CN103184362B - 合金线材及其制造方法 - Google Patents
合金线材及其制造方法 Download PDFInfo
- Publication number
- CN103184362B CN103184362B CN201210198918.2A CN201210198918A CN103184362B CN 103184362 B CN103184362 B CN 103184362B CN 201210198918 A CN201210198918 A CN 201210198918A CN 103184362 B CN103184362 B CN 103184362B
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- CN
- China
- Prior art keywords
- wire
- alloy
- silver
- palladium
- gold
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 179
- 239000000956 alloy Substances 0.000 title claims abstract description 179
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 239000013078 crystal Substances 0.000 claims abstract description 149
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 84
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 38
- 229910052737 gold Inorganic materials 0.000 claims abstract description 37
- 239000010931 gold Substances 0.000 claims abstract description 37
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001252 Pd alloy Inorganic materials 0.000 claims abstract description 17
- 229910001020 Au alloy Inorganic materials 0.000 claims abstract description 15
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims description 103
- 239000000463 material Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 41
- 238000007493 shaping process Methods 0.000 claims description 30
- 229910052709 silver Inorganic materials 0.000 claims description 28
- 239000004332 silver Substances 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 238000007747 plating Methods 0.000 claims description 16
- 238000005266 casting Methods 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000005482 strain hardening Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims 2
- 238000004100 electronic packaging Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000003353 gold alloy Substances 0.000 abstract 1
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 19
- 229910052802 copper Inorganic materials 0.000 description 19
- 239000010949 copper Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- 210000003746 feather Anatomy 0.000 description 17
- 230000008520 organization Effects 0.000 description 17
- 230000003595 spectral effect Effects 0.000 description 12
- 238000007669 thermal treatment Methods 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005272 metallurgy Methods 0.000 description 4
- 238000004377 microelectronic Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000009749 continuous casting Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- PSFDQSOCUJVVGF-UHFFFAOYSA-N harman Chemical compound C12=CC=CC=C2NC2=C1C=CN=C2C PSFDQSOCUJVVGF-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D25/00—Special casting characterised by the nature of the product
- B22D25/02—Special casting characterised by the nature of the product by its peculiarity of shape; of works of art
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- 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
- C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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Abstract
本发明提供一种电子封装用合金线材,其材质是选自由银-金合金、银-钯合金、银-金-钯合金所组成的群组中的任意一种,以及在此合金基材表面上再镀有一层或多层由纯金、纯钯、金-钯合金薄膜所组成的群组中的任意一种,此合金线材为面心立方晶相的多晶结构并且具有复数个晶粒,此合金线材的线材中心部位具有长条形晶粒或等轴晶粒,并且另外的部位由等轴晶粒构成,并且具有退火孪晶的晶粒的数量,占此合金线材的所有晶粒数量的20%以上。
Description
技术领域
本发明涉及一种合金线材及其形成方法,特别是涉及一种用于电子封装引线接合的合金线材及其形成方法。
背景技术
引线接合为半导体封装及发光二极管(LED)封装的工序上极为重要步骤,引线接合线材除了提供芯片与基板的讯号与功率传输,也可兼具散热功能。因此,作为引线接合的金属线材必须有极佳的导电性与导热性,并且需要有足够的强度与延展性。但为了避免引线接合的热压过程导致芯片破裂,同时使线材与焊垫接触良好以确保良好的接合性,线材的硬度不能太高,而由于封装的高分子封胶常含有腐蚀性氯离子,且高分子封胶本身具有环境吸湿性,线材必须有良好的抗氧化性与耐腐蚀性。此外,引线接合的第一接点(焊球点)从熔融状态冷却至室温过程会有高热量经由线材传出,因而,在焊球点附近的线材产生热影响区(Heat Affected Zone),也即此区域的线材将因为热量堆积而发生晶粒成长现象,产生局部的粗大晶粒,这些局部的粗大晶粒强度较低,导致拉线试验(Wire Pull Test)时,线材会由此热影响区断裂而影响接合强度。当半导体或发光二极管封装完成,产品在使用过程,通过线材的高电流密度也可能带动内部原子产生电迁移现象(ElectronMigration),使得线材一端形成孔洞,因而降低导电性与导热性,甚至造成断线。
现今,电子产业使用的引线接合线材以纯金与纯铝为主(请参考:GeorgeG.Harman,Reliability and Yield Problems of Wire Bonding in Microelectronics,National Institute of Standards and Technology,1991 by International Society forHybrid Microelectronics,p.49-89.)。最近,也有使用纯铜线(请参考:1.美国专利早期公开US20060186544A1;2.美国专利公告US 4986856)、铜线镀金(请参考:美国专利公告US 7645522B2)、铜线镀钯(请参考:美国专利早期公开US 20030173659A1)、铜线镀铂(请参考:美国专利早期公开US20030173659A1)或铝线镀铜(请参考:美国专利公告US 6178623B1)的复合金属线材。这些公知引线接合金属线材的内部组织均为等轴的微细晶粒(Fine Grain),此种传统微细晶粒组织可提供足够的拉伸强度与延展性,但是微细晶粒本身存在大量的高角度晶界(High Angle Grain Boundary),这些高角度晶界会阻碍电子的传输,因而增加线材的电阻率,同时也降低线材的导热性。另一方面,这些高角度晶界具有较高界面能,也提供了环境氧化、硫化及氯离子腐蚀的有利路径,使封装后的电子产品可靠度降低。此外,这种公知微细晶粒组织金属线材在引线接合过程中很容易在第一接点(焊球点)附近形成热影响区,降低引线接合强度,同时在半导体或发光二极管产品使用时也很容易产生电迁移现象,这些都是造成一般公知引线接合封装产品的品质及可靠度劣化的主要原因。
发明内容
有鉴于此,本发明提供一种合金线材,其材质是选自由银-金合金、银-钯合金、银-金-钯合金所组成的群组中的任意一种,此合金线材为面心立方晶相的多晶结构并且具有复数个晶粒,此合金线材的线材中心部位具有长条形晶粒或等轴晶粒,并且另外的部位由等轴晶粒构成,并且具有退火孪晶(Annealins Twin)的晶粒的数量,占上述合金线材的所有晶粒数量的20%以上。
在上述合金线材中,较优选为:上述银-金合金的金含量为0.01~30.00wt%,余量为银;上述银-钯合金的钯含量为0.01~10.00wt%,余量为银;上述银-金-钯合金的金含量为0.01~30.00wt%、钯含量为0.01~10.00wt%,余量为银。
在上述合金线材中,上述合金线材的线径较优选为10~50μm。
本发明又提供一种合金线材,包含:一基材线材,其材质是选自由银-金合金、银-钯合金、银-金-钯合金所组成的群组中的任意一种,上述基材线材为面心立方晶相的多晶结构并且具有复数个晶粒,此基材线材的线材中心部位具有长条形晶粒或等轴晶粒,并且另外的部位由等轴晶粒构成,并且具有退火孪晶的晶粒的数量,占上述合金线材的所有晶粒数量的20%以上;以及一层或多层薄膜金属镀层镀于上述基材线材上,上述镀层的材质是选自由实质上的纯金、实质上的纯钯、金-钯合金所组成的群组中的任意一种。
在上述合金线材中,较优选为:上述银-金合金的金含量为0.01~30.00wt%,余量为银;上述银-钯合金的钯含量为0.01~10.00wt%,余量为银;上述银-金-钯合金的金含量为0.01~30.00wt%、钯含量为0.01~10.00wt%,余量为银;以及在上述银-金、银-钯、银-金-钯合金表面上再镀有一层或多层厚度0.1~5.0μm的薄膜,其材质选自由实质上的纯金、实质上的纯钯、金-钯合金所组成的群组中的任意一种。
在上述合金线材中,上述合金线材的线径较优选为10~50μm。
本发明又提供一种合金线材的制造方法,包含:提供一粗线材,上述粗线材的材质是选自由银-金、银-钯、银-金-钯合金所组成的群组中的任意一种;以N道的冷加工成形步骤,逐次缩减上述粗线材的线径,成为线径小于上述粗线材的线径的一细线材,在上述冷加工成形步骤的第(N-1)道及第N道中,相对于前一道冷加工成形步骤后的中间材料的变形量为1%以上、不超过15%,其中N为大于或等于3的正整数;在上述冷加工成形步骤的第(N-1)道与第N道冷加工成形步骤之间进行的第(N-1)道退火步骤的退火温度为0.5Tm~0.7Tm、退火时间为1~10秒,其中Tm为上述粗线材的材质的绝对温标的熔点;以及在上述冷加工成形步骤的第N道冷加工成形步骤之后进行的第N道退火步骤的退火温度比上述第(N-1)道退火步骤的退火温度高20~100℃、退火时间为2~60秒,使上述细线材成为面心立方晶相的多晶结构而具有复数个晶粒,线材中心部位为长条形晶粒或等轴晶粒,并且,另外的部位为等轴晶粒,并在上述晶粒的至少一部分形成退火孪晶,并且,具有退火孪晶的晶粒的数量,占上述细线材的所有晶粒数量的20%以上。
在上述合金线材的制造方法中,上述冷加工成形步骤较优选为抽线、挤型或上述的组合。
在上述合金线材的制造方法中,上述粗线材的提供,较优选为包含下列步骤:将上述粗线材的材质的原料加热熔融后,经浇铸而成为一铸锭;以及对上述铸锭进行冷加工,制成上述粗线材。
在上述合金线材的制造方法中,上述粗线材的提供,较优选为包含下列步骤:将上述粗线材的材质的原料加热熔融后,以连续铸造的方式,制成上述粗线材。
在上述合金线材的制造方法中,在上述将粗线材冷加工成形为细线材步骤之前,较优选为更包含通过电镀、蒸镀或溅镀在该粗线材的表面镀上一层或多层薄膜金属,此镀层的材质是选自由实质上的纯金、实质上的纯钯、金-钯合金所组成的群组中的任意一种。
在上述合金线材的制造方法中,在上述倒数第一道退火步骤之后,较优选为更包含通过电镀、蒸镀或溅镀在上述细线材的表面镀上一层或多层薄膜金属,此镀层的材质是选自由实质上的纯金、实质上的纯钯、金-钯合金所组成的群组中的任意一种。
在上述合金线材的制造方法中,较优选为:上述银-金合金的金含量为0.01~30.00wt%,余量为银;上述银-钯合金的钯含量为0.01~10.00wt%,余量为银;上述银-金-钯合金的金含量为0.01~30.00wt%、钯含量为0.01~10.00wt%,余量为银;以及在上述银-金合金、银-钯合金、银-金-钯合金表面上再镀有一层或多层厚度0.1~5.0μm的实质上的纯金、实质上的纯钯或金-钯合金的薄膜。
在上述合金线材的制造方法中,上述粗线材的线径较优选为5~10mm、上述细线材的线径较优选为10~50μm。
附图说明
图1中(A)、(B)、(C)图是显示本发明的第一实施方式的合金线材,其中,(A)图是本发明的第一实施方式的合金线材的一部分的线段的示意图、(B)图是沿着平行于(A)图所示合金线材的长度方向的纵截面图、(C)图是沿着垂直于(A)图所示金属线材的长度方向的横截面图。
图2中(A)、(B)、(C)图显示本发明的第二实施方式的合金线材,其中,(A)图是本发明的第二实施方式的合金线材的一部分的线段的示意图、(B)图是沿着平行于(A)图所示合金线材的长度方向的纵截面图、(C)图是沿着垂直于(A)图所示金属线材的长度方向的横截面图。
图3是一流程图,显示本发明第一实施方式的合金线材的制造方法的一个实例。
图4是一流程图,显示本发明第二实施方式的合金线材的制造方法的一个实例。
图5是一流程图,显示本发明第二实施方式的合金线材的制造方法的另一个实例。
图6是一流程图,显示图3-5所示流程图中的提供粗线材的方法的一个实例。
图7是一步骤示意图,显示图3-5所示流程图中的提供粗线材的方法的另一个实例。
图8中(A)、(B)图分别是显示本发明实施例的合金线材的纵截面与横截面金相结构,其线材中心部位为长条形晶粒,另外的部位为等轴晶粒;(C)图是本发明实施例1的合金线材经过600℃空气炉放置30分钟热处理的纵截面金相结构。
图9中(A)、(B)图分别是显示本发明对照组传统合金线材纵截面与横截面金相结构,(C)图是发明对照组传统合金线材经过600℃空气炉放置30分钟热处理之纵截面金相结构。
图10中(A)图是本发明对照组商用4N纯金线材纵截面金相结构,(B)图是发明对照组商用4N纯金线材经过600℃空气炉放置30分钟热处理的纵截面金相结构。
图11中(A)图是本发明对照组铜镀钯线材纵截面金相结构,(B)图是本发明对照组铜镀钯线材经过600℃空气炉放置30分钟热处理的纵截面金相结构。
图12中(A)、(B)图是显示X光衍射谱线,其中,(A)图是显示本发明实施例1的合金线材的X光衍射谱线、(B)图是显示一般公知线材的X光衍射谱线。
图13是显示本发明实施例的合金线材在进行第一焊点结球后的焊球剖面金相结构。
图14是显示本发明对照组合金线材在进行第一焊点结球后的焊球剖面金相结构。
图15中(A)图是显示本发明的实施例2的合金线材的纵截面金相结构。(B)图是显示(A)图所示合金线材在600℃空气炉放置30分钟热处理后的纵截面金相结构。
其中,附图标记说明如下:
10合金线材 12等轴晶粒
14高角度晶界 16退火孪晶
18长条型晶粒 20合金线材
21基材线材 22等轴晶粒
24高角度晶界 25镀层
26退火孪晶 28长条型晶粒
102步骤 103步骤
104步骤 106步骤
108步骤 202浇铸步骤
204冷加工步骤 302连续铸造步骤
具体实施方式
为让本发明的上述和其它目的、特征和优点能更明显易懂,下文特举出较优选实施例,并配合附图,作详细说明如下。
要说明的是本申请说明书中以下的记载内容提供许多不同的实施例或范例,以实施本发明的不同特征。而本说明书以下的记载内容是叙述各个构件及其排列方式的特定范例,以求简化发明的说明。当然,这些特定的范例并非用以限定本发明。例如,若是本说明书以下的记载内容叙述了将一第一特征形成于一第二特征之上或上方,即表示其包含了所形成的上述第一特征与上述第二特征是直接接触的实施例,也包含了尚可将附加的特征形成于上述第一特征与上述第二特征之间,而使上述第一特征与上述第二特征可能未直接接触的实施例。另外,本说明书以下的记载内容可能在各个范例中使用重复的组件符号,以使说明内容更加简化、明确,但是重复的组件符号本身不会使不同的实施例及/或结构之间产生关联。
另外,在本申请说明书中,在数值相关叙述后接“以上”、“以下”之词来叙述数值范围的情况中,除非另有加注,相关的数值范围是包含上述“以上”、“以下”之词前接的数值。
请参考图1中(A)、(B)、(C)图,显示本发明第一实施方式的合金线材10。其中,(A)图是合金线材10的一部分的线段的示意图、(B)图是沿着平行于(A)图所示合金线材10的长度方向的纵截面图、(C)图是沿着垂直于(A)图所示合金线材10的长度方向的横截面图。
如(A)图所示的本发明第一实施方式的合金线材10,其材质是选自由银-金合金、银-钯合金、银-金-钯合金所组成的群组中的任意一种。如(B)图所示,此合金线材10的纵截面为面心立方晶相的多晶结构并且具有复数个晶粒,且大部分为等轴晶粒12,各等轴晶粒12之间是以高角度晶界14为界,其中具有退火孪晶16的晶粒的数量,是占此合金线材10的所有晶粒数量的20%以上,除了上述的等轴晶粒12,在线材中心部位也可能存在长条型晶粒18。
在本申请说明书中所述“线材中心部位”,在本申请说明书中指的是从线材的轴心起算沿着线材半径方向的30%的线材半径值的范围内的部位。在此“线材中心部位”的范围内,可完全由复数个长条型晶粒18或复数个等轴晶粒12所构成,也可具有长条型晶粒18与等轴晶粒12;在此“线材中心部位”的范围之外的另外的部位由复数个等轴晶粒构成。
接下来请参考图2中(A)、(B)、(C)图,显示本发明第二实施方式的合金线材20。其中,(A)图是合金线材20的一部分的线段的示意图、(B)图是沿着平行于(A)图所示合金线材20的长度方向的纵截面图、(C)图是沿着垂直于(A)图所示合金线材20的长度方向的横截面图。
本发明第二实施方式的合金线材20,是包含一基材线材21与一镀层25。此基材线材21的材质是选自由银-金、银-钯、银-金-钯合金所组成的群组中的任意一种,此基材线材21为面心立方晶相的多晶线材并且具有复数个晶粒,且大部分为等轴晶粒22,各晶粒之间是以高角度晶界24为界,其中具有退火孪晶26的晶粒的数量,是占此合金线材20的所有晶粒数量的20%以上,除了上述的等轴晶粒22,在线材中心部位也可能存在长条型晶粒28。也就是合金线材20的线材中心部位可具有长条型晶粒28、等轴晶粒22或上述的组合。上述镀层25是镀于上述基材线材21上,此镀层25可由单层或多层金属膜构成,此镀层25的材质是选自由实质上的纯金、实质上的纯钯、金-钯合金所组成的群组中的任意一种。通过此镀层25的材质的化学惰性,可保护其内的基材线材21而避免其受到腐蚀,同时在抽线成形时发挥润滑效果。另外,此镀层25的厚度较优选为0.1~5.0μm,且图2中(B)、(C)图中未显示镀层25的晶粒组织。
关于本申请说明书全文所述的实质上的纯金、实质上的纯钯等,以实质上的纯金为例,是指在设计上期望为完全不含其它元素、化合物等的杂质的纯金,但在实际冶炼、精炼、镀膜等的过程中却难以完全除去上述杂质而达成数学上或理论上含100%的纯金,而当上述杂质含量的范围落于对应的标准或规格所规定的允收范围内,就视为“实质上的纯金”。其它实质上的纯钯的意义也同。本发明所属技术领域中具有通常知识者应当了解依据不同的性质、条件、需求等等,上述对应的标准或规格会有所不同,故下文中并未列出特定的标准或规格。
上述银-金、银-钯、银-金-钯合金是指以银为主成分再添加金及/或钯的合金,且金、钯的含量不大于作为主成分的银的含量。
另外,上述本发明的第一、第二实施方式的合金线材,线径较优选为10~50μm,可以用于电子封装引线接合用的线材。当然,依使用者的需求,也可将本发明的合金线材应用于其它技术领域与用途,例如:音响线、讯号或功率传输线、变压器线等,而合金线材的线径也可依据需求加以变化,而不限定为上述例示的范围。
本发明的合金线材的特征之一,是此合金线材为多晶结构而具有复数个晶粒,线材中心部位为长条形晶粒,另外的部位为等轴晶粒,其晶粒的平均粒径为1~10μm,而略大于一般公知引线接合线材的晶粒的平均粒径0.5~3μm,因而相对地减少了高角度晶界的密度,而减少前述微细晶粒的大量高角度晶界所造成缺点。本发明的合金线材的更重要的特征在于其至少20%的晶粒内部含有退火孪晶(Annealing Twin)组织,这些退火孪晶组织的孪晶界(Twin Boundary)为调谐(Coherent)结晶构造,属于低能量的Σ3特殊晶界,其界面能仅为一般高角度晶界的5%(请参考:George E.Dieter,MechanicalMetallurgy,McGRAW-HILL Book Company,1976,P.135-141),由于孪晶界的较低的界面能,可以避免成为氧化、硫化及氯离子腐蚀的路径,因此展现较优选的抗氧化性与耐腐蚀性。另外,此种退火孪晶的对称晶格排列对电子传输的阻碍极小,因而展现较佳的导电性与导热性,此一效应在铜导线已获得证实(请参考:L.Lu,Y.Shen,X.Chen,L.Qian,and K.Lu,Ultrahigh Strengthand High Electrical Conductivity in Copper,Science,vol.304,2004,p.422-426)。同时由于较低的界面能而使此种低能量孪晶组织的孪晶界较一般高角度晶界稳定,不仅在高温状态孪晶界本身不易移动,更会对其所在晶粒之周围的高角度晶界产生固锁作用,使这些高角度晶界也无法移动,因而整体晶粒组织不会有明显晶粒成长现象,即使是引线接合过程第一接点(焊球点)从熔融状态冷却至室温,也可以维持原有晶粒尺寸,也即免除了传统微细晶粒结构的金属线材经过引线接合后,焊球点凝固热量在其附近线材累积,使其晶粒迅速成长而形成热影响区,降低拉线试验强度。另一方面,由于原子经由低能量孪晶界或跨越孪晶界的扩散速率极低,在电子产品使用时,高密度电流所伴随线材内部原子移动也极为困难,如此解决了前述发生于公知引线接合用金属线材的电迁移问题,在铜薄膜已有报导证实孪晶可抑制材料电迁移现象(请参考:K.C.Chen,W.W.Wu,C.N.Liao,L.J.Chen,and K.N.Tu,Observation of Atomic Diffusion at Twin-Modified Grain Boundaries in Copper,Science,vol.321,2008,p.1066-1069.)。综合上述优点,本发明的合金线材应用于半导体及发光二极管产品作为引线接合用线材时,较一般公知线材展现较佳的品质及可靠度。
另外,欲显现上述特性,在本发明的合金线材的所有晶粒中,至少20%的数量以上的晶粒含有退火孪晶组织时,才会具有上述特性。而在公知的引线接合用的金属线材的情况中,或许偶有出现退火孪晶组织的情况,但是含退火孪晶组织的晶粒数量通常为此线材所有的晶粒的10%以下或甚至完全不含退火孪晶组织,故无法展现前述本发明的合金线材的特性。
更进一步说明,虽然本发明的合金线材的晶粒略大于一般公知线材的晶粒,但其内部大部分晶粒含有退火孪晶,这些孪晶结构与其所在的晶粒具有不同结晶方位(Crystal Orientation),因此同样可以阻挡差排(Dislocation)的移动,而产生材料强化效应,此强化机构不同于一般公知微细晶粒组织金属线材需仰赖高角度晶界阻挡差排移动,却附带引发其它不利于引线接合品质与可靠度的问题。由此,本发明的具有退火孪晶组织的引线接合用合金线材可以维持与一般公知微细晶粒结构线材相近的拉伸强度,但由于差排及原子可经由孪晶界跨移(Cross Slip),其延展性反而高于一般公知线材,因此本发明的合金线材的机械性质优于一般公知线材。
根据物理冶金学原理(请参考George E.Dieter,Mechanical Metallurgy,McGRAW-HILL Book Company,1976,P.135-141.及R.W.Cahn,PhysicalMetallurgy,1970,P.1184-1185),退火孪晶组织的形成是由于冷加工在材料内部累积应变能,在后续退火热处理时,这些应变能驱动部分区域的原子均匀剪切位移(Shear)至与其所在晶粒内部未剪切位移原子形成相互镜面对称的晶格位置,此即为退火孪晶(Annealing Twin),而其相互对称的界面即为孪晶界(Twin Boundary)。退火孪晶主要发生在晶格排列最紧密的面心立方(Face Centered Cubic;FCC)结晶材料,其孪晶界为低能量的Σ3特殊晶界,结晶方位均为﹛111﹜面。相较于一般退火再结晶(Recrystallization)所形成高角度晶界(High Angle Grain Boundary),孪晶界的界面能大约只有高角度晶界的5%。除了面心立方结晶构造条件,通常叠差能(Stacking Fault Energy)愈小的材料愈容易产生退火孪晶,本发明所使用的合金元素:金、银、钯及其配制完成的银-金、银-钯、银-金-钯合金的叠差能均大约在50erg/cm2以下,最容易形成退火孪晶;相反地,铝虽为面心立方结晶构造材料,但其叠差能大约200erg/cm2,极少出现退火孪晶,不符合本发明材料选择条件。
在本发明的合金线材的材质是银-金合金、银-钯合金、银-金-钯合金的组成,无论所述银、金、钯的含量为何,其叠差能均大约在50erg/cm2以下;若考虑到其它因素例如原材料的成本、取得方便性、铸造过程的偏析、抽线成形性、抗氧化性、拉伸强度、硬度、延展性、引线接合结球品质及接合强度等,较优选为:上述银-金合金的金含量为0.01~30.00wt%,余量为银;上述银-钯合金的钯含量为0.01~10.00wt%,余量为银;上述银-金-钯合金的金含量为0.01~30.00wt%、钯含量为0.01~10.00wt%,余量为银。
此外,退火热处理前的冷加工变形量也为关键条件,足够的冷加工变形量所累积应变能可提供原子驱动力以产生退火孪晶,但如果冷加工变形量太大,在退火热处理初始再结晶(Primary Recrystallization)阶段即会引发多数晶粒成核(Nuclei of Recrystallized Grains),因而形成大量的微细晶粒,降低退火孪晶的产生机会,反而成为一般公知金属线材的组织。虽然微细晶粒提供良好的拉伸强度与延展性,但是此种公知金属线材内部大量的高角度晶界阻碍了电子流动与热传,也降低线材的抗氧化性与耐蚀性,同时在引线接合的第一焊点结球过程,这些由大量高角度晶界所构成微细晶粒会经由熔融焊球点凝固的高热量传导迅速成长为粗大晶粒,衍生出引线接合最困扰的热影响区问题,降低拉线试验强度,同时在后续电子产品通电运作时也很容易因为电流伴随材料内部原子传输产生电迁移,这些都会严重影响半导体封装及发光二极管(LED)封装产品的可靠度。
因此,关于前述本发明的第一实施方式的合金线材的制造方法的一个实例,请参考图3所示的流程图,可包含下列步骤:
步骤102:提供一粗线材,此粗线材的材质是选自由银-金、银-钯、银-金-钯合金所组成的群组中的任意一种;
步骤104:以N道的冷加工成形步骤,逐次缩减上述粗线材的线径,成为线径小于该粗线材的线径的一细线材,在上述冷加工成形步骤的第N-1道及第N道中,相对于前一道冷加工成形步骤后的中间材料的变形量为1%以上、不超过15%,其中N为大于或等于3的正整数;以及
步骤106:N道的退火步骤,分别在上述冷加工成形步骤的每一道之间及第N道冷加工成形步骤之后进行。在上述冷加工成形步骤的第(N-1)道与第N道冷加工成形步骤之间进行的第(N-1)道退火步骤的退火温度为0.5Tm~0.7Tm、退火时间为1~10秒,其中Tm为上述粗线材的材质的绝对温标的熔点。在上述冷加工成形步骤的第N道冷加工成形步骤之后进行的第N道退火步骤的退火温度比上述第(N-1)道退火步骤的退火温度高20~100℃、退火时间为2~60秒。
通过上述步骤102、104、106,使上述细线材成为面心立方晶相的多晶线材并且具有复数个晶粒,线材中心部位为长条形晶粒,另外的部位为等轴晶粒,并在上述晶粒的至少一部分形成退火孪晶,其中具有退火孪晶的晶粒的数量,占上述细线材的所有晶粒数量的20%以上,而完成前述本发明第一实施方式的合金线材。
另外,关于上述步骤106所述的N道退火步骤,可使用与公知线材相同的退火设备,上述第(N-1)道退火步骤之前的其它退火步骤的步骤数及退火条件,是在不抵触“N为大于或等于3的正整数”的条件下,可视需求及设备条件等因素来作适当决定,故仅列出作为本发明特征的退火条件,而省略关于退火设备、退火步骤及其它退火步骤的步骤数及退火条件的相关细节的详述。
在上述步骤中,上述细线材的线径较优选为10~50μm、上述粗线材的线径较优选为5~10mm,而如前所述,使本发明的合金线材可以用于引线接合用的线材。
在上述步骤中,上述粗线材的材质是选自银-金、银-钯、银-金-钯合金所组成的群组中的任意一种,其熔点Tm指的是相关平衡相图中对应成分的液化开始温度的绝对温标的温度。
在上述步骤中,上述“变形量”指的是因冷加工而对被冷加工材料造成的截面积缩减率。
关于前述本发明第二实施方式的合金线材的制造方法的一个实例,请参考图4所示的流程图,也就是在图3所示的步骤104之前,先执行步骤103:通过电镀、蒸镀或溅镀在上述粗线材的表面镀上一层或多层薄膜金属,此镀层的材质是选自由实质上的纯金、实质上的纯钯、金-钯合金所组成的群组中的任意一种。另外,此镀层的厚度较优选为0.1~5.0μm。由此,完成前述本发明第二实施方式的合金线材。
关于前述本发明第二实施方式的合金线材的制造方法的另一个实例,请参考图5所示的流程图,也就是在图3所示的步骤106之后,再执行步骤108:通过电镀、蒸镀或溅镀在上述细线材的表面镀上一层或多层薄膜金属,此镀层的材质是选自由实质上的纯金、实质上的纯钯、金-钯合金所组成的群组中的任意一种。另外,此镀层的厚度较优选为0.1~5.0μm。由此,完成前述本发明第二实施方式的合金线材。
在上述各方法中,上述步骤104的冷加工成形步骤较优选为抽线、挤型或上述的组合。
在上述各方法中,提供上述粗线材的方法的一个实例,请参考图6所示的流程图,较优选为包含下列步骤:
浇铸步骤202:将上述粗线材的材质的原料加热熔融后,经浇铸而成为一铸锭;以及
冷加工步骤204:对上述铸锭进行冷加工,制成上述粗线材。同样地,冷加工步骤204也可为抽线、挤型或上述的组合。
在上述各方法中,提供上述粗线材的方法的另一个实例,请参考图7所示的示意图,较优选为包含下列步骤:
连续铸造步骤302:将上述粗线材的材质的原料加热熔融后,以连续铸造的方式,制成上述粗线材。
在上述合金线材的制造方法中,较优选为:上述银-金、银-钯、银-金-钯合金的金含量为0.01~30.00wt%、钯含量为0.01~10.00wt%,余量为银。
除了前述制造方法的条件之外,如有通过其它方法例如不同的冷加工方式、冷加工变形量、退火条件等,而制得符合本说明书所述本发明的合金线材的线材时,该线材也包含于本发明的范围内。
本发明乃经过诸位发明人长久、精心的研究,寻找出大小适中的冷加工变形量条件,同时配合最优化的退火温度与时间,而获得内部含有大量退火孪晶的创新线材组织,提供了引线接合高导电性、高导热性、优良抗氧化性与氯离子腐蚀性。最吸引人的是经由孪晶界可以有效抑制电迁移现象,而且由于低能量孪晶界对其所在晶粒周围其它高角度晶界有固锁作用,使其不易移动,因而抑制晶粒成长,几乎不会产生热影响区。另一方面,孪晶与其所在晶粒的不同结晶方位,因此同样可以阻碍差排移动,发挥材料强化效应。因此,本发明的合金线材的拉伸强度与一般公知的微细晶粒组织线材相近,但其延展性反而高于一般公知金属线材,这些优点使得利用本发明含大量孪晶组织合金线材进行引线接合的半导体封装及发光二极管封装产品在可靠度试验时展现极佳的成绩。例如,最严苛的压力锅测试(Pressure Cooker Test;PCT),在Ta=121℃、100%RH、2atm的条件下可耐受128小时以上,远高于一般电子产品可靠度测试所要求96小时;另一同样严苛的高度加速寿命试验(Highly Accelerated Stress Test;HAST),在Ta=148℃、90%RH、3.6伏特的偏压的条件下可达到128小时以上,也远高于一般电子产品可靠度测试规范所要求的96小时。
实施例1
利用高周波电热熔炼银-8wt%金-3wt%钯合金,再以连续铸造(ContinuousCasting)方式获得线径6mm的粗线材,经过多次抽线延伸与退火热处理至线径22.6μm的细线材,然后经过倒数第二道抽线延伸而成为线径20μm的细线材,再经过530℃退火1.5秒,最后抽线至17.5μm的细线材,然后,进行最终退火热处理,退火温度为570℃、退火时间为4.8秒。完成最终退火后,卷线而完成引线接合所需要的合金线材产品。
为了验证大量退火孪晶组织所造成本发明创新线材的优异性能,另外取相同银-8wt%金-3wt%钯组成的合金采用公知抽线及退火条件制作17.5μm的细线材,作为有别于本发明具大量退火孪晶组织线材的对照组,此对照组合金线材预期不会产生大量退火孪晶组织晶粒。此外,也将本发明合金线材与商用4N纯金线材及铜镀钯线材的特性加以比较。
本发明上述实施例的合金线材的纵截面金相结构,如图8中(A)图所示,除了线材中心部位存在一些细长条晶粒,另外的部位均为等轴晶粒,其中超过总晶粒数量的30%的晶粒具有退火孪晶组织;图8中(B)图则为本发明上述实施例的合金线材的横截面金相组织,估计超过总晶粒数量的40%的晶粒具有退火孪晶组织。
对照组的传统合金线材的纵截面金相结构,如图9中(A)图所示,其中心部位同样呈现细长条晶粒,另外夹杂少数粗大晶粒,另外的部位则为微细晶粒组织,总晶粒数量只有10%以下具有退火孪晶组织。图9中(B)图为对照组合金线材的横截面金相组织,呈现微细晶粒组织,估计其内部仅有大约15%的晶粒出现退火孪晶组织。而在图10中(A)图的商用4N纯金线材及图11中(A)图的铜镀钯线材样品不论是纵截面或横截面的金相组织同样只有少量的晶粒出现退火孪晶组织,事实上,本发明所揭示的大量退火孪晶组织晶粒特征在一般公知引线接合金属线材从未报导(请参考:George G.Harman,Reliability and Yield Problems of Wire Bonding in Microelectronics,National Institute of Standards and Technology,1991by International Society forHybrid Microelectronics.)。
图12中(A)、(B)图是显示X光衍射谱线,其中,图12中(A)图是显示本发明的实施例1的合金线材的X光衍射谱线、(B)图是显示一般公知线材的X光衍射谱线。(A)、(B)图中的X轴是表示衍射角、Y轴是表示衍射强度。其中,衍射角的单位是“度”;关于衍射强度的单位,X光衍射谱线一般是标示“任意单位”(Arbitrary Unit)。
另外,比较图12中(A)、(B)图的X光衍射分析结果,(A)图所示本发明上述实施例1的合金线材出现明显的﹛111﹜结晶方位谱线,此﹛111﹜谱线为典型的退火孪晶的结晶方位谱线,(B)图的对照组合金线材的X光衍射图并无明显的﹛111﹜谱线,商用纯金线材及铜镀钯线材样品也同样未见到此﹛111﹜退火孪晶谱线,由此,确认本发明上述实施例1的合金线材的材料内部存在大量的退火孪晶组织。
为了验证本发明大量孪晶组织特征的合金线材所具备优异性能,以彰显本发明的改良功效,首先进行拉伸试验,结果显示本发明大量孪晶组织线材与对照组少量孪晶组织合金线材的拉伸强度均大约7.5g,与商用4N纯金线材及铜镀钯线材的拉伸强度相近(6.6-10.7g);但对照组少量孪晶组织合金线材的延伸率2.5%,本发明大量孪晶组织合金线材的延伸率可达4.5%,较接近商用4N纯金线材及铜镀钯线材的延伸率(4.0-6.0%)。
再来进行电性测试,显示本发明上述实施例1之大量孪晶组织合金线材的电阻率平均值大约5.0μΩ.cm,最小值甚至达到4.1μΩ.cm,低于对照组少量孪晶组织合金线材的5.5μΩ.cm。此外,本发明的合金线材的电阻率略高于商用4N纯金线材(2.3μΩ.cm)及铜镀钯线材(1.9μΩ.cm)。
为了验证本发明实施例1的大量孪晶组织合金线材的高温稳定性,将以上各种线材在600℃空气炉放置30分钟热处理,发现本发明实施例1的大量孪晶组织合金线材晶粒仅微幅成长(图8中(C)图),而对照组的传统合金线材的原先微细晶粒均大幅成长(图9中(C)图),其晶粒尺寸甚至远超过本发明实施例1的合金线材,另外商用4N纯金线材也发现晶粒严重成长至接近线材直径(图10中(B)图),而铜镀钯线材则几乎完全氧化(图11中(B)图),显示表面镀钯对于解决铜线材氧化问题并非万全之计;综合此实验可以确认本发明实施例1的合金线材的晶粒组织由于存在大量低能量孪晶,可以阻碍晶界移动,因而相较于传统合金线材、商用4N纯金线材及铜镀钯线材均展现极佳的高温稳定性,此一高温稳定性会关连到线材在引线接合后的热影响区形成及可靠度试验表现。
将本发明上述实施例1的大量孪晶组织合金线材与对照组的少量孪晶组织合金线材以焊线机台进行第一焊点结球,其焊球剖面金相结构分别示于图13与图14。图14显示对照组少量孪晶组织合金线材的热影响区长达60μm,且晶粒成长超过10倍,而图13则证实本发明上述实施例1的大量孪晶组织合金线材的热影响区仅大约15μm,且晶粒成长小于2倍,由此,可见本发明上述实施例1的大量孪晶组织合金线材的热影响区极小,且其晶粒成长几乎不会造成焊球接点的强度劣化。
使用本实施例1的大量孪晶组织合金线材进行引线接合所制作完成的半导体产品经过一系列可靠度试验,其结果综合示于表1,其中,最严苛的压力锅测试(Pressure Cooker Test,PCT)可耐受128小时以上,远高于一般电子产品可靠度测试所要求的96小时,另一同样严苛的高度加速寿命试验(Highly Accelerated Stress Test,HAST)可达到128小时以上,也远高于一般电子产品可靠度测试规范所要求的96小时。
表1
实施例2
利用高周波电热熔炼银-8wt%金-3wt%钯合金,再以连续铸造(ContinuousCasting)方式获得线径6mm的粗线材,经过多次抽线延伸与退火热处理至线径22.6μm的细线材,然后,经过倒数第二道抽线延伸而成为线径20μm的细线材,再经过650℃退火10秒,最后抽线至17.5μm的细线材,然后,进行最终退火热处理,退火温度为700℃、退火时间为60秒。完成最终退火后,卷线而完成引线接合所需要的实施例2的合金线材产品。实施例2的合金线材的纵截面金相结构,如图15中(A)图所示,整体线材均为等轴晶粒,其中超过总晶粒数量的30%的晶粒具有退火孪晶组织。如图15中(B)图所示,此实施例2的合金线材在600℃空气炉放置30分钟热处理,其晶粒也仅微幅成长。
虽然本发明已以较优选实施例记载如上,然其并非用以限定本发明,任何本发明所属技术领域中具有通常知识者,在不脱离本发明的精神和范围内,可作些许的更动与润饰,因此,本发明的保护范围当视后附的权利要求书所界定的范围为准。
Claims (15)
1.一种合金线材,其材质是选自由银-金合金、银-钯合金、银-金-钯合金所组成的群组中的任意一种,该合金线材是面心立方晶相的多晶结构并且具有复数个晶粒,在该合金线材的线材中心部位具有长条形晶粒或等轴晶粒,并且另外的部位由等轴晶粒构成,并且,具有退火孪晶的晶粒的数量,占该合金线材所有晶粒数量的20%以上。
2.如权利要求1所述的合金线材,其中,
所述银-金合金的金含量为0.01~30.00wt%,余量为银;
所述银-钯合金的钯含量为0.01~10.00wt%,余量为银;以及
所述银-金-钯合金的金含量为0.01~30.00wt%、钯含量为0.01~10.00wt%,余量为银。
3.如权利要求1或2所述的合金线材,其中,所述合金线材的线径为10~50μm。
4.一种合金线材,包含:
一基材线材,其材质是选自由银-金合金、银-钯合金、银-金-钯合金所组成的群组中的任意一种,该基材线材是面心立方晶相的多晶结构并且具有复数个晶粒,该基材线材的线材中心部位具有长条形晶粒或等轴晶粒,并且另外的部位由等轴晶粒构成,并且,具有退火孪晶的晶粒的数量,占所有晶粒数量的20%以上;以及
一层或多层薄膜金属镀层镀于该基材线材上,该镀层的材质是选自由实质上的纯金、实质上的纯钯、金-钯合金所组成的群组中的任意一种。
5.如权利要求4所述的合金线材,其中,
所述银-金合金的金含量为0.01~30.00wt%,余量为银;
所述银-钯合金的钯含量为0.01~10.00wt%,余量为银;以及
所述银-金-钯合金的金含量为0.01~30.00wt%、钯含量为0.01~10.00wt%,余量为银。
6.如权利要求4或5所述的合金线材,其中,所述合金线材的线径为10~50μm。
7.如权利要求4所述的合金线材,其中,所述镀层的厚度为0.1~5.0μm。
8.一种合金线材的制造方法,包含:
提供一粗线材,该粗线材的材质是选自由银-金、银-钯、银-金-钯合金所组成的群组中的任意一种;
以N道的冷加工成形步骤,逐次缩减该粗线材的线径,成为线径小于该粗线材的线径的一细线材,在上述冷加工成形步骤的第(N-1)道及第N道中,相对于前一道冷加工成形步骤后的中间材料的变形量为1%以上、不超过15%,并且N为大于或等于3的正整数;以及
N道的退火步骤,分别在上述冷加工成形步骤的每一道之间及第N道冷加工成形步骤之后进行,并且在上述冷加工成形步骤的第(N-1)道与第N道冷加工成形步骤之间进行的第(N-1)道退火步骤的退火温度为0.5Tm~0.7Tm、退火时间为1~10秒,并且Tm为该粗线材的材质的绝对温标的熔点;以及
在上述冷加工成形步骤的第N道冷加工成形步骤之后进行的第N道退火步骤的退火温度比该第(N-1)道退火步骤的退火温度高20~100℃、退火时间为2~60秒,使该细线材成为面心立方晶相的多晶线材并且具有复数个晶粒,该细线材的线材中心部位具有长条形晶粒或等轴晶粒,并且另外的部位由等轴晶粒构成,并在上述晶粒的至少一部分形成退火孪晶,并且,具有退火孪晶的晶粒的数量,占该细线材的所有晶粒数量的20%以上。
9.如权利要求8所述的合金线材的制造方法,其中,上述冷加工成形步骤为抽线、挤型或上述的组合。
10.如权利要求8所述的合金线材的制造方法,其中,该粗线材的提供,包含下列步骤:
将该粗线材的材质的原料加热熔融后,经浇铸而成为一铸锭;以及
对该铸锭进行冷加工,制成该粗线材。
11.如权利要求8所述的合金线材的制造方法,其中,该粗线材的提供,包含下列步骤:
将该粗线材的材质的原料加热熔融后,以连续铸造的方式,制成该粗线材。
12.如权利要求8所述的合金线材的制造方法,其中,在上述冷加工成形步骤之前,更包含通过电镀、蒸镀或溅镀在该粗线材的表面镀上一镀层,该镀层的材质是选自由实质上的纯金、实质上的纯钯、金-钯合金所组成的群组中的任意一种。
13.如权利要求8所述的合金线材的制造方法,其中,在该第N道退火步骤之后,还包含通过电镀、蒸镀或溅镀在该细线材的表面镀上一镀层,该镀层的材质是选自由纯金、纯钯、金-钯合金所组成的群组中的任意一种。
14.如权利要求8所述的合金线材的制造方法,其中,
所述银-金合金的金含量为0.01~30.00wt%,余量为银;
所述银-钯合金的钯含量为0.01~10.00wt%,余量为银;以及
所述银-金-钯合金的金含量为0.01~30.00wt%、钯含量为0.01~10.00wt%,余量为银。
15.如权利要求8所述的合金线材的制造方法,其中,所述粗线材的线径为5~10mm、所述细线材的线径为10~50μm。
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KR20130079452A (ko) | 2013-07-10 |
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US8940403B2 (en) | 2015-01-27 |
JP5670412B2 (ja) | 2015-02-18 |
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US20130171470A1 (en) | 2013-07-04 |
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