CN103958727A - Silver-alloy sputtering target for conductive-film formation, and method for producing same - Google Patents

Abstract

One embodiment of the sputtering target having a component composition containing Sn in the amount of 0.1-1.5 mass%, with the remainder comprising Ag and inevitable impurities, wherein the average particle diameter of the alloy crystal grains is 30mum or more and less than 120mum, and the variation in the particle diameter of the crystal grains is 20% or less of the average particle diameter. One embodiment of the method for producing the sputtering target in which a melt-cast ingot having the component composition is subjected to a hot-rolling step, a cooling step, and a machining step, in this order, wherein: the hot-rolling step involves one or more passes of finish hot rolling under conditions in which the rolling reduction for each pass is 20-50%, the strain rate is 3-15/sec, and the temperature after the pass is 400-650 DEG C; and the cooling step involves quickly cooling at a cooling rate of 200-1000 DEG C/min.

Description

Conductive film forms by silver alloy sputtering target and manufacture method thereof

Technical field

The present invention relates to a kind of silver alloy sputtering target and manufacture method thereof that is used to form the conductive film such as the reflecting electrode of organic EL and the wiring film of contact panel.

The application is based on No. 2012-005053 opinion right of priority of the Japanese patent application of on January 13rd, 2012 in Japanese publication.And its content is applied to the application.

Background technology

In organic EL, apply voltage being formed between the anode of organic EL luminescent layer both sides and negative electrode, respectively from anode and negative electrode by hole and electronic injection in organic EL film.And organic EL luminescent layer when hole and electronics in conjunction with time luminous.Organic EL is the luminous element that uses this principle of luminosity, receives much concern in recent years with luminous element as display equipment.In the type of drive of this organic EL, there are passive matrix-style and active matrix mode.This active matrix mode can be carried out high-speed transitions by more than one thin film transistor being set in a pixel.Therefore, active matrix mode is the type of drive that is conducive to high-contrast, high definition and can brings into play organic EL feature.

And, in the extracting mode of light, has from transparent substrate side and extract the bottom-emission mode of light and extract the top light emitting mode of light from the opposition side of substrate, and the higher top light emitting mode of aperture opening ratio is conducive to high brightness.

In order more effectively to reflect the light being sent by organic EL layer, preferably the reflective electrode film in this top lighting structure is that high-reflectivity and solidity to corrosion are high.And, as electrode, be also preferably low resistance electrode.As this material, known have Ag alloy and Al alloy, but in order to obtain the more organic EL of high brightness, be excellent from the viewpoint of the higher Ag alloy of visible reflectance.Wherein, in the time forming the reflective electrode film of organic EL, adopt sputtering method and use silver alloys target (patent documentation 1).

But, the maximization of the glass substrate while manufacture along with organic EL, the silver alloys target using in the time forming reflective electrode film also uses large-scale target gradually.Wherein, in the time that power that large-scale target is had high input carries out sputter, produce the phenomenon that is called as " splash " producing because of the paradoxical discharge of target.If produce this phenomenon, the micropartical of melting is attached on substrate and makes short circuit between distribution or electrode.Thus, there is the problem of the decrease in yield and so on of organic EL.The reflection electrode layer of the organic EL of top light emitting mode becomes the stratum basale of organic luminous layer, is therefore required higher flatness and needs further to suppress splash.

In order to solve such problem, even if propose to have in patent documentation 2 and patent documentation 3 along with the maximization of target forms by silver alloys target and manufacture method thereof the target reflective electrode film that power also can suppress the organic EL of splash that has high input.

The power that has high input forms and uses silver alloys target by the reflective electrode film of recording in these patent documentations 2 and patent documentation 3, even if also can suppress splash.But in large-scale silver alloys target, along with the consumption of target, arc-over number of times increases, and the tendency that has the splash meeting based on arc-over to increase, and requires further to improve.

And, except organic EL is with reflective electrode film, in the conductive films such as the wiring lead of contact panel, use silver alloy film to be also studied.As this wiring film, if use for example pure Ag, produce migration and the fault that is easily short-circuited.Therefore, the employing of silver alloy film is studied.

Patent documentation 1: No. 2002/077317th, International Publication

Patent documentation 2: TOHKEMY 2011-100719 communique

Patent documentation 3: TOHKEMY 2011-162876 communique

Summary of the invention

The present invention completes in light of this situation, and its object is to provide a kind of conductive film that can further suppress arc-over and splash to form by silver alloy sputtering target and manufacture method thereof.

The inventor etc. obtain following opinion through further investigation result, containing in the silver alloys target of Sn, increase along with the consumption of target in order to suppress arc-over number of times, by further crystal grain miniaturization, so that its median size is less than 120 μ m, by its deviation control in median size is effective below 20%.

According to this result of study, conductive film formation of the present invention by the 1st mode of silver alloy sputtering target is, having the one-tenth being made up of Ag and inevitable impurity containing Sn and the remainder of 0.1～1.5 quality % is grouped into, the median size of alloy grain is more than 30 μ m and be less than 120 μ m, and the particle diameter deviation of described crystal grain is at below 20% of median size.

Sn solid solution suppresses the crystal grain-growth of target in Ag, effective to the miniaturization of crystal grain.Sn improves the hardness of target, the warpage while therefore suppressing mechanical workout.Sn improves solidity to corrosion and the thermotolerance of the film being formed by sputter.If Sn content is less than 0.1 quality %, cannot obtain above-mentioned effect, if Sn content exceedes 1.5 quality %, the reflectivity of film or resistance decline.

The reason that median size is made as to 30 μ m above and is less than 120 μ m is below shown.The median size that is less than 30 μ m is not had feasibility and cause the increase of manufacturing cost.And, if median size more than 120 μ m, the tendency that paradoxical discharge increases along with the consumption of target when sputter becomes remarkable.

If the deviation of median size exceedes 20%, the tendency that paradoxical discharge increases along with the consumption of target when sputter becomes remarkable.

Conductive film formation of the present invention by the 2nd mode of silver alloy sputtering target is, the one-tenth any one or two kinds of and that remainder is made up of Ag and inevitable impurity that have containing the Sn of 0.1～1.5 quality %, also contain in Sb, the Ga of 0.1～2.5 quality % are altogether grouped into, and the median size of alloy grain is that 30 μ m are above and be less than 120 μ m, and the particle diameter deviation of described crystal grain is at below 20% of median size.

Sb and Ga have solid solution further suppresses crystal grain-growth effect in Ag.Solidity to corrosion and thermotolerance that Sb and Ga further improve the film being formed by sputter improve.Especially Ga improves the salt tolerance of film.If the content that amounts to of Sb and Ga is less than 0.1 quality %, cannot obtain above-mentioned effect, if the content that amounts to of Sb and Ga exceedes 2.5 quality %, not only the reflectivity of film or resistance decline, and produce the tendency of breaking while there is hot rolling.

Conductive film formation of the present invention by the 1st mode of the manufacture method of silver alloy sputtering target is, by the melting ingot casting being grouped into thering is the one-tenth that formed by Ag and inevitable impurity containing the Sn of 0.1～1.5 quality % and remainder, implement successively hot-rolled process, refrigerating work procedure and mechanical workout operation are manufactured silver alloy sputtering target, and in described hot-rolled process, taking the rolling rate of every a time as 20～50%, rate of straining is that the temperature after 3～15/sec and passage is to carry out smart hot rolling more than 1 passage under the condition of 400～650 DEG C, in described refrigerating work procedure, speed of cooling with 200～1000 DEG C/min is carried out quenching.

Conductive film formation of the present invention by the 2nd mode of the manufacture method of silver alloy sputtering target is, by to thering is the Sn containing 0.1～1.5 quality %, also contain the Sb of 0.1～2.5 quality % altogether, the melting ingot casting that the one-tenth that any one or two kinds of and remainder in Ga is made up of Ag and inevitable impurity is grouped into, implement successively hot-rolled process, refrigerating work procedure and mechanical workout operation are manufactured silver alloy sputtering target, in described hot-rolled process, taking the rolling rate of every a time as 20～50%, rate of straining is 3～15/sec, and temperature after passage is to carry out smart hot rolling more than 1 passage under the condition of 400～650 DEG C, in described refrigerating work procedure, speed of cooling with 200～1000 DEG C/min is carried out quenching.

Below illustrate the rolling rate of every a time of smart hot rolling is made as to 20～50% reason.If rolling rate is less than 20%, the miniaturization of crystal grain becomes insufficient.Exceed 50% rolling rate if obtain, the load load of milling train becomes excessive and does not have feasibility.

And, the reason that rate of straining is made as to 3～15/sec is below shown.If rate of straining is less than 3/sec, the miniaturization of crystal grain becomes insufficient, occurs the tendency of the mangcorn that produces microfine and thick grain.If rate of straining exceedes 15/sec, the load load of milling train becomes excessive and does not have feasibility.

If the temperature after each passage is less than 400 DEG C, dynamic recrystallization becomes insufficient, and the tendency that the deviation of crystallization particle diameter increases becomes remarkable.If the temperature after each passage exceedes 650 DEG C, carry out crystal grain-growth and more than average crystallite particle diameter becomes 150 μ m.

And, can suppress the growth of crystal grain by carry out quenching after this hot rolling, and can obtain the target that crystal grain is fine.If speed of cooling is less than 200 DEG C/min, suppress the weak effect of crystal grain-growth.Even if speed of cooling exceedes 1000 DEG C/min, do not contribute to more preferably miniaturization yet.

According to mode of the present invention, even if the power that can obtain having high input also can further suppress the target of arc-over and splash, by this target is carried out to sputter, can obtain having that reflectivity is high, the conductive film of excellent in te pins of durability in sputter procedure.

Embodiment

Below, conductive film formation of the present invention is described with the embodiment of silver alloy sputtering target and manufacture method thereof.In addition, need only outside the intrinsic situation of special expression and divider value, " % " is quality %.

The target surface (face for sputter side of target) of this target has 0.25m ²above area.The in the situation that of rectangular target, be more than 500mm at least on one side, from the processing viewpoint of target, the upper limit of length is preferably 3000mm.On the other hand, the viewpoint of the upper dimension bound that conventionally can be rolled from the milling train to be used hot-rolled process, the upper limit of width is preferably 1700mm.And from the viewpoint of the replacement frequency of target, more than the thickness of target is preferably 6mm, from the viewpoint of the discharge stability of magnetron sputtering, the thickness of target is preferably below 25mm.

The conductive film of the 1st embodiment forms and is made up of the silver alloys that has containing the Sn of 0.1～1.5 quality % and remainder by Ag and the one-tenth that unavoidably impurity forms is grouped into silver alloy sputtering target.The median size of this alloy grain is that 30 μ m are above and be less than 120 μ m, and the particle diameter deviation of crystal grain is at below 20% of median size.

Ag has the reflective electrode film of the organic EL to being formed by sputter or the wiring film of contact panel is given high-reflectivity and low-resistance effect.

Sn improves the hardness of target, the warpage while therefore suppressing mechanical workout.Especially can suppress target surface and there is 0.25m ²the warpage when mechanical workout of the large-scale target of above area.And Sn has solidity to corrosion and the stable on heating effect of the reflective electrode film that improves the organic EL being formed by sputter.This effect obtains according to following effect.Sn reduces the surfaceness of film when making the crystal grain miniaturization in film.And Sn solid solution improves the intensity of crystal grain in Ag, and suppress crystal grain because of heat chap.Therefore, In has the effect that surfaceness increases or inhibition declines because of the corrosion reflectivity of film that suppresses film.Thereby utilizing this conductive film to form in the reflective electrode film or wiring film forming with silver alloy sputtering target, the solidity to corrosion of film and thermotolerance can improve.Therefore, this conductive film forms the reliability that contributes to the distribution such as high brightness or contact panel that improves organic EL with silver alloy sputtering target.

The reason that the content of Sn is defined in to above-mentioned scope is below shown.If the content of Sn is less than 0.1 quality %, cannot obtain the effect based on adding Sn of above-mentioned record.If the content of Sn exceedes 1.5 quality %, the resistance of film increases, or the reflectivity of the film being formed by sputter or solidity to corrosion decline on the contrary.Therefore not preferred.Thereby the composition of film depends on the composition of target, the content that is therefore contained in the Sn in silver alloy sputtering target is set as 0.1～1.5 quality %.Sn content is 0.2～1.0 quality % more preferably.

The conductive film formation of the 2nd embodiment forms with the silver alloys that the one-tenth that silver alloy sputtering target is made up of Ag and inevitable impurity any one or two kinds of and remainder that has containing the Sn of 0.1～1.5 quality %, also contains in Sb, the Ga that amounts to 0.1～2.5 quality % are grouped into.The median size of this alloy grain is that 30 μ m are above and be less than 120 μ m, and the particle diameter deviation of crystal grain is at below 20% of median size.

In the 2nd embodiment, Sb and Ga have solid solution further suppresses crystal grain-growth effect in Ag.Further improve solidity to corrosion and the thermotolerance of the film being formed by sputter.Especially Ga improves the salt tolerance of film.In situation by the film being formed by sputter for the wiring lead film of contact panel, contact panel operates with finger touch, and therefore wiring film need to have tolerance to the salt component being contained in human sweat.Can form the film of salt tolerance excellence by adding Ga.

If the content that amounts to of these Sb and Ga is less than 0.1 quality %, cannot obtain above-mentioned effect.If the content that amounts to of Sb and Ga exceedes 2.5 quality %, not only the reflectivity of film or resistance decline, and produce the tendency of breaking while there is hot rolling.

In the embodiment of each composition, the median size of the silver alloys crystal grain in silver alloy sputtering target is more than 30 μ m and is less than 120 μ m above.About the median size of silver alloys crystal grain, the median size that is less than 30 μ m is not had feasibility and cause the increase of manufacturing cost.And, being difficult for manufacturing uniform crystal grain, it is large that the deviation of particle diameter becomes.Thus, in powerful sputter procedure, easily produce paradoxical discharge and produce splash.On the other hand, if median size more than 120 μ m, along with target consumes by sputter, and the different and difference of the sputter rate that produces of crystal orientation based on each crystal grain, the concavo-convex change of sputtering surface is large.Therefore, in powerful sputter procedure, easily produce paradoxical discharge and easily produce splash.

At this, the median size of silver alloys crystal grain is to measure as follows.

In the sputter face of target, take equably the rectangular parallelepiped sample for 10mm left and right on one side from 16 places.Particularly, target area be divided into vertical 4 × horizontal 4 16 places and take from the central part of each several part.In addition, in the present embodiment, be the above sputter face of 500 × 500 (mm) due to what conceive, target surface has 0.25m ²the large-scale target of above area, the method for taking therefore recorded is that rectangular target from being typically used as large-scale target is taked sample.But the present invention certainly also brings into play effect in the splash that suppresses to produce circular.Now, take method to be as the criterion with the sample in large-scale rectangular target, in the sputter face of target, divide into equably 16 places and take.

Then, grind sputter face one side of each sample strip.Now, grind with the waterproof paper of #180～#4000, then, carry out polishing with the abrasive particle of 3 μ m～1 μ m.

In addition, be etched to the degree of enough observing crystal boundary with optics microscopes.Wherein, the mixed solution of etching solution use aquae hydrogenii dioxidi and ammoniacal liquor floods at normal temperatures and 1～2 second crystal boundary was manifested.Then, with opticmicroscope, each sample is taken to the photo that multiplying power is 60 times or 120 times.The multiplying power of photo is selected the easily multiplying power of counting crystal grain.

In each photo, the line segment of 60mm is drawn to 4 lines altogether in length and breadth with well word shape (as mark #) interval 20mm, the quantity of the crystal grain being cut off by each straight line is counted.In addition, the crystal grain of the extremity of segment is counted 0.5.With L=60000/ (MN) (at this, M is true multiplying power, the mean value that N is cut number of die), (μ m) to obtain average slice length: L.

Then, (μ m), calculates the median size of sample: (μ m) for d to the average slice length by obtained: L with d=(3/2) L.

Like this, the median size using the mean value of the median size of the sample from 16 samplings as the silver alloys crystal grain of target.

If the particle diameter deviation of this silver alloys crystal grain is at below 20% of median size of silver alloys crystal grain, the injection can suppress sputter more reliably time.Wherein, calculate as follows the deviation of particle diameter.The absolute value (∣ of the deviation of specific and median size mean value in 16 median sizes obtaining at 16 places [(certain 1 place's median size)-(mean values of 16 place's median sizes)] ∣) become maximum median size.Then, utilize its specific median size (specific median size) to calculate particle diameter deviation by following formula.

{ ∣ [(specific median size)-(mean values of 16 place's median sizes)] ∣/(mean values of 16 place's median sizes) } × 100 (%)

Then, the conductive film formation of present embodiment is described by the manufacture method of silver alloy sputtering target.

Form with in the manufacture method of silver alloy sputtering target at the conductive film of the 1st embodiment, as raw material, use purity: more than 99.99 quality % Ag, purity: Sn more than 99.9 quality %.

First, Ag is carried out in high vacuum or inert gas atmosphere to melting, in obtained molten metal, add the Sn of regulation content.After this, in vacuum or inert gas atmosphere, carry out melting and make the melting ingot casting of the silver alloys being formed by Ag and inevitable impurity containing Sn:0.1～1.5 quality % and remainder.

Wherein, be preferably as follows and carry out the melting of Ag and the interpolation of Sn.Atmosphere is made as to vacuum for the time being, then replaces with argon, in this atmosphere, carry out the melting of Ag.Then, after the melting of carrying out Ag, in argon atmospher, Sn is made an addition in the molten metal of Ag.Thus, the ratio of components of Ag and Sn is stable.

And, form with in the manufacture method of silver alloy sputtering target at the conductive film of the 2nd embodiment, as raw material, use purity: more than 99.99 quality % Ag, purity: more than 99.9 quality % Sn, Sb and Ga.In the molten metal of Ag, add Sn:0.1～1.5 quality %, amount to any one or two kinds in Sb and the Ga of 0.1～3.0 quality %.In this case, also Ag is carried out in high vacuum or inert gas atmosphere to melting, in obtained molten metal, add Sn, Sb and the Ga of regulation content, after this, in vacuum or inert gas atmosphere, carry out melting.

And above melting or casting are preferably carried out in a vacuum or in rare gas element replacement atmosphere, but also can use smelting furnace in atmosphere.Use smelting furnace in atmosphere time, to molten metal surface winding-up rare gas element or be that melting, casting are carried out in coated molten metal surface limit, sealed solid material limit by carbon such as charcoals.Thus, can reduce oxygen in ingot or the content of non-metallic inclusion.

In order to make homogenization of composition, smelting furnace is preferably induction heater.

And, cast and obtain rectangular parallelepiped ingot as effectively preferred taking square mold, but also can obtain to processing with the cylindrical ingot of circular mold casting the roughly ingot of rectangular parallelepiped.

Obtained rectangular-shaped ingot is heated and is hot-rolled down to specific thickness, then carry out quenching.

In this situation, the smart hot-rolled condition of hot rolling terminal stage is very important, by suitably setting this essence hot-rolled condition, can manufacture the fine and uniform silver alloys plate of crystal grain.

Particularly, in smart hot rolling, the rolling rate of every a time is 20～50%, rate of straining is that rolling temperature after 3～15/sec and each rolling pass is 400～650 DEG C.More than this essence hot rolling is carried out to 1 passage.Total rolling rate of hot rolling is for example more than 70% as a whole.

Wherein, smart hot rolling refers to the crystallization particle diameter of sheet material after rolling is produced to the greatly rolling pass of impact, comprises final rolling pass, can consider as required from final rolling pass to the 3rd passage reciprocal.After this final rolling, in order to adjust sheet metal thickness, within the scope of described rolling temperature, also can append the rolling of rolling rate below 7%.

And, can obtain rate of straining ε (sec by following formula ^-1).

[several 1]

$\mathrm{\ϵ}=\frac{2\mathrm{\πn}}{60\sqrt{r^{\′}}}\text{\·}\sqrt{\frac{R}{H_0}}\·\ln \left(\frac{1}{1-r^{\′}}\right)$

In above formula, H ₀: sheet metal thickness (mm), n with respect to the inlet side of Rolling roller: Rolling roller speed of rotation (rpm), R: Rolling roller radius (mm), r: rolling rate (%) and r '=r/100.

By the rolling rate of every a time is made as to 20～50%, rate of straining is made as to 3～15/sec, under relative low temperature, force work according to larger energy.Can prevent that thus coarse grain from mixing, and can generate fine and uniform crystal grain as a whole by dynamic recrystallization.If the rolling rate of every a time is less than 20%, the miniaturization of crystal grain becomes insufficient.Exceed 50% rolling rate if expect, the load load of milling train becomes excessive and does not have feasibility.And if rate of straining is less than 3/sec, the miniaturization of crystal grain becomes insufficient, there is the tendency of the mangcorn that produces microfine and thick grain.Exceed the rate of straining of 15/sec if expect, the load load of milling train becomes excessive and does not have feasibility.

Rolling temperature after each passage is made as 400～650 DEG C of low temperature while being hot rolling.Suppress thus the coarsening of crystal grain.If rolling temperature is less than 400 DEG C, dynamic recrystallization becomes insufficient, and the tendency that the deviation of crystallization particle diameter increases becomes remarkable.If rolling temperature exceedes 650 DEG C, carry out crystal grain-growth and average crystallite particle diameter exceedes 120 μ m.

This final smart hot rolling is carried out to 1 passage as required to multi-pass.

More preferably the condition of the essence hot rolling rolling rate that is every a time is 25～50%, rate of straining is that rolling temperature after 5～15/sec and passage is 500～600 DEG C, preferably implements this more than 3 passages essence hot rollings.

In addition, it can not be also 400～650 DEG C that rolling starts temperature, and the temperature while end with each passage of the smart hot rolling of terminal stage becomes the mode of 400～650 DEG C and sets rolling and start temperature, pass schedule.

And, after this hot rolling, till for example becoming the temperature below 200 DEG C from the temperature of 400～650 DEG C, carry out quenching with the speed of cooling of 200～1000 DEG C/min.Can suppress the growth of crystal grain and obtain the milled sheet of fine-grain by this quenching.If speed of cooling is less than 200 DEG C/min, suppress the weak effect of crystal grain-growth.Even if speed of cooling exceedes 1000 DEG C/min, can not contribute to further miniaturization yet.As the method for quenching, carry out the water spray about 1 minute.

The milled sheet so obtaining is corrected by correcting punching press, roller leveler etc., then, complete desired size with the mechanical workout such as Milling Process, electrodischarge machining(E.D.M.).The arithmetic mean surface roughness (Ra) of the sputtering surface of the sputtering target finally obtaining is preferably 0.2～2 μ m.

The conductive film formation silver alloy sputtering target of the present embodiment so obtaining, even if the power that has high input in sputter also can suppress paradoxical discharge, and can suppress the generation of splash.By this target is carried out to sputter, can obtain reflectivity high and there is the conductive film of excellent weather resistance.And, by utilizing this conductive film formation silver alloy sputtering target to carry out sputter, can obtain thering is the conductive film that good solidity to corrosion and thermotolerance and resistance are lower.Especially be width: 500mm, length: 500mm, thickness at target size: effective large-scale target more than 6mm.

Embodiment

(embodiment 1)

Preparation purity is Ag more than 99.99 quality % and is Sn more than 99.9 quality % and fills in the high-frequency induction smelting furnace by plumbago crucible brickwork as the purity of adding raw material.Total mass when melting is made as about 1100kg.

In the time carrying out melting, first melting Ag, after Ag fusing, drops into interpolation raw material in the mode of the composition that becomes target shown in table 1.Fully stir alloy molten metal by the mixing effect based on induction heating, then, cast at casting mold made of iron.

The shrinkage cavity part of the ingot that excision obtains by this casting, face is pruned except the surface contacting with mold, is probably of a size of the rectangular-shaped ingot of 640 × 640 × 180 (mm) as complete portion.

This ingot is heated to 780 DEG C, repeats rolling and extend to 1700mm from 640mm in a direction.Make its 90-degree rotation, then, further repeat the rolling of the 640mm of other direction, be made as the sheet material of general 1700 × 2200 × 19 (mm) size.

In this hot rolling, repeat altogether 12 passages.Wherein, the condition from final passage to the 3rd passage reciprocal (the sheet material temperature the rate of straining of every a time, rate of compression, passage) is made as table 1.Total rolling rate of hot rolling entirety is 90%.

After hot rolling finishes, the sheet material after rolling is carried out cooling with the condition shown in table 3.

After cooling, make sheet material correct the strain being produced by quenching by roller leveler, mechanical workout is that the size of 1600 × 2000 × 15 (mm) is used as target.

(embodiment 2～10, comparative example 1～10)

Identical with embodiment 1, in following scope, change: to make the Heating temperature of the ingot before hot rolling be 510～880 DEG C, make sheet metal thickness after final rolling be 9.5～25.6mm, make total passage number of times is for 11～14 times and to make total rolling rate be 86～95%.And the condition of the speed of cooling the hot rolling shown in condition and the table 3 from final passage to the 3rd passage reciprocal shown in target composition, table 1, table 2 is made target as shown in Table 3.The speed of cooling of recording in table 3 refers to by water and sprays carry out cooling, " anhydrous cooling " refer to only place cooling.But the thickness of the target after mechanical workout is made as the scope of 6～21mm.

(embodiment 11～13, comparative example 11)

The mode identical with embodiment 1 carried out melting and casting and made the ingot of general 640 × 640 × 60 (mm) size.This ingot is heated to 680 DEG C, then, carries out hot rolling and be made as the sheet material of general 1200 × 1300 × 15 (mm) size.

6 passages in this hot rolling, are repeated altogether.Wherein, the condition from final passage to the 3rd passage reciprocal (the sheet material temperature the rate of straining of every a time, rolling rate, passage) is made as table 2.Total rolling rate of hot rolling entirety is 75%.

After hot rolling finishes, the sheet material after rolling is carried out cooling with the condition shown in table 3.

After cooling, make sheet material correct the strain being produced by quenching by roller leveler, mechanical workout is that the size of 1000 × 1200 × 12 (mm) is used as target.

(embodiment 14～21, comparative example 12～14)

Preparation purity is Ag more than 99.99 quality % and is Sn, Sb and Ga more than 99.9 quality % as the purity of adding raw material.Melting Ag first in the high-frequency induction smelting furnace by plumbago crucible brickwork, after Ag fusing, drops into interpolation raw material in the mode that becomes the target composition shown in table 3.Fully stir alloy molten metal by the mixing effect based on induction heating, then, in cast iron mold processed, cast.

In these embodiment 14～21, comparative example 12～14, after casting, identical with above-described embodiment 11～13, comparative example 11, from being probably the ingot of 640 × 640 × 60 (mm) size by casting that the ingot obtaining produces.And ingot is heated to 680 DEG C, then, carries out hot rolling same as described above and as being probably the sheet material of 1200 × 1300 × 15 (mm) size.

6 passages in this hot rolling, are repeated altogether.Wherein, the condition from final passage to the 3rd passage reciprocal (the sheet material temperature the rate of straining of every a time, rolling rate, passage) is made as shown in table 2.Total rolling rate of hot rolling entirety is 75%.And carry out cooling with the condition shown in table 3.Then, make sheet material correct the strain being produced by quenching by roller leveler, mechanical workout is that the size of 1000 × 1200 × 12 (mm) is used as target.

[table 3]

To obtained target, measure warpage, median size and deviation thereof after mechanical workout.And, the paradoxical discharge number of times when target being installed on to sputter equipment and measuring sputter.In addition, the conductive film obtaining by sputter is determined surfaceness, reflectivity, salt tolerance and compares resistance.

(1) warpage after mechanical workout

Silver alloy sputtering target after mechanical workout is measured the amount of warpage of every 1m length and its result is represented in table 4.

(2) median size, its deviation

Carried out the particle size determination of silver alloys crystal grain by the method for recording for the mode carrying out an invention.Specifically, take equably sample from 16 places as the above-mentioned target producing, measure the surperficial median size of observing from the sputtering surface of each sample.And calculate the mean value of each sample median size, i.e. the deviation of the median size of the median size of silver alloys crystal grain and silver alloys crystal grain.

(3) paradoxical discharge number of times when sputter

From as the arbitrary portion of the above-mentioned target producing, cut out diameter: the plectane of 152.4mm, thickness: 6mm is also welded in copper backing plate.Splash evaluation target when the target of this welding is used as to sputter, and measure the paradoxical discharge number of times in sputter.

Now, the target of welding be installed on to general magnetic control sputtering device and be vented to 1 × 10 ^-4pa.Then, with Ar air pressure: 0.5Pa, input power: DC1000W and target substrate spacing: the condition of 60mm is carried out sputter.Measure the number of times of the paradoxical discharge producing in 30 minutes use initial stages.And repeat the empty sputter of 4 hours and the replacing of Antisticking, make target consumption by the sputter of carrying out discontinuously 20 hours.After this and then carry out sputter, measure the number of times that consumes the paradoxical discharge that (sputters of 20 hours) produce in latter 30 minutes.The number of times of these paradoxical discharges is to measure by the arc tally function of MKS instrument (INSTRUMENTS.) company DC power supply processed (model: RPDG-50A).

(4) as the fundamental characteristics evaluation of conducting film

(4-1) surfaceness of film

Utilize described evaluation target to carry out sputter with described identical condition, on the glass substrate of 20 × 20 (mm), form the silver alloy film with 100nm thickness.In addition, be Evaluation of Heat Tolerance, this silver alloy film is implemented to the thermal treatment of 250 DEG C, 10 minutes.After this, utilize atomic force microscope to measure the average surface roughness (Ra) of silver alloy film.

(4-2) reflectivity

On the glass substrate of 30 × 30 (mm), to form silver alloy film with described identical mode.And utilize the wavelength of spectrophotometric determination silver alloy film for the absolute reflectance of 550nm.

In addition, be corrosion proof evaluation, be to keep 100 hours in 80 DEG C, the humidity high wet sump of constant temperature that is 85% silver alloy film in temperature.After this, utilize the wavelength of spectrophotometric determination silver alloy film for the absolute reflectance of 550nm.

(4-3) salt tolerance

In order to confirm Ga additive effect, use the target (embodiment 18～21, comparative example 13,14) that adds Ga to form silver alloy film with described identical mode.Then, at the NaCl aqueous solution of film surface spray 5 % by weight of silver alloy film.From the position that is 20cm apart from film surface elevation, be 10cm apart from the distance of edge of substrate, spray to being parallel to film surface direction, make to be sprayed at the NaCl aqueous solution on film freely falling body and being attached on film as far as possible.Repeated 5 sprayings every 1 minute, then, repeatedly carry out 3 times with pure water and rinse and clean.Jet drying air and dispel moisture and be dried.

Carrying out after above-mentioned brine spray visual inspection silver alloy film surface and evaluating surperficial state.As Evaluation of Salt Tolerance benchmark, cannot confirm gonorrhoea or spot or only can confirm a part of be evaluated as " well ".Be evaluated as " bad " of gonorrhoea or spot will can be confirmed on whole surface.As mentioned above, with two grade evaluations surperficial state.Due to the target that does not add Ga is not evaluated, therefore in table, be labeled as "-".

(4-4) the ratio resistance of film

To have measured the ratio resistance of the silver alloy film being formed with described identical mode.

These each evaluation results represent in table 4～6.

[table 4]

In the target material of embodiment, in the scope of the median size of silver alloys crystal grain more than 30 μ m and less than 120 μ m, the deviation of silver alloys size of microcrystal silver alloys crystal grain median size 20% in.Warpage after mechanical workout is also little, and paradoxical discharge number of times when sputter is not only few at the use initial stage, also few after consumption.And, the tendency that the target of interpolation Sb, Ga has average crystallite particle diameter to diminish, paradoxical discharge number of times is also below 1 time less.But the addition of Sb, the Ga too much target of (exceeding altogether 2.5 quality %) produces and breaks in the time of smart hot rolling, cannot measure warpage.

And the conductive film obtaining by the target material of embodiment has excellent reflectivity and than resistance, surface roughness Ra is also little is below 2 μ m.

And known have excellent salt tolerance and effective to the conductive film of contact panel etc. by adding conductive film that the target of Ga obtains.

In addition, the present invention is not limited to above-mentioned embodiment, in the scope that does not depart from main contents of the present invention, can append various changes.

Utilizability in industry

When being carried out to sputter, can suppress by the target of present embodiment the generation of arc-over and splash.And, there is excellent reflectivity and also less than resistance and surfaceness by the target of present embodiment being carried out to the conductive film that sputter obtains.Therefore, the target of present embodiment can be applicable to being applied as the target that is used to form the conductive film such as the reflection electrode layer of organic EL or the wiring film of contact panel.

Claims (4)

1. a conductive film formation silver alloy sputtering target, is characterized in that,

There is the one-tenth being formed by Ag and inevitable impurity containing Sn and the remainder of 0.1～1.5 quality % and be grouped into,

The median size of alloy grain is more than 30 μ m and be less than 120 μ m, and the particle diameter deviation of described crystal grain is at below 20% of median size.

2. a conductive film formation silver alloy sputtering target, is characterized in that,

There is containing the Sn of 0.1～1.5 quality %, also contain one-tenth any one or two kinds of in Sb, the Ga that amounts to 0.1～2.5 quality % and that remainder is made up of Ag and inevitable impurity and be grouped into,

The median size of alloy grain is more than 30 μ m and be less than 120 μ m, and the particle diameter deviation of described crystal grain is at below 20% of median size.

3. conductive film forms the manufacture method with silver alloy sputtering target, it is characterized in that,

By the melting ingot casting being grouped into thering is the one-tenth that formed by Ag and inevitable impurity containing the Sn of 0.1～1.5 quality % and remainder, implement successively hot-rolled process, refrigerating work procedure and mechanical workout operation and manufacture silver alloy sputtering target,

In described hot-rolled process, taking the rolling rate of every a time as 20～50%, the temperature of rate of straining after 3～15/sec and passage carry out smart hot rolling more than 1 passage as the condition of 400～650 DEG C,

In described refrigerating work procedure, carry out quenching with the speed of cooling of 200～1000 DEG C/min.

4. conductive film forms the manufacture method with silver alloy sputtering target, it is characterized in that,

By the melting ingot casting being grouped into thering is containing the Sn of 0.1～1.5 quality %, also contain one-tenth any one or two kinds of in Sb, the Ga that amounts to 0.1～2.5 quality % and that remainder is made up of Ag and inevitable impurity, implement successively hot-rolled process, refrigerating work procedure and mechanical workout operation and manufacture silver alloy sputtering target

In described hot-rolled process, taking the rolling rate of every a time as 20～50%, the temperature of rate of straining after 3～15/sec and passage carry out smart hot rolling more than 1 passage as the condition of 400～650 DEG C,

In described refrigerating work procedure, carry out quenching with the speed of cooling of 200～1000 DEG C/min.