CN102471831B - Preparation method of copper alloy for electronic equipment - Google Patents
Preparation method of copper alloy for electronic equipment Download PDFInfo
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- CN102471831B CN102471831B CN200980160752.1A CN200980160752A CN102471831B CN 102471831 B CN102471831 B CN 102471831B CN 200980160752 A CN200980160752 A CN 200980160752A CN 102471831 B CN102471831 B CN 102471831B
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- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/02—Alloys based on copper with tin as the next major constituent
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- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/495—Lead-frames or other flat leads
- H01L23/49579—Lead-frames or other flat leads characterised by the materials of the lead frames or layers thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/50—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
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
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Abstract
Provided is a heat-resistant copper alloy for electronic equipment, the strength of which is not diminished even at a high temperature of 500 DEG C. The material contains 1.5-2.4 mass% of Fe, 0.008-0.08 mass% of P, and 0.01-0.5 mass% of Zn. When observed using a transmission electron microscope, the peak value in a histogram of the diameters of precipitate particles per 1 [mu]m2 is in the range of 15-35 nm diameter, precipitate particles having diameters within said range are present at a frequency of 50% of the total frequency or higher, and their half-value width is 25nm or less.
Description
Technical field
The present invention relates to the copper alloy for electronic apparatus and the lead frame material that in the electronicss such as semiconductor device, electronic unit, use.
Background technology
At present, the lead frame of using in the semiconductor device such as IC or LSI, the terminal of various electronic units and junctor are implemented punch process by the thin plate to copper alloy and are made.
Wherein, in the lead frame of making by punch process etc., produce unrelieved stress.In order to remove this unrelieved stress, although the thermal treatment at conventionally the lead frame after punch process etc. being implemented to 400～450 ℃, yet known during due to this thermal treatment the crystal structure recrystallization of copper alloy make the strength decreased of copper alloy.Therefore, to the copper alloy for electronic apparatus using in lead frame etc. require thermotolerance with can not be due to above-mentioned thermal treatment strength decreased.
As this copper alloy for electronic apparatus, provide widely a kind of Cu-Fe-P of disclosed precipitation hardening type alloy in patent documentation 1,2 to be for example associated gold (so-called C194 is associated gold).This Cu-Fe-P is associated gold makes Fe-P based compound be dispersed in copper parent phase as precipitation particles, thereby realizes the raising of thermotolerance, intensity, specific conductivity.
Conventionally, known in above-mentioned precipitation hardening type alloy, the size that is dispersed in the precipitate particle in copper parent phase has larger impact to its characteristic.; oversize particle more than 1 μ m becomes main nucleation site when recrystallization; this size of particles more easily forms recrystallization core; therefore thermotolerance reduces; if but closely disperse the minuteness particle below tens nanometers in copper parent phase; utilize pinning effect constraint crystal boundary to move, recrystallizationization is suppressed, and thermotolerance improves.
It is alloy material with Cu-Fe that patent documentation 1 discloses lead frame, the Zn of the P of the Fe that contains 1.5～2.6 quality %, 0.01～0.1 quality %, 0.01～0.2 quality %, remainder contains Cu and inevitable impurity, its interior tissue is that in the Fe particle of separating out, diameter is that percentage by volume in the alloy of the Fe particle below 40nm is more than 0.2%, even if remove the heating of strain, the reduction of intensity is fewer, excellent heat resistance also.
Patent documentation 2 discloses the copper alloy of excellent heat resistance, and this copper alloy contains Fe, and the Orientation density in the Cube orientation after 1 minute of annealing at 500 ℃ is below 50%, and the average crystallite particle diameter of annealing after 1 minute at 500 ℃ is below 30 μ m.In the document, having recorded this Albatra metal-carries out after by the copper alloy hot rolling to containing Fe cold rolling while manufacturing cold rolling copper alloy, hot rolling and final at least respectively implement 2 cold rolling and annealing between cold rolling in, working modulus with 50～80% is carried out every 1 time cold rolling, final working modulus when cold rolling is 30～85% to manufacture, and also can cause hardly copper alloy and the method for making thereof of strength decreased, excellent heat resistance when carrying out the thermal treatments such as stress relieving (askew body is got り baked Pure).
Patent documentation 1: No. 11-80862, Japanese kokai publication hei
Patent documentation 2: No. 2007-113121, TOHKEMY
Yet, along with the raising of stamping technology, utilize the multi-pin of the lead frame of punch process making to be made progress, the trend that thereupon exists the unrelieved stress after processing to increase recently, in order to remove unrelieved stress, also carry out the thermal treatment under the high-temperature area of 500 ℃ of left and right.Require recently to stand these thermal treatments, can not cause that the reduction of intensity and then the Cu-Fe-P of excellent heat resistance are associated gold.
Summary of the invention
What the inventor furtherd investigate found that, diameter is less than the very fine precipitate particle (Fe-P based compound) of 15nm at the high-temperature areas of 500 ℃, the inhibition that the pinning effect of the movement of bound particle is little, almost can not expect recrystallization, in transmission electron microscope is observed, every 1 μ m
2peak value in chart of frequency distribution of the diameter of precipitate particle be in the diameter range of 15～35nm, and the precipitate particle in this diameter range exists with more than 50% frequency of total frequency, the half-breadth at the peak of this diameter range is that the precipitate particle (Fe-P based compound) below 25nm suppresses very effective to the recrystallizationization under the high-temperature area of 500 ℃ of left and right, and then goes far towards stable on heating raising.
; if the precipitate particle of the copper alloy for electronic apparatus the present invention relates to has the distribution of the peak value of diameter in the limited range value of above-mentioned chart of frequency distribution; even under the high-temperature area of 500 ℃ of left and right; also can bring into play pinning effect to greatest extent and suppress recrystallization, can prevent effectively the strength decreased under high temperature.If the peak value of the diameter of precipitate particle exceeds limited range value, pinning effect reduces, and can not suppress recrystallization, and the intensity maintaining under high temperature becomes difficult.
The invention is characterized in, the Fe of 1.5～2.4 quality % will be contained, the copper alloy of the Zn of the P of 0.008～0.08 quality % and 0.01～0.5 quality % melts casting, by after ingot casting building up by welding, with rolling rate, more than 60% implement hot rolling, then at 900～950 ℃, carry out the solution treatment of 2～4 hours, copper alloy plate after solution treatment is carried out at 450～575 ℃ to the ageing treatment of 3～12 hours, to the copper alloy plate after ageing treatment, with working modulus 60～80%, carry out the 1st cold rolling, copper alloy plate after cold rolling to the 1st at 200～400 ℃ carries out the 1st low-temperature annealing of 0.5 minute～3 hours, with the copper alloy plate after 30～60% pairs of the 1st low-temperature annealings of working modulus, carry out the 2nd cold rolling, copper alloy plate after cold rolling to the 2nd at 200～400 ℃ carries out the 2nd low-temperature annealing of 0.5 minute～3 hours, be manufactured on thus in transmission electron microscope observation, with every 1 μ m
2the peak value of the round equivalent diameter that equates of the area of precipitate particle in chart of frequency distribution be in the diameter range of 15～35nm, and the precipitate particle in this diameter range exists with more than 50% frequency of total frequency, the half-breadth at the peak of this diameter range is the copper alloy for electronic apparatus below 25nm.
In addition, can be after described the 2nd low-temperature annealing, the low-temperature annealing of 0.5 minute～3 hours at 200～400 ℃ that repeats that the cold rolling of working modulus 30～60% and this carry out after cold rolling.
In addition, described copper alloy, preferably contains the Ni of 0.003～0.5 quality % and the Sn of 0.003～0.5 quality %.
Further, described copper alloy, more than preferably containing at least one in Al, Be, Ca, Cr and Si, its content is set as 0.0007～0.5 quality %.
These elements have the effect of the characteristic that improves copper alloy for electronic apparatus, by optionally containing according to purposes, can improve characteristic.
Further, the manufacture method of the copper alloy for electronic apparatus the present invention relates to, it is more than 500MPa being preferably set to tensile strength, and specific conductivity is more than 50%IACS.Thus, can provide and possess the stable on heating while, the copper alloy for electronic apparatus of high strength, high conductivity, can realize the slimming of lead frame material.
According to the present invention, even if can obtain the high-temperature area 500 ℃ of left and right, also can not cause excellent heat resistance, the high strength of strength decreased, copper alloy for electronic apparatus and the lead frame material of high conductivity.
Accompanying drawing explanation
Fig. 1 is that the transmission electron microscope obtaining under 50,000 times of the observation multiplying powers of copper alloy for electronic apparatus of embodiments of the present invention is observed photo.
Fig. 2 is that the transmission electron microscope obtaining under 100,000 times of the observation multiplying powers of copper alloy for electronic apparatus of embodiments of the present invention is observed photo.
Fig. 3 be embodiments of the present invention copper alloy for electronic apparatus utilize the observable every 1 μ m of transmission electron microscope
2the detailed chart of frequency distribution of diameter of precipitate particle.
In the cold rolling and low-temperature annealing operation of Fig. 4 when representing the manufacture of copper alloy for electronic apparatus of embodiments of the present invention, utilize the observable every 1 μ m of transmission electron microscope
2the sketch of passing of detailed chart of frequency distribution of diameter of precipitate particle.
Fig. 5 is for representing 500 ℃ of figure that heat the thermotolerance (rheological parameters' change with time of conservation rate) under keeping of the copper alloy for electronic apparatus of embodiments of the present invention.
Embodiment
With reference to accompanying drawing, one embodiment of the present invention copper alloy for electronic apparatus is specifically described.
(one-tenth of copper alloy is grouped into)
In the present invention, as the lead frame material using in semiconductor device etc., need to have excellent heat resistance, tensile strength and be the above and electric conductivity of 500MPa is fundamental characteristics more than 50%IACS.Therefore, as Cu-Fe-P-Zn series copper alloy, form the P of Fe, 0.008～0.08 quality % and the Zn of 0.01～0.5 quality % that contain 1.5～2.4 quality %, the essentially consist that remainder contains Cu and inevitable impurity.For this essentially consist, can also and then optionally contain the elements such as Sn described later, Ni.
（Fe）
Fe has formed the precipitate particle being dispersed in copper parent phase and has had the intensity of raising and stable on heating effect, but when the content of Fe is less than 1.5 quality %, the number of precipitate is not enough, can not bring into play this effect.On the other hand, if content surpasses 2.4 quality %, there is the thick precipitate particle that is helpless to intensity and thermotolerance raising, not enough to the precipitate particle of the resultful size of thermotolerance.Therefore, the content of preferred Fe is in the scope of 1.5～2.4 quality %.
（P）
P has formed the precipitate particle being dispersed in copper parent phase and has had the intensity of raising and stable on heating effect together with Fe, but when the content of P is less than 0.008 quality %, the number of precipitate particle is not enough, can not bring into play this effect.On the other hand, if content surpasses 0.08 quality %, exist and be helpless to the thick precipitate particle that intensity and thermotolerance improve, in the time of to the precipitate particle deficiency of the resultful size of thermotolerance, specific conductivity and processibility reduce.Therefore, the content of preferred P is in the scope of 0.008～0.08 quality %.
（Zn）
Zn is solid-solubilized in copper parent phase and has the effect that improves solder heat resistance separability, while being less than 0.01 quality %, can not bring into play this effect.On the other hand, even if content surpasses 0.5 quality %, can not obtain further effect, and the solid solution capacity in parent phase increases and causes specific conductivity to reduce.Therefore, the content of preferred Zn is in the scope of 0.01～0.5 quality %.
（Ni）
Ni is solid-solubilized in parent phase and has and puies forward high-intensity effect, while being less than 0.003 quality %, can not bring into play this effect.On the other hand, if content surpasses 0.5 quality %, cause specific conductivity to reduce.Therefore,, in the situation that contains Ni, be preferably in the scope of 0.003～0.5 quality %.
（Sn）
Sn is solid-solubilized in parent phase and has and puies forward high-intensity effect, while being less than 0.003 quality %, can not bring into play this effect.On the other hand, if content surpasses 0.5 quality %, cause specific conductivity to reduce.Therefore,, in the situation that contains Sn, be preferably in the scope of 0.003～0.5 quality %.
And, more than copper alloy of the present invention can also contain at least one in Al, Be, Ca, Cr and the Si of 0.0007～0.5 quality %.These elements have the effect of the various characteristics raising that makes copper alloy, preferably according to purposes, optionally add.
(diameter of precipitate particle and number thereof)
Copper alloy for electronic apparatus of the present invention is characterised in that, as shown in Figure 3, in transmission electron microscope is observed, every 1 μ m
2peak value in chart of frequency distribution of the diameter of precipitate particle be in the diameter range of 15～35nm, and the precipitate particle in this diameter range exists with more than 50% frequency of total frequency, the half-breadth at the peak of this diameter range is below 25nm.
; if the diameter of precipitate particle has the distribution of peak value in the limited range value of above-mentioned chart of frequency distribution, even at the high-temperature area of 500 ℃ of left and right, also can spend to greatest extent and bring into play pinning effect; suppress recrystallization, prevent effectively the strength decreased under high temperature.If the peak value of the diameter of precipitate particle exceeds limited range value, pinning effect reduces, and can not suppress recrystallization, can not maintain the intensity under high temperature, causes stable on heating reduction.
Wherein, for the diameter of precipitate particle, in its cross-section, to have with circular diameter (circle equivalent diameter) form of the area equal areas of precipitate particle, calculate.Now, the area of precipitate particle is for being observed the observation of the shadow area utilization to image vertical direction multiplying power that image obtains and be scaled the value of real area by transmission electron microscope.
In addition, in transmission electron microscope is observed, for the precipitate particle below 5nm, owing to can not explicit recognition being precipitate particle or the shadow producing while observing, be therefore included in total number of having carried out the precipitate particle observed.
Further, in this is observed, multiplying power resolving power changes according to the observation, and the diameter of the precipitate particle of observation, number produce change.Therefore, by measure more than 15nm precipitate particle time observation multiplying power be made as 50,000 times, the observation multiplying power while measuring the precipitate particle that is less than 15nm is set as 100,000 times.
By the thin plate of copper alloy for electronic apparatus, make the film that transmission electron microscope is observed use, carry out structure observation observing under 50,000 times and 100,000 times of multiplying powers, the diameter of precipitate particle and number are measured.Fig. 1 represents to observe the observation photo under 50,000 times of multiplying powers, and Fig. 2 represents to observe the observation photo under 100,000 times of multiplying powers.And for the actual multiplying power of photo shown in Fig. 1, Fig. 2, the scale of being recorded by the bottom right of these photos converts.
In Fig. 1 and Fig. 2, the particle that arrow represents is precipitate.The particle that arrow A represents is the particle of diameter 15～35nm, and the particle that arrow B represents is the particle that diameter is less than 15nm, and the particle that arrow C represents is the particle that diameter surpasses 35nm.In addition, in observing, transmission electron microscope can also use the sample of making by replica method.
The visual field area of photo shown in Fig. 1 (observing 50,000 times of multiplying powers) is 2.6 μ m
2.Therefore, the number of the precipitate particle of this photo inside counting can be calculated to every 1 μ m divided by 2.6
2the number of precipitate.
Similarly, the visual field area of photo shown in Fig. 2 (observing 100,000 times of multiplying powers) is 0.65 μ m
2.Therefore, the number of the precipitate particle of this photo inside counting can be calculated to every 1 μ m divided by 0.65
2the number of precipitate.
And, because being viewed as locality, observes transmission electron microscope, and preferably change look-out station and carry out repeatedly this observation.
(thermal test)
The thermal test of preferred copper alloy for electronic apparatus of the present invention carries out by the following method, with conservation rate, evaluates.
Make copper alloy thin plate sample of the present invention, under keeping in stove to the heating at 500 ℃, keep respectively the Vickers' hardness after 1 minute, 3 minutes, 5 minutes, 10 minutes to measure, with the Vickers' hardness comparison before thermal treatment separately, with conservation rate, thermotolerance is evaluated.
Conservation rate is calculated by (Vickers' hardness after thermal treatment)/(Vickers' hardness before thermal treatment).Each heats typical example that conservation rate under the hold-time changes as shown in Figure 5.
Copper alloy for electronic apparatus of the present invention can be given full play to the pinning effect of precipitate particle, has excellent thermotolerance, and to keep the conservation rate after 10 minutes be more than 88% in heating at 500 ℃.
(creating conditions)
Then,, to thering is the creating conditions of Cu-Fe-P series copper alloy of precipitate particle of the present invention (Fe-P based compound), describe.Except the preferred ageing treatment of aftermentioned, cold rolling, stress relief annealed each condition, do not need significantly to change common manufacturing process itself.
In addition every 1 μ m of the copper alloy under cold rolling, the low-temperature annealing in this manufacturing process,
2precipitate particle diameter chart of frequency distribution variation as shown in Figure 4.Transverse axis is the particle diameter of precipitate particle, and the longitudinal axis is frequency.
First, to being adjusted into the copper alloy of above-mentioned preferred component scope, melt casting, by after ingot casting building up by welding, with rolling rate, more than 60% implement hot rolling, then at 900～950 ℃, carry out the solution treatment of 2～4 hours.
(ageing treatment)
Copper alloy plate after solution treatment is carried out at 450～575 ℃ to the ageing treatment of 3～12 hours, the precipitate particle with wide size-grade distribution is separated out, make for obtaining forming the matrix of the precipitate particle that ultimate aim forms.450 ℃ following or 3 hours when following, and precipitate particle can not fully be separated out, and 575 ℃ above or 12 hours when above, copper alloy organization softening.
(the 1st is cold rolling)
Copper alloy plate after ageing treatment is carried out cold rolling with working modulus 60～80%, when reducing precipitate particle diameter, further promote separating out of precipitate particle.Because the preferential nucleation site of precipitated phase becomes motivating force and be conducive to the dislocation elementary boundary of nucleation, therefore can promote nucleation frequency.Working modulus is 60% when following, insufficient concerning reducing the particle diameter of precipitate, and 80% when above, and the facilitation effect of nucleation frequency is brought to obstacle.As shown in Figure 4, can infer that this stage does not form the peak value of chart of frequency distribution of the diameter of precipitate particle.
(the 1st low-temperature annealing)
Copper alloy plate after cold rolling to the 1st at 200～400 ℃ carries out the low-temperature annealing of 0.5 minute～3 hours, and the diameter of precipitate particle is moved in certain value range in peak value, frequency, the half-breadth of chart of frequency distribution.In time below 200 ℃ or below 0.5 minute, there is no effect, 400 ℃ above or within 3 hours, cause the coarsening of precipitate particle when above, and the performance of pinning effect is brought to obstacle.As shown in Figure 4, can infer that the diameter of this stage precipitate particle is below 15nm at the peak value of chart of frequency distribution, can not give full play to pinning effect.Only carry out this 1 low-temperature annealing and just make the diameter of precipitate particle just fall in optimum range value and be difficult to accomplish in peak value, frequency, the half-breadth of chart of frequency distribution, need further cold rolling and low-temperature annealing.
(the 2nd is cold rolling)
With the copper alloy plate after 30～60% pairs of the 1st low-temperature annealings of working modulus, carry out cold rollingly, make the matrix in the scope of the peak value make precipitate particle move to the chart of frequency distribution of aimed dia, frequency, half-breadth.When working modulus 60% is above, rolling rate as a whole raises, thereby promotes recrystallization, in addition intensity, specific conductivity, Vickers' hardness is also brought to detrimentally affect.When working modulus 30% is following, almost there is no effect.As shown in Figure 4, although precipitate particle dia is below 15nm at chart of frequency distribution peak value under this stage, yet infer to having promoted separating out of further precipitate particle, make the optimized matrix of chart of frequency distribution of sening as an envoy to.
(the 2nd low-temperature annealing)
Copper alloy plate after cold rolling to the 2nd at 200～400 ℃ carries out the low-temperature annealing of 0.5 minute～3 hours, as shown in Figure 4, and every 1 μ m of precipitate particle
2the peak value of diameter in chart of frequency distribution in the scope of diameter 15～35nm, and form more than 50% frequency of total frequency, to be that 25nm is following can bring into play pinning effect to its half-breadth to greatest extent.Every 1 μ m of this precipitate particle
2diameter chart of frequency distribution specifically as shown in Figure 3.
Utilize the 2nd low-temperature annealing, every 1 μ m
2if the diameter of precipitate particle in chart of frequency distribution, do not move in target peak, frequency, half-breadth, need and then under above-mentioned working modulus, heat-treat condition, repeat cold rolling and low-temperature annealing.Now, repeat separately cold rolling or low-temperature annealing is also nonsensical, it is important carrying out low-temperature annealing after cold rolling.
Even if form the copper alloy for electronic apparatus of present embodiment of above-mentioned formation at the high-temperature area of 500 ℃ of left and right, also can bring into play to greatest extent pinning effect, the reduction of intensity be can not bring, the high strength of excellent heat resistance, the copper alloy for electronic apparatus of high conductivity and lead frame material formed.
Embodiment
Below embodiments of the invention and comparative example are specifically described.
The copper alloy forming shown in following table 1 (adding element composition is in addition Cu and inevitable impurity) utilizes electric furnace to melt under reducing atmosphere, makes the ingot casting of thick 30mm, wide 100mm, long 250mm.At 730 ℃, the heating of this ingot casting, after 1 hour, is carried out hot rolling with rolling rate 60% and become thickness 11mm, with milling cutter, building up by welding is carried out in its surface until after thickness of slab is 9mm, carry out at 920 ℃, after the solution treatment of 3 hours, carrying out cold rolling until thickness of slab is 2mm.Then, at 450～575 ℃, carry out after the ageing treatment of 3～12 hours, with working modulus 60～80%, carry out the 1st cold rollingly, at 200～400 ℃, carry out the 1st low-temperature annealing of 0.5 minute～3 hours.Then, with the copper alloy thin plate after 30～60% pairs of the 1st low-temperature annealings of working modulus carry out the 2nd cold rolling after, at 200～400 ℃, carry out the 2nd low-temperature annealing of 0.5 minute～3 hours, obtain the copper alloy thin plate of the 0.3mm shown in the embodiment 1～16 of table 1.And, for comparative example 1～16, change over be grouped into, cold rolling condition, low-temperature annealing condition make.
By the copper alloy thin plate that obtains, make the film that transmission electron microscope is observed use, at 10 positions arbitrarily, to observe 50,000 times and 100,000 times of multiplying powers, carry out structure observation, mensuration precipitate particle and number, using its mean value as measured value.
The diameter of precipitate particle is calculated to have circular diameter (circle equivalent diameter) form of the area equating with the area of precipitate particle.Now, the area of precipitate particle is for being observed the observation of the shadow area utilization to image vertical direction multiplying power that image obtains and be scaled the value of real area by transmission electron microscope.
For the precipitate particle below 5nm, can not identify clearly the shadow producing while being precipitate particle or observation, be not included in total number of the precipitate particle that has carried out observation, by measure more than 15nm precipitate particle time observation multiplying power be made as 50,000 times, the observation multiplying power while measuring the precipitate particle that is less than 15nm is set as 100,000 times.
The peak value of the precipitate particle dia of trying to achieve based on transmission electron microscope of these copper alloy thin plate, total frequency, half-breadth, specifically as shown in table 2 according to the mensuration number of particle diameter.
As shown in Table 2, for the copper alloy thin plate of the present embodiment, every 1 μ m
2peak value in chart of frequency distribution of the diameter of precipitate particle all in the scope of diameter 15～35nm, the precipitate particle within the scope of this 15～35nm exists with more than 50% frequency of total frequency, half-breadth is below 25nm.
In addition, the measurement result of the tensile strength of these copper alloy thin plate, Vickers' hardness, specific conductivity is as shown in table 3.
For tensile strength, make parallel with the rolling direction in the longitudinal direction JIS5 sheet of test film and measure.
For Vickers' hardness, make the test film of 10mm * 10mm, the load that uses the Vickers micro-hardness meter (trade(brand)name " micro-hardness tester ") of Song Zejing machine society system to apply 0.5kg carries out the measurement of hardness at 4 positions, the mean value that hardness is them.
For specific conductivity, by the thin rectangular test film of Milling Process 10mm * 30mm, by double bridge formula resistance measurement device, measure resistance, by average cross section method, calculate.
From following table 3, the copper alloy thin plate of the present embodiment, tensile strength is 517～570MPa, specific conductivity is 61～72%IACS.
In addition carry out, the thermal test of these copper alloy thin plate.Test method is, make the test film of 10mm * 10mm, to heating, keep adding test film in stove, at 500 ℃, keep respectively after 1 minute, 3 minutes, 5 minutes, 10 minutes, measure Vickers' hardness, compare with the Vickers' hardness before thermal treatment separately, utilize conservation rate to evaluate thermotolerance.
Conservation rate is calculated by (Vickers' hardness after thermal treatment)/(Vickers' hardness before thermal treatment).
The results are shown in table 3 of thermal test.
As shown in Table 3, the copper alloy thin plate of the present embodiment can be brought into play the pinning effect of precipitate particle to greatest extent, and the conservation rate of thermal treatment after 10 minutes is 88～93% at 500 ℃, has excellent thermotolerance.
Fig. 5 represents the rheological parameters' change with time of the conservation rate of representational embodiment 1,3,6,8 and comparative example 1,3,6,9.Also known thus, the copper alloy thin plate of the present embodiment has excellent thermotolerance.
From these results, electronics of the present invention Cu-Fe-P series copper alloy, tensile strength is more than 500MPa and specific conductivity is more than 50%IACS, can bring into play to greatest extent the pinning effect of precipitate particle, even if the high-temperature area 500 ℃ of left and right also can bring the reduction of intensity hardly, there is excellent thermotolerance, be suitable as lead frame material.
Claims (9)
1. the manufacture method of a copper alloy for electronic apparatus, it is characterized in that, the Fe of 1.5～2.4 quality % will be contained, the copper alloy of the Zn of the P of 0.008～0.08 quality % and 0.01～0.5 quality % melts casting, by after ingot casting building up by welding, with rolling rate, more than 60% implement hot rolling, then at 900～950 ℃, carry out the solution treatment of 2～4 hours, copper alloy plate after solution treatment is carried out at 450～575 ℃ to the ageing treatment of 3～12 hours, to the copper alloy plate after ageing treatment, with working modulus 60～80%, carry out the 1st cold rolling, copper alloy plate after cold rolling to the 1st at 200～400 ℃ carries out the 1st low-temperature annealing of 0.5 minute～3 hours, with the copper alloy plate after 30～60% pairs of the 1st low-temperature annealings of working modulus, carry out the 2nd cold rolling, copper alloy plate after cold rolling to the 2nd at 200～400 ℃ carries out the 2nd low-temperature annealing of 0.5 minute～3 hours, be manufactured on thus in transmission electron microscope observation, with every 1 μ m
2the peak value of the round equivalent diameter that equates of the area of precipitate particle in chart of frequency distribution be in the diameter range of 15～35nm, and the precipitate particle in this diameter range exists with more than 50% frequency of total frequency, the half-breadth at the peak of this diameter range is the copper alloy for electronic apparatus below 25nm.
2. the manufacture method of copper alloy for electronic apparatus according to claim 1, it is characterized in that, after described the 2nd low-temperature annealing, the low-temperature annealing of 0.5 minute～3 hours at 200～400 ℃ that repeats that the cold rolling of working modulus 30～60% and this carry out after cold rolling.
3. the manufacture method of copper alloy for electronic apparatus according to claim 1 and 2, is characterized in that, the Sn of the Ni that described copper alloy contains 0.003～0.5 quality % and 0.003～0.5 quality %.
4. the manufacture method of copper alloy for electronic apparatus according to claim 1 and 2, is characterized in that, more than described copper alloy contains at least one in Al, Be, Ca, Cr and Si, its content is set as 0.0007～0.5 quality %.
5. the manufacture method of copper alloy for electronic apparatus according to claim 3, is characterized in that, more than described copper alloy contains at least one in Al, Be, Ca, Cr and Si, its content is set as 0.0007～0.5 quality %.
6. the manufacture method of copper alloy for electronic apparatus according to claim 1 and 2, is characterized in that, the tensile strength of copper alloy for electronic apparatus is more than 500MPa, and specific conductivity is more than 50%IACS.
7. the manufacture method of copper alloy for electronic apparatus according to claim 3, is characterized in that, the tensile strength of copper alloy for electronic apparatus is more than 500MPa, and specific conductivity is more than 50%IACS.
8. the manufacture method of copper alloy for electronic apparatus according to claim 4, is characterized in that, the tensile strength of copper alloy for electronic apparatus is more than 500MPa, and specific conductivity is more than 50%IACS.
9. the manufacture method of copper alloy for electronic apparatus according to claim 5, is characterized in that, the tensile strength of copper alloy for electronic apparatus is more than 500MPa, and specific conductivity is more than 50%IACS.
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| PCT/JP2009/003994 WO2011021245A1 (en) | 2009-08-20 | 2009-08-20 | Copper alloy and lead frame material for electronic equipment |
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| JP5436349B2 (en) * | 2010-01-30 | 2014-03-05 | 三菱伸銅株式会社 | Bonding method of LED chip and lead frame |
| JP5710225B2 (en) * | 2010-11-25 | 2015-04-30 | 三菱伸銅株式会社 | Cu-Fe-P copper alloy strip for electronic equipment with excellent surface roughening and resin adhesion |
| JP2013057116A (en) * | 2011-09-09 | 2013-03-28 | Hitachi Cable Ltd | Copper alloy for electric and electronic part and method for producing the same |
| JP5687976B2 (en) * | 2011-09-09 | 2015-03-25 | 株式会社Ｓｈカッパープロダクツ | Manufacturing method of copper alloy for electric and electronic parts |
| JP5988794B2 (en) * | 2012-09-14 | 2016-09-07 | Ｄｏｗａメタルテック株式会社 | Copper alloy sheet and manufacturing method thereof |
| JP6210910B2 (en) * | 2014-03-18 | 2017-10-11 | 株式会社神戸製鋼所 | Fe-P copper alloy sheet with excellent strength, heat resistance and bending workability |
| JP2016211053A (en) * | 2015-05-12 | 2016-12-15 | 株式会社神戸製鋼所 | Copper alloy excellent in heat resistance |
| JP7234501B2 (en) * | 2018-03-28 | 2023-03-08 | 三菱マテリアル株式会社 | Copper alloy |
| JP7242996B2 (en) * | 2018-03-28 | 2023-03-22 | 三菱マテリアル株式会社 | Copper alloy |
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| JPH02111829A (en) * | 1988-10-20 | 1990-04-24 | Sumitomo Metal Mining Co Ltd | Copper alloy for lead frame |
| JP3344687B2 (en) * | 1996-08-09 | 2002-11-11 | 株式会社神戸製鋼所 | Copper alloy for lead frame |
| JPH10130755A (en) * | 1996-11-01 | 1998-05-19 | Kobe Steel Ltd | High strength and high conductivity copper alloy excellent in shearing workability |
| JP3772319B2 (en) * | 1997-03-24 | 2006-05-10 | 同和鉱業株式会社 | Copper alloy for lead frame and manufacturing method thereof |
| JPH1180862A (en) * | 1997-09-09 | 1999-03-26 | Kobe Steel Ltd | Copper-iron alloy material for lead frame, excellent in heat resistance |
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| KR20120048591A (en) | 2012-05-15 |
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| CN102471831A (en) | 2012-05-23 |
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