CN1226446C - Ag alloyed memberane and sputtering target for forming Ag alloyed membrane - Google Patents
Ag alloyed memberane and sputtering target for forming Ag alloyed membrane Download PDFInfo
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- CN1226446C CN1226446C CNB031079121A CN03107912A CN1226446C CN 1226446 C CN1226446 C CN 1226446C CN B031079121 A CNB031079121 A CN B031079121A CN 03107912 A CN03107912 A CN 03107912A CN 1226446 C CN1226446 C CN 1226446C
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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
- C23C14/06—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
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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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
Abstract
A composition of an Ag alloy film as a thin film for electronic devices and target material to form thereof by a sputtering process are disclosed. The Ag alloy film consists of 0.1 to 0.5 atomic % of any one element selected from the group of Sm, Dy and Tb, 0.1 to 1.0 atomic % in total of at least one element selected from the group of Au and Cu, and the balance of Ag and incidental impurities. The Ag alloy film may be used as a wiring film or a reflective film for flat panel display devices. The sputtering-target material for forming the Ag alloy film consists of 0.1 to 0.5 atomic % of any one element selected from the group of Sm, Dy and Tb, 0.1 to 1.0 atomic % in total of at least one element selected from the group of Au and Cu, and the balance of Ag and incidental impurities.
Description
Technical field
The present invention relates to a kind of Ag alloy film and Ag alloy film formation splash target that in thin-film devices such as various reflectance coatings, planar display or various semiconductor device, thin film sensor, magnetic head, needs erosion resistance, thermotolerance and tack.
Background technology
In recent years, especially as the film that uses in electron device, the Ag film with low resistance or high favorable characteristics such as luminous reflectance factor attracts tremendous attention.But, the metallic membrane that Ag forms, though in luminous reflectance factor, resistance, have superperformance,, exist tack for substrate low, produce shortcomings such as distortion that stress causes and then thermotolerance, erosion resistance are low.
In recent years, planar display (flat panel display is hereinafter referred to as FPD), instead the device of electron-beam tube has obtained development rapidly in the past.As this FPD, the electrophoresis type display device that utilizes in liquid crystal indicator (hereinafter referred to as LCD), plasma display dish (hereinafter referred to as PDP), field-emission display device (hereinafter referred to as FED), el display device (hereinafter referred to as ELD), the Electronic Paper etc. is for example arranged.When Ag is used as the wiring membrane of FPD or reflectance coating, exist for the tinsel as the glass of substrate or resin substrate, resin molding, stainless steel that erosion resistance is high etc., the tack of film is low, produce problem such as peel off in processing.
In addition, the heating process during manufacturing by various electron devices produces the distortion that is caused by stress, the smoothness on film surface reduces during film forming.And then, because the material or the heating atmosphere of substrate causes the film aggegation, because the asynechia of film causes that reflectivity descends significantly or the resistance increase.In addition, because the erosion resistance of Ag is low, after film forming on the substrate, only placing in atmosphere about 1 day will variable color, becomes to have the xanchromatic reflection characteristic.And then, exist because the soup that device uses when making, and be corroded, cause emittance to descend significantly or problem that resistance increases.
For addressing the above problem, the method for adding the Ag alloy target material more than the 0.1 atom % in Ag of using is disclosed in JP-A-8-260315.Open the alloy that has proposed to add 0.1～2.5 atom %Au, 0.3～3 atom %Cu in the flat 9-324264 communique the spy.Open the reflection display device electrode base board that has proposed in the flat 11-119664 communique to use at the alloy that in Ag, adds Pt, Pd, Au, Cu, Ni on the adhesive linkage the spy.In addition, in JP-A-2000-109943, proposed in Ag, to add the alloy of 0.5～4.9 atom %Pd.In JP-A-2001-192752, proposed in Ag, to add the alloy of Al, Au, the Pt etc. of Pd, 0.1～3 quality % of 0.1～3 quality %.In addition, open in the 2002-015464 communique the spy, reflectance coating as optical information recording medium is disclosed, the reflectance coating that adds Cu or Nd, Sn, Ge, Y, Au etc. in Ag is in the reflectivity of keeping for specific wavelength laser, also have tack, the scale resistance of optic disc base board or other film good, and effectively from information recording stability aspect.
But, do not propose, when adding elements by these disclosed methods, the increase that has a resistance, reflectivity, the alloy film that can make low resistance, high-reflectivity and tack, deformation resistance, erosion resistance, thermotolerance and deposit of degradation under the reflectivity of the low wavelength side of visible region especially.Specifically, for example, Nd, Pt, Ni, in case add more than the 0.2 atom %, reflectivity descends, and then, if content surpasses more than the 1 atom %, just surpass 5 μ Ω cm than resistance.In addition, during as if interpolation Au and Cu, the reduction of reflectivity or the increase of resistance are less, but have the problem of thermotolerance and tack.
Summary of the invention
The object of the present invention is to provide a kind of when keeping Ag inherent low resistance characteristic or high light reflectivity characteristic as far as possible, the splash target that can also have the Ag alloy film of tack, thermotolerance, erosion resistance or figure plasticity concurrently and be used to form this Ag alloy film.
The inventor, carried out research with keen determination for solving described problem, found that, form the Ag alloy film by in Ag, optionally making up the interpolation element, can at the reflectivity in keeping Ag inherent visible-range in certain value, can also keep the characteristic of high-reflectivity, keep low-resistance characteristic, improve erosion resistance and thermotolerance, and then improved the tack of substrate and figure plasticity etc. have been improved various characteristics, thereby finished the present invention.
That is, the present invention is that containing arbitrary element of selecting from Sm, Dy, Tb is that 0.1～0.5 atom %, Au and/or Cu add up to 0.1～1.0 atom %, the remaining alloy film that is made of Ag and unavoidable impurities.
In addition, the present invention is, contains 0.1～0.5 atom %Sm, and Au and/or Cu add up to 0.1～1.0 atom %, the remaining alloy film that is made of Ag and unavoidable impurities.At this moment, preferably contain Au and/or Cu and add up to 0.1～0.5 atom %.
In addition, the present invention is that a kind of Ag alloy film forms and uses the Ag alloy target material, and containing arbitrary element of selecting from Sm, Dy, Tb is that 0.1～0.5 atom %, Au and/or Cu add up to 0.1～1.0 atom %, remainingly is made of Ag and unavoidable impurities.
The present invention is that a kind of Ag alloy film forms and uses the Ag alloy target material in addition, contains Sm and be that 0.1～0.5 atom %, Au and/or Cu add up to 0.1～1.0 atom % and remainingly be made of Ag and unavoidable impurities.At this moment, preferably contain Au and/or Cu and add up to 0.1～0.5 atom %.
In addition, according to following drawings and Examples the features and advantages of the present invention as can be seen.
Description of drawings
Fig. 1 is the figure that concerns between the ratio resistance of the addition of rare earth element of the Ag alloy film of expression among the embodiment 1 and Ag alloy film.
Fig. 2 is the figure that concerns between the ratio resistance of the addition of interpolation element of the Ag alloy film of expression among the embodiment 2 and Ag alloy film.
Fig. 3 is the figure that concerns between the ratio resistance of the addition of rare earth element of the Ag alloy film of expression among the embodiment 3 and Ag alloy film.
Fig. 4 is the figure that concerns between the reflection differences of the addition of rare earth element of the Ag alloy film of expression among the embodiment 3 and Ag alloy film.
Fig. 5 is the figure that concerns between the average reflectance of the addition of Cu of the Ag alloy film of expression among the embodiment 4 and Ag alloy film.
Fig. 6 is the figure that concerns between the reflection differences of the addition of Cu of the Ag alloy film of expression among the embodiment 4 and Ag alloy film.
Fig. 7 is the figure that concerns between the average reflectance of the addition of Au of the Ag alloy film of expression among the embodiment 5 and Ag alloy film.
Fig. 8 is the figure that concerns between the reflection differences of the addition of Au of the Ag alloy film of expression among the embodiment 5 and Ag alloy film.
Fig. 9 is the figure of the reflectivity of optical wavelength in 400～700nm scope of the Ag alloy film among the expression embodiment 7.
Figure 10 is the figure of the reflectivity of optical wavelength in 400～700nm scope of the Ag alloy film among the expression embodiment 8.
Figure 11 is the figure that concerns between the ratio resistance of the film heat treated temperature of the Ag alloy film of expression among the embodiment 9 and Ag alloy film.
Figure 12 be the Ag gold film of expression among the embodiment 10 the film forming substrate of shape Heating temperature and and the ratio resistance of Ag alloy film between the figure that concerns.
Embodiment
The invention is characterized in, when keeping Ag inherent low resistance characteristic or high light reflectivity characteristic as far as possible, in revising, found that the composition of the suitableeest Ag alloy film constitutes as each characteristic shortcomings such as tack that the Ag film had and figure plasticity, erosion resistance, thermotolerances.
Below the qualification reason of the composition of Ag alloy film of the present invention is described.
If add element in Ag, resistance increases, and reflectivity descends, and still, thermotolerance, erosion resistance, tack, figure plasticity have the tendency of raising along with the increase of adding element.So the inventor finds, when keeping low resistance and high-reflectivity, for improving the shortcoming of above-mentioned Ag, is guaranteeing to add element in minimum necessary amount, the setting of specific and necessary amount that can obtain the element of effect of sufficient is very important.
As the interpolation element that described membrane property is improved, the inventor is conceived to rare earth element.So institute be owing to consider like this, by in Ag, adding rare earth element as the IIIa family of the periodic table of elements, film aggegation in the time of can suppressing to heat the Ag alloy film and have and improve stable on heating effect, in addition, because the intermetallic compound of formation and Ag is so can make the change of properties of Ag self and can improve erosion resistance.
By various researchs, the result, the inventor finds, in the element set of rare earth element, property difference is very big, even in rare earth element, to form the interpolation element of property very effective as solve thermotolerance, erosion resistance, figure in being used to of adding in the Ag alloy for Sm, Dy, Tb.
Though this reason is not very clear and definite, but, can consider it is because in rare earth element, the rare earth element that Sm, Dy, Tb and La, Nd etc. are light is compared because atomic radius is little and Ag is close, so when adding, the lattice disorder of Ag is less, hinders the low cause of effect of the motion of unbound electron.
But, in only adding the Ag alloy film of Sm, Dy or Tb, problem that in film formation process film is peeled off etc. with regard to being faced with, can not obtain enough effects for stopping property.
The inventor has explored the effect of not damaging Sm, Dy or Tb and other other element that tack is significantly improved, and finds by combination interpolation Au and/or Cu very effective to improving tack.And, and then find that the combination of these elements also has the effect of improving thermotolerance and erosion resistance in the zone of low resistance and high-reflectivity.
The reason that can improve tack by interpolation Au, Cu is not very clear, but can be presumed as follows.That is, think Ag and congeners Au and Cu, owing to moving of easy solid solution in Ag and obstruction Ag atom,, suppress the aggegation of Ag, thereby make the tack raising so form the film of fine and uniform formation.In addition, Sm, Dy or Tb since be not only can with Ag can also and Au, Cu form the element of intermetallics easily, so, the character of Ag is changed and improve erosion resistance by Au, Cu and Sm, Dy or Tb are made up interpolation.
In addition, add in combination under the situation of these elements, think when carrying out heat treated, by splash target these elements with nonequilibrium situations solid solution in the Ag of Ag alloy film lattice, separate out at intergranular as intermetallics, owing to suppress the growth of crystal grain, so stable on heatingly suppress intergranular corrosion simultaneously and improve erosion resistance improving.
As previously discussed, add the Au have (Sm, Dy, the Tb) that improves thermotolerance and erosion resistance effect and to have a tack effect and/Cu by combination, both characteristics do not offset as a result, but can and deposit, and this is a key character of the present invention.That is, add described two group elements, can obtain to have concurrently the Ag alloy film of erosion resistance, thermotolerance or tack by combination.In addition,, the effect of thermotolerance, tack, erosion resistance be can improve, still, on the other hand, the rising of resistance and the decline of reflectivity also caused if increase its addition.So the element that adds in Ag also will guarantee to obtain effect of sufficient in minimum necessary amount, both amounts and balance are extremely important.
So, below the addition of the element that adds in Ag is described.
The addition of (Sm, Dy, Tb) just shows it since 0.1 atom % and improves effect,, on the other hand, if surpass 0.5 atom %, and though erosion resistance and excellent heat resistance simultaneously resistance increase reflectivity and descend.And for obtaining lower resistance and high reflectivity, preferably the addition with (Sm, Dy, Tb) is located at below the 0.3 atom %.
In the presence of Sm, Dy, Tb, by adding the tack effect that Cu, Au produce, just can show from the addition of 0.1 atom %, but, on the other hand, for Cu, will cause that the increase of resistance and the decline of reflectivity become big if surpass 1.0 atom %.In addition, if during Au, even add more than the 1.0 atom %, the increase of resistance and the decline of reflectivity are less, still, in case surpass 0.5 atom %, just are easy to generate residue when etching.In addition, if surpass 1.0 atom %, residue becomes many and the figure plasticity reduces.So for obtaining better figure plasticity, preferably the addition with Au and Cu is located at below the 1.0 atom %.In addition,,, when etching, be easy to generate residue and figure plasticity and reduce, still, can remove residue by cleaning in earnest if surpass 0.5 atom % for Au.
Therefore, with respect to the addition of each element of Ag, the content of the arbitrary element in preferred (Sm, Dy, Tb) is that the total content of 0.1～0.5 atom %, Au and/or Cu is 0.1～1.0 atom %.And then in order to realize more high-reflectivity, more low resistance and the good Ag alloy film of figure plasticity, more preferably the content of the arbitrary element in (Sm, Dy, Tb) is that the total content of 0.1～0.5 atom %, Au and/or Cu is 0.1～0.5 atom %.
In addition, Sm, Dy, Tb and Y, Sc etc. relatively in rare earth element, owing to be difficult to oxidation, can stablize the advantage that obtains raw material so also have.Thus, can stablize splash target used when preparing formation Ag alloy film.In addition, in Sm, Dy and Tb, Dy, Tb are owing to the price height, so the low Sm of most preferably industrial cost.
Substrate as used when forming Ag alloy film of the present invention preferably uses sheet glass, silicon chip.These substrates are made the planar display aspect, owing to have advantages of excellent stability when handling, so when forming Ag alloy film of the present invention, also can heat substrate as described below.
Ag alloy film of the present invention after forming film, by the heat treated substrate, can further form low-resistance film.Especially by the heating of the temperature more than 150 ℃, the following low resistance Ag alloy film of 3 μ Ω cm can also be further formed,, the following low resistance Ag alloy film of 2.5 μ Ω cm can be formed further with the heating of the temperature more than 250 ℃.So Ag alloy film of the present invention forms the wiring membrane utilize glass substrate, silicon chip and to have the planar displays such as organic ELD, LCD of the multi-crystal TFT operation of heating process to use and is suitable for for having.
Even for present Ag-Cu alloy, Ag-Pd alloy, in case carry out heat treated, resistance reduces, and when low as if resistance, tack or thermotolerance are insufficient.Key character of the present invention is, also can solve the problem of this class.
In addition, by forming Ag alloy film of the present invention, to be made as ref (max) in maximum value as the reflectivity in optical wavelength 400～700nm scope in the visible-range, when minimum value is made as ref (min), its reflection differences is [(ref (max)-ref (min))/ref (max)] * 100≤6 just), can obtain making the reflectivity in the visible-range of necessity that planar display is used is certain value, and has the reflectance coating of the reflection characteristic of high-reflectivity and thermotolerance, erosion resistance, tack, figure plasticity.
In addition, Ag alloy film of the present invention, because after forming film, pass through heated substrates, and then, the reflectivity that is formed in the visible-range is a certain value, and has the Ag alloy film of the reflection characteristic of high-reflectivity, so be suitable for for the reflectance coating of planar display that utilizes glass substrate, silicon chip and have a reflective liquid crystal demonstration etc. of heating process.
Usually, for present Ag-Cu alloy, Ag-Pd alloy, reduce in case carry out the heat treated reflectivity more.As Ag alloy film of the present invention, the various reflectance coatings that the raising of reflectivity is used etc. as planar display are very useful, also are excellent characteristics of Ag alloy film of the present invention simultaneously.
In addition, when forming Ag alloy film of the present invention, the preferred splash method of utilizing target of using.By the splash method, form essentially identical film owing to can form, so can stably form Ag alloy film of the present invention with target.So, the present invention proposes the alloy film formation splash target that has with used for electronic device Ag alloy film same composition.
For the manufacture method of target, have a variety of, still, as long as it is just passable generally can to reach the desired high purity of target, uniform formation, high-density etc.For example,, the molten metal that is adjusted into definite composition is cast in the metal mold by the vacuum fusion method, and then, be processed into tabularly by forging, roll-in etc., can produce the target of definite shape by mechanical workout.In addition, and then be the acquisition uniform tissue, also can use the ingot bar of powder sintering and sputtering forming method quench solidifications such as (drop method of pilings).
In addition, Ag alloy film of the present invention forms uses the Ag alloy target material, element except that above-mentioned (Sm, Dy, Tb), Au and Cu composition is essentially Ag, but, in the scope of not damaging effect of the present invention, also can contain oxygen, nitrogen, carbon or transition-metal Fe, Co, Ni and unavoidable impurities such as metalloid Al, Si as gaseous constituent.
For example, the oxygen of gaseous constituent, carbon, nitrogen are respectively done for oneself below the 50ppm, and Fe, Ni, Co are below the 100ppm, and with inferior, preferably the purity except that the gas composition is more than 99.9% to Al at 500ppm.
In addition, used substrate when forming Ag alloy film of the present invention can be above-mentioned glass substrate, silicon chip etc., but, as long as can be film forming just passable, for example also can be resin substrate, metal substrate, other resin paper tinsel, tinsel etc.
Used for electronic device Ag alloy film of the present invention, for obtaining steady resistance, as thickness, preferred 100～300nm.If thickness is lower than 100nm, because film is thin, is subjected to electron surface influence at random and resistance is raise, simultaneously because printing opacity, reflectivity descends, and then the configuration of surface of film changes easily.On the other hand, if thickness surpasses 300nm, resistance is low, because membrane stress, film is peeled off easily, because grain growing, and the convex-concave of the configuration of surface of film becomes big, so when reflectivity reduces, want the decline of spended time and productivity when forming film.
Influence when adding rare earth element and Cu, Au for confirming in Ag, to make up, Cu or the Au of 0.3 atom % in Ag, have been added, and then the casting Ag alloy ingot bar that the addition of rare earth element (Y, La, Nd, Sm, Tb, Dy) is changed by the vacuum fusion manufactured respectively, by cold rolling be processed as tabular after, make the Ag alloy target material of diameter 100mm, thickness 5mm by mechanical workout.Then,, on glass substrate, form the Ag alloy film of thickness 200nm, compare resistance at room temperature measuring by 4 probe methods by sputtering method with this sputter Ag alloy target material.Its result as shown in Figure 1.
As shown in Figure 1 as can be known, for any rare earth element, if increase addition, resistance also increases.In rare earth element, the resistance of the Ag alloy film of the resistance ratio of the Ag alloy film of interpolation Sm, Tb or Dy interpolation La or Nd is low.Preferred Sm, Tb, Dy are as adding element in rare earth element.In addition, this addition then surpasses 4 μ Ω cm than resistance if surpass 0.5 atom %, the low-resistance advantage forfeiture of the inherent of Ag.So, as the addition of (Sm, Tb, Dy), preferably below 0.5 atom %.In addition, for obtaining the lower resistance below the 3 μ Ω cm, as the preferred 0.3 atom % of addition.If with Au replaced C u and when adding 0.3 atom %, same with Cu, along with the increase of the addition of Sm, the resistance increase still, can obtain the resistance lower than Cu.
The amount of the Sm that adds in Ag is fixed as 0.3 atom %, makes the casting Ag alloy ingot bar that the addition make Cu, Au or Pd, Ru, Ni changes respectively, and is identical with embodiment 1, makes the Ag alloy target material.And then, with this Ag alloy target material, on glass substrate, form the Ag alloy film of thickness 200nm by sputtering method, measure by the method identical and compare resistance with embodiment 1.Its result as shown in Figure 2.
As shown in Figure 2, along with the increase of addition, resistance also increases.Wherein, the increase of the resistance of the Ag alloy film of interpolation Cu, Au is lacked than the resistance increase of the alloy film that adds Ru, Ni, Pd.For Cu, Au, below 1.0 atom %, just can keep the following low resistivity of 4 μ Ω cm.Especially Au lacks than the increase of resistance, also can keep the following low resistivity of 4 μ Ω cm even add 1.5 atom % to.So the addition during as combination interpolation Cu or Au in Sm separately for Cu, preferably below 1.0 atom %, separately for Au, preferably is no more than 1.5 atom %.
Below, the amount of the Cu that adds in Ag is 0.2 atom %, the casting Ag alloy ingot bar that manufacturing changes the addition of rare earth element (Y, La, Nd, Sm, Tb) respectively is identical with embodiment 1, makes the Ag alloy target material.And then, with this Ag alloy target material, on glass substrate, form the Ag alloy film of thickness 200nm by sputtering method, measure the average reflectance of 400～700nm in the visible region with spectral photometric colour measuring meter (Minorta makes CM2002), measurement result as shown in Figure 3, the maximum value of the reflectivity in optical wavelength 400～700nm scope is made as ref (max), the relation of reflectivity when minimum value is made as ref (min), calculate the value of the difference of reflectivity by [(ref (max)-ref (min))/ref (max)] * 100, the result as shown in Figure 4.
As shown in Figure 3, the addition of rare earth element, if increase, average reflectance reduces.In rare earth element, add the Ag alloy film of Sm or Tb, to compare with the Ag alloy film that adds Y, La or Nd, the reduction of average reflectance is little.In addition, as shown in Figure 4 as can be known, the reflection differences of adding the Ag alloy film of Sm or Tb also has the tendency that diminishes.By above result as can be known, preferred Sm of element or Tb are added in conduct in Ag, by addition being located at below the 0.5 atom %, more preferably below the 0.3 atom %, can obtain to have the high average reflectance more than 97% and the value of reflection differences is the Ag alloy of the reflection characteristic of certain value at the reflectivity with in the approaching visible-range of paper white below 6.
The amount of the rare earth element that adds in Ag (Y, La, Nd, Sm, Tb) is 0.2 atom %, and the casting Ag alloy ingot bar that manufacturing changes the addition of Cu respectively is identical with embodiment 1, makes the Ag alloy target material.And then, with this Ag alloy target material, on glass substrate, form the Ag alloy film of thickness 200nm by sputtering method, identical with embodiment 3, measure the average reflectance of visible region 400～700nm, measurement result as shown in Figure 5, the value of the reflection differences in optical wavelength 400～700nm scope is as shown in Figure 6.
As shown in Figure 5, along with the increase of the addition of Cu, average reflectance reduces, but adds the Ag alloy film of Sm or Tb, compares the average reflectance height with the Ag alloy film that adds Y or Nd.In addition, as shown in Figure 6 as can be known, for the Ag alloy film that adds Sm or Tb, its reflection differences is also little, and the reflectivity that can obtain in the visible-range is that certain value gets reflection characteristic.And then when if the addition of Cu surpasses 0.5 atom %, reflectivity reduces a lot, and it is big that reflection differences also becomes.So the addition of the Cu when adding Sm or Tb and Cu as combination as can be known preferably is no more than 0.5 atom %.
In addition, the amount of the rare earth element that adds in Ag (Y, Nd, Sm, Dy) is 0.2 atom %, and the casting Ag alloy ingot bar that manufacturing changes the addition of Au respectively is identical with embodiment 1, makes the Ag alloy target material.And then, with this Ag alloy target material, on the silicon chip substrate, form the Ag alloy film of thickness 200nm by sputtering method, identical with embodiment 3, measure the average reflectance of visible region 400～700nm, measurement result as shown in Figure 7, the value of the reflection differences in optical wavelength 400～700nm scope is as shown in Figure 8.
As shown in Figure 7, along with the increase of the addition of Au, average reflectance reduces very little, but adds the Ag alloy film of Sm or Dy, compares the reflectivity height with the Ag alloy film that adds Y or Nd.In addition, for the Ag alloy film that adds Sm or Dy, its reflection differences is also little as can be known, and the reflectivity that can obtain in the visible-range is that certain value gets reflection characteristic.As can be known with respect to the variation of the reflectivity of the addition of Au, compare lessly with Cu, even addition increases, the variation of reflectivity is also little.But, the reflectivity Characteristics when adding rare earth element as can be known, better to add Sm or Dy.
Below, thermotolerance, erosion resistance, tack, figure plasticity during for combination interpolation Sm and Cu, Sm and Au and Sm and Au and Cu in Ag are estimated.
For process is estimated as resistance after the manufacturing process of an article made to order and reflectivity, for the pure Ag film, the Ag alloy film that form the 200nm thickness on glass substrate and silicon chip, ratio resistance during the evaluation of measuring film forming and average reflectance, 25 ℃ of temperature are carried out ratio resistance after 2 hours the heat treated and average reflectance, are placed ratio resistance and average reflectance after 24 hours as anti-corrosion test in the environment of 85 ℃ of temperature, humidity 90% in a vacuum.
In addition, for estimating thermotolerance, observe in atmosphere, the variable color situation on 1 hour pure Ag film of 250 ℃ of heat treated of temperature and Ag alloy film surface is evaluated as well with the film that does not have white point, milkiness and flavescence.
In addition, be the tack of evaluated for film, after carrying out on the pure Ag film of vacuum heating treatment, the Ag alloy film being cut into chessboard netted, on the film surface, stick adhesive tape, tear then with the interval of 2mm.The grid that be left on the substrate this moment is represented with area occupation ratio, as tack, estimates.
In addition, evaluation as the figure plasticity, on the pure Ag film of implementing described heat treated, Ag alloy film, should change system OFPR-800 resist by spin-coating method coating Tokyo, make resist after exposure under the ultraviolet ray with photomask, develop with organic bases developing solution NMD-3 and to make the resist figure, mixed solution with phosphoric acid, nitric acid, acetic acid carries out etching, forms pure Ag film and Ag alloy film figure.For observation by light microscope such as the shape at its edge and the residue around it, with do not have film to peel off, peel off the end and do not have the average evaluation of residue serves as good.Above evaluation of measuring result as shown in Table 1 and Table 2.
Table 1
| The sample sequence number | Form (atom %) | Than resistance (μ Ω cm) | Distinguish | ||
| During film forming | After the heating under vacuum | Behind the corrosion resistance test | |||
| 1 | Ag | 2.7 | 1.8 | 3.2 | Comparative example |
| 2 | Ag-0.7 Pd-1.0Cu | 4.1 | 3.0 | 4.3 | Comparative example |
| 3 | Ag-0.7 Ru-0.8Cu | 6.8 | 6.5 | 7.5 | Comparative example |
| 4 | Ag-1.5 Cu | 3.8 | 3.1 | 4.5 | Comparative example |
| 5 | Ag-2.0 Nd | 6.3 | 4.9 | 6.4 | Comparative example |
| 6 | Ag-0.3 Sm | 3.1 | 2.3 | 3.2 | Comparative example |
| 7 | Ag-0.3 Sm-0.05Cu | 3.2 | 2.3 | 3.2 | Comparative example |
| 8 | Ag-0.3 Sm-0.1Cu | 3.2 | 2.3 | 3.3 | Example of the present invention |
| 9 | Ag-0.3 Sm-0.5Cu | 3.2 | 2.4 | 3.2 | Example of the present invention |
| 10 | Ag-0.1 Sm-0.4Cu | 2.9 | 2.0 | 2.8 | Example of the present invention |
| 11 | Ag-0.3 Sm-1.0Cu | 3.8 | 2.5 | 3.8 | Example of the present invention |
| 12 | Ag-0.5 Sm-0.1Au | 3.4 | 2.7 | 3.2 | Example of the present invention |
| 13 | Ag-0.2 Sm-0.4Au | 3.0 | 2.5 | 3.0 | Example of the present invention |
| 14 | Ag-0.15 Sm-0.8Au | 3.0 | 2.9 | 3.1 | Example of the present invention |
| 15 | Ag-0.15 Sm-1.0Au | 3.3 | 3.5 | 3.5 | Example of the present invention |
| 16 | Ag-0.2 Sm-0.2Cu-0.2Au | 3.0 | 2.5 | 3.1 | Example of the present invention |
| 17 | Ag-0.3 Sm-0.5Cu-0.5Au | 3.4 | 2.9 | 3.6 | Example of the present invention |
| 18 | Ag-0.3 Sm-0.9Pd | 4.1 | 3.0 | 4.3 | Comparative example |
| 19 | Ag-0.3 Sm-0.4Ru | 8.5 | 6.2 | 7.9 | Comparative example |
| 20 | Ag-0.3 Sm-0.5cu | 3.2 | 2.4 | 3.2 | The present invention's example * |
| 21 | Ag-0.2 Sm-0.4Au | 3.0 | 2.5 | 3.0 | The present invention's example * |
Table 2
| The sample sequence number | Form (atom %) | Average reflectance (%) | Apparent condition | Tack | The figure plasticity | Distinguish | ||
| During film forming | After the heating under vacuum | Behind the corrosion resistance test | ||||||
| 1 | Ag | 98.5 | 92.3 | 78.0 | Milkiness | 50 | Film is peeled off | Comparative example |
| 2 | Ag-0.7 Pd-1.0Cu | 96.5 | 95.2 | 95.1 | White point is arranged | 70 | Residue is arranged | Comparative example |
| 3 | Ag-0.7 Ru-0.8Cu | 96.3 | 92.6 | 93.4 | White point is arranged | 65 | Residue is arranged | Comparative example |
| 4 | Ag-1.5 Cu | 98.0 | 85.2 | 90.8 | Milkiness (flavescence) | 70 | Well | Comparative example |
| 5 | Ag-2.0 Nd | 94.3 | 94.0 | 94.1 | White point is arranged | 75 | Peel off the end | Comparative example |
| 6 | Ag-0.3 Sm | 98.2 | 97.8 | 94.6 | White point is arranged | 60 | Film is peeled off | Comparative example |
| 7 | Ag-0.3 Sm-0.05Cu | 98.2 | 97.8 | 96.2 | White point is arranged | 60 | Film is peeled off | Comparative example |
| 8 | Ag-0.3 Sm-0.1Cu | 98.3 | 98.6 | 97.5 | Well | 75 | Well | Example of the present invention |
| 9 | Ag-0.3 Sm-0.5Cu | 97.9 | 98.5 | 97.2 | Well | 85 | Well | Example of the present invention |
| 10 | Ag-0.1 Sm-0.4Cu | 98.5 | 98.5 | 97.5 | Well | 80 | Well | Example of the present invention |
| 11 | Ag-0.3 Sm-1.0Cu | 97.0 | 97.1 | 97.0 | Well | 85 | Well | Example of the present invention |
| 12 | Ag-0.5 Sm-0.1Au | 97.9 | 98.3 | 97.6 | Well | 75 | Well | Example of the present invention |
| 13 | Ag-0.2 Sm-0.4Au | 98.4 | 98.6 | 98.2 | Well | 85 | Well | Example of the present invention |
| 14 | Ag-0.15 Sm-0.8Au | 97.8 | 97.5 | 97.4 | Well | 85 | Residue is arranged but to clean the back good | Example of the present invention |
| 15 | Ag-0.15 Sm-1.0Au | 97.8 | 97.6 | 97.4 | Well | 85 | Residue is arranged but to clean the back good | Example of the present invention |
| 16 | Ag-0.2 Sm-0.2 Cu-0.2Au | 98.0 | 98.4 | 98.0 | Well | 80 | Well | Example of the present invention |
| 17 | Ag-0.3 Sm-0.5 Cu-0.5Au | 97.2 | 96.9 | 96.9 | Well | 85 | Well | Example of the present invention |
| 18 | Ag-0.3 Sm-0.9Pd | 96.3 | 96.3 | 96.4 | Well | 80 | Film is peeled off | Comparative example |
| 19 | Ag-0.3 Sm-0.4Ru | 95.4 | 95.8 | 94.6 | Well | 65 | Well | Comparative example |
| 20 | Ag-0.3 Sm-0.5cu | 97.7 | 98.4 | 97.6 | Well | 80 | Well | The present invention's example * |
| 21 | Ag-0.2 Sm-0.4Au | 98.5 | 98.6 | 98.2 | Well | 80 | Well | The present invention's example * |
Distinguish the sample that is meant formation Ag alloy film on silicon chip of * mark in the hurdle in the above-mentioned table,
Remaining all is the sample that forms the Ag alloy film on glass substrate.
From table 1 and table 2 as can be known, in the pure Ag film (sample sequence number 1), when film forming, have the following low resistivity of 3.0 μ Ω cm, in case carry out heat treated, it is than the further reduction of resistance.But, behind the corrosion resistance test, by than resistance increase corrosion-resistant as can be known.In addition, the average reflectance during film forming is the highest, still, in case carry out heat treated, just reduces significantly, and thermotolerance is also poor as can be known by the film surface milkiness after the atmosphere heating.And then, low and produce film and peel off that the figure plasticity is also poor as can be known by its tack.In addition,, compare with Ag alloy film of the present invention for the Ag alloy film that in Ag, adds Pd, Cu, Ru (sample sequence number 2,3) that proposed in the past, higher and behind corrosion resistance test, increase than resistance than resistance.In addition, average reflectance is also low than Ag alloy film of the present invention, especially after heat treated, when average reflectance reduces, owing to the white point that produces on the film surface in atmosphere heating back as the spot in white circular footpath, so in thermotolerance problem is arranged.And then as can be known, tack is low and produce residue when etching.
In addition, for the Ag alloy film (sample sequence number 4) that adds Cu in Ag, thermotolerance is poor especially and after heat treated, average reflectance descends significantly, flavescence in the time of the milkiness of film surface.In addition, in Ag, add the Ag alloy film (sample sequence number 5) of rare earth element Nd, owing on the film surface, produce white point, thus problem is arranged in the thermotolerance, owing to peeling off the end, so the figure plasticity is also bad.
In Ag, add separately the Ag alloy film (sample sequence number 6) of Sm, on atmosphere heating caudacoria surface, produce white point, in the thermotolerance problem is arranged as can be known, in addition, low and produce film and peel off that the figure plasticity is also bad as can be known from tack.
On the other hand, the Ag alloy film (sample sequence number 8～17) of Sm and Cu, Sm and Au, Sm and Cu and Au is added in combination in Ag of the present invention, and the ratio resistance during film forming is 4 μ Ω cm, and is lower, even behind corrosion resistance test, also keeps lower ratio resistance.In addition, for average reflectance, behind heat treated and corrosion resistance test, also keep about 97%.And, not only keep described characteristic, tack also significantly is improved, and the figure plasticity is also good, and does not produce the variation of milkiness, white point, flavescence etc. on the film surface after the atmosphere heat treated, and thermotolerance that hence one can see that is also good.
In addition, sequence number 20 and 21 be the sample of formation Ag alloy film on silicon chip, but as known from Table 1, the result is identical with the situation that forms the Ag alloy film on glass substrate.
For Ag-0.3 atom %Sm-0.4 atom %Cu of the present invention, the spectral reflectance after the heat treated when having measured film forming and in 250 ℃ * 1 hour the vacuum, the result is as shown in Figure 9.Add the Ag alloy film of Sm and Cu for combination in Ag of the present invention, in case carry out heat treated, reflectivity increases, and the reflectivity of especially low wavelength side increases, and the reflectivity that can obtain in visible-range is the reflection characteristic of certain value.To be made as ref (max) in the maximum value of the reflectivity in optical wavelength 400～700nm scope, when minimum value is made as ref (min), (((ref (max)-ref (min))/ref (max) * 100≤6) is 3 to its reflection differences, characteristic good.So, in the planar display of liquid crystal indicator that must carry out heating treatment process etc., can produce planar display with the characteristic that did not in the past have.
Embodiment 8
The Ag alloy target material of the Ag-0.2 atom %Sm-0.3 atom %Au that utilization is made with embodiments of the invention 3, the spectral reflectance of the Ag alloy film when when being determined at film forming substrate being heated to 150 ℃, the result is as shown in figure 10.By substrate is heated and film forming, in the wavelength region of 400～700nm, can obtain the high-reflectivity about 0.5%.In addition, by substrate is heated and film forming, tack is increased to 90% from 85%.Having on such stable on heating glass substrate,, can obtain having the Ag alloy film of high-reflectivity and tack by substrate is heated.
Embodiment 9
Identical with embodiment 1, the target of manufacturing Ag-0.3 atom %Sm-0.5 atom %Au, Ag-0.3 atom %Sm-0.5 atom %Cu, the thickness with 200nm on silicon chip forms.After measuring, and then, measure after 1 hour with 150 ℃, 200 ℃, 250 ℃, 350 ℃ heat treated in a vacuum, calculate changes in resistance with respect to the heat treated temperature than resistance than resistance.Its result as shown in figure 11.
Along with the rising of heat treated temperature, reduce than resistance.Ag-0.3 atom %Sm-0.5 atom %Cu film particularly as mentioned above, rising along with Heating temperature, resistance reduces significantly, obtaining than resistance more than 200 ℃ under the temperature is low resistivity below the 2.5 μ Ω cm, is low resistivity below the 2.0 μ Ω cm obtaining under the temperature more than 300 ℃ than resistance.Even for pure Ag film, also form lower ratio resistance, its tack and corrosion-resistant.Like this, Ag alloy film of the present invention can obtain lower ratio resistance, so be applicable to the used for electronic device wiring membrane with heat treated by heat treated.By in the plane that especially the heat treated temperature is high shows with the multi-crystal TFT wiring film, using, can produce the more high-quality planar display of high-speed responsive.
Embodiment 10
Below, with the target of embodiment 4, when on glass substrate, forming the Ag alloy film of 200nm, the ratio changes in resistance when mensuration is heated to 100～250 ℃ with substrate, the result is as shown in figure 12.As shown in Figure 12, by substrate is heated and film forming, reduce than resistance.Especially with the heating of the Heating temperature more than 150 ℃, reduce significantly than resistance, in case be heated to 200 ℃, Ag-0.3 atom %Sm-0.5 atom %Cu, Ag-0.3 atom %Sm-0.5 atom %Au all obtain the following low resistivity of 2.5 μ Ω cm.In addition, by substrate is heated and film forming, tack is increased to 95% from 85%.Have on such stable on heating glass substrate, by substrate is heated, form the Ag alloy film with low resistance and tack, this film is applicable to the wiring membrane of electron device.
According to the present invention, can stably obtain low resistance, high-reflectivity, thermotolerance, environment resistant and improved and substrate between the Ag alloy film of tack.So, this film is applicable at must be low-resistance high meticulous LCD, organic ELD, PDP etc., is used to carry the planar display or the various membrane unit that require low reflection type LCD of power consumption etc. of information end etc., and very high value is arranged on industry.
The present invention is not limited to this; in the change under the situation of not leaving aim of the present invention or modify all in the claim protection domain in this case; this can further be understood by those skilled in the art, although carried out aforementioned description in an embodiment of the present invention.
Claims (8)
1, a kind of Ag alloy film is characterized in that, containing arbitrary element of selecting from Sm, Dy, Tb is that 0.1～0.5 atom %, Au and/or Cu add up to 0.1～1.0 atom %, remainingly is made of Ag and unavoidable impurities.
2, Ag alloy film according to claim 1 is characterized in that, arbitrary element of selecting from Sm, Dy, Tb is Sm, and Sm content is 0.1～0.5 atom %.
3, according to the Ag alloy film described in claim 1 or 2, it is characterized in that, contain described Au and/or Cu and add up to 0.1～0.5 atom %.
4, a kind of Ag alloy film according to claim 1 is as the application of the wiring membrane of planar display.
5, a kind of Ag alloy film according to claim 1 is as the application of the reflectance coating of planar display.
6, a kind of Ag alloy film forms and uses the Ag alloy target material, it is characterized in that containing arbitrary element of selecting from Sm, Dy, Tb is that 0.1～0.5 atom %, Au and/or Cu add up to 0.1～1.0 atom %, remainingly is made of Ag and unavoidable impurities.
7, Ag alloy film according to claim 6 forms and uses the Ag alloy target material, it is characterized in that arbitrary element of selecting from Sm, Dy, Tb is Sm, and Sm content is 0.1～0.5 atom %.
8, use the Ag alloy target material according to each described Ag alloy film formation in the claim 6～7, it is characterized in that, contain described Au and/or Cu and add up to 0.1～0.5 atom %.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002083167A JP4103067B2 (en) | 2002-03-25 | 2002-03-25 | Ag alloy reflective film for flat panel display |
| JP2002083167 | 2002-03-25 | ||
| JP2002098751A JP2003293054A (en) | 2002-04-01 | 2002-04-01 | Ag ALLOY FILM FOR ELECTRONIC PART AND SPUTTERING TARGET MATERIAL FOR FORMING Ag ALLOY FILM |
| JP2002098751 | 2002-04-01 |
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| Publication Number | Publication Date |
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| CN1446941A CN1446941A (en) | 2003-10-08 |
| CN1226446C true CN1226446C (en) | 2005-11-09 |
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| CNB031079121A Expired - Fee Related CN1226446C (en) | 2002-03-25 | 2003-03-24 | Ag alloyed memberane and sputtering target for forming Ag alloyed membrane |
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| Country | Link |
|---|---|
| US (1) | US20030180177A1 (en) |
| KR (1) | KR100506474B1 (en) |
| CN (1) | CN1226446C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102460233A (en) * | 2009-06-15 | 2012-05-16 | 株式会社神户制钢所 | Aluminum alloy reflective film, reflective film laminate, automotive lighting device, illumination device, and aluminum alloy sputtering target |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1698218A (en) * | 2003-03-26 | 2005-11-16 | 索尼株式会社 | Light-emitting device, method of manufacturing the same, and display unit |
| WO2005056850A1 (en) * | 2003-12-10 | 2005-06-23 | Tanaka Kikinzoku Kogyo K.K. | Silver alloy excelling in performance of reflectance maintenance |
| WO2005081021A1 (en) * | 2004-02-24 | 2005-09-01 | Matsushita Electric Works, Ltd. | Light reflector and lighting fixture including the same |
| TWI325134B (en) * | 2004-04-21 | 2010-05-21 | Kobe Steel Ltd | Semi-reflective film and reflective film for optical information recording medium, optical information recording medium, and sputtering target |
| KR100673744B1 (en) | 2004-10-28 | 2007-01-24 | 삼성에스디아이 주식회사 | Multi-layer Anode |
| KR100754144B1 (en) * | 2005-03-21 | 2007-08-31 | 삼성에스디아이 주식회사 | Light Emission Diode |
| KR100731739B1 (en) * | 2005-04-28 | 2007-06-22 | 삼성에스디아이 주식회사 | Organic Electroluminescence Display Device and Fabrication Method of the same |
| JP2007035104A (en) * | 2005-07-22 | 2007-02-08 | Kobe Steel Ltd | Ag ALLOY REFLECTION FILM FOR OPTICAL INFORMATION RECORDING MEDIUM, OPTICAL INFORMATION RECORDING MEDIUM AND Ag ALLOY SPUTTERING TARGET FOR FORMING Ag ALLOY REFLECTION FILM FOR OPTICAL INFORMATION RECORDING MEDIUM |
| US7951442B2 (en) * | 2006-11-17 | 2011-05-31 | Tanaka Kikinzoku Kogyo K.K. | Thin film for reflection film or for semi-transparent reflection film, sputtering target and optical recording medium |
| WO2008059581A1 (en) * | 2006-11-17 | 2008-05-22 | Tanaka Kikinzoku Kogyo K.K. | Thin film for reflection film or semi-transparent reflection film, sputtering target, and optical recording medium |
| WO2009041529A1 (en) * | 2007-09-25 | 2009-04-02 | Kabushiki Kaisha Kobe Seiko Sho | Reflective film, reflective film laminate, led, organic el display, and organic el illuminating device |
| EP2573208A4 (en) * | 2010-05-20 | 2014-05-21 | Jx Metals Trading Co Ltd | Electrolytically silver plated and/or electrolytically silver alloy plated article having oxide layer on surface |
| JP2012027226A (en) * | 2010-07-23 | 2012-02-09 | Seiko Epson Corp | Interference filter, optical module and analyzer |
| JP5682165B2 (en) * | 2010-07-23 | 2015-03-11 | セイコーエプソン株式会社 | Interference filter, optical module, and analyzer |
| JP2012042651A (en) * | 2010-08-18 | 2012-03-01 | Seiko Epson Corp | Interference filter, optical module and analyzer |
| JP5910099B2 (en) * | 2012-01-18 | 2016-04-27 | セイコーエプソン株式会社 | Interference filters, optical modules and electronics |
| JP5975186B1 (en) | 2015-02-27 | 2016-08-23 | 三菱マテリアル株式会社 | Ag alloy sputtering target and method for producing Ag alloy film |
| CN106756836A (en) * | 2017-01-06 | 2017-05-31 | 广州市祺虹电子科技有限公司 | A kind of transparent circuit board group of the lanthanides target and its manufacture method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG116432A1 (en) * | 2000-12-26 | 2005-11-28 | Kobe Steel Ltd | Reflective layer or semi-transparent reflective layer for use in optical information recording media, optical information recording media and sputtering target for use in the optical information recording media. |
| DE60305495T2 (en) * | 2002-06-28 | 2006-12-28 | Williams Advanced Materials Inc. | CORROSION RESISTANT SILVER METAL ALLOYS FOR OPTICAL RECORDING AND DESCRIBABLE OPTICAL RECORDING MEDIA CONTAINING THIS ALLOY |
-
2003
- 2003-03-07 KR KR10-2003-0014319A patent/KR100506474B1/en active IP Right Grant
- 2003-03-24 CN CNB031079121A patent/CN1226446C/en not_active Expired - Fee Related
- 2003-03-24 US US10/393,993 patent/US20030180177A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102460233A (en) * | 2009-06-15 | 2012-05-16 | 株式会社神户制钢所 | Aluminum alloy reflective film, reflective film laminate, automotive lighting device, illumination device, and aluminum alloy sputtering target |
| CN102460233B (en) * | 2009-06-15 | 2014-09-03 | 株式会社神户制钢所 | Aluminum alloy reflective film, reflective film laminate, automotive lighting device, illumination device, and aluminum alloy sputtering target |
Also Published As
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|---|---|
| KR20030077963A (en) | 2003-10-04 |
| US20030180177A1 (en) | 2003-09-25 |
| KR100506474B1 (en) | 2005-08-03 |
| CN1446941A (en) | 2003-10-08 |
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