TWI649434B - Alloyed silver wire - Google Patents

Alloyed silver wire Download PDF

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TWI649434B
TWI649434B TW105127125A TW105127125A TWI649434B TW I649434 B TWI649434 B TW I649434B TW 105127125 A TW105127125 A TW 105127125A TW 105127125 A TW105127125 A TW 105127125A TW I649434 B TWI649434 B TW I649434B
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wire
range
core
silver wire
alloyed silver
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TW105127125A
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TW201718887A (en
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卓容德
康一太
金鍾洙
丁炫碩
金泰燁
兮 張
穆拉利 薩蘭加帕尼
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新加坡賀利氏材料私人有限公司
德商賀利氏德國有限責任兩合公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3006—Ag as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
    • B23K35/0261—Rods, electrodes, wires
    • B23K35/0272—Rods, electrodes, wires with more than one layer of coating or sheathing material
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/43—Manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L24/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/02—Bonding areas; Manufacturing methods related thereto
    • H01L2224/04—Structure, shape, material or disposition of the bonding areas prior to the connecting process
    • H01L2224/05—Structure, shape, material or disposition of the bonding areas prior to the connecting process of an individual bonding area
    • H01L2224/0554—External layer
    • H01L2224/05599—Material
    • H01L2224/056—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/05617—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 400°C and less than 950°C
    • H01L2224/05624—Aluminium [Al] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/43—Manufacturing methods
    • H01L2224/438—Post-treatment of the connector
    • H01L2224/43848—Thermal treatments, e.g. annealing, controlled cooling
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/4501—Shape
    • H01L2224/45012—Cross-sectional shape
    • H01L2224/45014—Ribbon connectors, e.g. rectangular cross-section
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    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/4501—Shape
    • H01L2224/45012—Cross-sectional shape
    • H01L2224/45015—Cross-sectional shape being circular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45139—Silver (Ag) as principal constituent
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    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/4554—Coating
    • H01L2224/45565—Single coating layer
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    • H01L2224/85—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector
    • H01L2224/852—Applying energy for connecting
    • H01L2224/85201—Compression bonding
    • H01L2224/85205—Ultrasonic bonding
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    • H01—ELECTRIC ELEMENTS
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    • H01L2924/00014—Technical content checked by a classifier the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
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  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Wire Bonding (AREA)
  • Conductive Materials (AREA)

Abstract

一種包含線芯或由線芯組成之合金化銀線，該線芯本身由以下組成：(a)鈀，其量在0.1至3wt.-%範圍內，(b)金，其量在0.1至3wt.-%範圍內，(c)鎳，其量在20至700wt.-ppm範圍內，(d)鈣，其量在20至200wt.-ppm範圍內，(e)銀，其量在93.91至99.786wt.-%範圍內，及(f)0至100wt.-ppm之其他組分，其中所有以wt.-%及wt.-ppm為單位之量係基於該芯之總重量，其中該合金化銀線具有在8至80μm範圍內之平均直徑。 An alloyed silver wire comprising or consisting of a core, the core itself consisting of (a) palladium in an amount in the range of 0.1 to 3 wt .-%, and (b) gold in an amount of 0.1 to In the range of 3 wt .-%, (c) nickel in the range of 20 to 700 wt.-ppm, (d) calcium in the range of 20 to 200 wt.-ppm, and (e) silver in the amount of 93.91 To 99.786 wt .-%, and (f) 0 to 100 wt.-ppm of other components, wherein all amounts in wt .-% and wt.-ppm are based on the total weight of the core, where the The alloyed silver wire has an average diameter in a range of 8 to 80 μm.

Description

合金化銀線 Alloyed silver wire

本發明係關於一種8至80μm厚之合金化銀線，其包含以特定重量比包含銀、鈀、金、鎳及鈣之線芯。本發明進一步關於用於製造此類線之方法。 The present invention relates to an alloyed silver wire having a thickness of 8 to 80 μm, which includes a core including silver, palladium, gold, nickel, and calcium in a specific weight ratio. The invention further relates to a method for manufacturing such a thread.

接線在電子及微電子應用中之用途為眾所周知的現有技術水平。儘管一開始接線係由金製得，但如今使用較便宜之材料，諸如銅、銅合金、銀及銀合金。 The use of wiring in electronic and microelectronic applications is well known in the art. Although the wiring was initially made of gold, today cheaper materials such as copper, copper alloys, silver, and silver alloys are used.

關於線幾何結構，最常見的為圓形橫截面之接線及具有近乎矩形橫截面之接合帶。兩種類型之線幾何結構皆具有使其適用於特定應用之其優勢。 Regarding line geometry, the most common are wires with a circular cross section and bonding tapes with a nearly rectangular cross section. Both types of wire geometry have their advantages that make them suitable for specific applications.

本發明之一目標為提供適合用於線接合應用之合金化銀線，合金化銀線尤其在抗腐蝕性及抗濕性方面得到改善，且亦呈現與線接合應用相關之總體上非常均衡之特性範圍，其包括(例如)寬針腳式接合窗、形成具有良好再現性之軸對稱無空氣焊球(FAB)、低FAB硬度、高針腳式接合拉伸強度、軟線、低電阻率、低電遷移等。 One of the goals of the present invention is to provide alloyed silver wires suitable for wire bonding applications. The alloyed silver wires have improved corrosion resistance and moisture resistance in particular, and also present a very well balanced overall relationship to wire bonding applications. A range of characteristics including, for example, wide pin joint windows, formation of axisymmetric airless solder balls (FAB) with good reproducibility, low FAB hardness, high pin joint tensile strength, flexible wires, low resistivity, low power Migration, etc.

該物品解決方案之貢獻係由形成類別之請求項的標的物提供。形成類別之請求項的從屬性附屬項表示本發明之較佳實施例，其標的物亦對解決上文提及之目標作出貢獻。 The contribution of the item solution is provided by the subject matter forming the category of the claim. Dependent sub-items that form a category of request items represent preferred embodiments of the present invention, and their subject matter also contributes to solving the above-mentioned goals.

在第一態樣中，本發明係關於一種合金化銀線，其包含電線芯或由電線芯組成(下文中亦稱簡稱為「芯」)，電線芯本身由以下組 成：(a)鈀，其量在0.1至3wt.-%(重量%)範圍內，較佳在0.5至1.5wt.-%範圍內，(b)金，其量在0.1至3wt.-%範圍內，較佳在0.2至1.5wt.-%範圍內，(c)鎳，其量在20至700wt.-ppm(百萬分之重量、按重量計百萬分之一)範圍內，較佳在275至325wt.-ppm範圍內，(d)鈣，其量在20至200wt.-ppm範圍內，較佳在20至50wt.-ppm範圍內，(e)銀，其量在93.91至99.786wt.-%範圍內，較佳在96.9625至99.2595wt.-%範圍內，及(f)0至100wt.-ppm之其他組分(鈀、金、鎳、鈣及銀以外之組分),其中所有以wt.-%及wt.-ppm為單位之量係基於芯之總重量，其中合金化銀線具有在8至80μm範圍內、或甚至在12至55μm範圍內之平均直徑。 In a first aspect, the present invention relates to an alloyed silver wire that includes or consists of a core of a wire (hereinafter also referred to simply as a "core"). The core of the wire itself is composed of As: (a) palladium, the amount of which is in the range of 0.1 to 3 wt .-% (% by weight), preferably in the range of 0.5 to 1.5 wt .-%, (b) gold, which is in the amount of 0.1 to 3 wt .-% In the range, preferably in the range of 0.2 to 1.5 wt .-%, (c) the amount of nickel is in the range of 20 to 700 wt.-ppm (parts per million by weight, part per million by weight), Preferably in the range of 275 to 325 wt.-ppm, (d) the amount of calcium is in the range of 20 to 200 wt.-ppm, preferably in the range of 20 to 50 wt.-ppm, and (e) the amount of silver is 93.91 to 99.786 wt .-%, preferably 96.9625 to 99.2595 wt .-%, and (f) 0 to 100 wt.-ppm of other components (components other than palladium, gold, nickel, calcium, and silver) , Where all the amounts in wt .-% and wt.-ppm are based on the total weight of the core, where the alloyed silver wire has an average diameter in the range of 8 to 80 μm, or even in the range of 12 to 55 μm.

合金化銀線較佳為用於微電子中之接合的接線。合金化銀線較佳為單件式物品。眾多形狀為已知的且顯得適用於本發明之合金化銀線。較佳形狀為(在橫截面圖中)圓形、橢圓形及矩形形狀。 The alloyed silver wire is preferably a wire for bonding in microelectronics. The alloyed silver wire is preferably a one-piece article. Numerous shapes are known and appear to be suitable for the alloyed silver wire of the present invention. Preferred shapes are (in a cross-sectional view) circular, oval and rectangular shapes.

簡言之，可藉由「量尺寸方法」獲得線或線芯之平均直徑或直徑。根據此方法測定限定長度之合金化銀線的物理重量。基於此重量，使用線材料密度計算線或線芯直徑。直徑經計算為特定線之五個切口上的五個量測值之算術平均值。 In short, the average diameter or diameter of a wire or wire core can be obtained by the "measurement method". The physical weight of the alloyed silver wire of a defined length is determined according to this method. Based on this weight, the wire or core diameter is calculated using the wire material density. The diameter is calculated as the arithmetic mean of five measurements on five cuts of a particular line.

對於本發明，術語「接線」包含所有橫截面形狀及所有常見線直徑，但具有圓形橫截面及薄直徑之接線為較佳的。 For the present invention, the term "wiring" includes all cross-sectional shapes and all common wire diameters, but wiring with a circular cross-section and a thin diameter is preferred.

與前述一致，線芯以前文揭示之成比例的比率包含(a)鈀、(b) 金、(c)鎳、(d)鈣及(e)銀。然而，本發明之合金化銀線的芯可以0至100wt.-ppm之總量包含(f)其他組分。在本上下文中，常亦稱為「不可避免的雜質」之其他組分為來源於存在於所用原材料中之雜質或來源於線製造方法之少量化學元素及/或化合物，亦即(f)型其他組分之存在可(例如)來源於存在於銀、鈀、金、鎳及鈣中之一或多者中的雜質。此類其他組分之實例為：Cu、Fe、Si、Mn、Cr、Ce、Mg、La、Al、B、Zr、Ti、S等。其他組分(f)之0至100wt.-ppm的低總量確保線特性之良好再現性。通常不分開添加存在於芯中之其他組分(f)。 Consistent with the foregoing, the proportional ratio previously disclosed for the core contains (a) palladium, (b) Gold, (c) nickel, (d) calcium and (e) silver. However, the core of the alloyed silver wire of the present invention may contain (f) other components in a total amount of 0 to 100 wt.-ppm. In this context, other components often also referred to as "unavoidable impurities" are small amounts of chemical elements and / or compounds derived from impurities present in the raw materials used or derived from the method of line manufacturing, that is, type (f) The presence of other components may, for example, originate from impurities present in one or more of silver, palladium, gold, nickel, and calcium. Examples of such other components are: Cu, Fe, Si, Mn, Cr, Ce, Mg, La, Al, B, Zr, Ti, S, and the like. The low total amount of 0 to 100 wt.-ppm of the other components (f) ensures good reproducibility of the line characteristics. The other components (f) present in the core are usually not added separately.

在一實施例中，本發明之合金化銀線的芯包含小於以下量之其他組分(f)：(i)Cu，其量<30wt.-ppm；(ii)Cr、Ce、Mg、La、Al、Be、In、Mn、Ti中之任一者，其量各<2wt.-ppm；(iii)Si、Fe、S中之任一者，其量各<15wt.-ppm。 In one embodiment, the core of the alloyed silver wire of the present invention contains other components (f) less than: (i) Cu, the amount of which is <30wt.-ppm; (ii) Cr, Ce, Mg, La , Al, Be, In, Mn, Ti, each of which amount is <2wt.-ppm; (iii) Any of Si, Fe, S, each of which amount is <15wt.-ppm.

本上下文中之合金化銀線的芯經定義為塊狀材料之均質區域。因為任何塊狀材料始終具有可在一定程度上呈現不同特性之表面區域，所以線芯之特性理解為塊狀材料均質區域之特性。塊狀材料區域之表面就形態、組成(例如硫、氯及/或氧氣含量)及其他特徵而言可為不同的。表面可為線芯之外表面；在此實施例中，本發明之合金化銀線由線芯組成。在一替代方案中，表面可為線芯及疊加於線芯上之塗層之間的界面區域。 The core of an alloyed silver wire in this context is defined as a homogeneous region of a bulk material. Because any block material always has a surface area that can exhibit different characteristics to a certain extent, the characteristics of the core are understood as the characteristics of the homogeneous region of the block material. The surface of the bulk material region may be different in terms of morphology, composition (such as sulfur, chlorine, and / or oxygen content) and other characteristics. The surface may be the outer surface of the wire core; in this embodiment, the alloyed silver wire of the present invention is composed of a wire core. In an alternative, the surface may be the interface area between the core and a coating superimposed on the core.

在本發明之上下文中，術語「疊加」用於描述例如線芯之第一物品相對於例如塗層之第二物品的相對位置。「疊加」特徵在於諸如中間層之其他物品可(但不需要)配置於第一及第二物品之間。較佳地，各相對於第一物品之總表面，第二物品至少部分地疊加於第一物品上，例如達至少30%、50%、70%或達至少90%。最佳地，第二物 品完全疊加於第一物品上。 In the context of the present invention, the term "overlay" is used to describe the relative position of a first item, such as a core, relative to a second item, such as a coating. "Overlay" is characterized in that other items, such as an intermediate layer, can be (but need not be) disposed between the first and second items. Preferably, with respect to the total surface of the first article, the second article is at least partially superimposed on the first article, such as at least 30%, 50%, 70%, or at least 90%. Optimally second The item is completely superimposed on the first item.

在本發明之上下文中，術語「中間層」係指在合金化銀線之芯及疊加於其上之塗層之間的合金化銀線之區域。在此區域中，存在芯及塗層兩者的材料之組合。 In the context of the present invention, the term "intermediate layer" refers to the area of the alloyed silver wire between the core of the alloyed silver wire and the coating superimposed thereon. In this area, there is a combination of materials for both the core and the coating.

在本發明之上下文中，術語「厚度」用於定義層在垂直於芯之縱向軸線的方向上的尺寸，該層至少部分地疊加於芯之表面上。 In the context of the present invention, the term "thickness" is used to define the dimension of a layer in a direction perpendicular to the longitudinal axis of the core, the layer being at least partially superimposed on the surface of the core.

在一實施例中，芯具有表面，其中將塗層疊加於芯之表面上。 In one embodiment, the core has a surface, wherein a coating is superimposed on the surface of the core.

在一實施例中，各相對於芯之總質量，塗層之質量不超過5wt.-%，較佳不超過2wt.-%或更低。當存在塗層時，各相對於芯之總質量，其常具有0.1wt.-%或更高、或0.5wt.-%或更高之最小質量。將少量材料塗覆為塗層保持由線芯材料定義之特徵。另一方面，塗層賦予線表面以特定特徵，諸如相對於環境之惰性、抗腐蝕性、改善之黏結性等。舉例而言，對於直徑為18μm之線，塗層之厚度在20至120nm範圍內。對於具有25μm之直徑的線，塗層可具有(例如)在30至150nm範圍內之厚度。 In one embodiment, the mass of the coating layer does not exceed 5 wt .-%, and preferably does not exceed 2 wt .-% or less, relative to the total mass of the core. When a coating is present, each often has a minimum mass of 0.1 wt .-% or higher, or 0.5 wt .-% or higher, relative to the total mass of the core. Applying a small amount of material as a coating maintains the characteristics defined by the core material. On the other hand, the coating imparts certain characteristics to the surface of the wire, such as inertness to the environment, corrosion resistance, improved adhesion, and the like. For example, for a wire with a diameter of 18 μm, the thickness of the coating is in the range of 20 to 120 nm. For a wire having a diameter of 25 μm, the coating may have a thickness in the range of, for example, 30 to 150 nm.

在一實施例中，塗層可由貴金屬元素製成。塗層可為該元素之一的單層。在另一實施例中，塗層可為多層，其包括多個疊加相鄰子層，其中各子層由不同貴金屬元素製成。用於沈積此類貴金屬元素於芯上之常用技術為諸如電鍍及無電極電鍍之鍍覆、諸如濺鍍、離子電鍍、真空蒸發及物理氣相沈積之材料自氣相之沈積、及材料自熔融物之沈積。 In one embodiment, the coating may be made of a noble metal element. The coating may be a single layer of one of the elements. In another embodiment, the coating may be a multilayer including a plurality of superimposed adjacent sub-layers, wherein each sub-layer is made of a different precious metal element. Common techniques used to deposit such precious metal elements on the core are plating such as electroplating and electrodeless plating, deposition of materials such as sputtering, ion plating, vacuum evaporation, and physical vapor deposition from the gas phase, and self-melting of materials The deposition of things.

在一實施例中，本發明之合金化銀線或其芯至少特徵在於以下固有特性中之一者(參見如下所述之「測試方法A」)：(1)平均線粒度(平均粒度)小於10μm，例如在2至6μm範圍內，較佳在2至4μm範圍內，(2)線晶粒[100]或[101]或[111]定向平面小於7%，例如在1%至5% 範圍內，較佳在2%至3.5%範圍內，(3)線孿晶間界分數小於60%，例如在30%至50%範圍內，較佳在40%至45%範圍內，(4)FAB呈現柱狀晶粒(晶粒經伸長)，(5)FAB平均粒度18μm，例如在6至14μm範圍內，較佳在8至12μm範圍內，(6)FAB晶粒[101]定向平面小於45%，例如在30%至40%範圍內，較佳在32%至36%範圍內，(7)FAB孿晶間界分數小於70%，例如在30%至65%範圍內，較佳在60%至65%範圍內，及/或至少特徵在於以下非固有特性中之一者：(α)抗腐蝕性具有不超過5%接合球上升之值，例如在0至5%範圍內(參見如下所述之「測試方法B」)，(β)抗濕性具有不超過5%接合球上升之值，例如在0至5%範圍內(參見如下所述之「測試方法C」)，(γ)線芯之硬度不超過85HV，例如在50至85HV範圍內，較佳在65至75HV範圍內(參見如下所述之「測試方法D」)，(δ)用於針腳式接合之製程窗區域具有至少12000mA．g之值，例如對於直徑為18μm之線，值為13000至14400mA．g(參見如下所述之具體揭示內容及「測試方法E」)，(ε)線之電阻率小於2.5μΩ．cm，例如在1.7至2.4μΩ．cm範圍內，較佳在2.2至2.4μΩ．cm範圍內(參見如下所述之「測試方法F」)，(ζ)線之屈服強度不超過170MPa，例如在140至170MPa範圍內(參見如下所述之「測試方法G」)，(η)線之銀樹突狀生長不超過4μm/s，例如在2至4μm/s範圍內，較佳在2至3μm/s範圍內(參見如下所述之「測試方法H」)。 In one embodiment, the alloyed silver wire or its core of the present invention is characterized by at least one of the following inherent characteristics (see "Test Method A" described below): (1) the average line grain size (average grain size) is less than 10 μm, for example, in the range of 2 to 6 μm, preferably in the range of 2 to 4 μm, (2) the orientation plane of the wire grain [100] or [101] or [111] is less than 7%, for example, in the range of 1% to 5% Within the range of 2% to 3.5%, (3) the fraction of the twins of the wire is less than 60%, for example, within the range of 30% to 50%, preferably within the range of 40% to 45%, (4) FAB presents columnar grains (grains are stretched), (5) average grain size of FAB 18 μm, for example in the range of 6 to 14 μm, preferably in the range of 8 to 12 μm, (6) FAB grain [101] orientation plane is less than 45%, for example in the range of 30% to 40%, preferably in the range of 32% to Within 36%, (7) FAB twin boundary fraction is less than 70%, for example in the range of 30% to 65%, preferably in the range of 60% to 65%, and / or at least characterized by the following non-inherent characteristics One of them: (α) the corrosion resistance has a value that does not exceed 5% of the joint ball, for example, in the range of 0 to 5% (see "Test Method B" described below), (β) the humidity resistance has no A value that rises above 5% of the engagement ball, for example, in the range of 0 to 5% (see "Test Method C" described below), (γ) the hardness of the core does not exceed 85HV, for example, in the range of 50 to 85HV, Preferably in the range of 65 to 75 HV (see "Test Method D" described below), (δ) The process window area for pin bonding has at least 12000 mA. The value of g, for example, for a wire with a diameter of 18 μm, is 13,000 to 14400 mA. g (see the specific disclosure and “Test Method E” below), the resistivity of the (ε) line is less than 2.5 μΩ. cm, for example between 1.7 and 2.4 μΩ. In the range of cm, preferably 2.2 to 2.4 μΩ. In the range of cm (see "Test Method F" described below), the yield strength of the (ζ) line does not exceed 170 MPa, for example in the range of 140 to 170 MPa (see "Test Method G" described below), (η) The linear dendritic growth of the wire does not exceed 4 μm / s, for example in the range of 2 to 4 μm / s, preferably in the range of 2 to 3 μm / s (see "Test Method H" described below).

本文所用之術語「固有特性」及「非固有特性」係關於線芯或FAB。固有特性意謂線芯或FAB本身具有之特性(獨立於其他因素),而非固有特性係視線芯或FAB與其他因素(如所用之量測方法及/或量測條件)之關係而定。 As used herein, the terms "inherent characteristics" and "non-inherent characteristics" refer to cores or FABs. Inherent characteristics mean the characteristics of the core or the FAB itself (independent of other factors), while non-inherent characteristics depend on the relationship between the core or the FAB and other factors (such as the measurement method and / or measurement conditions used).

在本發明之一較佳實施例之情況下，線芯之硬度(即接合之前的硬度)小於85HV，較佳在65至75HV範圍內。此外，在接合之前使用本發明之線所處理之FAB的硬度小於80HV，較佳在60至70HV範圍內。線芯及FAB之此硬度或(更精確而言)柔軟度有助於在接合過程中防止損害敏感性基體。實驗亦已顯示本發明之此類軟線呈現極軟FAB特性。若機械敏感性結構排列於結合襯墊之下，則FAB硬度之此限制為尤其有用的。若結合襯墊由如鋁或金之軟材料組成，則此尤為正確。舉例而言，敏感性結構可包含一個或若干個多孔二氧化矽層，其尤其具有小於2.5之介電常數。因為材料可有助於提昇裝置效能，所以此多孔及因此薄弱材料變得愈加常用。因此，本發明之接線的機械特性可經優化以避免此類薄弱層之開裂或其他損害。 In the case of a preferred embodiment of the present invention, the hardness of the core (that is, the hardness before bonding) is less than 85 HV, preferably in the range of 65 to 75 HV. In addition, the hardness of the FAB treated with the wire of the present invention before bonding is less than 80 HV, preferably in the range of 60 to 70 HV. This hardness or (more precisely) softness of the core and FAB helps prevent damage to the sensitive substrate during the bonding process. Experiments have also shown that such cords of the present invention exhibit extremely soft FAB characteristics. This limitation of FAB hardness is particularly useful if the mechanically sensitive structure is arranged below the bonding pad. This is especially true if the bonding pad consists of a soft material such as aluminum or gold. For example, the sensitive structure may include one or several porous silicon dioxide layers, which in particular have a dielectric constant of less than 2.5. Because materials can help improve device performance, this porous and therefore weak material is becoming more common. Therefore, the mechanical properties of the wiring of the present invention can be optimized to avoid cracking or other damage to such weak layers.

在一特定實施例中，本發明之合金化銀線呈現銀樹突狀生長，其速率小於4μm/s，例如在2至小於4μm/s範圍內，較佳在2至3μm/s範圍內，其為4N純銀線之約25μm/s生長速率的約1/10至1/7。 In a specific embodiment, the alloyed silver wire of the present invention exhibits silver dendritic growth at a rate of less than 4 μm / s, for example, in the range of 2 to less than 4 μm / s, preferably in the range of 2 to 3 μm / s. It is about 1/10 to 1/7 of a growth rate of about 25 μm / s of a 4N pure silver wire.

在另一有利實施例中，線之電阻率小於3.2μΩ．cm，例如在2.0至2.4μΩ．cm範圍內，較佳在2.2至2.4μΩ．cm範圍內，亦即意謂適用於許多應用。 In another advantageous embodiment, the resistivity of the line is less than 3.2 μΩ. cm, for example between 2.0 and 2.4 μΩ. In the range of cm, preferably 2.2 to 2.4 μΩ. The range of cm means that it is suitable for many applications.

在另一態樣中，本發明亦關於用於製造上文揭示之其實施例中任一者之合金化銀線的方法。方法至少包含以下步驟：(1)提供前驅體物品，其由以下組成：(a)鈀，其量在0.1至3wt.-%範圍內，較佳在0.5至1.5wt.-%範圍內， (b)金，其量在0.1至3wt.-%範圍內，較佳在0.2至1.5wt.-%範圍內，(c)鎳，其量在20至700wt.-ppm範圍內，較佳在275至325wt.-ppm範圍內，(d)鈣，其量在20至200wt.-ppm範圍內，較佳在20至50wt.-ppm範圍內，(e)銀，其量在93.91至99.786wt.-%範圍內，較佳在96.9625至99.2595wt.-%範圍內，及(f)0至100wt.-ppm之其他組分，其中所有以wt.-%及wt.-ppm為單位之量係基於前驅體物品之總重量，(2)伸長前驅體物品以形成線前驅體，直至獲得線芯之所要最終直徑；及(3)最終，在完成方法步驟(2)後，在400至600℃範圍內之烘箱設定溫度下，對所獲得之線前驅體進行帶材退火達0.4至0.8秒範圍內之暴露時間以形成合金化銀線，其中步驟(2)包括在400至800℃之烘箱設定溫度下，對伸長前驅體物品進行中度分批退火達50至150分鐘範圍內之暴露時間的一或多個子步驟，及/或在400至800℃之烘箱設定溫度下，對伸長前驅體物品進行中度帶材退火達0.4秒至1.2秒範圍內之暴露時間的一或多個子步驟。 In another aspect, the invention also relates to a method for manufacturing an alloyed silver wire of any of its embodiments disclosed above. The method includes at least the following steps: (1) providing a precursor article consisting of: (a) palladium in an amount in the range of 0.1 to 3 wt .-%, preferably in the range of 0.5 to 1.5 wt .-%, (b) gold in an amount in the range of 0.1 to 3 wt .-%, preferably in the range of 0.2 to 1.5 wt .-%, (c) nickel in an amount in the range of 20 to 700 wt.-ppm, preferably at In the range of 275 to 325 wt.-ppm, (d) the amount of calcium is in the range of 20 to 200 wt.-ppm, preferably in the range of 20 to 50 wt.-ppm, and (e) the amount of silver is 93.91 to 99.786 wt. In the range of .-%, preferably in the range of 96.9625 to 99.2595 wt .-%, and (f) 0 to 100 wt.-ppm of other components, all of which are in amounts of wt .-% and wt.-ppm Based on the total weight of the precursor article, (2) extending the precursor article to form a wire precursor until the desired final diameter of the wire core is obtained; and (3) finally, after completing method step (2), between 400 and 600 Oven in the range of ℃. The obtained wire precursor is subjected to strip annealing at an exposure time in the range of 0.4 to 0.8 seconds to form an alloyed silver wire. Step (2) includes an oven at 400 to 800 ° C. One or more sub-steps of moderately batch annealing an elongated precursor article for an exposure time in the range of 50 to 150 minutes at a set temperature, and / or an extended precursor at an oven set temperature of 400 to 800 ° C Thing One or more sub-steps performed within the exposure time of the annealed strip was moderate from 0.4 to 1.2 seconds range.

在本文中使用術語「帶材退火」。其為允許快速生產具有高再現性之線的連續製程。帶材退火意謂動態地進行退火，此時伸長線前驅體物品或待退火之線前驅體經移動穿過退火烘箱且在已離開退火箱後經纏繞於卷軸上。 The term "strip annealing" is used herein. It is a continuous process that allows rapid production of lines with high reproducibility. Strip annealing means that the annealing is performed dynamically, at this time the elongated wire precursor item or the wire precursor to be annealed is moved through the annealing oven and wound on a reel after it has left the annealing box.

在本文中使用術語「烘箱設定溫度」。其意謂退火烘箱之溫度控 制器中所固定之溫度。退火烘箱可為室爐型烘箱(在分批退火之情況下)或管狀退火烘箱(在帶材退火之情況下)。 The term "oven set temperature" is used herein. It means the temperature control of annealing oven The temperature fixed in the controller. The annealing oven can be a chamber furnace type (in the case of batch annealing) or a tubular annealing oven (in the case of strip annealing).

本發明區分前驅體物品、線前驅體及合金化銀線。術語「前驅體物品」用於彼等線前階段，其尚未達到線芯之所要最終直徑，而術語「線前驅體」用於具有所要最終直徑之線前階段。在完成方法步驟(3)後，亦即在對具有所要最終直徑之線前驅體進行最終帶材退火後，獲得本發明意義上之合金化銀線。 The invention distinguishes precursor articles, wire precursors and alloyed silver wires. The term "precursor article" is used for their pre-line stage, which has not yet reached the desired final diameter of the wire core, while the term "wire precursor" is used for the pre-wire stage with the desired final diameter. After the method step (3) is completed, that is, after the final strip annealing is performed on the wire precursor having the desired final diameter, an alloyed silver wire in the sense of the present invention is obtained.

可藉由以所要量之鈀、金、鎳及鈣摻合/摻雜銀來獲得如方法步驟(1)中所提供之前驅體物品。銀合金本身可藉由熟習金屬合金之技術者已知的習知方法來製備，例如藉由以所要比率將銀、鈀、金、鎳及鈣熔融在一起。在此情況下，有可能使用一或多種習知母合金。可例如使用感應爐進行熔融過程，且有利的是在真空下或在惰性氣體氛圍下操作。所用材料可具有例如99.99wt.-%及更高之純度級。可冷卻如此產生之熔融物以形成基於銀之前驅體物品的均質件。通常，此前驅體物品呈棒狀物形式，其具有(例如)2至25mm之直徑及(例如)5至100m之長度。可藉由將該銀合金熔融物澆鑄於室溫之合適模具中，隨後冷卻及固化來製造此棒狀物。 The precursor article as provided in method step (1) can be obtained by doping / doping silver with the required amounts of palladium, gold, nickel, and calcium. The silver alloy itself can be prepared by conventional methods known to those skilled in metal alloys, for example, by melting silver, palladium, gold, nickel, and calcium together at a desired ratio. In this case, it is possible to use one or more conventional master alloys. The melting process can be performed, for example, using an induction furnace, and is advantageously operated under vacuum or under an inert gas atmosphere. The materials used may have a purity level of, for example, 99.99 wt .-% and higher. The melt so produced can be cooled to form a homogeneous piece based on a silver precursor article. Generally, the precursor article is in the form of a rod, which has, for example, a diameter of 2 to 25 mm and a length of, for example, 5 to 100 m. The rod can be made by casting the silver alloy melt in a suitable mold at room temperature, followed by cooling and solidification.

若如本發明之第一態樣之一些實施例所揭示，呈單層或多層形式之塗層存在於合金化銀線之芯上，則較佳將此塗層塗覆至線前驅體物品上，該物品可尚未經伸長，未經最終伸長或甚至充分伸長至所要最終直徑。技術人員知道如何計算前驅體物品上之此塗層的厚度，以獲得具有線之實施例所揭示之厚度的塗層，亦即在伸長具有塗層之前驅體物品以形成線前驅體之後。如上文已揭示，根據實施例用於在銀合金表面上形成材料之塗層的眾多技術為已知的。較佳技術為諸如電鍍及無電極電鍍之鍍覆、諸如濺鍍、離子電鍍、真空蒸發及物理氣相沈積之材料自氣相之沈積、及材料自熔融物之沈積。 If, as disclosed by some embodiments of the first aspect of the present invention, a coating in the form of a single layer or multiple layers is present on the core of an alloyed silver wire, it is preferred to apply this coating to the wire precursor article The article may not have been stretched, has not been finally stretched, or is even sufficiently stretched to the desired final diameter. The skilled person knows how to calculate the thickness of this coating on the precursor article to obtain a coating having the thickness disclosed in the embodiment of the wire, that is, after elongating the coated precursor article to form a wire precursor. As has been disclosed above, numerous techniques for forming a coating of a material on the surface of a silver alloy according to embodiments are known. Preferred techniques are plating such as electroplating and electrodeless plating, deposition of materials from the gas phase such as sputtering, ion plating, vacuum evaporation, and physical vapor deposition, and deposition of materials from the melt.

為了將呈單層或多層之金屬塗層疊加至本發明之第一態樣的一些實施例揭示之線芯上，有利的是一旦達到前驅體物品之所要直徑，即中斷方法步驟(2)。此直徑可在(例如)80至200μm範圍內。隨後可(例如)藉由一或多種電鍍方法步驟來塗覆單層或多層金屬塗層。其後持續方法步驟(2)直至獲得線芯之所要最終直徑。 In order to superimpose a single-layer or multi-layer metal coating on the core disclosed in some embodiments of the first aspect of the present invention, it is advantageous to interrupt method step (2) once the desired diameter of the precursor article is reached. This diameter can be, for example, in the range of 80 to 200 μm. Single or multiple metal coatings can then be applied, for example, by one or more plating method steps. Thereafter, method step (2) is continued until the desired final diameter of the wire core is obtained.

在方法步驟(2)中，伸長前驅體物品以形成線前驅體，直至獲得線芯之所要最終直徑。在本發明之上下文中，伸長前驅體物品以形成線前驅體之技術為已知的且顯得實用。較佳技術為輥軋、型鍛、模拉伸或類似者，其中模拉伸尤佳。在後一情況中，在若干方法步驟中拉伸前驅體物品直至達到線芯之所要及最終直徑。 In method step (2), the precursor article is stretched to form a wire precursor until the desired final diameter of the wire core is obtained. In the context of the present invention, techniques for stretching precursor articles to form wire precursors are known and appear practical. Preferred techniques are rolling, swaging, die stretching, or the like, with die stretching being particularly preferred. In the latter case, the precursor article is stretched in several method steps until the desired and final diameter of the core is reached.

線芯之所要及最終直徑可在8至80μm範圍內，或較佳在12至55μm範圍內。熟習此項技術者熟知此線模拉伸方法。可使用習知碳化鎢及金剛石拉伸模，且可使用習知拉伸潤滑劑以支援拉伸。 The desired and final diameter of the core can be in the range of 8 to 80 μm, or preferably in the range of 12 to 55 μm. Those skilled in the art are familiar with this wire drawing method. Conventional tungsten carbide and diamond stretching dies can be used, and conventional stretching lubricants can be used to support stretching.

本發明之方法的步驟(2)包括在400至800℃之烘箱設定溫度下，對伸長前驅體物品進行中度分批退火達50至150分鐘範圍內之暴露時間的一或多個子步驟，及/或在400至800℃之烘箱設定溫度下，對伸長前驅體物品進行中度帶材退火達0.4秒至1.2秒範圍內之暴露時間的一或多個子步驟。可在兩個或多於兩個多伸長或拉伸步驟之間進行一或多個伸長前驅體物品之中度退火步驟。為了藉由實例說明此步驟，在拉伸期間可在三個不同階段進行三個中度退火步驟，例如，第一中度分批退火：在400至800℃之烘箱設定溫度範圍內，將棒狀物拉伸至2mm之直徑且纏繞於捲筒上達50至150分鐘之暴露時間，第二中度帶材退火：在400至800℃之烘箱設定溫度範圍內，將前驅體物品拉伸至47μm之直徑達0.4至1.2秒之暴露時間，及第三中度帶材退火：在400至800℃之烘箱設定溫度範圍內，進一步將前驅體物品拉伸至27μm之直徑達0.4至1.2秒之暴露時間。 Step (2) of the method of the present invention includes one or more sub-steps of subjecting the elongated precursor article to moderate batch annealing at an oven setting temperature of 400 to 800 ° C for an exposure time in the range of 50 to 150 minutes, and / Or one or more sub-steps of moderately strip annealing the elongated precursor article for an exposure time in the range of 0.4 seconds to 1.2 seconds at an oven set temperature of 400 to 800 ° C. One or more intermediate precursor annealing steps may be performed between two or more multi-elongation or stretching steps. In order to illustrate this step by way of example, three intermediate annealing steps can be performed in three different stages during stretching, for example, the first intermediate batch annealing: within the oven set temperature range of 400 to 800 ° C, the rod The object is stretched to a diameter of 2mm and wound on a reel for an exposure time of 50 to 150 minutes, the second moderate strip annealing: the precursor article is stretched to 47 μm in an oven set temperature range of 400 to 800 ° C Exposure time with a diameter of 0.4 to 1.2 seconds, and third moderate strip annealing: within the oven set temperature range of 400 to 800 ° C, the precursor article was further stretched to 27 μm with a diameter of 0.4 to 1.2 seconds for exposure time.

在方法步驟(3)中，最終對完成方法步驟(2)後所獲得之伸長線前驅體進行帶材退火。在(例如)400至600℃烘箱設定溫度範圍內進行最終帶材退火達0.4至0.8秒之暴露時間，或在一較佳實施例中，在400至500℃範圍內達0.5至0.7秒。 In the method step (3), strip elongation is finally performed on the elongated wire precursor obtained after the completion of the method step (2). The final strip annealing is performed, for example, in an oven set temperature range of 400 to 600 ° C for an exposure time of 0.4 to 0.8 seconds, or in a preferred embodiment, 0.5 to 0.7 seconds in a range of 400 to 500 ° C.

通常藉由以指定退火速度將伸長線前驅體拉伸穿過習知退火烘箱來進行最終帶材退火，該退火箱通常呈具有指定長度及限定溫度分佈之圓柱管形式，該速度經選擇介於例如10至60公尺/分鐘範圍內。這樣做可限定及設定退火時間/烘箱溫度參數。 The final strip annealing is usually performed by stretching the precursor of the elongation wire through a conventional annealing oven at a specified annealing speed, which is usually in the form of a cylindrical tube with a specified length and a limited temperature distribution. The speed is selected between For example, in the range of 10 to 60 meters / minute. Doing so limits and sets the annealing time / oven temperature parameters.

在一較佳實施例中，在水中淬滅最終經帶材退火之合金化銀線，在一實施例中，水可含有一或多種添加劑，例如0.01至0.07體積%之添加劑。在水中淬滅意謂(例如)藉由浸漬或滴注，立即或快速(亦即在0.2至0.6秒內)將最終經帶材退火之合金化銀線自其在方法步驟(3)中經歷之溫度冷卻至室溫。 In a preferred embodiment, the alloyed silver wire that is finally annealed by the strip is quenched in water. In one embodiment, water may contain one or more additives, such as 0.01 to 0.07% by volume of additives. Quenching in water means, for example, by dipping or dripping, immediately or quickly (i.e., within 0.2 to 0.6 seconds) to anneal the finally annealed silver wire of the strip from the one it undergoes in method step (3) Cool to room temperature.

關於本發明之一實施例，發現在低於最大伸長率之溫度的溫度下進行最終帶材退火可引起有益線特性，此係因為可以積極方式影響線形態。藉由此調整，可以積極方式影響如(例如)線硬度、球接合性能等之其他特性。 Regarding one embodiment of the present invention, it has been found that annealing the final strip at a temperature below the maximum elongation can cause beneficial line characteristics because the line morphology can be positively affected. By this adjustment, other characteristics such as, for example, line hardness, ball joint performance, and the like can be positively affected.

在一實施例中，可在比藉由退火獲得最大伸長率值之溫度至少低150℃、例如低210至240℃之溫度下進行最終帶材退火；此可導致退火後線之伸長率值不超過最大伸長率值之70%，例如最大伸長率值之30%至60%。舉例而言，可在比最大伸長率之溫度T△L(max)至少低150℃、較佳至少低180℃、或至少低200℃之溫度下進行方法步驟(3)。方法步驟(3)之溫度常不比T△L(max)低超過250℃。藉由測試樣品(線)在不同溫度下之斷裂伸長率來測定最大伸長率之溫度T△L(max)。在曲線圖中收集資料點，其顯示作為溫度(℃)之函數的伸長率(以%計)。所得曲線圖常稱為「退火曲線」。在基於銀之線的情況下，當伸 長率(以%計)達至最大時觀測溫度。此為最大伸長率之溫度T△L(max)。一實例顯示於圖1中，其顯示樣品1之18μm合金化銀線的例示性退火曲線(表1)。退火溫度為x軸之可變參數。曲線圖顯示線之斷裂負載(BL，以公克計)及伸長率(EL，以%計)的量測值。藉由拉伸測試來測定伸長率。伸長率量測值呈現在所顯示之實例中約19%之典型局部最大值，其在約700℃之退火溫度下獲得。若不在此最大伸長率之溫度下，而是在比最大伸長率之溫度低220℃之480℃下對樣品1之線進行最終帶材退火，則結果為約8%之伸長率值，其比最大伸長率值低超過40%。 In one embodiment, the final strip annealing may be performed at a temperature that is at least 150 ° C lower than the temperature at which the maximum elongation value is obtained by annealing, such as 210 to 240 ° C; this may cause the elongation value of the wire after annealing to be different. Exceeds 70% of the maximum elongation value, such as 30% to 60% of the maximum elongation value. For example, the method step (3) can be performed at a temperature at least 150 ° C lower than the temperature TΔL (max) of the maximum elongation, preferably at least 180 ° C lower, or at least 200 ° C lower. The temperature in method step (3) is usually not lower than T ΔL (max) by more than 250 ° C. The temperature T ΔL (max) of the maximum elongation is determined by testing the elongation at break of the sample (wire) at different temperatures. Data points were collected in a graph showing elongation (in%) as a function of temperature (° C). The resulting graph is often referred to as the "annealing curve". In the case of a silver-based wire, the temperature is observed when the elongation (in%) reaches a maximum. This is the temperature T ΔL (max) of the maximum elongation. An example is shown in FIG. 1, which shows an exemplary annealing curve of the 18 μm alloyed silver wire of Sample 1 (Table 1). The annealing temperature is a variable parameter of the x-axis. The graph shows the measured values of the breaking load (BL, in grams) and elongation (EL, in%) of the wire. The elongation was measured by a tensile test. The elongation measurements show a typical local maximum of about 19% in the example shown, which is obtained at an annealing temperature of about 700 ° C. If the temperature of the maximum elongation is not at this temperature, but the final strip annealing is performed on the wire of sample 1 at 480 ° C lower than the temperature of the maximum elongation, the result is an elongation value of about 8%. The maximum elongation value is lower than 40%.

可在惰性或還原氛圍中進行方法步驟(2)之中度退火以及方法步驟(3)之最終帶材退火。眾多類型之惰性氛圍以及還原氛圍為此項技術中已知的且用於吹洗退火烘箱。在已知惰性氛圍中，氮或氬為較佳的。在已知還原氛圍中，氫為較佳的。另一較佳還原氛圍為氫及氮之混合物。較佳氫及氮之混合物為90至98vol.-%之氮及相應地2至10vol.-%之氫，其中總vol.-%為100vol.-%。較佳氮/氫之混合物等於93/7、95/5及97/3vol.-%/vol.-%，其各基於混合物之總體積。若合金化銀線表面之某些部分對由空氣之氧所致之氧化反應具有敏感性，則尤佳在退火中施加還原氛圍。用該等類型之惰性或還原氣體吹洗較佳在處於10至125min-1範圍內、更佳處於15至90min-1範圍內、最佳處於20至50min-1範圍內之氣體交換速率(=氣體流動速率[公升/分鐘]：烘箱內體積[公升])下進行。 Moderate annealing in method step (2) and final strip annealing in method step (3) can be performed in an inert or reducing atmosphere. Numerous types of inert atmospheres and reducing atmospheres are known in the art and are used for purge annealing ovens. In a known inert atmosphere, nitrogen or argon is preferred. In a known reducing atmosphere, hydrogen is preferred. Another preferred reducing atmosphere is a mixture of hydrogen and nitrogen. A preferred mixture of hydrogen and nitrogen is 90 to 98 vol .-% nitrogen and correspondingly 2 to 10 vol .-% hydrogen, with the total vol .-% being 100 vol .-%. Preferred nitrogen / hydrogen mixtures are equal to 93/7, 95/5, and 97/3 vol .-% / vol .-%, each based on the total volume of the mixture. If some parts of the surface of the alloyed silver wire are sensitive to the oxidation reaction caused by oxygen in the air, it is particularly preferable to apply a reducing atmosphere during annealing. Such a type of inert or reducing gas purge is preferably in the range of 10 to 125min -1, more preferably in the range of 15 to 90min -1, optimal gas exchange rate at the range 20 to 50min -1 (= Gas flow rate [liters / minute]: Volume inside the oven [liters]).

咸信前驅體物品材料之組成(其與成品合金化銀線芯之彼者相同)及在方法步驟(2)及(3)期間之主要退火參數的獨特組合對獲得呈現至少一種上文揭示之固有及/或非固有的特性之本發明的線而言為重要的。中度及最終帶材退火步驟之溫度/時間條件允許獲得或調整合金化銀線芯之固有及非固有的特性。 The unique combination of the material of the Xianxin precursor article (which is the same as that of the finished alloyed silver wire core) and the main annealing parameters during method steps (2) and (3), obtain at least one of the above-disclosed Inherent and / or non-inherent characteristics are important for the threads of the present invention. The temperature / time conditions of the intermediate and final strip annealing step allow obtaining or adjusting the inherent and non-inherent characteristics of the alloyed silver wire core.

完成方法步驟(3)後，完成本發明之合金化銀線。為了充分受益於其特性，有利的是或立即(亦即毫不耽擱)將其用於線接合應用，例如在完成方法步驟(3)後不超過10天內。或者，為了保持合金化銀線之寬線接合製程窗特性且為了防止其氧化或受到其他化學侵蝕，通常在完成方法步驟(3)之後立即(亦即毫不耽擱)將成品線纏繞及真空密封，例如在完成方法步驟(3)後<1至5小時內，且隨後儲存以供進一步用作接線。儲存於真空密封條件下不應超出6個月。在打開真空密封件後，應在不超過10天內將合金化銀線用於線接合。 After the method step (3) is completed, the alloyed silver wire of the present invention is completed. In order to fully benefit from its characteristics, it is advantageous to use it for wire bonding applications, either immediately (ie without delay), for example within no more than 10 days after completion of method step (3). Alternatively, in order to maintain the characteristics of the wide wire bonding process window of the alloyed silver wire and to prevent its oxidation or other chemical attack, the finished wire is usually wound and vacuum sealed immediately after completing method step (3) (that is, without delay). , For example within <1 to 5 hours after method step (3) is completed, and then stored for further wiring. Storage under vacuum-tight conditions should not exceed 6 months. After opening the vacuum seal, the alloyed silver wire should be used for wire bonding within 10 days.

較佳的是，在無塵室條件(US FED STD 209E無塵室標準，1k標準)下進行所有方法步驟(1)至(3)以及纏繞及真空密封。 Preferably, all method steps (1) to (3) and winding and vacuum sealing are performed under clean room conditions (US FED STD 209E clean room standard, 1k standard).

本發明之第三態樣為藉由前文揭示的本發明之第二態樣的方法或其一實施例，合金化銀線為可獲得的。已發現該合金化銀線較適合用作線接合應用中之接線。線接合技術為技術人員所熟知。在線接合過程中，典型的是形成球接合(第1接合)及針腳式接合(第2接合，楔形接合)。在形成接合期間施加某一力(通常以公克計)，藉由施加超音波能(通常以毫安計)來支持該力。線接合方法中之施加力上限及下限之差及施加超聲波能上限及下限之差的數學乘積定義線接合製程窗：(施加力上限-施加力下限)．(施加超聲波能上限-施加超聲波能下限)=線接合製程窗。 The third aspect of the present invention is the method or the embodiment of the second aspect of the present invention disclosed above, and an alloyed silver wire is available. This alloyed silver wire has been found to be more suitable for wiring in wire bonding applications. Wire bonding techniques are well known to the skilled person. In the wire bonding process, a ball joint (first joint) and a pin joint (second joint, wedge joint) are typically formed. A certain force (typically in grams) is applied during the formation of the bond, and this force is supported by the application of ultrasonic energy (typically in milliamps). The mathematical product of the difference between the upper and lower limit of applied force and the difference between the upper and lower limit of applied ultrasonic energy in the wire bonding method defines the wire bonding process window: (upper limit of applied force-lower limit of applied force) . (Upper limit of applied ultrasonic energy-lower limit of applied ultrasonic energy) = wire bonding process window.

線接合製程窗定義力/超聲波能組合之區域，該區域允許形成符合規格之線接合，亦即該線接合通過如(僅舉幾個為例)習知拉伸測試、球剪切測試及球拉伸測試之習知測試。 The wire bonding process window defines the area of the force / ultrasonic energy combination that allows the formation of wire bonding that meets the specifications, that is, the wire bonding passes the conventional tensile test, ball shear test, and ball such as (to name a few) Custom test for tensile test.

換句話說，第1接合(球接合)製程窗區域為用於接合中之力上限及下限之差與施加超聲波能上限及下限之差的乘積，其中所得接合必須符合某些球剪切測試規格，例如0.0085公克/平方微米之球剪切、黏附於接合襯墊上等，而第2接合(針腳式接合)製程窗區域為用於接合 中之力上限及下限之差與施加超聲波能上限及下限之差的乘積，其中所得接合必須符合某些拉伸測試規格，例如2.5公克之拉力，黏附於鉛上等。 In other words, the first joint (ball joint) process window area is the product of the difference between the upper and lower limits of the force used in the joint and the difference between the upper and lower limits of the applied ultrasonic energy, where the resulting joint must meet certain ball shear test specifications , Such as 0.0085 g / square micron ball shearing, sticking to the bonding pad, etc., and the second bonding (pin bonding) process window area is for bonding The product of the difference between the upper and lower limit of the force and the difference between the upper and lower limit of the applied ultrasonic energy, in which the resulting joint must meet certain tensile test specifications, such as a tensile force of 2.5 grams, adhered to lead, etc.

對於工業應用，出於線接合方法魯棒性之原因，期望具有寬線接合製程窗(力(以g計)比超聲波能(以mA計))。本發明之線呈現極寬線接合製程窗。 For industrial applications, for reasons of the robustness of the wire bonding method, it is desirable to have a wide wire bonding process window (force (in g) to ultrasonic energy (in mA)). The wire of the present invention presents an extremely wide wire bonding process window.

以下非限制性實例說明本發明。此等實例用於本發明之例示性闡明，且無論如何並不意欲限制本發明之範疇或申請專利範圍。 The following non-limiting examples illustrate the invention. These examples are used for illustrative explanation of the present invention and are not intended to limit the scope of the present invention or the scope of patent application in any way.

實例Examples

製備FAB： Preparation of FAB:

根據描述於KNS Process User Guide for Free Air Ball(Kulicke & Soffa工業公司，Fort Washington，PA，美國，2002年，2009年5月31日)中之程序進行操作。藉由進行習知電火炬(EFO)焙燒，藉由標準焙燒(單步驟，18mA之EFO電流，455μs之EFO時間)來製備FAB。 Operation was performed according to the procedure described in the KNS Process User Guide for Free Air Ball (Kulicke & Soffa Industries, Fort Washington, PA, USA, 2002, May 31, 2009). FAB was prepared by performing conventional electric torch (EFO) firing, and by standard firing (single step, EFO current of 18 mA, EFO time of 455 μs).

測試方法A.至J.Test methods A. to J.

在T=20℃及相對濕度RH=50%下進行所有測試及量測。 All tests and measurements were performed at T = 20 ° C and relative humidity RH = 50%.

A.線及FAB之電子反向散射繞射(EBSD)圖分析： A. Line and FAB electron backscatter diffraction (EBSD) diagram analysis:

量測線及FAB結構所用之主要步驟為樣品製備，從而獲得良好菊池(Kikuchi)圖及組分計算值：首先使用環氧樹脂罐封有或無FAB之線，且按照標準金相技術進行拋光。在最終樣品製備步驟中應用離子研磨以移除線表面之任何機械變形、污染及氧化層。用金濺鍍經離子研磨之橫截面樣品表面。隨後進行兩個另外回合之離子研磨及金濺鍍。不進行化學蝕刻或離子蝕刻。 The main steps for measuring lines and FAB structures are sample preparation, so as to obtain good Kikuchi diagrams and component calculation values: first use epoxy resin cans with or without FAB lines, and polish according to standard metallographic techniques . Ion milling is applied in the final sample preparation step to remove any mechanical deformation, contamination, and oxide layers on the wire surface. The surface of the ion-milled cross-section sample was sputtered with gold. Two additional rounds of ion milling and gold sputtering were subsequently performed. No chemical or ion etching is performed.

將樣品載入至具有與正常FESEM(場發射掃描電子顯微鏡)樣品固持器表面成70°角之固持器的FESEM中。FESEM另外配備有EBSD 偵測器。獲得含有線結晶信息之電子反向散射圖案(EBSP)。 The sample was loaded into a FESEM having a holder at an angle of 70 ° to the surface of a normal FESEM (field emission scanning electron microscope) sample holder. FESEM is additionally equipped with EBSD Detector. An electron backscattering pattern (EBSP) containing linear crystal information was obtained.

進一步分析此等圖案之晶粒定向分數、平均粒度等(使用稱作QUANTAX EBSD程式之軟體，其由Bruker研發)。類似定向之點分組在一起以形成結構組分。 The grain orientation fraction, average grain size, etc. of these patterns were further analyzed (using software called QUANTAX EBSD program, which was developed by Bruker). Similar oriented points are grouped together to form structural components.

為了區分不同結構組分，使用15°之最大公差角度。將線拉伸方向設定為參考定向。藉由量測具有平行於參考定向之[100]、[101]及[111]定向平面之晶體的百分比來計算[100]、[101]及[111]結構百分比。 In order to distinguish between different structural components, a maximum tolerance angle of 15 ° is used. Set the line stretch direction to the reference orientation. [100], [101], and [111] structure percentages were calculated by measuring the percentage of crystals with [100], [101], and [111] orientation planes parallel to the reference orientation.

分析界定大於最小值(本文為10°)之相鄰晶格點之間的結晶定向之平均粒度，以確定晶界位置。EBSD軟體計算各晶粒之面積且將其轉化為等效圓直徑，等效圓直徑定義為「平均晶粒尺寸」。計算沿長度在~100μm內之線的縱向方向之所有晶粒，以確定平均晶粒尺寸之平均值及標準差。 The average grain size of the crystal orientation between adjacent lattice points defined as larger than the minimum value (herein 10 °) is analyzed to determine the position of the grain boundary. The EBSD software calculates the area of each grain and converts it into an equivalent circle diameter, which is defined as the "average grain size". Calculate all grains in the longitudinal direction along a line with a length within ~ 100 μm to determine the average and standard deviation of the average grain size.

平均粒度計算中不包括孿晶間界(亦稱作Σ3 CSL孿晶間界)。孿晶間界係由圍繞相鄰結晶晶疇之間的<111>定向平面之60°旋轉描述。點之數量取決於步長，其小於平均晶粒尺寸之1/5。 Twin grain boundaries (also known as Σ3 CSL twin boundaries) are not included in the average particle size calculation. The twin boundary system is described by a 60 ° rotation around the <111> orientation plane between adjacent crystalline domains. The number of points depends on the step size, which is less than 1/5 of the average grain size.

B.接合球之鹽溶液浸泡測試： B. Salt solution immersion test of bonding ball:

將線球接合至Al-0.5wt.-%Cu接合墊。在25℃下將具有如此接合之線的測試裝置浸泡於鹽溶液中達10分鐘，用去離子(DI)水洗滌，且隨後用丙酮洗滌。鹽溶液包含20wt.-ppm NaCl於去離子水中。在低倍顯微鏡(Nikon MM-40)下以100X放大率檢測上升球之數量。較高上升球數量之觀測結果表明重度界面電流腐蝕。 The ball was bonded to an Al-0.5wt .-% Cu bonding pad. The test device with the wires thus bonded was immersed in a saline solution at 25 ° C for 10 minutes, washed with deionized (DI) water, and then washed with acetone. The salt solution contained 20 wt.-ppm NaCl in deionized water. The number of ascending balls was detected under a low magnification microscope (Nikon MM-40) at 100X magnification. Observations of higher numbers of ascending balls indicate severe interface current corrosion.

C.接合球之抗濕性測試： C. Moisture resistance test of joint ball:

將線球接合至Al-0.5wt.-%Cu接合墊。在高加速應力測試(HAST)室中將具有如此接合線之測試裝置儲存在130℃溫度、85%相對濕度(RH)下達8小時，且隨後在低倍顯微鏡(Nikon MM-40)下以100X放大 率檢測上升球之數量。較高上升球數量之觀測結果表明重度界面電流腐蝕。 The ball was bonded to an Al-0.5wt .-% Cu bonding pad. The test device having such a bonding wire was stored in a high acceleration stress test (HAST) chamber at a temperature of 130 ° C. and a relative humidity of 85% (RH) for 8 hours, and then under a low magnification microscope (Nikon MM-40) at 100X amplification Rate to detect the number of ascending balls. Observations of higher numbers of ascending balls indicate severe interface current corrosion.

D.維氏微硬度(Vickers Micro-hardness)： D. Vickers Micro-hardness:

使用具有維氏(Vickers)壓痕器之Mitutoyo HM-200測試設備量測硬度。將10mN壓痕負載之力施加至線之測試樣品達12秒之停留時間。在線芯之中心上及FAB上進行測試。 The hardness was measured using a Mitutoyo HM-200 testing device with a Vickers indenter. A force of 10 mN indentation load was applied to the test sample of the wire for a dwell time of 12 seconds. Tested on the core of the core and on the FAB.

E.針腳式接合製程窗區域： E. Pin-joint process window area:

藉由標準程序進行接合製程窗區域之量測。使用KNS-iConn接合機工具(Kulicke & Soffa工業公司，Fort Washington，PA，美國)接合測試線。製程窗值係基於具有18μm之平均直徑的線，其中與線接合之引線指狀物由銀組成。 Measurement of the bonding process window area is performed by standard procedures. A KNS-iConn bonding machine tool (Kulicke & Soffa Industries, Fort Washington, PA, USA) was used to bond the test leads. The process window value is based on a wire with an average diameter of 18 μm, where the lead fingers bonded to the wire are composed of silver.

藉由克服兩個主要故障模式導出製程窗之四個角：(1)供應過低力及超聲波能導致線無法黏附於引線指狀物上(NSOL，non-stick on lead finger)，及(2)供應過高力及超聲波能導致線短尾(SHTL)。 The four corners of the process window are derived by overcoming two major failure modes: (1) the supply of too low force and ultrasonic energy can prevent the wire from sticking to lead fingers (NSOL), and (2 ) Excessive supply of high force and ultrasonic energy can cause wire short tail (SHTL).

F.電阻率： F. Resistivity:

將測試樣品(亦即長度為1.0公尺之線)的兩端連接至提供恆定電流/電壓之電源。用裝置記錄針對供應電壓之電阻。量測裝置為HIOKI模型3280-10，且用至少10個測試樣品來重複測試。量測值之算術平均值用於以下給出之計算。 Connect both ends of the test sample (ie, a 1.0-meter line) to a power source that provides a constant current / voltage. Record the resistance against the supply voltage with the device. The measuring device is HIOKI model 3280-10, and the test is repeated with at least 10 test samples. The arithmetic mean of the measured values is used in the calculations given below.

根據R=V/I計算電阻R。 Calculate the resistance R according to R = V / I.

根據ρ=(R x A)/L計算比電阻ρ，其中A為線之平均截面積，且L為用於量測電壓之裝置的兩個量測點之間的線長度。 Calculate the specific resistance ρ according to ρ = (R x A) / L, where A is the average cross-sectional area of the line, and L is the line length between two measurement points of the device for measuring voltage.

根據σ=1/ρ計算比電導率。 Calculate the specific conductivity according to σ = 1 / ρ.

G.伸長率(EL)： G. Elongation (EL):

使用Instron-5564儀器測試線之拉伸特性。以2.54cm/min速度針 對254mm標距(L)測試線。按照ASTM標準F219-96獲取斷裂(fracture或break)上之負載及伸長率。伸長率為拉伸測試起始及結束之間線之標距(△L)之差，其通常報告為(100．△L/L)(以百分比計)，其用所記錄之負載比延伸率拉伸圖來計算。用斷裂及屈服負載除以線區域來計算拉伸強度及屈服強度。藉由量尺寸方法、稱重標準長度之線及使用其密度來量測線之實際直徑。 The tensile properties of the wires were tested using an Instron-5564 instrument. Needle at 2.54cm / min For 254mm gage (L) test line. Obtain load and elongation at break (fracture or break) according to ASTM standard F219-96. The elongation is the difference between the gauge distance (△ L) of the line between the start and end of the tensile test, which is usually reported as (100. △ L / L) (in percentage), which uses the recorded elongation at load ratio Stretch the figure to calculate. The tensile and yield strengths are calculated by dividing the fracture and yield load by the line area. Measure the actual diameter of the wire by measuring the size, weighing the standard length of the wire, and using its density.

H.線之電遷移測試： H. Wire electromigration test:

在50X放大率之低倍顯微鏡Nikon MM40的接物鏡下，在PTFE板上以公釐內之距離使兩條線保持平行。藉由微量吸管在待用電連接之兩條線之間形成水滴。將一條線連接至正極且將另一條連接至負極，且向線施加5V。在閉路中對兩條線施加5V偏壓，將其串聯至10kΩ電阻器。藉由使用作為電解質之數滴去離子水潤濕兩條線來使電路閉合。銀在電解質中自陰極電遷移至陽極形成銀樹突，有時兩條線橋接在一起。銀樹突生長之速率強烈依賴於合金添加。所測試之線的直徑為75μm。 With a 50X magnification Nikon MM40 objective, the two lines are kept parallel on the PTFE plate at a distance of within millimeters. Water droplets were formed between the two wires to be electrically connected by a micro pipette. One wire was connected to the positive electrode and the other was connected to the negative electrode, and 5V was applied to the wire. Apply 5V bias to both lines in a closed circuit and connect them in series to a 10kΩ resistor. The circuit is closed by wetting the two wires with a few drops of deionized water as an electrolyte. Silver electromigrate in the electrolyte from the cathode to the anode to form silver dendrites, sometimes the two wires are bridged together. The rate of silver dendrite growth is strongly dependent on alloy addition. The diameter of the tested wire was 75 μm.

實例1Example 1

在各情況下，在坩堝中熔融一定量的具有至少99.99%純度(「4N」)之銀(Ag)、鈀(Pd)及金(Au)。將少量銀-鎳及銀-鈣母合金添加至熔融物中，且藉由攪拌確定所添加之組分的均勻分佈。使用以下銀-鎳及銀-鉑母合金： In each case, a certain amount of silver (Ag), palladium (Pd), and gold (Au) having a purity of at least 99.99% ("4N") was melted in the crucible. A small amount of silver-nickel and silver-calcium master alloy is added to the melt, and the uniform distribution of the added components is determined by stirring. The following silver-nickel and silver-platinum master alloys are used:

針對表1之合金，添加母合金Ag-0.5wt.-%Ni及Ag-0.5wt.-%Ca之相應組合。 For the alloys in Table 1, the corresponding combinations of the master alloys Ag-0.5wt .-% Ni and Ag-0.5wt .-% Ca were added.

隨後用熔融物連續鑄造呈8mm棒狀物形式之線芯前驅體物品。隨後在若干拉伸步驟中拉伸線芯前驅體物品以形成具有18±0.5μm之 指定直徑的線芯前驅體。線芯之橫斷面基本上為圓形形狀。 The core precursor article was then continuously cast in the form of an 8mm rod from the melt. The core precursor article is then stretched in several stretching steps to form a layer having a thickness of 18 ± 0.5 μm. Core precursor with specified diameter. The cross section of the core is substantially circular.

在500℃之烘箱設定溫度下對拉伸至2mm直徑及捲繞於捲筒上之棒狀物進行中度分批退火達60分鐘之暴露時間。在600℃之烘箱設定溫度下對拉伸至47μm之直徑的前驅體物品進行第二中度帶材退火達0.8秒之暴露時間，且在600℃之烘箱設定溫度下對拉伸至27μm之直徑的前驅體物品進行第三中度帶材退火達0.6秒之暴露時間。在480℃之烘箱設定溫度下對18μm線芯前驅體進行最終帶材退火達0.6秒之暴露時間，隨後在含有0.05vol.-%界面活性劑之水中淬滅如此獲得之線。使用氬吹洗氣體進行中度分批退火，而使用95vol.-%氮：5vol.-%氮吹洗混合氣體進行帶材退火。 The batches stretched to a diameter of 2 mm and wound on a roll were subjected to moderate batch annealing at an exposure time of 60 minutes at an oven set temperature of 500 ° C. The precursor article stretched to a diameter of 47 μm was subjected to a second moderate strip annealing at an oven set temperature of 600 ° C. for an exposure time of 0.8 seconds, and was stretched to a diameter of 27 μm at an oven set temperature of 600 ° C. The precursor article was subjected to a third moderate strip annealing for an exposure time of 0.6 seconds. The 18 μm wire core precursor was subjected to a final strip annealing at an oven set temperature of 480 ° C. for an exposure time of 0.6 seconds, and then the wire thus obtained was quenched in water containing 0.05 vol .-% surfactant. Moderate batch annealing was performed using an argon purge gas, and strip annealing was performed using a 95 vol .-% nitrogen: 5 vol .-% nitrogen purge mixed gas.

藉由此程序，製造本發明之合金化銀線的若干不同樣品1至5及4N純度之比較性銀線(參考)。 With this procedure, several different samples of the alloyed silver wire of the present invention were produced with comparative silver wires of 1 to 5 and 4N purity (reference).

表1顯示本發明之不同線(樣品1至5)的組成。鈀含量在1至3wt.-%範圍內。金含量在1至1.5wt.-%範圍內。鎳添加量在30至300wt.-ppm間變化。鈣含量各自地保持在30及50wt.-ppm。 Table 1 shows the composition of the different lines (samples 1 to 5) of the present invention. The palladium content is in the range of 1 to 3 wt .-%. The gold content is in the range of 1 to 1.5 wt .-%. The amount of nickel added varies from 30 to 300 wt.-ppm. The calcium content was maintained at 30 and 50 wt.-ppm, respectively.

量測線樣品1至5之粒度且報告平均粒度。在各情況下，結果在2至5μm範圍內。針對樣品1，平均粒度為2.91μm。 The particle sizes of line samples 1 to 5 are measured and the average particle size is reported. In each case, the results were in the range of 2 to 5 μm. For Sample 1, the average particle size was 2.91 μm.

以下表2顯示接合線之抗腐蝕性及抗濕性、第2接合製程窗之性能及FAB形成之效能的評估結果。將上文所定義之線樣品1至5以及4N純銀比較性線接合至Al-0.5wt.-%Cu接合墊，且根據上文揭示之測試 方法進行測試。除了針對75μm線進行之電遷移測試，所有測試係針對18μm鎳進行。 Table 2 below shows the evaluation results of the corrosion resistance and moisture resistance of the bonding wire, the performance of the second bonding process window, and the effectiveness of FAB formation. The wire samples 1 to 5 and 4N pure silver comparative wires as defined above were bonded to Al-0.5wt .-% Cu bonding pads, and according to the tests disclosed above Method for testing. Except for electromigration tests performed on 75 μm wires, all tests were performed on 18 μm nickel.

所有線樣品產生較適用於工業應用之程序窗。觀測到接合球之抗腐蝕性及抗濕性的顯著改善。特定言之，線樣品1顯示接近零之值(亦即2球上升)，相較於4N純銀線(參考)其為特別的改善。 All line samples produce program windows that are more suitable for industrial applications. Significant improvements in corrosion resistance and moisture resistance of the joint ball were observed. In particular, line sample 1 shows a value close to zero (that is, a 2-ball rise), which is a special improvement compared to a 4N pure silver line (reference).

此外，線樣品1至5之銀樹突狀生長大大低於4N純銀線之銀樹突狀生長。 In addition, the silver dendrite growth of the wire samples 1 to 5 is much lower than that of the 4N pure silver wire.

表3顯示線樣品1之平均粒度及結構組分(線、FAB及熱影響區(HAZ))。 Table 3 shows the average particle size and structural composition of line sample 1 (line, FAB, and heat-affected zone (HAZ)).

圖1顯示18μm銀-鈀-金-鎳-鈣合金線(樣品1，參見表1)之例示性退火曲線。藉由調整移動線之速度將退火時間選擇為恆定值。退火溫度為x軸之可變參數。曲線圖顯示線之斷裂負載(BL，以公克計)及伸長率(EL，以%計)的量測值。藉由拉伸測試來測定伸長率。伸長率量測值呈現在所顯示之實例中約19%之典型局部最大值，其在約700℃之退火溫度下獲得。樣品線1之退火在480℃下進行，根據圖1其比最大伸長率之溫度低220℃。此產生約8%之伸長率值，其比最大伸長率值低超過40%。 FIG. 1 shows an exemplary annealing curve of an 18 μm silver-palladium-gold-nickel-calcium alloy wire (Sample 1, see Table 1). The annealing time is selected to be a constant value by adjusting the speed of the moving line. The annealing temperature is a variable parameter of the x-axis. The graph shows the measured values of the breaking load (BL, in grams) and elongation (EL, in%) of the wire. The elongation was measured by a tensile test. The elongation measurements show a typical local maximum of about 19% in the example shown, which is obtained at an annealing temperature of about 700 ° C. The annealing of sample line 1 is performed at 480 ° C, which is 220 ° C lower than the temperature of the maximum elongation according to FIG. 1. This results in an elongation value of about 8%, which is more than 40% lower than the maximum elongation value.

圖2顯示18μm銀-鈀-金-鎳-鈣合金線(樣品1，表1)之例示性離子研磨橫截面圖像。三個不同位置線之晶粒形態、HAZ及FAB為明顯的。在480℃、7.5% EL下對線樣品1進行退火。應用1.8之球與線尺寸比率(BSR)及18mA之EFO電流及455μs之EFO時間。 FIG. 2 shows an exemplary ion milling cross-sectional image of an 18 μm silver-palladium-gold-nickel-calcium alloy wire (Sample 1, Table 1). The grain morphology, HAZ and FAB of three different position lines are obvious. The wire sample 1 was annealed at 480 ° C and 7.5% EL. A ball-to-line size ratio (BSR) of 1.8, an EFO current of 18 mA, and an EFO time of 455 μs were applied.

Claims (15)

一種包含線芯或由線芯組成之合金化銀線，該線芯本身由以下組成：(a)鈀，其量在0.1至3wt.-%範圍內，(b)金，其量在0.1至3wt.-%範圍內，(c)鎳，其量在20至700wt.-ppm範圍內，(d)鈣，其量在20至200wt.-ppm範圍內，(e)銀，其量在93.91至99.786wt.-%範圍內，及(f)0至100wt.-ppm之其他組分，其中所有以wt.-%及wt.-ppm為單位之量係基於該芯之總重量，其中該合金化銀線具有在8至80μm範圍內之平均直徑。An alloyed silver wire containing or consisting of a wire core, the wire core itself consisting of: (a) palladium in an amount ranging from 0.1 to 3 wt .-%, and (b) gold in an amount ranging from 0.1 to 3wt .-% range, (c) nickel, its amount is in the range of 20 to 700wt.-ppm, (d) calcium, its amount is in the range of 20 to 200wt.-ppm, (e) silver, its amount is 93.91 To 99.786 wt .-% range, and (f) 0 to 100 wt.-ppm of other components, wherein all amounts in wt .-% and wt.-ppm are based on the total weight of the core, where the The alloyed silver wire has an average diameter in the range of 8 to 80 μm. 如請求項1之合金化銀線，其具有在12至55μm範圍內之平均直徑。The alloyed silver wire according to claim 1, which has an average diameter in the range of 12 to 55 μm. 如請求項1之合金化銀線，其中該鈀量在0.5至1.5wt.-%範圍內。The alloyed silver wire of claim 1, wherein the amount of palladium is in the range of 0.5 to 1.5 wt .-%. 如請求項1之合金化銀線，其中該金量在0.2至1.5wt.-%範圍內。The alloyed silver wire of claim 1, wherein the amount of gold is in the range of 0.2 to 1.5 wt .-%. 如請求項1之合金化銀線，其中該鎳量在275至325wt.-ppm範圍內。The alloyed silver wire of claim 1, wherein the amount of nickel is in the range of 275 to 325 wt.-ppm. 如請求項1之合金化銀線，其中該鈣量在20至50wt.-ppm範圍內。The alloyed silver wire of claim 1, wherein the amount of calcium is in the range of 20 to 50 wt.-ppm. 如請求項1之合金化銀線，其中該銀量在96.9625至99.2595wt.-%範圍內。The alloyed silver wire of claim 1, wherein the amount of silver is in the range of 96.9625 to 99.2595 wt .-%. 如請求項1之合金化銀線，其在橫截面圖中具有圓形、橢圓形或矩形形狀。The alloyed silver wire according to claim 1, which has a circular, elliptical or rectangular shape in a cross-sectional view. 如請求項1之合金化銀線，其中該線芯具有表面，其中該表面為外表面或介於該線芯及疊加於該線芯上之塗層之間的界面區域。The alloyed silver wire of claim 1, wherein the wire core has a surface, wherein the surface is an outer surface or an interface area between the wire core and the coating layer superimposed on the wire core. 如請求項9之合金化銀線，其具有疊加於該線芯上之塗層，其中該塗層為由貴金屬元素製成之單層或包括多個疊加相鄰子層之多層，其中各子層由不同貴金屬元素製成。The alloyed silver wire according to claim 9, which has a coating superimposed on the core, wherein the coating is a single layer made of precious metal elements or a multilayer including a plurality of superimposed adjacent sub-layers, wherein each sub-layer The layers are made of different precious metal elements. 如請求項1之合金化銀線，其中該線芯至少特徵在於以下固有特性中之一者：(1)平均線粒度小於10μm，(2)線晶粒[100]或[101]或[111]定向平面小於7%，(3)線孿晶間界分數小於60%，(4)FAB呈現柱狀晶粒，(5)FAB平均粒度
Figure TWI649434B_C0001
18μm，(6)FAB晶粒[101]定向平面小於45%，(7)FAB孿晶間界分數小於70%，及/或至少特徵在於以下非固有特性中之一者：(α)抗腐蝕性具有不超過5%接合球上升之值，(β)抗濕性具有不超過5%接合球上升之值，(γ)該線芯之硬度不超過85HV，(δ)用於針腳式接合之製程窗區域具有至少12000mA．g之值，(ε)該線之電阻率小於2.5μΩ．cm，(ζ)該線之屈服強度不超過170MPa，(η)該線之銀樹突狀生長不超過4μm/s。The alloyed silver wire according to claim 1, wherein the wire core is characterized by at least one of the following inherent characteristics: (1) The average wire grain size is less than 10 μm, (2) The wire grains [100] or [101] or [111 ] Orientation plane is less than 7%, (3) Line twin boundary fraction is less than 60%, (4) FAB presents columnar grains, (5) FAB average particle size
Figure TWI649434B_C0001
18 μm, (6) FAB grain [101] orientation plane is less than 45%, (7) FAB twin boundary fraction is less than 70%, and / or is at least characterized by one of the following non-intrinsic characteristics: (α) corrosion resistance It has a value of no more than 5% rise of the bonding ball, (β) moisture resistance has a value of no more than 5% rise of the bonding ball, (γ) the hardness of the core does not exceed 85HV, (δ) is used for stitch bonding The process window area has at least 12000mA. The value of g, (ε) The resistivity of the line is less than 2.5μΩ. cm, (ζ) the yield strength of the line does not exceed 170MPa, (η) the silver dendritic growth of the line does not exceed 4μm / s. 一種用於製造如請求項1至11中任一項之合金化銀線的方法，其中該方法至少包含以下步驟：(1)提供具有如請求項1之線芯組成的前驅體物品，(2)伸長該前驅體物品以形成線前驅體，直至獲得該線芯之所要最終直徑；及(3)在完成方法步驟(2)後，在400至600℃範圍內之烘箱設定溫度下，對所獲得之線前驅體進行最終帶材退火達0.4至0.8秒範圍內之暴露時間以形成該合金化銀線，其中步驟(2)包括在400至800℃之烘箱設定溫度下，對該伸長前驅體物品進行中度分批退火達50至150分鐘範圍內之暴露時間的一或多個子步驟，及/或在400至800℃之烘箱設定溫度下，對該伸長前驅體物品進行中度帶材退火達0.4秒至1.2秒範圍內之暴露時間的一或多個子步驟。A method for manufacturing the alloyed silver wire according to any one of claims 1 to 11, wherein the method includes at least the following steps: (1) providing a precursor article having a core composition as in claim 1, (2 ) Elongate the precursor article to form a wire precursor until the desired final diameter of the wire core is obtained; and (3) after completing step (2) of the method, at an oven set temperature in the range of 400 to 600 The obtained wire precursor is subjected to final strip annealing for an exposure time in the range of 0.4 to 0.8 seconds to form the alloyed silver wire, wherein step (2) includes the elongated precursor at an oven set temperature of 400 to 800 ° C The article is subjected to one or more sub-steps of moderate batch annealing for an exposure time in the range of 50 to 150 minutes, and / or moderate strip annealing of the elongated precursor article at an oven set temperature of 400 to 800 ° C One or more substeps of exposure time in the range of 0.4 seconds to 1.2 seconds. 如請求項12之方法，其中在400至500℃範圍內之烘箱設定溫度下進行該最終帶材退火達0.5至0.7秒範圍內之暴露時間。The method of claim 12, wherein the final strip annealing is performed at an oven set temperature in the range of 400 to 500 ° C for an exposure time in the range of 0.5 to 0.7 seconds. 如請求項12之方法，其中在可含有一或多種添加劑之水中淬滅該經最終帶材退火之合金化銀線。The method of claim 12, wherein the final strip annealed alloyed silver wire is quenched in water that may contain one or more additives. 如請求項12之方法，其中在惰性或還原氛圍中進行方法步驟(2)之該中度退火以及方法步驟(3)之該最終帶材退火。The method of claim 12, wherein the intermediate annealing of method step (2) and the final strip annealing of method step (3) are performed in an inert or reducing atmosphere.
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