CN102191402A - High-strength high-heat-resistance copper alloy - Google Patents
High-strength high-heat-resistance copper alloy Download PDFInfo
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- CN102191402A CN102191402A CN2011100600613A CN201110060061A CN102191402A CN 102191402 A CN102191402 A CN 102191402A CN 2011100600613 A CN2011100600613 A CN 2011100600613A CN 201110060061 A CN201110060061 A CN 201110060061A CN 102191402 A CN102191402 A CN 102191402A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/00—Alloys based on copper
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- C22C9/02—Alloys based on copper with tin as the next major constituent
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- H01L23/50—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor for integrated circuit devices, e.g. power bus, number of leads
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- H—ELECTRICITY
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Abstract
The present invention provides a high-strength high-heat-resistance copper alloy which has the following advantages: high tensile strength which is above 750MPa, high strength which is above Hv220, high heat resistance, and excellent jointing performance with an oxide film. The high-strength high-heat-resistance copper alloy comprises the following components in total weight: 0.4-1.0% of Ni;0.03-0.3% of Fe and/or Co (called M below); 0.05-0.2% of P; 0.1-3% of Sn; 0.05-2.5% of Zn; and 0.0005-0.05% of Cr; wherein a ratio (Ni+M)/P is 4-12; Ni/M is 3-12; the number of fine phosphide precipitation particles with grain diameters in 1-20 nm is above 300/mu m<2>; the number of coarse crystal precipitation particles with grain diameters which exceed 100 nm is less than 0.5/mu m<2>; and Sn/(Ni+M+P+Sn) is above 0.01.
Description
Technical field
The lead frame that the present invention relates to former material, particularly QFP (Quad Flat Pcakage) encapsulation as electrical and electronic parts or QFN (Quad Flat no Lead Package) encapsulation is with the high-intensity high heat-resistance copper alloy material with former material the connecting airtight property excellence suitable, oxide film of lead frame such as the semiconductor device of former material etc.
Background technology
Always, high-intensity lead frame with former material in, mostly use the copper alloy plate that constitutes by the Cu-Ni-Si series copper alloy that contains Ni and Si.In addition, among this Cu-Ni-Si copper alloy, the copper alloy (C70250 copper alloy) that for example contains Ni:2.2～4.2 quality %, Si:0.25～1.2 quality %, Mg:0.05～0.30 quality % is owing to intensity and excellent heat resistance, so be widely used as general-purpose alloy.
Recently, along with high capacity, miniaturization and the multifunction of semiconductor device, the fine cloth linearize of lead frame is developed, and in order to make this fine wiring easy, the thickness of slab of the copper alloy plate that lead frame is used requires thin.Thereupon, further require high strength and the high heat resistance of these semiconductor devices with the used copper alloy plate of lead frame.The high strength of copper alloy plate requires guaranteeing of the processing that descends along with thin plateization and guaranteeing as the intensity of final component parts.In addition, stable on heating raising requires to prevent to be used to form go that strain thermal treatment causes softening after the punch process of lead frame and softening when preventing to be subjected to thermal process in the semiconductor component assembling procedure.These are not only lead frame, and relate to other electrical and electronic parts, for example the employed copper alloy plate of electroconductive component of junctor, terminal, switch, rly. etc.In addition, process as fine wiring in the etching and processing of the processing method that is suitable for, stain can not take place, the smoothness excellence of the etching and processing face of copper alloy plate is attracted attention as the desired important factor of copper alloy plate.
Also have, from viewpoint cheaply, the encapsulation of semiconductor device by the semi-conductor chip of thermosetting resin sealing changes into and is main flow, and the reliability that remains potted is very important.The reliability of encapsulation exists with ... the connecting airtight property of moulded resin and lead frame, because the thermal process in the assembling procedure of semiconductor device, when formation makes the oxide film of surface deterioration of lead frame, the connecting airtight property reduction of moulded resin and lead frame, because the heat-seal crackle when the real dress of printed base plate and peel off generation, the reliability decrease of encapsulation.Thus, for the reliability that remains potted, the connecting airtight property of the oxide film of maintenance lead frame is very important.
Under this background, by Cu-Ni-Si copper alloy (C70250 copper alloy) though the copper alloy plate intensity and the excellent heat resistance that constitute,, have in etching and processing as the processing method that is suitable for fine wiring processing, produce stain, the problem of the smoothness difference of etching and processing face.
Therefore, in order to improve the smoothness of this etching face, applicant of the present invention has proposed a kind of copper alloy plate, is mother metal with the Cu-Fe-P series copper alloy, be made of the Cu-Ni-Fe-P series copper alloy that has added Ni, the Ni-Fe-P compound is separated out (patent documentation 1) in this metal structure.
Patent documentation 1 spy opens the 2001-335864 communique
But this patent documentation 1 disclosed Cu-Ni-Fe-P series copper alloy plate is though realized the purpose that it is desired, but, tensile strength only is about 700MPa, is difficult to obtain higher intensity, exists to be difficult to the corresponding and existing problem of comparing the thin-walled property of further lead frame.In addition, this existing C u-Ni-Fe-P series copper alloy plate carries out finish to gauge (finally cold rolling) with high working modulus, so though possible high strength,, this high strength that forces can cause stable on heating reduction, nor practical.
Summary of the invention
The present invention forms in view of the above problems, its purpose is, provide and to realize simultaneously that tensile strength is more than the 750MPa, hardness is above high strength and high heat resistance of Hv220, punch process not only, and in the etching and processing as the processing method that is suitable for fine wiring processing stain can not take place, the smoothness excellence of etching and processing face yet, in addition, the high-intensity high heat-resistance copper alloy material of connecting airtight property excellence that is used to the oxide film of the reliability that remains potted.
At least a element M that high-intensity high heat-resistance copper alloy material of the present invention contains Ni:0.4～1.0 quality %, selects from the group of Fe and Co formation: in total amount 0.03～0.3 quality %, P:0.05～0.2 quality %, Sn:0.1～3 quality %, Zn:0.05～2.5 quality %, Cr:0.0005～0.05 quality %, ratio (the Ni+M)/P of the content of Ni and M and the content of P is 4～12, the ratio Ni/M of Ni and M is 3～12, surplus is Cu and unavoidable impurities
In metal structure, particle diameter is that the number of the fine Pization thing precipitation particles of 1～20nm is 300/μ m
2More than, the number that particle diameter surpasses the thick brilliant precipitate particle of 100nm is 0.5/μ m
2Below,
The Sn content of described Pization thing precipitation particles, the quality % ratio by the EDX assay determination: count more than 0.01 with Sn/ (Ni+M+P+Sn),
The disrumpent feelings extensibility of the tension test of the direction parallel with rolling direction is more than 5%.
It is the energy dispersion type x-ray fluorescence analysis that so-called EDX analyzes.
Also have, in the present invention, symbol M is represented at least a element selected from the group who is made of Fe and Co, be Fe and/or Co.The present invention contains this Fe and/or the Co of 0.03～0.3 quality % with total amount (be total amount when containing Fe and Co, be the amount of this element in the time of independent) meter.In addition, when the content of Ni, element M and P is respectively as Ni, M, P among the present invention, satisfy the inequality of 4≤(Ni+M)/P≤12,3≤Ni/M≤12.
In addition, copper alloy material of the present invention is not limited to copper alloy plate, and the former material of copper alloy that also can be used as the different shape of copper alloy piece etc. constitutes, and can be used for the purposes of the connecting airtight property excellence of requirement and oxide film.
In the present invention, the Ni and element M and P and the Sn that contain specified amount, and, in metal structure, the Pization thing precipitation particles of regulation particle diameter generates more than the regulation number, and the Sn content of this Pization thing precipitation particles is more than the prescribed value, thus, the anchorage force that suppresses the Pization thing precipitation particles that moves and eliminate of dislocation improves, and the intensity of copper alloy plate and thermotolerance improve.In addition, in the etching and processing of copper alloy plate, the Pization thing precipitation particles that becomes the essential factor of stain generation is inhibited, and therefore, the smoothness of etching and processing face improves.
In addition; by containing the Zn of specified amount, the plating that uses in the joint of copper alloy and the hot soarfing of scolder be from being inhibited, and; the protectiveness of mother metal increases; the growth of oxide film is suppressed, therefore, and the connecting airtight property raising of oxide film; by containing the Cr of specified amount; during the manufacturing of copper alloy plate, Cr is in the boundary multiviscosisty of ingot casting, and hot workability improves.In addition, to go out the number of particle be 0.5/μ m to the particle diameter thick partial crystallization that surpasses 100nm
2Below, thus, the smoothness of etching and processing face and plating raising.
In described Pization thing precipitation particles, Sn is detected, and therefore, in the present invention, limits the Sn content of described Pization thing precipitation particles.Sn has in described Pization thing and the spissated situation of parent material interface in being contained in the Pization thing that is made of Ni-M-P the time.In the present invention, limit the content of the Sn that comprises whole these situations.
In addition, the copper alloy material of the high-intensity high heat-resistance of the connecting airtight property excellence of oxide film of the present invention, in described copper alloy material also in total amount contain 0.0005～0.05 quality % from Al and Mn, select at least a.By Al and/or the Mn that contains specified amount, can be reduced in the S amount of sneaking into as unavoidable impurities in the copper alloy, the hot workability of copper alloy plate improves.
In addition, preferred this high-intensity high heat-resistance copper alloy material, is below 0.35 in the peak area value of the C1s on the surface that the XPS analysis of carrying out after the alkali catholyte is cleaned is measured with respect to the ratio C1s/Cu2p of the peak area value of Cu2p, and the fine-grain that the diameter of equivalent circle when analyzing the surface by EBSD is lower than 0.5 μ m is below 0.90 with respect to the area ratio of viewing area.
In this constituted, by reducing the surperficial C and the amount of crystal boundary, the defective that C or crystal boundary cause was imported in the oxide film and is suppressed, and forms the few oxide film of defective, thus, and the connecting airtight property raising of oxide film.In addition, by forming the few oxide film of defective, oxide film improves the protectiveness of mother metal, and the growth of inhibited oxidation film helps the raising of the connecting airtight property of oxide film.
In addition, the copper alloy material of preferred high-intensity high heat-resistance of the present invention, the disrumpent feelings extensibility of the tension test of the direction parallel with rolling direction is more than 5%.
According to this formation, owing to have suitable disrumpent feelings extensibility, thereby can keep the bendability of lead frame, therefore, can form as former material, the particularly semiconductor device of electrical and electronic parts with the copper alloy plate of lead frame with former material with the needed appropriateness of former material.
According to copper alloy material of the present invention, intensity (tensile strength and hardness) and thermotolerance improve, and, punch process type not only, and stain can not take place, the smoothness of etching and processing face and plating excellence in the etching and processing as the processing method that is suitable for fine wiring processing yet.In addition, according to copper alloy material of the present invention, when the joint of copper alloy material, the hot soarfing that plating and scolder can not take place from.In addition, according to copper alloy material of the present invention, the hot workability in the time of can improving the copper alloy material manufacturing.In addition, the connecting airtight property excellence of copper alloy material oxide film of the present invention.
Embodiment
Below, the high-intensity high heat-resistance copper alloy of the connecting airtight property excellence of oxide film of the present invention is elaborated.Also have, below explanation is not limited to the situation that copper alloy material is tabular former material, and blocky former material etc. are suitable for too.
At first, the composition in the copper alloy plate is added reason and the qualification reason of compositing range and the number and the Sn content of Pization thing precipitation particles, the number of thick brilliant precipitate particle limits reason and describes.
(Ni:0.4～1.0 quality %)
Ni separates out the Pization thing precipitation particles that contains fine Sn in alloy structure, improve the intensity of copper alloy plate and the element of stable on heating necessity.When Ni content is lower than 0.4 quality %, contain the fine Pization thing precipitation particles deficiency of Sn.Therefore, in order effectively to bring into play the effect of high strength and high heat resistanceization, need contain the above Ni of 0.4 quality %.But Ni contains sometimes above 1.0 quality % are excessive, and thick brilliant precipitate particle generates in the alloy structure, and the smoothness of the etching and processing face of copper alloy plate descends, and hot workability also descends.Therefore, Ni content is the scope of 0.4～1.0 quality %.In addition, in this scope, the preferable range of Ni is 0.5～0.9 quality %.
(at least a element M of from the group of Fe and Co formation, selecting :) in total amount 0.03～0.3 quality %
By contain more than one that select from Fe and Co, particularly to improving the thermotolerance of copper alloy plate, softening of the thermal process in thermal treatment after the punching press of inhibition lead frame and the semi-conductor assembling operation is effective.Fe or Co and Ni are same, and the fine Pization thing precipitation particles that contains Sn is separated out in alloy structure, are to improve the intensity of copper alloy plate and the element of stable on heating necessity.When the content of more than one among Fe and the Co is lower than 0.03 quality %, the fine Pization thing precipitation particles deficiency that contains Sn, and, Pization thing precipitation particles becomes the precipitation particles based on Ni and P, can not effectively bring into play the effect of high strength and high heat resistanceization, therefore, need contain more than the 0.03 quality %.But, containing sometimes above 0.3 quality % is excessive, thick brilliant precipitate particle generates in the alloy structure, and the smoothness of the etching and processing face of copper alloy plate descends, and hot workability also descends.Therefore, Fe in the copper alloy plate and more than one the content among the Co are the scope of 0.03～0.3 quality %.In addition, in this scope, preferred range is 0.05～0.2 quality %.
(P:0.05～0.2 quality %)
P also is combined in Ni and M (Fe and/or Co) and forms the fine Pization thing precipitation particles that contains Sn in the alloy structure except desoxydatoin, is the element that makes intensity and necessity that thermotolerance improves of copper alloy plate.When P content is lower than 0.05 quality %, contain the fine Pization thing precipitation particles deficiency of Sn, therefore, can not effectively bring into play the effect of high strength and high heat resistanceization.Therefore, P need contain more than the 0.05 quality %.But P contains sometimes above 0.2 quality % is excessive, and thick brilliant precipitate particle generates in the alloy structure, and the smoothness of the etching and processing face of copper alloy plate descends, and hot workability also descends.In addition, P contains sometimes above 0.2 quality % is excessive, and the P solid solution capacity increases the connecting airtight property decline of oxide film.Therefore, P content is the scope of 0.05～0.2 quality %.In addition, in this scope, the P preferred range is the scope of 0.07～0.18 quality %.
(Sn:0.1～3 quality %)
Being added with of Sn helps improve the intensity of copper alloy plate under solid solution condition, but in the present invention, when the precipitation particles of analyzing by EDX based on Ni-M (Fe and/or Co)-P, detects Sn.Sn is also indeterminate in the reason that the part of precipitation particles is detected, but be thought of as inferior mechanism: contain Sn and exist in the precipitation particles based on Ni-M (Fe and/or Co)-P, perhaps the part Ni-M of the Sn multiviscosisty in mother metal (Fe and/or Co)-P particle is preferentially separated out and is detected.But each situation all is that Sn promotes separating out of Ni-M (Fe and/or Co)-P particle.According to this mechanism, can infer the intensity of copper alloy plate of the present invention and compare and further to improve with the effect of only Sn solid solution with thermotolerance.When Sn content is lower than 0.1 quality %, of the present invention based on Ni-M (Fe and/or Co)-P, and the fine precipitation particles that contains Sn can not form.Therefore, in order effectively to bring into play the effect of high strength and high heat resistanceization, need contain the above Sn of 0.1 quality %.But Sn surpasses that 3 quality % are excessive to be contained sometimes, and its effect is saturated, and segregation and the thick brilliant precipitate particle of Sn generate in a large number during fusion casting during the manufacturing of copper alloy plate, and hot workability also descends.In addition, the electroconductibility of copper alloy plate also descends, the connecting airtight property decline of oxide film.Therefore, Sn content is the scope of 0.1～3 quality %.In addition, in this scope, the scope of preferred Sn is the scope of 0.2～2.5 quality %.
(Zn:0.05～2.5 quality %)
Zn suppresses peeling off of Sn plating used in the joint of copper alloy plate and scolder, improves heat-resisting separability, and, be the element of necessity that is used to improve the connecting airtight property of oxide film.In order effectively to bring into play this effect, Zn need contain more than the 0.05 quality %.But Zn contains sometimes above 2.5 quality % are excessive, and thick brilliant precipitate particle generates easily, and the effect of the connecting airtight property of raising oxide film is also saturated.Therefore, Zn content is the scope of 0.05～2.5 quality %.In addition, in this scope, the preferable range of Zn is 0.1～2.5 quality %.
(Cr:0.0005～0.05 quality %)
Cr is when the manufacturing of copper alloy plate, is used to improve the element of necessity of the hot workability of ingot casting.Cr improves the intensity of the crystal boundary of hot processing temperature in the crystal boundary multiviscosisty of ingot casting, helps the improvement of hot workability.In copper alloy plate of the present invention, in order to realize high strength and high heat resistance simultaneously, contain P and Sn than higher concentration, therefore, hot workability is difficult.Therefore, this element with grain-boundary strengthening effect raising hot workability of Cr is necessary.In order effectively to bring into play this effect, Cr need contain more than the 0.0005 quality %.
But Cr contains sometimes above 0.05 quality % is excessive, and not only its additive effect is saturated, and thick brilliant precipitate particle generates easily in the alloy structure, and the smoothness of the etching and processing face of copper alloy plate reduces.Therefore, Cr content is the scope of 0.0005～0.05 quality %.In addition, in this scope, the scope of preferred Cr is 0.001～0.03 quality %.
(4≤(Ni+M)/P≤12, and 3≤Ni/M≤12)
The relation of the ratio of the quality % by making Ni and M (Fe and/or Co) and P satisfies 4≤(Ni+M)/P≤12, and 3≤Ni/M≤12, can significantly improve the intensity and the thermotolerance of copper alloy plate.In addition, separate out as described later, need above-mentioned 2 formulas to set up,, can not have concurrently as the object of the invention high strength and high heat resistanceization if do not satisfy this 2 formula in order to make the fine Pization thing precipitation particles that contains Sn among the present invention.Therefore, the relation of the ratio of the quality % of Ni, M and P satisfies 4≤(Ni+M)/P≤12, and 3≤Ni/M≤12.In addition, in this scope, preferred range is 5≤(Ni+M)/P≤10, and 4≤Ni/M≤10.
(unavoidable impurities)
Unavoidable impurities among the present invention is elements such as Si, Ti, Zr, Be, V, Nb, Mo, W, Mg for example.When containing these elements, thick brilliant precipitate particle generates easily, in addition, hinders two of high strength and high heat resistance and stands.Therefore, unavoidable impurities is preferably counted few content below the 0.5 quality % with total amount.In addition, the element of B, the C that trace also has in the copper alloy plate, Na, S, Ca, As, Se, Cd, In, Sb, Pb, Bi, MM (thulium) etc. also is a unavoidable impurities.When containing these elements, thick brilliant precipitate particle generates easily, and hot workability also descends.Preferably suppressing in total amount is few content below the 0.1 quality %.
((particle diameter is that 1～20nm) number is 300/μ m to Pization thing precipitation particles
2More than, the Sn content of Pization thing precipitation particles: with Sn/ (Ni+M+P+Sn) than counting more than 0.01)
So-called Pization thing precipitation particles is meant by the infiltration type electron microscope observation copper alloy more than 100,000 times and organizes detected particle among the present invention, is that particle diameter is the precipitation particles of 1～20nm.The number of this Pization thing precipitation particles is 300/μ m
2More than.Also have the Pization thing of these Pization thing precipitation particles to constitute, the quality % ratio that the Sn content in this precipitation particles is measured by EDX: count more than 0.01 with Sn/ (Ni+M+P+Sn) by Ni-M (Fe and/or Co)-P.
In the present invention, the particle diameter of precipitation particles is the maximum diameter (with the diameter in the external garden of each precipitation particles) of each precipitation particles.Equally, the number of precipitation particles be measure by the precipitation particles number in the field of view of the infiltration type electron microscope more than 100,000 times (particle diameter: 1～20nm), be converted into per 1 μ m
2The number of mensuration be number among the present invention, observe any 3 visuals field at least, its measurement result is averaged.
This fine Pization thing precipitation particles that contains Sn is when the manufactured copper alloy sheets, and is for example newly-generated during the annealing after cold rolling.Being this fine precipitation particles, is from the fine compound phase of separating out of parent phase by annealing.Therefore, not being is to be created in the copper alloy tissue the thick brilliant precipitate particle of existence originally when when casting or hot rolling.Therefore, if, just can not observe this fine precipitation particles not by the infiltration type electron microscope observation copper alloy tissue more than 100,000 times.
In the present invention, the number of the fine Pization thing precipitation particles of this Sn of containing is 300/μ m
2More than.The anchorage force that moves and eliminate that this fine Pization thing precipitation particles that contains Sn suppresses dislocation is more a lot of greatly than thick brilliant precipitate particle.Therefore, in copper alloy plate of the present invention, making particle diameter is that following fine Ni-M (Fe and/or the Co)-P-Sn compound of 20nm is the precipitation particles existence in the copper alloy tissue as much as possible of main body, thus, improve above-mentioned anchorage force, can realize high strength and high heat resistanceization.
In addition, this particle diameter is the fine Pization thing precipitation particles that contains Sn below the 20nm, and in the etching and processing of the processing method that is fit to as fine wiring processing, the essential factor that can the composition stain take place can not make the smoothness decline of etching and processing face.To this, thick brilliant precipitate particle is not only little for the help of high strength and high heat resistanceization, and in etching and processing, becomes the dirty essential factor that takes place, and, be the essential factor that makes the smoothness decline of etching and processing face.
The particle diameter of precipitation particles surpasses the thick brilliant precipitate particle of 20nm, as mentioned above, and a little less than the anchorage force.Therefore, in the present invention, contain Sn fine Pization thing precipitation particles median size on be limited to 20nm.Even and particle diameter is lower than the infiltration type electron microscope of fine precipitate more than 100,000 times of 1nm and also is difficult to observe and measures, and, described anchorage force on the contrary a little less than.Therefore, in the present invention, the number that contains the fine Pization thing precipitation particles of Sn is to be the qualification that the Pization thing precipitate more than the 1nm carries out to particle diameter.
The number of the fine Pization thing precipitation particles of this Sn of containing is lower than 300/μ m
2The time, can bring into play the number of particles deficiency of effect, can not obtain tensile strength is the above high strength of 750MPa (hardness Hv220), and thermotolerance descends.
In addition, the Sn content that contains the fine Pization thing precipitation particles of Sn is lower than at 0.01 o'clock in quality % ratio, and can not obtain tensile strength is the above high strength of 750MPa (hardness Hv220), and thermotolerance descends.Also have, the compositional analysis of precipitation particles (Sn content) is analyzed by EDX and is carried out, from the peak strength calculated mass % of each composition (Ni, Fe, Co, P, Sn).Each quality % is 100% calculating with Ni+Fe+Co+P+Sn, and the quality % ratio of Sn is to calculate with the formula of Sn/ (Ni+Fe+Co+P+Sn) from quality %.In addition, analyze at least more than 5 in the precipitation particles below the above 20nm of 1nm in the field of view, with its measurement result equalization.In addition, the representative of Pization thing precipitation particles is formed in the % mass ratio by the EDX assay determination, and by Ni:30～70%, M (Fe and/or Co): 5～60%, the scope about P:5～35%, Sn:1～30% constitutes.
(number of thick brilliant precipitate particle (more than the particle diameter 100nm) is 0.5/μ m
2Below)
In the present invention, to particle diameter is that the amount of the fine Pization thing precipitation particles that contains Sn below the above 20nm of 1nm limits, if satisfy this qualification, the thick brilliant precipitate particle that then allows the particle diameter of brilliant precipitate particle to surpass 20nm exists in the copper alloy tissue with suitable amount.But when organizing by the observation of the scanning electron microscope more than 10,000 times copper alloy, the number that particle diameter surpasses the brilliant precipitate particle of 100nm need be 0.5/μ m
2Below.The number that particle diameter surpasses the thick brilliant precipitate particle of 100nm surpasses 0.5/μ m
2The time, the essential factor that the stain when becoming etching and processing takes place, and, become the smoothness that causes the etching and processing face and descend, and the essential factor of the problem of plating decline (generation projection).In addition, also hinder the generation of the fine Pization thing precipitation particles of the described Sn of containing.
When the manufactured copper alloy sheets, the thick brilliant precipitate particle that particle diameter surpasses 100nm generates when casting or during hot rolling.At this, so-called brilliant precipitate particle be in the copper alloy tissue as the isolating brilliant precipitate particle of crystallization phases, do not form the precipitate particle that is separated as solid of clear and definite crystallization phases or their mixture.Also have,, have Pization system (Ni-Fe-P system, Ni-Co-P system, Ni-P system etc.) and Ni-Sn system as the thick brilliant precipitate particle of these particle diameters above 100nm.
In the present invention, the particle diameter of thick brilliant precipitate particle is the maximum diameter (going out the circular diameter that beyond the region of objective existence connects with each partial crystallization) of each brilliant precipitate particle.Equally, the number of thick brilliant precipitate particle is to measure brilliant precipitate population (particle diameter surpasses 100nm) in the field of view of the scanning electron microscope more than 10,000 times, as per 1 μ m
2The mensuration number and the number that converts.At this moment, observe 3 visuals field arbitrarily at least, with the mean value of measurement result as measured value.Also have, observe and also can be undertaken by the infiltration type electron microscope, but because particle diameter is big, so scanning electron microscope is easy.
(the disrumpent feelings extensibility of the tension test of the direction parallel with rolling direction is more than 5%)
The disrumpent feelings extensibility of the tension test of the direction parallel with rolling direction of copper alloy plate of the present invention is more than 5%.Thus,, can keep lead frame with the necessary suitable bendability of former material, therefore, can become in the former material etc. of electrical and electronic parts as semiconductor device with the suitable copper alloy plate of the former material of lead frame by having suitable disrumpent feelings extensibility.To this, the disrumpent feelings extensibility of the tension test of the direction parallel with rolling direction is lower than at 5% o'clock, can not guarantee lead frame with the necessary suitable bendability of former material, therefore, can not become in the former material etc. of electrical and electronic parts as semiconductor device with the suitable copper alloy plate of the former material of lead frame.Thus, the disrumpent feelings extensibility of the tension test of the direction parallel with rolling direction is more than 5%.Also have, more preferably more than 6%.
(that selects from Al and Mn is at least a: in total amount 0.0005～0.05 quality %)
Al and/or Mn are the elements of sneaking into as impurity in copper alloy, are the S that reduction descends hot workability is measured element effectively.Thus, if Al and/or Mn also can contain below specified amount.In order to bring into play above-mentioned effect effectively, need Al and/or Mn to count more than the 0.0005 quality % with total amount.But Al and/or Mn contain sometimes above 0.05 quality % is excessive, and not only effect is saturated, and thick brilliant precipitate particle is separated out the smoothness decline of the etching and processing face of copper alloy plate easily.Therefore, the content of the Al of copper alloy plate and/or Mn is in the scope of 0.0005～0.05 quality %.In addition, in this scope, the preferable range of Al and/or Mn is 0.001～0.03 quality %.
(is below 0.35 with respect to the ratio C1s/Cu2p of the peak area value of Cu2p in the peak area value of the C1s on the copper alloy plate surface that the XPS analysis of carrying out after the alkali catholyte is cleaned is measured)
Copper alloy plate of the present invention is below 0.35 in the peak area value of the C1s on the copper alloy plate surface that the XPS analysis of carrying out after the alkali catholyte is cleaned is measured with respect to the ratio C1s/Cu2p of the peak area value of Cu2p, and preferably the fine-grain footpath (diameter of equivalent circle is lower than 0.5 μ m) by EBSD analysis and observation copper alloy plate surface the time is below 0.90 with respect to the area ratio of viewing area.
Also have, what is called is meant the relative C amount on the copper alloy plate surface of carrying out after the alkali catholyte is cleaned with respect to the ratio of the peak area value of Cu2p in the peak area value of the C1s on the surface that the XPS analysis of carrying out after the alkali catholyte is cleaned is measured.In addition, so-called XPS analysis is the x-ray photoelectron spectrum analysis, is also referred to as esca analysis, is the method for being good at carrying out the composition and the state analysis of surperficial thin layer.The C that detects from the surface of copper alloy plate is generally from various pollution substances (organism, inorganics), and, from the organic rust preventing film of handling for the look that prevents copper alloy plate becomes (outside the benzotriazole) etc.When these goods and materials are present in the surface, can detrimentally affect be arranged to the connecting airtight property of whole oxide films.The defective that these materials cause is imported in the oxide film, thus, generates the many oxide films of defective.
Used copper alloy plate in the lead frame of semiconductor device, after carrying out pre-treatment such as electrolytic degreasing, the part is carried out plating and is handled in assembling procedure, the reliability that encapsulates about the connecting airtight property of the oxide film that generates owing to the thermal process of this assembling procedure.Therefore, the C that the connecting airtight property of oxide film is exerted an influence must unify this for the C after the pre-treatment of copper alloy plate being carried out electrolytic degreasing etc.Thus, in the present invention, be conceived to as the most normally used C such as the pre-treatment of electrolytic degreasing etc. on the surface that the XPS analysis of carrying out after the alkali catholyte is cleaned is measured.Also have, be used to prevent the organic rust preventing film (outside the benzotriazole) of the variable color of copper alloy plate, owing to clean and can easily remove by the alkali catholyte, so no problem.
At this, it is in alkaline aqueous solution that so-called alkali catholyte is cleaned, and object is carried out electrolysis as negative electrode, and the mechanical agitation that the hydrogen that produces by the surface from object carries out improves the method for cleaning of clearing power.The employed alkaline aqueous solution of present method is a matrix at the basic salt with sodium hydroxide, water glass, sodium phosphate, yellow soda ash etc. usually, add the organism of interfacial agent or chelate compound etc. and constitute, object is carried out electrolysis as negative electrode, therefore, oxidation and dissolving can not carried out in the surface of copper alloy plate, and the surface of former material does not have any damage.Therefore, in the alkali catholyte is cleaned, can easily remove pollution substance and organic rust preventing film, but can not remove unusual pollution substance (organism of strong adhesion (arborescens)).When inexpungible pollution substance etc. was attached to copper alloy plate surperficial in this alkali catholyte is cleaned, the connecting airtight property of oxide film declined to a great extent, the reliability decrease of encapsulation.Therefore, preferred little in the peak area value of the C1s on the surface that the XPS analysis of carrying out after the alkali catholyte is cleaned is measured with respect to the ratio C1s/Cu2p of the peak area value of Cu2p, be below 0.35.Also have, C1s/Cu2p is more preferably below 0.30.
(fine-grain that the diameter of equivalent circle when analyzing the surface by EBSD is lower than 0.5 μ m is below 0.90 with respect to the area ratio of viewing area)
Fine-grain (diameter of equivalent circle is lower than 0.5 μ m) when in addition, what is called is analyzed the surface by EBSD is with respect to the area of the viewing area ratio more shared than the fine-grain that is meant the copper alloy plate surface.At this, it is the backscattering electron diffraction analysis that so-called EBSD analyzes, and is the analytical procedure of the analysis in the size of being good at crystal grain, distribution, orientation etc.In addition, being meant that at this so-called crystal grain to analyze azimuth difference between adjacent measuring point by EBSD be that situation more than 5 ° is a crystal boundary, is crystal grain with the zone that is surrounded fully by this crystal boundary.
The area of the fine-grain on copper alloy plate surface is meant that than greatly fine-grain exists in a large number, has a large amount of crystal boundaries, and the defective that these a large amount of crystal boundaries cause is imported in the oxide film, thus, and the connecting airtight property decline of oxide film.Thus, the area of the fine-grain on copper alloy plate surface ratio is preferably littler, is below 0.90.In addition, more preferably below 0.85.
(manufacture method of copper alloy plate)
Then, the manufacture method to copper alloy plate of the present invention describes.For the alloy structure of the copper alloy plate that makes manufacturing forms above-mentioned tissue, do not need very big change to have known manufacturing process self now, can be by the operation manufacturing identical with common method.That is, the molten alloyed copper that is adjusted to the mentioned component composition is cast.And, ingot casting carried out face cutting after, heat or the thermal treatment that homogenizes after, carry out hot rolling, the copper alloy plate after the hot rolling is carried out water-cooled., repeatedly carry out several cold rolling, annealing and clean, carry out finally cold rolling (finish to gauge) again, form the copper alloy plate of goods thickness of slab thereafter.
Also have, preferably carry out low-temperature annealing (going strain annealing) after cold rolling final.Along with the fine cloth linearize of the miniaturization of semiconductor device, lead frame that highly denseization causes, the quality requirements that the planarity of plate is relevant with internal stress grows to even greater heights, and low-temperature annealing improves effectively this quality.In addition, low-temperature annealing is effective to the ductility of recovering former material, is that the disrumpent feelings extensibility with the tension test of the direction parallel with rolling direction is controlled to be 5% above effective means.The temperature range of low-temperature annealing about 200～500 ℃, the time range about 1～300 second is carried out, so that the disrumpent feelings extensibility of the tension test of the direction parallel with rolling direction is controlled to be more than 5%.
Wherein, be that the number of the Pization thing precipitation particles that contains Sn of 1～20nm is 300/μ m in order to be controlled to be above-mentioned particle diameter
2Above form is annealed effectively with following condition in the mill.Also having, is more than 0.01 in order to be controlled to be the Sn content that the makes Pization thing precipitation particles quality % ratio by the EDX assay determination, is undertaken effectively by Ni, Fe in the adjustment copper alloy and/or Co, P and Sn content.
That is, as mentioned above, the fine Pization thing precipitation particles that contains Sn of the present invention is because annealing is new for the fine compound phase of separating out of parent phase.For this fine Pization thing precipitation particles that contains Sn is separated out, in the manufacturing process of above-mentioned copper alloy plate, after cold rolling, anneal.
But only once annealing is difficult to make this fine Pization thing precipitation particles that contains Sn to be separated out in a large number, and raising is during annealing temperature, along with the increase of the quantity of precipitation particles, causes the growth and thickization of precipitation particles.Therefore, preferably anneal several times, and annealing temperature each time is controlled at below 430 ℃, the growth and thickization of control precipitation particles are controlled to form the above-mentioned fine mode of separating out form.Annealing time is that the scope about 5 minutes～20 hours is carried out.
In addition, between this annealing and annealing, carry out when cold rolling because cold rolling lattice imperfection increases, after annealing in formation separate out nuclear, therefore, can obtain the above-mentioned fine form of separating out easily.
Therefore, in view of these conditions, in the manufacturing process of above-mentioned copper alloy plate, till arriving finally cold rolling (finish to gauge) after the hot rolling, carry out cold rolling and annealed operation for 2 times 2 times repeatedly and can easily obtain the form of separating out of the described fine Pization thing precipitation particles that contains Sn, therefore preferably.In addition, control casting condition and hot-rolled condition, the number that makes particle diameter surpass the thick brilliant precipitate particle of 100nm is 0.5/μ m
2Below, can promote the generation of the fine Pization thing precipitation particles that contains Sn, therefore preferred.
Be controlled at 0.5/μ m as the number that particle diameter is surpassed the thick brilliant precipitate particle of 100nm
2Following casting condition and hot-rolled condition, the speed of cooling when quickening casting, and, improving hot rolled Heating temperature and end temp, the speed of cooling after the acceleration hot rolling is effective.The back of solidifying that the condition of so-called speed of cooling when quickening casting is to use the speed of cooling when the solidifying of the thick crystallisate of control and is used to control thick precipitate is more than 0.1 ℃/second to 500 ℃ speed of cooling, is preferably more than 0.5 ℃/second.Therefore, for example preferably water is but cold.In addition, the so-called condition that improves hot rolled Heating temperature and end temp is that hot-rolled temperature is more than 850 ℃, and end temp is more than 650 ℃.In addition, the condition of the speed of cooling after the so-called quickening hot rolling is that the speed of cooling to 300 ℃ was more than 1 ℃/second after hot rolling finished, and is preferred more than 5 ℃/second.Therefore, for example carry out water-cooled.Speed of cooling during casting is crossed time slack, and thick brilliant precipitate particle generates in a large number.In addition, when the hot rolled Heating temperature was hanged down, the thick brilliant precipitate particle solid solution that generates when casting was insufficient, and the hot rolled end temp also descends, and therefore, thick brilliant precipitate particle generates in a large number.In addition, when the speed of cooling after the hot rolling is slow, also there are a large amount of thick brilliant precipitate particles to generate.
Also have, for the peak area value of the C1s that makes on the copper alloy plate surface that the XPS analysis of carrying out after the alkali catholyte is cleaned is measured is below 0.35 with respect to the ratio of the peak area value of Cu2p, and, fine-grain (diameter of equivalent circle is lower than 0.5 μ m) when analyzing copper alloy surface by EBSD is below 0.90 with respect to the area ratio of viewing area, can implement following operation.
First-selection, for the peak area value of the C1s that makes on the copper alloy plate surface that the XPS analysis of carrying out after the alkali catholyte is cleaned is measured is below 0.35 with respect to the ratio of the peak area value of Cu2p, the clean processing before and after annealing is very important.Usually after annealing, in order to remove the oil content residue that the oxide film that generates and ROLLING OIL cause in annealing, though carry out various clean processing (pickling clean, grinding etc.), but only in the cleaning after annealing, particularly be difficult to carry out the cleaning of C of effective oil content residue etc., producing needs the long-time defective of cleaning time etc.Therefore, for cleaning of the oil content residue of the reason that becomes C effectively etc., before annealing, clean handle effective, particularly, must before low-temperature annealing, clean processing as final operation, and, after low-temperature annealing, carry out removing of the clean oxide film that waits of pickling and handle effectively.Various clean processing such as solvent is cleaned, alkali cleaning is clean, alkali electrolytic degreasing are arranged as the clean processing before this annealing, can use suitable method of cleaning as required.
Then, fine-grain (diameter of equivalent circle is lower than 0.5 μ m) when analyzing copper alloy surface in order to make by EBSD is below 0.90 with respect to the area ratio of viewing area, by after annealing, not carrying out mechanical mill, perhaps strengthen the numbering of mechanical mill, reduce the granularity of abrasive, guarantee that as wide as possible the crystal grain on top layer is very important.In addition, even carry out mechanical mill, by chemical dissolution processing and electrochemical dissolution etc., the fine crystalline layer of removing the mechanical mill generation also is effective means thereafter.Always, after annealing, carry out mechanical mill mostly.This is because the oxide film that annealing generates is strong, is difficult to only remove only by pickling.Thus,, perhaps reduce the load of mechanical mill and the area ratio of fine-grain is maintained little, annealing atmosphere is fully managed, so that it is very important not generate strong oxide film in order not carry out mechanical mill.Specifically, annealing atmosphere formation reducing atmosphere (contains H
2Atmosphere with the reduction composition of CO etc.), oxidisability composition (O
2And H
2O etc.) management does not make strong oxide film very important for alap concentration.Particularly in low-temperature annealing operation,, be controlled to be and do not make strong oxide film generation, can only remove oxide film only, do not carry out mechanical mill ground and do not carry out surface adjustment by pickling by annealing atmosphere is fully managed as final operation.
Embodiment 1
Then, the embodiment that can confirm effect of the present invention and the experimental result of comparative example are described.As the manufacture method of copper alloy plate, in high frequency furnace, to having shown in the following table 1 after the molten alloyed copper of forming carries out melting, inject volume (book) type mold of graphite system with pouring-type, obtaining thickness is that 50mm, width are that 200mm, length are the ingot casting of 200mm.In mold behind the ingot solidification, from 700 to 800 ℃ temperature water-cooled.Also have, the mold of graphite system has sufficient thermal capacity and thermal conductivity, and the speed of cooling that 2 branches between dendritic arm are tried to achieve at interval when solidifying is more than 1 ℃/second.Also have, copper alloy shown in the table 1 is as unavoidable impurities, contain elements such as Si, Ti below the 0.01 quality %, Zr, Be, V, Nb, Mo, W, Mg in total amount, contain B, C, Na, S, Ca, As, Se, Cd, In, Sb, Pb, Bi, MM elements such as (thuliums) below the 0.005 quality % in total amount.Also have, in table 1, composition outside the scope of the invention or composition ratio are given underscore.
And cutting out thickness from each ingot casting is that 50mm, width are that 180mm, length are the piece of 80mm, and rolling surface is carried out the face cutting, and heating keeps after 0.5 to 1 hour after arriving 900 ℃, and hot rolling is 16mm to thickness, from the temperature water-cooled more than 700 ℃.After the surface of this milled sheet carried out face cutting and remove descaling, respectively carry out twice cold rolling and annealing (cold rolling number of times is identical with the number of times of annealing) repeatedly, thereafter, carry out final cold rollingly, obtain the copper alloy plate that thickness is 0.2mm.At this moment, annealing temperature is controlled at below 430 ℃, and annealing time is that 5 minutes to 20 hours scope is carried out, and the growth and thickization of precipitation particles are inhibited, and are controlled to be the fine form of separating out.And, final cold rolling after, carry out low-temperature annealing.Final cold rolling working modulus is 50%.Low-temperature annealing is 200 to 500 ℃ temperature range, and the time range about 1 to 300 second is carried out so that the disrumpent feelings extensibility of the tension test of the direction parallel with rolling direction is controlled to be more than 5%.
Table 1
At this, annealing is twice annealing and low-temperature annealing, and, at N
2+ 10%H
2Atmosphere (dew point: below-20 ℃, O
2Concentration: 50ppm is following) carry out following the carrying out of clean processing before and after the annealing.About 2 times annealing, before annealing, carry out solvent and clean (the ultrasonic cleansing of hexane: 20kHz), after annealing, carry out pickling clean (10% sulfuric acid), thereafter, carry out mechanical mill (No. 600 water-fast pouncing papers).About low-temperature annealing, before annealing, carry out solvent and clean (the ultrasonic cleansing of hexane: 20kHz), after annealing, carry out pickling clean (10% sulfuric acid), thereafter, do not carry out mechanical mill.
For the copper alloy plate that so obtains, in each embodiment and comparative example, cut out test portion from copper alloy plate, carry out structure observation and surface analysis, mensuration contains the number of the Pization thing precipitation particles (below, be called fine precipitation particles) of Sn, carries out compositional analysis (Sn content).In addition, measure the number of thick brilliant precipitate particle (hereinafter referred to as thick brilliant precipitate particle), the C1s/Cu2p that XPS analysis after the alkali catholyte on the surface of mensuration copper alloy plate is cleaned is measured (below, be called relative C amount), measure the copper alloy plate surface the EBSD assay determination fine-grain (diameter of equivalent circle is lower than 0.5 μ m) to the area of viewing area than (below, the area ratio that is called fine-grain), in addition, measure disrumpent feelings extensibility and tensile strength by tension test, measure hardness, measure electric conductivity, thermotolerance, that estimates etching and processing (etching) and oxide film connects airtight the maintenance temperature.These results show in table 2 and table 3.Also has the project mark underscore in table 2 outside the scope of the invention.In addition, in table 3, the insufficient mark underscore of characteristic.
Table 2
The observation of fine precipitation particles is by the said determination method, and the particle diameter when mensuration is observed the copper alloy tissue with 300,000 times infiltration type electron microscope is the number of the precipitation particles of 1nm～20nm, as individual/μ m
2Calculate.In addition, the compositional analysis of fine precipitation particles (Sn content) by EDX analyze (beam diameter: 1nm) quality measurement % (Ni+M+P+Sn=100%), calculate as quality % ratio.
The observation of thick brilliant precipitate particle is by the said determination method, and the particle diameter when mensuration is observed the copper alloy tissue with 100,000 times scanning electron microscope surpasses the thick number through the precipitate particle of 100nm, as individual/μ m
2Calculate.
Relatively the mensuration of C amount is by the said determination method, and the copper alloy plate surface is carried out after the alkali catholyte cleans, and by XPS analysis, measures the peak area value of Cu2P on surface and the peak area value of C1s, calculates as C1s/Cu2p.At this, it is to be principal constituent (40%) with sodium hydroxide that the alkali catholyte is cleaned, clean in the aqueous solution of with medicament with the concentration fusion of 50g/L at the alkali catholyte of the representational market sale that contains other phosphoric acid salt, silicate, carbonate, interfacial agent, the liquid temperature: 60 ℃, cathode current density: 5A/dm
2, the time: 30 seconds condition is carried out.
The area of fine-grain is than passing through the said determination method, and the viewing area when measuring by EBSD analysis and observation copper alloy plate surface and the occupied area of fine-grain (diameter of equivalent circle is lower than 0.5 μ m) are calculated as the area ratio of fine-grain.
In tension test, make the JIS5 test film that cuts out abreast with rolling direction, measure disrumpent feelings extensibility and tensile strength.Hardness test is undertaken by the loading that the microcosmic Vickers hardness tester applies 4.9N.Tensile strength is more than the 750MPa, and hardness is that 220Hv is above for good.
Electric conductivity is processed into the test film of the short strip shape of width 10mm, length 300mm by milling (milling), measures resistance by doube bridge formula resistance measurement device, calculates by the average area method.Electric conductivity be more than 25% for good.
Thermotolerance is to be heated to 450 ℃ of hardness after a minute by above-mentioned determination of hardness test, estimates with hardness conservation rate (%)=(hardness before the hardness/heating after the heating) * 100 (%).The hardness conservation rate be more than 90% for good.
Etching and processing (etching) is used chlorination two molten iron solution (proportion 1.4), and with the liquid temperature: 45 ℃, spray is pressed: 1.5kgf/mm
2Carry out etching and processing, observe etching face (etching and processing face) by scanning electron microscope, smoothness is divided into A: good, B: surface irregularity takes place, C: the big three phases evaluation of surface irregularity.
Oxide film connects airtight and maintains the temperature at the copper alloy plate surface and carry out the alkali catholyte and clean, in addition, wash-＞pickling clean (10% sulfuric acid)-＞washing-＞drying after, in atmosphere, after 10 minutes, estimate by the stickup test of adhesive tape in the specified temperature heating.It is to be principal constituent (40%) with sodium hydroxide that the alkali catholyte is cleaned, the alkali catholyte of representational market sale that contains other phosphoric acid salt, silicate, carbonate, interfacial agent is cleaned in the aqueous solution of with medicament with the concentration fusion of 50g/L, the liquid temperature: 60 ℃, cathode current density: 5A/dm
2, the time: 30 seconds condition is carried out.The stickup test of adhesive tape is the adhesive tape (the system メ of Sumitomo ス リ one エ system society Application デ イ Application グ テ one プ) of sticking obedient market sale, is undertaken by stripping means.At this moment, Heating temperature changes with 10 ℃ of scales, the top temperature of peeling off that oxide film does not take place is connected airtight as oxide film keep the temperature evaluation.
As shown in table 1, embodiment 1～8 satisfies first compositing range of the present invention, and embodiment 9,10 satisfies second compositing range of the present invention.And as shown in table 2, embodiment 1～10 satisfies the mother metal tissue and the surface texture of regulation of the present invention.Thus, as shown in table 3, it is more than the 750MPa that the copper alloy plate of embodiment 1～10 has tensile strength, and hardness is the above mechanical characteristics of Hv220, and electric conductivity is more than the 25%IACS.In addition, stable on heating hardness conservation rate is more than 90%, can have high strength and high heat resistance concurrently.In addition, etching and processing is also good, and oxide film connects airtight and keeps temperature also is more than 240 ℃, for well.
To this, the Ni content of comparative example 11, (Ni+M)/P and Ni/M ratio are lower than lower value, and therefore, the number of fine precipitation particles is lower than 300/μ of lower value m
2, tensile strength, hardness, thermotolerance (hardness conservation rate) are low.In addition, (Ni+M)/P is lower than lower value, thus, the solid solution capacity of P increases, and therefore, oxide film connects airtight and keeps temperature low.
The number of the fine precipitation particles of comparative example 12 satisfies scope of the present invention, and tensile strength, hardness, thermotolerance are all good, but Ni content surpasses higher limit, and therefore, thick brilliant precipitate particle increases, and etching reduces.
The Fe content of comparative example 13 is that 0.02 quality % is lower than lower value, and Ni/M surpasses higher limit, and therefore, the number of fine precipitation particles is lower than 300/μ of lower value m
2, tensile strength, hardness, thermotolerance (hardness conservation rate) are low.
The number of the fine precipitation particles of comparative example 14 satisfies scope of the present invention, and tensile strength, hardness are good, but Fe content surpasses higher limit, Ni/M is lower than lower value, and therefore, thermotolerance (hardness conservation rate) is low, and thick brilliant precipitate particle increases, and etching reduces.
The P content of comparative example 15 is lower than lower value, (Ni+M)/P is above higher limit, and therefore, the number of fine precipitation particles is lower than lower value, and tensile strength, hardness, thermotolerance are all low.
The number of the fine precipitation particles of comparative example 16 satisfies scope of the present invention, and tensile strength, hardness, thermotolerance are all good, but P content surpasses higher limit, (Ni+M)/P is lower than lower value, and therefore, thick brilliant precipitate particle increases, and etching reduces.In addition, P content surpasses higher limit, and (Ni+M)/P is lower than lower value, therefore, the solid solution capacity of P increases, and oxide film connects airtight and keeps temperature low.
The number of the fine precipitation particles of comparative example 17 satisfies scope of the present invention, but Sn content is lower than lower value, and therefore, the Sn content of fine precipitation particles also is lower than lower value, tensile strength and hardness deficiency.
The number of the fine precipitation particles of comparative example 18 satisfies scope of the present invention, and tensile strength, hardness are good, but Sn content surpasses higher limit, thick brilliant precipitate particle increases, thermotolerance (hardness conservation rate), etching reduce, and electric conductivity also significantly reduces.In addition, Sn content surpasses higher limit, and therefore, oxide film connects airtight and keeps temperature low.
The number of the fine precipitation particles of comparative example 19 satisfies scope of the present invention, and tensile strength, hardness, thermotolerance are all good, but Zn content is lower than lower value, and therefore, oxide film connects airtight and keeps temperature low.
The number of the fine precipitation particles of comparative example 20 satisfies scope of the present invention, and tensile strength, hardness, thermotolerance are all good, but Zn content surpasses higher limit, and therefore, thick brilliant precipitate particle generates, and etching descends.In addition, this comparative example 20 is compared as can be known with embodiment 7,8, and it is saturated that oxide film connects airtight the raising effect that keeps temperature.
Table 3
Embodiment 2
Then, the experimental result that surface texture and oxide film are connected airtight the relation that keeps temperature describes.In this embodiment 2, from the ingot casting of the embodiment 2 of table 1, method and condition by identical with embodiment 1 obtain the copper alloy plate that thickness is 0.2mm.Therefore, form, composition is more identical with the embodiment 2 of table 3 than the characteristic of, mother metal tissue and tensile strength, general section extensibility, hardness, electric conductivity, thermotolerance, etching.
But annealing is twice annealing and low-temperature annealing, and, at N
2+ 10%H
2Atmosphere (dew point: below-20 ℃, O
2Below concentration: the 50ppm) carry out, make the clean processing variation of annealing front and back, thus, the surface texture (the area ratio of C amount, fine-grain relatively) of copper alloy plate is changed, carry out oxide film and connect airtight the evaluation that keeps temperature.At this moment, the clean processing before and after 2 times the annealing is carried out with identical method and condition.
These treatment condition show in table 4 and table 5.But, in table 4 and table 5, alkali steeping is cleaned, the alkali catholyte is cleaned to use respectively with sodium hydroxide and is principal constituent, and the alkali catholyte of representational market sale that contains other phosphoric acid salt, silicate, carbonate, interfacial agent cleans with medicament and the alkali catholyte is cleaned with medicament.In addition, the chemical dissolution that carries out of a part is handled and is used with sulfuric acid and the hydrogen peroxide aqueous solution as the representational market sale of principal constituent in 2 annealed aftertreatments.In addition, resulting surface texture and characteristic are displayed in Table 6.Also have, in table 6,, also have the insufficient underscore that also marks of characteristic the mark underscore outside the scope of the invention.
Table 4
Table 5
Table 6
Shown in table 4 and table 5, embodiment 1～10 carries out twice annealing and low-temperature annealing, and, carry out suitable clean processing before and after annealing separately, therefore, the C1s/Cu2p (C amount relatively) that carries out the surface of the XPS analysis mensuration after the alkali catholyte is cleaned on the copper alloy plate surface is good, be below 0.35, and the fine-grain of the EBSD assay determination on copper alloy plate surface (diameter of equivalent circle is lower than 0.5 μ m) is good with respect to the area ratio of viewing area, is below 0.90.
Its result, it is good that the oxide film of the copper alloy plate of embodiment 1～10 connects airtight the maintenance temperature, is more than 240 ℃.In addition, the area ratio that confirms relative C amount and fine-grain is respectively the more little tendency that oxide film connects airtight maintenance temperature (uprising) that can improve more.
To this, comparative example 11～13 carried out 2 annealing and stress relief annealed any, the clean processing before the annealing only has alcoholic acid dipping to clean, therefore, the C amount surpasses higher limit relatively, it is low that oxide film connects airtight the maintenance temperature.
In addition, comparative example 14～16 is owing to grind after low-temperature annealing, and thus, the area of fine-grain is more than 0.90 than becoming big, and therefore, oxide film connects airtight and keeps the temperature reduction.
Copper alloy plate of the present invention has excellent connecting airtight property of oxide film, in addition, according to copper alloy plate of the present invention, has the bendability of lead frame with the desired appropriateness of former material.Thus, copper alloy material of the present invention not only is defined in as lead frame and uses with former material, and the electrical and electronic parts that also can be applicable to other is with all former materials.
Claims (3)
1. high-intensity high heat-resistance copper alloy material, it is characterized in that, contain Ni:0.4～1.0 quality %, at least a element M of from the group of Fe and Co formation, selecting: in total amount 0.03～0.3 quality %, P:0.05～0.2 quality %, Sn:0.1～3 quality %, Zn:0.05～2.5 quality %, Cr:0.0005～0.05 quality %, ratio (the Ni+M)/P of the content of Ni and M and the content of P is 4～12, the ratio Ni/M of Ni and M is 3～12, surplus is Cu and unavoidable impurities
In metal structure, particle diameter is that the number of the fine Pization thing precipitation particles of 1～20nm is 300/μ m
2More than, the number that particle diameter surpasses the thick brilliant precipitate particle of 100nm is 0.5/μ m
2Below,
Sn content in the described Pization thing precipitation particles is that Sn/ (Ni+M+P+Sn) counts more than 0.01 with the quality % ratio that obtains by the EDX assay determination,
The disrumpent feelings extensibility of the tension test of the direction parallel with rolling direction is more than 5%.
2. high-intensity high heat-resistance copper alloy material according to claim 1 is characterized in that, also contains at least a element of selecting from Al and Mn of 0.0005～0.05 quality % in total amount.
3. high-intensity high heat-resistance copper alloy material according to claim 1 and 2, it is characterized in that, carrying out after the alkali catholyte cleans, the peak area value of the C1s on the surface of measuring by XPS analysis is below 0.35 with respect to the ratio C1s/Cu2p of the peak area value of Cu2p, and the fine-grain that observed diameter of equivalent circle is lower than 0.5 μ m during by EBSD analysis and observation surface is below 0.90 with respect to the area ratio of viewing area.
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| CN104789812A (en) * | 2014-01-18 | 2015-07-22 | 株式会社神户制钢所 | Fe-P based copper alloy sheet excellent in strength, heat resistance and bending processibility |
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| JP5572754B2 (en) | 2012-12-28 | 2014-08-13 | 三菱マテリアル株式会社 | Copper alloy for electronic and electrical equipment, copper alloy sheet for electronic and electrical equipment, conductive parts and terminals for electronic and electrical equipment |
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| CN103160703A (en) * | 2011-12-09 | 2013-06-19 | 株式会社神户制钢所 | High-strength copper alloy plate excellent in oxide film adhesiveness |
| CN103502489B (en) * | 2012-01-06 | 2015-11-25 | 三菱综合材料株式会社 | The manufacture method of electronic electric equipment copper alloy, electronic electric equipment copper alloy thin plate, electronic electric equipment copper alloy, electronic electric equipment conducting element and terminal |
| CN103502489A (en) * | 2012-01-06 | 2014-01-08 | 三菱综合材料株式会社 | Copper alloy for electronic/electric device, copper alloy thin plate for electronic/electric device, method for manufacturing copper alloy for electronic/electric device, and conductive part and terminal for electronic/electric device |
| CN105154713A (en) * | 2012-01-06 | 2015-12-16 | 三菱综合材料株式会社 | Copper alloy for electronic/electric device, copper alloy thin plate for electronic/electric device, and conductive part and terminal for electronic/electric device |
| CN105143479A (en) * | 2013-03-11 | 2015-12-09 | 株式会社Uacj | Copper alloy seamless tube for heat transfer tube |
| CN105074024A (en) * | 2013-03-11 | 2015-11-18 | 株式会社Uacj | Copper alloy seamless tube for cold and hot water supply |
| CN105074024B (en) * | 2013-03-11 | 2017-05-17 | 株式会社Uacj | Copper alloy seamless tube for cold and hot water supply |
| CN105143479B (en) * | 2013-03-11 | 2017-05-17 | 株式会社Uacj | Copper alloy seamless tube for heat transfer tube |
| CN104789812A (en) * | 2014-01-18 | 2015-07-22 | 株式会社神户制钢所 | Fe-P based copper alloy sheet excellent in strength, heat resistance and bending processibility |
| 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 |
| TWI647320B (en) * | 2017-03-30 | 2019-01-11 | 日商Ｊｘ金屬股份有限公司 | Cu-Ni-Si copper alloy strip and manufacturing method thereof |
| CN112585699A (en) * | 2018-08-21 | 2021-03-30 | 住友电气工业株式会社 | Covered electric wire, electric wire with terminal, copper alloy wire, copper alloy stranded wire, and method for producing copper alloy wire |
| CN112585699B (en) * | 2018-08-21 | 2022-05-13 | 住友电气工业株式会社 | Covered electric wire, electric wire with terminal, copper alloy wire, copper alloy stranded wire, and method for producing copper alloy wire |
| CN110643850A (en) * | 2019-10-24 | 2020-01-03 | 宁波博威合金材料股份有限公司 | Copper alloy with excellent bending performance and preparation method and application thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5468423B2 (en) | 2014-04-09 |
| DE102011013399A1 (en) | 2011-09-15 |
| JP2011184775A (en) | 2011-09-22 |
| KR20110102242A (en) | 2011-09-16 |
| CN102191402B (en) | 2013-03-13 |
| KR101231549B1 (en) | 2013-02-07 |
| DE102011013399B4 (en) | 2017-09-07 |
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