CN103608910B - The manufacture method of closing line copper wires and closing line copper wires - Google Patents
The manufacture method of closing line copper wires and closing line copper wires Download PDFInfo
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- CN103608910B CN103608910B CN201280028930.7A CN201280028930A CN103608910B CN 103608910 B CN103608910 B CN 103608910B CN 201280028930 A CN201280028930 A CN 201280028930A CN 103608910 B CN103608910 B CN 103608910B
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- H01L24/42—Wire connectors; Manufacturing methods related thereto
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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Abstract
Closing line copper wires of the present invention is the copper wires of the closing line being less than 180 μm for the formation of wire diameter.The gauge or diameter of wire of copper wires is more than 0.15mm below 3.0mm.Copper wires has following composition, and namely to amount to containing more than one the Addition ofelements be selected from Mg, Ca, Sr, Ba, Ra, Zr, Ti and rare earth element in the scope of below more than 0.0001 quality % 0.01 quality %, and surplus is copper and inevitable impurity.In copper wires, special grain boundary ratio (L σ/L) is more than 50%, and described special grain boundary ratio is with the ratio of the length L σ of the special grain boundary of EBSD method mensuration relative to the length L of whole crystal boundary.
Description
Technical field
The present invention relates to a kind of manufacture method producing closing line copper wires and the closing line copper wires used when wire diameter is the closing line of less than 180 μm.
The application advocates based on the priority of on July 22nd, 2011 in No. 2011-161036, the Japanese patent application of Japanese publication, and its content is applied at this.
Background technology
Usually, be equipped with in the semiconductor device of semiconductor element, connect semiconductor element and lead-in wire by above-mentioned closing line.In the past, as closing line, mainly use Au line from the viewpoint such as stringiness and conductivity.But Au is expensive, the closing line of therefore instead this Au line use, provides Cu closing line.
At this, compared with Au, Cu is comparatively hard, there is the risk that the sphere being formed at line front end can destroy the Al distribution tunicle being such as formed at Si semiconductor component surfaces when therefore engaging.Further, compared with Au, the percentage elongation of Cu is lower, therefore there is the problem of the wire loop shape that cannot remain suitable.
For this reason, such as propose to have in patent documentation 1,2 to utilize purity to be the Cu closing line of the ultrahigh-purity copper (6NCu) of more than 99.9999 quality %.In addition, propose have trace to be added with the Cu closing line of Ti, Zr, Hf, V, Cr and B in patent documentation 3.
But, as recorded in patent documentation 1,2, when utilizing purity to be ultrahigh-purity copper (6NCu) of more than 99.9999 quality %, in order to obtain ultrahigh-purity copper (6NCu), need to carry out purification processes operation.Therefore, there is the problem that manufacturing cost significantly increases.
In addition, in the closing line recorded in patent documentation 3, still comparatively hard and percentage elongation is also lower compared with Au.Therefore, as the substitute product of Au line, characteristic is also insufficient.
And in recent years, require the graph thinning of the closing line be made up of Cu line, for closing line copper wires, also can not there is the processability of broken string in requirement.
Patent documentation 1: Japanese Laid-Open Patent Publication 62-111455 publication
Patent documentation 2: Japanese Unexamined Patent Publication 04-247630 publication
Patent documentation 3: Japanese Patent Publication 04-012623 publication
Summary of the invention
The present invention completes in view of afore-mentioned, its object is to provide a kind of hardness lower and percentage elongation is higher and the closing line copper wires of excellent in workability and the manufacture method of closing line copper wires.
In order to solve above-mentioned problem, closing line copper wires involved by a mode of the present invention is the copper wires of the closing line being less than 180 μm for the formation of wire diameter, wherein, gauge or diameter of wire is more than 0.15mm below 3.0mm, and there is following composition, namely to amount in the scope of below more than 0.0001 quality % 0.01 quality % containing being selected from Mg, Ca, Sr, Ba, Ra, Zr, more than one Addition ofelements in Ti and rare earth element, and surplus is copper and inevitable impurity, and special grain boundary ratio (L σ/L) is more than 50%, described special grain boundary ratio is with the ratio of the length L σ of the special grain boundary of EBSD method mensuration relative to the length L of whole crystal boundary.
In this closing line copper wires, there is following composition, namely to amount to containing more than one the Addition ofelements be selected from Mg, Ca, Sr, Ba, Ra, Zr, Ti and rare earth element in the scope of below more than 0.0001 quality % 0.01 quality %, and surplus is copper and inevitable impurity.Therefore, S in copper and above-mentioned element reaction is contained in form compound.Thus, the impact of S reduces, and can reduce recrystallization temperature, and can reduce hardness.
Further, special grain boundary ratio (L σ/L) is more than 50%, and described special grain boundary ratio is with the ratio of the length L σ of the special grain boundary of EBSD method mensuration relative to the length L of whole crystal boundary.Therefore, it is possible to improve percentage elongation and processability when being maintained lower by hardness.
In addition, by utilizing the EBSD determinator of field emission scanning electron microscopy, carrying out specific to crystal boundary, special grain boundary, calculating the length L of whole crystal boundary and the length L σ of special grain boundary.The special grain boundary ratio (L σ/L) in the manner can be obtained by these length.
Crystal boundary is defined as follows, namely through the result that two-dimensional section is observed, and the border between this crystallization when misorientation between two adjacent crystallizations becomes more than 15 °.
In addition, special grain boundary is defined as, and the Σ value that crystallography defines according to CSL theory (Kronbergetal:Trans.Met.Soc.AIME, 185,501 (1949)) meets the corresponding crystal boundary (Coincidence-SiteLattice of 3≤Σ≤29; CSL), the intrinsic corresponding position crystal lattice orientation defect Dq and in this corresponding crystal boundary meets Dq≤15 °/Σ
1/2the crystal boundary of (D.G.Brandon:Acta.Metallurgica.Vol.14, p.1479, (1966)).
In closing line copper wires involved by a mode of the present invention, the content of preferred described Addition ofelements add up to below more than 0.0003 quality % 0.002 quality %.
Now, recrystallization temperature reliably can be suppressed for lower, and can hardness be reduced.
Further, the content of preferred described inevitable impurity and Fe, Pb and S is, Fe is below 0.0001 quality %, Pb be below 0.0001 quality %, S is below 0.005 quality %.
By specifying the content of impurity as described above, recrystallization temperature reliably can be suppressed for lower, and can hardness be reduced.
Preferably by closing line copper wires heating for dissolving described in 100g in the number of residue thing being not dissolved in acid that the particle diameter that salpeter solution obtains is more than 30 μm be less than 1000.
Now, the particle diameter of residue thing being not dissolved in acid being present in closing line copper wires inside is less and number is less.Therefore, it is possible to suppress the broken string produced during the Wire Drawing when manufacturing closing line.
The amount being not dissolved in the residue thing of acid preferably described closing line copper wires heating for dissolving obtained in salpeter solution is below 0.00015 quality %.
Now, be present in closing line copper wires inside be not dissolved in acid residue thing there is ratio less.Therefore, it is possible to suppress the broken string produced during the Wire Drawing when manufacturing closing line.
The manufacture method of the closing line copper wires involved by a mode of the present invention is the manufacture method of described closing line copper wires, having: copper motlten metal generation process, is add more than one the Addition ofelements that is selected from Mg, Ca, Sr, Ba, Ra, Zr, Ti and rare earth element in the copper raw material of below more than 99.99 quality % 99.998 quality % to generate copper motlten metal in purity; Continuous casting operation, produces ingot bar by described copper feeding molten metal continuously to belt wheel continuous casting machine; And continuous rolling operation, the ingot bar under the condition of initial temperature for more than 800 DEG C manufactured by continuous rolling.
According to the manufacture method of this closing line copper wires, purity is utilized to be the copper raw material of the so-called 4NCu of below more than 99.99 quality % 99.998 quality %.Therefore, compared with when utilizing 6NCu, the manufacturing cost of closing line copper wires can significantly be reduced.
And, have the continuous rolling operation of the ingot bar under the condition of initial temperature for more than 800 DEG C manufactured by continuous rolling.Therefore, it is possible to the special grain boundary ratio (L σ/L) in closing line copper wires is set to more than 50%.
In addition, the manufacture method of the closing line copper wires involved by other modes of the present invention is the manufacture method of described closing line copper wires, having: copper motlten metal generation process, is add more than one the Addition ofelements that is selected from Mg, Ca, Sr, Ba, Ra, Zr, Ti and rare earth element in the copper raw material of below more than 99.99 quality % 99.998 quality % to generate copper motlten metal in purity; Casting process, injects mold by described copper motlten metal and produces ingot bar; Extrusion process, carries out extrusion process to obtained ingot bar, thus produces extruding wire rod under the condition of initial temperature for more than 800 DEG C; Processing/annealing operation, for obtained extruding wire rod, implements any one in rolling processing or Wire Drawing and annealing repeatedly; And light rolling process, be rolled with rolling rate less than more than 5% 25%, make final wire diameter be more than 0.15mm below 3.0mm.
According to the manufacture method of this closing line copper wires, purity is utilized to be the copper raw material of the so-called 4NCu of below more than 99.99 quality % 99.998 quality %.Therefore, compared with when utilizing 6NCu, the manufacturing cost of closing line copper wires can significantly be reduced.
And, have: processing/annealing operation, for extruding wire rod, repeatedly implement any one in rolling processing or Wire Drawing and annealing; And light rolling process, be rolled with rolling rate less than more than 5% 25%, make final wire diameter be more than 0.15mm below 3.0mm.Therefore, it is possible to the special grain boundary ratio (L σ/L) in closing line copper wires is set to more than 50%.
According to a mode of the present invention, a kind of hardness can be provided lower and percentage elongation is higher and the closing line copper wires of excellent in workability and the manufacture method of closing line copper wires.
Accompanying drawing explanation
The key diagram of the continuous casting rolling device that Fig. 1 uses when being and manufacturing one embodiment of the present invention and closing line copper wires.
Fig. 2 is the flow chart of the manufacture method of one embodiment of the present invention and closing line copper wires.
Fig. 3 is the flow chart of the manufacture method of another embodiment of the present invention and closing line copper wires.
Fig. 4 is the chart being not dissolved in the evaluation result of the residue thing of acid represented in example 1 of the present invention.
Embodiment
Below, the manufacture method of the closing line copper wires involved by one embodiment of the present invention and closing line copper wires is described.
It is less than 180 μm that closing line copper wires involved by present embodiment is used as to manufacture wire diameter, raw material when more preferably wire diameter is the closing line of more than 20 μm less than 180 μm.
In addition, the gauge or diameter of wire of the closing line copper wires involved by present embodiment is more than 0.15mm below 3.0mm.
This closing line copper wires has following composition, namely to amount to containing more than one the Addition ofelements be selected from Mg, Ca, Sr, Ba, Ra, Zr, Ti and rare earth element in the scope of below more than 0.0001 quality % 0.01 quality %, and surplus is copper and inevitable impurity.What be preferably selected from the content of more than one the Addition ofelements in Mg, Ca, Sr, Ba, Ra, Zr, Ti and rare earth element adds up to below more than 0.0003 quality % 0.002 quality %.
Further, the content of described inevitable impurity and Fe, Pb and S is, Fe is below 0.0001 quality %, Pb be below 0.0001 quality %, S is below 0.005 quality %.
Wherein, rare earth element is Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
The special grain boundary ratio (L σ/L) of this closing line copper wires is more than 50%.Wherein, special grain boundary ratio is the ratio of length L σ relative to the length L of whole crystal boundary of special grain boundary.By utilizing the EBSD determinator of field emission scanning electron microscopy, carrying out specific to crystal boundary, special grain boundary, calculating the length L of whole crystal boundary and the length L σ of special grain boundary.Special grain boundary ratio can be obtained from this length calculated.That is, as in the closing line copper wires of present embodiment, special grain boundary exists more than general crystal boundary.
Crystal boundary is defined as follows, namely through the result that two-dimensional section is observed, and the border between this crystallization when misorientation between two adjacent crystallizations becomes more than 15 °.
In addition, special grain boundary is defined as, according to CSL theory (Kronbergetal:Trans.Met.Soc.AIME in crystallography, 185,501 (1949)) the Σ value defined meets the corresponding crystal boundary of 3≤Σ≤29, and the intrinsic corresponding position crystal lattice orientation defect Dq in this corresponding crystal boundary meets Dq≤15 °/Σ
1/2the crystal boundary of (D.G.Brandon:Acta.Metallurgica.Vol.14, p.1479, (1966)).
In addition, using 100g be the number of residue thing being not dissolved in acid of more than 30 μm as the closing line copper wires heating for dissolving of present embodiment in the particle diameter that salpeter solution obtains is less than 1000.And the above-mentioned ratio that exists being not dissolved in the residue thing of acid is below 0.00015 quality %.
Implement the evaluation of the residue thing being not dissolved in acid in the following order.
First, the test portion of scheduled volume (100g) that sample from the closing line copper wires of clean surface, heating for dissolving is in the salpeter solution heated.After lysate is cooled to room temperature, filter with filter, thus trapping residue thing.
The filter trapping residue thing is weighed, measures the mass of residue of residue thing.Further, the ratio (quality %) of amount (mass of residue) relative to the amount of test portion (closing line copper wires) of residue thing is calculated.By more than, measure the amount (there is ratio) of residue thing being not dissolved in acid closing line copper wires heating for dissolving obtained in salpeter solution.
Then, the filter trapping residue thing is observed by scanning electron microscope, shooting SEM photo.Graphical analysis is carried out to SEM photo, measures size and the number of residue thing.And obtain the number that particle diameter is the residue thing of more than 30 μm.By more than, measuring 100g closing line copper wires heating for dissolving is the number of residue thing being not dissolved in acid of more than 30 μm in the particle diameter that salpeter solution obtains.
Then, the manufacture method of the closing line copper wires as present embodiment is described.
The special grain boundary overall length L σ of special grain boundary is that the closing line copper wires of more than 50% is by casting the extruding method manufacture of milling method or ingot bar continuously relative to the ratio (L σ/L) of the crystal boundary overall length L of crystal boundary.
In present embodiment, be described to utilize the example of the continuous casting rolling device 10 shown in Fig. 1.
Continuous casting rolling device 10 shown in Fig. 1 has melting furnace 11, keeps stove 12, casts conduit 13, belt wheel continuous casting machine 30, continuous rolling device 15 and up-coiler 18.
In present embodiment, utilize the shaft furnace with cylindrical furnace main body as melting furnace 11.In the bottom of furnace main body, multiple burner (omitting diagram) is equipped with to circumferencial direction and is vertically equipped with multistage shape.Further, from top charging feedstock and the cathode copper of furnace main body.Cathode copper is melted, continuous manufactured copper motlten metal by the burning of described burner.
At maintenance stove 12, to the fine copper motlten metal manufactured in melting furnace 11, temporarily accumulate under the state kept with predetermined temperature, and the copper motlten metal of constant basis is delivered to casting conduit 13.
Casting conduit 13 is transferred to from the copper motlten metal keeping stove 12 to carry the funnel (タ Application デ ィ シ ュ) 20 be configured at above belt wheel continuous casting machine 30.This casting conduit 13 is such as sealed by the inert gases such as Ar or reducibility gas.In addition, the agitating member (not shown) of stirring of inert gas copper motlten metal is provided with in this casting conduit 13.
Be provided with in funnel 20 and add component 21 to by the element of copper motlten metal Addition ofelements transferred.Further, the flow direction end side of the copper motlten metal of funnel 20 is configured with pouring nozzle 22.Copper motlten metal in funnel 20 is supplied to belt wheel continuous casting machine 30 via this pouring nozzle 22.
Belt wheel continuous casting machine 30 has the cast wheel 31 that outer peripheral face is formed with groove and the endless belt 32 be rotated around in the mode of the localized contact of the outer peripheral face with this cast wheel 31.Inject to the space be formed between described groove and endless belt 32 the copper motlten metal supplied via pouring nozzle 22 and cool, thus casting bar-shaped ingot bar 40 continuously.
And this belt wheel continuous casting machine 30 is linked to continuous rolling device 15.The bar-shaped ingot bar 40 that this continuous rolling device 15 continuous rolling produces from belt wheel continuous casting machine 30, thus produce the copper cash base 50 of predetermined outer diameter.The copper cash base 50 produced from continuous rolling device 15 is wound onto up-coiler 18 via cleaning cooling device 16 and crack detector 17.
Then, Fig. 1, Fig. 2 manufacture method to the closing line copper wires utilizing this belt wheel continuous casting machine 30 is utilized to be described.
First, drop into melting furnace 11 copper raw material (so-called 4NCu) that purity is below more than 99.99 quality % 99.998 quality % and carry out melting to obtain copper motlten metal (melting operation S01).In this melting operation S01, the air-fuel ratio of multiple burners of adjustment shaft furnace makes the inside of melting furnace 11 become reducing atmosphere.
The copper motlten metal obtained by melting furnace 11 is transferred to funnel 20 via maintenance stove 12 and casting conduit 13.
Wherein, by being stirred by aforementioned agitating member by the copper motlten metal of the casting conduit 13 of inert gas or reducibility gas sealing.Thus, the reaction of copper motlten metal and inert gas or reducing gas is promoted.
Then, add component (device) 21 by element and add more than one the element (element adds operation S02) be selected from Mg, Ca, Sr, Ba, Ra, Zr, Ti and rare earth element to the copper motlten metal in funnel 20 continuously.Thus, the content generating more than one the element be selected from Mg, Ca, Sr, Ba, Ra, Zr, Ti and rare earth element is adjusted to add up to below more than 0.0001 quality % 0.01 quality %, is more preferably the copper motlten metal of below more than 0.0003 quality % 0.002 quality %.
The copper motlten metal to be so adjusted to point is supplied to belt wheel continuous casting machine 30 via pouring nozzle 22, produces bar-shaped ingot bar 40(continuously and casts operation S03 continuously).Wherein, in continuous casting operation S03, the space be formed between the groove of cast wheel 31 and endless belt 32 is trapezoidal.Therefore cross section is produced in roughly trapezoidal bar-shaped ingot bar 40.
This bar-shaped ingot bar 40 is supplied to continuous rolling device 15 and imposes the processing of rolling system, thus produces the copper cash base 50(continuous rolling operation S04 of predetermined outer diameter (being diameter 8mm in present embodiment)).In this continuous rolling operation S04, implement rolling the scopes of 400 ~ 900 DEG C.In present embodiment, the initial temperature of rolling is set to more than 800 DEG C.The initial temperature of rolling is preferably more than 800 DEG C less than 1050 DEG C.
The copper cash base 50 produced from continuous rolling device 15 is wound in up-coiler 18 via cleaning cooling device 16 and crack detector 17.Cleaning cooling device 16 cleans the surface of the copper cash base 50 produced from continuous rolling device 15 with cleaning agents such as alcohol and cools.Further, crack detector 17 detects the damage of the copper cash base 50 carried from cleaning cooling device 16.
Then, Wire Drawing is implemented to obtained copper cash base 50, make final wire diameter be more than 0.15mm below 3.0mm (being diameter 0.9mm in present embodiment) (Wire Drawing operation S05).
And, after above-mentioned Wire Drawing operation S05, carry out dynamic recrystallization treatment (finished heat treatment operation S06) with more than 150 DEG C less than 250 DEG C.In present embodiment, implement the atmosphere heat treatment of 2 hours with 220 DEG C.
By as above step, produce the closing line copper wires as present embodiment.
As the closing line copper wires of present embodiment, implement stretch process further and become the fine rule that diameter is less than 180 μm, as closing line.
According to the closing line copper wires of present embodiment with this feature, there is following composition, namely to amount to containing more than one the Addition ofelements be selected from Mg, Ca, Sr, Ba, Ra, Zr, Ti and rare earth element in the scope of below more than 0.0001 quality % 0.01 quality %, and surplus is copper and inevitable impurity.More preferably above-mentioned Addition ofelements content add up to below more than 0.0003 quality % 0.002 quality %.Therefore, S in copper is contained in and above-mentioned Addition ofelements forms compound.Therefore, the impact of S reduces, so can reduce recrystallization temperature and reduce hardness.
Further, the special grain boundary ratio (L σ/L) as the closing line copper wires of present embodiment is more than 50%.In addition, by utilizing the EBSD determinator of field emission scanning electron microscopy, carrying out specific to crystal boundary, special grain boundary, calculating the length L of whole crystal boundary and the length L σ of special grain boundary.And, special grain boundary ratio can be obtained from this length calculated.When this special grain boundary ratio is higher, the matching degree of the crystal boundary of organized whole is improved, and is difficult to accumulate dislocation.Therefore, it is possible to improve percentage elongation and processability when being maintained lower by hardness.
In addition, using 100g be the number of residue thing being not dissolved in acid of more than 30 μm as the closing line copper wires heating for dissolving of present embodiment in the particle diameter that salpeter solution obtains is less than 1000.And the amount (there is ratio) being not dissolved in the residue thing of acid is below 0.00015 quality %.
So, the particle diameter of residue thing being not dissolved in acid is less and number is less, and it exists ratio and is also suppressed.Therefore, it is possible to suppress the broken string when closing line copper wires Wire Drawing being become closing line.
In addition, according to the manufacture method of the closing line copper wires as present embodiment, use purity is the copper raw material of the so-called 4NCu of below more than 99.99 quality % 99.998 quality %.Therefore, compared with when utilizing 6NCu, the manufacturing cost of closing line copper wires can significantly be reduced.
And, have the continuous rolling operation S04 utilizing belt wheel continuous casting machine 30 to produce the continuous casting operation S03 of bar-shaped ingot bar 40 and the bar-shaped ingot bar 40 under the condition of initial temperature for more than 800 DEG C manufactured by continuous rolling continuously.Therefore, it is possible to the special grain boundary ratio (L σ/L) of manufactured closing line copper wires is set to more than 50%.
Above, embodiments of the present invention are illustrated, but the present invention is not limited thereto, can suitably change in the scope not departing from technological thought of the present invention.
Utilize belt wheel continuous casting machine to manufacture closing line copper wires in present embodiment to be illustrated, but be not limited thereto.
Such as, as shown in Figure 3, also produce by implementing copper motlten metal generation process S11, casting process S12, hot extrusion operation S13, processing/annealing operation S14 and light rolling process S15 the closing line copper wires that special grain boundary ratio (L σ/L) is more than 50%.
In copper motlten metal generation process S11, be add more than one the Addition ofelements that is selected from Mg, Ca, Sr, Ba, Ra, Zr, Ti and rare earth element to obtain copper motlten metal in the copper raw material (so-called 4NCu) of below more than 99.99 quality % 99.998 quality % in purity.
In casting process S12, copper poured with molten metal is obtained to mold the ingot bar that diameter is 200mm ~ 400mm.
In hot extrusion operation S13, be that under the condition of more than 800 DEG C, extrusion process ingot bar obtains extruding wire rod in initial temperature.The initial temperature of extrusion process is preferably more than 800 DEG C, less than 1050 DEG C.
In processing/annealing operation S14, any one in rolling processing or Wire Drawing is implemented repeatedly to extruding wire rod and anneals.Annealing is implemented when cross section slip becomes more than 80%.
In light rolling process S15, be rolled with rolling rate less than more than 5% 25%, make final wire diameter be more than 0.15mm below 3.0mm.
Embodiment
(embodiment 1)
Below, the result for the aforesaid evaluation test evaluated as the closing line copper wires of present embodiment is described.
The closing line copper wires of example 1 ~ 5 of the present invention and comparative example 1,2 is produced by the method shown in the flow chart of Fig. 2.Specifically, the Addition ofelements recorded in interpolation table 1 in 4NCu obtains copper motlten metal.Copper poured with molten metal is carried out continuous casting rolling to belt wheel continuous casting machine.Further enforcement Wire Drawing and finished heat treatment, thus the closing line copper wires producing that diameter is 0.9mm.
The closing line copper wires of example 6 ~ 10 of the present invention and comparative example 3,4 is produced by the method shown in the flow chart of Fig. 3.Specifically, the Addition ofelements recorded in interpolation table 1 in 4NCu obtains copper motlten metal.Copper motlten metal is utilized to produce the ingot bar that diameter is 240mm.This ingot bar is processed to produce the extruding wire rod that diameter is 8mm with 800 DEG C of hot extrusions.This extruding wire rod is repeatedly rolled and is annealed and produces the copper wires that wire diameter is 1mm.Afterwards, this copper wires is implemented to the rolling of rolling rate 10%.Then, carry out finished heat treatment with 220 DEG C, thus produce the closing line copper wires that diameter is 0.9mm.
Produce the closing line copper wires of conventional example by the following method.First, the Zr of 0.0030 quality % is added at 4NCu to obtain copper motlten metal.Copper motlten metal is utilized to produce the ingot bar that diameter is 240mm.This ingot bar is processed to produce the extruding wire rod that diameter is 8mm with 800 DEG C of hot extrusions.Wire Drawing is implemented to this extruding wire rod.Then, carry out finished heat treatment with 220 DEG C, thus produce the closing line copper wires that diameter is 0.9mm.
In addition, Wire Drawing is implemented to the closing line copper wires of obtained example of the present invention 1 ~ 10, comparative example 1 ~ 4 and conventional example and produce the closing line that diameter is 180 μm.
(special grain boundary ratio)
To the closing line copper wires of obtained example of the present invention 1 ~ 10, comparative example 1 ~ 4 and conventional example, measure special grain boundary ratio (L σ/L) by the following method.
To each test portion, waterproof abrasive paper and diamond abrasive is utilized to carry out mechanical lapping.Then, colloidal silica solution is utilized to carry out smooth grinding.
And, by EBSB determinator (S4300-SEM, EDAX/TSL Inc. of HITACHI Inc. OIMDataCollection) and analysis software (EDAX/TSL Inc. OIMDataAnalysisver.5.2), carry out specific to crystal boundary, special grain boundary, calculate the length L of whole crystal boundary and the length L σ of special grain boundary.The analysis of crystallization particle diameter and the special grain boundary length ratio of being averaged thus.The detailed content of assay method is below shown.
First, utilize scanning electron microscope to irradiate electron ray to each measuring point in the measurement range on test portion surface, make electron ray two-dimensional scan to test portion surface.By utilizing the orientation analysis of Electron Back-Scattered Diffraction, as crystal boundary between the measuring point misorientation between adjacent measuring point being become more than 15 °.
Crystal boundary overall length (length of the whole crystal boundary) L of the crystal boundary in measurement range is measured.Further, determine that adjacent crystal grain boundary is the grain boundary sites of special grain boundary, and measure crystal boundary overall length (length of all special grain boundaries) the L σ of special grain boundary.And, the ratio L σ/L of the crystal boundary overall length L of the crystal boundary that the length L σ obtaining special grain boundary goes out relative to said determination, and be set to special grain boundary ratio (L σ/L).
(hardness test)
Then, to the closing line copper wires of example 1 ~ 10 of the present invention, comparative example 1 ~ 4 and conventional example and the closing line that produced by these closing line copper wires, hardness is measured.
In addition, hardness test utilizes AKASHI micro-vickers hardness testing machine MVK-700 and implements according to JISZ2241.
(percentage elongation)
Then, to the closing line copper wires of example 1 ~ 10 of the present invention, comparative example 1 ~ 4 and conventional example and the closing line that produced by these closing line copper wires, AKASHI AMSLER formula longitudinal type cupping machine is utilized to implement tension test and evaluate percentage elongation.
(processability)
Wire Drawing is implemented further to make the line that diameter is 87 μm, 50 μm or 20 μm to the closing line copper wires of obtained example of the present invention 1 ~ 10, comparative example 1 ~ 4 and conventional example.Evaluate broken string number of times during Wire Drawing.
To the result that the broken string number of times when hardness of the special grain boundary ratio (L σ/L) of closing line wire rod, hardness and percentage elongation, closing line and percentage elongation and Wire Drawing is evaluated shown in table 1.
In example 1 ~ 10 of the present invention, confirming special grain boundary ratio (L σ/L) becomes more than 50%.On the other hand, in comparative example 1 ~ 4 and conventional example, special grain boundary ratio (L σ/L) is less than 50%.If contrast example 6 ~ 10 of the present invention and conventional example, then can confirming the processing by implementing rolling rate 10% before implementing finished heat treatment to the wire rod with final wire diameter, special grain boundary ratio (L σ/L) can be increased.
Special grain boundary ratio (L σ/L) is that in the example of the present invention 1 ~ 10 of more than 50%, under confirming the state being the closing line of 180 μm in wire diameter, hardness is low to moderate below 40Hv.
And confirm, compared with comparative example, in example 1 ~ 10 of the present invention, broken string during wire drawing is suppressed, can wire drawing extremely thin footpath.
(embodiment 2)
Then, the closing line copper wires evaluation of example 1 ~ 10 of the present invention is utilized to be not dissolved in level of residue and the particle size distribution of the residue thing of acid.
With nitric acid, etch processes is carried out to test portion, remove the impurity being attached to surface.Then, the test portion of 100g is taken.By this test portion heating for dissolving in salpeter solution.Heating-up temperature is set to 60 DEG C.Repeatedly carry out this operation.
Then, be cooled to room temperature, and carry out filtration with filter and trap residue.
At this, polycarbonate filter (aperture is 0.4 μm) is utilized to filter.Critically weigh in clean room indoor the polycarbonate filter having trapped residue thing, measure the mass of residue of residue thing.
Further, the particle size distribution of the residue thing being not dissolved in acid is measured.Trap the filter of residue thing described in being observed by scanning electron microscope, and take SEM image.Image is read in computer, with graphical analysis software (WinRoof software), image is carried out to the analysis of binary conversion treatment.And, measure the projected area of residue thing, calculate the diameter of a circle (equivalent circle diameter) with the area identical with this projected area.This equivalent circle diameter is used as the particle diameter of residue thing.Measure size (equivalent circle diameter) and the number of residue thing.In addition, particle size distribution chart is made by the data of example 1 of the present invention.The results are shown in Fig. 4.
The image analysis result of WinRoof software confirms, and by test portion (closing line copper wires) heating for dissolving of the example of the present invention 1 ~ 10 of 100g when the salpeter solution, particle diameter is that the number being not dissolved in the residue thing of acid of more than 30 μm is less than 1000.Further, the results verification measuring the mass of residue of residue thing with said method arrives, and the mass ratio being not dissolved in the residue thing of acid in the test portion of example 1 ~ 10 of the present invention is below 0.00015 quality %.
Utilizability in industry
The hardness of the closing line copper wires of present embodiment is lower and percentage elongation is higher, and excellent in workability.Therefore, the copper wires of present embodiment can be applicable to the manufacturing process being applicable to the Cu closing line replacing Au line to use.
Symbol description
30-belt wheel continuous casting machine.
Claims (7)
1. a closing line copper wires, it is the copper wires of the closing line being less than 180 μm for the formation of wire diameter, it is characterized in that,
Gauge or diameter of wire is more than 0.15mm below 3.0mm,
And there is following composition, namely to amount to containing more than one the Addition ofelements be selected from Mg, Ca, Sr, Ba, Ra, Zr, Ti and rare earth element in the scope of below more than 0.0001 quality % 0.01 quality %, and surplus is copper and inevitable impurity,
Special grain boundary ratio L σ/L is more than 50%, and described special grain boundary ratio is with the ratio of the length L σ of the special grain boundary of EBSD method mensuration relative to the length L of whole crystal boundary.
2. closing line copper wires according to claim 1, is characterized in that,
The content of described Addition ofelements add up to below more than 0.0003 quality % 0.002 quality %.
3. closing line copper wires according to claim 1 and 2, is characterized in that,
Content as Fe, Pb and S of described inevitable impurity is as follows: Fe is below 0.0001 quality %, Pb be below 0.0001 quality % and S is below 0.005 quality %.
4. closing line copper wires according to claim 1 and 2, is characterized in that,
By closing line copper wires heating for dissolving described in 100g in the number of residue thing being not dissolved in acid that the particle diameter that salpeter solution obtains is more than 30 μm be less than 1000.
5. closing line copper wires according to claim 1 and 2, is characterized in that,
The amount being not dissolved in the residue thing of acid described closing line copper wires heating for dissolving obtained in salpeter solution is below 0.00015 quality %.
6. a manufacture method for closing line copper wires, is characterized in that, the manufacture method of its closing line copper wires according to any one of Claims 1 to 5, possesses:
Copper motlten metal generation process is add more than one the Addition ofelements that is selected from Mg, Ca, Sr, Ba, Ra, Zr, Ti and rare earth element in the copper raw material of below more than 99.99 quality % 99.998 quality % to generate copper motlten metal in purity;
Continuous casting operation, produces ingot bar by described copper feeding molten metal continuously to belt wheel continuous casting machine; And
Continuous rolling operation, the ingot bar under the condition of initial temperature for more than 800 DEG C manufactured by continuous rolling.
7. a manufacture method for closing line copper wires, is characterized in that, the manufacture method of its closing line copper wires according to any one of Claims 1 to 5, possesses:
Copper motlten metal generation process, adds more than one the Addition ofelements that is selected from Mg, Ca, Sr, Ba, Ra, Zr, Ti and rare earth element to generate copper motlten metal at the purity copper raw material that is below more than 99.99 quality % 99.998 quality %;
Casting process, injects mold by described copper motlten metal and produces ingot bar;
Extrusion process, carries out extrusion process to obtained ingot bar, thus produces extruding wire rod under the condition of initial temperature for more than 800 DEG C;
Processing and annealing operation, for obtained extruding wire rod, implement any one in rolling processing or Wire Drawing and annealing repeatedly; And
Light rolling process, is rolled with rolling rate less than more than 5% 25%, makes final wire diameter be more than 0.15mm below 3.0mm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2011161036 | 2011-07-22 | ||
| JP2011-161036 | 2011-07-22 | ||
| PCT/JP2012/068090 WO2013015154A1 (en) | 2011-07-22 | 2012-07-17 | Copper strand for bonding wire and method for producing copper strand for bonding wire |
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| CN103608910A CN103608910A (en) | 2014-02-26 |
| CN103608910B true CN103608910B (en) | 2016-03-02 |
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| JP (1) | JP5344070B2 (en) |
| KR (1) | KR101926215B1 (en) |
| CN (1) | CN103608910B (en) |
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| JP6175932B2 (en) * | 2013-06-24 | 2017-08-09 | 三菱マテリアル株式会社 | Drawing copper wire, drawing copper wire manufacturing method and cable |
| KR101519075B1 (en) * | 2013-12-03 | 2015-05-21 | (주)신동 | Electromagnetic wave shielding Fe-Cu wire, rod and Manufacturing method for the same |
| JP6056876B2 (en) | 2015-01-07 | 2017-01-11 | 三菱マテリアル株式会社 | Superconducting stabilizer |
| JP6299803B2 (en) * | 2016-04-06 | 2018-03-28 | 三菱マテリアル株式会社 | Superconducting wire and superconducting coil |
| JP6299802B2 (en) | 2016-04-06 | 2018-03-28 | 三菱マテリアル株式会社 | Superconducting stabilizer, superconducting wire and superconducting coil |
| CN106119597A (en) * | 2016-08-30 | 2016-11-16 | 芜湖楚江合金铜材有限公司 | The different in nature copper wires of a kind of environment-friendly and high-performance and processing technique thereof |
| CN106947881A (en) * | 2017-05-05 | 2017-07-14 | 三门峡宏鑫有色金属有限公司 | Multielement rare earth high conductivity Cu alloy material and preparation method thereof |
| WO2019088080A1 (en) * | 2017-10-30 | 2019-05-09 | 三菱マテリアル株式会社 | Superconductivity stabilizing material, superconducting wire, and superconducting coil |
| JP6926245B2 (en) * | 2018-01-30 | 2021-08-25 | タツタ電線株式会社 | Bonding wire |
| CN111661953A (en) * | 2020-06-16 | 2020-09-15 | 包头稀土研究院 | Method for separating fluorine and phosphorus in mixed rare earth alkaline wastewater and application |
| JP2022103567A (en) | 2020-12-28 | 2022-07-08 | 日立金属株式会社 | Rough drawing wire production method and rough drawing wire production device |
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| US4676827A (en) * | 1985-03-27 | 1987-06-30 | Mitsubishi Kinzoku Kabushiki Kaisha | Wire for bonding a semiconductor device and process for producing the same |
| CN1924049A (en) * | 2005-09-02 | 2007-03-07 | 日立电线株式会社 | Copper alloy material and method of making same |
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| JPS63286212A (en) * | 1987-05-16 | 1988-11-22 | Sumitomo Electric Ind Ltd | Manufacture of metal wire for wiring of semiconductor |
| JPH02207541A (en) * | 1989-02-07 | 1990-08-17 | Sumitomo Electric Ind Ltd | Manufacture of semiconductor element connection wire |
| JP5396939B2 (en) * | 2009-03-16 | 2014-01-22 | 三菱マテリアル株式会社 | Rough drawn copper wire manufacturing method, rough drawn copper wire manufacturing apparatus, and rough drawn copper wire |
| JP5499933B2 (en) * | 2010-01-12 | 2014-05-21 | 三菱マテリアル株式会社 | Phosphorous copper anode for electrolytic copper plating, method for producing the same, and electrolytic copper plating method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4676827A (en) * | 1985-03-27 | 1987-06-30 | Mitsubishi Kinzoku Kabushiki Kaisha | Wire for bonding a semiconductor device and process for producing the same |
| CN1924049A (en) * | 2005-09-02 | 2007-03-07 | 日立电线株式会社 | Copper alloy material and method of making same |
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| WO2013015154A1 (en) | 2013-01-31 |
| TW201323104A (en) | 2013-06-16 |
| MY171026A (en) | 2019-09-23 |
| KR101926215B1 (en) | 2018-12-06 |
| JP5344070B2 (en) | 2013-11-20 |
| CN103608910A (en) | 2014-02-26 |
| KR20140050630A (en) | 2014-04-29 |
| JP2013048225A (en) | 2013-03-07 |
| TWI586448B (en) | 2017-06-11 |
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