CN102959107A - Cu-Ga alloy, and Cu-Ga alloy sputtering target - Google Patents
Cu-Ga alloy, and Cu-Ga alloy sputtering target Download PDFInfo
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- CN102959107A CN102959107A CN201180031289.8A CN201180031289A CN102959107A CN 102959107 A CN102959107 A CN 102959107A CN 201180031289 A CN201180031289 A CN 201180031289A CN 102959107 A CN102959107 A CN 102959107A
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- 229910000807 Ga alloy Inorganic materials 0.000 title claims abstract description 100
- 238000005477 sputtering target Methods 0.000 title claims abstract description 33
- 239000000956 alloy Substances 0.000 claims abstract description 28
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims description 46
- 238000005096 rolling process Methods 0.000 abstract description 43
- 238000000034 method Methods 0.000 abstract description 29
- 238000005266 casting Methods 0.000 abstract description 24
- 238000005336 cracking Methods 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 5
- 238000007731 hot pressing Methods 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 238000004544 sputter deposition Methods 0.000 abstract description 3
- 239000002184 metal Substances 0.000 description 86
- 229910052751 metal Inorganic materials 0.000 description 86
- 239000010949 copper Substances 0.000 description 54
- 238000001816 cooling Methods 0.000 description 42
- 229910052802 copper Inorganic materials 0.000 description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 27
- 238000003490 calendering Methods 0.000 description 26
- 229910052799 carbon Inorganic materials 0.000 description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 23
- 238000002844 melting Methods 0.000 description 21
- 230000008018 melting Effects 0.000 description 21
- 239000010408 film Substances 0.000 description 13
- 238000002347 injection Methods 0.000 description 13
- 239000007924 injection Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 239000007769 metal material Substances 0.000 description 9
- 208000037656 Respiratory Sounds Diseases 0.000 description 8
- 229910052733 gallium Inorganic materials 0.000 description 8
- 235000010724 Wisteria floribunda Nutrition 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000005204 segregation Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910001370 Se alloy Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000007499 fusion processing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
- B22D21/025—Casting heavy metals with high melting point, i.e. 1000 - 1600 degrees C, e.g. Co 1490 degrees C, Ni 1450 degrees C, Mn 1240 degrees C, Cu 1083 degrees C
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Vapour Deposition (AREA)
- Continuous Casting (AREA)
Abstract
Disclosed is a Cu-Ga alloy which comprises 25-30 mass% of Ga and a reminder made up by Cu, and which is characterized in that a gamma-phase (that is a phase having a Ga concentration appearing on a structure image obtained on an electron microscope of 30-35 mass%) has an average equivalent circle diameter of 50 [mu]m or less and a largest equivalent circle diameter of 200 [mu]m or less. The Cu-Ga alloy rarely undergoes breakage, cracking or the like even when produced by a casting method due to the specific phase structure contained in the structure thereof, and therefore the alloy can be subjected to rolling processing in spite of a fact that the alloy contains Ga at a concentration as high as 25-30 mass%. Therefore, it becomes possible to produce a sputtering target having a high Ga content by rolling, and the productivity of the sputtering target can be improved. When the Cu-Ga alloy is produced by a casting method, the sputtering rate becomes higher compared with that for a Cu-Ga alloy sputtering target that is produced by a powder sintering method such as hot pressing
Description
Technical field
The present invention relates to a kind of Cu-Ga alloy and Cu-Ga alloy sputtering targets, more specifically, even relate to the more Cu-Ga alloy of rolling processing and the Cu-Ga alloy sputtering targets that is obtained by described alloy of also can carrying out of the amount of Ga.
Background technology
In recent years, the thin-film solar cells that is obtained by compound semiconductor is practical.In this thin-film solar cells, generally speaking, being formed with on the soda-lime glass substrate becomes the Mo of positive electrode electrode layer, on this Mo electrode layer, be formed with the light absorbing zone that contains the Cu-In-Ga-Se alloy film, on this light absorbing zone, be formed with the buffer layer that contains ZnS, CdS etc., and on this buffer layer, be formed with the transparent electrode layer that becomes negative potential.
As the formation method of the light absorbing zone that contains the Cu-In-Ga-Se alloy film, proposed to form by sputtering method the method for Cu-In-Ga-Se alloy film, to replace film forming speed slowly and the vapour deposition method of Expenses Cost.
As the method that makes this Cu-In-Ga-Se alloy film film forming by sputtering method, following method has been proposed, namely, use the Cu-Ga target and make Cu-Ga alloy film film forming by sputter, thereby and by on this Cu-Ga alloy film, using the In target to carry out sputter formation composite membrane, afterwards, in Se atmosphere, this composite membrane is heat-treated, thus the method for formation Cu-In-Ga-Se alloy film.The method also can by make the reversed order that forms composite membrane, namely form the Cu-Ga film and implement on the In film.As the Cu-Ga alloys target, the known Ga of weight percent 1～40% and the Cu-Ga alloys target that surplus is made of Cu of containing.
As the manufacture method of this Cu-Ga alloy sputtering targets, can use the casting of the powder sintering of hot pressing etc. and vacuum melting method etc.As the Cu-Ga alloy sputtering targets that produces by powder sintering, for example, disclose a kind of Cu-Ga alloy sputtering targets in TOHKEMY 2008-138232 communique, described Cu-Ga alloy sputtering targets is that Cu-Ga powdered alloy and the amount of fine copper powder or the Ga mixed powder that be mass percent Cu-Ga powdered alloy 15% below of mass percent more than 30% carries out hot pressing and obtain by the amount to Ga.But the Cu-Ga alloy sputtering targets of making by pressure sintering has fine tissue on the one hand, and exists on the other hand oxygen concn higher, and the shortcoming that waits more slowly of sputter rate.
With respect to this, it is lower that the Cu-Ga alloy sputtering targets by the casting manufacturing then has an oxygen concn, and very fast etc. the advantage of sputter rate.But, it because the ingot bar of the Cu-Ga alloy that produces by casting can't form fine tissue, and is easy to occur segregation on the other hand, therefore and easily crack, exist the plastic working that is difficult to by calendering etc. to make the shortcoming of sputtering target shaping etc.If can not sputtering target be shaped by calendering, then can't realize the raising of the productivity of sputtering target.Because when the Ga of Cu-Ga alloy concentration is mass percent 25% when above, hardness can be higher, thereby the possibility of generation crackle will be obviously larger, so especially be difficult to carry out the plastic working of calendering etc.
As the technology that solves the shortcomings such as the caused this segregation of casting and brittle crack, when in TOHKEMY 2000-073163 communique, disclosing a kind of casting mold that possesses heating unit and cooling unit in utilization speed of cooling is controlled, the Cu-Ga alloy material of the Ga that contains mass percent 15～70% is cast and made ingot bar, and be the emptying aperture of island the setting of this ingot bar, thereby in this emptying aperture, inject the ingot bar that the molten metal of In produces.
Technical literature formerly
Patent documentation
Patent documentation 1: TOHKEMY 2008-138232 communique
Patent documentation 2: TOHKEMY 2000-073163 communique
Summary of the invention
Invent problem to be solved
Although the disclosed described ingot bar of TOHKEMY 2000-073163 communique is by slowing down speed of cooling, thereby segregation and fragility are suppressed, and then can form sputtering target by machining, but because when speed of cooling slows down, crystallization one by one will become greatly, therefore can't roll.
The object of the invention is to, even even provide the more Cu-Ga alloy that also can implement rolling processing of a kind of Ga amount and Ga amount the more Cu-Ga alloy sputtering targets that also can make by rolling processing.
Be used for solving the method for problem
The inventor finds, for the fragility of the ingot bar that obtains by casting, contain the Cu-Ga alloy, it is the phase of mass percent 30～35%, for example is called as the mutually relevant of γ phase with Ga concentration, and can by to this γ phase the size and exist ratio to regulate to control the cracking difficulty, finished thus the present invention.
Namely, the present invention is a kind of Cu-Ga alloy, it contains the Ga of mass percent 25～30%, and surplus is Cu, described Cu-Ga alloy is characterised in that, present on the tissue image that obtains by electron microscope, Ga concentration be mass percent 30～35% be that the average equivalent diameter of γ phase is below the 50 μ m mutually, and the maximum equivalent circular diameter is below the 200 μ m.
As the optimal way of described Cu-Ga alloy,
This sputtering target manufacturing is with in alloy, is 5～70% with respect to the ratio of the total of area area, the γ phase of described tissue image.
In addition, other inventions are a kind of Cu-Ga alloy sputtering targets, and it obtains by described Cu-Ga alloy is rolled.
The effect of invention
Cu-Ga alloy of the present invention, because by making tissue have specific phase structure, even thereby in the situation that make by casting and also to be difficult to crack or breach etc., therefore, can contain at the higher concentration with mass percent 25～30% in the situation of Ga and implement rolling processing.Therefore, can make the more sputtering target of amount of Ga by calendering, and can realize the raising of the productivity of sputtering target.In addition, in the situation that make Cu-Ga alloy of the present invention by casting, compare with the Cu-Ga alloy sputtering targets that powder sintering by hot pressing etc. produces, sputter rate is very fast.
Description of drawings
Fig. 1 is, the cross section of the Cu-Ga alloy of the present invention that utilizes the carbon mold and produce observed with 200 times multiplying power by scanning electron microscope, thus an example of the tissue image that obtains.
Fig. 2 is, the Cu-Ga alloy of the present invention cross section that utilizes the water-cooled copper mold and produce observed with 200 times multiplying power by scanning electron microscope, thus an example of the tissue image that obtains.
Embodiment
Cu-Ga alloy of the present invention is characterised in that, the Ga and the surplus that contain mass percent 25～30% are Cu, and the average equivalent diameter of the γ phase that presents on the tissue image that obtains by electron microscope is below the 50 μ m, and the maximum equivalent circular diameter is below the 200 μ m.At this, γ refers to that mutually Ga concentration is the phase of mass percent 30～35%.Whether the phase that presents on the tissue image is that γ can confirm mutually in the following way, namely, the image corresponding with mean atomic weight that utilization is obtained by electron microscope (composition picture, COMPO picture) observed to confirm to the difference of the contrast that caused by the Ga concentration difference.Equivalent diameter refers to, the Ga concentration of the composition picture that is obtained by aforesaid way is the zone of mass percent 30～35%, namely has and the area of γ phase circular diameter of the same area.Average equivalent diameter refers to the mean value of the equivalent circular diameter of the whole γ phase that presents on the described tissue image.The maximum equivalent circular diameter refers to, equivalent diameter in the equivalent diameter of the whole γ phase that presents on described tissue image, maximum.
As the concrete acquiring method of the equivalent diameter of γ phase, at the 0.3mm that obtains with 200 times multiplying power
2The composition picture in, judge after γ phase and other boundary between mutually, process the area that calculates this γ phase thereby carry out image, and hypothesis has the circle of this area, thereby with the equivalent diameter of its diameter as this γ phase.The average equivalent diameter of γ phase can obtain in the following way, that is, by trying to achieve in the above described manner equivalent diameter for the whole γ phase that presents on the described composition picture, and these equivalent diameters are averaged and obtain.In addition, try to achieve in the above described manner equivalent diameter for the whole γ phase that presents on the described composition picture, and with the maximum equivalent circular diameter of the maximum value in these equivalent diameters as the γ phase.
Confirm according to electron microscope observation, although generally speaking, the Cu-Ga alloy is in the amount of the Ga situation less than about mass percent 25%, it is mutually (β phase) formation of mass percent 20～25% with Ga concentration that the phase of Ga is arranged by solid solution among the Cu, but when the amount of Ga becomes approximately mass percent 25% when above, then by Ga concentration be mass percent 30～35% phase (γ phase) and β mutually this two-phase consist of.
In Cu-Ga alloy of the present invention, the average equivalent diameter of the γ phase that presents on the tissue image that obtains by electron microscope is below the 50 μ m, and the maximum equivalent circular diameter of γ phase is below the 200 μ m.That is to say, Cu-Ga alloy of the present invention has uniform tissue, and it is that 50 μ m are following and to contain equivalent diameter be the following γ phases of 200 μ m that described tissue contains average equivalent diameter.
If the average equivalent diameter of γ phase, then easily cracks in the man-hour that adds of calendering etc. greater than 200 μ m greater than 50 μ m or maximum equivalent circular diameter.Think that its reason is, be the lower phase of softness and fragility mutually with respect to β, because the phase that γ is mutually with β compares firmly mutually and fragility is higher, therefore, if exist average equivalent diameter greater than 50 μ m or the equivalent diameter γ phase greater than 200 μ m, the part of the γ phase that then equivalent diameter is larger when alloy is applied in physically power easily cracks.On the other hand, because when the average equivalent diameter of γ phase is below the 50 μ m and the maximum equivalent circular diameter is that 200 μ m are when following, even do not have this larger γ phase that easily cracks or exist lessly yet, therefore think to be difficult to man-hour crack in adding of calendering etc.
Based on this reason, the average equivalent diameter of γ phase and maximum equivalent circular diameter are less then more to be preferred.As the average equivalent diameter of γ phase, be preferably below the 45 μ m, more preferably below the 30 μ m.As the maximum equivalent circular diameter of γ phase, be preferably below the 150 μ m, more preferably below the 120 μ m.
In addition, for the foregoing reasons, average equivalent diameter and the maximum equivalent circular diameter of γ phase are not limited especially.If according to the common manufacture method of Cu-Ga alloy of the present invention described later, then the lower value of the average equivalent diameter of γ phase is roughly 10 μ m, and the lower value of maximum equivalent circular diameter is roughly 30 μ m.
In addition, in Cu-Ga alloy of the present invention, being preferably, is 5～70% with respect to the ratio of the total of area area, the γ phase of described tissue image (below, be also referred to as Area Ratio).Generally speaking, although the amount of contained Ga is more in this alloy, the total of the area of the γ phase that then presents on the described tissue image more increases, but, even because in the situation that the amount of contained Ga is identical in alloy, Ga be comprised in γ still be comprised in β in mutually also can be according to each alloy and difference in mutually, therefore, the total of the area of the γ phase that presents on the described tissue image may be different.When described Area Ratio greater than 70% the time, because the mutually shared ratio of the γ that fragility is higher becomes large, therefore even the average equivalent diameter of γ phase is that the following and maximum equivalent circular diameter of 50 μ m is below the 200 μ m, adding the possibility that cracks man-hour and will uprise in calendering etc.In addition, be in the situation of mass percent 25～30% at the Ga of Cu-Ga alloy amount, common described Area Ratio can be less than mass percent 5%.
When with above-mentioned same mode, area to whole γ phase of being presented on the composition picture that obtains with 200 times multiplying power calculates, and this aggregate values is made as S γ, when the area of composition picture is made as S, passes through R(%)=(S γ/S) * the 100 and ratio R with respect to the total of area area, the γ phase of described tissue image is calculated.
Cu-Ga alloy of the present invention contains the Ga of mass percent 25～30%, and surplus is Cu.When the Cu-Ga alloy has this composition, can produce and to form effective Cu-Ga film with the sputtering target as light absorbing zone of solar cell etc.In addition, because when the Cu-Ga alloy has this composition, as indicated above will easily cracking, the necessity of therefore controlling this crackle is higher.In addition, Cu-Ga alloy of the present invention might contain inevitable impurity except Ga and Cu.
The shape of Cu-Ga alloy of the present invention is not limited especially, can determine according to the purposes of this alloy suitable shape.
As mentioned above, even because Cu-Ga alloy of the present invention is had power physically also to be difficult to produce cracking by load, therefore can pass through to implement suitable plastic working, thereby produce various products.For example, by Cu-Ga alloy of the present invention is implemented rolling processing, thereby can make sputtering target.
As the calendering process of when making sputtering target by Cu-Ga alloy of the present invention, implementing, can list the known calendering process that common alloy is implemented, for example, alloy sheets is adjusted to predetermined rolling temperature, and roll with predetermined rolling rate alloy by rolling press, and suitably repeat these operations and the thickness that the makes alloy method of attenuation gradually.
As rolling temperature, be generally 500～850 ℃, be preferably 700～850 ℃, more preferably 750～800 ℃.Because when rolling temperature is lower than 500 ℃, mutually not fully deliquescing of β, so alloy will be difficult to bear and roll caused distortion, and can produce skin breakage or cracking because of calendering, thus be difficult to obtain durable sputtering target.On the other hand, when rolling temperature is higher than 850 ℃, following phenomenon might occur, that is, the heating of following owing to the distortion that causes because of calendering melts, and perhaps part melts in heating.
As rolling press, can use employed common rolling press in the calendering of alloy, for example, possess the rolling press of a pair of stack.
Rolling rate is preferably 2～23%.Since when rolling rate less than 2% the time, the number of times that becomes the calendering procedure that desired thickness carried out in the past in alloy sheets will increase, so productivity can reduce.When rolling rate greater than 23% the time, on alloy sheets, will easily crack, in addition, it is very big that the load that rolling press bears will become.In the scope that alloy sheets does not crack, rolling rate is set as higher value, for the productivity this point for preferably.Even the rolling rate of operable maximum, the maximum value of namely rolling the rolling rate that also can not crack exist with ... rolling temperature and Ga concentration, rolling temperature is higher, and Ga concentration is lower, and then maximum rolling rate is higher.The thickness of the alloy sheets after will once rolling is made as h
1, the thickness of the alloy sheets before the calendering is made as h
2The time, can calculate rolling rate r by following formula.
［ mathematical expression 1 ］
r（%）﹦［（h
2－h
1）/h
2］×100
The sputtering target that obtains in the above described manner is engaged with on the backboard, thereby is used to sputter.
The manufacture method of Cu-Ga alloy of the present invention is not limited especially, for example, can use vacuum melting casting, atmosphere to melt the casting of casting and semicontinuous casting method etc.Cu-Ga alloy of the present invention can be made method and effectively make by the following melting cast that melts operation and casting process that comprises.
［ melting operation ］
Thereby by being mixed and melt, each metallic substance obtains molten metal.
As metallic substance, the pure metal of Cu, pure metal and the Cu-Ga alloy of Ga can be used, and the combination of the pure metal of the pure metal of Cu and Ga, any one in the combination of the pure metal of the pure metal of the combination of the pure metal of combination, the Ga of the pure metal of Cu-Ga alloy, Cu and Cu-Ga alloy and Cu-Ga alloy and Cu and Ga and Cu-Ga alloy only can be.
The mixture ratio of each metallic substance is made as, makes via this melting operation and casting process and the amount of the Ga in the Cu-Ga alloy that produces becomes the ratio of mass percent 25～30%.
In calciner, the mixed metallic substance that forms is melted.As calciner, can use employed calciner in common melting casting, for example, can use high-frequency melting stove and electric furnace etc.Preferred high-frequency melting stove wherein.In the high-frequency melting stove, owing to can in fusion processes, stir fully, distribute thereby make molten metal have uniform composition, therefore, in the ingot bar that produces via casting process, be difficult for producing segregation or oversize particle, and be easy to make the equivalent diameter of γ phase to reduce.With respect to this, in electric furnace, because the stirring in the fusion processes easily becomes insufficient, thereby it is higher to occur to form the possibility that distributes in molten metal, therefore, in the ingot bar that produces via casting process, easily produce segregation or oversize particle, and be difficult to make the equivalent diameter of γ phase to diminish.Especially, as metallic substance, as the combination of the pure metal of the pure metal of Cu and Ga, in the situation that the metallic substance that composition is differed widely mixes to use, the inadequate possibility that becomes of the stirring in electric furnace in the fusion processes is higher.But, even use electric furnace, also can stir fully by utilizing stirring rod etc. the metallic substance after melting, thereby obtain having the molten metal that uniform composition distributes, and then can eliminate above-mentioned problem points.But, exist because stirring rod etc. and possibility that molten metal is polluted.
As melting temperature (Tm), be preferably 1200～1400 ℃, more preferably 1200～1300 ℃.When melting temperature (Tm) is lower than 1200 ℃, will solidifies at the stage molten metal that molten metal is injected mold, thereby will be difficult to obtain the target ingot bar.For fear of such problem, thereby be preferably set to high about 300～500 ℃ melting temperature (Tm) of fusing point than the alloy of manufacturing.On the other hand, when melting temperature (Tm) is higher than 1400 ℃, owing to cooling time in casting process is elongated, therefore, the growth of tissue will occur during this period, thereby easily produce segregation or oversize particle, and then be difficult to make the equivalent diameter of γ phase to diminish, and become the ingot bar that easily cracks.
［ casting process ］
The molten metal that will obtain in melting engineering injects mold, then it is cooled off and obtains ingot bar.
In mold, inject molten metal speed, be that pouring speed is larger, the equivalent diameter of γ phase is reduced, be preferred therefore.Owing to there being relation as described later between the equivalent diameter of γ phase and the speed of cooling of molten metal, therefore think, when pouring speed hour, to be difficult to carry out rapidly the cooling of whole molten metals, thereby the growth of γ phase will occur in process of cooling, and then the equivalent diameter of γ phase is increased.On the other hand, when pouring speed is larger, owing to can carry out rapidly the cooling of whole molten metals, therefore, can suppress the growth of the γ phase in the process of cooling, its result is to think that the equivalent diameter of γ phase diminishes.But, as long as can cool off the molten metal that is injected in the mold rapidly, even then pouring speed is less, the equivalent diameter of γ phase is reduced.Therefore, in the situation that used the water-cooled copper mold, compare with the situation of having used the carbon mold, even pouring speed is less, make the equivalent diameter of γ phase less also than being easier to.
For example, in the situation in 1200～1400 ℃ the carbon mold of poured with molten metal at 550mm * 145mm * 30mm, pouring speed is preferably 200～1000g/sec, more preferably 400～800g/sec.In with the situation in 1200～1400 ℃ the water-cooled copper mold of poured with molten metal at 460mm * 160mm * 30mm, pouring speed is preferably 200～800g/sec, more preferably 250～600g/sec.
The speed of cooling of molten metal is important factor in making Ga-Cu alloy of the present invention.When speed of cooling hour, the growth of γ phase can occur, thereby the equivalent diameter of γ phase will increase in process of cooling.On the other hand, when speed of cooling was larger, the speed of growth of γ phase was less, and the tissue of alloy is with granular, thereby the equivalent diameter of γ phase will diminish.Suitable speed of cooling is 5～500 ℃/min.When speed of cooling during less than 5 ℃/min, the tissue of alloy is thickization, thereby it is following or make the maximum equivalent circular diameter become comparatively difficulty of 200 μ m to make the average equivalent diameter of γ phase become 50 μ m.On the other hand, when speed of cooling during greater than 500 ℃/min, at short notice hardening when molten metal enters mold, thereby can't become continuous ingot bar, and then exist and produce the tendency that fold or ingot bar become stratiform on the ingot bar.More preferably speed of cooling is 10～150 ℃/min, and further preferred speed of cooling is 20～100 ℃/min.
As mold, can use employed mold in the common melting casting, for example, can use water-cooled copper mold and carbon mold etc.Wherein, the water-cooled copper mold can adopt larger speed of cooling, thereby makes the granular of organizing of alloy as mentioned above, and is easy to make on this point that the equivalent diameter of γ phase reduces for preferred.In the situation that use the water-cooled copper mold, speed of cooling can be made as 40～200 ℃/min usually, in the situation that use the carbon mold, speed of cooling can be made as 5～20 ℃/min usually.
About shape and the size of mold, although do not limit especially,, because preferred speed of cooling is larger as mentioned above, therefore, be preferably shape and size that speed of cooling is increased.
In Fig. 1, illustrate, thus an example of the tissue image of the cross section of the Cu-Ga alloy of the present invention that uses the carbon mold and produce being observed to obtain with 200 times multiplying power by scanning electron microscope; In Fig. 2, illustrate, thus an example of the tissue image of the cross section of the Cu-Ga alloy of the present invention that uses the water-cooled copper mold and produce being observed to obtain with 200 times multiplying power by scanning electron microscope.For above-mentioned any one Cu-Ga alloy, the mode that all becomes mass percent 28% with Ga concentration is carried out weighing to pure Cu and pure Ga, and melt under 1200 ℃ by the high-frequency melting stove and to produce molten metal, afterwards, about the former Cu-Ga alloy, by with this molten metal Implantation mold, and cool off and obtain with the speed of cooling of 10～20 ℃/min, and about the latter's Cu-Ga alloy, by this molten metal is injected the water-cooled Copper casting mould, and cool off and obtain with the speed of cooling of 20～60 ℃/min.In any one tissue image, the part that represents with light color is the γ phase, and the part that represents with dark color is the β phase.Although two kinds of Cu-Ga alloys only are that employed mold and speed of cooling are different in its manufacturing processed, but by the relatively discovery between Fig. 1 and Fig. 2, in the Cu-Ga alloy of the present invention that uses the water-cooled copper mold to produce, with the Cu-Ga alloy phase ratio of the invention of using the carbon mold to produce, the equivalent diameter of γ phase is less.
By comprising above melting operation and the manufacture method of casting process, thereby obtained the ingot bar as Cu-Ga alloy of the present invention.
Embodiment
(relatively Production Example 1)
To pure Cu and pure Ga carries out weighing so that Ga concentration becomes mass percent 28%, (Fuji's electric wave industry (strain) is made to use the high-frequency vacuum calciner, FVM-30), in Ar atmosphere, heat up with 15 ℃/min, after having confirmed the raw material fusing, molten metal temperature is remained on 1000 ℃.The molten metal of the gained pouring speed with 500g/sec is injected in the carbon mold of 550mm * 145mm * 30mm.At this moment, molten metal has begun to solidify before injection is finished.The molten metal that is injected in the carbon mold is cooled to 200 ℃ with the about speed of cooling of 13 ℃/min, thereby has obtained ingot bar.Because solidifying intermittently of this ingot bar occurs, and therefore is stratiform, thereby do not become good ingot bar.The result is concluded to table 1.
(relatively Production Example 2)
Under the condition identical with Production Example relatively 1, produce molten metal.The pouring speed of this molten metal with 500g/sec is injected in the water-cooled copper mold of 460mm * 160mm * 30mm.At this moment, molten metal has begun to solidify before injection is finished.The molten metal that is injected in the water-cooled copper mold is cooled to 50 ℃ with the about speed of cooling of 100 ℃/min, thereby has obtained ingot bar.This ingot bar has produced a plurality of defectives in the position of solidifying, thereby does not become good ingot bar.The result is concluded to table 1.
(relatively Production Example 3)
To pure Cu and pure Ga carries out weighing so that Ga concentration becomes mass percent 28%, (Fuji's electric wave industry (strain) is made to use the high-frequency vacuum calciner, FVM-30), in Ar atmosphere, heat up with 15 ℃/min, after having confirmed the raw material fusing, molten metal temperature is remained on 1100 ℃.The molten metal of the gained pouring speed with 500g/sec is injected in the carbon mold of 550mm * 145mm * 30mm.At this moment, molten metal has begun to solidify before injection is finished.The molten metal that is injected in the carbon mold is cooled to 200 ℃ with the about speed of cooling of 13 ℃/min, thereby has obtained ingot bar.Because solidifying intermittently of this ingot bar occurs, therefore, although do not reach the degree of the ingot bar that is obtained by comparison Production Example 1, still be stratiform, thereby do not become good ingot bar.The result is concluded to table 1.
(relatively Production Example 4)
Under the condition identical with Production Example relatively 3, produce molten metal.The pouring speed of this molten metal with 500g/sec is injected in the water-cooled copper mold of 460mm * 160mm * 30mm.At this moment, molten metal has begun to solidify before injection is finished.The molten metal that is injected in the water-cooled copper mold is cooled to 50 ℃ with the about speed of cooling of 100 ℃/min, thereby has obtained ingot bar.Although do not reach the degree of the ingot bar that is obtained by comparison Production Example 2, this ingot bar has still produced a plurality of defectives in the position of solidifying, thereby does not become good ingot bar.The result is concluded to table 1.
(Production Example 1)
To pure Cu and pure Ga carries out weighing so that Ga concentration becomes mass percent 28%, (Fuji's electric wave industry (strain) is made to use the high-frequency vacuum calciner, FVM-30), in Ar atmosphere, heat up with 15 ℃/min, after having confirmed the raw material fusing, molten metal temperature is remained on 1200 ℃.The molten metal of the gained pouring speed with 500g/sec is injected in the carbon mold of 550mm * 145mm * 30mm.At this moment, molten metal does not begin to solidify before injection is finished.The molten metal that is injected in the carbon mold is cooled to 200 ℃ with the about speed of cooling of 13 ℃/min, thereby has obtained ingot bar.This ingot bar is cut to the approximately tetragonal size of 10mm, and carries out mirror ultrafinish, make by scanning electron microscope (JEOL(strain), JSM-6380A) with 200 times multiplying power its cross section is observed.By above-mentioned method, tried to achieve average equivalent diameter and the maximum equivalent circular diameter of γ phase by the tissue image of gained.The result is concluded to table 1.According to above creating conditions, thereby obtained good ingot bar as Cu-Ga alloy of the present invention.
(Production Example 2)
Under the condition identical with Production Example 1, make molten metal.The pouring speed of this molten metal with 500g/sec is injected in the water-cooled copper mold of 460mm * 160mm * 30mm.At this moment, molten metal does not begin to solidify before injection is finished.The molten metal that is injected in the water-cooled copper mold is cooled to 50 ℃ with the about speed of cooling of 100 ℃/min, thereby has obtained ingot bar.About this ingot bar, under the condition identical with Production Example 1, carry out scanning electron microscope and observe, and try to achieve average equivalent diameter and the maximum equivalent circular diameter of γ phase.The result is concluded to table 1.According to above creating conditions, and obtained good ingot bar as Cu-Ga alloy of the present invention.
(relatively Production Example 5)
To pure Cu and pure Ga carries out weighing so that Ga concentration becomes mass percent 28%, (Fuji's electric wave industry (strain) is made to use the high-frequency vacuum calciner, FVM-30), in Ar atmosphere, heat up with 15 ℃/min, after the fusing of having confirmed raw material, molten metal temperature is remained on 1300 ℃.The molten metal of the gained pouring speed with 500g/sec is injected in the carbon mold of 550mm * 145mm * 30mm.At this moment, molten metal does not begin to solidify before injection is finished.The molten metal that is injected in the carbon mold is cooled to 200 ℃ with the about speed of cooling of 13 ℃/min, thereby has obtained ingot bar.About this ingot bar, under the condition identical with Production Example 1, carry out scanning electron microscope and observe, and try to achieve average equivalent diameter and the maximum equivalent circular diameter of γ phase.The result is concluded to table 1.Although in above creating conditions, obtained good ingot bar, the average equivalent diameter of γ phase is greater than 50 μ m, thereby fails to obtain Cu-Ga alloy of the present invention.
(Production Example 3)
Under the condition identical with Production Example relatively 5, produce molten metal.The pouring speed of this molten metal with 500g/sec is injected in the water-cooled copper mold of 460mm * 160mm * 30mm.At this moment, molten metal does not begin to solidify before injection is finished.The molten metal that is injected in the water-cooled copper mold is cooled to 50 ℃ with the about speed of cooling of 100 ℃/min, thereby has obtained ingot bar.About this ingot bar, under the condition identical with Production Example 1, carry out scanning electron microscope and observe, and try to achieve average equivalent diameter and the maximum equivalent circular diameter of γ phase.The result is summarized in table 1.According to above creating conditions, obtained the good ingot bar as Cu-Ga alloy of the present invention.
(relatively Production Example 6)
To pure Cu and pure Ga carries out weighing so that Ga concentration becomes mass percent 28%, (Fuji's electric wave industry (strain) is made to use the high-frequency vacuum calciner, FVM-30), in Ar atmosphere, heat up with 15 ℃/min, after having confirmed the raw material fusing, molten metal temperature is remained on 1400 ℃.The molten metal of the gained pouring speed with 500g/sec is injected in the carbon mold of 550mm * 145mm * 30mm.At this moment, molten metal does not begin to solidify before injection is finished.The molten metal that is injected in the carbon mold is cooled to 200 ℃ with the about speed of cooling of 13 ℃/min, thereby has obtained ingot bar.For this ingot bar, under the condition identical with Production Example 1, carry out scanning electron microscope and observe, and try to achieve average equivalent diameter and the maximum equivalent circular diameter of γ phase.The result is summarized in table 1.Although under above creating conditions, obtained good ingot bar, the average equivalent diameter of γ phase is greater than 50 μ m, thereby fails to obtain Cu-Ga alloy of the present invention.
(relatively Production Example 7)
Under the condition identical with Production Example relatively 6, produce molten metal.The pouring speed of this molten metal with 500g/sec is injected in the water-cooled copper mold of 460mm * 160mm * 30mm.At this moment, molten metal does not begin to solidify before injection is finished.The molten metal that is injected in the water-cooled copper mold is cooled to 50 ℃ with the about speed of cooling of 100 ℃/min, thereby has obtained ingot bar.About this ingot bar, under the condition identical with Production Example 1, carry out scanning electron microscope and observe, and try to achieve average equivalent diameter and the maximum equivalent circular diameter of γ phase.The result is summarized in table 1.Although under above creating conditions, obtained good ingot bar, the average equivalent diameter of γ phase is greater than 50 μ m, thereby fails to obtain Cu-Ga alloy of the present invention.
［ table 1 ］
According to the result shown in the table 1 as can be known, when not making melting temperature (Tm) exceed 300～500 ℃ of left and right sides of fusing point of Cu-Ga alloy of manufacturing, molten metal solidifies beginning before finishing to the injection of mold, thereby can't obtain good ingot bar.
And as can be known, compare during with use carbon mold, when having used the water-cooled copper mold, can access the less Cu-Ga alloy of average equivalent diameter of γ phase.Think that its reason is, as narrate, speed of cooling is increased.
In addition as can be known, when melting temperature (Tm) uprises, the average equivalent diameter of γ phase will increase.Therefore think that its reason is, because tissue will be grown largely with elongated cooling time when melting temperature (Tm) is higher.
(Production Example 4)
Be that the Cu-Ga alloy of mass percent 28% replaces pure Cu and pure Ga with Ga concentration, in addition, under the condition identical with Production Example 1, produce ingot bar.About this ingot bar, carrying out scanning electron microscope under the condition identical with Production Example 1 observes, and try to achieve average equivalent diameter and the maximum equivalent circular diameter of γ phase, and the average equivalent diameter of γ phase is below the 50 μ m, the maximum equivalent circular diameter is below the 200 μ m.
(Production Example 5)
Be that the Cu-Ga alloy of mass percent 32% replaces pure Cu and pure Ga with pure Cu and Ga concentration, and both are carried out weighing so that Ga concentration becomes mass percent 28%, in addition, under the condition identical with Production Example 1, produce ingot bar.About this ingot bar, carrying out scanning electron microscope under the condition identical with Production Example 1 observes, and try to achieve average equivalent diameter and the maximum equivalent circular diameter of γ phase, and the average equivalent diameter of γ phase is below the 50 μ m, the maximum equivalent circular diameter is below the 200 μ m.
(Production Example 6)
Be that the Cu-Ga alloy of mass percent 20% replaces pure Cu and pure Ga with pure Ca and Ga concentration, and both are carried out weighing so that Ga concentration becomes mass percent 28%, in addition, under the condition identical with Production Example 1, produce ingot bar.About this ingot bar, carrying out scanning electron microscope under the condition identical with Production Example 1 observes, and try to achieve average equivalent diameter and the maximum equivalent circular diameter of γ phase, and the average equivalent diameter of γ phase is below the 50 μ m, the maximum equivalent circular diameter is below the 200 μ m.
The result of these results and Production Example 1 together is shown in table 2.
［ table 2 ］
| ? | Metallic substance | The state of ingot bar | Average equivalent diameter | The maximum equivalent circular diameter |
| Production Example 1 | Pure Cu, pure Ga | Well | Below the 50 μ m | Below the 200 μ m |
| Production Example 4 | The Cu-Ga alloy | Well | Below the 50 μ m | Below the 200 μ m |
| Production Example 5 | Pure Cu, Cu-Ga alloy | Well | Below the 50 μ m | Below the 200 μ m |
| Production Example 6 | Pure Ga, Cu-Ga alloy | Well | Below the 50 μ m | Below the 200 μ m |
According to the result of table 2 as can be known, as metallic substance, in the combination of the pure metal of the pure metal that uses Cu and Ga, only in the situation of any one in the combination of the pure metal of combination, the Ga of the pure metal of Cu-Ga alloy, Cu and Cu-Ga alloy and Cu-Ga alloy, the average equivalent diameter that all can access the γ phase is that the following and maximum equivalent circular diameter of 50 μ m is the following Cu-Ga alloys of 200 μ m.Can infer according to this result, even the combination of the pure metal of the pure metal of Cu and Ga and Cu-Ga alloy, the average equivalent diameter that also can access the γ phase is below the 50 μ m and the maximum equivalent circular diameter is the following Cu-Ga alloys of 200 μ m.
Embodiment 1～3, comparative example 1～3
To pure Cu and pure Ga carries out weighing so that Ga concentration becomes the value shown in the table 3, and (Fuji's electric wave industry (strain) is made to use the high-frequency vacuum calciner, FVM-30), in Ar atmosphere, heat up with 15 ℃/min, after having confirmed the raw material fusing, molten metal temperature is remained on 1200 ℃.The molten metal of gained is injected in the carbon mold of 550mm * 145mm * 30mm with the pouring speed shown in the table 3.At this moment, molten metal does not begin to solidify before injection is finished.The molten metal that is injected in the carbon mold is cooled to 200 ℃ with the about speed of cooling of 13 ℃/min, thereby has obtained the ingot bar of 450mm * 13.5mm * 28mm.This ingot bar is cut to the approximately tetragon of 10mm, and carries out mirror ultrafinish, make by scanning electron microscope (JEOL(strain), JSM-6380A) with 200 times multiplying power its cross section is observed.Try to achieve the average equivalent diameter, maximum equivalent circular diameter of γ phase and with respect to the total ratio (Area Ratio) of the area of the γ phase of the area of described tissue image according to the tissue image of gained and by above-mentioned method.In comparative example 1, fail to confirm the γ phase owing on tissue image, only presenting the β phase, therefore, fail to try to achieve average equivalent diameter and the maximum equivalent circular diameter of γ phase.In comparative example 3, because tissue image only comprises the γ phase, therefore fail to try to achieve average equivalent diameter and the maximum equivalent circular diameter of γ phase.Show the result in table 3.
In addition, for the ingot bar beyond the ingot bar that is obtained by comparative example 1, under following condition, implement calendering, and according to following benchmark, by visual be whether to have produced crackle on the sputtering target and slight crack is estimated to the calendering plate.Show the result in table 3.In addition, "-" on the rolling temperature hurdle in the table 3 refers to the situation not implementing to roll.
A: on the calendering plate, do not observe crackle or slight crack
B: observed crackle at the calendering plate
C: do not observe crackle in calendering on the plate but observed slight crack
D: ingot bar melts and can't roll in the calendering
［ rolling condition ］
Ingot bar was heated 30 minutes under the rolling temperature shown in the table 3 by electric furnace.(Japanese Cross calendering (strain) is made to use milling train, the 9LCD/500W double roller calender), and with the roller speed of the rolling rate shown in the table 3,1.0m/sec ingot bar is rolled operation repeatedly, until its thickness is till become 11mm as the 30mm of thickness before the calendering.
［ table 3 ］
According to the result of table 3 as can be known, the average equivalent diameter of γ phase is below the 50 μ m and the maximum equivalent circular diameter is that the following ingot bar of 200 μ m can roll, and average equivalent diameter and the maximum equivalent circular diameter of γ phase are less, but then the rolling temperature scope is just wider.In addition as can be known, shown in embodiment 3 and comparative example 2, even Ga concentration is identical, but compare with the ingot bar of making under the condition faster in pouring speed at the ingot bar of producing under the slower condition of pouring speed, it is large that the average equivalent diameter of γ phase and maximum equivalent circular diameter become, thereby fail to obtain observing the calendering plate of crackle and slight crack.
(embodiment 4～7, comparative example 4～5)
To pure Cu and pure Ga carries out weighing so that Ga concentration becomes the value shown in the table 4, and (Fuji's electric wave industry (strain) is made to use the high-frequency vacuum calciner, FVM-30), in Ar atmosphere, heat up with 15 ℃/min, after having confirmed the raw material fusing, molten metal temperature is remained on 1200 ℃.This molten metal is injected in the water-cooled copper mold of 460mm * 160mm * 30mm with the pouring speed shown in the table 4.At this moment, molten metal does not begin to solidify before injection is finished.The molten metal that is injected in the water-cooled copper mold is cooled to 50 ℃ with the about speed of cooling of 100 ℃/min, thereby has obtained the ingot bar of 410mm * 155mm * 29mm.In the mode identical with embodiment 1 this ingot bar being carried out scanning electron microscope observes.Try to achieve the average equivalent diameter, maximum equivalent circular diameter of γ phase and with respect to the total ratio (Area Ratio) of the area of the γ phase of the area of described tissue image according to the tissue image of gained and by above-mentioned method.In comparative example 4, fail to confirm the γ phase owing on tissue image, only presenting the β phase, therefore, fail to try to achieve average equivalent diameter and the maximum equivalent circular diameter of γ phase.In comparative example 5, because tissue image only comprises the γ phase, therefore fail to try to achieve average equivalent diameter and the maximum equivalent circular diameter of γ phase.Show the result in table 5.
In addition, for the ingot bar beyond the ingot bar that is obtained by comparative example 4, under the condition identical with embodiment 1, roll, and according to the benchmark identical with embodiment 1, by visual to the calendering plate be on the sputtering target whether institute produced crackle and slight crack is estimated.Show the result in table 4.In addition, "-" on the rolling temperature hurdle in the table 4 refers to the situation not implementing to roll.
［ table 4 ］
According to the result of table 4 as can be known, even make in the situation that use the water-cooled copper mold, the average equivalent diameter of γ phase is below the 50 μ m and the maximum equivalent circular diameter is that the following ingot bar of 200 μ m also can roll, and average equivalent diameter and the maximum equivalent circular diameter of γ phase are less, but then the rolling temperature scope is just wider.
Different from the situation of using the carbon mold to make, make in the situation that use the water-cooled copper mold, shown in embodiment 6 and embodiment 7, in the situation that Ga concentration is identical, the ingot bar of making under the slower condition of pouring speed, and the ingot bar made under the condition faster of pouring speed between, the average equivalent diameter of γ phase does not have larger difference.In addition as can be known, the ingot bar that uses the water-cooled copper mold to make is compared with the ingot bar that uses the carbon mold to make, in the situation that Ga concentration is identical, average equivalent diameter and the maximum equivalent circular diameter of γ phase are less.Think that its reason is, compare with the carbon mold, the speed of cooling of water-cooled copper mold is larger.
In addition, for the ingot bar beyond the ingot bar that is obtained by comparative example 4 and embodiment 7, adopt the rolling rate different from embodiment 1, in addition, under the condition identical with embodiment 1, roll.Select several rolling rates that will adopt, and under each rolling rate, roll.In the rolling rate that adopts, the highest rolling rate (maximum rolling rate) that does not crack on the calendering plate is shown in table 5." B " in the table 5, " D " and "-" represent respectively and " B " shown in the table 3, implication that " D " and "-" is identical.
［ table 5 ］
According to table 5 as can be known, in Cu-Ga alloy of the present invention, can roll with 9～23% this larger rolling rates.Therefore, if make the Cu-Ga alloy sputtering targets by Cu-Ga alloy of the present invention by calendering, then can guarantee higher productivity.
Claims (4)
1. Cu-Ga alloy contains the Ga of mass percent 25～30%, and surplus is Cu, and described Cu-Ga alloy is characterised in that,
Present on the tissue image that obtains by electron microscope, Ga concentration be mass percent 30～35% be that the average equivalent diameter of γ phase is below the 50 μ m mutually, and the maximum equivalent circular diameter is below the 200 μ m.
2. Cu-Ga alloy as claimed in claim 1 is characterized in that,
Ratio with respect to the total of area area, the γ phase of described tissue image is 5～70%.
3. such as claim 1 or Cu-Ga alloy claimed in claim 2, wherein,
Described Cu-Ga alloy is sputtering target manufacturing alloy.
4. Cu-Ga alloy sputtering targets, it obtains by Cu-Ga alloy claimed in claim 3 is rolled.
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| JP2010-153880 | 2010-07-06 | ||
| JP2010153880A JP2012017481A (en) | 2010-07-06 | 2010-07-06 | Cu-Ga ALLOY AND Cu-Ga ALLOY SPUTTERING TARGET |
| PCT/JP2011/063802 WO2012005098A1 (en) | 2010-07-06 | 2011-06-16 | Cu-ga alloy, and cu-ga alloy sputtering target |
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| CN110218981A (en) * | 2019-06-28 | 2019-09-10 | 先导薄膜材料（广东）有限公司 | A kind of copper gallium target and preparation method thereof |
| CN114086132A (en) * | 2021-11-26 | 2022-02-25 | 先导薄膜材料（广东）有限公司 | Copper-gallium target material and preparation method and application thereof |
| CN114086132B (en) * | 2021-11-26 | 2023-11-17 | 先导薄膜材料（广东）有限公司 | Copper-gallium target material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2012017481A (en) | 2012-01-26 |
| WO2012005098A1 (en) | 2012-01-12 |
| TW201204844A (en) | 2012-02-01 |
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