CN102191402B - High-strength high-heat-resistance copper alloy - Google Patents
High-strength high-heat-resistance copper alloy Download PDFInfo
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- CN102191402B CN102191402B CN2011100600613A CN201110060061A CN102191402B CN 102191402 B CN102191402 B CN 102191402B CN 2011100600613 A CN2011100600613 A CN 2011100600613A CN 201110060061 A CN201110060061 A CN 201110060061A CN 102191402 B CN102191402 B CN 102191402B
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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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- 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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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-strength high-heat-resistance copper alloy with the former material adhesion excellence that be suitable for, 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 is consisted of by the Cu-Ni-Si series copper alloy that contains Ni and Si.In addition, among this Cu-Ni-Si copper alloy, for example contain the copper alloy (C70250 copper alloy) of Ni:2.2～4.2 quality %, Si:0.25～1.2 quality %, Mg:0.05～0.30 quality % 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 these semiconductor devices high strength and the high heat resistance of the used copper alloy plate of lead frame.The high strength of copper alloy plate requires guaranteeing of the treatability that descends along with thin plate and guaranteeing as the intensity of final component parts.In addition, stable on heating raising require to prevent to be used to form after the punch process of lead frame go that strain thermal treatment causes softening, and softening when preventing from being subject to thermal process in the semiconductor component assembling procedure.These are not only lead frame, and relate to other electrical and electronic parts, such as the employed copper alloy plate of electroconductive component of junctor, terminal, switch, rly. etc.In addition, in the etching and processing as the applicable processing method of fine wiring machining, stain can not occur, the smoothness of the etching and processing face of copper alloy plate is excellent, 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 adhesion 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 adhesion of moulded resin and lead frame reduces, because the heat-seal crackle during to the actual load of printed base plate and peel off generation, the reliability decrease of encapsulation.Thus, for the reliability that remains potted, the adhesion of the oxide film of maintenance lead frame is very important.
Under this background, by Cu-Ni-Si copper alloy (C70250 copper alloy) although the copper alloy plate intensity and the excellent heat resistance that consist of,, have in the etching and processing as the processing method that is suitable for fine wiring processing, produce stain, the problem that the smoothness of etching and processing face is poor.
Therefore, in order to improve the smoothness of this etching face, applicant of the present invention has proposed a kind of copper alloy plate, take the Cu-Fe-P series copper alloy as mother metal, 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 JP 2001-335864 communique
But this patent documentation 1 disclosed Cu-Ni-Fe-P series copper alloy plate is although 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 Cu-Ni-Fe-P series copper alloy plate carries out finish to gauge (finally cold rolling) with high working modulus, so although 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 occur yet, the smoothness of etching and processing face is excellent, in addition, the high-strength high-heat-resistance copper alloy of adhesion excellence that is used for the oxide film of the reliability remain potted.
At least a element M that high-strength high-heat-resistance copper alloy 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 %, the ratio (Ni+M) of the content of Ni and M and the content of P/P is 4～12, the ratio Ni/M of Ni and M is 3～12, surplus is Cu and inevitable impurity
In metal structure, particle diameter is that the number of the fine P compound 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 P compound precipitation particles, analyze the quality % ratio of measuring by EDX: 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 represents 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 % take total amount (as total amount, being the amount of this element in the time of independent when containing Fe and Co) 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. consists of, and can be used for requiring the purposes with the adhesion excellence of 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 P compound precipitation particles of regulation particle diameter generates more than the regulation number, and the Sn content of this P compound precipitation particles is more than the prescribed value, thus, the anchorage force of the movement of inhibition dislocation and the P compound precipitation particles of elimination improves, and the intensity of copper alloy plate and thermotolerance improve.In addition, in the etching and processing of copper alloy plate, the P compound 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, and therefore, the adhesion of oxide film improves; 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 P compound precipitation particles, Sn is detected, and therefore, in the present invention, limits the Sn content of described P compound precipitation particles.Sn has in described P compound and the concentrated situation of parent material interface in being contained in the P compound 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 adhesion 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 inevitable impurity in the copper alloy, the hot workability of copper alloy plate improves.
In addition, preferred this high-strength high-heat-resistance copper alloy, be 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, 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 consisted of, by reducing 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, and thus, the adhesion of oxide film improves.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 adhesion 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 lead frame with the bendability of the needed appropriateness of former material, 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.
According to copper alloy material of the present invention, intensity (tensile strength and hardness) and thermotolerance improve, and, punch process type not only, and in the etching and processing as the processing method that is suitable for fine wiring processing stain can not occur yet, the smoothness of etching and processing face and plating are excellent.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 occur 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 adhesion of copper alloy material oxide film of the present invention is excellent.
Embodiment
Below, the high-intensity high heat-resistance copper alloy of the adhesion 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 block former material etc. are applicable too.
At first, to the restriction reason of the interpolation reason of the composition in the copper alloy plate and compositing range, and the number of P compound precipitation particles and Sn content, the number of thick brilliant precipitate particle limits reason and describes.
(Ni:0.4～1.0 quality %)
Ni separates out the P compound 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 was lower than 0.4 quality %, the fine P compound precipitation particles that contains Sn was not enough.Therefore, in order effectively to bring into play the effect of high strength and high heat resistance, need to 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 treatment after the punching press of inhibition lead frame and the thermal process in the semiconductor assembling operation is effective.Fe or Co and Ni are same, and the fine P compound 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 P compound precipitation particles that contains Sn is not enough, and, P compound precipitation particles becomes the precipitation particles take Ni and P as main body, can not effectively bring into play the effect of high strength and high heat resistance, therefore, need to 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, the 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 scope 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 P compound 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 was lower than 0.05 quality %, the fine P compound precipitation particles that contains Sn was not enough, therefore, can not effectively bring into play the effect of high strength and high heat resistance.Therefore, P need to 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 adhesion that the P solid solution capacity increases oxide film descends.Therefore, P content is the scope of 0.05～0.2 quality %.In addition, in this scope, the preferred scope of P 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 take Ni-M (Fe and/or Co)-P as main body, detects Sn.Sn is also indefinite in the reason that the part of precipitation particles is detected, but be thought of as such as inferior mechanism: contain Sn and exist in take Ni-M (Fe and/or Co)-P as the precipitation particles of main body, 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 take Ni-M (Fe and/or Co)-P as main body, 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 resistance, need to 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 melting casting during the manufacturing of copper alloy plate, and hot workability also descends.In addition, the electroconductibility of copper alloy plate also descends, and the adhesion of oxide film descends.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 for necessity of the adhesion that improves oxide film.In order effectively to bring into play this effect, Zn need to 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 adhesion 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, be used for 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 simultaneously high strength and high heat resistance, contain P and the Sn of higher concentration, therefore, hot workability is relatively more 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 to 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 intensity and the thermotolerance of copper alloy plate.In addition, separate out as described later in order to make the fine P compound precipitation particles that contains Sn among the present invention, need above-mentioned 2 formulas to set up, if do not satisfy this 2 formula, can not have concurrently as the object of the invention high strength and high heat resistance.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 scope is 5≤(Ni+M)/P≤10, and 4≤Ni/M≤10.
(inevitably impurity)
Inevitable impurity among the present invention is elements such as Si, Ti, Zr, Be, V, Nb, Mo, W, Mg.When containing these elements, thick brilliant precipitate particle generates easily, in addition, hinders two of high strength and high heat resistance and stands.Therefore, inevitably impurity 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 inevitable impurity.When containing these elements, thick brilliant precipitate particle generates easily, and hot workability also descends.Preferably suppress as the few content below the 0.1 quality % take total amount.
((particle diameter is that 1～20nm) number is 300/μ m to P compound precipitation particles
2More than, the Sn content of P compound precipitation particles: with Sn/ (Ni+M+P+Sn) than counting more than 0.01)
So-called P compound precipitation particles refers to organize detected particle by the infiltration type electron microscope observation copper alloy more than 100,000 times among the present invention, is that particle diameter is the precipitation particles of 1～20nm.The number of this P compound precipitation particles is 300/μ m
2More than.Also have, these P compound precipitation particles are take the P compound that is made of Ni-M (Fe and/or Co)-P as main body, 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).
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 at least any 3 visuals field, its measurement result is averaged.
This fine P compound 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 originally thick brilliant precipitate particle of existence when when casting or hot rolling.Therefore, if not by the infiltration type electron microscope observation copper alloy tissue more than 100,000 times, just can not observe this fine precipitation particles.
In the present invention, the number of the fine P compound precipitation particles of this Sn of containing is 300/μ m
2More than.It is more much larger than thick brilliant precipitate particle that this fine P compound precipitation particles that contains Sn suppresses the anchorage force of the movement of dislocation and elimination.Therefore, in copper alloy plate of the present invention, making particle diameter is that the following fine Ni-M (Fe and/or Co) of 20nm-P-Sn compound is the as much as possible existence in the copper alloy tissue of precipitation particles of main body, thus, improve above-mentioned anchorage force, can realize high strength and high heat resistance.
In addition, this particle diameter is the fine P compound 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 machining, the essential factor that can the composition stain occur can not make the smoothness of etching and processing face descend.To this, thick brilliant precipitate particle is not only little for the help of high strength and high heat resistance, and in etching and processing, becomes the dirty essential factor that occurs, 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 P compound precipitation particles median size on be limited to 20nm.Even and particle diameter is lower than the infiltration type electron microscope of nano-precipitation 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 P compound precipitation particles of Sn is to be the restriction that the P compound precipitate more than the 1nm carries out to particle diameter.
The number of the fine P compound precipitation particles of this Sn of containing is lower than 300/μ m
2The time, the number of particles that can bring into play effect is not enough, and 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 P compound 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 take Ni+Fe+Co+P+Sn as 100% calculating, 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 P compound precipitation particles forms to analyze the % mass ratio of measuring by EDX, and by Ni:30～70%, M (Fe and/or Co): 5～60%, the scope about P:5～35%, Sn:1～30% consists of.
(number of thick brilliant precipitate particle (more than the particle diameter 100nm) is 0.5/μ m
2Below)
In the present invention, be that the amount of the fine P compound precipitation particles that contains Sn below the above 20nm of 1nm limits to particle diameter, if satisfy this restriction, 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 to 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 occurs, 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 P compound 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 is the brilliant precipitate particle that separates as crystallization phases in the copper alloy tissue, do not form the precipitate particle that separates as solid-phase of clear and definite crystallization phases or their mixture.Also have, as the thick brilliant precipitate particle of these particle diameters above 100nm, exist P compound system (Ni-Fe-P system, Ni-Co-P system, Ni-P system etc.) and Ni-Sn to be.
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 at least arbitrarily 3 visuals field, 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 large, 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, by having suitable disrumpent feelings extensibility, 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.To this, when the disrumpent feelings extensibility of the tension test of the direction parallel with rolling direction is lower than 5%, 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 effectively element.Thus, if Al and/or Mn also can contain below specified amount.In order effectively to bring into play above-mentioned effect, 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 %.
(be 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)
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, the peak area value of the C1s on so-called surface carrying out the XPS analysis mensuration after the alkali catholyte is cleaned refers to carrying out the relative C amount on the copper alloy plate surface after the alkali catholyte is cleaned with respect to the ratio of the peak area value of Cu2p.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 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 (outside the benzotriazole) of processing for the look that prevents copper alloy plate becomes etc.When these goods and materials are present in the surface, can detrimentally affect be arranged to the adhesion 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 the pre-treatment such as electrolytic degreasing, the part is carried out plating and is processed in assembling procedure, the reliability that encapsulates about the adhesion of the oxide film that generates owing to the thermal process of this assembling procedure.Therefore, the C that the adhesion 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 on the surface that the XPS analysis of carrying out after the alkali catholyte is cleaned is measured such as the pre-treatment of electrolytic degreasing etc.Also have, for the organic rust preventing film (outside the benzotriazole) of the variable color that prevents 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 usually take the basic salt of sodium hydroxide, water glass, sodium phosphate, yellow soda ash etc. as matrix, add the organism of interfacial agent or chelate compound etc. and consist of, 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 adhesion of oxide film declined to a great extent, the reliability decrease of encapsulation.Therefore, preferred little with respect to the ratio C1s/Cu2p 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, 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 refers to the shared ratio of fine-grain on copper alloy plate surface with respect to the Area Ratio of viewing area.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, this so-called crystal grain refer to take analyze by EBSD between adjacent measuring point azimuth difference as the situation more than 5 ° as crystal boundary, take the zone that surrounded fully by this crystal boundary as crystal grain.
The Area Ratio of the fine-grain on copper alloy plate surface refers to that 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, and thus, the adhesion of oxide film descends.Thus, the Area Ratio of the fine-grain on copper alloy plate surface is preferably less, is below 0.90.In addition, more preferably below 0.85.
(manufacture method of copper alloy plate)
Then, the manufacture method of copper alloy plate of the present invention described.For the alloy structure of the copper alloy plate that makes manufacturing forms above-mentioned tissue, do not need very large 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 again finally cold rolling (finish to gauge), form the copper alloy plate of goods thickness of slab thereafter.
Also have, in the final cold rolling rear low-temperature annealing (going strain annealing) of preferably carrying out.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 is effective to this quality improvement.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 P compound 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 have, to analyze the quality % ratio of measuring by EDX be more than 0.01 in order to be controlled to be the Sn content that makes P compound precipitation particles, undertaken effectively by adjusting Ni, Fe in the copper alloy and/or Co, P and Sn content.
That is, as mentioned above, the fine P compound 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 P compound 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 P compound precipitation particles that contains Sn to be separated out in a large number, when improving annealing temperature, along with the increase of the quantity of precipitation particles, causes growth and thickization of precipitation particles.Therefore, preferably anneal several times, and annealing temperature each time is controlled at below 430 ℃, 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 easily the above-mentioned fine form of separating out.
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, repeatedly carry out operation cold rolling and annealing for 2 times 2 times and can easily obtain the form of separating out of the described fine P compound precipitation particles that contains Sn, therefore preferred.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 P compound 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 accelerating casting, and, improving Heating temperature and the end temp of hot rolling, the speed of cooling after the acceleration hot rolling is effective.The condition of so-called speed of cooling when accelerating casting is that the speed of cooling when being used in the solidifying of the thick crystallisate of control and being used for controls that the speed of cooling to 500 ℃ is more than 0.1 ℃/second after the solidifying of thick precipitate, is preferably more than 0.5 ℃/second.Therefore, preferred cooling by water for example.In addition, the Heating temperature of so-called raising hot rolling and the condition of end temp are 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 Heating temperature of hot rolling was hanged down, the thick brilliant precipitate particle solid solution that generates when casting was insufficient, and the end temp of hot rolling 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, the oil content residue that causes in order to remove the oxide film that in annealing, generates and ROLLING OIL, although 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 effectively becomes C etc., before annealing, clean process effective, particularly, must before the low-temperature annealing as final operation, clean processing, and, after low-temperature annealing, carry out removing of the clean oxide film that waits of pickling and process effectively.The 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, mostly carry out afterwards mechanical mill in annealing.This is because the oxide film that annealing generates is strong, is difficult to only only remove by pickling.Thus, in order not carry out mechanical mill, 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.Specifically, annealing atmosphere formation reducing atmosphere (contains H
2Atmosphere with the reducing component of CO etc.), oxidisability composition (O
2And H
2O etc.) management does not make strong oxide film very important for alap concentration.Particularly in the low-temperature annealing operation as final operation, by annealing atmosphere is fully managed, be controlled to be and do not make strong oxide film generation, can only only remove oxide film by pickling, do not carry out mechanical mill ground and do not carry out surface adjustment.
Embodiment 1
Then, the embodiment that can confirm effect of the present invention and the experimental result of comparative example are described.Manufacture method as copper alloy plate, in high frequency furnace to having shown in the following table 1 after the molten alloyed copper that forms carries out melting, with volume (book) type mold of pouring-type injection graphite-made, 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-made has sufficient thermal capacity and thermal conductivity, try to achieve from 2 branch intervals between dendritic arm solidify the time speed of cooling be more than 1 ℃/second.Also have, copper alloy shown in the table 1 is as inevitable impurity, contain the elements such as Si, Ti below the 0.01 quality %, Zr, Be, V, Nb, Mo, W, Mg in total amount, contain the elements such as B, C below the 0.005 quality %, Na, S, Ca, As, Se, Cd, In, Sb, Pb, Bi, MM (thulium) in total amount.Also have, in table 1, the 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 ℃.Face cutting is carried out except behind the descaling in the surface of this milled sheet, repeatedly respectively carry out twice cold rolling and annealing (cold rolling number of times is identical with the number of times of annealing), 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 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 P compound 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), the EBSD that measures the copper alloy plate surface analyze the fine-grain (diameter of equivalent circle is lower than 0.5 μ m) measured to the Area Ratio of viewing area (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 mark underscore of characteristic deficiency.
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 take 300,000 times infiltration type electron microscope is as 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 (40%) take sodium hydroxide as principal constituent that the alkali catholyte is cleaned, clean in the aqueous solution of with medicament with the concentration melting of 50g/L at the alkali catholyte of the representational market sale that contains other phosphoric acid salt, silicate, carbonate, interfacial agent, liquid temperature: 60 ℃, cathode current density: 5A/dm
2, the time: 30 seconds condition is carried out.
The Area Ratio of fine-grain is by 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 Double-bridge type 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 after the heating/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 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 occurs, C: the large 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,, estimate by the stickup test of adhesive tape after 10 minutes in the specified temperature heating.It is take sodium hydroxide as principal constituent (40%) 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 that with medicament melts with the concentration of 50g/L, 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 Sumitomo ス リ one メ Application processed デ イ of エ system society Application グ テ one プ) of sticking note 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 occur is connected airtight as oxide film keep the temperature evaluation.
As shown in table 1, embodiment 1～8 satisfies the first compositing range of the present invention, and embodiment 9,10 satisfies the second compositing range of the present invention.And as shown in table 2, embodiment 1～10 satisfies 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, and tensile strength and hardness are not enough.
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, effects on surface proterties and the oxide film experimental result of connecting 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, the characteristic of composition, composition ratio, mother metal tissue and tensile strength, general section extensibility, hardness, electric conductivity, thermotolerance, etching is identical with the embodiment 2 of table 3.
But 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, make the clean processing variation of annealing front and back, thus, the surface texture (the relatively Area Ratio of C amount, fine-grain) 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 and used respectively with sodium hydroxide as 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 processed and is used with sulfuric acid and the hydrogen peroxide aqueous solution as the representational market sale of principal constituent in the aftertreatment of 2 annealing.In addition, resulting surface texture and characteristic are displayed in Table 6.Also have, in table 6, to the mark underscore outside the scope of the invention, also have the also mark underscore of characteristic deficiency.
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 (relatively C amount) 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 it is good with respect to the Area Ratio of viewing area that the EBSD on copper alloy plate surface analyzes the fine-grain (diameter of equivalent circle is lower than 0.5 μ m) of measuring, and 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 more can improve.
To this, comparative example 11～13 carried out 2 annealing and stress relief annealed any, the clean processing before the annealing only has the dipping of ethanol 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, it is large that the Area Ratio of fine-grain becomes, and is more than 0.90, and therefore, oxide film connects airtight and keeps the temperature reduction.
Copper alloy plate of the present invention has excellent oxide film adhesion, in addition, according to copper alloy plate of the present invention, has lead frame with the bendability of 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-strength high-heat-resistance copper alloy, 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 %, the ratio (Ni+M) of the content of Ni and M and the content of P/P is 4～12, the ratio Ni/M of Ni and M is 3～12, surplus is Cu and inevitable impurity, wherein, described M represents at least a element selected from the group who is made of Fe and Co, Fe and/or Co
In metal structure, particle diameter is that the number of the fine P compound 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 P compound precipitation particles is that Sn/ (Ni+M+P+Sn) counts more than 0.01 to measure the quality % ratio that obtains by the EDX analysis,
The disrumpent feelings extensibility of the tension test of the direction parallel with rolling direction is more than 5%.
2. high-strength high-heat-resistance copper alloy, 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 %, at least a element of from Al and Mn, selecting that also contains 0.0005～0.05 quality % in total amount, the ratio (Ni+M) of the content of Ni and M and the content of P/P is 4～12, the ratio Ni/M of Ni and M is 3～12, surplus is Cu and inevitable impurity, wherein, described M represents at least a element selected from the group who is made of Fe and Co, Fe and/or Co
In metal structure, particle diameter is that the number of the fine P compound 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 P compound precipitation particles is that Sn/ (Ni+M+P+Sn) counts more than 0.01 to measure the quality % ratio that obtains by the EDX analysis,
The disrumpent feelings extensibility of the tension test of the direction parallel with rolling direction is more than 5%.
3. high-strength high-heat-resistance copper alloy 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 the diameter of equivalent circle of observing during by EBSD analysis and observation surface is lower than 0.5 μ m is below 0.90 with respect to the Area Ratio of viewing area.
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| JP5700834B2 (en) * | 2011-12-09 | 2015-04-15 | 株式会社神戸製鋼所 | High strength copper alloy sheet with excellent oxide film adhesion |
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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 |
| CN104919066A (en) * | 2013-01-09 | 2015-09-16 | 三菱综合材料株式会社 | Copper alloy for electronic or electrical device, copper alloy thin sheet for electronic or electrical device, process for manufacturing copper alloy for electronic or electrical device, conductive component for electronic or electrical device, and terminal |
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| CN110643850B (en) * | 2019-10-24 | 2020-12-01 | 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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| JPH0694390A (en) * | 1992-09-10 | 1994-04-05 | Kobe Steel Ltd | Copper alloy tube for heat exchanger heat transfer tube and manufacture thereof |
| US5820701A (en) * | 1996-11-07 | 1998-10-13 | Waterbury Rolling Mills, Inc. | Copper alloy and process for obtaining same |
| 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 |
| US5893953A (en) * | 1997-09-16 | 1999-04-13 | Waterbury Rolling Mills, Inc. | Copper alloy and process for obtaining same |
| JPH11264038A (en) * | 1998-03-18 | 1999-09-28 | Nippon Mining & Metals Co Ltd | Copper alloy foil |
| JP3465108B2 (en) * | 2000-05-25 | 2003-11-10 | 株式会社神戸製鋼所 | Copper alloy for electric and electronic parts |
| JP4041803B2 (en) * | 2004-01-23 | 2008-02-06 | 株式会社神戸製鋼所 | High strength and high conductivity copper alloy |
| JP3871064B2 (en) * | 2005-06-08 | 2007-01-24 | 株式会社神戸製鋼所 | Copper alloy plate for electrical connection parts |
| JP5075438B2 (en) * | 2007-03-20 | 2012-11-21 | Ｄｏｗａメタルテック株式会社 | Cu-Ni-Sn-P copper alloy sheet and method for producing the same |
| JP2009179864A (en) * | 2008-01-31 | 2009-08-13 | Kobe Steel Ltd | Copper alloy sheet superior in stress relaxation resistance |
| US7928541B2 (en) * | 2008-03-07 | 2011-04-19 | Kobe Steel, Ltd. | Copper alloy sheet and QFN package |
| JP5291494B2 (en) * | 2008-09-30 | 2013-09-18 | 株式会社神戸製鋼所 | High strength high heat resistance copper alloy sheet |
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| CN101525702A (en) * | 2008-03-07 | 2009-09-09 | 株式会社神户制钢所 | Copper alloy sheet and QFN package |
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| JP特开2009-179864A 2009.08.13 |
| JP特开2010-106355A 2010.05.13 |
| JP特开平6-94390A 1994.04.05 |
Also Published As
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| DE102011013399A1 (en) | 2011-09-15 |
| DE102011013399B4 (en) | 2017-09-07 |
| CN102191402A (en) | 2011-09-21 |
| JP5468423B2 (en) | 2014-04-09 |
| KR20110102242A (en) | 2011-09-16 |
| JP2011184775A (en) | 2011-09-22 |
| KR101231549B1 (en) | 2013-02-07 |
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