CN115386767B - Lead frame copper alloy strip for packaging ultra-large scale integrated circuit chip and preparation method thereof - Google Patents
Lead frame copper alloy strip for packaging ultra-large scale integrated circuit chip and preparation method thereof Download PDFInfo
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- CN115386767B CN115386767B CN202210986101.5A CN202210986101A CN115386767B CN 115386767 B CN115386767 B CN 115386767B CN 202210986101 A CN202210986101 A CN 202210986101A CN 115386767 B CN115386767 B CN 115386767B
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 112
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005452 bending Methods 0.000 claims abstract description 50
- 239000010949 copper Substances 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims description 64
- 239000002245 particle Substances 0.000 claims description 43
- 238000005096 rolling process Methods 0.000 claims description 28
- 238000005097 cold rolling Methods 0.000 claims description 26
- 230000035882 stress Effects 0.000 claims description 26
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 239000000956 alloy Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 238000005098 hot rolling Methods 0.000 claims description 18
- 238000010791 quenching Methods 0.000 claims description 18
- 230000000171 quenching effect Effects 0.000 claims description 18
- 239000006104 solid solution Substances 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 238000005266 casting Methods 0.000 claims description 9
- 238000003723 Smelting Methods 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910001369 Brass Inorganic materials 0.000 claims description 5
- 239000010951 brass Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910018559 Ni—Nb Inorganic materials 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000012545 processing Methods 0.000 description 26
- 239000000126 substance Substances 0.000 description 19
- 238000001556 precipitation Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000005728 strengthening Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 7
- 239000011651 chromium Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000017525 heat dissipation Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- -1 iron bronze series Chemical class 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229910017758 Cu-Si Inorganic materials 0.000 description 1
- 229910017931 Cu—Si Inorganic materials 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001887 electron backscatter diffraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0268—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment between cold rolling steps
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/495—Lead-frames or other flat leads
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B2003/005—Copper or its alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a lead frame copper alloy strip for packaging a very large scale integrated circuit chip, which comprises the following components in percentage by weight: ni:2.0 to 4.0 weight percent, co:0.001 to 1.0 weight percent, si:0.3 to 1.2 weight percent, nb:0.001 to 0.3 weight percent, and the balance of Cu. The copper alloy strip has the yield strength of more than or equal to 850MPa, the conductivity of more than or equal to 45 percent IACS, the stress relaxation of less than or equal to 20 percent when heat is preserved for 1000 hours at 175 ℃, the Badway 90-degree bending R/t of less than or equal to 2.0 does not crack, and the hardness value is more than 180HV after heat is preserved for 1 hour at 650 ℃. The copper alloy strip is an ideal material for producing and manufacturing lead frames for packaging very large scale integrated circuit chips. The invention provides a copper alloy strip with excellent comprehensive performance and a preparation method thereof for the lead frame for packaging the ultra-large scale integrated circuit chip, which has multifunction, high-density pins, narrow spacing and long-time operation without failure.
Description
Technical Field
The invention relates to the field of lead frame materials, in particular to a lead frame copper alloy strip for packaging a very large scale integrated circuit chip and a preparation method thereof.
Background
The lead frame for chip packaging mainly plays roles of supporting chips, transmitting signals and energy, dissipating heat and the like. With the rapid development of chip technology, the lead frame has more and more pins and smaller terminal spacing after chip packaging. In order to maintain good chip supporting and fixing effects, higher requirements are put on the yield strength of the copper alloy strip for the lead frame; in order to ensure efficient transmission of energy and signals and heat dissipation of chips, copper alloy strips for lead frames must have high conductivity; in order to ensure that the chip does not fail during long-term operation, the copper alloy strip for the lead frame must have good stress relaxation resistance; in order to facilitate efficient stamping preparation, the copper alloy strip for the lead frame must have good bending properties. The development trend brings higher and higher requirements on the yield strength, the conductivity, the stress relaxation resistance and the bending performance of the copper alloy strip for the lead frame, the yield strength of the copper alloy strip is more than or equal to 850MPa, the conductivity is more than or equal to 45 percent IACS, the stress relaxation of the copper alloy strip at 175 ℃ for 1000 hours is less than or equal to 20 percent, and the bending performance is required to meet the requirement that Badway 90-degree bending R/t is less than or equal to 2.0 and the copper alloy strip does not crack (R is the bending radius and t is the thickness of the strip).
At present, copper alloy strips for lead frames for chip packaging mainly comprise C19210, C19400, C15100, C18045, C70250, C70350 and the like, and the alloy has the best comprehensive performance of C70350.
The known lead frame is made of C19210 and C19400 alloy strips which belong to copper alloy strips of iron bronze series, and the two copper alloy strips have higher conductivity (the conductivity of SH state with the best mechanical property is more than or equal to 60 percent IACS) and can play a good role in signal and energy transmission and heat dissipation, but the yield strength is only about 550MPa at most, and can only meet the mechanical property requirement of the medium-scale integrated circuit chip package with larger pin size, but can not meet the mechanical property requirement of the lead frame for the ultra-large-scale integrated circuit chip package with smaller and smaller pin size.
The known C15100 alloy strip for lead frames belongs to the copper alloy strip of the zirconium bronze series and the C18045 strip belongs to the copper alloy strip of the chromium bronze series. The copper alloy strips for the two lead frames have high conductivity (more than or equal to 70 percent IACS) and have advantages in the aspects of signal and energy transmission, chip heat dissipation and the like, but also have poor mechanical properties (the highest yield strength can only reach about 500 MPa), so that the requirements of the mechanical properties required by the smaller and smaller lead frame pin size for the ultra-large-scale integrated circuit chip package cannot be met.
Two other known lead frame strips of C70250, C70350 alloys belong to the copper alloy strips of the kesen series. Although the yield strength of the strip corresponding to the state with the optimal mechanical properties of the two copper alloys can reach more than 850MPa, the conductivity can also reach more than 45% IACS, the mechanical properties and the conductivity of the strip can meet the requirements of mechanical properties and conductivity required by smaller and smaller sizes of pins of the lead frame for packaging the ultra-large scale integrated circuit chip, energy, signal transmission, heat dissipation and the like, but the strip cannot meet the requirement of non-failure for long-time use of the lead frame for packaging the ultra-large scale integrated circuit chip due to poor stress relaxation resistance (the stress relaxation is more than or equal to 25% when the strip is insulated for 1000 hours at 175 ℃).
Disclosure of Invention
Aiming at the requirements of the lead frame for packaging the current and future ultra-large scale integrated circuit chips on the yield strength, the conductivity, the stress relaxation resistance and the bending performance of the copper alloy strip, the invention provides a copper alloy strip with the yield strength of more than 850MPa, the conductivity of more than 45 percent IACS, the stress relaxation of less than or equal to 20 percent when the copper alloy strip is insulated for 1000 hours at 175 ℃, the Badway 90-degree bending R/t of less than or equal to 2.0 and no crack (R is the bending radius and t is the thickness of the strip) and a preparation method thereof.
The technical scheme adopted for solving the technical problems is as follows: a lead frame copper alloy strip for packaging a very large scale integrated circuit chip comprises the following components in percentage by weight: ni:2.0 to 4.0 weight percent, co:0.001 to 1.0 weight percent, si:0.3 to 1.2 weight percent, nb:0.001 to 0.3 weight percent, and the balance of Cu.
In the invention, ni, co and Si are essential elements, and the solid solubility of Ni element in Cu is large, thus forming connection with CuThe continuous solid solution has a wider single-phase region, so that the mechanical property of the copper alloy can be greatly improved, and the Ni element is often combined with Si or Co element in the copper alloy as common alloying, so that the aim of improving the alloy strength is fulfilled. In the present invention, ni, co and Si atoms form supersaturated solid solutions in the copper matrix and form Ni during aging 2 Si and Co 2 The Si precipitates, plays roles of pinning dislocation and inhibiting growth of crystal grains, and greatly improves the strength of the alloy. At the same time, due to partial Ni, co, si and Ni 2 Si and Co 2 The Si precipitate phase is separated out from the copper matrix, so that the purity of the matrix is improved, and the scattering effect of solute atoms in the copper matrix on electron waves is reduced, so that the conductivity of the copper alloy strip is greatly improved. When the Ni content is less than 2.0wt%, the Co content is less than 0.001wt% and the Si content is less than 0.3wt%, the Ni precipitated after aging in the copper alloy strip of the present invention 2 Si and Co 2 The Si precipitation is less, the dispersion strengthening effect is not obvious, and the yield strength is lower than 850MPa. When the Ni content is more than 4.0wt%, the Co content is more than 1.0wt% and the Si content is more than 1.2wt%, too many precipitation strengthening phases are precipitated, and the scattering effect of strengthening phase particles on electron waves is enhanced, so that the conductivity of the copper alloy strip is lower than 45% IACS. The components of Ni, co and Si in the copper alloy strip of the invention are as follows: 2.0 to 4.0 weight percent, co:0.001 to 1.0 weight percent, si: and most preferably in the range of 0.3wt% to 1.2 wt%.
Nb is an essential element in the invention, and exists in the copper alloy strip in the form of Nb simple substance. The Nb simple substance in the copper alloy can prevent atoms from diffusing, and improves the stress relaxation resistance and the high temperature resistance of the copper alloy strip. When the Nb content in the invention is less than 0.001wt%, the barrier effect of Nb simple substance on atomic diffusion is not obvious, and the stress relaxation resistance and the high temperature resistance of the copper alloy strip can not be effectively improved; when the Nb content is more than 0.3wt%, the stress relaxation resistance of the copper alloy strip of the invention can be greatly improved, but the redundant Nb particles can reduce the bending performance of the copper alloy strip of the invention, thereby causing the bending of the copper alloy strip of the inventionThe bending performance cannot meet the performance requirement that Badway 90-degree bending R/t is less than or equal to 2.0 and does not crack (R is bending radius and t is strip thickness), so that the Nb component in the copper alloy strip is optimal in the range of 0.001-0.3 wt%. In addition, nb and Ni precipitated during the double-stage aging treatment 2 Si and Co 2 The Si precipitate phase plays a role in cooperative coupling strengthening and has a beneficial effect on further improving the yield strength of the copper alloy strip.
The area ratio of the cubic texture in the copper alloy strip material in the invention in the measured area is 10% -20%. The area occupation ratio of the cubic texture in the finished product of the strip is within the range of 10-20%, so that the bending performance of the copper alloy strip can be ensured to meet the performance requirement that the Badway 90-degree bending R/t is less than or equal to 2.0 and the strip is not cracked (R is the bending radius and t is the thickness of the strip). When the area ratio of the cubic texture is below 10%, the bending performance of the strip cannot meet the requirement, and cracking can occur in the stamping process; when the area ratio of the cubic texture exceeds 20%, the area ratio of other types of textures is reduced, and the bending performance of the strip material can meet the requirement, but the yield strength of the strip material is weakened, so that the area ratio of the cubic texture is optimal in the range of 10% -20%.
Preferably, in the copper alloy strip of the present invention, the area ratio of the cubic texture, the copper-type texture and the brass texture satisfies the relational expression of 0.5 (a+c)/b.ltoreq.1.2, wherein a is the area ratio of the cubic texture in the measurement area, b is the area ratio of the brass texture in the measurement area, and c is the area ratio of the copper-type texture in the measurement area. The texture of the copper alloy strip meets the formula, so that the bending performance of the copper alloy strip can be ensured to meet the performance requirement that the Badway 90-degree bending R/t is less than or equal to 2.0 and the copper alloy strip does not crack (R is the bending radius and t is the strip thickness).
Preferably, nb is present in the copper alloy strip in elemental form, the size of Nb elemental particles in the copper alloy strip being controlled to be between 0.01 μm and 0.5 μm, wherein the ratio of Nb elemental particles having a size of between 0.01 μm and 0.1 μm is 10% to 30%, the ratio of Nb elemental particles having a size of between 0.1 μm and 0.3 μm is 40% to 70%, and the size is 0.3 μm to 0.3 μmThe proportion of Nb elementary particles between 0.5 μm is 10% to 30%. By controlling different particle sizes and percentage contents thereof, nb particles and Ni with different sizes are obtained 2 Si and Co 2 The Si precipitate phase plays a role in cooperative reinforcement, and ensures good balance of conductivity and stress relaxation resistance while improving the yield strength of the copper alloy strip.
Preferably, the copper alloy strip of the present invention comprises, in addition to the main elements Ni, co, si, nb, etc., less than 0.3wt% in total of one or more of the following optional elements: mg:0.001 to 0.3 weight percent of Ag:0.001 to 0.1 weight percent, cr:0.001 to 0.1 weight percent of Zr:0.001 to 0.1 weight percent.
The main function of Mg and Ag is to be solid-solution-strengthened in the copper matrix, thereby being beneficial to improving the yield strength of the copper alloy strip. In addition, mg and Ag can also improve the stress relaxation resistance of the copper alloy strip. When the content of Mg and Ag is less than 0.001wt%, the effect of improving the yield strength and the stress relaxation resistance of the copper alloy strip is not obvious; when the content of Mg is more than 0.3wt% and the content of Ag is more than 0.1wt%, excessive Mg and Ag are dissolved in the copper matrix in a solid solution, which increases scattering of electron waves, resulting in a decrease in the electrical conductivity of the copper alloy strip of the present invention.
Cr atoms form Cr with Zr atoms 2 Zr precipitated phase and precipitated Ni 2 Si、Co 2 The precipitated phases such as Si and the simple substance Nb have a synergistic dispersion strengthening effect, and are helpful for further improving the yield strength of the copper alloy strip. If the content of the optional elements Cr and Zr in the copper alloy strip is lower than the lower limit, the effect is not obvious; if the upper limit is exceeded, excessive Cr is precipitated 2 Zr precipitates, increases scattering of electron waves, and leads to poor conductivity of the copper alloy strip.
Preferably, the yield strength of the copper alloy strip is more than or equal to 850MPa, the conductivity is more than or equal to 45% IACS, the stress relaxation is less than or equal to 20% after heat preservation for 1000 hours at 175 ℃, and the Badway 90-degree bending R/t is less than or equal to 2.0 and does not crack, wherein R is the bending radius, and t is the thickness of the strip.
The whole process preparation procedure of the copper alloy strip comprises the following steps: batching, smelting and casting, sawing, hot rolling and cogging, milling faces, rough rolling, solid solution and quenching, cold rolling, primary aging, cold rolling, secondary aging, finish rolling, stretch bending and straightening and strip finished product. The smelting temperature of the copper alloy is 1250-1300 ℃ in the invention, thus ensuring that various added materials are fully melted. The casting temperature is 1200-1250 ℃, and the fluidity of the copper alloy melt is ensured. Nb is added in the form of Ni-Nb intermediate alloy during smelting, and electromagnetic stirring is adopted during casting to ensure that Nb is uniformly distributed in the copper alloy. The hot rolling heating temperature is 1000-1030 ℃, the heating and heat preserving time is 2-4 hours, and the uniform temperature of the slab is ensured. The hot rolling start temperature of the copper alloy strip is controlled within the range of 990-1020 ℃, the total hot rolling processing rate is more than 92%, the finish rolling temperature is kept above 900 ℃, the hot rolling is performed at more than 900 ℃, dynamic recrystallization can be performed, and the area ratio of copper texture in the hot rolled strip obtained after hot rolling cogging in the measured area is ensured to be more than 45%. After subsequent solid solution and quenching treatment, ensuring that more than 40% of cubic texture is formed in the copper alloy strip (the area ratio of the cubic texture in the strip after quenching to the measured area is more than 40%); if the final rolling temperature is lower than 900 ℃, the dynamic recrystallization in the hot rolling process is insufficient, the area ratio of the copper texture is lower than 45%, and more than 40% of cubic texture can not be ensured in the copper alloy strip of the invention after the subsequent solid solution and quenching treatment.
In order to store enough strain energy in the copper alloy strip before solution quenching treatment, the total working rate of rough rolling is controlled to be more than 95%, so that most of copper textures which are more than 45% formed in the hot rolling cogging process can be converted into cubic textures during solution quenching treatment, and the area ratio of the cubic textures in the strip after solution quenching treatment in a measured area is more than 40%. If the rough rolling processing rate is lower than 95%, the energy storage is insufficient, more than 40% of cube texture can not be formed during solid solution and quenching treatment, so that the area ratio of the prepared finished product of the strip can not reach 10% -20%, and the bending performance of the finished product of the strip can not reach the performance requirement that Badway 90 DEG R/t is less than or equal to 2.0.
The solid solution temperature of the copper alloy strip is controlled between 960 ℃ and 1000 ℃, and the heat preservation time is 60 seconds to 300 seconds. The strip is subjected to solution treatment at 960-1000 ℃, firstly, the solute atoms such as Ni, co, si and the like are ensured to be completely dissolved in a copper matrix to form a supersaturated solid solution, so that enough precipitated phases are conveniently separated out in the subsequent two-stage aging treatment process, and the yield strength of the strip is ensured to reach above 850 MPa; secondly, the copper texture in the strip is ensured to be converted into cubic texture, so that more than 40% of cubic texture is formed. The heat preservation time is 60-300 seconds, and aims to enable solute atoms such as Ni, co, si and the like to be fully diffused in the solution treatment process, so that supersaturated solid solution is formed. The heat preservation time is less than 60 seconds, which can lead to insufficient solid solution of solute atoms such as Ni, co, si and the like; the heat preservation time exceeds 300 seconds, so that coarse grains (more than or equal to 20 mu m) can be caused, and the bending performance of the finished product of the strip is affected.
The final rolling temperature of the hot rolling cogging process is controlled to be more than 900 ℃, the solution treatment temperature is controlled to be between 960 ℃ and 1000 ℃, and the final rolling temperature and the solution treatment temperature of the hot rolling cogging process are controlled to be at the above temperatures, so that the area ratio of the cubic texture, the copper texture and the brass texture is controlled to be within the range of 0.5-1.2, and the Badway 90-degree R/t is controlled to be less than or equal to 2.0, and the bending is not cracked. When the finishing temperature is lower than 900 ℃ and the solution treatment temperature is out of the range of 960-1000 ℃, the texture transformation is incomplete, the texture proportion control requirement can not be met, and the improvement of the bending performance of the alloy is further affected.
The copper alloy strip is subjected to cold rolling processing after solution quenching treatment, and the cold rolling processing rate between quenching and primary aging is controlled to be more than 40%, so that the copper alloy strip is reserved with strain energy for primary aging. If the processing rate is lower than 40%, the energy storage is insufficient, so that a little precipitated phase is precipitated in the primary aging treatment process, and the formation of a sufficient amount of precipitated phases in the secondary aging process is not facilitated.
And performing primary aging treatment after cold rolling, wherein the primary aging temperature is 420-460 ℃, and the heat preservation time is 5-8 h. The purpose is to precipitate part of Ni in the strip 2 Si、Co 2 The precipitation phases of Si and the like and Nb simple substance particles are subjected to preliminary precipitation in the subsequent cold rolling processing processThe precipitated phase particles form a large number of dislocations as the center, and the dislocations provide diffusion channels for solute atoms in the secondary aging treatment process, thereby being beneficial to the sufficient precipitation of solute atoms to form enough Ni in the secondary aging process 2 Si、Co 2 Precipitation strengthening phase particles such as Si, nb simple substances and the like can ensure the improvement of conductivity and mechanical properties. The primary aging temperature is better in the range of 420-460 ℃, if the primary aging temperature is lower than 420 ℃, the heat preservation time is lower than 5 hours, the diffusion speed of solute atoms is slower, and enough primary precipitation phase cannot be formed; if the primary aging temperature is higher than 460 ℃ and the heat preservation time is longer than 8 hours, the precipitated phase particles separated out by the primary aging grow up, the size and proportion control requirements on Nb simple substance particles cannot be met, the number of the primary precipitated phase particles is reduced, the formation of dislocation number in the subsequent cold rolling process is not facilitated, and the improvement of the comprehensive performance of the alloy is further affected.
The cold rolling process rate between the primary aging and the secondary aging of the copper alloy strip is controlled between 20% and 40%. If the total processing rate of the cold rolling after the primary aging is lower than 20%, enough dislocation cannot be formed around the precipitated phase precipitated by the primary aging, so that the precipitation of the secondary aging precipitated phase is affected, and the yield strength of the finished strip product is less than 850 MPa; if the total processing rate of the cold rolling after the primary aging exceeds 40%, most of the cube textures in the strip are converted into other textures, so that the bending performance of the finished strip product cannot meet the requirement that Badway 90 degrees R/t is less than or equal to 2.0 bending and is not cracked.
The copper alloy strip is subjected to secondary aging after primary aging and cold rolling processing, the secondary aging temperature is 300-350 ℃, and the heat preservation time is 3-5 h. The secondary aging treatment is favorable for further precipitation of precipitated phase particles and further regulation and control of Nb simple substance particles, so that the size and distribution of the Nb simple substance particles are controlled to be between 0.01 and 0.5 mu m, wherein the Nb simple substance particles with the size of between 0.01 and 0.1 mu m account for 10 to 30 percent, the Nb simple substance particles with the size of between 0.1 and 0.3 mu m account for 40 to 70 percent, and the Nb simple substance particles with the size of between 0.3 and 0.5 mu m account for 10 to 30 percent, and Ni can be treated under the condition 2 Si、Co 2 The synergistic coupling strengthening effect of the precipitated phase particles such as Si and the Nb elementary particles is exerted to the maximum. After primary aging and cold rolling, a large number of dislocations are formed around the primary aging precipitated phase and Nb simple substance particles, and in the secondary aging process, solute atoms such as Ni, co, si and the like are precipitated by taking the dislocations as precipitation channels, so that secondary aging precipitated phase particles are formed around the primary aging precipitated phase and Nb simple substance particles. When the secondary aging temperature is lower than 300 ℃ and the heat preservation time is lower than 3 hours, the diffusion rate of solute atoms in the secondary aging process is slow due to the lower aging temperature, so that enough precipitation strengthening phases cannot be effectively separated out; when the secondary aging temperature is higher than 350 ℃ and the heat preservation time is higher than 5 hours, the precipitated phase particles separated out by the primary aging and the secondary aging can grow large, resulting in Ni 2 Si、Co 2 The quantity of the precipitated phase particles such as Si is greatly reduced, so that the strengthening effect of the precipitated phase particles cannot be fully exerted, the yield strength of the strip cannot reach more than 850MPa, and meanwhile, the stress relaxation resistance and the high temperature resistance cannot reach the control targets.
In the invention, the copper alloy strip is subjected to finish rolling after secondary aging, and the finish rolling processing rate is controlled between 5% and 15%. If the total processing rate of finish rolling is lower than 5%, enough work hardening cannot be formed, so that the yield strength of a finished product of the strip cannot be further improved, and the purpose that the yield strength of the invention reaches more than 850MPa cannot be achieved; if the total processing rate of finish rolling processing is higher than 15%, although the yield strength of the finished product of the strip can be greatly improved, the area ratio of the cubic texture in the finished product is lower than 10% due to the fact that the cubic texture in the strip is further converted into other textures, and the bending performance of the strip cannot reach the performance target that Badway 90-degree bending R/t is less than or equal to 2.0 and the strip is not cracked.
The copper alloy strip is subjected to stretch bending straightening treatment after finish rolling, so that the shape of the strip is improved.
The copper alloy strip is processed into a copper alloy strip finished product according to the preparation method, wherein the area ratio of the cubic texture in the strip finished product is 10% -20%, and the balance is other types of textures. The texture type and the area occupation ratio of the copper alloy strip enable the copper alloy strip with excellent comprehensive performance to have good bending performance, namely: badway 90-degree bending R/t is less than or equal to 2.0 and does not crack.
Compared with the prior known technology, the invention has the following advantages:
1. the content of Nb in the copper alloy strip is within the range of 0.001-0.3 wt%, and the Nb simple substance particles are in contact with Ni 2 Si、Co 2 The precipitated phase particles such as Si play a role in cooperative coupling reinforcement, so that the yield strength of the copper alloy strip is improved, and meanwhile, the Nb elementary particles can prevent atoms from diffusing, so that the stress relaxation resistance of the copper alloy strip is improved, and the stress relaxation of the copper alloy strip is less than or equal to 20 percent when the copper alloy strip is insulated for 1000 hours at 175 ℃.
2. According to the copper alloy strip, the area ratio of the cubic texture in the finished product of the strip is controlled within the range of 10% -20% by the preparation method, so that the bending performance of the copper alloy strip can achieve the effect that Badway 90-degree bending R/t is less than or equal to 2.0 and the copper alloy strip is not cracked.
3. The strip preparation method adopts two-stage aging treatment, and the processing rate of cold rolling between the primary aging and the secondary aging is controlled between 20 percent and 40 percent, thereby separating out Ni in the primary aging 2 Si、Co 2 Dislocation is formed around the Si and other precipitation phase particles and Nb simple substance particles, a channel is provided for precipitation of Ni, co, si and other solute atoms in the secondary aging treatment process, and secondary precipitation phase particles are formed around the primary aging precipitation phase particles and Nb simple substance particles, so that the synergistic coupling strengthening effect of the primary aging precipitation phase particles, the secondary aging precipitation phase particles and Nb simple substance particles is formed, and the yield strength of the copper alloy strip can reach more than 850MPa.
Detailed Description
The present invention is described in further detail below with reference to examples and comparative examples.
20 example alloys and C70350 comparative example materials were selected, and the example alloys were each processed to 0.2mm thick strip products using the full-flow preparation process and technique of the present invention. The copper alloy strip with high yield strength, good conductivity, excellent stress relaxation resistance and good bending forming performance disclosed by the invention is prepared by the following steps of: batching, smelting and casting, sawing, hot rolling and cogging, milling faces, rough rolling, solid solution and quenching, cold rolling, primary aging, cold rolling, secondary aging, finish rolling, stretch bending and straightening, and obtaining a finished product of the strip, and specifically comprises the following steps:
1) Batching and casting: according to the chemical components of the copper alloy, raw materials are prepared and proportioned, an induction furnace is adopted for smelting, and the adding sequence of the alloy is as follows: cu is added firstly, ni and Co are added after melting, then Cu-Si intermediate alloy and Ni-Nb intermediate alloy are added after melting, and one or more elements of Mg, ag, cr, zr are selectively added. Detecting components by adopting an ICP method, casting after the components meet the requirements and are fully deaerated and deslagged, wherein the smelting temperature is 1270 ℃, and the casting temperature is 1220 ℃.
2) Sawing: sawing the cast ingot to remove the head and tail of the cast ingot.
3) Hot rolling cogging: heating the cast ingot at 1000-1030 ℃ and preserving heat for 2-4 h, then performing hot rolling cogging, wherein the hot rolling cogging temperature is 990-1020 ℃, the total hot rolling processing rate is above 92%, and the final rolling temperature is above 900 ℃.
4) Milling: and (3) carrying out surface milling treatment on the hot rolled strip to remove oxides on the surface of the strip.
5) Rough rolling: and (3) carrying out rough rolling processing on the strip after the surface milling, wherein the total processing rate of the rough rolling processing is more than 95%.
6) Solid solution and quenching: after rough rolling, carrying out solid solution and quenching treatment on the strip, wherein the solid solution temperature is 960-1000 ℃, the heat preservation time is 60-300 seconds, and then carrying out online quenching treatment.
7) Cold rolling: and cleaning the strip subjected to solution and quenching treatment, and then performing cold rolling processing, wherein the cold rolling processing rate is controlled to be more than 40%.
8) Primary aging: and (3) carrying out primary aging treatment on the strip after cold rolling, wherein the aging temperature is 420-460 ℃, and the heat preservation time is 5-8 h.
9) Cold rolling: and cleaning the strip subjected to primary aging treatment, and then performing cold rolling processing, wherein the processing rate is 20% -40%.
10 Secondary aging): and (3) carrying out secondary aging treatment on the strip after cold rolling processing, wherein the aging temperature is 300-350 ℃ and the aging time is 3-5 h.
11 Finish rolling: and (3) cleaning the strip subjected to the secondary aging treatment, and then performing finish rolling processing, wherein the processing rate is 5% -15%.
12 Stretch bending and straightening: and (3) stretch bending and straightening the strip after finish rolling processing, and controlling the shape of the strip to obtain a copper alloy strip finished product of which the shape meets the application requirements of the lead frame for packaging the ultra-large-scale integrated circuit chip.
Yield strength, conductivity, texture type and area ratio, stress relaxation rate and Badway 90-degree bending detection are respectively carried out on the strips of the examples and the comparative examples.
Yield strength test according to GB/T228.1-2010 Metal tensile test part 1: the room temperature test method is carried out on an electronic universal mechanical property tester, and strip samples with the thickness of 0.2mm are adopted for the examples and the comparative examples, and the stretching speed is 5mm/min.
The conductivity of the strips of the examples and comparative examples was tested using the GB/T32791-2016 copper and copper alloy conductivity vortex test method.
The test examples and comparative examples were tested for their stress relaxation properties by the method "JCBA T309-2004 Standard method for stress relaxation test by bending for thin sheets and strips".
The bending properties of the strips of the examples and comparative examples were tested using "JCBA T307-2007 Test method of bend formability for sheets and strips of copper and copper alloys" (evaluated by whether the Badway 90 DEG R/t.ltoreq.2.0 bend cracked or not).
The example tapes were analyzed for texture type and texture area ratio using EBSD. The area ratio of the texture means the ratio of the texture area to the measured area within 15 degrees of each orientation deviation angle.
The Vickers hardness test method is to air-cool after heat preservation for 1h at 650 ℃, and test the hardness of the sample by using a Vickers hardness tester.
The components, specific preparation process parameters, textures and properties of the examples and comparative examples are shown in tables 1, 2 and 3.
As can be seen from tables 1, 2 and 3, the yield strength of the embodiment of the invention can reach more than 850MPa, the conductivity can reach more than 45% IACS, the stress relaxation is less than or equal to 20% after the insulation is carried out for 1000 hours at 175 ℃, and the Badway 90-degree bending R/t is less than or equal to 2.0 without cracking. Although the yield strength of the C70350 alloy strip can reach more than 850MPa (861.3 MPa), the conductivity can reach more than 45% IACS, and the Badway 90-degree bending R/t is less than or equal to 2.0, the stress relaxation of the alloy strip after heat preservation at 175 ℃ for 1000 hours is 28%, and the stress relaxation resistance of the alloy strip is inferior to that of the alloy strip (the stress relaxation of the copper alloy strip in the embodiment of the invention after heat preservation at 175 ℃ for 1000 hours is all lower than 20%).
Table 1 the ingredients of the examples and comparative examples
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Claims (10)
1. The lead frame copper alloy strip for packaging the ultra-large scale integrated circuit chip is characterized by comprising the following components in percentage by weight: ni:2.0 to 4.0 weight percent, co:0.001 to 1.0 weight percent, si:0.3 to 1.2 weight percent, nb:0.13 to 0.3 weight percent, and the balance of Cu; nb is present in the copper alloy strip in elemental form, the size of Nb elemental particles in the copper alloy strip being controlled between 0.01 μm and 0.5 μm, wherein the ratio of Nb elemental particles having a size between 0.01 μm and 0.1 μm is 10% to 30%, the ratio of Nb elemental particles having a size between 0.1 μm and 0.3 μm is 40% to 70%, and the ratio of Nb elemental particles having a size between 0.3 μm and 0.5 μm is 10% to 30%; the whole process preparation procedure of the copper alloy strip comprises the following steps: batching, smelting and casting, sawing, hot rolling and cogging, milling faces, rough rolling, solid solution and quenching, cold rolling, primary aging, cold rolling, secondary aging, finish rolling, stretch bending and straightening, and obtaining a finished product of the strip, wherein the final rolling temperature of the hot rolling is above 900 ℃, and the solid solution heat preservation time is 60-300 seconds.
2. The copper alloy strip for a lead frame for packaging a very large scale integrated circuit chip according to claim 1, wherein the area ratio of the cubic texture in the measured area of the copper alloy strip is 10% to 20%.
3. The copper alloy strip for a lead frame for packaging a very large scale integrated circuit chip according to claim 2, wherein the area ratio of the cubic texture, the copper-type texture and the brass texture in the copper alloy strip satisfies the relation 0.5 (a+c)/b.ltoreq.1.2, wherein a is the area ratio of the cubic texture in the measurement area, b is the area ratio of the brass texture in the measurement area, and c is the area ratio of the copper-type texture in the measurement area.
4. The leadframe copper alloy strip for very-large-scale-integrated-circuit-chip packaging according to any one of claims 1 to 3, further comprising, in weight percentage composition, less than 0.3wt% in total of one or more of the following optional elements: mg:0.001 to 0.3 weight percent of Ag:0.001 to 0.1 weight percent, cr:0.001 to 0.1 weight percent of Zr:0.001 to 0.1 weight percent.
5. The copper alloy strip for a lead frame for packaging a very large scale integrated circuit chip according to claim 1, wherein the copper alloy strip has yield strength of not less than 850MPa, conductivity of not less than 45% iacs, stress relaxation of not more than 20% when heat is preserved for 1000 hours at 175 ℃, and Badway 90 ° bending R/t of not more than 2.0, wherein R is bending radius, and t is strip thickness.
6. The copper alloy strip for a lead frame for packaging a very large scale integrated circuit chip according to claim 1, wherein the copper alloy strip is air-cooled after being heat-preserved at 650 ℃ for 1 hour, and has a vickers hardness value of 180HV or more.
7. The copper alloy strip for lead frame for very large scale integrated circuit chip package according to claim 1, wherein Nb is added as Ni-Nb intermediate alloy during smelting and electromagnetic stirring is used during casting to ensure uniform Nb distribution in the copper alloy.
8. The copper alloy strip for a lead frame for packaging a very large scale integrated circuit chip according to claim 1, wherein an area ratio of a copper texture in a hot rolled strip obtained after hot rolling and cogging to a measured area is 45% or more.
9. The copper alloy strip for a lead frame for packaging a very large scale integrated circuit chip according to claim 1, wherein the total working ratio of rough rolling is controlled to be 95% or more, the solid solution temperature is controlled to be 960 ℃ to 1000 ℃, and the area ratio of the cubic texture in the strip after quenching in the measured area is 40% or more.
10. The copper alloy strip for a lead frame for packaging a very large scale integrated circuit chip according to claim 1, wherein a working ratio of cold rolling between quenching and primary aging is controlled to be 40% or more, a working ratio of cold rolling between primary aging and secondary aging is controlled to be 20% to 40%, and a working ratio of finish rolling is controlled to be 5% to 15%.
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| CN109072341A (en) * | 2016-03-31 | 2018-12-21 | 同和金属技术有限公司 | Cu-Ni-Si series copper alloy plate and autofrettage |
| CN111485132A (en) * | 2020-04-10 | 2020-08-04 | 宁波博威合金板带有限公司 | Copper alloy strip with excellent comprehensive performance and preparation method thereof |
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| JP2002294368A (en) * | 2001-03-30 | 2002-10-09 | Kobe Steel Ltd | Copper alloy for terminal and connector and production method therefor |
| CN109072341A (en) * | 2016-03-31 | 2018-12-21 | 同和金属技术有限公司 | Cu-Ni-Si series copper alloy plate and autofrettage |
| CN111485132A (en) * | 2020-04-10 | 2020-08-04 | 宁波博威合金板带有限公司 | Copper alloy strip with excellent comprehensive performance and preparation method thereof |
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