CN107978577B - A kind of low-impedance composite palladium ruthenium copper wire and its manufacturing method - Google Patents
A kind of low-impedance composite palladium ruthenium copper wire and its manufacturing method Download PDFInfo
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- CN107978577B CN107978577B CN201711170734.4A CN201711170734A CN107978577B CN 107978577 B CN107978577 B CN 107978577B CN 201711170734 A CN201711170734 A CN 201711170734A CN 107978577 B CN107978577 B CN 107978577B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/49—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions wire-like arrangements or pins or rods
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
- H01L21/4814—Conductive parts
- H01L21/4885—Wire-like parts or pins
- H01L21/4889—Connection or disconnection of other leads to or from wire-like parts, e.g. wires
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/02—Bonding areas; Manufacturing methods related thereto
- H01L2224/04—Structure, shape, material or disposition of the bonding areas prior to the connecting process
- H01L2224/05—Structure, shape, material or disposition of the bonding areas prior to the connecting process of an individual bonding area
- H01L2224/05001—Internal layers
- H01L2224/05099—Material
- H01L2224/051—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
- H01L2224/05138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/05147—Copper [Cu] as principal constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/02—Bonding areas; Manufacturing methods related thereto
- H01L2224/04—Structure, shape, material or disposition of the bonding areas prior to the connecting process
- H01L2224/05—Structure, shape, material or disposition of the bonding areas prior to the connecting process of an individual bonding area
- H01L2224/05001—Internal layers
- H01L2224/05099—Material
- H01L2224/051—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
- H01L2224/05163—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than 1550°C
- H01L2224/05164—Palladium [Pd] as principal constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/02—Bonding areas; Manufacturing methods related thereto
- H01L2224/04—Structure, shape, material or disposition of the bonding areas prior to the connecting process
- H01L2224/05—Structure, shape, material or disposition of the bonding areas prior to the connecting process of an individual bonding area
- H01L2224/05001—Internal layers
- H01L2224/05099—Material
- H01L2224/051—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
- H01L2224/05163—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than 1550°C
- H01L2224/05176—Ruthenium [Ru] as principal constituent
Abstract
The composite palladium ruthenium copper wire of a kind of Low ESR, high reliability, it is characterised in that including core wire, the palladium layers being coated on outside core wire and the palladium ruthenium composite membrane being coated on outside palladium layers；The core wire is pure copper wire；The palladium ruthenium composite membrane is mainly made of nanometer Pd-Ru alloy and macromolecule stabilizer, and wherein macromolecule stabilizer is one of polyvinylpyrrolidone, polyvinyl alcohol, polyethyleneimine and polyacrylic acid；The palladium layers with a thickness of 0-15 nanometers, the palladium ruthenium composite membrane with a thickness of 11-18 nanometers.The present invention also provides a kind of manufacturing methods of above-mentioned composite palladium ruthenium copper wire.Composite palladium ruthenium copper wire of the invention can be used for semiconductor packages, have the advantages that Low ESR, high reliability.
Description
Technical field
The present invention relates to bonding wires, and in particular to a kind of low-impedance composite palladium ruthenium copper wire and its manufacturing method.
Background technique
Bonding wire (bonding wire) is connection chip and outer enclosure substrate (substrate) and/or multilayer line
The main connection type of plate (PCB).Bonding wire development trend is mainly line footpath imperceptibility, high workshop service life from application direction
The product of (floor life) and high spool length；Chemically on ingredient, mainly have copper wire (including bare copper wire, plating palladium copper wire,
Dodge gold plating palladium copper wire) significantly replace gold thread in semiconductor field, and silver wire and silver alloy wire are answered in LED and part IC package
With substitution gold thread.
For gold thread, the main advantage of copper wire is: 1. product costs are low；2. wire rod high mechanical strength is being formed
Strong shock resistance during encapsulating after bank loop reduces the shaking (wire sweep) of wire rod, more suitable for thin
Pitch packages；3. electric conductivity height (resistivity: copper 1.69*10-6Ωcm ；2.2 * 10 of gold-6Ω cm)；4. with Al-Au eutectic phase
Compare, the growth rate of Al-Cu eutectic phase is much lower, so reliability is significantly promoted.But copper wire (copper bonding wire) have with
Lower problem: 1. wire rods are easy to oxidize；2. wire rod hardness is high, it is easy that IC is caused to damage in routing；3. easily corroding；4. In
In Thermal Cycling after plastic packaging, ball neck is easy to produce fatigue failure.
In order to overcome the above problem of copper wire, the method that industry mainly uses at present is using plating palladium copper wire, some also exist
Plate surface one layer of thin gold of flash again of palladium copper wire.Plating palladium dodges the thickness of palladium layers in golden copper wire product mostly at 40-110 nanometers at present
Near, the thickness of layer gold is then between 2-5 nanometers, and the weight rate of palladium is between 1.7-2.3%.
Plating palladium dodges golden copper wire technology and solves the problems, such as copper wire oxidation, and the bonding performance of second point has obtained very big mention
It rises, but simultaneously because a large amount of introducings of palladium need higher ultrasonic energy that could obtain so that copper wire more stiffened in ball bonding
Bond strength, increase the probability for breaking chip, and a large amount of research shows that plating on palladium copper wire in first ball bonding
Palladium can't be distributed in the shape-changeable ball bottom (deformed Free air ball) automatically to increase the reliability of solder joint, therefore,
How to allow palladium enrichment is in the position that industry is ground to increase the reliability of solder joint with the outer surface of FAB (Free air ball)
Study carefully one of hot spot.
It is at present that application speedup of the wire rod on automotive electronics exists using another upper main trend in bonding wire
Accelerate, correspondingly the requirement to the reliability of wire rod is also being promoted, and traditional plating palladium copper wire is also faced using upper serious adjustment,
Such as Nippon Steel is newest research shows that its conventional EX1 plating palladium copper wire integrity problem occurs in automotive field, needs to combine
Special alloy technology solves.
The main function that bonding wire is played after connection chip and substrate is electrical connection and heat transfer.In terms of electrical connection
Respectively power line (power line) and signal wire (signal line), both effects, which are intended to wire rod, low resistance
Rate.For signal wire, it is especially desirable to the impedance when transmitting high-frequency signal is paid attention to, because existing when transmitting high-frequency signal
Skin effect, electric signal mainly conducted by the surface of conductor, signal frequency is higher, via surface thickness it is thinner.
For example, for copper wire, its skin depth is about 660 nanometers when the frequency of signal is 10GHz；When the frequency of signal reaches
When 100GHz, for copper wire, its skin depth is then 134 nanometers.It obviously, if can be by the palladium layers thickness of current plating palladium copper wire
10 nanometers are reduced to from 40-110 nanometers hereinafter, being then conducive to the transmission of high-frequency signal, because of the resistivity (resistivity of palladium of palladium
For 9.93*10-6Ω cm) it is much higher than copper.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of composite palladium ruthenium copper wire and this composite palladium ruthenium copper wire
Manufacturing method, this composite palladium ruthenium copper wire are used for semiconductor packages, have the advantages that Low ESR, high reliability.The technology of use
Scheme is as follows:
A kind of low-impedance composite palladium ruthenium copper wire, it is characterised in that including core wire, the palladium layers being coated on outside core wire and
The palladium ruthenium composite membrane being coated on outside palladium layers；The core wire is pure copper wire；The palladium ruthenium composite membrane is mainly by nanometer Pd-Ru alloy
It is formed with macromolecule stabilizer, wherein macromolecule stabilizer is polyvinylpyrrolidone, polyvinyl alcohol, polyethyleneimine and poly- third
One of olefin(e) acid；The palladium layers with a thickness of 0-15 nanometers, the palladium ruthenium composite membrane with a thickness of 11-18 nanometers.
During the burning ball of ball bonding (electric flame off, EFO), arc high pressure punctures protection gas when ball bonding
Body (95% nitrogen and 5% hydrogen) releases a large amount of heat, the end of bonding wire is melted, due to the effect of surface tension, in bonding wire
End forms a ball, that is, free air ball (Free air ball), since palladium can form solid solution with copper, so palladium
It can fuse into the main body of copper ball, to disappear on the surface of FAB.It has been generally acknowledged that highest temperature during EFO, on FAB
Degree appears in the bottom of FAB, and body temperature is not necessarily higher than 1554.9 DEG C of fusing point of palladium, but the dissolution due to palladium in copper
The flowing of liquid in property and the adjoint FAB of the process, palladium is the surrounding for being difficult to be uniformly distributed in FAB, especially cannot
It is enriched in the part that the bottom FAB is contacted with IC aluminum pad, however, enrichment of the palladium in the region is ten to the reliability of subsequent solder joint
Divide beneficial.Palladium ruthenium composite membrane in the present invention can effectively promote palladium ruthenium in the enrichment of the surface the FAB especially bottom FAB, and one
Together with aspect, palladium and ruthenium originally dissolve each other in the present invention, for palladium, the fusing point of Pd-Ru alloy is higher
(2334 DEG C of the fusing point of ruthenium), on the other hand, the presence of organic film and carbonization process during EFO can also delay Technique of Nano Pd
The fusing of ruthenium alloy hinders palladium to fuse into copper main body, in addition, since the density of palladium and ruthenium is all higher than copper so that palladium and
Ruthenium meeting priority enrichment is in the bottom FAB, to improve the reliability of product.
In addition, in composite palladium ruthenium copper wire of the invention, since the palladium coating on copper surface only has 0-15 microns, much smaller than existing
There is the 40-110 micron of plating palladium copper wire product, therefore the electric conductivity of composite palladium ruthenium copper wire of the invention increases, and hardness meeting
Sharp fall.When the palladium coating of copper line surface only has 0-15 microns, preventing the oxidation resistant ability of copper wire is also significantly
Decline, but because there is the presence of palladium ruthenium composite membrane, the antioxygenic property of composite palladium ruthenium copper wire can also be guaranteed.
In a kind of concrete scheme, above-mentioned palladium layers are palladium coating of the plating on core wire (pure copper wire)；Palladium ruthenium composite membrane is to apply
Apply the composite membrane being mainly made of nanometer Pd-Ru alloy and macromolecule stabilizer in palladium layers.In palladium layers with a thickness of 0 nanometer
In the case where, palladium ruthenium composite membrane is directly coated on outside core wire.
It is preferred that above-mentioned macromolecule stabilizer is polyvinylpyrrolidone.
It is preferred that macromolecule stabilizer is palladium in nanometer Pd-Ru alloy with the molal quantity that monomer calculates in above-mentioned palladium ruthenium composite membrane
With 2-4 times of the total mole number of ruthenium.
It is preferred that the molar ratio of ruthenium and palladium is (4:6)-(6:4) in above-mentioned nanometer Pd-Ru alloy.
For the consistency for promoting palladium ruthenium composite membrane, preferably above-mentioned palladium ruthenium composite membrane also contains oleamide, wherein oleic acid acyl
The molal quantity of amine is 0.1-1 times of the total mole number of palladium and ruthenium in nanometer Pd-Ru alloy.
It is preferred that in above-mentioned palladium ruthenium composite membrane, nanometer Pd-Ru alloy is using liquid reduction method while to restore palladium salt and ruthenium salt obtains
The nanometer Pd-Ru alloy particle obtained, the size of obtained nanometer Pd-Ru alloy particle is between 5-15 nanometers.Macromolecule stabilizer
Shield to nanometer Pd-Ru alloy particle, to prevent between nanometer Pd-Ru alloy particle it is poly- simultaneously.Since macromolecule is steady
Determine the thickness of agent itself, therefore the thickness of palladium ruthenium composite membrane is between 11-18 nanometers.It is worth noting that palladium ruthenium is solid in room temperature
Be under state completely it is immiscible, phenomenon of phase separation can be generated, but if available atom level in the case where nano particle
Not mixed uniformly solid solution.
The method for being preferably formed as above-mentioned palladium ruthenium composite membrane includes the following steps:
(1 ') is by ruthenic chloride (RuCl3 ·nH2) and potassium chloropalladate (K O2[PdCl4]) be added in 800-1200 grams of water, chlorine
The total amount for changing ruthenium and potassium chloropalladate is 2 moles, obtains solution I；
The macromolecule stabilizer for calculating 4-8 moles with monomer is added to 2-4 to rise in triethylene glycol, stirring is equal to mixing
It is even, and 160-240 DEG C (preferably 200 DEG C) are heated to, obtain solution II；
Solution I is added gradually in solution II by (2 '), is stirred while adding, and ensures the whole temperature of solution in adition process
Degree variation is within 5 DEG C；After solution I is all added in solution II, 8-12 minutes are kept the temperature at 160-240 DEG C, then cool down
To 20-30 DEG C, sediment is isolated using the principle of centrifuge separation, which is the Technique of Nano Pd protected by macromolecule stabilizer
Ruthenium alloy particle；
(3 ') will be centrifugally separating to obtain sediment and be scattered in 1000-2000 milliliters of ethyl alcohol again, obtain after mixing evenly
Glue；
Glue is put into a storage tank by (4 '), passes through the core wire for being plated palladium in glue, core wire immerses in glue simultaneously
Length of wires is greater than or equal to 1 meter, and core wire residence time in glue is greater than or equal to 5 seconds, allows and plates on palladium layers surface
It applies evenly and applies one layer of glue；
(5 ') are in the lehr to make to plate the glue on palladium layers surface between 110-150 DEG C in temperature under the atmosphere of nitrogen
Layer solidifies (the mainly evaporation of ethyl alcohol), obtains the palladium ruthenium composite membrane with a thickness of 11-18 nanometers.
In preferred steps (1 '), the molar ratio of ruthenic chloride and potassium chloropalladate is (4:6)-(6:4).
In above-mentioned steps (2 '), the effect of stirring is to disperse the nanometer Pd-Ru alloy particle to be formed rapidly, while making molten
Solution integrally keeps more uniform temperature (during solution I is added, can pass through heating and control after liquid I and solution II mix
The temperature of solution entirety processed makes the variation of solution bulk temperature within 5 DEG C).
In preferred steps (3 '), it will be centrifugally separating to obtain after sediment is scattered in again in 1000-2000 milliliters of ethyl alcohol,
0.2-2 mole of oleic acid amide is added, obtains glue after mixing evenly.
The present invention also provides a kind of manufacturing methods of above-mentioned composite palladium ruthenium copper wire, it is characterised in that successively includes following steps
It is rapid:
(1) core wire is manufactured
Using the copper raw material of purity 4N or more, the core wire that diameter is 18-50 microns is obtained through founding, wire drawing；
(2) palladium is plated
After the oxidation film for removing core wire surface, palladium plating operation is carried out, forms thickness at 0-15 nanometers on core wire surface
Between palladium coating；
(3) glue is applied
It allows and is passed through in prepared glue through the core wire of step (2) plating palladium, core wire immerses the length of wires in glue simultaneously
More than or equal to 1 meter, and core wire residence time in glue is greater than or equal to 5 seconds, and plating palladium layers is allowed to apply uniformly over the surface
Upper one layer of glue；
The glue is using the nanometer Pd-Ru alloy particle protected by macromolecule stabilizer as dispersed phase, and the glue is with second
Alcohol is as continuous phase；
It (4) is to make to plate the glue on palladium layers surface between 110-150 DEG C in temperature in the lehr under the atmosphere of nitrogen
Layer solidifies (the mainly evaporation of ethyl alcohol), obtains the palladium ruthenium composite membrane with a thickness of 11-18 nanometers, is subsequently cooled to 20-30 DEG C, obtains
Obtain required composite palladium ruthenium copper wire.
In step (1), drawing process generally include it is rough, in it is rough, it is thin draw, it is micro- draw etc. four-stages.In above-mentioned wire drawing
It needs to take annealing more than two times in total with after wire drawing in the process, pure nitrogen gas or Forming can be used in annealing
Gas is as annealing atmosphere.
In a kind of concrete scheme, above-mentioned steps (1) manufacture core wire includes the following steps:
(1-1) founding: using the copper raw material of purity 4N or more, continuously draw casting process by vacuum melting and orientation, obtain
The core wires that diameter is 6-8 millimeters；
(1-2) wire drawing: wire drawing is carried out to the core wires that step (1) obtains, obtains the core wire that diameter is 18-50 microns；
In drawing process, intermediate annealing at least once is carried out to core wires, using N2 as moving back in annealing process
Internal heat atmosphere, 450-600 DEG C of annealing temperature, annealing furnace effective length is 600-800mm, annealing speed 50-100m/min；
It after (1-3) wire drawing, anneals to core wires, using Forming gas as moving back in annealing process
Internal heat atmosphere, 450-600 DEG C of annealing temperature, annealing furnace effective length is 600-800mm, and annealing speed 50-100m/min is obtained
Core wire.
Step (2) carries out plating palladium operation using common electro-plating method.
In above-mentioned steps (3), the particle diameter distribution of nanometer Pd-Ru alloy primary particle (primary particle) in glue
Between 5-15 nanometers, each nanometer of Pd-Ru alloy primary particle is uniformly mixed on atomic size by palladium and ruthenium.
It is preferred that the method for applying glue successively includes the following steps: in above-mentioned steps (3)
(3-1) is by ruthenic chloride (RuCl3 ·nH2) and potassium chloropalladate (K O2[PdCl4]) be added in 800-1200 grams of water, chlorine
The total amount for changing ruthenium and potassium chloropalladate is 2 moles, obtains solution I；
The macromolecule stabilizer for calculating 4-8 moles with monomer is added to 2-4 to rise in triethylene glycol, stirring is equal to mixing
It is even, and 160-240 DEG C (preferably 200 DEG C) are heated to, obtain solution II；
Solution I is added gradually in solution II by (3-2), is stirred while adding, and ensures that solution is whole in adition process
Temperature change is within 5 DEG C；After solution I is all added in solution II, 8-12 minutes are kept the temperature at 160-240 DEG C, then cold
But to 20-30 DEG C, sediment is isolated using the principle of centrifuge separation, which is the nanometer protected by macromolecule stabilizer
Pd-Ru alloy particle；
(3-3) will be centrifugally separating to obtain sediment and be scattered in 1000-2000 milliliters of ethyl alcohol again, obtain after mixing evenly
Glue；
Glue is put into a storage tank by (3-4), passes through the core wire for plating palladium through step (2) in glue, core wire immerses simultaneously
Length of wires in glue is greater than or equal to 1 meter, and core wire residence time in glue is greater than or equal to 5 seconds, allows and plates palladium layers
It applies uniformly over the surface and applies one layer of glue.
In step (3-1), the molar ratio of ruthenic chloride and potassium chloropalladate is (4:6)-(6:4).
In above-mentioned steps (3-2), the effect of stirring is to disperse the nanometer Pd-Ru alloy particle to be formed rapidly, while making molten
Solution integrally keeps more uniform temperature (during solution I is added, can pass through heating and control after liquid I and solution II mix
The temperature of solution entirety processed makes the variation of solution bulk temperature within 5 DEG C).
In step (3-3), will be centrifugally separating to obtain sediment be scattered in 1000-2000 milliliters of ethyl alcohol again and then
0.2-2 mole of oleic acid amide is added, obtains glue after mixing evenly.
Composite palladium ruthenium copper wire of the invention compared with prior art, has the advantages that
(1) present invention uses with a thickness of 11-18 nanometers by nanometer Pd-Ru alloy and macromolecule stabilizer (such as polyethylene pyrrole
Pyrrolidone) composition composite membrane, the oxidation of copper wire can be effectively prevented, so that palladium and ruthenium are enriched in the bottom of FAB when burning ball
And outer surface, be conducive to the reliability for improving bonding wire；
(2) present invention uses purity, as core wire raw material, not add any doped chemical, in addition core wire in the copper of 4N or more
The thickness of the palladium layers on surface only has 0-15um, the hardness for being conducive to the conductivity for improving wire rod and reducing wire rod.
Detailed description of the invention
Fig. 1 is the test result of the value of thrust of the second solder joint of wire rod of the embodiment of the present invention 1, comparative example 1 and comparative example 2
Figure；
Fig. 2 is the test result of the shear stress of the first solder joint of wire rod of the embodiment of the present invention 1, comparative example 1 and comparative example 2
Figure.
Specific embodiment
Below with reference to the embodiment content that the present invention is furture elucidated, but the contents of the present invention be not limited solely to it is following
Embodiment.
Embodiment 1
In the present embodiment, the manufacturing method of composite palladium ruthenium copper wire successively includes the following steps:
(1) core wire is manufactured
This step (1) manufacture core wire includes the following steps:
(1-1) founding: using the copper raw material of purity 4N or more, continuously draw casting process by vacuum melting and orientation, obtain
The core wires that diameter is 8 millimeters；
(1-2) wire drawing: wire drawing is carried out to the core wires that step (1) obtains, obtains the core wire that diameter is 20 microns；
In drawing process, intermediate annealing at least once is carried out to core wires, using N2 as moving back in annealing process
Internal heat atmosphere, 500 DEG C of annealing temperature, annealing furnace effective length is 600mm, annealing speed 60m/min；
It after (1-3) wire drawing, anneals to core wires, using Forming gas as moving back in annealing process
Internal heat atmosphere, 500 DEG C of annealing temperature, annealing furnace effective length is 600mm, and annealing speed 60m/min obtains core wire；
(2) palladium is plated
After the oxidation film for removing core wire surface, palladium plating operation is carried out, is formed on core wire surface with a thickness of 10 nanometers
Palladium coating；
(3) glue is applied
In this step (3), the method for applying glue successively includes the following steps:
(3-1) is by ruthenic chloride (RuCl3 ·nH2) and potassium chloropalladate (K O2[PdCl4]) be added in 1000 grams of water, ruthenic chloride
Total amount with potassium chloropalladate is 2 moles (molar ratio of ruthenic chloride and potassium chloropalladate is 1:1), obtains solution I；
The polyvinylpyrrolidone for calculating 6 moles with monomer is added in 3 liters of triethylene glycols, stirring to be uniformly mixed,
And 200 DEG C are heated to, obtain solution II；
Solution I is added gradually in solution II by (3-2), is stirred while adding, and ensures that solution is whole in adition process
Temperature change is within 5 DEG C；After solution I is all added in solution II, 10 minutes are kept the temperature at 200 DEG C, is cooled to 25
DEG C, sediment is isolated using the principle of centrifuge separation, which is to be protected by macromolecule stabilizer polyvinylpyrrolidone
Nanometer Pd-Ru alloy particle；
(3-3) will be centrifugally separating to obtain sediment and be scattered in 1500 milliliters of ethyl alcohol again, add 0.2 mole of oleic acid acyl
Amine obtains glue after mixing evenly；
Glue is put into a storage tank by (3-4), passes through the core wire for plating palladium through step (2) in glue, core wire immerses simultaneously
Length of wires in glue is 1.2 meters, and core wire residence time in glue is 6 seconds, and plating palladium layers is allowed to apply uniformly over the surface
Apply one layer of glue；
(4) in the lehr under the atmosphere of nitrogen, make to plate the glue layer solidification on palladium layers surface at being 120 DEG C in temperature
(the mainly evaporation of ethyl alcohol) obtains palladium ruthenium composite membrane (palladium ruthenium composite membrane with a thickness of 12 nanometers), is subsequently cooled to 25 DEG C, obtains
Obtain required composite palladium ruthenium copper wire.
Composite palladium ruthenium copper wire obtained includes core wire, the palladium layers being coated on outside core wire and the palladium being coated on outside palladium layers
Ruthenium composite membrane；The core wire is pure copper wire；The palladium ruthenium composite membrane is by nanometer Pd-Ru alloy, polyvinylpyrrolidone and oleic acid acyl
(in palladium ruthenium composite membrane, polyvinylpyrrolidone is palladium and ruthenium in nanometer Pd-Ru alloy with the molal quantity that monomer calculates to amine composition
3 times of total mole number；In nanometer Pd-Ru alloy, the molar ratio of ruthenium and palladium is 1:1；The molal quantity of oleamide is Technique of Nano Pd
0.1 times of the total mole number of palladium and ruthenium in ruthenium alloy)；The palladium layers with a thickness of 10 nanometers, the thickness of the palladium ruthenium composite membrane
It is 12 nanometers.
Embodiment 2
In the present embodiment, the manufacturing method of composite palladium ruthenium copper wire successively includes the following steps:
(1) core wire is manufactured
This step (1) manufacture core wire includes the following steps:
(1-1) founding: using the copper raw material of purity 4N or more, continuously draw casting process by vacuum melting and orientation, obtain
The core wires that diameter is 8 millimeters；
(1-2) wire drawing: wire drawing is carried out to the core wires that step (1) obtains, obtains the core wire that diameter is 50 microns；
In drawing process, intermediate annealing at least once is carried out to core wires, using N2 as moving back in annealing process
Internal heat atmosphere, 600 DEG C of annealing temperature, annealing furnace effective length is 800mm, annealing speed 100m/min；
It after (1-3) wire drawing, anneals to core wires, using Forming gas as moving back in annealing process
Internal heat atmosphere, 600 DEG C of annealing temperature, annealing furnace effective length is 800mm, and annealing speed 100m/min obtains core wire；
(2) palladium is plated
After the oxidation film for removing core wire surface, palladium plating operation is carried out, is formed on core wire surface with a thickness of 15 nanometers
Palladium coating；
(3) glue is applied
In this step (3), the method for applying glue successively includes the following steps:
(3-1) is by ruthenic chloride (RuCl3 ·nH2) and potassium chloropalladate (K O2[PdCl4]) be added in 900 grams of water, ruthenic chloride
Total amount with potassium chloropalladate is 2 moles (molar ratio of ruthenic chloride and potassium chloropalladate is 6:4), obtains solution I；
The polyethyleneimine for calculating 8 moles with monomer is added in 4 liters of triethylene glycols, stirring to be uniformly mixed, and add
Heat obtains solution II to 180 DEG C；
Solution I is added gradually in solution II by (3-2), is stirred while adding, and ensures that solution is whole in adition process
Temperature change is within 5 DEG C；After solution I is all added in solution II, 12 minutes are kept the temperature at 180 DEG C, is cooled to 20
DEG C, sediment is isolated using the principle of centrifuge separation, which is to be received by what macromolecule stabilizer polyethyleneimine was protected
Rice Pd-Ru alloy particle；
(3-3) will be centrifugally separating to obtain sediment and be scattered in 2000 milliliters of ethyl alcohol again, add 1 mole of oleic acid acyl
Amine obtains glue after mixing evenly；
Glue is put into a storage tank by (3-4), passes through the core wire for plating palladium through step (2) in glue, core wire immerses simultaneously
Length of wires in glue is 1 meter, and core wire residence time in glue is 5 seconds, and plating palladium layers is allowed to apply uniformly over the surface
Upper one layer of glue；
(4) in the lehr under the atmosphere of nitrogen, make to plate the glue layer solidification on palladium layers surface at being 110 DEG C in temperature
(the mainly evaporation of ethyl alcohol) obtains the palladium ruthenium composite membrane with a thickness of 11 nanometers, is subsequently cooled to 20 DEG C, obtains required compound
Palladium ruthenium copper wire.
Composite palladium ruthenium copper wire obtained includes core wire, the palladium layers being coated on outside core wire and the palladium being coated on outside palladium layers
Ruthenium composite membrane；The core wire is pure copper wire；The palladium ruthenium composite membrane is by nanometer Pd-Ru alloy, polyethyleneimine and oleamide group
At (in palladium ruthenium composite membrane, polyethyleneimine is the total mole number of palladium and ruthenium in nanometer Pd-Ru alloy with the molal quantity that monomer calculates
4 times；In nanometer Pd-Ru alloy, the molar ratio of ruthenium and palladium is 6:4；The molal quantity of oleamide is palladium in nanometer Pd-Ru alloy
With 0.5 times of the total mole number of ruthenium)；The palladium layers with a thickness of 15 nanometers, the palladium ruthenium composite membrane with a thickness of 11 nanometers.
Embodiment 3
In the present embodiment, the manufacturing method of composite palladium ruthenium copper wire successively includes the following steps:
(1) core wire is manufactured
This step (1) manufacture core wire includes the following steps:
(1-1) founding: using the copper raw material of purity 4N or more, continuously draw casting process by vacuum melting and orientation, obtain
The core wires that diameter is 6 millimeters；
(1-2) wire drawing: wire drawing is carried out to the core wires that step (1) obtains, obtains the core wire that diameter is 30 microns；
In drawing process, intermediate annealing at least once is carried out to core wires, using N2 as moving back in annealing process
Internal heat atmosphere, 450 DEG C of annealing temperature, annealing furnace effective length is 700mm, annealing speed 80m/min；
It after (1-3) wire drawing, anneals to core wires, using Forming gas as moving back in annealing process
Internal heat atmosphere, 450 DEG C of annealing temperature, annealing furnace effective length is 700mm, and annealing speed 80m/min obtains core wire；
(2) palladium is plated
After the oxidation film for removing core wire surface, palladium plating operation is carried out, is formed on core wire surface with a thickness of 0.5 nanometer
Palladium coating；
(3) glue is applied
In this step (3), the method for applying glue successively includes the following steps:
(3-1) is by ruthenic chloride (RuCl3 ·nH2) and potassium chloropalladate (K O2[PdCl4]) be added in 1200 grams of water, ruthenic chloride
Total amount with potassium chloropalladate is 2 moles (molar ratio of ruthenic chloride and potassium chloropalladate is 4:6), obtains solution I；
The polyvinyl alcohol for calculating 5 moles with monomer is added in 2 liters of triethylene glycols, stirring and is heated to being uniformly mixed
To 240 DEG C, solution II is obtained；
Solution I is added gradually in solution II by (3-2), is stirred while adding, and ensures that solution is whole in adition process
Temperature change is within 5 DEG C；After solution I is all added in solution II, 8 minutes are kept the temperature at 240 DEG C, is cooled to 30
DEG C, sediment is isolated using the principle of centrifuge separation, which is the nanometer protected by macromolecule stabilizer polyvinyl alcohol
Pd-Ru alloy particle；
(3-3) will be centrifugally separating to obtain sediment and be scattered in 1200 milliliters of ethyl alcohol again, add 2 mole of oleic acid acyls
Amine obtains glue after mixing evenly；
Glue is put into a storage tank by (3-4), passes through the core wire for plating palladium through step (2) in glue, core wire immerses simultaneously
Length of wires in glue is 2 meters, and core wire residence time in glue is 10 seconds, and plating palladium layers is allowed to apply uniformly over the surface
Apply one layer of glue；
(4) in the lehr under the atmosphere of nitrogen, make to plate the glue layer solidification on palladium layers surface at being 150 DEG C in temperature
(the mainly evaporation of ethyl alcohol) obtains the palladium ruthenium composite membrane with a thickness of 18 nanometers, is subsequently cooled to 30 DEG C, obtains required compound
Palladium ruthenium copper wire.
Composite palladium ruthenium copper wire obtained includes core wire, the palladium layers being coated on outside core wire and the palladium being coated on outside palladium layers
Ruthenium composite membrane；The core wire is pure copper wire；The palladium ruthenium composite membrane is made of nanometer Pd-Ru alloy, polyvinyl alcohol and oleamide
(in palladium ruthenium composite membrane, polyvinyl alcohol is 2.5 of the total mole number of palladium and ruthenium in nanometer Pd-Ru alloy with the molal quantity that monomer calculates
Times；In nanometer Pd-Ru alloy, the molar ratio of ruthenium and palladium is 4:6；The molal quantity of oleamide be in nanometer Pd-Ru alloy palladium and
1 times of the total mole number of ruthenium)；The palladium layers with a thickness of 0.5 nanometer, the palladium ruthenium composite membrane with a thickness of 18 nanometers.
Comparative example 1
4N copper (purity 99.99%) raw material are chosen, are successively handled as follows:
(1) founding: melting is carried out by the oxygen-containing 4N copper lower than 5ppm is predefined, oriented continuous drawing process obtains straight
Diameter is the wire rod of 7mm.
(2) wire drawing: by multiple wire drawing, it is rough, small draw, it is thin draw, it is micro- the processes such as draw, obtaining diameter is between 20 microns
Bonding wire；
In above-mentioned drawing process, intermediate annealing process is carried out under the conditions of N2 to wire rod；After the completion of wire drawing, In
Wire rod is finally made annealing treatment under Forming gas；
(3) palladium plating: to draw to final size wire rod carry out palladium plating processing, palladium layers with a thickness of 50 nanometers；
(4) plating palladium wire rod is carried out dodging golden processing, layer gold obtains plating palladium and dodge gold thread material with a thickness of 4 nanometers.
Comparative example 2
4N copper (purity 99.99%) raw material are chosen, are successively handled as follows:
(1) founding: melting is carried out by the oxygen-containing 4N copper lower than 5ppm is predefined, oriented continuous drawing process obtains straight
Diameter is the wire rod of 7mm；
(2) wire drawing: by processes such as multiple wire drawing, rough, small drawing, thin drawing, micro- drawings (in above-mentioned drawing process, to line
Material carries out intermediate annealing process under the conditions of N2)；After the completion of wire drawing, wire rod is carried out at last annealing at Forming gas
Reason obtains the bonding wire that diameter is 20 microns.
The performance of the wire rod of above embodiments 1, comparative example 1 and comparative example 2 is tested, test method and result are such as
Under:
1, antioxygenic property
It by above-mentioned three kinds of wire rods after normal routing, is placed in the toilet of 25 DEG C of conditions of room temperature, after 1,2,3,5 day
It is welded again, takes the value of thrust of the second solder joint as the characterization of routing performance (because of the oxidation with copper line surface, the second weldering
The welding performance of point is most significant).
It with reference to Fig. 1, is characterized using the value of thrust of the second solder joint, the scale of the ordinate in Fig. 1 is gram that abscissa is day
Number.Obviously, the antioxygenic property of composite palladium ruthenium copper wire of the present invention is far better than comparative example 2, and close to comparative example 1.
2, hardness and process window
Since the hardness of palladium is higher than copper, after the thickness of palladium layers in the present invention is thinned, the palladium content in FAB declines, phase
The hardness of the FAB answered declines, this is as shown in figure 2 on the shear stress of the first solder joint.
Obviously, compared with bare copper wire (comparative example 2), the hardness of composite palladium ruthenium copper wire of the present invention is slightly higher；But with normal plating
Palladium copper wire (comparative example 1, palladium layers are with a thickness of 50 nanometers) compares, and the wire rod of composite palladium ruthenium copper wire of the present invention is softer.It can from Fig. 2
See, under the action of same ultrasonic energy, the shear stress ratio comparative example 2 for the ball bonding that composite palladium ruthenium copper wire of the invention obtains
Wire rod wants small, and bigger than the wire rod of comparative example 1, illustrates that degree of deformation (softness) is smaller than the former, bigger than the latter.
3, reliability
The ball bonding of the first solder joint is carried out using three kinds of wire rods, then carries out encapsulating encapsulation.The condition for being 200 DEG C in temperature
Under, it carries out High temperature storage and tests 1000 hours (HTS:High Temperature Test), be finally peeled away casting glue, then
The shear strength test of the first solder joint is carried out, to assess performance of three kinds of wire rods in high temperature storage reliability.Test result is such as
Shown in the following table 1, shear strength less than 5 grams to be poor, be between 5-8 grams it is good, it is excellent for being greater than 8 grams.
Table 1
| Experiment | Embodiment 1 | Comparative example 1 | Comparative example 2 |
| Shear strength (gram) | 9(is excellent) | 6(is good) | 4(is poor) |
Claims (10)
1. a kind of low-impedance composite palladium ruthenium copper wire, it is characterised in that including core wire, the palladium layers being coated on outside core wire and packet
Overlay on the palladium ruthenium composite membrane outside palladium layers；The core wire is pure copper wire；The palladium ruthenium composite membrane mainly by nanometer Pd-Ru alloy and
Macromolecule stabilizer composition, wherein macromolecule stabilizer is polyvinylpyrrolidone, polyvinyl alcohol, polyethyleneimine and polypropylene
One of acid；The palladium layers with a thickness of 0.5-15 nanometers, the palladium ruthenium composite membrane with a thickness of 11-18 nanometers.
2. composite palladium ruthenium copper wire according to claim 1, it is characterized in that: in the palladium ruthenium composite membrane, macromolecule stabilizer
With 2-4 times that the molal quantity that monomer calculates is the total mole number of palladium and ruthenium in nanometer Pd-Ru alloy.
3. composite palladium ruthenium copper wire according to claim 1 or 2, it is characterized in that: in the nanometer Pd-Ru alloy, ruthenium and palladium
Molar ratio is (4:6)-(6:4).
4. composite palladium ruthenium copper wire according to claim 1 or 2, it is characterized in that: the palladium ruthenium composite membrane also contains oleic acid acyl
Amine, wherein the molal quantity of oleamide is 0.1-1 times of the total mole number of palladium and ruthenium in nanometer Pd-Ru alloy.
5. composite palladium ruthenium copper wire according to claim 1 or 2, it is characterized in that: forming the method packet of the palladium ruthenium composite membrane
Include following step:
Ruthenic chloride and potassium chloropalladate are added in 800-1200 grams of water by (1 '), and the total amount of ruthenic chloride and potassium chloropalladate is 2 moles,
Obtain solution I；
By the macromolecule stabilizer for calculating 4-8 moles with monomer be added to 2-4 rise triethylene glycol in, stirring to be uniformly mixed, and
It is heated to 160-240 DEG C, obtains solution II；
Solution I is added gradually in solution II by (2 '), is stirred while adding, and ensures that solution bulk temperature becomes in adition process
Change within 5 DEG C；After solution I is all added in solution II, 8-12 minutes are kept the temperature at 160-240 DEG C, is cooled to 20-
30 DEG C, sediment is isolated using the principle of centrifuge separation, which is that the Technique of Nano Pd ruthenium protected by macromolecule stabilizer closes
Gold particle；
(3 ') will be centrifugally separating to obtain sediment and be scattered in 1000-2000 milliliters of ethyl alcohol again, obtain glue after mixing evenly；
Glue is put into a storage tank by (4 '), passes through the core wire for being plated palladium in glue, core wire immerses the wire rod in glue simultaneously
Length is greater than or equal to 1 meter, and core wire residence time in glue is greater than or equal to 5 seconds, allows and plates palladium layers uniformly over the surface
Painting applies one layer of glue；
(5 ') are in the lehr between 110-150 DEG C in temperature, the glue layer for making to plate on palladium layers surface is solid under the atmosphere of nitrogen
Change, obtains the palladium ruthenium composite membrane with a thickness of 11-18 nanometers.
6. the manufacturing method of composite palladium ruthenium copper wire described in claim 1, it is characterised in that successively include the following steps:
(1) core wire is manufactured
Using the copper raw material of purity 4N or more, the core wire that diameter is 18-50 microns is obtained through founding, wire drawing；
(2) palladium is plated
After the oxidation film for removing core wire surface, palladium plating operation is carried out, forms thickness in 0.5-15 nanometer on core wire surface
Between palladium coating；
(3) glue is applied
It allows and is passed through in prepared glue through the core wire of step (2) plating palladium, the length of wires that core wire immerses in glue simultaneously is greater than
Or it is equal to 1 meter, and core wire residence time in glue is greater than or equal to 5 seconds, it allows plating palladium layers to apply uniformly over the surface and applies one
Layer glue；
The glue is using the nanometer Pd-Ru alloy particle protected by macromolecule stabilizer as dispersed phase, and the glue is made with ethyl alcohol
For continuous phase；
It (4) is between 110-150 DEG C in temperature, the glue layer for making to plate on palladium layers surface is solid in the lehr under the atmosphere of nitrogen
Change, obtains the palladium ruthenium composite membrane with a thickness of 11-18 nanometers, be subsequently cooled to 20-30 DEG C, obtain required composite palladium ruthenium copper wire.
7. the manufacturing method of composite palladium ruthenium copper wire according to claim 6, it is characterised in that the step (1) manufactures core wire
Include the following steps:
(1-1) founding: using the copper raw material of purity 4N or more, continuously draw casting process by vacuum melting and orientation, obtain diameter
For 6-8 millimeters of core wires；
(1-2) wire drawing: wire drawing is carried out to the core wires that step (1) obtains, obtains the core wire that diameter is 18-50 microns；
In drawing process, intermediate annealing at least once is carried out to core wires, using N2 as annealing gas in annealing process
Atmosphere, 450-600 DEG C of annealing temperature, annealing furnace effective length is 600-800mm, annealing speed 50-100m/min；
It after (1-3) wire drawing, anneals to core wires, using Forming gas as annealing gas in annealing process
Atmosphere, 450-600 DEG C of annealing temperature, annealing furnace effective length is 600-800mm, and annealing speed 50-100m/min obtains core
Line.
8. the manufacturing method of composite palladium ruthenium copper wire according to claim 6, it is characterised in that in the step (3), coating
The method of glue successively includes the following steps:
Ruthenic chloride and potassium chloropalladate are added in 800-1200 grams of water by (3-1), and the total amount of ruthenic chloride and potassium chloropalladate is rubbed for 2
You, obtains solution I；
By the macromolecule stabilizer for calculating 4-8 moles with monomer be added to 2-4 rise triethylene glycol in, stirring to be uniformly mixed, and
It is heated to 160-240 DEG C, obtains solution II；
Solution I is added gradually in solution II by (3-2), is stirred while adding, and ensures solution bulk temperature in adition process
Variation is within 5 DEG C；After solution I is all added in solution II, 8-12 minutes are kept the temperature at 160-240 DEG C, is cooled to
20-30 DEG C, sediment is isolated using the principle of centrifuge separation, which is the Technique of Nano Pd ruthenium protected by macromolecule stabilizer
Alloying pellet；
(3-3) will be centrifugally separating to obtain sediment and be scattered in 1000-2000 milliliters of ethyl alcohol again, obtain glue after mixing evenly
Liquid；
Glue is put into a storage tank by (3-4), passes through the core wire for plating palladium through step (2) in glue, core wire immerses glue simultaneously
In length of wires be greater than or equal to 1 meter, and core wire in glue residence time be greater than or equal to 5 seconds, allow plating palladium layers surface
On one layer of glue is uniformly coated.
9. the manufacturing method of composite palladium ruthenium copper wire according to claim 8, it is characterised in that: in step (3-1), ruthenic chloride
Molar ratio with potassium chloropalladate is (4:6)-(6:4).
10. the manufacturing method of composite palladium ruthenium copper wire according to claim 8, it is characterised in that:, will be from step (3-3)
The isolated sediment of the heart is scattered in 1000-2000 milliliters of ethyl alcohol again and then is added 0.2-2 mole of oleic acid amide, stirs
Glue is obtained after mixing uniformly.
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| US4405104A (en) * | 1977-12-14 | 1983-09-20 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Panel breaking apparatus |
| CN100359657C (en) * | 2002-03-26 | 2008-01-02 | 株式会社野毛电气工业 | Bonding wire and an integrated circuit device using the same |
| CN105023902A (en) * | 2009-07-30 | 2015-11-04 | 新日铁住金高新材料株式会社 | Bonding wire for semiconductor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60217693A (en) * | 1984-04-13 | 1985-10-31 | 古河電気工業株式会社 | Lead wire for electronic part |
| US9217205B2 (en) * | 2007-12-11 | 2015-12-22 | Enthone Inc. | Electrolytic deposition of metal-based composite coatings comprising nano-particles |
| CA2711790A1 (en) * | 2008-01-09 | 2009-10-29 | Dan V. Goia | Method for preparing dispersions of precious metal nanoparticles and for isolating such nanoparticles from said dispersions |
| CN102467987A (en) * | 2010-11-19 | 2012-05-23 | 钰成材料科技股份有限公司 | Lead wire for capsulation and manufacturing method thereof |
| JP2016537819A (en) * | 2013-11-21 | 2016-12-01 | ヘレウス ドイチェラント ゲーエムベーハー ウント カンパニー カーゲー | Coated wire for bonding applications |
| CN106057374B (en) * | 2016-05-20 | 2018-07-27 | 西北有色金属研究院 | A kind of preparation method of Bi-2212 superconducting wires barrier layer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4405104A (en) * | 1977-12-14 | 1983-09-20 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Panel breaking apparatus |
| CN100359657C (en) * | 2002-03-26 | 2008-01-02 | 株式会社野毛电气工业 | Bonding wire and an integrated circuit device using the same |
| CN105023902A (en) * | 2009-07-30 | 2015-11-04 | 新日铁住金高新材料株式会社 | Bonding wire for semiconductor |
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