with the method shown in the embodiment.Adopt this silver alloy sputtering target material, have the silver alloy reflective that forms above-mentioned composition on the quartz glass substrate of smooth-flat-surface with sputtering method.Thickness is 200nm.In air, under 250 ℃, this silver alloy film is carried out 1 hour heat treated.With this as embodiment 5.Silver alloy film to embodiment 5 also carries out the AFM observation in the same manner with embodiment 1, and afm image is shown among Fig. 8 (c).At this moment, carry out surface roughness analysis, Ra (nm) is 2.128, and RMS (nm) is 2.289, and P-V (nm) is 22.89.
(comparative example 4)
In order to compare, the afm image of comparative example 4 is shown among Fig. 8 (d).Reflectivity is shown among Fig. 9.
With reference to Fig. 8, embodiment 3～5 compares with comparative example 4, has suppressed the growth of the columnar-shaped particle that causes because of heat treated.This is considered to because of the synergy owing to Cu and Ge thermotolerance is improved.And in Fig. 9, embodiment 3 is also higher than the reflectivity of comparative example 4.This is considered to because kept flat surfaces by the thermotolerance raising.And, also think because suppressed the sulfuration of reflectance coating.At this moment, if use visual observations, comparative example 4 yellowing a little, relative therewith, embodiment 3～5 does not have painted.From the result of Fig. 7 and Fig. 9 as can be known: the described silver alloy film of present embodiment carries out 1 hour 550nm after the heat treated air, under 250 ℃ reflection of light rate is 90% or higher.
Then, be the evaluation that silver alloys has carried out the high-temp resisting high-humidity resisting that causes because of the Ge content to Ag-Pd-Cu-Ge.
(embodiment 6)
Make the silver alloy sputtering target material of 98.4Ag-0.8Pd-0.3Cu-0.5Ge with the method shown in the embodiment.Adopt this silver alloy sputtering target material, have the silver alloy reflective that forms above-mentioned composition on the quartz glass substrate of smooth-flat-surface with sputtering method.Thickness is 200nm.In air, under 85 ℃, 90%RH, this silver alloy film was carried out heat treated 0.5 hour.With this as embodiment 6.Silver alloy film to embodiment 6 also carries out the AFM observation in the same manner with embodiment 1, and afm image is shown among Figure 10 (a).At this moment, carry out surface roughness analysis, Ra (nm) is 1.471, and RMS (nm) is 1.884, and P-V (nm) is 20.76.
(embodiment 7)
Make the silver alloy sputtering target material of 97.9Ag-0.8Pd-0.3Cu-1.0Ge with the method shown in the embodiment.Adopt this silver alloy sputtering target material, have the silver alloy reflective that forms above-mentioned composition on the quartz glass substrate of smooth-flat-surface with sputtering method.Thickness is 200nm.In air, under 85 ℃, 90%RH, this silver alloy film is carried out hot and humid processing 0.5 hour.With this as embodiment 7.Silver alloy film to embodiment 7 also carries out the AFM observation in the same manner with embodiment 1, and afm image is shown among Figure 10 (b).At this moment, carry out surface roughness analysis, Ra (nm) is 0.9948, and RMS (nm) is 1.486, and P-V (nm) is 30.55.
(embodiment 8)
Make the silver alloy sputtering target material of 97.4Ag-0.8Pd-0.3Cu-1.5Ge with the method shown in the embodiment.Adopt this silver alloy sputtering target material, have the silver alloy reflective that forms above-mentioned composition on the quartz glass substrate of smooth-flat-surface with sputtering method.Thickness is 200nm.In air, under 85 ℃, 90%RH, this silver alloy film is carried out hot and humid processing 0.5 hour.With this as embodiment 8.Silver alloy film to embodiment 8 also carries out the AFM observation in the same manner with embodiment 1, and afm image is shown among Figure 10 (c).At this moment, carry out surface roughness analysis, Ra (nm) is 0.8017, and RMS (nm) is 1.016, and P-V (nm) is 9.146.
(comparative example 7)
Make the silver alloy sputtering target material of 98.9Ag-0.8Pd-0.3Cu with the method shown in the embodiment.Adopt this silver alloy sputtering target material, have the silver alloy reflective that forms above-mentioned composition on the quartz glass substrate of smooth-flat-surface with sputtering method.Thickness is 200nm.In air, under 85 ℃, 90%RH, this silver alloy film is carried out hot and humid processing 0.5 hour.With this as a comparative example 7.Silver alloy film to comparative example 7 also carries out the AFM observation in the same manner with embodiment 1, and afm image is shown among Figure 10 (d).At this moment, carry out surface roughness analysis, Ra (nm) is 1.302, and RMS (nm) is 1.646, and P-V (nm) is 14.40.
With reference to Figure 10, embodiment 6～8, comparative example 7 do not see that grain is grown up and columnar-shaped particle is grown up under above-mentioned hot and humid condition.
Then, be the evaluation that silver alloys has carried out the sulfidation-resistance that causes because of the Ge content to Ag-Pd-Cu-Ge.
(embodiment 9)
Mensuration will the silver alloy film (thickness be 200nm) identical with embodiment 1 be exposed to the reflectivity after 48 hours in the hydrogen sulfide atmosphere of 100ppm.The results are shown in the table 1.
(embodiment 10)
Make the silver alloy sputtering target material of 97.9Ag-0.8Pd-0.3Cu-1.0Ge with the method shown in the embodiment.Adopt this silver alloy sputtering target material, have on the quartz glass substrate of smooth-flat-surface the silver alloy reflective that forms above-mentioned composition with sputtering method, with this as embodiment 10.Mensuration is exposed to the silver alloy film (thickness is 200nm) of embodiment 10 reflectivity after 48 hours in the hydrogen sulfide atmosphere of 100ppm.The results are shown in the table 1.
(comparative example 8)
Mensuration is exposed to fine silver film (thickness is 200nm) reflectivity after 48 hours in the hydrogen sulfide atmosphere of 100ppm.The results are shown in the table 1.
(comparative example 9)
Mensuration will the silver alloy film (thickness be 200nm) identical with comparative example 3 be exposed to the reflectivity after 48 hours in the hydrogen sulfide atmosphere of 100ppm.The results are shown in the table 1.
Just can know clearly with reference to table 1: contain the embodiment 9,10 of Ge, sulfidation-resistance is excellent especially, and particularly embodiment 10, and the reduction of its reflectivity is few.By table 1 result as can be known: embodiment 10 described silver alloy films, the reflection of light rate that at room temperature is exposed to the 550nm after 48 hours in the hydrogen sulfide atmosphere of 100ppm has surpassed 75%.
[table 1]
Then, be the evaluation (the long-time evaluation) that silver alloys has carried out the high-temp resisting high-humidity resisting that causes because of the Ge content to Ag-Pd-Cu-Ge.
(embodiment 11)
Make the silver alloy sputtering target material of 98.4Ag-0.8Pd-0.3Cu-0.5Ge with the method shown in the embodiment.Adopt this silver alloy sputtering target material, have the silver alloy reflective that forms above-mentioned composition on the quartz glass substrate of smooth-flat-surface with sputtering method.Thickness is 200nm.In air, under 85 ℃, 90%RH, this silver alloy film is carried out hot and humid processing 200 hours.With this as embodiment 11.Silver alloy film to embodiment 11 is also measured reflectivity in the same manner with embodiment 1.The results are shown in the table 2.
(embodiment 12)
Make the silver alloy sputtering target material of 97.9Ag-0.8Pd-0.3Cu-1.0Ge with the method shown in the embodiment.Adopt this silver alloy sputtering target material, have the silver alloy reflective that forms above-mentioned composition on the quartz glass substrate of smooth-flat-surface with sputtering method.Thickness is 200nm.In air, under 85 ℃, 90%RH, this silver alloy film is carried out hot and humid processing 200 hours.With this as embodiment 12.Silver alloy film to embodiment 12 is also measured reflectivity in the same manner with embodiment 1.The results are shown in the table 2.
(embodiment 13)
Make the silver alloy sputtering target material of 97.4Ag-0.8Pd-0.3Cu-1.5Ge with the method shown in the embodiment.Adopt this silver alloy sputtering target material, have the silver alloy reflective that forms above-mentioned composition on the quartz glass substrate of smooth-flat-surface with sputtering method.Thickness is 200nm.In air, under 85 ℃, 90%RH, this silver alloy film is carried out hot and humid processing 200 hours.With this as embodiment 13.Silver alloy film to embodiment 13 is also measured reflectivity in the same manner with embodiment 1.The results are shown in the table 2.
(comparative example 10)
Make the sputter target material of fine silver with the method shown in the embodiment.Adopt this silver sputter target material, have the silver-colored reflectance coating of formation on the quartz glass substrate of smooth-flat-surface with sputtering method.Thickness is 200nm.In air, under 85 ℃, 90%RH, this silver film is carried out hot and humid processing 200 hours.With this as a comparative example 10.Measure reflectivity in the same manner with embodiment 1.The results are shown in the table 2.
[table 2]
Just can know clearly with reference to table 2: the embodiment 11,12 and 13 that contains Ge is excellent on weathering resistance, and the reduction of reflectivity is few.That is, the described silver alloy film of the present embodiment reflection of light rate that is exposed to the 550nm after 200 hours in 85 ℃, the hot and humid processing atmosphere of 90RH% is 90% or higher as can be known.Therefore, the described silver alloy film of present embodiment is preferably as CD media, headlight or the projector reflectance coating with lamp.In addition, also preferred reflectance coating, distribution, electrode or reflecting electrode as electronic units such as LED.In addition, also preferably as the electromagnetic wave shielding protective membrane.
Then, be the research that silver alloys has carried out Ge upper content limit value to Ag-Pd-Cu-Ge.
(embodiment 14)
Prepare the silver alloy film identical, in air, under 85 ℃, 90%RH, carry out hot and humid processing 200 hours with embodiment 13.With this as embodiment 14.Measure reflectivity in the same manner with embodiment 1.The results are shown among Figure 11.
(comparative example 11)
Except making with the method shown in the embodiment the silver alloy sputtering target material of 97.3Ag-0.8Pd-0.3Cu-1.6Ge, test in the same manner with embodiment 11.With this as a comparative example 11.Measure reflectivity in the same manner with embodiment 1.The results are shown among Figure 11.
(reference example 1)
Except sputter target material being made as aluminium (100Al), test in the same manner with embodiment 14, promptly get the aluminium film.In air, under 85 ℃, 90%RH, this aluminium film is carried out hot and humid processing 200 hours.With this as a reference example 1.Measure reflectivity in the same manner with embodiment 1.The results are shown among Figure 11.
Contain the comparative example 11 of 1.6wt%Ge, by long high temperature and humidity test, reflectivity greatly reduces, and for example the reflection of light rate of the 650nm that uses in the reading of optical recording medium is also lower than the aluminium film of reference example 1.On the other hand, contain the embodiment 14 of 1.5wt%Ge, even by identical high temperature and humidity test, the reduction of reflectivity is few, greater than the reflection of light rate of the 550nm wavelength aluminium film height than reference example 1.Therefore as can be known, be silver alloys for Ag-Pd-Cu-Ge, Ge content preferably is made as 1.5wt% or lower.
Then, be silver alloys to Ag-Pd-Cu-Ge, carried out research because of the reflectivity due to the silver content.
(embodiment 15)
Make the silver alloy sputtering target material of 98.9Ag-0.6Pd-0.3Cu-0.2Ge with the method shown in the embodiment.Adopt this silver alloy sputtering target material, have the silver alloy reflective that forms above-mentioned composition on the quartz glass substrate of smooth-flat-surface with sputtering method.Thickness is 200nm.With this silver alloy film as embodiment 15.
(comparative example 12)
Except the composition of silver alloy sputtering target material is made as the 95.7Ag-1.0Pd-3.0Cu-0.3Ge, test in the same manner with embodiment 15, promptly get silver alloy film.With this silver alloy film as a comparative example 12.
(comparative example 13)
Except the composition of silver alloy sputtering target material is made as the 95.8Ag-3.0Pd-1.0Cu-0.2Ge, test in the same manner with embodiment 15, promptly get silver alloy film.With this silver alloy film as a comparative example 13.
(reference example 2)
Except sputter target material being made as aluminium (100Al), test in the same manner with embodiment 15, promptly get the aluminium film.With this aluminium film as a reference example 2.
Measured the reflectivity of silver alloy film and aluminium film in the same manner with embodiment 1.The results are shown among Figure 12.Embodiment 15 has been owing to the containing ratio of silver has shown high reflectivity up to 98.9%, and comparative example 12 and comparative example 13 is because the containing ratio of silver less than 97% and reflectivity is low all.Even compare with the aluminium film of reference example 2, for example reflectivity is low under 650nm.By the comparison of embodiment 15, comparative example 12 and comparative example 13, be that the silver alloys preferred silver content reaches 97wt% or higher for Ag-Pd-Cu-Ge as can be known.
In addition, the composition with embodiment, comparative example and reference example is summarised in the table 3.
[table 3]
| Form (weight %) | |
| Embodiment 1 | 98.7Ag-0.8Pd-0.3Cu-0.2Ge |
| Embodiment 2 | 98.7Ag-0.8Pd-0.3Cu-0.2Ge |
| Embodiment 3 | 98.4Ag-0.8Pd-0.3Cu-0.5Ge |
| Embodiment 4 | 97.9Ag-0.8Pd-0.3Cu-1.0Ge |
| Embodiment 5 | 97.4Ag-0.8Pd-0.3Cu-1.5Ge |
| Embodiment 6 | 98.4Ag-0.8Pd-0.3Cu-0.5Ge |
| Embodiment 7 | 97.9Ag-0.8Pd-0.3Cu-1.0Ge |
| Embodiment 8 | 97.4Ag-0.8Pd-0.3Cu-1.5Ge |
| Embodiment 9 | 98.7Ag-0.8Pd-0.3Cu-0.2Ge |
| Embodiment 10 | 97.9Ag-0.8Pd-0.3Cu-1.0Ge |
| Embodiment 11 | 98.4Ag-0.8Pd-0.3Cu-0.5Ge |
| Embodiment 12 | 97.9Ag-0.8Pd-0.3Cu-1.0Ge |
| Embodiment 13 | 97.4Ag-0.8Pd-0.3Cu-1.5Ge |
| Embodiment 14 | 97.4Ag-0.8Pd-0.3Cu-1.5Ge |
| Embodiment 15 | 98.9Ag-0.6Pd-0.3Cu-0.2Ge |
| Comparative example 1 | 99.2Ag-0.8Pd |
| Comparative example 2 | 99.2Ag-0.8Pd |
| Comparative example 3 | 98.9Ag-0.8Pd-0.3Cu |
| Comparative example 4 | 98.9Ag-0.8Pd-0.3Cu |
| Comparative example 5 | 99.0Ag-0.8Pd-0.2Ge |
| Comparative example 6 | 99.0Ag-0.8Pd-0.2Ge |
| Comparative example 7 | 98.9Ag-0.8Pd-0.3Cu |
| Comparative example 8 | 100Ag |
| Comparative example 9 | 98.9Ag-0.8Pd-0.3Cu |
| Comparative example 10 | 100Ag |
| Comparative example 11 | 97.3Ag-0.8Pd-0.3Cu-1.6Ge |
| Comparative example 12 | 95.7Ag-1.0Pd-3.0Cu-0.3Ge |
| Comparative example 13 | 95.8Ag-3.0Pd-1.0Cu-0.2Ge |
| Reference example 1 | 100Al |
| Reference example 2 | 100Al |
Claims (21)
1, silver alloys is characterized in that, has the composition that only contains 4 kinds of elements, wherein,
Ag content is that 97.00～99.79wt%, Pd content are that 0.10～2.89wt%, Cu content are that 0.10～2.89wt%, Ge content are 0.01～1.50wt%,
And the total content of Pd, Cu and Ge is 0.21～3.00wt%,
The reflection of light rate of having carried out 1 hour 550nm after the heat treated in air, under 250 ℃ is 90% or higher, has the thermotolerance that suppresses the degree that projection takes place after this heat treated.
2, the described silver alloys of claim 1 is characterized in that, is that Cu content/Ge content is made as (1/20)～(20/1) with the content ratio of Cu and Ge.
3, the described silver alloys of claim 1 is characterized in that, the reflection of light rate that at room temperature is exposed to the 550nm after 48 hours in the hydrogen sulfide atmosphere of 100ppm is 75% or higher.
4, the described silver alloys of claim 2 is characterized in that, the reflection of light rate that at room temperature is exposed to the 550nm after 48 hours in the hydrogen sulfide atmosphere of 100ppm is 75% or higher.
5, the described silver alloys of claim 1 is characterized in that, the reflection of light rate that is exposed to the 550nm after 200 hours in 85 ℃, the hot and humid atmosphere of 90RH% is 88% or higher.
6, the described silver alloys of claim 2 is characterized in that, the reflection of light rate that is exposed to the 550nm after 200 hours in 85 ℃, the hot and humid atmosphere of 90RH% is 88% or higher.
7, the silver alloy sputtering target material is characterized in that, is to form with claim 1,2,3,4,5 or 6 described silver alloys.
8, silver alloy film, it is characterized in that, be to form with claim 1,2,3,4,5 or 6 described silver alloys, the reflection of light rate of having carried out 1 hour 550nm after the heat treated in air, under 250 ℃ is 90% or higher, has the thermotolerance that suppresses the degree that projection takes place after this heat treated.
9, the described silver alloy film of claim 8 is characterized in that, the reflection of light rate that at room temperature is exposed to the 550nm after 48 hours in the hydrogen sulfide atmosphere of 100ppm is 75% or higher.
10, the described silver alloy film of claim 8 is characterized in that, the reflection of light rate that is exposed to the 550nm after 200 hours in 85 ℃, the hot and humid atmosphere of 90RH% is 88% or higher.
11, claim 8,9 or 10 described silver alloy films is characterized in that, described silver alloy film is a reflectance coating.
12, claim 8,9 or 10 described silver alloy films is characterized in that, described silver alloy film is slim semi-permeable membranes.
13, claim 8,9 or 10 described silver alloy films is characterized in that, described silver alloy film is for forming the electrode or the distribution of pattern.
14, self-luminous display is characterized in that, possess the described reflectance coating of claim 11 or on the described reflectance coating of claim 11, form make light hole that a part of incident light sees through the pass semi-permeable membranes arranged.
15, flat-panel monitor is characterized in that, possess the described reflectance coating of claim 11 or on the described reflectance coating of claim 11, form make light hole that a part of incident light sees through the pass semi-permeable membranes arranged.
16, reflecting electrode is characterized in that, possess reflectance coating as claimed in claim 11 or on the described reflectance coating of claim 11, form make light hole that a part of incident light sees through the pass semi-permeable membranes arranged.
17, electronic unit is characterized in that, adopts claim 8,9,10,11,12 or 13 described silver alloy films.
18, CD media is characterized in that, possess described reflectance coating of claim 11 or the described slim semi-permeable membranes of claim 12 at least either party.
19, illuminace component is characterized in that, possesses the described reflectance coating of claim 11.
20, the described silver alloy film of claim 11 is characterized in that, described silver alloy film is the electromagnetic wave shielding protective membrane.
21, silver alloys slurry material is characterized in that, is to form with claim 1,2,3,4,5 or 6 described silver alloys.
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| JP2003335760 | 2003-09-26 | ||
| JP335760/2003 | 2003-09-26 | ||
| JP120080/2004 | 2004-04-15 |
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| CN1856587A CN1856587A (en) | 2006-11-01 |
| CN100443609C true CN100443609C (en) | 2008-12-17 |
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| CNB2004800277184A Expired - Lifetime CN100443609C (en) | 2003-09-26 | 2004-07-23 | Silver alloy, sputtering target material thereof, and thin film thereof |
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| CN102337506B (en) * | 2011-09-21 | 2012-09-05 | 广州市尤特新材料有限公司 | Manufacturing method of silver alloy sputtering target |
| CN110284021B (en) * | 2019-06-27 | 2020-06-30 | 袁海 | Intermediate alloy for improving hardness of pure gold and pure silver and preparation method and application thereof |
| CN111235425B (en) * | 2020-02-19 | 2021-04-06 | 基迈克材料科技（苏州）有限公司 | AgPdCu alloy and preparation method thereof, and AgPdCu alloy sputtering target and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05341066A (en) * | 1992-06-01 | 1993-12-24 | Dowa Mining Co Ltd | Magnetic shield and its manufacture |
| JPH09183181A (en) * | 1995-03-22 | 1997-07-15 | Toppan Printing Co Ltd | Forming of multi-layer conductive film |
| JPH10282907A (en) * | 1997-04-10 | 1998-10-23 | Toppan Printing Co Ltd | Electrode substrate |
| JPH11260269A (en) * | 1998-03-11 | 1999-09-24 | Omron Corp | Plasma display device and plasma display substrate thereof |
| JP2001324713A (en) * | 2000-05-15 | 2001-11-22 | Hitachi Ltd | Liquid crystal display element and liquid crystal display device using the same |
| JP2002332568A (en) * | 2001-05-09 | 2002-11-22 | Ishifuku Metal Ind Co Ltd | Sputtering target material |
| JP2002350840A (en) * | 2001-05-28 | 2002-12-04 | Hitachi Ltd | Reflective liquid crystal display device |
| JP2003208801A (en) * | 2001-11-06 | 2003-07-25 | Hitachi Ltd | Light source for projector and projection type image display device using it |
-
2004
- 2004-07-23 CN CNB2004800277184A patent/CN100443609C/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05341066A (en) * | 1992-06-01 | 1993-12-24 | Dowa Mining Co Ltd | Magnetic shield and its manufacture |
| JPH09183181A (en) * | 1995-03-22 | 1997-07-15 | Toppan Printing Co Ltd | Forming of multi-layer conductive film |
| JPH10282907A (en) * | 1997-04-10 | 1998-10-23 | Toppan Printing Co Ltd | Electrode substrate |
| JPH11260269A (en) * | 1998-03-11 | 1999-09-24 | Omron Corp | Plasma display device and plasma display substrate thereof |
| JP2001324713A (en) * | 2000-05-15 | 2001-11-22 | Hitachi Ltd | Liquid crystal display element and liquid crystal display device using the same |
| JP2002332568A (en) * | 2001-05-09 | 2002-11-22 | Ishifuku Metal Ind Co Ltd | Sputtering target material |
| JP2002350840A (en) * | 2001-05-28 | 2002-12-04 | Hitachi Ltd | Reflective liquid crystal display device |
| JP2003208801A (en) * | 2001-11-06 | 2003-07-25 | Hitachi Ltd | Light source for projector and projection type image display device using it |
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| CN1856587A (en) | 2006-11-01 |
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