CN103160703A - High-strength copper alloy plate excellent in oxide film adhesiveness - Google Patents
High-strength copper alloy plate excellent in oxide film adhesiveness Download PDFInfo
- Publication number
- CN103160703A CN103160703A CN2012105090363A CN201210509036A CN103160703A CN 103160703 A CN103160703 A CN 103160703A CN 2012105090363 A CN2012105090363 A CN 2012105090363A CN 201210509036 A CN201210509036 A CN 201210509036A CN 103160703 A CN103160703 A CN 103160703A
- Authority
- CN
- China
- Prior art keywords
- copper alloy
- alloy plate
- oxide film
- annealing
- cu2p
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
-
- 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
- C22C9/02—Alloys based on copper with tin as the next major constituent
-
- 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
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- 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
-
- 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
- H01L23/495—Lead-frames or other flat leads
- H01L23/49579—Lead-frames or other flat leads characterised by the materials of the lead frames or layers thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Abstract
The present invention is a Cu-Fe-P system copper alloy plate comprising Fe: 0.02-0.5% and P: 0.01-0.25% in mass % with the balance consisting of copper and unavoidable impurities and having the ratio Fe/P of Fe to P in mass % being 2.0 to 5.0, wherein: a ratio of the area of fine crystal grains less than 0.5 mum in equivalent circle diameter to an observation area when a surface is observed by EBSD analysis is 0.90 or less; and the ratio C1s/Cu2p of a peak area of C1s to a peak area of Cu2p on the surface by XPS analysis is 0.35 or less.
Description
Technical field
The present invention relates to make the copper alloy plate of the oxide film adhesion improves Cu-Fe-P system.
Background technology
In the following description, as the representational purposes example of copper alloy plate of the present invention, describe centered by the situation as the lead frame of semiconductor device being used for.
As the semiconductor lead frame copper alloy, general what use is the copper alloy that contains the Cu-Fe-P system of Fe and P.
On the other hand, as the plastic package of semiconductor device, by the main flow that is encapsulated into of thermosetting resin encapsulation of semiconductor chip.
But, have when assembling and the encapsulation crackle that when use occurs and the problem of peeling off.
At this, described problem is to cause because the adhesion of resin and lead frame is bad.What this adhesion was caused maximum effect is the oxide film of lead frame mother metal.In the various heating processes that lead frame is made, on the surface of mother metal, can form the oxide film of tens of～hundreds of nm thickness, copper alloy contacts with resin via this oxide film.Peeling off of this oxide film and lead frame mother metal directly brought peeling off of resin and lead frame, and the adhesion of lead frame and resin is significantly reduced.
Therefore, encapsulate crackle and the problem of peeling off, be the adhesion of this oxide film and lead frame mother metal.Therefore, for the copper alloy plate that the described Cu-Fe-P as the lead frame mother metal is, require the adhesion of its oxide film that is formed at the surface through various heating processes high.
For this problem, JP 2008-45204 communique (below, be called patent documentation 1.) the middle proposition, in the composition that Fe content is reduced to below 0.50 quality %, by set tissue and the average crystal grain diameter on control copper alloy plate surface, and the oxide film adhesion is improved.Namely, in patent documentation 1, has following set tissue, namely, distribution of orientations density that measure as the crystalline orientation analytical procedure of EBSP by the EBSD that has used the copper alloy plate surface, Brass orientation is more than 25%, and to make average crystal grain diameter be below 6.0 μ m.
In addition, JP 2008-127606 communique (below, be called patent documentation 2.) in propose, make during Fe content is reduced to composition below 0.50 quality % equally, by controlling surfaceness and the configuration of surface on copper alloy plate surface, and the oxide film adhesion is improved.That is, the center line average roughness Ra of the surface finish measurement on copper alloy plate surface is below 0.2 μ m, and maximum height Rmax is below 1.5 μ m, and the gradient of roughness curve (steepness) Rku is below 5.0.
But this patent documentation 1,2 disclosed Cu-Fe-P series copper alloy plates can not be realized desired in recent years higher levels of oxide film adhesion.
Summary of the invention
The object of the invention is to, provide a kind of and make during Fe content reduces in fact composition below 0.5 quality %, the Cu-Fe-P series copper alloy plate that the desired higher levels of oxide film adhesion in recent years of high strength is existed side by side.
in order to reach this purpose, the high strength copper alloy plate of oxide film adhesion excellence of the present invention, it is characterized in that, has following composition, namely in quality %, contain respectively Fe:0.02～0.5%, P:0.01～0.25%, surplus is made of copper and inevitable impurity, the quality % of Fe and P is 2.0～5.0 than Fe/P, in addition, when analyzing effects on surface and observe by EBSD, be below 0.90 with respect to the diameter of equivalent circle of viewing area lower than the Area Ratio of the fine-grain of 0.5 μ m, and, be below 0.35 based on the peak area value of the C1s on the surface of XPS analysis for the ratio C1s/Cu2p of the peak area value of Cu2p.
In the high strength copper alloy plate of above-mentioned oxide film adhesion excellence, the C1s/Cu2p on the surface that is obtained by XPS analysis, as described later, the meaning is the C amount of the relativity on copper alloy plate surface.For the C1s/Cu2p that makes the copper alloy plate surface is reduced to below 0.35, before the alkaline catholyte that generally is carried out as the processing of the pre-treatment of plating etc. cleans, need to be in advance from the surface of copper alloy plate, during alkaline catholyte is cleaned, inexpungible C removes in the source substantially fully.
In other words be exactly, if the surface of the copper alloy plate before cleaning from alkaline catholyte, during alkaline catholyte is cleaned, inexpungible C source is removed substantially fully, after carrying out alkaline catholyte cleaning, the C1s/Cu2p that can access the surface that obtains by XPS analysis is below 0.35, the copper alloy plate of oxide film adhesion excellence.
Copper alloy plate of the present invention, with patent documentation 1,2 described existing copper alloy plates be equal high strength.In addition, by analyzing with EBSD the Area Ratio of the fine-grain when observing for the surface of copper alloy plate of the present invention, be limited in below 0.35 with the C1s/Cu2p on the surface that obtains by XPS analysis, can realize desired in recent years higher levels of oxide film adhesion.Consequently, according to the present invention, can provide prevent from encapsulating crackle and peel off, the semiconductor device that reliability is high.
For copper alloy plate, as processing of the pre-treatment of plating etc., generally carrying out alkaline catholyte cleans, if but the surface of the copper alloy plate before cleaning from this alkalescence catholyte, during alkaline catholyte is cleaned, inexpungible C removes in the source substantially fully, can access after alkaline catholyte cleans, the C1s/Cu2p by XPS analysis resulting surface is below 0.35, the copper alloy plate of oxide film adhesion excellence.
Embodiment
Below, use etc. as semiconductor lead frame, illustrate meaning and embodiment be used to each important document of the Cu-Fe-P series copper alloy plate performance of satisfying the demand, of the present invention.
" one-tenth of copper alloy plate is grouped into "
In the present invention, use as semiconductor lead frame etc., in order to reach in the lump high strength and excellent oxide film adhesion, Cu-Fe-P series copper alloy plate has as an essentially consist: in quality %, the content of Fe is 0.02～0.5% scope, the content of P is 0.01～0.25% scope, and the quality % of Fe and P is 2.0～5.0 than Fe/P, and surplus is made of Cu and inevitable impurity.
Also following mode can be arranged, namely for this essentially consist, contain again the mode of a kind of of Sn, Zn or two kinds in following ranges.In addition, other inevitable impurity element, containing also in the scope that does not hinder characteristic allows.Also have, the expression % of the content of the inevitable impurity element of alloying element is all the meaning of quality %.
(Fe)
Fe separates out as Fe or Fe base intermetallic compound, is to make the intensity of copper alloy and the principal element that thermotolerance improves.The content of Fe is lower than 0.02% the time, and the growing amount of above-mentioned precipitation particles is few, and is not enough to the help that intensity improves, undercapacity.On the other hand, if the content of Fe surpasses 0.5%, thick crystallization/precipitate particle easily generates, and etching (smoothness of etching and processing face) and plating (smoothness of Ag plating etc.) reduce, in addition, also saturated to the help of intensity raising.Therefore, the content of Fe is 0.02～0.5% scope.In addition, be preferably 0.04～0.4%, more preferably 0.06～0.35%.
(P)
P also forms compound with Fe except desoxydatoin is arranged, be to make the intensity of copper alloy and the principal element that thermotolerance improves.P content is lower than 0.01% the time, and separating out of compound is insufficient, the intensity that therefore can not get expecting.On the other hand, if P content surpasses 0.25%, hot workability and oxide film adhesion reduce.Therefore, the content of P is 0.01～0.25% scope.In addition, be preferably 0.015～0.2%, more preferably 0.02～0.15%.
(Fe/P)
The quality % of Fe and P is than the regulation that is Fe/P, is in order to make the fine Fe that helps intensity and the compound of P separate out expeditiously needed regulation.Fe/P was lower than 2.0 o'clock, and with respect to the quality % of Fe, the quality % of P is too high, therefore help the growing amount deficiency of the fine Fe-P compound of intensity, and the P of solid solution condition was residual in a large number, and the adhesion of intensity and oxide film reduces.On the other hand, if Fe/P surpasses 5.0, with respect to the quality % of Fe, the quality % of P is too low, therefore help equally the growing amount deficiency of the fine Fe-P compound of intensity, and the Fe of solid solution condition is residual in a large number, and the adhesion of intensity and oxide film reduces.Therefore, Fe/P is 2.0～5.0 scope.In addition, be preferably 2.2～4.7, more preferably 2.4～4.4.
(Sn)
Sn helps the intensity of copper alloy to improve.The content of Sn is helpless to high strength lower than 0.005% the time.On the other hand, if the content of Sn contains over 3% superfluously, the solid solution capacity of Fe or Fe-P compound reduces, and the thick crystallization of Fe or Fe-P compound/precipitate particle easily generates, the effect that intensity improves diminishes, and hot workability and the reduction of oxide film adhesion.Therefore, optionally contain Sn content sometimes, the balance of intensity desired according to purposes and oxide film adhesion, the scope from 0.005～3% is selected.In addition, be preferably 0.008～2.7%, more preferably 0.01～2.4%.
(Zn)
Zn improves the welding of the needed copper alloys such as lead frame and the heat-resisting separability of Sn plating, and improves the oxide film adhesion, helps the intensity of copper alloy to improve.The content of Zn lower than 0.005% the time, the effect that can not get expecting.On the other hand, if surpass 3%, the solid solution capacity of Fe or Fe-P compound reduces, and the thick crystallization of Fe or Fe-P compound/precipitate particle easily generates, and the effect that intensity improves diminishes, and hot workability reduces.In addition, the oxide film adhesion to improve effect also saturated.Therefore, optionally contain the content of Zn sometimes, consider the desired intensity of purposes and oxide film adhesion, the scope from 0.005～3% is selected.In addition, be preferably 0.008～2.7%, more preferably 0.01～2.4%.
(impurity that can not keep away)
The said impurity that can not keep away of the present invention is such as the element that Mn, Mg, Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Ni, Au, Pt etc. are arranged.If contain these elements, thick crystallization/precipitate particle easily generates, and makes in addition strength decreased.Therefore, preferably in total amount, making it is the following few content of 0.2 quality %.The element of Hf, the Th that in addition, trace contains in copper alloy, Li, Na, K, Sr, Pd, W, S, Si, C, Nb, Al, V, Y, Mo, Pb, In, Ga, Ge, As, Sb, Bi, Te, B, norium etc. is also the impurity that can not keep away.Easily generate if contain thick crystallization of these elements/precipitate particle, hot workability is reduced, therefore in total amount, preferably it is suppressed at the few content of De Very Xia 0.1 quality % Yi.In addition, the O that trace contains in copper alloy makes and adds the element oxidation, and effective interpolation amount of element is reduced, and makes strength decreased, preferably it is suppressed at thus the few content below 50 quality ppm.In addition, the H that trace contains in copper alloy becomes makes the essential factor that produces defective (pore and expansion etc.) in copper alloy, therefore preferably it is suppressed at the few content below 5 quality ppm.
" with respect to the EBSD analysis and observation viewing area in when surface, diameter of equivalent circle is below 0.90 lower than the Area Ratio of the fine-grain of 0.5 μ m "
During with EBSD analysis and observation copper alloy plate surperficial, the Area Ratio of so-called fine-grain (diameter of equivalent circle is lower than 0.5 μ m) with respect to viewing area, the meaning be exactly the copper alloy plate surface fine-grain occupy ratio.At this, so-called EBSD analyzes, and is exactly Electron Back-Scattered Diffraction analysis (Electron Backscatter Diffraction Analysis), is the method for analyzing the distribution of the size of crystal grain and orientation etc.In addition, at this said crystal grain, be to analyze by EBSD, be that situation more than 5 ° is considered as crystal boundary with the misorientation between the measurement point of adjacency, the zone that surrounds fully of crystal boundary thus.The said diameter of equivalent circle of the present invention is to have circular diameter of the same area with described zone.This Area Ratio does not change in the front and back that alkaline catholyte cleans.
The Area Ratio of the fine-grain on copper alloy plate surface is large, and fine crystal grain exists in a large number, has a large amount of crystal grain boundaries, and the defective that is caused by crystal grain boundary is imported in oxide film in a large number, and the adhesion of oxide film reduces.Therefore, the less side of Area Ratio of the fine-grain on expectation copper alloy plate surface is below 0.90.In addition, be preferably below 0.85, more preferably below 0.80.
" being below 0.35 for the ratio C1s/Cu2p of the peak area value of Cu2p based on the peak area value of the C1s on the surface of XPS analysis "
The peak area value of the C1s on so-called surface based on XPS analysis is for the ratio C1s/Cu2p of the peak area value of Cu2p, and the meaning can be described as the relative C amount on copper alloy plate surface.So-called XPS analysis is X-ray photoelectron spectroscopic analysis, also claims esca analysis (Electron Spectroscopy for Chemical Analysis), is to be good at the composition of surface layer as thin as a wafer and the analytical procedure of state analysis.The C that detects from the surface of copper alloy plate, usually from various pollution substances (organism, inorganics), and the organic rust preventing film (benzotriazole etc.) of also processing from being used for preventing the variable color of copper alloy plate etc.Be attached to the amount in these C source on copper alloy plate surface, be reflected as the size of the described C1s/Cu2p on copper alloy plate surface.
If above-mentioned C source is present in the copper alloy plate surface, all the adhesion of oxide film is caused detrimentally affect.This be considered to due to, the defective that is caused by above-mentioned C source is imported in oxide film, causes thus easily generating the many oxide films of defective.Therefore, the less side of value of the described C1s/Cu2p of expectation is below 0.35 in the present invention.In addition, be preferably below 0.30, more preferably below 0.25.
, the copper alloy plate that the lead frame of semiconductor device uses after having carried out comprising the pre-treatment that alkaline catholyte cleans, can partially carry out the plating of Ag plating etc. and is provided to assembly process.The adhesion of the oxide film that generates through the thermal process of this assembly process is with the reliability of left and right encapsulation.Therefore, the adhesion of oxide film being impacted, is to comprise C amount after the pre-treatment that alkaline catholyte cleans for copper alloy plate.If this C amount is many, the surface of the copper alloy plate before alkaline catholyte cleans, can be attached with in a large number and can not be cleaned the C source of removing by alkaline catholyte.Also have, the general organic rust preventing film (benzotriazole etc.) that uses for the variable color that prevents copper alloy plate is cleaned by alkaline catholyte and easily removes.
At this, so-called alkaline catholyte cleans, and is in the aqueous solution of alkalescence, and making object is that negative electrode carries out electrolysis, the stirring action of the machinery that the hydrogen that utilization occurs from the surface of object brings improves the purging method of cleaning force, itself is from known purging method.The alkaline aqueous solution that present method is used, generally take the alkali salt of sodium hydroxide, water glass, sodium phosphate, sodium carbonate etc. as the basis, add the organism of tensio-active agent and chelate compound etc. and consist of, owing to carrying out electrolysis with object as negative electrode, so oxidation and dissolving etc. can not occur in the surface of copper alloy plate, can not be subject to any damage.Therefore, if adopt alkaline catholyte to clean, the organic rust preventing film of the organism of the rolling wet goods that uses when the manufactured copper alloy sheets and benzotriazole etc. can be removed at an easy rate.
But even use alkaline catholyte to clean, rolling wet goods is under the effect of heat etc. and rotten, deteriorated organism etc. (roasting hard shape etc.) occurs still can not remove.The surface of the copper alloy plate before alkaline catholyte cleans, thisly can not clean the organism removed etc. by alkaline catholyte if be attached with, after alkaline catholyte cleans, it still can remain in the copper alloy plate surface as the C source, the value of the C1s/Cu2p on copper alloy plate surface uprises, the adhesion of oxide film reduces, and the reliability of encapsulation reduces.Therefore, in the stage before alkaline catholyte cleans, importantly from the surface of copper alloy plate, remove in advance and can not clean the C source of removing by alkaline catholyte.
" tensile strength of the direction parallel with rolling direction is more than 500MPa, and the tension set of the direction parallel with rolling direction is more than 5% "
Copper alloy plate of the present invention, as the target of high strength material, the tensile strength that is preferably the direction parallel with rolling direction is more than 500MPa.In addition, the tension set that is preferably the tension test of the direction parallel with rolling direction is more than 5%.Copper alloy plate of the present invention, by having the tension set of appropriateness, therefore the bendability that can keep the needed appropriateness of the former material of used for lead frame becomes the former material, particularly lead frame for semiconductor device that are suitable as electric, electronic unit with the copper alloy plate of former material.With respect to this, the tension set of the tension test of the direction parallel with rolling direction is lower than 5% the time, the bendability that can not keep the needed appropriateness of the former material of used for lead frame be cannot say for sure to be suitable as the former material of former material, particularly lead frame for semiconductor device electric, electronic unit.Also have, the tension set more than 5% if copper alloy of the present invention forms, can be reached by manufacture method described later at an easy rate.In addition, about the tensile strength more than 500MPa, remove alloying element amount extremely thin zone, also can be reached at an easy rate by manufacture method described later.
(creating conditions)
Next, carry out following explanation with regard to the creating conditions of expectation that is used for making copper alloy plate be organized as the tissue of the invention described above regulation.
That is, at first, casting is adjusted into the molten soup of copper alloy that above-mentioned one-tenth is grouped into.Then, after ingot bar is carried out face milling, heat or the thermal treatment that homogenizes, carry out thereafter hot rolling, the plate of delaying for heat carries out water-cooled.This hot rolling can be common condition.
Thereafter, the once cold rolling of rolling in being called after annealing, cleaning, then processes that (finally) is cold rolling, low-temperature annealing (also claim final annealing, mechanical refining, go strain annealing etc.), becomes the copper alloy plate of goods thickness of slab etc.These annealing and cold rollingly also can repeatedly carry out.Also have, along with the miniaturization of semiconductor device, the fine distribution of the highly integrated lead frame that brings, about the planeness of plate (Off ラ Star ト ネ ス: flatness) and the quality requirements that reduces of internal stress day by day improve, the low-temperature annealing of process after cold rolling improves effective to this quality.The semi-conductor that is used for lead frame etc. is about 0.1～0.4mm with the goods thickness of slab in this situation of copper alloy plate of material.
Also have, before once cold rolling, also can carry out the solution treatment of copper alloy plate and the quench treatment of being undertaken by water-cooled.At this moment, solid solution temperature is for example selected from the scope of 750～1000 ℃.
The final cold rolling ordinary method of also following.
Fine-grain (diameter of equivalent circle is lower than 0.5 μ m) when surperficial by the aforesaid copper alloy plate of EBSD analysis and observation in order to make is below 0.90 with respect to the Area Ratio of viewing area, and make based on the peak area value of the C1s on the surface of XPS analysis for the ratio C1s/Cu2p of the peak area value of Cu2p below 0.35, implement following such operation and get final product.
At first, fine-grain (diameter of equivalent circle is lower than 0.5 μ m) when surperficial by the aforesaid copper alloy plate of EBSD analysis and observation in order to make is below 0.90 with respect to the Area Ratio of viewing area, importantly do not carry out mechanical mill after annealing, or (kind hand) of increase mechanical mill, reduce thus the granularity of abrasive, make the crystal grain on top layer keep greatly as far as possible.In addition, even carry out mechanical mill, thereafter, and the dissolution process by chemistry and electrochemical dissolution process etc., removing the fine crystalline layer that generates in mechanical mill is also effective means.Always, mostly carry out afterwards mechanical mill in annealing.This is because the oxide film that generates in annealing is firm, has the situation that only is difficult to remove by pickling.Therefore, in order not carry out mechanical mill, perhaps reduce the load of mechanical mill and reduce the Area Ratio of fine-grain, importantly fully manage annealing atmosphere, firm oxide film is generated.Specifically, importantly making annealing atmosphere is that also first atmosphere (contains H
2The also atmosphere of unit's property composition with CO etc.), oxidisability composition (O
2And H
2O etc.) management in alap concentration, does not generate firm oxide film.Particularly expectation in the low-temperature annealing operation as final operation, is fully managed annealing atmosphere, so that the mode that firm oxide film does not generate is controlled, can carry out thus only removing with the oxide film of pickling, does not carry out mechanical mill.
Then, be below 0.35 in order to make based on the peak area value of the C1s on the copper alloy plate surface of XPS analysis for the ratio C1s/Cu2p of the peak area value of Cu2p, importantly carry out clean in the front and back of annealing.In general, after annealing, for the residue removing the oxide film that generates in annealing and caused by ROLLING OIL and carry out pickling and grinding etc., but only have cleaning after annealing to be difficult to effectively to carry out removing of residue of particularly being caused by ROLLING OIL etc., it is carrying out after alkaline catholyte as the pre-treatment of plating cleans, still can remain in the copper alloy plate surface, the C quantitative change on copper alloy plate surface is many, and the oxide film adhesion reduces.In addition, if only want by the cleaning after annealing, fully carry out removing of the residue that caused by ROLLING OIL etc., also can produce the time of cleaning that extends, or reduce the loss of the designation (increasing the granularity of abrasive) etc. of abrasive.Also have, if reduce kind hand of abrasive, the fine-grain on copper alloy plate surface increases, and roughness also becomes greatly, becomes on the contrary the essential factor of reduction oxide film adhesion.Therefore, in order effectively to carry out removing of such residue that is caused by ROLLING OIL etc., effectively not only after annealing, but also carry out clean before annealing, particularly must carry out clean before the low-temperature annealing as final operation, carry out after this external low-temperature annealing the oxide film that undertaken by pickling etc. to remove processing also effective.As the clean before such annealing, the various clean such as solvent cleaning, alkali cleaning, alkaline electrolysis cleaning are arranged, use as required suitable purging method.
For the copper alloy plate that is obtained by above manufacture method (alkaline catholyte clean before), then carry out alkaline catholyte and clean, the C1s/Cu2p ratio based on the surface of XPS analysis is reduced to below 0.35.This copper alloy plate as the electrical and electronic parts of semiconductor lead frame etc. with using, but at this moment, as the pre-treatment of plating, the processing of cleaning by comprising alkaline catholyte, the C1s/Cu2p ratio on plate surface is reduced to below 0.35, can access excellent oxide film adhesion.
[embodiment 1]
Below, just be used for confirming that the example of effect of the present invention and the test-results of comparative example describe.
As the manufacture method of copper alloy plate, at first after the molten soup of smelting copper alloy, be cast to pouring-type in the book mold of graphite-made in high frequency furnace, obtain the ingot bar of the composition shown in the table 1,2 of thick 50mm, wide 200mm, long 100mm.
Thereafter, downcut thick 50mm, wide 180mm from each ingot bar, the briquet of long 80mm carries out face milling and heats for rolling surface, after arriving 950 ℃, after keeping between 0.5 to 1 hour, is hot-rolled down to thick 16mm, carries out water-cooled from the temperature more than 700 ℃.Carry out face milling and except after descaling, carry out cold rolling and annealing for the surface of this milled sheet, thereafter, carry out final cold rolling and obtain the copper alloy plate of thick 0.2mm.Final cold rolling after, carry out low-temperature annealing.The temperature range of from 200 to 500 ℃ of left and right of low-temperature annealing and the time range about 1 to 300 second selected can guarantee that strength decreased is few, tension set condition of (tension set when carrying out the tension test of the direction parallel with rolling direction) more than 5%.
At this, annealing and low-temperature annealing are at N
2+ 10%H
2Atmosphere (dew point: below-20 ℃, O
2Concentration: 50ppm is following) in carry out, the clean before and after annealing is carried out as follows.About annealing, utilize the ultrasound of hexane to clean before annealing (20kHz, 1 minute), carry out sulfuric acid cleaned (10% sulfuric acid, 10 seconds) after annealing after, carry out mechanical mill (the water-fast pouncing paper of #2400).About low-temperature annealing, utilize the ultrasound of hexane to clean before annealing (20kHz, 1 minute), only carry out sulfuric acid cleaned (10% sulfuric acid, 10 seconds) after low-temperature annealing, do not carry out mechanical mill.
Also have, each copper alloy shown in table 1, remove the Cu that consists of of the surplus of recording and narrating amount of element, as other impurity element, the element total amount of Mn, Mg, Ca, Zr, Ag, Cr, Cd, Be, Ti, Co, Ni, Au, Pt etc. is below 0.2 quality %, the element of Hf, Th, Li, Na, K, Sr, Pd, W, S, Si, C, Nb, Al, V, Y, Mo, Pb, In, Ga, Ge, As, Sb, Bi, Te, B, norium etc., total amount is below 0.1 quality %.
For the copper alloy plate that obtains as above-mentioned, each example is all downcut test portion from copper alloy plate, estimate surface texture (Area Ratio of C1s/Cu2p ratio, fine-grain), the mechanical properties (tensile strength, tension set) on each test portion plate surface, and oxide film connects airtight the characteristic that keeps temperature etc.These results are presented at respectively in table 1,2.In table 2, the composition or the composition ratio that break away from claim 1～4 of the present invention have underscore.
(Area Ratio of fine-grain)
The Area Ratio of fine-grain with the method for previous record, is measured with EBSD and is analyzed viewing area when the copper alloy plate surface is observed and the area of fine-grain (diameter of equivalent circle is lower than 0.5 μ m), the Area Ratio that the meter place occupies as fine-grain.
(C1s/Cu2p ratio)
The C1s/Cu2p ratio is to carry out after alkaline catholyte cleans for the copper alloy plate surface, and the peak area value of the Cu2p by the XPS analysis surface measurements and the peak area value of C1s are calculated.At this, alkaline catholyte cleans, and uses the aqueous solution that contains sodium hydroxide 20g/L, and with liquid temperature: 60 ℃, cathode current density: 5A/dm2, the time: the condition of 30 seconds is carried out.
(mechanical properties)
Mechanical properties is to make the JIS-5 test film of the direction parallel with rolling direction, measures tensile strength and tension set in tension test.
(oxide film connects airtight and keeps temperature)
Oxide film connects airtight the maintenance temperature, alkaline catholyte is carried out on the copper alloy plate surface cleans, then wash → pickling (10% sulfuric acid) → washing → drying after, carry out the heating of 5 minutes and 10 minutes with the temperature of stipulating in atmosphere, with the spalling test that adhere to adhesive tape estimate thereafter.The alkalescence catholyte cleans, and the alkaline catholyte with the measurement of C1s/Cu2p ratio the time cleans identical condition to carry out.Carrying out spalling test by the adhesive gel band is by pasting the adhesive tape (the Sumitomo ス リ one メ Application processed デ イ of エ system society Application グ テ one プ) of market sale, and the method for tearing is carried out.At this moment, the every 10 ℃ of variations of Heating temperature once, the highest temperature of peeling off that oxide film will not occur is connected airtight as oxide film and is kept temperature to estimate.
[table 1]
[table 2]
As shown in table 1, example 1～13 among copper alloy plate of the present invention (example 1～21), satisfy claim 1,2 compositing range, example 14～16 satisfies the compositing range of claim 3, and example 17～21 satisfies the compositing range of claim 4.In addition, example 1～21 satisfies the surface texture (Area Ratio of fine-grain, C1s/Cu2p ratio) of claim 1,2 defineds.
Thus, the copper alloy plate of example 1～21, have oxide film connect airtight maintain the temperature at 390 ℃ * more than 5 minutes, 340 ℃ * good characteristic more than 10 minutes.
Also have, the oxide film exfoliation temperature of patent documentation 1 (JP 2008-45204 communique)-Biao 1-example 9 is (to connect airtight the maintenance temperature if be converted into oxide film in 370 ℃ * 5 minutes, it is 360 ℃ * 5 minutes), with respect to this, the oxide film of the application of similar composition-Biao 1-example 10～11 connects airtight and keeps temperature is 410～400 ℃ * 5 minutes, with patent documentation 1 more as can be known, the oxide film adhesion further improves.In addition, the oxide film exfoliation temperature of patent documentation 2 (JP 2008-127606 communique)-Biao 2-example 6 is (to connect airtight the maintenance temperature if be converted into oxide film in 400 ℃ * 5 minutes, it is 390 ℃ * 5 minutes), with respect to this, the oxide film of the application of similar composition-Biao 1-example 10 connects airtight and keeps temperature is 410 ℃ * 5 minutes, with patent documentation 2 more as can be known, the oxide film adhesion also further improves.
On the other hand, comparative example 22～33, as shown in table 2, do not satisfy the composition of claim 1～4 or/and the composition ratio.Therefore, describe individually as following, compare with example 1～21, the poor or oxide film of tensile strength connects airtight and keeps temperature low.
Comparative example 22, Fe/P be lower than lower value, helps the growing amount of fine Fe-P compound of intensity not enough, and the P of solid solution condition increases, therefore with example 1 relatively, tensile strength and oxide film connect airtight and keep temperature low.
Comparative example 23 because P content is lower than lower value, the growing amount of Fe-P compound is insufficient, so with example 1 relatively, tensile strength reduces.
Comparative example 24 because Fe/P surpasses higher limit, helps the growing amount of fine Fe-P compound of intensity not enough, and the Fe of solid solution condition increases, therefore with example 2 relatively, tensile strength and oxide film connect airtight and keep temperature low.
Comparative example 25 is also because Fe/P surpasses higher limit, helps the growing amount of fine Fe-P compound of intensity not enough, and the Fe of solid solution condition increases, thus with example 4 relatively, tensile strength and oxide film connect airtight and keep temperature low.
Comparative example 26 because Fe/P lower than lower value, helps the growing amount of fine Fe-P compound of intensity not enough, and the P of solid solution condition increases, so with example 6 relatively, tensile strength and oxide film connect airtight and keep temperature low.
Comparative example 27 because Fe/P surpasses higher limit, helps the growing amount of fine Fe-P compound of intensity not enough, and the Fe of solid solution condition increases, thus with example 9 relatively, tensile strength and oxide film connect airtight and keep temperature low.
Comparative example 28 because Fe/P lower than lower value, helps the growing amount of fine Fe-P compound of intensity not enough, and the P of solid solution condition increases, so with example 11 relatively, tensile strength and oxide film connect airtight and keep temperature low.
Comparative example 29 because Fe/P surpasses higher limit, helps the growing amount of fine Fe-P compound of intensity not enough, and the Fe of solid solution condition increases, thus with example 12 relatively, tensile strength and oxide film connect airtight and keep temperature low.
Comparative example 30 because P surpasses higher limit, and Fe/P is lower than lower value, helps the growing amount of fine Fe-P compound of intensity not enough, and the P of solid solution condition increases, so with example 13 relatively, tensile strength and oxide film connect airtight and keep temperature low.
Comparative example 31, because Fe content surpasses higher limit, thick crystallization/precipitate particle easily generates, thus little to the help of intensity raising, compare with example 13, tensile strength reduces.
Comparative example 32 because Sn content surpasses higher limit, thick crystallization/precipitate particle easily generates, diminish so intensity improves effect, with example 16 relatively, tensile strength is saturated substantially, and oxide film connects airtight and keeps temperature low.
Comparative example 33 because Zn content surpasses higher limit, thick crystallization/precipitate particle easily generates, diminish so intensity improves effect, with example 19 relatively, tensile strength reduces, and oxide film to connect airtight the raising effect that keeps temperature also saturated.
[embodiment 2]
Next, (Area Ratio of fine-grain C1s/Cu2p) describes with the test-results that oxide film connects airtight the relation that keeps temperature for relevant surface texture.In this embodiment 2, with the example 5,10 of table 1,21 ingot bar, according to method and condition similarly to Example 1, make the copper alloy plate of thick 0.2mm.
But, in this embodiment 2, make the clean method variation of annealing front and back, make thus surface texture (Area Ratio of fine-grain, C1s/Cu2p) variation of copper alloy plate.
Then, carry out similarly to Example 1 surface texture (Area Ratio of fine-grain, C1s/Cu2p) and oxide film connect airtight the evaluation that keeps temperature.
The clean method that each is routine, and surface texture (Area Ratio of fine-grain, C1s/Cu2p) and oxide film connect airtight the evaluation result that keeps temperature and be presented in table 3,4.In table 3,4, example 5-1～5-3 and comparative example 5-4～5-5, it is the copper alloy plate of being made by the ingot bar of the example 5 of table 1, example 10-1 and comparative example 10-2～10-3, it is the copper alloy plate of being made by the ingot bar of the example 10 of table 1, example 21-1～21-5 and comparative example 21-6～21-9 are the copper alloy plates of being made by the ingot bar of the example 21 of table 1.
In table 3,4, alkalescence dipping cleans and uses with sodium hydroxide as principal constituent, contains the alkalescence dipping cleaning pharmaceutical dissolution of representational market sale of other phosphoric acid salt, silicate, carbonate, tensio-active agent.In addition, the dissolution process of the chemistry that carries out in the aftertreatment of annealing is used with sulfuric acid and the hydrogen peroxide aqueous solution as the representational market sale of principal constituent.Also have, in surface texture one hurdle of table 4, show with underscore for the project that breaks away from claim.
[table 3]
[table 4]
As shown in table 3, copper alloy plate of the present invention (example 5-1～5-3,10-1,21-1～21-5), because annealing and low-temperature annealing have all been carried out suitable clean before and after each annealing, so after carrying out alkaline catholyte cleaning for the surface of copper alloy plate, be good below 0.35 based on the C1s/Cu2p on the surface of XPS analysis, and be also good below 0.90 in the fine-grain (diameter of equivalent circle is lower than 0.5 μ m) of analyzing based on EBSD on copper alloy plate surface with respect to the Area Ratio of viewing area.Also have, example 5-2 is identical with the example 5 of table 1, and example 10-1 is identical with the example 10 of table 1, and example 21-2 is identical with the example 21 of table 1.
Consequently, copper alloy plate of the present invention (example 5-1～5-3,10-1,21-1～21-5) have oxide film connect airtight keep temperature be 400 ℃ * more than 5 minutes, 350 ℃ * good characteristic more than 10 minutes.In addition, if identical composition, the Area Ratio of C1s/Cu2p and fine-grain is separately less, and oxide film connects airtight and keeps temperature more further to improve.
Comparative example 5-4, annealing and low-temperature annealing all in the clean before annealing, have been used for the ethanol a little less than the cleaning force of rolling wet goods, and only having carried out dipping cleans, therefore C1s/Cu2p surpasses higher limit, with example 5-1 relatively, oxide film connects airtight and keeps temperature low.
Comparative example 5-5, same annealing and low-temperature annealing all in the clean before annealing, have used for the ethanol a little less than the cleaning force of rolling wet goods, and only carried out dipping and cleaned, so C1s/Cu2p are over higher limits.In addition, owing to grinding after low-temperature annealing, so the Area Ratio of fine-grain also surpasses higher limit, with example 5-1 relatively, oxide film connects airtight and keeps temperature lower.
Comparative example 10-2, annealing and low-temperature annealing all in the clean before annealing, have been used for the ethanol a little less than the cleaning force of rolling wet goods, and only having carried out dipping cleans, therefore C1s/Cu2p surpasses higher limit, with example 10-1 relatively, oxide film connects airtight and keeps temperature low.
Comparative example 10-3, same, annealing and low-temperature annealing all in the clean before annealing, have used for the ethanol a little less than the cleaning force of rolling wet goods, and only carried out dipping and cleaned, so C1s/Cu2p are over higher limits.In addition, grind after low-temperature annealing, so the Area Ratio of fine-grain also surpasses higher limit, with example 10-1 relatively, oxide film connects airtight and keeps temperature lower.
Comparative example 21-6 is because annealing and low-temperature annealing all in the clean before annealing, have been used for the ethanol a little less than the cleaning force of rolling wet goods, and only having carried out dipping cleans, so C1s/Cu2p surpasses higher limit, with example 21-1 relatively, oxide film connects airtight and keeps temperature low.
Comparative example 21-7, same, annealing and low-temperature annealing all in the clean before annealing, have used for the ethanol a little less than the cleaning force of rolling wet goods, and only carried out dipping and cleaned, so C1s/Cu2p are over higher limits.In addition, grind after low-temperature annealing, the Area Ratio of fine-grain also surpasses higher limit thus, with example 21-1 relatively, oxide film connects airtight and keeps temperature lower.
Comparative example 21-8, because annealing and the low-temperature annealing all clean before annealing have been used hexane, although C1s/Cu2p satisfies the regulation of claim, but grind after low-temperature annealing, so the Area Ratio of fine-grain surpasses higher limit, with example 21-1 relatively, oxide film connects airtight and keeps temperature lower.
Comparative example 21-9, annealing and low-temperature annealing all in the clean before annealing, have been used for the ethanol a little less than the cleaning force of rolling wet goods, and have only carried out dipping and cleaned, so C1s/Cu2p is over higher limit.In addition, do not grind after low-temperature annealing, used little (granularity of abrasive the is large) pouncing paper of kind hand in the grinding after annealing, so the Area Ratio of fine-grain surpasses higher limit, with example 21-1 relatively, oxide film connects airtight and keeps temperature low.
Copper alloy plate of the present invention has excellent oxide film adhesion.In addition, according to copper alloy plate of the present invention, has the bendability of the needed high strength of the former material of used for lead frame and appropriateness.Thus, copper alloy material of the present invention is suitable as the former material of wire frame.In addition, copper alloy plate of the present invention, except lead frame for semiconductor device, the various electrical and electronic parts such as mechanism part that also are suitable as the electrical/electronic components material, derailing switch parts, bus-bar, terminal connection etc. of other semiconductor device, printing distributing board etc. use.
Claims (8)
1. the high strength copper alloy plate of an oxide film adhesion excellence, is characterized in that, contains Fe:0.02～0.5%, P:0.01～0.25% in quality %, and surplus is copper and inevitable impurity, and the quality % of Fe and P is 2.0～5.0 than Fe/P,
And, when analyzing effects on surface and observe by Electron Back-Scattered Diffraction, diameter of equivalent circle is below 0.90 lower than the fine-grain of 0.5 μ m with respect to the Area Ratio of viewing area, and the peak area value of the C1s on the surface that obtains by XPS analysis is below 0.35 with respect to the ratio C1s/Cu2p of the peak area value of Cu2p.
2. the high strength copper alloy plate of oxide film adhesion excellence according to claim 1, wherein, also contain Sn:0.005～3% in quality %.
3. the high strength copper alloy plate of oxide film adhesion excellence according to claim 1 and 2, wherein, also contain Zn:0.005～3% in quality %.
4. the high strength copper alloy plate of the described oxide film adhesion of any one excellence according to claim 1～3, wherein, tensile strength on the direction parallel with rolling direction of described copper alloy plate is more than 500MPa, and the tension set on the direction parallel with rolling direction is more than 5%.
5. the high strength copper alloy plate of oxide film adhesion excellence according to claim 1, wherein, described XPS analysis is the XPS analysis of carrying out after alkaline catholyte cleans.
6. the high strength copper alloy plate of oxide film adhesion excellence according to claim 5, wherein, also contain Sn:0.005～3% in quality %.
7. the high strength copper alloy plate of according to claim 5 or 6 described oxide film adhesion excellences, wherein, also contain Zn:0.005～3% in quality %.
8. the high strength copper alloy plate of the described oxide film adhesion of any one excellence according to claim 5～7, wherein, tensile strength on the direction parallel with rolling direction of described copper alloy plate is more than 500MPa, and the tension set on the direction parallel with rolling direction is more than 5%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-270676 | 2011-12-09 | ||
| JP2011270676A JP5700834B2 (en) | 2011-12-09 | 2011-12-09 | High strength copper alloy sheet with excellent oxide film adhesion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103160703A true CN103160703A (en) | 2013-06-19 |
Family
ID=48464682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012105090363A Pending CN103160703A (en) | 2011-12-09 | 2012-12-03 | High-strength copper alloy plate excellent in oxide film adhesiveness |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20130149189A1 (en) |
| JP (1) | JP5700834B2 (en) |
| KR (1) | KR20130065615A (en) |
| CN (1) | CN103160703A (en) |
| DE (1) | DE102012022794B4 (en) |
| SG (1) | SG191491A1 (en) |
| TW (1) | TWI500782B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111051547A (en) * | 2017-07-27 | 2020-04-21 | 威兰德-沃克公开股份有限公司 | Wire material and net composed of copper alloy and culture cage suitable for aquaculture |
| CN111557043A (en) * | 2018-03-23 | 2020-08-18 | 古河电气工业株式会社 | Lead frame material, method for producing same, and semiconductor package using same |
| CN113106288A (en) * | 2021-04-07 | 2021-07-13 | 太原晋西春雷铜业有限公司 | Method for preparing KFC (KFC) special-shaped strip blank with excellent softening resistance |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6246502B2 (en) * | 2013-06-13 | 2017-12-13 | Ｊｘ金属株式会社 | Copper alloy sheet with excellent conductivity and bending deflection coefficient |
| JP5851000B1 (en) * | 2014-08-22 | 2016-02-03 | 株式会社神戸製鋼所 | Copper alloy strip for LED lead frame |
| CN105609156A (en) * | 2016-02-01 | 2016-05-25 | 安徽华峰电缆集团有限公司 | High-performance gallium-alloy cable |
| JP6860435B2 (en) * | 2017-06-29 | 2021-04-14 | 福田金属箔粉工業株式会社 | A sintered body composed of a copper-based alloy powder for powder metallurgy and the copper-based alloy powder. |
| CN113969364B (en) * | 2021-09-10 | 2022-05-03 | 中南大学 | High-strength high-conductivity copper-niobium alloy and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2045344A1 (en) * | 2006-07-21 | 2009-04-08 | Kabushiki Kaisha Kobe Seiko Sho | Copper alloy sheets for electrical/electronic part |
| CN102191402A (en) * | 2010-03-10 | 2011-09-21 | 株式会社神户制钢所 | High-strength high-heat-resistance copper alloy |
| JP2011246772A (en) * | 2010-05-27 | 2011-12-08 | Mitsubishi Shindoh Co Ltd | Cu-Fe-P BASED COPPER ALLOY SHEET EXCELLENT IN CONDUCTIVITY AND HEAT RESISTANCE, AND METHOD OF MANUFACTURING THE SAME |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3720941B2 (en) * | 1997-03-10 | 2005-11-30 | 株式会社神戸製鋼所 | Copper alloy material for lead frames with excellent oxide film adhesion |
| JP3729662B2 (en) * | 1998-09-28 | 2005-12-21 | 株式会社神戸製鋼所 | High strength and high conductivity copper alloy sheet |
| JP2000328157A (en) * | 1999-05-13 | 2000-11-28 | Kobe Steel Ltd | Copper alloy sheet excellent in bending workability |
| JP3766051B2 (en) * | 2002-09-03 | 2006-04-12 | 株式会社神戸製鋼所 | Copper alloy having excellent heat resistance and method for producing the same |
| JP4041803B2 (en) * | 2004-01-23 | 2008-02-06 | 株式会社神戸製鋼所 | High strength and high conductivity copper alloy |
| WO2006019035A1 (en) * | 2004-08-17 | 2006-02-23 | Kabushiki Kaisha Kobe Seiko Sho | Copper alloy plate for electric and electronic parts having bending workability |
| JP4168077B2 (en) * | 2006-07-21 | 2008-10-22 | 株式会社神戸製鋼所 | Copper alloy sheet for electrical and electronic parts with excellent oxide film adhesion |
| KR20120041808A (en) * | 2006-10-02 | 2012-05-02 | 가부시키가이샤 고베 세이코쇼 | Copper alloy plate for electrical and electronic components |
| JP4197718B2 (en) * | 2006-11-17 | 2008-12-17 | 株式会社神戸製鋼所 | High strength copper alloy sheet with excellent oxide film adhesion |
| US7928541B2 (en) * | 2008-03-07 | 2011-04-19 | Kobe Steel, Ltd. | Copper alloy sheet and QFN package |
-
2011
- 2011-12-09 JP JP2011270676A patent/JP5700834B2/en active Active
-
2012
- 2012-11-20 US US13/681,747 patent/US20130149189A1/en not_active Abandoned
- 2012-11-21 DE DE102012022794.9A patent/DE102012022794B4/en active Active
- 2012-11-28 SG SG2012087532A patent/SG191491A1/en unknown
- 2012-12-03 CN CN2012105090363A patent/CN103160703A/en active Pending
- 2012-12-04 TW TW101145453A patent/TWI500782B/en active
- 2012-12-07 KR KR1020120141864A patent/KR20130065615A/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2045344A1 (en) * | 2006-07-21 | 2009-04-08 | Kabushiki Kaisha Kobe Seiko Sho | Copper alloy sheets for electrical/electronic part |
| CN102191402A (en) * | 2010-03-10 | 2011-09-21 | 株式会社神户制钢所 | High-strength high-heat-resistance copper alloy |
| JP2011246772A (en) * | 2010-05-27 | 2011-12-08 | Mitsubishi Shindoh Co Ltd | Cu-Fe-P BASED COPPER ALLOY SHEET EXCELLENT IN CONDUCTIVITY AND HEAT RESISTANCE, AND METHOD OF MANUFACTURING THE SAME |
Non-Patent Citations (1)
| Title |
|---|
| 刘勇等: "热处理工艺对Cu-Fe-P合金显微硬度及导电率的影响", 《金属热处理》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111051547A (en) * | 2017-07-27 | 2020-04-21 | 威兰德-沃克公开股份有限公司 | Wire material and net composed of copper alloy and culture cage suitable for aquaculture |
| CN111557043A (en) * | 2018-03-23 | 2020-08-18 | 古河电气工业株式会社 | Lead frame material, method for producing same, and semiconductor package using same |
| CN113106288A (en) * | 2021-04-07 | 2021-07-13 | 太原晋西春雷铜业有限公司 | Method for preparing KFC (KFC) special-shaped strip blank with excellent softening resistance |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102012022794B4 (en) | 2017-09-14 |
| KR20130065615A (en) | 2013-06-19 |
| JP2013122070A (en) | 2013-06-20 |
| TW201331391A (en) | 2013-08-01 |
| TWI500782B (en) | 2015-09-21 |
| SG191491A1 (en) | 2013-07-31 |
| DE102012022794A1 (en) | 2013-06-13 |
| US20130149189A1 (en) | 2013-06-13 |
| JP5700834B2 (en) | 2015-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103160703A (en) | High-strength copper alloy plate excellent in oxide film adhesiveness | |
| EP2339038B1 (en) | Copper alloy sheet for electric and electronic part | |
| CN102191402B (en) | High-strength high-heat-resistance copper alloy | |
| KR101158113B1 (en) | Copper alloy plate for electrical and electronic components | |
| KR101114656B1 (en) | Copper alloy sheet for qfn package superior in dicing processability and qfn package | |
| TW201118190A (en) | Sintered CU-GA sputtering target and method for producing the target | |
| JP4168077B2 (en) | Copper alloy sheet for electrical and electronic parts with excellent oxide film adhesion | |
| CN102286675A (en) | Copper alloy material for electrical and electronic parts and method for producing same | |
| JP5214282B2 (en) | Copper alloy plate for QFN package with excellent dicing workability | |
| JP2008127606A (en) | High-strength copper alloy sheet having oxide film superior in adhesiveness | |
| CN104928521B (en) | The Fe-P series copper alloy plates of intensity, heat resistance and excellent in bending workability | |
| CN104789812B (en) | Fe-P based copper alloy sheet excellent in strength, heat resistance and bending processibility | |
| CN102286672A (en) | Copper alloy material for electrical and electronic parts and method for producing same | |
| JP5236973B2 (en) | Copper alloy plate for QFN package with excellent dicing workability | |
| US20240071978A1 (en) | Al BONDING WIRE FOR SEMICONDUCTOR DEVICES | |
| JP5755892B2 (en) | Method for producing copper alloy sheet | |
| CN115369282A (en) | Copper alloy material for high-precision etched lead frame and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130619 |