CN108290254A - 经涂覆的线材 - Google Patents

经涂覆的线材 Download PDF

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Publication number
CN108290254A
CN108290254A CN201680068236.6A CN201680068236A CN108290254A CN 108290254 A CN108290254 A CN 108290254A CN 201680068236 A CN201680068236 A CN 201680068236A CN 108290254 A CN108290254 A CN 108290254A
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China
Prior art keywords
wire rod
silver
ppm
scope
content
Prior art date
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Granted
Application number
CN201680068236.6A
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English (en)
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CN108290254B (zh
Inventor
姜逸泰
卓永德
曹梦铉
金忠秀
郑贤硕
金泰叶
张兮
穆拉利·萨兰加帕尼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Heraeus Deutschland GmbH and Co KG
Heraeus Materials Singapore Pte Ltd
Original Assignee
Heraeus Oriental Hitec Co Ltd
Heraeus Materials Singapore Pte Ltd
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Publication of CN108290254A publication Critical patent/CN108290254A/zh
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Publication of CN108290254B publication Critical patent/CN108290254B/zh
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/002Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating specially adapted for particular articles or work
    • B23K20/004Wire welding
    • B23K20/005Capillary welding
    • B23K20/007Ball bonding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0227Rods, wires
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0255Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
    • B23K35/0261Rods, electrodes, wires
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/30Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3006Ag as the principal constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/40Making wire or rods for soldering or welding
    • B23K35/404Coated rods; Coated electrodes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
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    • C22C5/06Alloys based on silver
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    • C22C5/08Alloys based on silver with copper as the next major constituent
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/14Changing 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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    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14Metallic material, boron or silicon
    • C23C14/16Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10Electroplating with more than one layer of the same or of different metals
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    • C25D5/12Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
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    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48After-treatment of electroplated surfaces
    • C25D5/50After-treatment of electroplated surfaces by heat-treatment
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    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25D7/00Electroplating characterised by the article coated
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Abstract

本发明涉及一种包含具有表面的线芯的线材,在所述线芯的表面上叠置有涂层。

Description

经涂覆的线材
本发明涉及一种经涂覆的线材,其包含银或银基线芯和叠置在所述线芯的表面上的涂层。本发明进一步涉及用于制造这类经涂覆的线材的方法。
焊接线材在电子和微电子应用中的用途是众所周知的现有技术。虽然焊接线材一开始是由金制成,但现今使用较廉价的材料,例如铜、铜合金、银和银合金。这类线材可具有金属涂层。
就线材几何形状来说,最常见的是圆形横剖面的焊接线材和具有大致矩形横剖面的焊接带材。两种类型的线材几何形状均具有使它们可用于特定应用的优势。
本发明的目的是提供适用于线材焊接应用的经涂覆的银或银合金线材,所述线材特别在FAB(无空气球)形成(即使在空气氛围下)(无需以惰性或还原气体净化所述FAB)、FAB柔软度、可焊接性和抗腐蚀性及抗氧化性方面得到改善,并且还显示整体均衡的性质范围,所述性质与线材和其焊接应用相关,包括(例如)宽针脚式焊接(stitch bonding)窗、以优良再现性形成轴对称FAB、高针脚抗拉强度、软线材、低电阻率、低电迁移、长车间寿命(floor life)等。
本文使用术语“轴对称FAB”。该术语意指不显示下列缺陷中的任一缺陷的固化球形FAB:
-突出尖端(FAB尖端处熔融金属的流出),
-苹果咬口形尖端(FAB尖端处熔融金属的流入),
-桃形尖端(FAB尖端处具有不同半球的两个平线区),
-FAB相对于线材轴倾斜的角度小于5°,优选≤1°。
本文使用术语“球形FAB”。该术语不应理解为绝对性;反之,其应理解为包括真正球形形状的FAB以及基本上球形形状的FAB,即显示纵横比(沿FAB径向轴的最长和最短对角线(或直径)的商)在1:1(真正球形)到1.1:1(基本上球形)范围内的FAB。
对该目的的解决方案的贡献由独立权利要求的主题提供。独立权利要求的从属权利要求呈现本发明的优选实施例,其主题还有助于解决上文提及的目的。
第一方面,本发明涉及一种包含具有表面的线芯(下文中也简称“芯”)的线材,所述线芯的表面上叠置有涂层,其中所述线芯本身由以下组成:
(a)由以下组成的纯银:(a1)含量在99.99到100wt.-%(重量-%,重量%)范围内的银和(a2)总量为0到100wt.-ppm(重量-ppm,重量ppm)的其它组分(除银外的组分)
(b)由以下组成的掺杂银:(b1)含量在99.69到99.987wt.-%(优选99.93到99.987wt.-%)范围内的银;(b2)总量为30到3000wt.-ppm(优选30到600wt.-ppm)的至少一种掺杂元素,所述掺杂元素选自钙、镍、铂、铜、铑和钌组成的元素群(优选由钙和镍组成的元素群);和(b3)总量为0到100wt.-ppm的其它组分(除银、钙、镍、铂、铜、铑和钌外的组分)
(c)由以下组成的银合金:(c1)含量在95.99到99.49wt.-%(优选97.49到99.09wt.-%)范围内的银;(c2)含量在0.5到4wt.-%(优选0.9到2.5wt.-%)范围内的钯;和(c3)总量为0到100wt.-ppm的其它组分(除银和钯外的组分)
(d)由以下组成的银合金:(d1)含量在93.99到99.39wt.-%(优选95.39到96.59wt.-%)范围内的银;(d2)含量在0.5到4wt.-%(优选2.7到3.3wt.-%)范围内的钯;(d3)含量在0.1到2wt.-%(优选0.7到1.3wt.-%)范围内的金;和(d4)总量为0到100wt.-ppm的其它组分(除银、钯和金外的组分)
(e)由以下组成的掺杂银合金:(e1)含量在93.69到99.387wt.-%(优选95.33到96.587wt.-%)范围内的银;(e2)含量在0.5到4wt.-%(优选2.7到3.3wt.-%)范围内的钯;(e3)含量在0.1到2wt.-%(优选0.7到1.3wt.-%)范围内的金;(e4)总量为30到3000wt.-ppm(优选30到600wt.-ppm)的至少一种掺杂元素,所述掺杂元素选自钙、镍、铂、铜、铑和钌组成的元素群,优选由铂、钙和镍组成的元素群;和(e5)总量为0到100wt.-ppm的其它组分(除银、钯、金、钙、镍、铂、铜、铑和钌外的组分),
其中任何其它组分的单独量小于30wt.-ppm,
其中任何掺杂元素的单独量为至少30wt.-ppm,
其中按wt.-%和wt.-ppm计的所有量是按所述线芯的总重量计,并且
其中所述涂层为1到1000nm(优选10到460nm)厚的金或钯单层,或包含1到100nm(优选1到20nm)厚的镍或钯内层和1到200nm(优选1到40nm)厚的相邻金外层(顶层)的双层。
本发明的线材优选为在微电子学中用于焊接的焊接线材。其优选为单件式物体。已知许多形状且它们显得适用于本发明的线材。优选的形状是横剖面图呈圆形、椭球体和矩形形状。就本发明来说,尽管具有圆形横剖面和细直径的焊接线材是优选的,但术语“焊接线材”包含所有形状的横剖面和所有常见的线材直径。平均横剖面在例如50到5024μm2或优选在110到2400μm2的范围内;因此在优选的圆形横剖面的情况下,所述平均直径在例如8到80μm或优选在12到55μm的范围内。
线材或线芯的平均直径或(简单地说)直径可通过“确定尺寸方法”得到。根据此方法,测定所定义长度的线材的物理重量。基于此重量,利用线材的密度计算线材或线芯的直径。所述直径按照对特定线材的五次切割的五次测量值的算术平均值计算。
根据上文所提及,在使用上文公开的组合物的每种情况下,线芯由以下组成:(a)纯银;(b)掺杂银;(c)和(d)银合金或(e)掺杂银合金。本发明线材的芯可包含总量在0到100wt.-ppm(例如10到100wt.-ppm)范围内的所谓其它组分。在本文中,所述其它组分(通常也称为“不可避免的杂质”)是源自所用原材料中存在的杂质或来自线材制造工艺的少量化学元素和/或化合物。其它组分0到100wt.-ppm的低总量确保线材性质的优良再现性。存在于线芯中的其它组分通常并非分开添加。每种单独其它组分的含量按线芯的总重量计小于30wt.-ppm。
线材的线芯是块状材料的均质区域。由于任何块状材料始终具有可在某种程度上显示不同性质的表面区域,因此将所述线材的线芯的性质理解为块状材料的均质区域的性质。块状材料区域的表面可在形态、组成(例如硫、氯和/或氧含量)和其它特征方面不同。所述表面是在线芯与叠置在所述线芯上的涂层之间的界面区域。通常,所述涂层是完全叠置在所述线芯的表面上。在线材的线芯与叠置在其上的涂层之间的线材区域中,可存在线芯和涂层两者的材料组合。
叠置在线材表面上的涂层为1到1000nm,优选10到460nm和更优选10到200nm厚的金或钯单层,或包含1到100nm,优选1到20nm厚的镍或钯内层和1到200nm,优选1到40nm厚的金外层的双层。在本文中,术语“厚”或“涂层厚度”意指涂层在线芯纵轴的垂直方向上的尺寸。
就金或钯单层的组成来说,按涂层的总重量计,其金或钯含量为例如至少50wt.-%,优选至少95wt.-%。特别优选地,所述涂层是由纯金或钯组成。按涂层的总重量计,纯金或钯通常具有小于1wt.-%的其它组分(除金或钯外的组分)。
就所述双层的组成来说,按内涂层的总重量计,其内层的镍或钯含量为例如至少50wt.-%,优选至少95wt.-%。特别优选地,所述内涂层是由纯镍或钯组成。按所述内涂层的总重量计,纯镍或钯通常具有小于1wt.-%的其它组分(除镍或钯外的组分)。按外涂层的总重量计,相邻外金层的金含量为例如至少50wt.-%,优选至少95wt.-%。特别优选地,所述外涂层是由纯金组成。按所述外涂层的总重量计,纯金通常具有小于1wt.-%的其它组分(除金外的组分)。
在一个实施例中,本发明的线材的芯特征至少在于下列固有性质(1)到(6)中的一种(参见如下文描述的“测试方法A”):
(1)平均线材晶粒尺寸(平均晶粒尺寸)不大于10μm,例如在2到10μm的范围内,优选在2到5μm的范围内,
(2)线材晶粒[100]或[101]或[111]定向平面是不大于15%,例如在2到15%范围内,优选在2到7%范围内,
(3)线材孪晶界分率不大于70%,例如在50到70%范围内,优选在50到60%范围内,
(4)FAB平均晶粒尺寸不大于30μm,例如在8到30μm范围内,优选在8到16μm范围内,
(5)FAB晶粒[111]定向平面不大于30%,例如在10到30%范围内,优选在10到20%范围内,
(6)FAB孪晶界分率不大于50%,例如在40到50%范围内。
在一个实施例中,本发明的线材特征至少在于下列非固有性质(α)到(θ)中的一种:
(α)耐锈蚀性具有不大于5%的焊球脱落(bonded ball lift)值,例如在0到5%的范围内(参见如下文描述的“测试方法B”),
(β)耐湿性具有不大于5%的焊球脱落值,例如在0到5%的范围内(参见如下文描述的“测试方法C”),
(γ)所述线材的电阻率小于4.0μΩ·cm,例如在1.6到4.0μΩ·cm的范围内,优选在1.63到3.4μΩ·cm的范围内(参见如下文描述的“测试方法D”),
(δ)所述线材的银枝蔓状生长不大于12μm/s,例如在0到12μm/s的范围内,优选在0到4μm/s的范围内(参见如下文描述的“测试方法E”),
(ε)线芯的硬度不大于80HV(10mN/12s),例如在50到80HV的范围内,优选在50到70HV的范围内(参见如下文描述的“测试方法F”),
(ζ)针对针脚式焊接到金手指(gold finger)的直径为17.5μm的线材,针脚式焊接的工艺窗区域具有至少36100mA·g,例如36100到38000mA·g的值(参见如下文描述的“测试方法G”),
(η)针对球形焊接到Al-0.5wt.-%Cu焊垫的直径为17.5μm的线材,球形焊接的工艺窗区域具有至少960mA·g,例如960到1000mA·g的值(参见如下文描述的“测试方法H”),
(θ)所述线材的屈服强度不大于170MPa,例如在140到170MPa的范围内(参见如下文描述的“测试方法J”)。
术语“固有性质”和“非固有性质”在本文中是针对线芯或FAB使用。固有性质意指线芯或FAB本身具有的性质(独立于其它因素),而非固有性质取决于线芯或FAB与其它因素(如所采用的测量方法和/或测量条件)的关系。
本发明的经涂覆的线材的意外的优点在于,即使是在空气氛围下,其也允许轴对称FAB形成;即,在FAB形成过程期间无需以惰性或还原气体净化。
在另一方面中,本发明还涉及一种制造上文公开的任一实施例中的本发明的经涂覆的线材的方法。所述方法包括至少步骤(1)到(5):
(1)提供由以下组成的前驱物品:
(a)由以下组成的纯银:(a1)含量在99.99到100wt.-%范围内的银和(a2)总量为0到100wt.-ppm的其它组分(除银外的组分)
(b)由以下组成的掺杂银:(b1)含量在99.69到99.987wt.-%(优选99.93到99.987wt.-%)范围内的银;(b2)总量为30到3000wt.-ppm(优选30到600wt.-ppm)的至少一种掺杂元素,所述掺杂元素选自钙、镍、铂、铜、铑和钌组成的元素群(优选由钙和镍组成的元素群);和(b3)总量为0到100wt.-ppm的其它组分(除银、钙、镍、铂、铜、铑和钌外的组分)
(c)由以下组成的银合金:(c1)含量在95.99到99.49wt.-%(优选97.49到99.09wt.-%)范围内的银;(c2)含量在0.5到4wt.-%(优选0.9到2.5wt.-%)范围内的钯;和(c3)总量为0到100wt.-ppm的其它组分(除银和钯外的组分)
(d)由以下组成的银合金:(d1)含量在93.99到99.39wt.-%(优选95.39到96.59wt.-%)范围内的银;(d2)含量在0.5到4wt.-%(优选2.7到3.3wt.-%)范围内的钯;(d3)含量在0.1到2wt.-%(优选0.7到1.3wt.-%)范围内的金;和(d4)总量为0到100wt.-ppm的其它组分(除银、钯和金外的组分)
(e)由以下组成的掺杂银合金:(e1)含量在93.69到99.387wt.-%(优选95.33到96.587wt.-%)范围内的银;(e2)含量在0.5到4wt.-%(优选2.7到3.3wt.-%)范围内的钯;(e3)含量在0.1到2wt.-%(优选0.7到1.3wt.-%)范围内的金;(e4)总量为30到3000wt.-ppm(优选30到600wt.-ppm)的至少一种掺杂元素,所述掺杂元素选自钙、镍、铂、铜、铑和钌组成的元素群(优选由铂、钙和镍组成的元素群);和(e5)总量为0到100wt.-ppm的其它组分(除银、钯、金、钙、镍、铂、铜、铑和钌外的组分),
其中任何其它组分的单独量小于30wt.-ppm,
其中任何掺杂元素的单独量为至少30wt.-ppm,
其中按wt.-%和wt.-ppm计的所有量是按所述前驱物品的总重量计,
(2)拉伸所述前驱物品以形成伸长的前驱物品,直到得到7850到31400μm2范围内的中间横剖面或100到200μm(优选130到140μm)范围内的中间直径,
(3)在方法步骤(2)完成后得到的伸长的前驱物品的表面上沉积金或钯单层涂层,或镍或钯内层(基层)和相邻的金外层(顶层)的双层涂层,
(4)进一步拉伸方法步骤(3)完成后得到的经涂覆的前驱物品,直到得到所需的最终横剖面或直径,及
(5)最终在200到600℃范围内的烘箱设定温度下,对方法步骤(4)完成后得到的经涂覆的前驱物进行曝露时间在0.4到0.8秒范围内的分股退火(strand annealing),以形成经涂覆的线材,
其中步骤(2)包括在400到800℃的烘箱设定温度下对所述前驱物品进行曝露时间在50到150分钟范围内的中间分批退火的一或多个子步骤。
本文使用术语“分股退火”。其是允许以高度再现性快速制造线材的连续工艺。在本发明的上下文中,分股退火意指动态地进行退火,同时拉动或移动待退火的经涂覆的前驱物通过常规的退火烘箱且在已离开退火烘箱后卷绕于卷轴上。此处,所述退火烘箱通常呈给定长度的圆柱形管的形式。凭借可在例如10到60米/分钟范围内选择的给定退火速度下的所定义温度分布,可定义和设定退火时间/烘箱温度参数。
本文使用术语“烘箱设定温度”。其意指通过退火烘箱的温度控制器所固定的温度。所述退火烘箱可以是室炉型烘箱(在分批退火的情况下)或管状退火烘箱(在分股退火的情况下)。
本公开在前驱物品、伸长的前驱物品、经涂覆的前驱物品、经涂覆的前驱物和经涂覆的线材之间作出了区分。术语“前驱物品”是用于尚未达到线芯的所需最终横剖面或最终直径的那些前期线材,而术语“前驱物”用于处于所需最终横剖面或所需最终直径时的前期线材。在方法步骤(5)完成后,即,处于所需最终横剖面或所需最终直径的经涂覆的前驱物进行最终分股退火后,得到本发明意义上的经涂覆的线材。
在第一替代选项中,如方法步骤(1)中提供的前驱物品是由(a)前文所公开组成的纯银组成。通常,这类前驱物品呈棒形式,其具有例如2到25mm的直径和例如2到100m的长度。此银棒可通过使用适当的模具连续铸银,接着冷却和固化而制成。
在第二到第四替代选项中,在上文所公开组成的各种情况下,如方法步骤(1)中提供的前驱物品是由(b)掺杂银或(c)银合金或(d)银合金或(e)掺杂银合金组成。这类前驱物品可通过合金化、掺杂或合金化和掺杂银与所需量的组分(b2)或(c2)或(d2)和(d3)或(e2)、(e3)和(e4)来得到。所述掺杂银或银合金或掺杂银合金可以通过熟悉金属合金技术的人员已知的常规方法制成,例如通过按所需的比例比率将所述组分熔融在一起。在进行此操作时,可使用一或多种常规的母合金。熔融工艺可以例如使用感应炉进行且宜在真空下或在惰性气体氛围下操作。使用的材料可以具有例如99.99wt.-%及以上的纯度等级。如此产生的熔体可冷却以形成银基前驱物品的均质件。通常,此前驱物品呈棒形式具有例如2到25mm的直径和例如2到100m的长度。此棒可通过使用适当的模具连续铸造所述掺杂银或(掺杂)银合金熔体,接着冷却及固化而制成。
在方法步骤(2)中,拉伸前驱物品以形成伸长的前驱物品,直到得到7850到31400μm2范围内的中间横剖面或100到200μm(优选130到140μm)范围内的中间直径。已知拉伸前驱物品的技术且所述技术在本发明的背景中显得有用。优选的技术是辊制、锻制、模拉制等,其中特别优选模拉制。在后一种情况下,在数个方法步骤中拉制所述前驱物品直到实现所期望的中间横剖面或所期望的中间直径。所属领域的技术人员悉知这类线材模拉制方法。可以采用常规的碳化钨和金刚石拉制模且可以采用常规的拉制润滑剂来支持拉制。
本发明方法的步骤(2)包括在400到800℃范围内的烘箱设定温度下对伸长的前驱物品进行曝露时间在50到150分钟范围内的中间分批退火的一或多个子步骤。所述中间分批退火可以例如使用拉制到2mm直径且盘绕于圆桶上的棒进行。
在方法步骤(3)中,在方法步骤(2)完成后得到的伸长的前驱物品的表面上沉积金或钯单层涂层,或包含镍或钯内层和相邻的金外层的双层涂层,以在所述表面上叠置涂层。
所属领域的技术人员已知如何计算此涂层在伸长的前驱物品上的厚度,以最终(即在最终拉伸所述经涂覆的前驱物品后)得到针对线材的实施例所公开的层厚度的涂层。所属领域的技术人员已知在银或银合金表面上形成根据实施例的材料涂层的许多技术。优选的技术是电镀(如有电电镀和无电电镀)、从气相沉积材料(如溅镀、离子镀、真空蒸镀和物理气相沉积)及从熔体沉积材料。在本发明的背景下,有电电镀是优选的技术。
在方法步骤(4)中,进一步拉伸方法步骤(3)完成后得到的经涂覆的前驱物品,直到得到所期望的最终横剖面或直径的线材。拉伸经涂覆的前驱物品的技术是与上文在方法步骤(2)的公开内容中所提及的那些技术相同的拉伸技术。
在方法步骤(5)中,使方法步骤(4)完成后得到的经涂覆的前驱物最终在200到600℃(优选200到400℃)范围内的烘箱设定温度下进行曝露时间在0.4到0.8秒范围内的分股退火,以形成经涂覆的线材。
在一个优选的实施例中,使最终分股退火的经涂覆的前驱物(即,仍热的经涂覆的线材)在水中淬火,在一个实施例中,所述水可以含有一或多种添加剂,例如0.01到0.07体积%的添加剂。在水中淬火意指使最终分股退火的经涂覆的前驱物从其在方法步骤(5)中经历的温度立即或迅速(即,在0.2到0.6秒内)冷却到室温,例如通过浸渍或滴液。
方法步骤(2)的中间分批退火可以在惰性或还原氛围下进行。所述领域中已知许多类型的惰性氛围和还原氛围且它们是用于净化退火烘箱。在已知的惰性氛围中,优选氮气或氩气。在已知的还原氛围中,优选氢气。另一种优选的还原氛围是氢气和氮气的混合物。优选的氢气和氮气混合物是90到98vol.-%氮气,和相应地,2到10vol.-%氢气,其中vol.-%的总和为100vol.-%。优选的氮气/氢气混合物等于93/7、95/5和97/3vol.-%/vol.-%,各按所述混合物的总体积计。
相信前驱物品材料的组成(其与线芯的组成相同)与在方法步骤(2)和(5)期间主要的退火参数的独特组合是得到展现上文公开的固有和/或非固有性质中的至少一种的本发明线材所必不可少的。中间分批和最终分股退火步骤的温度/时间条件允许实现或调节所述线材或线芯的固有和非固有性质。
在方法步骤(5)和任选的淬火完成后,完成本发明的经涂覆的线材。为充分受益于其性质,宜将其立即用于线材焊接应用中,即,无延迟,例如在方法步骤(5)完成后不超过28天内。或者,为了保持所述线材的宽线材焊接工艺窗性质且为了防止其受氧化或其它化学腐蚀,通常在方法步骤(5)完成后立即将成品线材盘卷且真空密封,即,无延迟,例如在方法步骤(5)完成后的<1到5小时内,且然后存储以进一步用作焊接线材。在真空密封条件下的存储应不超过12个月。在打开真空密封后,所述线材应在不超过28天内用于线材焊接。
所有方法步骤(1)到(5)和盘卷和真空密封优选是在无尘室条件下进行(US FEDSTD 209E无尘室标准,1k标准)。
本发明的第三方面是能通过上文公开的方法根据其任何实施例得到的经涂覆的线材。已发现本发明的经涂覆的线材极适用作线材焊接应用中的焊接线材。所属领域的技术人员悉知线材焊接技术。在线材焊接的过程中,通常形成球形焊接(第1次焊接)和针脚式焊接(第2次焊接,楔形焊接)。在焊接成形期间,施加特定的力(通常以克测量),并通过施加超声波能量(通常以mA测量)支持。在线材焊接过程中施加力的上限值与下限值间的差值与所施加超声波能量的上限值与下限值间的差值的数学乘积定义线材焊接工艺窗:
(施加力的上限值-施加力的下限值)·(所施加超声波能量的上限值-所施加超声波能量的下限值)=线材焊接工艺窗。
线材焊接工艺窗定义了允许形成满足规格(即,其通过常规测试,仅列举数项,如常规抗拉测试、球剪切测试和球抗拉测试)的线材焊接的力/超声波能量组合的范围。
换句话说,第1次焊接(球形焊接)工艺窗区域是焊接中使用的力的上限值与下限值间的差值与所施加超声波能量的上限值与下限值间的差值的乘积,其中所得的焊接必须满足某些球剪切测试规格,例如0.0085克/μm2的球剪切、焊垫上无不粘性等,而第2次焊接(针脚式焊接)工艺窗区域是焊接中使用的力的上限值与下限值间的差值与所施加超声波能量的上限值与下限值间的差值的乘积,其中所得的焊接必须满足某些抗拉测试规格,例如2克的拉力、铅上无不粘性等。
就工业应用来说,出于线材焊接工艺稳健性的原因,需要具有宽的线材焊接工艺窗(以g计的力相对于以mA计的超声波能量)。本发明的线材展现相当宽的线材焊接工艺窗。
下列非限制性实例阐述本发明。这些实例用于本发明的示例性阐释且不希望以任何方式限制本发明或权利要求书的范围。
实例
FAB的制造:
其是根据FAB的KNS工艺用户指南(KNS Process User Guide for FAB)(库力索法工业公司(Kulicke&Soffa Industries Inc),美国宾夕法尼亚州华盛顿堡,2002,2009年5月31日)中所述的程序操作。FAB是通过使用标准烧制(单一步骤,17.5μm线材,50mA的EFO电流,EFO时间125μs)进行常规的电子点火(electric flame-off)(EFO)烧制而制得。
测试方法A.到J.
所有测试和测量是在T=20℃及相对湿度RH=50%下进行。
A.电子背散射绕射(EBSD)图案分析:
用以测量线材纹理的主要步骤是样品制备、得到优良的菊池(Kikuchi)图案和组分计算:
首先使用环氧树脂封装线材且根据标准金相技术抛光。在最终样品制备步骤中应用离子研磨以去除线材表面的任何机械变形、污染物和氧化层。用金溅镀经离子研磨的横剖面样品表面。然后再进行两轮离子研磨和金溅镀。不进行化学蚀刻或离子蚀刻。
将样品装载于FESEM(场发射扫描电子显微镜)中,所述FESEM的支架与标准FESEM样品固持台表面成70°角。所述FESEM进一步配备有EBSD检测器。得到含有线材结晶信息的电子背散射图案(EBSP)。
进一步分析这些图案的晶粒定向分率、平均晶粒尺寸等(使用由布鲁克尔(Bruker)开发的称为QUANTAX EBSD程序的软件)。将类似定向的点一起归类以形成纹理组分。
为区分不同的纹理组分,使用15°的最大公差角。将线材拉制方向设定为参考定向。[100]、[101]和[111]纹理百分率是通过测量[100]、[101]和[111]定向平面平行于参考定向的晶体的百分率来计算。
通过定义相邻网格点间大于最小值(本文中10°)的结晶定向来分析平均晶粒尺寸,以确定晶界的位置。EBSD软件计算各晶粒的面积且将其换算为等效圆直径,将其定义为“平均晶粒尺寸”。对在约100μm长度内沿线材纵向方向的所有晶粒计数以确定平均晶粒尺寸的平均值和标准偏差。
孪晶界(也称为Σ3CSL孪晶界)不包括在平均晶粒尺寸计算中。所述孪晶界是通过在相邻结晶域之间围绕<111>定向平面旋转60°进行描述。点的数量取决于步长,其小于平均晶粒尺寸的1/5。
B.焊球的盐溶液浸渍测试:
将线材球形焊接到Al-0.5wt.-%Cu焊垫。将具有经如此焊接的线材的测试装置在25℃盐溶液中浸渍10分钟,用去离子(DI)水且随后用丙酮清洗。所述盐溶液在DI水中含有20wt.-ppm NaCl。在低倍显微镜(尼康(Nikon)MM-40)下在100X放大率下检查脱落球的数量。观察到较高数量的脱落球指示严重的界面电流腐蚀。
C.焊球的耐湿性测试:
将线材球形焊接到Al-0.5wt.-%Cu焊垫。将具有经如此焊接的线材的测试装置在高加速应力测试(HAST)室中、在130℃温度、85%相对湿度(RH)下存储8小时且随后在低倍显微镜(尼康MM-40)下在100X放大率下检查脱落球的数量。观察到较高数量的脱落球指示严重的界面电流腐蚀。
D.电阻率:
将测试试样(即,长度1.0米的线材)的两端连接到提供恒定电流/电压的电源。使用装置针对供应电压记录电阻。测量装置是HIOKI型号3280-10,且使用至少10个测试试样重复所述测试。将测量值的算术平均值用于以下给定的计算。
电阻R是根据R=V/I计算。
比电阻率ρ是根据ρ=(R x A)/L计算,其中A是线材的平均横剖面面积且L是线材在用于测量电压的装置的两个测量点间的长度。
比电导率σ是根据σ=1/ρ计算。
E.线材的电迁移测试:
使直径75μm的两根线材在低倍显微镜尼康MM40型号的物镜下在50X放大率下在PTFE板上在1毫米距离内保持平行。在待电连接的两根线材之间通过微量吸管形成水滴。将一根线材连接到正极且将另一根线材连接到负极且向所述线材施加5V。使所述两根线材在与10kΩ电阻器串联连接的闭合电路中用5V直流电流偏压。所述电路是通过用几滴去离子水作为电解质润湿所述两根线材而闭合。银在电解质中从阴极电迁移到阳极,从而形成银枝蔓,有时桥接两根线材。银枝蔓状生长速率主要取决于所述线材的涂层,且在银合金线芯的情况下取决于合金化添加。
F.维氏(Vickers)微硬度:
使用具有维氏压头的三丰(Mitutoyo)HM-200测试设备来测量硬度。将10mN压痕负载的力施加到线材的测试试样,历时12秒的留置时间。所述测试是在线材或FAB的中心上进行。
G.针脚式焊接工艺窗区域:
通过标准程序进行针脚式焊接工艺窗区域的测量。测试线材是使用KNS-iConn焊接工具(库力索法工业公司,美国宾夕法尼亚州华盛顿堡)进行针脚式焊接。所述工艺窗值是以具有17.5μm的平均直径的线材为基础,其中焊接所述线材的引脚是由金组成。
工艺窗的四个转角是通过克服两个主要故障模式得到:
(1)供应过低的力和超声波能量导致所述线材的引脚上的不粘性(NSOL),及
(2)供应过高的力和超声波能量导致线材短尾(SHTL)。
H.球形焊接工艺窗区域:
通过标准程序进行球形焊接工艺窗区域的测量。测试线材是使用KNS-iConn焊接工具(库力索法工业公司,美国宾夕法尼亚州华盛顿堡)进行球形焊接。所述工艺窗值是以具有17.5μm的平均直径的线材为基础,其中所述线材所焊接的焊垫是由Al-0.5wt.-%Cu组成。
工艺窗的四个转角是通过克服两个主要故障模式得到:
(1)供应过低的力和超声波能量导致所述线材的焊点不粘粘(non-stick on pad,NSOP),及
(2)供应过高的力和超声波能量导致线材短尾(SHTL)。
J.伸长率(EL):
使用英斯特朗(Instron)-5564仪器测试线材的抗拉性质。以2.54cm/min速度,针对254mm标距(L)测试所述线材。根据ASTM标准F219-96得到破裂(断裂)时的负载和伸长率。所述伸长率是线材的标距在抗拉测试开始与结束之间的差值(△L),其通常以百分率报告为(100·△L/L),根据所记录的负载相对于延长拉力图计算而得。抗拉强度和屈服强度是利用断裂和屈服负载除以线材面积计算而得。所述线材的实际直径是通过确定尺寸方法、称重标准长度的线材及使用其密度进行测量。
实例1:线材样品1到8
在各种情况下将一定量的银(Ag)、钯(Pd)和至少99.99%纯度(“4N”)的金(Au)熔融于坩埚中。将少量的银-镍、银-钙、银-铂或银-铜母合金添加到熔体中且通过搅拌确定所添加组分的均匀分布。使用下列母合金:
就表1的合金来说,添加母合金的对应组合。
然后从熔体连续铸造呈8mm棒形式的线芯前驱物品。然后在数个拉制步骤中拉制所述棒以形成具有直径为134μm的圆形横剖面的线芯前驱物。在500℃的烘箱设定温度下对所述线芯前驱物进行曝露时间为60分钟的中间分批退火,然后有电电镀775nm厚的由至少99%纯度的金组成的涂层,且此后进一步拉制到17.5μm的最终直径和103nm的最终金涂层厚度,接着在220℃的烘箱设定温度下最终进行曝露时间为0.6秒的分股退火,接着立即使如此得到的经涂覆的线材在含有0.07vol.-%表面活性剂的水中淬火。
藉助于此程序,制得镀金的银线材和银基线材的数个不同的样品1到8和4N纯度的未经涂覆的参考银线材(参考)。表1显示所述线材的组成。
测量线材样品1到8的晶粒尺寸且报告平均晶粒尺寸。在各种情况下,结果均在2到5μm的范围内。就样品1来说,平均晶粒尺寸是3.12μm。
下表2显示某些测试结果。所有测试均使用17.5μm直径的线材进行,但电迁移测试除外,其使用75μm直径的线材进行(评估:++++绝佳;+++优良;++符合要求;+差)。
“形成期气体净化”意指FAB在其形成期间经95/5vol.-%/vol.-%氮气/氢气净化,而“在大气下”意指FAB形成是在空气氛围下进行。
图2中显示典型的经离子研磨的横剖面图像,其公开线材中的晶粒形态、HAZ(热影响区域)和FAB位置。表3显示线材样品1的平均晶粒尺寸和纹理组分(线材、FAB和HAZ)。
实例2:线材样品9到12
其是使用下列母合金类似于实例1进行处理:
施加由钯组成的153nm厚的涂层(20nm的最终钯层厚度)来替代有电电镀金。表4显示线材样品9到12的组成。
下表5显示某些测试结果。所有测试均使用17.5μm直径的线材进行,但电迁移测试除外,其使用75μm直径的线材进行。
实例3:线材样品13到17
其是使用下列母合金类似于实例1进行处理:
施加由内钯(或镍)层和外金层组成的双层涂层(最终钯或镍层厚度=2.6nm,最终金层厚度=13nm)来替代有电电镀金的单层。表6显示线材样品13到17的组成。
下表7显示某些测试结果。所有测试均使用17.5μm直径的线材进行,但电迁移测试除外,其使用75μm直径的线材进行。
附图说明
图1显示直径17.5μm的经103nm金涂覆的4N银芯线材(对应于表1的样品1的组成)的示例性退火曲线。退火温度是x轴的可变参数。所述图显示所述线材的断裂负载(BL,以克计)和伸长率(EL,以%计)的测量值。所述伸长率是通过抗拉测试测定。伸长率测量值在所展示的实例中展现约16.5%的典型局部最大值,这在约400℃的退火温度下实现。根据样品1的线材在此最大伸长率的温度下不退火,但在220℃下退火,220℃比根据图1的最大伸长率的温度低180℃。此导致约8%的伸长率值,比最大伸长率值低超过35%。
图2显示直径17.5μm的经100nm金涂覆的4N银芯线材(表1的样品1)的示例性离子研磨型横剖面图像。三种不同位置(线材、热影响区域(HAZ)和FAB)的晶粒形态是明显的。所述FAB是使用樱桃核模式形成。球相对于线材尺寸的比率(BSR)是1.8。

Claims (15)

1.一种包含具有表面的线芯的线材,在所述线芯的表面上叠置有涂层,其中所述线芯本身由以下组成:
(a)由以下组成的纯银:(a1)含量在99.99到100wt.-%范围内的银和(a2)总量为0到100wt.-ppm的其它组分
(b)由以下组成的掺杂银:(b1)含量在99.69到99.987wt.-%范围内的银;(b2)总量为30到3000wt.-ppm的至少一种掺杂元素,所述掺杂元素是选自钙、镍、铂、铜、铑和钌组成的元素群;和(b3)总量为0到100wt.-ppm的其它组分
(c)由以下组成的银合金:(c1)含量在95.99到99.49wt.-%范围内的银;(c2)含量在0.5到4wt.-%范围内的钯;和(c3)总量为0到100wt.-ppm的其它组分
(d)由以下组成的银合金:(d1)含量在93.99到99.39wt.-%范围内的银;(d2)含量在0.5到4wt.-%范围内的钯;(d3)含量在0.1到2wt.-%范围内的金;和(d4)总量为0到100wt.-ppm的其它组分
(e)由以下组成的掺杂银合金:(e1)含量在93.69到99.387wt.-%范围内的银;(e2)含量在0.5到4wt.-%范围内的钯;(e3)含量在0.1到2wt.-%范围内的金;(e4)总量为30到3000wt.-ppm的至少一种掺杂元素,所述掺杂元素是选自钙、镍、铂、铜、铑和钌组成的元素群;和(e5)总量为0到100wt.-ppm的其它组分,
其中任何其它组分的单独量小于30wt.-ppm,
其中任何掺杂元素的单独量为至少30wt.-ppm,
其中以wt.-%和wt.-ppm表示的所有量均是按所述线芯的总重量计,并且
其中所述涂层为1到1000nm厚的金或钯单层或包含1到100nm厚的镍或钯内层和1到200nm厚的相邻金外层的双层。
2.根据权利要求1所述的线材,其中所述至少一种掺杂元素(b2)和所述至少一种掺杂元素(e4)是选自铂、钙和镍组成的元素群。
3.根据权利要求1或2所述的线材,其具有50到5024μm2范围内的平均横剖面。
4.根据权利要求1或2所述的线材,其具有平均直径在8到80μm范围内的圆形横剖面。
5.根据前述权利要求中任一权利要求所述的线材,其中所述涂层为10到460nm厚的金或钯单层或包含1到20nm厚的镍或钯内层和1到40nm厚的相邻金外层的双层。
6.根据前述权利要求中任一权利要求所述的线材,其中所述线芯至少具有下列固有性质(1)到(6)中的一种特征:
(1)平均线材晶粒度不大于10μm,
(2)线材晶粒的[100]或[101]或[111]定向平面不超过15%,
(3)线材孪晶界分率不大于70%,
(4)FAB平均晶粒度不大于30μm,
(5)FAB晶粒的[111]定向平面不超过30%,
(6)FAB孪晶界分率不大于50%。
7.根据前述权利要求中任一权利要求所述的线材,其特征在于至少由下列非固有性质(α)到(θ)中的一种表征:
(α)耐锈蚀性具有不大于5%的焊球脱落值,
(β)耐湿性具有不大于5%的焊球脱落值,
(γ)所述线材的电阻率小于4.0μΩ·cm,
(δ)所述线材的银枝蔓状生长不大于12μm/s,
(ε)所述线芯的硬度不大于80HV(10mN/12s),
(ζ)针对针脚式焊接到金手指的直径17.5μm的线材,针脚式焊接的工艺窗区域具有至少36100mA·g的值,
(η)针对球形焊接到Al-0.5wt.-%Cu焊垫的直径17.5μm的线材,球形焊接的工艺窗区域具有至少960mA·g的值,
(θ)所述线材的屈服强度不大于170MPa。
8.一种用于制造根据前述权利要求中任一权利要求所述的经涂覆的线材的方法,其中所述方法至少包括步骤(1)到(5):
(1)提供由以下组成的前驱物品:
(a)由以下组成的纯银:(a1)含量在99.99到100wt.-%范围内的银和(a2)总量为0到100wt.-ppm的其它组分
(b)由以下组成的掺杂银:(b1)含量在99.69到99.987wt.-%范围内的银;(b2)总量为30到3000wt.-ppm的至少一种掺杂元素,所述掺杂元素是选自钙、镍、铂、铜、铑和钌组成的元素群;和(b3)总量为0到100wt.-ppm的其它组分
(c)由以下组成的银合金:(c1)含量在95.99到99.49wt.-%范围内的银;(c2)含量在0.5到4wt.-%范围内的钯;和(c3)总量为0到100wt.-ppm的其它组分
(d)由以下组成的银合金:(d1)含量在93.99到99.39wt.-%范围内的银;(d2)含量在0.5到4wt.-%范围内的钯;(d3)含量在0.1到2wt.-%范围内的金;和(d4)总量为0到100wt.-ppm的其它组分
(e)由以下组成的掺杂银合金:(e1)含量在93.69到99.387wt.-%范围内的银;(e2)含量在0.5到4wt.-%范围内的钯;(e3)含量在0.1到2wt.-%范围内的金;(e4)总量为30到3000wt.-ppm的至少一种掺杂元素,所述掺杂元素是选自钙、镍、铂、铜、铑和钌组成的元素群;和(e5)总量为0到100wt.-ppm的其它组分,
其中任何其它组分的个别量小于30wt.-ppm,
其中任何掺杂元素的个别量为至少30wt.-ppm,
其中以wt.-%和wt.-ppm表示的所有量均是按所述前驱物品的总重量计,
(2)拉伸所述前驱物品以形成伸长的前驱物品,直到得到在7850到31400μm2范围内的中间横剖面或在100到200μm范围内的中间直径,
(3)在方法步骤(2)完成后得到的所述伸长的前驱物品的表面上沉积金或钯单层涂层,或镍或钯内层和相邻金外层的双层涂层,
(4)进一步拉伸方法步骤(3)完成后得到的所述经涂覆的前驱物品,直到得到所需最终横剖面或直径,及
(5)最终在200到600℃范围内的烘箱设定温度下,对方法步骤(4)完成后得到的经涂覆的前驱物进行曝露时间在0.4到0.8秒范围内的分股退火,以形成所述经涂覆的线材,
其中步骤(2)包括在400到800℃的烘箱设定温度下对所述前驱物品进行曝露时间在50到150分钟范围内的中间分批退火的一或多个子步骤。
9.根据权利要求8所述的方法,其中所述至少一种掺杂元素(b2)和所述至少一种掺杂元素(e4)是选自铂、钙和镍组成的元素群。
10.根据权利要求8或9所述的方法,其中所述最终分股退火是在200到400℃范围内的烘箱设定温度下进行。
11.根据权利要求8到10中任一权利要求所述的方法,其中使经最终分股退火的经涂覆的前驱物在可以含有一或多种添加剂的水中淬火。
12.根据权利要求8到11中任一权利要求所述的方法,其中方法步骤(2)的所述中间分批退火是在惰性或还原氛围中进行。
13.一种经涂覆的线材,其通过根据权利要求8到12中任一权利要求所述的方法得到。
14.一种根据权利要求1到7或13中任一权利要求所述的经涂覆的线材用于在球形焊接所述经涂覆的线材的过程中制备FAB的用途,其特征在于所述FAB制备是在未经惰性或还原气体净化的空气氛围下进行。
15.根据权利要求14所述的用途,其中所述FAB是轴对称的。
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US20180345421A1 (en) 2018-12-06
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