CN102560181A - Copper alloy material for electrical and electronic component - Google Patents
Copper alloy material for electrical and electronic component Download PDFInfo
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- CN102560181A CN102560181A CN2011103917536A CN201110391753A CN102560181A CN 102560181 A CN102560181 A CN 102560181A CN 2011103917536 A CN2011103917536 A CN 2011103917536A CN 201110391753 A CN201110391753 A CN 201110391753A CN 102560181 A CN102560181 A CN 102560181A
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Abstract
The present invention provides a copper alloy material for electrical and electronic components, which can stably inhibit the growth of intermetallic compounds and improve the solder joint reliability. The copper alloy material contains 0.05-0.5 by mass % of Fe, 0.05-0.5 % by mass of Ni, 0.02-0.2 by mass of P, 0.1-3% by mass of Zn, 0.02-0.3% by mass of Sn, while he rest is composed of Cu and unavoidable impurities. The mass ratio of above components satisfies the relationships of (Fe + Ni) / p = 3-10, Fe / Ni = 0.8-1.2, Zn / (Fe + Ni) is greater than or equal to 0.5, Sn / (Fe + Ni) is less than or equal to 0.5.
Description
Technical field
The present invention relates to as the for example copper alloy material for electrical/electronic part of the material of electrical and electronic parts such as semiconductor lead frame, bonder terminal.
Background technology
With regard to the installation of the semiconductor packages that is used for mobile telephone, notebook personal computer etc., utilize usually and used the joint of scolder and carry out.In the past, scolder mainly was a SnPb eutectic system scolder, but in recent years, Pb is restricted as objectionable impurities, and the lead-free solder that the Sn concentration ratio was higher in the past is widely used.
For above-mentioned semiconductor packages, to miniaturized, slimming development.Be accompanied by the material that uses thinner thickness of slab in the lead frame, thus the high material of desired strength.As the Cu alloy material that is used for above-mentioned lead frame, it is alloy (for example with reference to patent documentation 1) that the Cu-Fe-P that contains Fe and P is arranged.
As its representational example, the copper alloy (C19400) that for example contains Fe:2.1～2.6 quality %, P:0.015～0.15 quality %, Zn:0.05～0.2 quality % is as the alloy of standard and be widely known by the people.This alloy has following advantage: utilize thermal treatment and Fe or Fe-P compound are separated out in the parent phase of copper, thereby improve electroconductibility simultaneously respectively, heat conductivity, intensity.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 1-139736 communique
Summary of the invention
The problem that invention will solve
Along with developing to lead-free solder from widely used SnPb eutectic solder in the past, the problem that has not had before having produced.That is, most of lead-free solder is compared with SnPb eutectic solder in the past, and fusing point is high.Therefore, owing to use lead-free solder, thereby the Heating temperature during part bonding is higher than in the past.
When in the assembling procedure of electrical and electronic parts, heating repeatedly,, thereby promote the Sn mutual diffusion mutually in Cu and the scolder in the material because joint interface is high temperature.The result promotes formation, the growth of the intermetallic compound of Cu and Sn, and has exceeded degree in the past.Formed intermetallic compound is mainly Cu
6Sn
5And Cu
3Sn.Especially Cu
3Sn enbrittles, and when joint interface was grown, the safety of solder bonds can reduce greatly.Therefore, in order to improve the safety of solder bonds, suppress the important main points of being grown to serve as of this intermetallic compound.
In addition, the Cu-Fe-P that is widely used as above-mentioned materials is that Fe contained in the alloy is fast to the velocity of diffusion of solder layer, has the effect of the formation of the intermetallic compound that promotes Cu and Sn.Therefore, Cu-Fe-P is that Fe contained in the alloy measures when increasing, and intermetallic compound becomes and grows easily, is not preferred.
Therefore, the object of the present invention is to provide a kind of growth that can stably suppress intermetallic compound, improve the copper alloy material for electrical/electronic part of the safety of solder bonds.
Solve the method for problem
The inventor has carried out active research, and the result finds, when only the content of Fe, Ni, P, Zn and Sn being defined in a certain specific scope, stably suppresses the effect of growth of intermetallic compound and insufficient.The inventor etc. further find to be used for more stably to suppress the quality relation of the mass ratio of Sn/ (Fe+Ni) when of mass ratio, Zn/ (Fe+Ni) of mass ratio, Fe/Ni of (Fe+Ni)/P of the growth of intermetallic compound, thereby have accomplished the present invention.
Promptly; The present invention provides a kind of copper alloy material for electrical/electronic part; It is characterized in that; Contain the Fe of 0.05～0.5 quality %, the Ni of 0.05～0.5 quality %, the P of 0.02～0.2 quality %, the Zn of 0.1～3 quality %, the Sn of 0.02～0.3 quality %, there is the relation of (Fe+Ni)/P=3～10, Fe/Ni=0.8～1.2, Zn/ (Fe+Ni)>=0.5, Sn/ (Fe+Ni)≤0.5 in the mass ratio of these compositions, and remainder is made up of Cu and unavoidable impurities.
The present invention further provides a kind of copper alloy material for electrical/electronic part; It is characterized in that; Contain the Fe of 0.05～0.5 quality %, the Ni of 0.05～0.5 quality %, the P of 0.02～0.2 quality %, the Zn of 0.1～3 quality %, the Sn of 0.02～0.3 quality %; There is the relation of (Fe+Ni)/P=310, Fe/Ni=0.8～1.2, Zn/ (Fe+Ni)>=0.5, Sn/ (Fe+Ni)≤0.5 in the mass ratio of these compositions; Further contain more than one the composition among Zr, Cr, the Ti that is selected from that adds up to 0.03～1 quality %, remainder is made up of Cu and unavoidable impurities.
The invention effect
According to the present invention, can have HS and electroconductibility concurrently, and in solder bonds, keep stable joint quality.
Embodiment
Preferred implementation of the present invention below is described particularly.
The related copper alloy material for electrical/electronic part of this embodiment is used as the for example material of the lead frame of semiconductor packages aptly.
(composition of copper alloy)
With regard to the copper alloy in this embodiment; To contain the Fe of 0.05～0.5 quality %, the Ni of 0.05～0.5 quality %, the P of 0.02～0.2 quality %, the Zn of 0.1～3 quality %, the Sn of 0.02～0.3 quality %, the copper alloy that remainder is made up of Cu and unavoidable impurities is as base mateiral.Because the composition of this Albatra metal-, the Cu-Fe-P that can obtain to have than in the past is excellent more intensity of alloy and the harmonious material that has both intensity and electroconductibility well.
This Ni and Fe form P-compound through adding with P, and in material, disperse to separate out, thereby have the good specific conductivity of keeping material and the effect that improves intensity.
If the addition that makes P then can't form the P-compound of q.s less than 0.02 quality %, can't obtain can gratifying intensity.On the other hand, if the addition of P surpasses 0.2 quality % and adds,, thereby be not preferred then owing to when casting, during hot-work, break because of the segregation of P-compound causes easily.Therefore, preferably the compositing range of P is defined in the scope of 0.02～0.2 quality %.
To the compositing range of this P, have HS and high conductivity well concurrently in order to form compound and harmony effectively, need the compositing range of Fe be defined in 0.05～0.5 quality %, the compositing range of Ni is defined in 0.05～0.5 quality %.The content of Fe and Ni is lower than the following of above-mentioned compositing range prescribes a time limit, and the formation amount of P-compound is insufficient, undercapacity.On the other hand, the content of Fe and Ni surpasses going up in limited time of above-mentioned compositing range, and remaining Fe, Ni can be solid-solubilized among the Cu and specific conductivity is descended.
Zn is enriched in the boundary member with the joint interface place of scolder, becomes Cu and the Sn obstacle of mutual diffusion mutually, thereby has the formation that suppresses intermetallic compound, the effect of growth.In addition, Zn also has big effect for the improvement as the needed solder wettability of electronic unit material, Sn coating adaptation and resistance to migration when having the effect that improves intensity.
Zn is when being less than the content of specialized range of 0.1 quality %, is enriched on the interface with solder layer and to hinder the effect of Cu diffusion less, surpasses the specialized range of 3 quality % and contains sometimes, and is not preferred because of producing under the specific conductivity degradation detrimentally affect.
Raising has useful effect to Sn to intensity.Sn is when being less than the content of specialized range of 0.02 quality %; The effect that improves intensity is less, surpasses the specialized range of 0.3 quality % and contains sometimes, owing to produce degradation detrimentally affect under the specific conductivity; Make simultaneously intermetallic compound with the interface of solder layer on excess growth, therefore not preferred.
But, only when containing the composition of copper alloy of Fe, Ni, P, Zn and Sn, for the growth that stably suppresses intermetallic compound and insufficient.With regard to the basic comprising of this embodiment; Find: the quality of the mass ratio through will (Fe+Ni)/P, the mass ratio of Fe/Ni, Zn/ (Fe+Ni) the when mass ratio of Sn/ (Fe+Ni) is defined in the specified range, can stablize the growth of inhibition intermetallic compound.As these mass ratioes, satisfy (Fe+Ni)/P=310, Fe/Ni=0.8～1.2, Zn/ (Fe+Ni)>=0.5 and Sn/ (Fe+Ni)≤the 0.5th, very important.
Through being defined in the scope of (Fe+Ni)/P=3～10 and Fe/Ni=0.8～1.2; Can suppress to make the solid solution element amount among the Cu that specific conductivity descends; And effectively utilize because of the caused intensity of the dispersion of precipitate improves, thereby can obtain to have both the material of specific conductivity and intensity with the ideal harmony.
(Fe+Ni)/and the mass ratio of P was less than 3 o'clock, and P is superfluous during compound formation, and (Fe+Ni)/mass ratio of P surpasses at 10 o'clock, conversely, Fe, Ni are superfluous.Because it is not such excess components exists with solid solution condition in Cu, causes damaging the result of specific conductivity, therefore preferred.Be more preferably:, preferably select the scope of (Fe+Ni)/P=3～6 in order to make excess components still less.
Fe and Ni are for expecting the element that same effect is added to intensity and specific conductivity.But, be in the alloy at the Cu-Fe-P that has only added Fe, become the characteristic of low strength, high conductivity easily, and when only adding Ni, become the characteristic of HS, low conductivity easily.Therefore, in order to obtain the harmonious good material of intensity and specific conductivity, Fe and Ni made up to add be effective.Study it and cooperate ratio, the result can know: through adding with 1 to 1 ratio roughly, can obtain desirable characteristic.Therefore, as clog-free scope in the practicality, the mass ratio of Fe and Ni is defined as Fe/Ni=0.8～1.2.
In addition; Mass ratio through with Zn/ (Fe+Ni) is defined as more than 0.5; Have the Zn of growth inhibitory effect with Ni with certain above ratio interpolation with respect to Fe, thereby can synthetically suppress the growth of intermetallic compound with the effect that promotes intermetallic compound growth.In addition, be defined as more than 0.5, can add the Sn of appropriate amount through mass ratio with Zn/ (Fe+Ni).
The mass ratio of Zn/ (Fe+Ni) is less than 0.5 o'clock and since with the interface of solder layer on the enrichment of Zn composition insufficient, the obstruction effect of mutual diffusion is little mutually to Cu and Sn, thereby can not fully obtain the growth inhibitory effect of intermetallic compound, so not preferred.
On the other hand, the mass ratio of Sn/ (Fe+Ni) surpasses at 0.5 o'clock because with respect to the amount of suitable (Fe+Ni), the Sn amount increases, thereby with the interface of solder layer on can promote the growth of intermetallic compound, therefore not preferred.
If the excessive interpolation of Sn, then performance promotes the effect of the growth of intermetallic compound.If but addition is few, then the effect of intensity raising is also little.Mass ratio through with Sn/ (Fe+Ni) is defined in the scope below 0.5, can add the Sn of appropriate amount.
As stated, contain the mass ratio of moity of the copper alloy of Fe, Ni, P, Zn, Sn through special stipulation, can stably suppress the growth of intermetallic compound.
(minor component of copper alloy)
The related copper alloy of this embodiment also can be further adds more than one the composition that is selected among Zr, Cr and the Ti with the scope that adds up to 0.03 quality %～1 quality %.The element of these Zr, Cr and Ti plays a role to the raising of intensity effectively, has the effect that improves thermotolerance and prevent the strength degradation under the high temperature simultaneously.Can further expect the stable superperformance that suppresses the growth of intermetallic compound.
Zr and Cr are to have the intensity of raising, stable on heating effect, the less minor component as characteristic of detrimentally affect that simultaneously specific conductivity is caused.But,, then produce detrimentally affects such as castibility variation if content is too much.Ti also is the minor component that improves intensity, stable on heating effect excellence.
The element of these Zr, Cr and Ti can be expected the stable such effect of growth that suppresses intermetallic compound through separately or make up and add.But, if it adds up to content to surpass 1 quality %, then because detrimentally affects such as specific conductivity decline, castibility variation are significantly and not preferred.Therefore, as the total compositing range of Zr, Cr and Ti, preferably be defined as below the 1 quality %.
(effect of embodiment)
The related copper alloy of above-mentioned embodiment has following effect.
(1) is the alloy phase ratio with in the past Cu-Fe-P, has more excellent intensity,, also keep good characteristic for electroconductibility.
(2) has following characteristic: in the growth of the intermetallic compound that produces at the interface, prevent the embrittlement at junction surface after the inhibition solder bonds, in the installation of having used lead-free solder, have good joint quality.
(3) this material is suitable as lead frame most, especially for electrical and electronic parts such as semiconductor packages, supports from the material aspect with the mode of the material of supplying with low price and high characteristic, can go far towards its development.
Embodiment
Below, with reference to table 1 with 2 on one side enumerate embodiment 1～13 (sample No.1～13) and comparative example 1～13 (sample No.1～13) as of the present invention more concrete embodiment be elaborated on one side.In addition, enumerate a typical example of above-mentioned embodiment among this embodiment, the present invention is not limited to these embodiment and comparative example certainly.
Below table 1 expression is as the composition and the mass ratio of the sample of embodiment 1～13 and comparative example 1～13, and below table 2 is represented the characteristic value of embodiment 1～13 and comparative example 1～13.
[embodiment 1]
To with oxygen free copper mother metal; The copper alloy starting material that contain Fe:0.2 quality %, Ni:0.2 quality %, P:0.1 quality %, Zn:0.4 quality %, Sn:0.1 quality % carry out melting in high-frequency melting furnace, be cast as the ingot of thick 25mm, wide 30mm, long 150mm.Be heated to 950 ℃, be hot-rolled down to thickness 8mm after, be cold-rolled to thickness 2mm, 450 ℃ annealing 1 minute.Further it is cold-rolled to thickness 0.25mm, 450 ℃ of annealing 1 minute, thus the copper alloy shown in the embodiment 1 of making table 1.
For the as above copper alloy of such embodiment 1 that makes, measure each characteristic value of tensile strength, elongation, specific conductivity.The result can obtain tensile strength 612MPa, elongation 10%, the such superperformance that is suitable for the object of the invention of specific conductivity 64%IACS.
After further the sample No.1 of embodiment 1 being carried out the degreasing pickling, impregnated in the fused Sn-3 quality %Ag-0.5 quality %Cu scolder, at the two sided coatings scolder of sample No.1.Put it in the thermostatic bath that remains on 200 ℃, implement heating in 1 hour.Imbed in the resin sample No.1 after the heating and cut-out, carry out the observation of section, be determined at the thickness of the Cu-Sn intermetallic compounds layer of the interface portion formation between resin material and the scolder.There is zero defect (crackle, hole) at inside, the interface observed then at intermetallic compounds layer.As a result, intermetallic compounds layer is thinner, is 4 μ m, does not also find defectives such as crackle, hole.
[embodiment 2～13]
Next, melting and casting has shown in the table 1 copper alloy of sample No.2～13 of forming (embodiment 2～13), according to processing thermal treatment with the foregoing description 1 identical operation, thereby makes the sample of thickness 0.25mm.For these samples No.2～13, also through measuring each characteristic value of tensile strength, elongation and specific conductivity with the same method of the foregoing description 1, and the thickness of research coating scolder and the intermetallic compounds layer when heating and zero defect is arranged.
The characteristic conclusion of the copper alloy among each embodiment 2～13 is shown in table 2.Can find out that by table 2 embodiment 2～13 all has above the high conductivity of 60%IACS simultaneously and surpasses the HS of 600MPa, can obtain to have the lead frame of the copper alloy of sufficient conductivity and intensity as slim encapsulation.In addition, also thinner with the intermetallic compound at the interface of scolder, do not find defectives such as crackle, hole yet, embodiment 2～13 all has both the superperformance that is suitable for the object of the invention.
[comparative example]
Next, enumerate the qualification reason that comparative example explains that the related copper alloy of above-mentioned embodiment is formed.
Melting and casting has shown in the table 1 copper alloy of the comparative example of forming 1～13 (sample No.1～13), according to processing thermal treatment with the foregoing description 1 identical operation, thereby makes sample No.1～13 of thickness 0.25mm.
For sample No.1～13 of the comparative example of gained, through measuring each characteristic value of tensile strength, elongation and specific conductivity with the foregoing description 1 same method, and the thickness of research coating scolder and the intermetallic compound when heating and zero defect is arranged.The characteristic conclusion of the copper alloy in the comparative example 1～13 is shown in table 2.
[comparative example 1 and 2]
As shown in table 1, the sample No.1 of comparative example and No.2 are the example of addition beyond the specialized range of the related copper alloy composition of above-mentioned embodiment of Fe, Ni and P.The sample No.1 of comparative example is the low excessively example of the addition of Fe, Ni and P composition.Can be found out that by table 2 this situation is compared with the foregoing description, the result is: tensile strength is low, can not obtain abundant intensity.
On the other hand, as shown in table 1, the sample No.2 of comparative example is the too much example of the addition of Fe, Ni and P composition.Can be found out that by table 2 this situation is compared with the foregoing description, specific conductivity reduces, and the value of elongation reduces.The low material of elongation is owing to break through the bending machining of lead frame easily, so can not satisfy the object of the invention.
[comparative example 3 and 4]
As shown in table 1, the sample No.3 and the No.4 of comparative example is the example of mass ratio beyond the specialized range of the related copper alloy composition of above-mentioned embodiment of (Fe+Ni)/P.Can be found out that by table 2 result is: when Fe and Ni are superfluous and P when superfluous, compare with the foregoing description, specific conductivity all descends.In addition, from tensile strength, comparing with the foregoing description also is low value.
[comparative example 5 and 6]
As shown in table 1, the example of the mass ratio that the sample No.5 of comparative example and No.6 are Fe/Ni beyond the specialized range of the related copper alloy composition of above-mentioned embodiment.Can be found out that by table 2 result is: the sample No.5 of the comparative example that the ratio of Fe is too high compares with the foregoing description, and tensile strength is not enough.The sample No.6 of the comparative example that the ratio of Ni is too high compares with the foregoing description, and specific conductivity is lower.
[comparative example 7 and 8]
As shown in table 1, the example of the mass ratio of addition that the sample No.7 of comparative example and No.8 are Zn or Zn/ (Fe+Ni) beyond the specialized range of the related copper alloy composition of above-mentioned embodiment.Can find out by table 2, the sample No.7 of the insufficient comparative example of mass ratio of, Zn/ (Fe+Ni) few for the addition of Zn, the growth inhibitory effect of the intermetallic compounds layer that is caused by Zn is insufficient, and intermetallic compounds layer is grown than heavy back.In addition, on the interface of material and intermetallic compounds layer, observe hole, the safety of solder bonds is insufficient.The sample No.8 of the comparative example that the addition of Zn is too much compares with the foregoing description, and specific conductivity worsens.
[comparative example 9 and 10]
As shown in table 1, the mass ratio of addition that the sample No.9 of comparative example and No.10 are Sn or Sn/ (Fe+Ni) is beyond the specialized range of the related copper alloy composition of above-mentioned embodiment and an example of the excessive interpolation of Sn.Can be found out that by table 2 sample No.9 compares with the foregoing description with No.10, specific conductivity all reduces, and the intermetallic compounds layer of solder interface is all grown than heavy back.In addition, on the interface of material and intermetallic compounds layer, observe hole, the safety of solder bonds is insufficient.
[comparative example 11～13]
As shown in table 1, sample No.11～the 13rd of comparative example, the addition of Zr, Cr and the Ti that adds as minor component is beyond the specialized range of the related copper alloy composition of above-mentioned embodiment and an excessive example.Can be found out that by table 2 this situation is compared with the foregoing description, specific conductivity worsens, and elongation also reduces greatly simultaneously, thus the problem that the processibility of generation bending machining etc. worsens.
By on can know, do not meet the compositing range stipulated in the related copper alloy of above-mentioned embodiment and the above-mentioned comparative example of mass ratio and compare with above-mentioned each embodiment, all can only obtain inadequate characteristic.
The copper alloy related according to the foregoing description compared with copper alloy in the past, can keep good intensity, specific conductivity, and in the joint that has used lead-free solder, keeps stable joint quality.Such characteristic can be used to develop the electric/electronic device of miniaturized effectively, and the degree of freedom of expansion design significantly.In addition, aspect manufacturing cost, the related copper alloy of the foregoing description can be making with equal the becoming originally of copper alloy in the past, thereby do not have the problem in the practicality.
Table 1
Table 2
Claims (2)
1. copper alloy material for electrical/electronic part; It is characterized in that; Contain the Fe of 0.05～0.5 quality %, the Ni of 0.05～0.5 quality %, the P of 0.02～0.2 quality %, the Zn of 0.1～3 quality %, the Sn of 0.02～0.3 quality %; There is the relation of (Fe+Ni)/P=3～10, Fe/Ni=0.8～1.2, Zn/ (Fe+Ni)>=0.5, Sn/ (Fe+Ni)≤0.5 in the mass ratio of these compositions, and remainder is made up of Cu and unavoidable impurities.
2. copper alloy material for electrical/electronic part; It is characterized in that; Contain the Fe of 0.05～0.5 quality %, the Ni of 0.05～0.5 quality %, the P of 0.02～0.2 quality %, the Zn of 0.1～3 quality %, the Sn of 0.02～0.3 quality %; There is the relation of (Fe+Ni)/P=310, Fe/Ni=0.8～1.2, Zn/ (Fe+Ni)>=0.5, Sn/ (Fe+Ni)≤0.5 in the mass ratio of these compositions; Further contain more than one the composition among Zr, Cr, the Ti that is selected from that adds up to 0.03～1 quality %, remainder is made up of Cu and unavoidable impurities.
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| JP2010273454A JP5715399B2 (en) | 2010-12-08 | 2010-12-08 | Copper alloy material for electrical and electronic parts |
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| CN103088229A (en) * | 2012-11-06 | 2013-05-08 | 北京有色金属研究总院 | Low-cost copper alloy for socket connectors and processing method thereof |
| CN103088229B (en) * | 2012-11-06 | 2015-04-15 | 北京有色金属研究总院 | Low-cost copper alloy for socket connectors and processing method thereof |
| CN104870672A (en) * | 2012-12-28 | 2015-08-26 | 三菱综合材料株式会社 | Copper alloy for electrical and electronic equipment, copper alloy thin sheet for electrical and electronic equipment, and conductive part and terminal for electrical and electronic equipment |
| CN103643076A (en) * | 2013-11-27 | 2014-03-19 | 余姚市士森铜材厂 | Preparation method of precipitation hardening type copper alloy |
| CN103667775A (en) * | 2013-11-27 | 2014-03-26 | 余姚市士森铜材厂 | Copper alloy semiconductor lead frame |
| CN103643076B (en) * | 2013-11-27 | 2016-01-06 | 余姚市士森铜材厂 | A kind of preparation method of precipitation hardenable copper alloy |
| CN103667775B (en) * | 2013-11-27 | 2016-04-13 | 余姚市士森铜材厂 | A kind of Copper alloy semiconductor lead frame |
| CN105063418A (en) * | 2015-07-24 | 2015-11-18 | 宁波金田铜业(集团)股份有限公司 | Low-alloying copper belt and preparation method thereof |
| CN105220007A (en) * | 2015-10-29 | 2016-01-06 | 安徽鑫科新材料股份有限公司 | A kind of high-strength copper ferrophosphor(us) and production method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5715399B2 (en) | 2015-05-07 |
| JP2012122095A (en) | 2012-06-28 |
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