CN109996898A - Electrical and Electronic component and the copper alloy of semiconductor and preparation method thereof are used for high-intensitive and high conductivity - Google Patents
Electrical and Electronic component and the copper alloy of semiconductor and preparation method thereof are used for high-intensitive and high conductivity Download PDFInfo
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 153
- 239000004065 semiconductor Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 29
- 239000011572 manganese Substances 0.000 claims abstract description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 239000013049 sediment Substances 0.000 claims description 69
- 238000000034 method Methods 0.000 claims description 45
- 239000000047 product Substances 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000005098 hot rolling Methods 0.000 claims description 24
- 229910015136 FeMn Inorganic materials 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 21
- 238000005266 casting Methods 0.000 claims description 20
- 238000005097 cold rolling Methods 0.000 claims description 15
- 230000001376 precipitating effect Effects 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims 1
- 239000000956 alloy Substances 0.000 description 28
- 229910045601 alloy Inorganic materials 0.000 description 25
- 239000000203 mixture Substances 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 10
- 239000010931 gold Substances 0.000 description 10
- 229910052737 gold Inorganic materials 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- 238000000992 sputter etching Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000002950 deficient Effects 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000036314 physical performance Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- 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
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B2003/005—Copper or its alloys
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
Electrical and Electronic component and the copper alloy of semiconductor and preparation method thereof are used for high-intensitive and high conductivity the invention discloses a kind of.The copper alloy includes the iron (Fe) of 0.09 to 0.20 weight %, the phosphorus (P) of 0.05 to 0.09 weight %, the manganese (Mn) of 0.05 to 0.20 weight %, the copper (Cu) of surplus and the 0.05 inevitable impurity of weight % or less, and has 470MPa or bigger tensile strength, 145Hv or bigger hardness, 75%IACS or bigger conductivity and 400 DEG C or higher anti-softening temperature.
Description
Technical field
The copper conjunction for being used for Electrical and Electronic component and semiconductor with high-intensitive and high conductivity that the present invention relates to a kind of
Gold and preparation method thereof includes the copper alloy and its system of copper (Cu), iron (Fe), phosphorus (P) and manganese (Mn) more particularly, to one kind
Preparation Method.
Background technique
As (that is, being used as the material for semiconductor lead frame, Electrical and Electronic component etc.) for numerous purposes
Copper alloy, usually using the Cu-Fe-P- based alloy for including Fe and P.For example, among copper alloy, including 0.05-0.15 weight
Measure the copper alloy C19210 of the P of the Fe and 0.025-0.04 weight % of % or Fe, 0.015- including 2.1-2.6 weight %
The C194 copper alloy 00 of the Zn of the P and 0.05-0.2 weight % of 0.15 weight % has excellent intensity and conductivity, therefore quilt
It is widely used as the material for lead frame.The reason of Fe and P are mainly used as addition element is that they are formed in copper-based matter
Precipitated phase is to assign excellent intensity and conductivity.
However, intensity and conductivity collide with one another in the various characteristics of copper alloy, that is, it is inversely proportional to one another example, therefore,
As intensity improves, conductivity is inversely reduced, and as conductivity improves, intensity is inversely reduced.Therefore, have
Traditional copper alloy C19210 of the conductivity of the tensile strength and 80%IACS of 400MPa is with poor intensity but has excellent
Conductivity, and be accordingly used in the product for needing high conductivity, the conductance of tensile strength and 60%IACS with 500Mpa
Traditional C194 copper alloy 00 of rate is with poor conductivity but has excellent intensity, and is accordingly used in needing high-intensitive production
In product.
Recently, according to the slimming and trend toward miniaturization of Electrical and Electronic component, the characteristic of material becomes more important.With
For electronic equipment, vehicle etc. semiconductor devices towards large capacity, miniaturization and highly integrated trend development, now into
The miniaturization and slimming of lead frame used in row semiconductor devices.Therefore, it is necessary to simultaneously compared to traditional copper alloy
High-intensitive, high conductivity and excellent machinability are provided and 470MPa is met according to the reduction of the thickness of electronic product simultaneously
Or the copper alloy of bigger tensile strength and 75%IACS or bigger conductivity.Therefore, in order to meet this in industrial circle
The demand of sample is being dedicated to improving both the intensity to collide with one another and conductivity.
In order to improve the intensity of copper alloy, increasing the content of Fe and P or add the third element of such as Sn, Mg or Ni,
But when the content of these elements increases, the intensity of copper alloy is improved, but the conductivity of copper alloy reduces.Therefore, instead of adding
Added elements refine the size and distribution of crystal grain or control crystallization or deposit to improve the characteristic of copper alloy.However, herein
In the case of, there are the various problems of surface defect, reliability reduction, uneven micro-structure etc..Therefore, improve copper alloy
Both intensity and conductivity are a difficulties and important research theme.
In addition, executing heating process in the field of application copper alloy, therefore copper alloy needs heat resistance, such performance
The softening resistance of anti-softening temperature can be referred to as be evaluated as.Anti-softening temperature is indicated when the alcu alloy film of measurement preparation is in Re Chu
Heat treatment temperature when hardness number of the reason after 1 minute changes, corresponds to the 80% of initial hardness value (before heat treatment).As above
Described, anti-softening temperature, which is used as, indicates the relevant index of the whether heat-resisting and reliability to finished product of corresponding material.In tradition
Semiconductor package part or electronic component in, the copper alloy with about 380 DEG C of anti-softening temperature product manufacture and at
There is no problem in terms of the reliability of product.However, being applied to the copper alloy of semiconductor package part, electronic component etc. recently due to producing
It adds the heating process of such as solder or wire bonding in product processing and needs better softening resistance, it is soft therefore, it is necessary to resist
The property changed is improved to 400 DEG C or higher anti-softening temperature.
It has had submitted relevant each to for the acquisition of intensity and conductivity needed for the Cu alloy material of lead frame
Kind patent.
10-2008-0019274 Korean Patent Application Publication improves Cu-Fe-P- based alloy by addition Mg
Intensity.However, the conductivity of alloy inversely reduces when Mg is added to alloy.It is closed when to traditional Cu-Fe-P- base
When gold addition Mg, the alloy shows the tensile strength of 450MPa and the conductivity of 70%IACS, most lower than lead frame
The characteristic (470Mpa or bigger tensile strength and 75%IACS or bigger conductivity) closely required, the reason is that due to thick
Caused by Mg-P base junction eutectic substance.When adding Mg to alloy, due to terminate to be inevitably generated to hot rolling since casting
Thick Mg-P base junction eutectic substance and defect, the intensity and conductivity of alloy inevitably reduce.
In addition, the ruler of 10-2005-0076767 Korean Patent Application Publication by the sediment in control alloy
The very little intensity to improve Cu-Fe-P- based alloy.However, in the patent document, in order to finely control the particle ruler of sediment
It is very little, cold rolling and annealing process two or more times are executed, therefore there are various variables, and be difficult to practical system at industrial scale
Standby this alloy.In addition, being 1% or bigger and sediment granule number which patent document describes the volume fraction of sediment
It is 300/ μm2Or it is bigger, but volume fraction is the value for including coarse granule number.
In addition, 10-2013-0136183 Korean Patent Application Publication improves Cu- by adding Mn to alloy
The intensity of Fe-P- based alloy, but prepared alloy is unsatisfactory in industry spot intensity actually required and conductivity.Separately
Outside, the patent application is 10-30 μm claim 4 describes the particle size of sediment, but substantially, 10-30 μm
Particle size is excessive, and these particles correspond to casting flaw or foreign substance rather than sediment, therefore will not improve strong
Degree and conductivity.On this point, if there is the particle having a size of 10-30 μm in copper alloy, the characteristic of copper alloy is bad
Change, and semiconductor packaging process is difficult to carry out due to the surface quality of difference.In addition, above-mentioned patent document do not describe it is any
Analysis result or reason determine the type of sediment, and only observed in sem analysis result shown in Fig. 3 crystal boundary without
It is sediment, and may not provide technical basis.
Summary of the invention
Technical problem
Biography is satisfied with the characteristic needed recently in industry is satisfied with the object of the present invention is to provide a kind of
The intensity and conductivity of system technology and the copper alloy for being used for Electrical and Electronic component and semiconductor with excellent softening resistance
And preparation method thereof.
Technical solution
In order to realize these purposes and other advantages, according to the purpose of invention, as in this implementation and broadly described, use
In iron (Fe), 0.05 to 0.09 weight % that the copper alloy of Electrical and Electronic component and semiconductor includes 0.09 to 0.20 weight %
Phosphorus (P), the manganese (Mn) of 0.05 to 0.20 weight %, the copper (Cu) of surplus and 0.05 weight % or less it is inevitable
Impurity, wherein the inevitable impurity includes in the group being made of Si, Zn, Ca, Al, Ti, Be, Cr, Co, Ag and Zr
At least one, and the copper alloy have 470MPa or bigger tensile strength, 145Hv or bigger hardness, 75%IACS
Or bigger conductivity and 400 DEG C or higher anti-softening temperature.The impurity can have 0.01 weight % or lower and contain
Amount.The copper alloy for Electrical and Electronic component and semiconductor can also include the Ni or Sn of 0.0001 to 0.03 weight %
At least one of.
The copper alloy can have 20 μm or smaller average grain size and 5 μm or smaller standard deviation, pass through
Crystallite dimension is measured using the analysis of the crystal orientation of field emission scanning electron microscope (FE-SEM).
The copper alloy includes (FeMn)2P sediment.(FeMn)2P sediment can be saturating by using high-resolution
Electron microscope (HR-TEM) or Flied emission transmission electron microscope (FE-TEM) is penetrated to see with the enlargement ratio of 100000x or bigger
It examines through the sample of carbon extraction replica method preparation and measures, and (FeMn)2P sediment is flat with 50nm or smaller
Equal particle size and 1.0 × 1010/cm2Or bigger area density.
The copper alloy can be prepared as piece or plate.
In the another aspect of invention, preparation for the method for Electrical and Electronic component and the copper alloy of semiconductor include: by
Above-mentioned component fusing is to cast ingot casting；900-1000 DEG C at a temperature of homogenize that be heat-treated ingot casting 1-4 obtained small
When, hot rolling is then carried out with the working modulus of 85-95%；The product obtained with the working modulus cold rolling of 87-98% by previous step；?
Precipitating heat treatment is obtained by previous step at a temperature of 430-520 DEG C product 1-10 hours；And with the reduction ratio of 10-90%
Rolling is by product that previous step obtains to produce finished product.
Beneficial effect
Copper alloy according to the present invention has excellent intensity and conductivity, and has anti-softening characteristic outstanding.Separately
Outside, when by preparation process according to the present invention to prepare copper alloy, although process costs reduce, copper obtained is closed
Gold shows excellent intensity and conductivity, other than discrete transistor and semiconductor lead frame, copper alloy obtained
Apply also for various Electrical and Electronic components.
Detailed description of the invention
Fig. 1 is the curve graph for showing the anti-softening characteristic of the copper alloy and traditional copper alloy that prepare according to embodiment 5.
Fig. 2 a is the temperature indicated in the technique for the copper alloy that preparation has the composition stated in embodiment 1 at 870 DEG C
The FE-SEM photo of micro-structure after lower hot rolling.
Fig. 2 b is the temperature indicated in the technique for the copper alloy that preparation has the composition stated in embodiment 1 at 900 DEG C
The FE-SEM photo of micro-structure after lower hot rolling.
Fig. 2 c is the temperature indicated in the technique for the copper alloy that preparation has the composition stated in embodiment 1 at 950 DEG C
The FE-SEM photo of micro-structure after lower hot rolling.
Fig. 3 is the FE-SEM photo for indicating the micro-structure of the copper alloy prepared according to embodiment 5.
Fig. 4 a is to pass through ion milling method system to determine the sediment in the copper alloy of the composition with embodiment 5
The FE-TEM photo of standby sample.
Fig. 4 b is to pass through carbon extraction replica method to determine the sediment in the copper alloy of the composition with embodiment 5
The FE-TEM photo of the sample of preparation.
Specific embodiment
Electrical and Electronic is used for high-intensitive and conductivity and excellent softening resistance the present invention provides a kind of
Component and the copper alloy of semiconductor and preparation method thereof.In the following description, unless otherwise stated, indicating component
Content % be weight %.
According to the copper alloy of invention
Copper alloy according to the present invention includes the phosphorus of the iron (Fe) of 0.09 to 0.20 weight %, 0.05 to 0.09 weight %
(P), the manganese (Mn) of 0.05 to 0.20 weight %, the copper (Cu) of surplus and 0.05 weight % or less are inevitably miscellaneous
Matter, the inevitable impurity include in the group for selecting to be made of Si, Zn, Ca, Al, Ti, Be, Cr, Co, Ag and Zr at least
One kind, and the copper alloy is that have 470Mpa or bigger tensile strength, 145Hv or bigger hardness, 75%IACS or more
Big conductivity and 400 DEG C or higher anti-softening temperature for Electrical and Electronic component and the copper alloy of semiconductor.
Hereinafter, the group for describing copper alloy according to the present invention is grouped as.In the following description, unless otherwise saying
It is bright, otherwise indicate that the % of the content of element is weight %.
[Fe]
Fe is to form thin (FeMn)2P sediment is to improve intensity or electric conductivity necessary element.Fe content 0.09 to
In the range of 0.20%.If Fe content less than 0.09%, forms the deficiency of particle necessary to sediment, and due to precipitating
The inhibitory effect of grain growth caused by object reduces.Therefore, the standard deviation mistake of average grain size or average grain size
Degree increases, therefore strength reduction.Therefore, in order to effectively show effect, Fe content needs to be 0.09% or bigger.However,
If Fe content is more than 0.20%, that is, it is excessively increased, then causes the roughening of sediment, the standard deviation of average grain size is excessive
Increase, therefore bendability and conductivity reduce.
[P]
Other than depickling, P is in conjunction with Fe and Mn, to form thin (FeMn)2P sediment, to improve the strong of copper alloy
Degree or electric conductivity.P content is 0.05 to 0.09%.If P content, less than 0.05%, the formation of thin sediment is insufficient, and
And since the inhibitory effect of grain growth caused by sediment reduces.Therefore, average grain size or average grain size
Standard deviation is excessively increased, therefore strength reduction.Therefore P content needs to be 0.05% or bigger.However, if P content is more than
0.09%, that is, it is excessively increased, then raw sediment particle increases, and the standard deviation of average grain size excessively increases, therefore is bent
Processability reduces.In addition, conductivity reduces.
[Mn]
It is reported that the Mn for being added to copper alloy typically facilitates the intensity for improving copper alloy, but if simply by Mn
It is added to copper alloy to improve intensity, then the conductivity of the copper alloy products finally obtained inevitably reduces.According to this
In the copper alloy of invention, formed (FeMn)2P sediment, therefore both intensity and conductivity of copper alloy can be improved simultaneously.?
In copper alloy according to the present invention, Mn content is 0.05 to 0.20%.If Mn content is less than 0.05%, the formation of sediment
It is insufficient, and since the inhibitory effect of grain growth caused by sediment reduces, intensity is dropped as in Fe
It is low.However, both intensity and conductivity are dropped due to coarse crystallization substance or casting flaw if Mn content is more than 0.20%
It is low.
[inevitable impurity]
In addition, copper alloy according to the present invention include 0.05% or less selected from by Si, Zn, Ca, Al, Ti, Be, Cr,
At least one of the group of Co, Ag and Zr composition.Preferably, impurity content is 0.01% or less.These elements are for changing
The element of the various characteristics of kind copper alloy, and can selectively be added according to application.
In copper alloy according to the present invention, closed if the widely known Mg with excellent reinforcing effect is added to copper
Jin Zhong, then the intensity for the product of copper alloy finally obtained makes moderate progress, but the conductivity of the product inevitably drops
It is low, and Mg reacts with P and terminates to cause thick Mg-P base junction eutectic substance and defect to hot rolling since casting.Therefore, it should not wrap
Include Mg.
[Ni] and [Sn]
Copper alloy according to the present invention can also include 0.0001% to 0.03% at least one of Ni or Sn.Ni is molten
In Cu matrix, therefore have the effect of improving intensity, and effectively provide heat resistance.If Ni content is less than
0.0001%, then it cannot improve the intensity of copper alloy, if Ni content is more than 0.03%, the conductivity of copper alloy is reduced.
Sn is dissolved in Cu matrix the solid solution strengthened alloy element for improving intensity.If Sn content is less than
0.0001%, then it is difficult to it is expected the improved strength of copper alloy, if Sn content is more than 0.03%, the conductivity of copper alloy drops
It is low.
According to the characteristic of the copper alloy of invention
In general, as the intensity of copper alloy improves, the conductivity of copper alloy reduces, and therefore, it is difficult to control in copper alloy
Two kinds of characteristics.
The intensity of copper alloy according to the present invention can satisfy 470MPa or bigger tensile strength and 145Hv or bigger
Both hardness.These are to reflect the value of nearest required characteristic in industry, and if it is considered that there is copper inversely to close
The intensity and conductivity of gold, then can be regarded as limiting.
In addition, copper alloy used in semiconductor or Electrical and Electronic component should have 75%IACS or bigger conductance
Rate.If the conductivity of copper alloy is less than 75%IACS, the transmission of electric signal is not effective, therefore the copper alloy cannot be
It is used in product.The conductivity of copper alloy according to the present invention is big for 75%IACS or more.
That is, copper alloy according to the present invention has excellent characteristic, that is, both improved intensity and conductivity.
Copper alloy according to the present invention has 400 DEG C or higher excellent anti-softening temperature.Below in preparation according to this
The detailed description of anti-softening temperature will be provided in the method for the copper alloy of invention.
The method for preparing the copper alloy according to invention
Copper alloy according to the present invention can be prepared by the method being described below.Firstly, will be according to above-mentioned group
At component melt to cast ingot casting.By ingot casting obtained 900-1000 DEG C at a temperature of carry out the heat treatment that homogenizes
1-4 hours, hot rolling is carried out with the working modulus of 85-95% immediately after.While completing hot rolling, the product of acquisition is subjected to water
It is quenched to execute the solution treatment of solute element, cold rolling is then carried out with the working modulus of 87-98%.It is accumulated by this cold rolling
Large strain can and therefore increase generate sediment driving force after, by the product of acquisition 430-520 DEG C at a temperature of carry out
Precipitating heat treatment 1-10 hours.Then, it is rolled with product of the reduction ratio of 10-90% to acquisition, so that it is determined that finished product
Final thickness.
In more detail, description is prepared to each operation of the method for copper alloy according to the present invention.
Firstly, melting above-mentioned component to cast ingot casting.
Later, by the product of acquisition 900-1000 DEG C at a temperature of homogenize and be heat-treated 1-4 hours after, so
Hot rolling is carried out with the working modulus of 85-95% immediately afterwards.The heat treatment that homogenizes is a kind of necessary technique prepared for hot rolling, so that
Ingot casting carries out hot rolling in sufficient heated condition rather than under cold working state, and cast structure and being formed new is tied again to remove
Crystal structure.Hot rolling is most important operation in the method for prepare copper alloy according to the present invention.Hot-rolled condition is to alloy characteristic
In metal structure there is the factor of great influence, different structure after hot rolling is formed according to hot-rolled condition, to be changed to
The characteristic of product.Hot-rolled condition includes hot-rolled temperature, the number of hot rolling, cooling condition etc., and changes heat according to corresponding condition
Structure obtained after rolling.
In order to realize the characteristic of copper alloy according to the present invention, hot-rolled temperature should be in the range of 900 to 1000 DEG C.Work as heat
When rolling temperature in such range, the isotropism recrystallization texture with non-directional can be obtained.Such as from will then have to retouch
It is believed that retaining processing structure (rolled structure) if hot-rolled temperature is lower than 900 DEG C in the embodiment stated.In tradition
The copper alloy for common lead frame in, the deterioration of finished product characteristic, Ying Tianjia are dissolved one or more times in order to prevent
Processing and depositing technology, this will lead to increased costs and reduces yield.On the other hand, copper alloy according to the present invention is not being appointed
Its characteristic is showed in the case where what additional technique, therefore process costs can be reduced, and yield can be improved.
When being heat-treated when the temperature 1-4 that ingot casting is heated to 900-1000 DEG C is small with homogenize, obtain it is each to
While same sex recrystallization texture, solution treatment effect is showed.If heating the time that ingot casting is less than 1 hour, part is protected
Processing structure is stayed, and ingot casting cannot fully show the characteristic of isotropism recrystallization texture, if heating ingot casting is more than 4
The time of hour, then ingot casting can partially melt.Solution treatment is that the amount of the element more than solubility is dissolved in hypersaturated state
Under Cu matrix in technique, therefore, sedimentation effect maximize.In general precipitation strengthening alloy, for film thickness
The alloy of degree needs individually additional solid solution treatment process, and therefore, process costs increase and productivity reduces.However,
In copper alloy according to the present invention, solution treatment effect is obtained by the heat treatment in hot rolling technology, therefore, by subsequent
Large strain energy can be accumulated in the material with the strong rolling of the processing ratio of 87-98% in cold-rolling process.Height in material is answered
Become the driving force that can serve as the depositing technology after cold rolling, therefore thin sediment can be evenly distributed in depositing technology.
Later, while completing hot rolling, water quenching is carried out to the product obtained by previous step and is gone out to execute solute element
Solution treatment, cold rolling is then carried out with the working modulus of 87-98%.Large strain energy is accumulated in cold rolling in this way, therefore can
To increase the driving force for generating sediment.
Later, by previous step obtain product 430-520 DEG C at a temperature of carry out precipitating heat treatment 1-10 hours.According to
Copper alloy of the invention is precipitation strength type alloy, therefore depositing technology is important.In addition, copper alloy quilt according to the present invention
It is designed as including additionally Mn, but since the suitable strength and conductivity of copper alloy cannot be obtained by simply addition Mn, because
This obtains such performance by being evenly distributed thin sediment via depositing technology.In traditional Cu-Fe-P- based alloy
In, Fe is primarily present in copper alloy2P sediment, but thick FeP sediment is locally present, therefore keep the characteristic of copper alloy bad
Change.On the other hand, in the method for preparing copper alloy according to the present invention, precipitating heat treatment is carried out in the above conditions, therefore
Carefully (FeMn)2Both high intensity and high conductivity may be implemented in copper alloy in P precipitate distribution.
Finally, being rolled by the product that previous step obtains with the reduction ratio of 10-90%.Here, by with 10-90%
The cold rolling of working modulus roll the product, thus to obtain target physical performance.Here, the preferred scope of working modulus is 30-
70%, and in such range, the strengthened efficiency of the processing quality of copper alloy according to the present invention maximizes.
In addition, in the above methods, after precipitating heat treatment and before the final rolling of finished product, if it is desired,
It can execute with the cold rolling of the working modulus of 30-90%, then can carry out intermediate heat-treatment.Such processing with 30-90%
The cold rolling of rate and intermediate heat-treatment are not required, and are performed to solve surface quality problems, such as may be due to criticizing
Measure the precipitating Equipment for Heating Processing of production line technique or preparation condition and generate burning (due to heat with pressure caused by part
In conjunction with) and the scratch etc. that generates due to the surface acid-washing technique after precipitating heat treatment.If after precipitating heat treatment
There are big difference and finished product exceeds target physical performance (intensity between the thickness of finished product after product thickness and final rolling
And conductivity) range or be difficult to obtain target property, then intermediate heat-treatment is applicable.Here, due to intermediate heat-treatment
Main purpose be reduce copper alloy intensity, but must make copper alloy conductivity reduce minimize, therefore to intermediate heat at
It is important that making the range of conductivity reduction 0.1-3%IACS for reason.If conductivity is reduced less than 0.1%IACS's
Value, then be heat-treated no effect, if conductivity reduces the value more than 3%IACS, heat treatment have the effect of it is big, still
Due to the reduction of its conductivity and intensity, copper alloy may deviate from target property.
In the method for preparing copper alloy according to the present invention, hot rolling and precipitating heat treatment process close the copper finally obtained
The characteristic of gold has great influence, and in order to incite somebody to action thin (FeMn)2P precipitate distribution needs in copper alloy according to the present invention
Hot rolling technology accurately successively to be controlled to depositing technology.In order to determine the thin sediment generated in copper alloy, FE-SEM is used
Observation with FE-TEM is necessary.
Copper alloy prepared according to the methods of the invention includes thin (FeMn)2P sediment, and when by using FE-TEM
Crystal orientation analysis when observing micro-structure with the enlargement ratio of 100000x or bigger, (FeMn)2The average grain of P sediment
Having a size of 50nm or smaller, and (FeMn)2The area density of P sediment is 1.0 × 1010/cm2Or it is bigger.
In order to observe sediment, TEM sample is usually prepared by common ion milling method.However, using in this way
Sample, it is difficult to observe particle size be several nm to tens nm thin sediment.Even with attempt to the thin sediment of observation, it is also difficult to
Sediment in the TEM sample prepared by ion milling method is distinguished with impurity or foreign matter, and not can determine that precipitating
Crystalline texture, composition of object etc..On the other hand, can by the tem analysis of the sample prepared via carbon extraction replica method come
Observe the thin sediment in copper alloy according to the present invention.
In copper alloy according to the present invention, thin (FeMn)2P sediment is evenly distributed in crystal boundary and intra-die, and
And (FeMn)2The average particle size particle size of P sediment is 50nm or smaller.If the average particle size particle size of sediment is more than 50nm,
Then conductivity inevitably declines, and leads to the reliability of difference during semiconductor technology.It can be by via Flied emission
Transmission electron microscope (FE-TEM) crystal orientation analyzes the observation with the enlargement ratio of 100000x to measure being averaged for sediment
Particle size.On this point, the copper according to the present invention that Fig. 4 a and Fig. 4 b is shown in the embodiment that will then have to description closes
The FE-TEM of gold analyzes result.
Furthermore it is possible to based on FE-TEM result shown in Fig. 4 a and Fig. 4 b come measurement area density.Area density refers to
Determine the quantity of existing sediment in region, and is used as the index of the distribution of estimation sediment.In general, in order to estimate sediment
Distribution, using volume fraction, but volume fraction indicates the percentage of the sediment in specified region, therefore, if generating tool
There is large-sized coarse granule, then error range is sizable.On the other hand, if the concept of usable floor area density, thick
The presence not influence area density of grain, and can more accurately determine the distributed degrees of sediment.Copper according to the present invention closes
The area density of gold is 1.0 × 1010/cm2Or it is bigger.Due to (FeMn) of copper alloy according to the present invention2P sediment is averaged
Particle size is very thin, i.e. 50nm or smaller, therefore in order to show the characteristic of copper alloy according to the present invention, largely
Sediment is necessary, so if the quantity (that is, area density) of sediment is less than 1.0 × 1010/cm2, then copper alloy cannot
With enough intensity.
The anti-softening temperature of copper alloy according to the present invention is 400 DEG C or higher.In order in Electrical and Electronic component and half
Enough anti-softening characteristics are showed in conductor, the anti-softening temperature of copper alloy is necessary for 400 DEG C or higher.In the present invention,
As the means for the intensity for improving copper alloy, precipitation strength is executed rather than crystal grain refinement, therefore copper alloy has excellent resist
Softening properties.If executing serious plastic deformation to realize crystal grain refinement, can occur defective due to high internal stress
Softening.Defective softening means to reduce material due to heating during material processes the encapsulation with semiconductor devices
Hardness, and lead to defective product.
Copper alloy according to the present invention for Electrical and Electronic component and semiconductor can be prepared as piece or plate.In this way
Piece or plate type copper alloy be suitable for semiconductor or IC lead frame or connector and terminal.
Copper alloy according to the present invention has excellent both intensity and conductivity, and compared with traditional product, root
Have according to copper alloy of the invention by being mixed the component for being used for copper alloy and accurately controlling preparation process as described above
There is excellent anti-softening characteristic, therefore not only especially suitable for Electrical and Electronic component (such as, conventional use of semiconductor leads
Frame, terminal, connector, switch, relay etc.), but also the discrete transistor especially suitable for increasing demand recently (that is,
Vehicle power controls semiconductor).
Embodiment
Embodiment 1 to 16
The sample of embodiment 1 to 16 is prepared according to composition disclosed in following table 1.Hereinafter, it prepared by description
The method of the sample.
Every 1kg each composition mixing according to disclosed in table 1 includes the alloying element of copper, by the mixture of acquisition in high frequency
It is melted in melting furnace, the ingot casting that then manufacturing is 50mm with a thickness of 20mm, width and length is 160-180mm.It is all in order to remove
It is such as quickly cooled down the bad part of part and contraction chamber, by the length of the bottom and top partial cut 20mm of the ingot casting of manufacture,
Then 900 DEG C at a temperature of in batch-type furnace ingot casting homogenize heat treatment 2 hours.It is stood after the heat treatment that homogenizes
Hot rolling is executed with 90% working modulus, and executes the solution treatment gone out by water quenching while completing hot rolling, to inhibit
The precipitating of solute element.Before depositing technology, cold rolling is executed with 90% working modulus, so that cold rolling in this way is accumulated
Large strain energy, and thus increase the driving force for generating sediment.Later, small in 450 DEG C of at a temperature of execution precipitating heat treatment 3
When, cold rolling is then executed with 50% working modulus.Finally, preparing the finished product of copper alloy as with 0.3t × 30w × 200l
The sample of size, and the sample is used in following test to be executed.The expression of table 2 discloses in testing example
Embodiment 1 to 16 prepare copper alloy sample specificity analysis result.
Comparative example 1 to 16
By with the preparation method of the condition of embodiment 1 to 16 under the same conditions formed according to disclosed in table 1 come
Prepare the sample of comparative example 1 to 16.Table 2 also illustrates that the specificity analysis result of copper alloy sample prepared by comparative example 1 to 16.
[table 1]
Embodiment 1 to 14 is implementation of the evaluation such as the most important property of the compositing range of Cu, Fe, Mn and P for indicating in table 1
Example.Embodiment 14 to 16 is to determine the embodiment of the effect of addition element of such as Ni and Sn.The component of comparative example 1 and extensively use
It is identical in the component of the alloy C19210 of lead frame.In addition, the component of comparative example 8 to 13 divides it in addition to the group of alloy C19210
It further include outside Mn.
Testing example
Hereinafter, the characteristic analysis method of copper alloy sample description manufactured according to embodiment and comparative example.
Tensile strength is measured using the omnipotent test machine Z100 from ZWICK ROELL limited liability company, by using
Vickers hardness test meter TUKON 2500 from INSTRON company applies the load of 1kg to measure hardness, and use comes from
The SIGMATEST of FOERSTER limited liability company measures conductivity.
In anti-softening temperature analysis, the Thermolyne 5.8L D1 from THERMO SCIENTIFIC company is used
Desk-top Muffle furnace executes heat treatment.In more detail, respectively in 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600
DEG C, execute at a temperature of 650 DEG C and 700 DEG C heat treatment 1 minute of sample after, measure the hardness number of sample, draw wherein Y-axis
It indicates hardness and X-axis indicates the dashed line view of temperature, and calculate the temperature intersected with the point of the initial hardness value corresponding to 80%
Value is anti-softening temperature.Result is shown in Fig. 1, wherein by the copper alloy of embodiment 5 illustratively with traditional copper alloy
C19400 is compared with C19210.
The average crystal grain ruler of the micro-structure of sample is measured using the Quanta650FEG (FE-SEM) from FEI Co.
It is very little.In order to measure average grain size, after the surface to sample executes electrolyte polishing, sample is inserted into FE-SEM furnace
In, the indoor pressure of chamber is maintained 1 × 10-5Support is smaller, then by via the crystal orientation point for using ion beam to irradiate
Analysis is to observe sample.Fig. 3 shows the observation result of the micro-structure of the copper alloy of implementation 5.
In order to measure the average particle size particle size and area density of sediment, the JEM-2100F from JEOL company is used
(FE-TEM).Sample is observed in order to use FE-TEM, is analyzed by two methods, Fig. 4 a indicates to use general sample
The FE-TEM of preparation method (that is, ion milling method) analyzes result.As being exemplarily illustrated in Fig. 4 a, it is difficult to determine and divide
Analyse thin sediment.Therefore, the unascertainable thin sediment of ion milling method is used in order to analyze, Fig. 4 b indicates to extract by carbon
The FE-TEM of the sample of replication method preparation analyzes result.
Following table 2 indicates the measurement result according to above-mentioned characteristic analysis method.
[table 2]
In table 2 above, through embodiment 4 compared between embodiment 8, the copper in addition to embodiment 8 can be determined
The copper alloy of the also embodiment 4 with P increment provides enough P to form thin (FeMn) except the composition of alloy2P precipitating
Object, therefore there is improved both intensity and conductivity.In addition, from the result of embodiment 5 it is ensured that embodiment 5
Copper alloy realizes excellent both intensity and electric conductivity simultaneously.
On the other hand, even if carrying out the control of sediment, the copper alloy of comparative example 1 to 16 by optimization preparation process
It is unsatisfactory for intensity corresponding with one of characteristic needed for industry.Its reason is that copper alloy deviates from copper according to the present invention and closes
The best composition composition of gold, therefore, it is difficult to form thin (FeMn)2P sediment.
Among above-mentioned comparative example, comparative example 8 to 13 is to determine to traditional alloy C19210 simply whether add Mn
Effective comparative example.Can from the result of comparative example 8 to 13 it is well established that any component only pass through simply addition Mn all cannot
Characteristic needed for meeting.The reason is that simply addition Mn cannot form (FeMn)2P sediment, and Mn is dissolved in Cu matrix,
To reduce conductivity, such problems is by forming (FeMn)2Caused by the deficiency of P content needed for P sediment.Specifically
Ground, it was determined that the simple solution strengthening of addition element can slightly improve intensity, but drastically reduce conductivity.
Specificity analysis in summary as a result, it will be acknowledged that even with show copper according to the present invention and close
Identical preparation method and analysis method in the embodiment 1 to 16 of the characteristic of gold, the composition of traditional copper alloy C19210 is not yet
Improved alloy characteristic can be showed.
In order to evaluate the characteristic of the copper alloy according to hot-rolled temperature condition, prepared under the conditions of different hot-rolled temperatures respectively
Then the copper alloy sample of composition with embodiment 1 evaluates the physical property of copper alloy sample.
[table 3]
As determined from table 3, if hot-rolled temperature is lower than 900 DEG C, the spy of copper alloy according to the present invention is not showed
Property.The result of Fig. 2 a to 2c expression table 3.Fig. 2 a shows (general with the copper alloy for lead frame in 870 DEG C of temperature
Hot-rolled condition is corresponding) under the copper alloy standby by hot rolling retain processing structure and when observing copper alloy after hot rolling
(rolled structure) influences subsequent technique and causes the reduction of finished product characteristic.In the copper alloy of Fig. 2 b and 2c, hot-rolled temperature is
900 DEG C or higher, therefore, isotropism recrystallization texture is formed after hot rolling, and can show according to the present invention
The characteristic of copper alloy.
In order to determine the average grain size and micro-structure of copper alloy according to the present invention, according to the composition system of embodiment 5
The FE-SEM photo of standby copper alloy sample is shown in Fig. 3.As being exemplarily illustrated in Fig. 3, the sample of embodiment 5 is put down
Equal crystallite dimension is 20 μm or smaller, and its standard deviation is 5 μm or smaller.In this way as a result, basis can be determined
Copper alloy of the invention has good micro-structure, therefore can be used for Electrical and Electronic component and semiconductor and ask without any
Topic, such as surface defect.
It is shown in figs. 4 a and 4b using the analysis result of the copper alloy sample of the embodiment 5 of FE-TEM.
Fig. 4 a is the FE-TEM photo of the sample prepared by usually used ion milling method, is implemented with determining to have
Sediment in the copper alloy of the composition of example 5, and in the FE-TEM photo, it is difficult to determine the presence of sediment in copper alloy
And whether sediment is distributed in copper alloy, therefore, it is difficult to accurately be analyzed.In order to solve the problems, it is necessary to adopt
With new analysis method.
In order to overcome the limitation of traditional ion milling method, Fig. 4 b is the sample prepared by carbon extraction replica method
FE-TEM photo, to determine the sediment in the copper alloy formed with embodiment 5.If observation passes through carbon extraction replica side
The sample of method preparation, then can accurately carry out thin sediment includes the analysis of shape, size, composition, area density etc..It can
To determine that there is only sediments from Fig. 4 a, but it can determine and be formed uniformly in traditional Cu-Fe-P- base conjunction from Fig. 4 b
(FeMn) unobservable in gold2P sediment, and (FeMn)2P sediment have 50nm or smaller average particle size particle size with
And 1.0 × 1010/cm2Or bigger area density.
Claims (6)
1. a kind of for Electrical and Electronic component and the copper alloy of semiconductor, comprising:
The iron (Fe) of 0.09 to 0.20 weight %, the phosphorus (P) of 0.05 to 0.09 weight %, 0.05 to 0.20 weight % manganese
(Mn), the copper (Cu) of surplus and the 0.05 inevitable impurity of weight % or less, the inevitable impurity include
Selected from least one of the group being made of Si, Zn, Ca, Al, Ti, Be, Cr, Co, Ag and Zr；And
(FeMn)2P sediment, in which:
(FeMn)2P sediment is aobvious by using high resolution transmission electron microscope (HR-TEM) or Flied emission transmitted electron
Micro mirror (FE-TEM) is measured with the enlargement ratio observation of 100000x or bigger by sample prepared by carbon extraction replica method,
And (FeMn)2P sediment has 50nm or smaller average particle size particle size and 1.0 × 1010/cm2Or bigger area
Density；
The copper alloy has 470Mpa or bigger tensile strength, 145Hv or bigger hardness, 75%IACS or bigger electricity
Conductance and 400 DEG C or higher anti-softening temperature.
2. the copper alloy according to claim 1 for being used for Electrical and Electronic component and semiconductor, wherein the impurity has
0.01 weight % or lower content.
3. the copper alloy according to claim 1 for Electrical and Electronic component and semiconductor, further include 0.0001 to
At least one of the Ni or Sn of 0.03 weight %.
4. the copper alloy according to claim 1 for being used for Electrical and Electronic component and semiconductor, wherein the copper alloy tool
There are 20 μm or smaller average grain size and 5 μm or smaller standard deviation, by using field emission scanning electron microscope
(FE-SEM) crystal orientation is analyzed to measure crystallite dimension.
5. the copper alloy according to claim 1 for being used for Electrical and Electronic component and semiconductor, wherein the copper alloy quilt
It is prepared as piece or plate.
6. a kind of method for preparing the copper alloy for Electrical and Electronic component and semiconductor, comprising:
Component according to any one of claims 1 to 3 is melted to cast ingot casting；
900-1000 DEG C at a temperature of homogenize and be heat-treated ingot casting 1-4 hours obtained, then with the working modulus of 85-95%
Carry out hot rolling；
The product obtained with the working modulus cold rolling of 87-98% by previous step；
Product 1-10 hours obtained in 430-520 DEG C of at a temperature of precipitating heat treatment by previous step；And
With the rolling of the reduction ratio of 10-90% by product that previous step obtains to produce finished product.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2017-0145414 | 2017-11-02 | ||
| KR1020170145414A KR101834335B1 (en) | 2017-11-02 | 2017-11-02 | Copper alloy for electrical and electronic parts and semiconductor with high strength and high electrical conductivity and a method of preparing same |
| PCT/KR2018/009428 WO2019088419A1 (en) | 2017-11-02 | 2018-08-17 | Copper alloy having high strength and high electrical conductivity characteristics for electrical and electronic component and semiconductor, and method for manufacturing same |
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| CN109996898A true CN109996898A (en) | 2019-07-09 |
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| CN201880003539.9A Pending CN109996898A (en) | 2017-11-02 | 2018-08-17 | Electrical and Electronic component and the copper alloy of semiconductor and preparation method thereof are used for high-intensitive and high conductivity |
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| Country | Link |
|---|---|
| US (1) | US20210332459A1 (en) |
| JP (1) | JP6837541B2 (en) |
| KR (1) | KR101834335B1 (en) |
| CN (1) | CN109996898A (en) |
| MY (1) | MY192447A (en) |
| TW (1) | TWI681933B (en) |
| WO (1) | WO2019088419A1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000328157A (en) * | 1999-05-13 | 2000-11-28 | Kobe Steel Ltd | Copper alloy sheet excellent in bending workability |
| CN1269979C (en) * | 2004-01-23 | 2006-08-16 | 株式会社神户制钢所 | High-strength high-conductivity copper alloy |
| CN101180412A (en) * | 2005-07-07 | 2008-05-14 | 株式会社神户制钢所 | Copper alloy with high strength and excellent processability in bending and process for producing copper alloy sheet |
| CN100510131C (en) * | 2004-08-17 | 2009-07-08 | 株式会社神户制钢所 | Copper alloy plate for electric and electronic parts having bending workability |
| CN102782168A (en) * | 2010-02-08 | 2012-11-14 | 株式会社豊山 | Copper alloy having high strength and high conductivity, and preparation method thereof |
| KR20130136183A (en) * | 2012-06-04 | 2013-12-12 | 박효주 | Copper alloy element and the method for production same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1862560A4 (en) * | 2005-03-02 | 2013-09-18 | Furukawa Electric Co Ltd | Copper alloy and method for production thereof |
-
2017
- 2017-11-02 KR KR1020170145414A patent/KR101834335B1/en active IP Right Grant
-
2018
- 2018-08-17 CN CN201880003539.9A patent/CN109996898A/en active Pending
- 2018-08-17 JP JP2019512912A patent/JP6837541B2/en active Active
- 2018-08-17 WO PCT/KR2018/009428 patent/WO2019088419A1/en active Application Filing
- 2018-08-17 US US16/327,480 patent/US20210332459A1/en not_active Abandoned
- 2018-08-17 MY MYPI2019000594A patent/MY192447A/en unknown
- 2018-09-10 TW TW107131725A patent/TWI681933B/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000328157A (en) * | 1999-05-13 | 2000-11-28 | Kobe Steel Ltd | Copper alloy sheet excellent in bending workability |
| CN1269979C (en) * | 2004-01-23 | 2006-08-16 | 株式会社神户制钢所 | High-strength high-conductivity copper alloy |
| CN100510131C (en) * | 2004-08-17 | 2009-07-08 | 株式会社神户制钢所 | Copper alloy plate for electric and electronic parts having bending workability |
| CN101180412A (en) * | 2005-07-07 | 2008-05-14 | 株式会社神户制钢所 | Copper alloy with high strength and excellent processability in bending and process for producing copper alloy sheet |
| CN102782168A (en) * | 2010-02-08 | 2012-11-14 | 株式会社豊山 | Copper alloy having high strength and high conductivity, and preparation method thereof |
| KR20130136183A (en) * | 2012-06-04 | 2013-12-12 | 박효주 | Copper alloy element and the method for production same |
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| JP2020504231A (en) | 2020-02-06 |
| JP6837541B2 (en) | 2021-03-03 |
| MY192447A (en) | 2022-08-21 |
| US20210332459A1 (en) | 2021-10-28 |
| TW201922619A (en) | 2019-06-16 |
| KR101834335B1 (en) | 2018-04-13 |
| WO2019088419A1 (en) | 2019-05-09 |
| TWI681933B (en) | 2020-01-11 |
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