TWI587317B - Corrosion and moisture resistant bonding wire - Google Patents
Corrosion and moisture resistant bonding wire Download PDFInfo
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- TWI587317B TWI587317B TW104142565A TW104142565A TWI587317B TW I587317 B TWI587317 B TW I587317B TW 104142565 A TW104142565 A TW 104142565A TW 104142565 A TW104142565 A TW 104142565A TW I587317 B TWI587317 B TW I587317B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
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- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
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Description
本發明係關於一種包括銅芯、粗度為8μm至80μm之線,該銅芯包括:銅;鎳,其量處於自0.005wt.-%(重量-%、重量%)至5wt.-%之範圍中;及視情況,銀,其量處於自0.005wt.-%至1wt.-%之範圍中,其中以wt.-%計之所有量皆基於該芯之總重量;其中該銅芯具有處於自1.5μm至30μm之範圍中之平均晶粒大小。本發明進一步係關於一種用於製造此種線之程序。 The present invention relates to a wire comprising a copper core having a thickness of from 8 μm to 80 μm, the copper core comprising: copper; nickel in an amount of from 0.005 wt.-% (weight-%, weight%) to 5 wt.-% In the range; and optionally, the amount of silver is in the range from 0.005 wt.-% to 1 wt.-%, wherein all amounts in wt.-% are based on the total weight of the core; wherein the copper core has It is in the average grain size in the range from 1.5 μm to 30 μm. The invention further relates to a procedure for making such a line.
接合線在電子應用及微電子應用中之使用係所習知的目前技術現狀。儘管在開始接合線係由金製成,但當今使用較不昂貴之材料,諸如銅。儘管銅線提供非常良好之導電性及導熱性,但銅線接合仍具有挑戰。此外,銅線易於受到腐蝕及氧化。 The use of bonding wires in electronic applications and microelectronic applications is well known in the art. Although the bonding wire is made of gold at the beginning, less expensive materials such as copper are used today. Although copper wire provides very good electrical and thermal conductivity, copper wire bonding is still challenging. In addition, copper wires are susceptible to corrosion and oxidation.
就線幾何形狀而言,最常用者係具有圓形剖面之接合線及具有大致矩形剖面之接合帶。兩種類型之線幾何形狀皆具有使其可用於特定應用之優點。 In terms of line geometry, the most common are those having a circular cross section and a joint strip having a generally rectangular cross section. Both types of line geometry have the advantage of making them useful for a particular application.
某些最新研發涉及具有銅芯之接合線。作為芯材料,因高導電性而選擇銅。已尋找銅材料之不同摻雜劑以使接合性質最佳化。舉例而言,US 7,952,028 B2闡述若干具有大量不同摻雜劑及濃度之基於銅之不同測試線。 Some of the latest developments involve bonding wires with copper cores. As the core material, copper is selected for high conductivity. Different dopants of the copper material have been sought to optimize the bonding properties. For example, US 7,952,028 B2 describes several different copper-based test lines with a large number of different dopants and concentrations.
然而,就接合線本身及接合程序而言,持續需要進一步改良接合線技術。 However, in terms of the bonding wire itself and the bonding process, there is a continuing need to further improve the bonding wire technology.
因此,本發明之一目標係提供改良之接合線。 Accordingly, it is an object of the present invention to provide improved bonding wires.
本發明之另一目標係提供就針腳式接合而言展現極佳可接合性之接合線。 Another object of the present invention is to provide a bond wire that exhibits excellent bondability in terms of stitch bonding.
本發明之另一目標係提供具有改良之可靠性以及改良之耐腐蝕性及耐濕性之接合線。 Another object of the present invention is to provide a bond wire having improved reliability and improved corrosion resistance and moisture resistance.
本發明之另一目標係提供就球接合而言展現改良之可靠性及可接合性之接合線。 Another object of the present invention is to provide a bond wire that exhibits improved reliability and bondability in terms of ball bonding.
本發明之另一目標係提供就球楔接合而言展現改良之經接合球圓度及同心性之接合線。 Another object of the present invention is to provide a bond line that exhibits improved roundness and concentricity of the joined ball in terms of ball wedge engagement.
已發現本發明之線至少解決改良耐腐蝕性及耐濕性之目標。此外,已找到用於製造此等線之程序。 It has been found that the wire of the present invention addresses at least the goal of improving corrosion resistance and moisture resistance. In addition, procedures have been found for manufacturing such lines.
類別形成請求項之標的物促成了上述目標之解決方案。類別形成請求項之附屬子請求項代表本發明之較佳實施例,該等附屬子請求項之標的物亦促進解決上文所提及之目標。 The subject matter of the category forming request item contributes to the solution of the above objectives. The sub-claims of the category forming request represent representative embodiments of the present invention, and the subject matter of the sub-claims also facilitates solving the above-mentioned objectives.
本發明之第一態樣係一種包括芯之線,該芯包括以下各項或由以下各項組成(a)鎳,其量處於自0.005wt.-%至5wt.-%、較佳0.1wt.-%至0.6wt.-%或甚至0.45wt.-%至0.55wt.-%之範圍中,(b)視情況,銀,其量處於自0.005wt.-%至1wt.-%、較佳0.1wt.-%至0.6wt.-%或甚至0.45wt.-%至0.55wt.-%之範圍中,(c)銅,其量處於自94wt.-%至99.98wt.-%、較佳98.5wt.-%至99.6wt.-%或甚至99.4wt.-%至99.6wt.-%之範圍中,及(d)0wt.-ppm至100wt.-ppm(重量-ppm、重量ppm)之其他組分,其中以wt.-%及wt.-ppm計之所有量皆基於該芯之總重量,其中該芯具有處於自1.5μm至30μm之範圍中之平均晶粒大小,該平均大小係根據線截取方法而判定, 其中該線具有處於自8μm至80μm或甚至12μm至55μm之範圍中之平均直徑。 A first aspect of the invention is a wire comprising a core comprising or consisting of (a) nickel in an amount from 0.005 wt.-% to 5 wt.-%, preferably 0.1 wt. .-% to 0.6 wt.-% or even 0.45 wt.-% to 0.55 wt.-%, (b) as the case may be, silver, the amount is from 0.005 wt.-% to 1 wt.-%, Preferably, in the range of 0.1 wt.-% to 0.6 wt.-% or even 0.45 wt.-% to 0.55 wt.-%, (c) copper, in an amount ranging from 94 wt.-% to 99.98 wt.-%, Preferably in the range of 98.5 wt.-% to 99.6 wt.-% or even 99.4 wt.-% to 99.6 wt.-%, and (d) 0 wt.-ppm to 100 wt.-ppm (weight-ppm, weight ppm) The other components, wherein all amounts in wt.-% and wt.-ppm are based on the total weight of the core, wherein the core has an average grain size in the range from 1.5 μm to 30 μm, the average size Determined according to the line interception method, Wherein the line has an average diameter in the range from 8 μm to 80 μm or even 12 μm to 55 μm.
該線較佳係用於微電子裝置中之接合之接合線。該線較佳係一體式物件。已知且出現了眾多適用於本發明之線之形狀。在剖面圖中,較佳形狀係圓形、橢圓形及矩形形狀。 The wire is preferably used for bonding wires in a microelectronic device. The line is preferably an integral item. A wide variety of shapes suitable for use in the present invention are known and appear. In the cross-sectional view, the preferred shape is a circular shape, an elliptical shape, and a rectangular shape.
平均直徑係藉由「大小測定方法」來獲得。根據此種方法,判定所界定長度之線之實體重量。基於此重量,使用線材料之密度(銅之密度:ρCu=8.92g/cm3)來計算線之直徑。將平均直徑作為在五次切割特定線時所得之五個量測值之算術平均值來計算。 The average diameter is obtained by the "size measurement method". According to this method, the physical weight of the line of defined length is determined. Based on this weight, the diameter of the wire (the density of copper: ρ Cu = 8.92 g/cm 3 ) was used to calculate the diameter of the wire. The average diameter is calculated as the arithmetic mean of the five measurements obtained when five lines are cut.
對於本發明而言,術語「接合線」包括所有形狀之剖面及所有常用線直徑,但具有圓形剖面及細直徑之接合線係較佳的。 For the purposes of the present invention, the term "joining line" includes both the cross-section of all shapes and all common line diameters, but a bonding line having a circular cross-section and a fine diameter is preferred.
用於判定平均晶粒大小之線截取方法係標準金相實踐。此處,垂直於線的方向對線進行切割,且蝕刻由此產生之剖面。在本發明上下文中,晶粒之大小被界定為可通過晶粒之直線之所有剖面中之最長者。平均晶粒大小係芯/塊體材料中之至少七個晶粒量測值之算術平均值。測試係根據ASTM E112-96標準(第16.3章,第13頁)來執行。 The line intercept method used to determine the average grain size is a standard metallographic practice. Here, the line is cut perpendicular to the direction of the line, and the resulting profile is etched. In the context of the present invention, the size of the grains is defined as the longest of all profiles through the straight line of the grains. The average grain size is the arithmetic mean of at least seven grain measurements in the core/block material. The test was performed in accordance with ASTM E112-96 (Chapter 16.3, page 13).
如已提及,線芯包括(a)0.005wt.-%至5wt.-%之鎳及(c)94wt.-%至99.98wt.-%之銅。線芯可或可不包括組分(b),即銀。若線芯包括銀,則銀之量處於自0.005wt.-%至1wt.-%之範圍中。 As already mentioned, the core comprises (a) 0.005 wt.-% to 5 wt.-% nickel and (c) 94 wt.-% to 99.98 wt.-% copper. The core may or may not comprise component (b), ie silver. If the core comprises silver, the amount of silver is in the range from 0.005 wt.-% to 1 wt.-%.
本發明之線芯包括(d)0wt.-ppm至100wt.-ppm之其他組分。此等其他組分之低量確保線性質之良好再現性。在本發明上下文中,該等其他組分(常常亦稱作「不可避免的雜質」)係源自用於或來自線製造程序之原始材料中存在之雜質之微量化學元素及/或化合物。此等其他組分之實例係:Mn、Pt、Cr、Ca、Ce、Mg、La、Al、B、Zr、Ti、S、Fe。 The core of the present invention comprises (d) from 0 wt.-ppm to 100 wt.-ppm of other components. The low amount of these other components ensures good reproducibility of the nature of the wire. In the context of the present invention, these other components (often also referred to as "inevitable impurities") are derived from trace amounts of chemical elements and/or compounds present in or derived from the raw materials of the wire manufacturing process. Examples of such other components are: Mn, Pt, Cr, Ca, Ce, Mg, La, Al, B, Zr, Ti, S, Fe.
換言之,該芯包括以下各項或由以下各項組成 (a)鎳,其量處於自0.005wt.-%至5wt.-%、較佳0.1wt.-%至0.6wt.-%或甚至0.45wt.-%至0.55wt.-%之範圍中,(b)銀,其量處於自0.005wt.-%至1wt.-%、較佳0.1wt.-%至0.6wt.-%或甚至0.45wt.-%至0.55wt.-%之範圍中,(c)銅,其量處於自94wt.-%至99.98wt.-%、較佳98.5wt.-%至99.6wt.-%或甚至99.4wt.-%至99.6wt.-%之範圍中,及(d)0wt.-ppm至100wt.-ppm之其他組分,或(a)鎳,其量處於自0.005wt.-%至5wt.-%、較佳0.1wt.-%至0.6wt.-%或甚至0.45wt.-%至0.55wt.-%之範圍中,(b)無銀,(c)銅,其量處於自94wt.-%至99.98wt.-%、較佳98.5wt.-%至99.6wt.-%或甚至99.4wt.-%至99.6wt.-%之範圍中,及(d)0wt.-ppm至100wt.-ppm之其他組分,其中以wt.-%及wt.-ppm計之所有量皆基於芯之總重量。 In other words, the core comprises or consists of the following (a) nickel in an amount ranging from 0.005 wt.-% to 5 wt.-%, preferably 0.1 wt.-% to 0.6 wt.-% or even 0.45 wt.-% to 0.55 wt.-%, (b) silver in an amount ranging from 0.005 wt.-% to 1 wt.-%, preferably 0.1 wt.-% to 0.6 wt.-% or even 0.45 wt.-% to 0.55 wt.-%, (c) copper in an amount ranging from 94 wt.-% to 99.98 wt.-%, preferably 98.5 wt.-% to 99.6 wt.-% or even 99.4 wt.-% to 99.6 wt.-%, And (d) 0 wt.-ppm to 100 wt.-ppm of other components, or (a) nickel, the amount of which is from 0.005 wt.-% to 5 wt.-%, preferably 0.1 wt.-% to 0.6 wt. -% or even in the range of 0.45 wt.-% to 0.55 wt.-%, (b) no silver, (c) copper, the amount of which is from 94 wt.-% to 99.98 wt.-%, preferably 98.5 wt. -% to 99.6 wt.-% or even 99.4 wt.-% to 99.6 wt.-%, and (d) 0 wt.-ppm to 100 wt.-ppm of other components, wherein wt.-% and All amounts in wt.-ppm are based on the total weight of the core.
根據上述,本發明之實施例係一種包括以下各項之線:(a)鎳,(b)視情況,銀;及(c)銅,如上文所揭示。芯中存在之其他組分通常並非單獨地添加。其他組分之存在源自鎳、銀及銅中之一或多者中存在之雜質。 In accordance with the above, embodiments of the present invention are a line comprising: (a) nickel, (b) optionally, silver; and (c) copper, as disclosed above. Other components present in the core are typically not added separately. The presence of other components is derived from impurities present in one or more of nickel, silver and copper.
在一實施例中,本發明之線芯包括少於以下量之其他組分:(i)Mn,其<15wt.-ppm;(ii)Pt、Cr、Ca、Ce、Mg、La、Al、B、Zr、Ti中之任一者,其各自<2wt.-ppm;(iii)S、Fe中之任一者,其各自<10wt.-ppm。 In one embodiment, the core of the present invention comprises less than the following other components: (i) Mn, <15 wt.-ppm; (ii) Pt, Cr, Ca, Ce, Mg, La, Al, Any of B, Zr, and Ti, each of which is <2 wt.-ppm; (iii) any of S and Fe, each of which is <10 wt.-ppm.
形成芯之材料更佳滿足上述限值中之至少兩者,形成芯之材料最佳滿足所有限值。 Preferably, the material forming the core satisfies at least two of the above limits, and the material forming the core preferably satisfies all of the limits.
在一實施例中,線芯包括元素磷作為摻雜劑,基於芯之總重量,其量處於自40wt.-ppm至80wt.-ppm之範圍中。 In one embodiment, the core comprises elemental phosphorus as a dopant, the amount being in the range of from 40 wt.-ppm to 80 wt.-ppm, based on the total weight of the core.
在本發明上下文中,線芯被界定為塊體材料之同質區域。因任一塊體材料始終具有可在一定程度上展現不同性質之表面區域,故線芯之性質應理解為塊體材料之同質區域之性質。塊體材料區域之表面可在形態、組成(例如氧含量)及其他特徵方面有所不同。表面可係線芯之外表面。在替代方案中,其可係線芯與疊置於線芯上之塗層之間的界面區域。 In the context of the present invention, a core is defined as a homogeneous region of bulk material. Since any bulk material always has a surface area that exhibits different properties to some extent, the nature of the core is understood to be the nature of the homogeneous region of the bulk material. The surface of the bulk material region may vary in morphology, composition (e.g., oxygen content), and other characteristics. The surface can be attached to the outer surface of the core. In the alternative, it can tie the interfacial region between the core and the coating superimposed on the core.
在本發明之上下文中,術語「疊置」用於闡述第一物項(例如銅芯)相對於第二物項(例如塗層)之相對位置。「疊置」表徵,其他物項(例如中間層)可(但無需)配置於第一物項與第二物項之間。較佳地,關於第一物項之總表面,第二物項至少部分地疊置於第一物項上,例如至少30%、50%、70%或至少90%。最佳地,第二物項完全疊置於第一物項上。 In the context of the present invention, the term "overlay" is used to describe the relative position of a first item (e.g., a copper core) relative to a second item (e.g., a coating). "Overlay" characterization, other items (such as the middle layer) may be (but need not be) configured between the first item and the second item. Preferably, with respect to the total surface of the first item, the second item is at least partially superimposed on the first item, such as at least 30%, 50%, 70% or at least 90%. Optimally, the second item is completely superimposed on the first item.
在本發明之上下文中,術語「中間層」係指芯與塗層之間的線區域。在此區域中,存在芯及塗層兩者之材料之組合。 In the context of the present invention, the term "intermediate layer" refers to the area of the line between the core and the coating. In this region, 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」用於界定層在垂直於芯之縱軸之方向上之大小,該層至少部分地疊置於芯之表面上。 In the context of the present invention, the term "thickness" is used to define the size of the layer in a direction perpendicular to the longitudinal axis of the core, the layer being at least partially superposed on the surface of the core.
在一實施例中,芯直徑與平均晶粒大小之間的比率處於自2至14或甚至2至7之範圍中。 In one embodiment, the ratio between the core diameter and the average grain size is in the range from 2 to 14 or even 2 to 7.
在一實施例中,線之平均直徑處於自15μm至28μm之範圍中。在此情形中,芯中之平均晶粒大小較佳處於自1.5μm至6μm之範圍中。 In one embodiment, the average diameter of the wires is in the range of from 15 μm to 28 μm. In this case, the average grain size in the core is preferably in the range of from 1.5 μm to 6 μm.
在另一實施例中,線之平均直徑處於自>28μm至38μm之範圍中。在此情形中,芯中之平均晶粒大小較佳處於自2μm至10μm之範圍中。 In another embodiment, the average diameter of the wires is in the range from >28 [mu]m to 38 [mu]m. In this case, the average grain size in the core is preferably in the range of from 2 μm to 10 μm.
在另一實施例中,線之平均直徑處於自>38μm至50μm之範圍中。在此情形中,芯中之平均晶粒大小較佳處於自5μm至15μm之範圍中。 In another embodiment, the average diameter of the wires is in the range from >38 [mu]m to 50 [mu]m. In this case, the average grain size in the core is preferably in the range of from 5 μm to 15 μm.
在另一實施例中,芯之平均直徑處於自>50μm至80μm之範圍中。在此情形中,芯中之平均晶粒大小較佳處於自7μm至30μm之範圍中。 In another embodiment, the average diameter of the core is in the range from >50 [mu]m to 80 [mu]m. In this case, the average grain size in the core is preferably in the range of from 7 μm to 30 μm.
在一實施例中,芯具有表面,其中塗層疊置於芯之表面上。 In an embodiment, the core has a surface, wherein the coating is superposed on the surface of the core.
在一實施例中,相對於芯之總質量,塗層之質量不大於2.5wt.-%、較佳不大於2wt.-%或更小。當存在塗層時,相對於芯之總質量,其常常具有0.1wt.-%或更大或者0.5wt.-%或更大之最小質量。應用低量之材料作為塗層保存了由線芯之材料所界定之特性。另一方面,塗層為線表面賦予特定特性,諸如對環境呈惰性、耐腐蝕性、改良之可接合性等。舉例而言,對於平均直徑為18μm之線,塗層之厚度處於自60nm至70nm之範圍中。舉例而言,對於具有25μm之平均直徑之線,塗層可具有處於自90nm至100nm之範圍中之厚度。 In one embodiment, the mass of the coating is no greater than 2.5 wt.-%, preferably no greater than 2 wt.-% or less, relative to the total mass of the core. When a coating is present, it often has a minimum mass of 0.1 wt.-% or greater or 0.5 wt.-% or greater relative to the total mass of the core. The use of a low amount of material as a coating preserves the properties defined by the material of the core. On the other hand, the coating imparts specific characteristics to the surface of the wire, such as inertness to the environment, corrosion resistance, improved bondability, and the like. For example, for a line having an average diameter of 18 μm, the thickness of the coating is in the range from 60 nm to 70 nm. For example, for a line having an average diameter of 25 μm, the coating may have a thickness in the range from 90 nm to 100 nm.
在一實施例中,塗層係由選自由鈀、鉑及銀組成之群組之元素製成。該塗層可係該等元素中之一者之單層。在另一實施例中,該塗層可係若干個經疊置毗鄰層之多層,其中每一層係由選自由鈀、鉑及銀組成之群組之一種元素製成。作為塗層一部分之每一層係自上述純金屬元素中之一者個別地沈積。用於在芯上沈積此等元素之常見技術係鍍覆(諸如電鍍及無電極鍍覆)、自氣相沈積材料(諸如濺鍍、離子鍍覆、真空蒸鍍及物理氣相沈積)以及自熔體沈積材料。 In one embodiment, the coating is made of an element selected from the group consisting of palladium, platinum, and silver. The coating can be a single layer of one of the elements. In another embodiment, the coating can be a plurality of layers of overlapping adjacent layers, each layer being made of an element selected from the group consisting of palladium, platinum, and silver. Each layer that is part of the coating is deposited separately from one of the above pure metal elements. Common techniques for depositing such elements on a core are plating (such as electroplating and electroless plating), self-vapor deposition materials (such as sputtering, ion plating, vacuum evaporation, and physical vapor deposition) and Melt deposition material.
在一實施例中,另一塗層疊置於該塗層上。在一實施例中,各相對於芯之總質量,另一塗層之質量不大於0.2wt.-%、較佳不大於0.1wt.-%。 In one embodiment, another coating is superposed on the coating. In one embodiment, the mass of the other coating is no greater than 0.2 wt.-%, preferably no greater than 0.1 wt.-%, relative to the total mass of the core.
舉例而言,對於具有18μm之平均直徑之線,該另一塗層之厚度 處於自2nm至4nm之範圍中。舉例而言,對於具有25μm之平均直徑之線,該另一塗層可具有自3.5nm至5.5nm之厚度。 For example, for a line having an average diameter of 18 μm, the thickness of the other coating It is in the range from 2 nm to 4 nm. For example, for a line having an average diameter of 25 μm, the other coating may have a thickness from 3.5 nm to 5.5 nm.
在一實施例中,該另一塗層係金層。 In an embodiment, the other coating is a gold layer.
在一實施例中,本發明之線至少由以下特徵中之一者來表徵: In an embodiment, the line of the invention is characterized by at least one of the following features:
α)耐腐蝕性具有至多0%經接合球剝離之值;參見如下文所述之「測試方法G」。 α) Corrosion resistance has a value of at most 0% of the bonded ball peeling; see "Test Method G" as described below.
β)耐濕性具有至多0%經接合球剝離之值;參見如下文所述之「測試方法I」。 β) Moisture resistance has a value of at most 0% of the bonded ball peeling; see "Test Method I" as described below.
γ)線芯之硬度不大於120HV、較佳不大於115HV或不大於110HV;參見如下文所述之「測試方法J」。 The hardness of the γ) core is not more than 120 HV, preferably not more than 115 HV or not more than 110 HV; see "Test Method J" as described below.
δ)針腳式接合之程序窗面積具有至少40μm.g或至少90μm.g或至少120μm.g之值,每一值皆係在線具有18μm之平均直徑之前提下提供;參見如下文所述之章節「測試方法C」。 δ) The stitching of the program window area has a minimum of 40μm. g or at least 90μm. g or at least 120μm. The value of g, each value is provided before the line has an average diameter of 18 μm; see the section "Test Method C" as described below.
ε)線之電阻率不大於1.80μΩ.cm。 The resistivity of the ε) line is not more than 1.80μΩ. Cm.
ζ)平均經接合球圓度具有至多0.0025μm或至多0.002μm或至多0.0018μm之值,每一值皆係在線具有18μm之平均直徑之前提下提供;參見如下文所述之章節「測試方法E」。 ζ) The average bonded ball roundness has a value of at most 0.0025 μm or at most 0.002 μm or at most 0.0018 μm, each value being provided before the line has an average diameter of 18 μm; see the section "Test Method E" as described below "."
η)平均經接合球同心性具有至多0.00056μm或至多0.0005μm或至多0.0004μm之值,每一值皆係在線具有18μm之平均直徑之前提下提供;參見如下文所述之章節「測試方法E」。 η) The average joined ball concentricity has a value of at most 0.00056 μm or at most 0.0005 μm or at most 0.0004 μm, each value being provided before the line has an average diameter of 18 μm; see the section "Test Method E" as described below "."
本發明之第二態樣係一種用於製造上文所揭示實施例中之任一者中之線之程序。在其最一般實施例中,該程序至少包括以下程序步驟 A second aspect of the invention is a program for making a line in any of the above disclosed embodiments. In its most general embodiment, the program includes at least the following program steps
(1)提供前驅物項,其包括以下各項或由以下各項組成:(a)鎳,其量處於自0.005wt.-%至5wt.-%、較佳0.1wt.-%至0.6wt.-%或甚至0.45wt.-%至0.55wt.-%之範圍中, (b)視情況,銀,其量處於自0.005wt.-%至1wt.-%、較佳0.1wt.-%至0.6wt.-%或甚至0.45wt.-%至0.55wt.-%之範圍中,(c)銅,其量處於自94wt.-%至99.98wt.-%、較佳98.5wt.-%至99.6wt.-%或甚至99.4wt.-%至99.6wt.-%之範圍中,及(d)0wt.-ppm至100wt.-ppm之其他組分,其中以wt.-%及wt.-ppm計之所有量皆基於前驅物項之總重量,(2)將該前驅物項伸長以形成線前驅物,直至獲得線芯之所要直徑為止;以及(3)對在完成程序步驟(2)之後獲得之經伸長線前驅物進行退火。 (1) Providing a precursor item comprising or consisting of: (a) nickel in an amount of from 0.005 wt.-% to 5 wt.-%, preferably 0.1 wt.-% to 0.6 wt. .-% or even in the range of 0.45 wt.-% to 0.55 wt.-%, (b) optionally, the amount of silver is from 0.005 wt.-% to 1 wt.-%, preferably 0.1 wt.-% to 0.6 wt.-% or even 0.45 wt.-% to 0.55 wt.-% In the range, (c) copper, in an amount ranging from 94 wt.-% to 99.98 wt.-%, preferably 98.5 wt.-% to 99.6 wt.-% or even 99.4 wt.-% to 99.6 wt.-% And (d) 0 wt.-ppm to 100 wt.-ppm of other components, wherein all amounts in wt.-% and wt.-ppm are based on the total weight of the precursor item, (2) The precursor item is elongated to form a line precursor until the desired diameter of the core is obtained; and (3) the elongated line precursor obtained after completion of the procedure step (2) is annealed.
如在程序步驟(1)中所提供之前驅物項可係藉由用所要量之鎳及視情況銀對銅進行合金化及/或摻雜而獲得。藉由產生該等組分與銅之熔體並使該熔體冷卻以形成一塊基於銅之同質前驅物項來實現合金化及摻雜。通常,此種前驅物項係呈直徑例如為2mm至25mm且長度例如為5m至100m之桿之形式。此種桿可係藉由在具有室溫之適當模具中鑄造包括以下各項或由以下各項組成之銅合金熔體、後續接著進行冷卻及凝固來製成:(a)鎳,其量處於自0.005wt.-%至5wt.-%之範圍中,(b)視情況,銀,其量處於自0.005wt.-%至1wt.-%之範圍中,(c)銅,其量處於自94wt.-%至99.98wt.-%之範圍中,及(d)0wt.-ppm至100wt.-ppm之其他組分,其中以wt.-%及wt.-ppm計之所有量皆基於銅合金熔體之總重量。可藉由熟習金屬合金技術者已知的習用程序來製備銅合金本身,舉例而言,藉由將銅、鎳及視情況銀以所要比率熔化在一起。如此一來,可利用習用銅-鎳及銅-銀母合金。舉例而言,可利用感應爐來執行熔化程序,且在真空下或在惰性氣體氛圍下工作係有利的。所使用材料可具有例如99.99wt.-%及更高之純度級。 The precursor item as provided in step (1) of the procedure can be obtained by alloying and/or doping copper with a desired amount of nickel and optionally silver. Alloying and doping are achieved by creating a melt of the components and copper and cooling the melt to form a copper-based homogenous precursor term. Typically, such precursor items are in the form of rods having a diameter of, for example, 2 mm to 25 mm and a length of, for example, 5 m to 100 m. Such a rod may be made by casting a copper alloy melt comprising or consisting of the following in a suitable mold having room temperature, followed by cooling and solidification: (a) nickel in an amount From the range of 0.005 wt.-% to 5 wt.-%, (b) depending on the case, silver, the amount is in the range from 0.005 wt.-% to 1 wt.-%, (c) copper, the amount is in self Other components in the range of 94 wt.-% to 99.98 wt.-%, and (d) 0 wt.-ppm to 100 wt.-ppm, wherein all amounts in wt.-% and wt.-ppm are based on copper The total weight of the alloy melt. The copper alloy itself can be prepared by conventional procedures known to those skilled in the art of metal alloys, for example, by melting together copper, nickel, and optionally silver at a desired ratio. In this way, conventional copper-nickel and copper-silver master alloys can be utilized. For example, an induction furnace can be used to perform the melting procedure, and it is advantageous to operate under vacuum or under an inert gas atmosphere. The materials used may have a purity level of, for example, 99.99 wt.-% and higher.
若如針對本發明第一態樣之實施例中之某些實施例所揭示在線上存在一或多個塗層,則此等塗層較佳係施加至線前驅物。熟習此項 技術者知曉如何以針對線實施例所揭示之厚度(即,在將前驅物項與一或多個塗層一起伸長為線前驅物之後)來計算前驅物項上之此等塗層之厚度以獲得該等塗層。如上文已揭示,已知用於根據該等實施例在銅或銅合金表面上形成材料之塗層之眾多技術。較佳技術係鍍覆(諸如電鍍及無電極鍍覆)、呈氣相之材料之沈積(諸如濺鍍、離子鍍覆、真空蒸鍍及物理氣相沈積)以及熔融材料之沈積。 If one or more coatings are present on the wire as disclosed in certain embodiments of the first aspect of the invention, then such coatings are preferably applied to the wire precursor. Familiar with this item The skilled person knows how to calculate the thickness of such coatings on the precursor item by the thickness disclosed for the line embodiment (ie, after elongating the precursor item with one or more coatings into a line precursor). These coatings are obtained. As disclosed above, numerous techniques for forming coatings of materials on the surface of copper or copper alloys in accordance with such embodiments are known. Preferred techniques are plating (such as electroplating and electroless plating), deposition of materials in the vapor phase (such as sputtering, ion plating, vacuum evaporation, and physical vapor deposition) and deposition of molten materials.
如針對本發明第一態樣之實施例中之某些實施例所揭示,為給線芯疊置單層或多層金屬塗層,一旦達到處於例如80μm至200μm之範圍中之某一前驅物直徑,中斷程序步驟(2)即為有利的。然後,可例如藉由一或多個電鍍程序步驟來施加單層或多層金屬塗層。此後,繼續程序步驟(2),直至獲得線芯之所要及最終直徑。 As disclosed in certain embodiments of the first aspect of the invention, in order to stack a single or multiple layers of metal coating to the core, once a precursor diameter in the range of, for example, 80 μm to 200 μm is reached It is advantageous to interrupt the program step (2). The single or multiple layer metal coating can then be applied, for example, by one or more plating procedure steps. Thereafter, the program step (2) is continued until the desired and final diameter of the core is obtained.
在程序步驟(2)中,將前驅物項伸長以形成線前驅物,直至獲得線芯之所要直徑為止。已知用以將前驅物項伸長以形成線前驅物的眾多技術且其在本發明之上下文中顯現為有用的。較佳技術係軋延、型鍛、模拉等,其中模拉尤其較佳。在後一情形中,以數個程序步驟拉製前驅物項,直至達到線芯之所要及最終直徑為止。 In process step (2), the precursor item is elongated to form a line precursor until the desired diameter of the core is obtained. Numerous techniques are known for elongating precursor items to form line precursors and appear to be useful in the context of the present invention. The preferred technique is rolling, swaging, die drawing, etc., wherein die pulling is particularly preferred. In the latter case, the precursor item is drawn in several procedural steps until the desired and final diameter of the core is reached.
線芯之所要及最終直徑可處於自8μm至80μm之範圍中或較佳處於自12μm至55μm之範圍中。此種線模拉程序係熟習此項技術者眾所習知的。 The desired and final diameter of the core may be in the range of from 8 μm to 80 μm or preferably in the range of from 12 μm to 55 μm. Such wire drawing processes are well known to those skilled in the art.
可採用習用碳化鎢及金剛石拉模,且可採用習用拉製潤滑劑來支援拉製。舉例而言,可以8個主要階段來拉製前驅物項,且每一階段具有15至25個程序步驟,其中在每一拉製程序步驟中,執行將前驅物項之長度伸長自6%至18%之範圍。對於每一拉製程序步驟,伸長%可相同或不同。 Conventional tungsten carbide and diamond die can be used, and conventional drawn lubricant can be used to support drawing. For example, the precursor items can be drawn in 8 major stages, and each stage has 15 to 25 program steps, wherein in each drawing procedure step, the length of the precursor item is extended from 6% to 18% range. The elongation % may be the same or different for each drawing procedure step.
在程序步驟(3)中,較佳在管式爐中將在完成程序步驟(2)之後獲得之經伸長線前驅物退火。較佳,退火係股線退火(最終退火),其為 一種用於允許以高再現性快速生產線之連續程序。股線退火意指,在使線前驅物移動穿過較佳管式退火爐並在離開該爐之後纏繞於捲軸上之同時以動態方式進行退火。退火係在例如440℃至700℃之範圍中之目標溫度下執行達0.1秒至0.4秒,較佳在470℃至650℃之範圍中之目標溫度下執行達0.1秒至0.3秒;此等溫度/時間條件允許達成或調整線芯之所要平均晶粒大小。 In the process step (3), the elongated wire precursor obtained after the completion of the process step (2) is preferably annealed in a tube furnace. Preferably, the annealed strand is annealed (final annealing), which is A continuous program for allowing rapid production lines with high reproducibility. Strand annealing means that the wire precursor is annealed in a dynamic manner while moving through a preferred tube annealing furnace and wound onto a reel after exiting the furnace. The annealing is performed at a target temperature in the range of, for example, 440 ° C to 700 ° C for 0.1 second to 0.4 seconds, preferably at a target temperature in the range of 470 ° C to 650 ° C for 0.1 second to 0.3 seconds; The /time condition allows the average grain size of the core to be achieved or adjusted.
退火通常係藉由將經伸長線前驅物拉動穿過習用退火爐來執行,該退火爐通常呈具有給定長度之圓柱形管之形式且在給定退火速度下具有所界定溫度量變曲線,該給定退火速度可係在例如自4公尺/分鐘至30公尺/分鐘或自14公尺/分鐘至16公尺/分鐘之範圍中選擇。如此一來,可界定並設定退火時間/目標溫度參數。 Annealing is typically performed by pulling an elongated wire precursor through a conventional annealing furnace, typically in the form of a cylindrical tube of a given length and having a defined temperature profile at a given annealing speed. The given annealing speed can be selected, for example, from 4 meters/minute to 30 meters/minute or from 14 meters/minute to 16 meters/minute. In this way, the annealing time/target temperature parameter can be defined and set.
關於本發明之實施例,已發現,在低於最大伸長率溫度之溫度下進行之退火可產生有益線性質,乃因可以積極方式影響線形態。此外,已發現,將退火溫度選擇為高於最大伸長率溫度同時維持退火時間常數具有進一步優點。舉例而言,可使用此製造原理將線之平均晶粒大小調整至(例如)較大平均晶粒大小。藉由此調整,可以積極方式影響其他性質,例如線硬度、球接合行為等。 With respect to embodiments of the present invention, it has been discovered that annealing at temperatures below the maximum elongation temperature can produce beneficial line properties because the line morphology can be affected in a positive manner. Furthermore, it has been found that it is further advantageous to select the annealing temperature above the maximum elongation temperature while maintaining the annealing time constant. For example, this manufacturing principle can be used to adjust the average grain size of the line to, for example, a larger average grain size. By this adjustment, other properties such as line hardness, ball bonding behavior, and the like can be affected in a positive manner.
因此,在一實施例中,退火係在高於最大伸長率溫度之溫度下執行,其中線在退火之後之伸長率值不大於最大伸長率值之98%。舉例而言,程序步驟(3)可係在比最大伸長率溫度T△L(max)至少高10℃、較佳至少高50℃或至少高80℃之溫度下執行。通常,程序步驟(3)中之溫度比T△L(max)高不超過200℃。最大伸長率溫度T△L(max)係藉由測試試樣(線)在不同溫度下斷裂時之伸長率來判定。以曲線圖來收集資料點,其展示隨溫度(℃)而變之伸長率(%)。所得曲線圖通常稱為「退火曲線」。在基於銅之線之情形中,觀察伸長率(%)達到最大值時之溫度。此即為最大伸長率溫度T△L(max)。圖1中展示實例,其根據樣品3 (表1)展示以鎳合金化之18μm銅線之實例性退火曲線。退火溫度係x軸之變數參數。該曲線圖展示線之斷裂負荷(BL,克)及伸長率(EL,%)之所量測值。藉由拉伸測試來判定伸長率。在所顯示實例中,伸長率量測值展現約10%之典型局部最大值,此係在大約470℃之退火溫度下達成。若根據樣品3之線並非係在此最大伸長率溫度下而是在560℃(其比最大伸長率溫度高90℃)下退火,則結果係約9.8%之伸長率值,其比最大伸長率值低2%。 Thus, in one embodiment, the annealing is performed at a temperature above the maximum elongation temperature, wherein the elongation value of the wire after annealing is no greater than 98% of the maximum elongation value. For example, the program step (3) can be performed at a temperature at least 10 ° C higher than the maximum elongation temperature T ΔL (max) , preferably at least 50 ° C higher, or at least 80 ° C higher. Generally, the temperature in the procedure step (3) is not higher than T ΔL(max) by more than 200 °C. The maximum elongation temperature T ΔL(max) is determined by the elongation at break of the test sample (line) at different temperatures. Data points were collected in a graph showing the elongation (%) as a function of temperature (°C). The resulting graph is often referred to as the "annealing curve." In the case of a copper-based wire, the temperature at which the elongation (%) reaches the maximum value is observed. This is the maximum elongation temperature T ΔL(max) . An example is shown in Figure 1, which shows an exemplary annealing profile of a 18 [mu]m copper wire alloyed with nickel according to Sample 3 (Table 1). The annealing temperature is a variable parameter of the x-axis. The graph shows the measured values of the line breaking load (BL, gram) and elongation (EL, %). The elongation was judged by a tensile test. In the example shown, the elongation measurement exhibited a typical local maximum of about 10%, which was achieved at an annealing temperature of about 470 °C. If the line according to sample 3 is not annealed at this maximum elongation temperature but at 560 ° C (which is 90 ° C higher than the maximum elongation temperature), the result is an elongation value of about 9.8%, which is greater than the maximum elongation. The value is 2% lower.
該退火可係在惰性或還原氛圍中執行。眾多類型之惰性氛圍以及還原氛圍在此項技術中係已知的且用於清掃退火爐,該退火爐通常係管式退火爐。在已知惰性氛圍中,氮係較佳的。在已知還原氛圍中,氫係較佳的。另一較佳還原氛圍係氫氮混合物。較佳氫氮混合物係90vol.-%至98vol.-%氮及因此2vol.-%至10vol.-%氫,其中總vol.-%係100vol.-%。較佳氮/氫混合物等於93/7、95/5及97/3vol.-%/vol.-%,其各自係基於混合物之總體積。若線表面之某些部分易於被空氣中之氧進行氧化(例如,若線之銅被曝露於其表面),則在退火中應用還原氛圍係尤其較佳的。以該等類型之惰性氣體或還原氣體進行清掃較佳以處於43min-1至125min-1、更佳43min-1至75min-1、最佳50min-1至63min-1之範圍中之氣體交換速率(=氣體流率[升/分鐘]:內爐體積[升])執行。 The annealing 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 in sweeping annealing furnaces, which are typically tubular annealing furnaces. Nitrogen is preferred in known inert atmospheres. Hydrogen is preferred in known reducing atmospheres. Another preferred reducing atmosphere is a mixture of hydrogen and nitrogen. Preferably, the hydrogen-nitrogen mixture is from 90 vol.-% to 98 vol.-% nitrogen and thus from 2 vol.-% to 10 vol.-% hydrogen, wherein the total vol.-% is 100 vol.-%. Preferably, the nitrogen/hydrogen mixture is equal to 93/7, 95/5 and 97/3 vol.-%/vol.-%, each based on the total volume of the mixture. It is especially preferred to apply a reducing atmosphere during annealing if portions of the wire surface are susceptible to oxidation by oxygen in the air (e.g., if the copper of the wire is exposed to its surface). In such type of an inert gas or a reducing gas to be cleaned is preferred to 43min -1 125min -1, more preferably 43min -1 to 75min -1, the optimal range of 50min -1 to 63min -1 in the gas exchange rate (=Gas flow rate [L/min]: Inner furnace volume [L]) is executed.
據信,前驅物項材料之組成(其與成品線芯之組成相同)與在程序步驟(3)期間佔主導之程序參數之獨特組合對於獲得本發明之線係必不可少的。該等程序參數之一較佳組合係:目標溫度500℃至650℃,達0.1秒至0.3秒,較佳進一步結合使用90vol.-%至98vol.-%氮/2vol.-%至10vol.-%氫混合物作為清掃氣體,以處於50min-1至63min-1之範圍中之氣體交換速率。 It is believed that the unique combination of the composition of the precursor item material (which is identical to the composition of the finished core) and the program parameters prevailing during the procedure step (3) is essential to obtaining the line of the present invention. One of the program parameters is preferably a combination of a target temperature of 500 ° C to 650 ° C for 0.1 second to 0.3 seconds, preferably further combined with 90 vol.-% to 98 vol.-% nitrogen / 2 vol.-% to 10 vol.- % of hydrogen as a sweep gas mixture, the gas exchange rate to be in the range of 50min -1 to 63min -1 in the.
在完成程序步驟(3)之後,即完成本發明之線。為了充分地自其 性質獲益,將該線立即用於線接合應用(即,無延遲地,例如,在完成程序步驟(3)之後不超過7天內)係有利的。另一選擇為,為了保持線之寬線接合程序窗性質且為了防止其受氧化或其他化學侵蝕,通常在完成程序步驟(3)之後立即(即,無延遲地,例如,在完成程序步驟(3)之後<1小時至5小時內)將成品線進行纏繞及真空密封且隨後儲存以供進一步用作接合線。以真空密封條件進行儲存不應超過6個月。在開啟真空密封之後,線應在不超過7天內用於線接合。 After the completion of the procedure step (3), the line of the present invention is completed. In order to fully The nature benefits, and it is advantageous to use the line immediately for wire bonding applications (i.e., without delay, for example, no more than 7 days after the completion of program step (3)). Alternatively, in order to maintain the wide line of the wire in conjunction with the nature of the program window and to prevent it from being oxidized or otherwise chemically attacked, typically immediately after completion of program step (3) (ie, without delay, for example, at the completion of the program step ( 3) The finished wire is wound and vacuum sealed after <1 hour to 5 hours and then stored for further use as a bonding wire. Storage under vacuum tight conditions should not exceed 6 months. After the vacuum seal is turned on, the wire should be used for wire bonding for no more than 7 days.
較佳地,所有程序步驟(1)至(3)以及纏繞及真空密封係在潔淨室條件(US FED STD 209E潔淨室標準,1k標準)下執行。 Preferably, all of the process steps (1) through (3) and the winding and vacuum sealing are performed under clean room conditions (US FED STD 209E cleanroom standard, 1k standard).
本發明之第三態樣係一種可藉由根據本發明第二態樣或其實施例之程序而獲得之線。已發現,該線非常適合用作線接合應用中之接合線。線接合技術係熟習此項技術者所習知的。在線接合過程中,通常形成球接合(第一接合)及針腳式接合(第二接合,楔接合)。在接合形成期間,在所施加擦洗幅度(通常以μm為單位來量測)的支援下,施加一特定力(通常以克為單位來量測)。在線接合程序中所施加力之上限與下限間之差與所施加擦洗幅度之下限與下限間之差的算術乘積界定線接合程序窗:(所施加力之上限-所施加力之下限).(所施加擦洗幅度之上限-所施加擦洗幅度之下限)=線接合程序窗。 A third aspect of the invention is a line obtainable by a procedure according to the second aspect of the invention or its embodiment. This wire has been found to be very suitable for use as a bond wire in wire bonding applications. Wire bonding techniques are well known to those skilled in the art. During the wire bonding process, a ball joint (first joint) and a stitch joint (second joint, wedge joint) are usually formed. During the formation of the joint, a specific force (usually measured in grams) is applied with the aid of the applied scrubbing amplitude (usually measured in units of μm). The arithmetic product of the difference between the upper and lower limits of the applied force in the online bonding procedure and the difference between the lower and lower limits of the applied scrubbing amplitude defines the line bonding program window: (the upper limit of the applied force - the lower limit of the applied force). (Upper limit of applied scrubbing amplitude - lower limit of applied scrubbing amplitude) = wire bonding program window.
線接合程序窗界定允許形成滿足規範(即,通過習用測試如習用拉力測試、球剪力測試及球拉力測試,此處僅列出幾個)之線接合之力/擦洗幅度組合之面積。 The wire bond program window definition allows for the formation of areas of force/scouring amplitude combinations that meet the specifications (ie, by custom tests such as conventional tensile tests, ball shear tests, and ball pull tests, just to name a few).
對於工業應用,出於線接合程序穩健性之原因,期望具有寬線接合程序窗(以g為單位之力對以μm為單位之擦洗幅度)。本發明之線展現相當寬之線接合程序窗。舉例而言,對於針腳式接合,本發明直徑為18μm之線展現處於例如40μm至120μm之範圍中之線接合程序 窗。 For industrial applications, it is desirable to have a wide wire bond window (force in g versus scrub range in μm) for reasons of line bonding robustness. The wire of the present invention exhibits a relatively wide line of joint programming windows. For example, for stitch bonding, the line of 18 μm in diameter of the present invention exhibits a wire bonding procedure in the range of, for example, 40 μm to 120 μm. window.
以下非限制性實例說明本發明。 The following non-limiting examples illustrate the invention.
測試方法A.至J. Test method A. to J.
所有測試及量測皆係在T=20℃及相對濕度RH=50%下進行。 All tests and measurements were performed at T = 20 ° C and relative humidity RH = 50%.
A.藉由線截取方法得出平均晶粒大小: A. The average grain size is obtained by the line intercept method:
使用標準金相技術(ASTM E112-96,第16.3章,第13頁)來判定晶粒大小。對線芯之樣品進行剖切且然後進行蝕刻。在本發明情形中,使用2g FeCl3及6ml濃HCl在200ml去離子水中之溶液來進行蝕刻。根據線截取原理來判定晶粒大小。在本發明上下文中,晶粒之大小被界定為通過晶粒之直線之所有剖面中之最長者。所量測平均晶粒大小係芯材料中之晶粒之至少七個量測值之算術平均值。 The grain size was determined using standard metallographic techniques (ASTM E112-96, Chapter 16.3, page 13). The sample of the core is cut and then etched. In the case of the present invention, etching was carried out using a solution of 2 g of FeCl 3 and 6 ml of concentrated HCl in 200 ml of deionized water. The grain size is determined according to the line interception principle. In the context of the present invention, the size of the grains is defined as the longest of all profiles through the straight line of the grains. The measured average grain size is the arithmetic mean of at least seven measurements of the grains in the core material.
B.伸長率(EL): B. Elongation (EL):
使用Instron-5300儀器測試線之拉伸性質。以1英吋/分鐘速度在10英吋標距長度內對線進行測試。根據ASTM標準F219-96來獲取折斷(斷裂)時之負荷及伸長率。伸長率係線長度在拉伸測試之前及之後的差(△L/L),其係根據所記錄負荷對延伸拉伸曲線圖而計算出。 The tensile properties of the wire were tested using an Instron-5300 instrument. The line was tested at a speed of 1 inch per minute over a 10 inch gauge length. The load and elongation at break (break) were obtained according to ASTM standard F219-96. Elongation The difference between the length of the tether line before and after the tensile test (ΔL/L), which is calculated from the extended tensile profile based on the recorded load.
C.針腳式接合程序窗面積: C. Pin-type joint program window area:
藉由標準程序來進行對接合程序窗面積之量測。測試線係使用KNS-iConn接合器工具(庫力索法工業公司,華盛頓堡,美國賓夕法尼亞州(Kulicke & Soffa Industries Inc,Fort Washington,PA,USA))而接合。第二接合(針腳式接合)程序窗面積係在接合時所使用之力之上限與下限之差與所施加擦洗幅度之上限與下限之差的乘積,其中所得接合必須滿足某些拉力測試規範,例如2.5克之拉力、引線上無非黏處等。程序窗值係基於具有18μm之平均直徑之線,其中線被接合至的引線指由銀組成。 The measurement of the bonding program window area is performed by a standard procedure. The test lines were joined using a KNS-iConn adapter tool (Kulicke & Soffa Industries Inc, Fort Washington, PA, USA). The second joint (pin stitch) program 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 scrub range, wherein the resulting joint must meet certain tensile test specifications, For example, the pulling force of 2.5 grams, the non-stick on the lead, and the like. The program window value is based on a line having an average diameter of 18 μm, wherein the lead fingers to which the wires are bonded are composed of silver.
藉由克服以下兩種主要故障模式來導出程序窗之四個拐角:(1)供應太低力及擦洗幅度會導致線之引線上非黏處(NSOL),及(2)供應太高力及擦洗幅度會導致短尾(SHTL)。 The four corners of the program window are derived by overcoming the following two main failure modes: (1) supply too low force and scrubbing amplitude will result in non-stick on the wire lead (NSOL), and (2) supply too high force and The scrub level will result in a short tail (SHTL).
D.自由空氣球(FAB): D. Free Air Ball (FAB):
藉由以如下2種不同模式執行習用電火炬(EFO)點火來評估FAB:(a)標準點火-單個步驟,及(b)進階點火-兩個步驟,參見下表:
該表係根據自由空氣球KNS程序用戶指南(庫力索法工業公司,華盛頓堡,美國賓夕法尼亞州,2002,2009年5月31日)中所述之程序而得出。以μm標度使用光學顯微鏡在200X至500X放大率下來量測FAB直徑。使用掃描電子顯微鏡(SEM)來觀察FAB之形態。評估在針腳式接合之前懸掛於線端處之線材料熔融液滴之形狀及對稱性。 The table is based on the procedure described in the Free Air Ball KNS Program User Guide (Kursofarmer Industries, Fort Washington, Pennsylvania, USA, May 31, 2009). The FAB diameter was measured at a magnification of 200X to 500X using an optical microscope on a μm scale. Scanning electron microscopy (SEM) was used to observe the morphology of FAB. The shape and symmetry of the molten droplets of the wire material suspended at the wire ends prior to stitch bonding were evaluated.
對FAB構形之效能之評估: Assessment of the effectiveness of the FAB configuration:
+,線熔融液滴凝固,但球大小小於規範及/或係尖狀的 +, the line melt droplets solidify, but the ball size is smaller than the gauge and / or tip
++,線熔融液滴以球體形狀凝固,但球大小不符合規範及/或係傾斜的 ++, the wire melt droplets solidify in the shape of a sphere, but the size of the sphere does not conform to the specification and/or is inclined
+++,線熔融液滴以球體形狀且在規範之內凝固,但略微傾斜 +++, the wire melt droplets solidify in the shape of a sphere and within the specification, but slightly tilted
++++,線熔融液滴以球體及軸對稱球狀形狀凝固, ++++, the wire melt droplets solidify in a spherical and axisymmetric spherical shape.
E.平均經接合球圓度及同心性: E. Average joint ball roundness and concentricity:
藉由量測平均圓度及同心性來量化經接合球(第一接合)形態。使用標準點火模式或進階點火模式而對線進行接合。4N裸露的以銅及鎳合金化之銅線係使用標準點火模式而接合,而以銀-鎳合金化之銅線係使用進階點火模式而接合。 The joined sphere (first joint) morphology is quantified by measuring the average circularity and concentricity. The wires are joined using a standard ignition mode or an advanced ignition mode. The 4N bare copper and nickel alloyed copper wires are joined using a standard ignition mode, while the silver-nickel alloyed copper wires are joined using an advanced ignition mode.
在高倍率尼康顯微鏡MM40中以500X放大率來觀察經接合球。與顯微鏡互連之e-max軟體版本5.3針對16個所量測邊緣點藉由最小平方法來預測理論圓。求出每一邊緣與理論圓半徑之偏差。最大偏差值與最小偏差值之差被界定為DevE,即經接合球之平均圓度。圓度良好之球展示出0.001μm平均圓度且較差球展露0.003μm平均圓度。 The conjugated spheres were observed at a magnification of 500X in a high magnification Nikon microscope MM40. The e-max software version 5.3 interconnected with the microscope predicts the theoretical circle by the least squares method for the 16 measured edge points. Find the deviation of each edge from the theoretical circle radius. The difference between the maximum deviation value and the minimum deviation value is defined as DevE, which is the average circularity of the joined balls. Balls with good roundness exhibited an average circularity of 0.001 μm and a poorer spherical exhibiting an average circularity of 0.003 μm.
在平均經接合球同心性之情形中,沿著外圓標記12個邊緣。e-max軟體藉由最小平方法來預測理論圓且求出外圓之中心。類似地,其預測內圓及其中心。計算外圓與內圓在X方向及Y方向兩者上之中 心差,根據此中心差按照來計算同心性。同心性良好之經接合球展示出0.0001μm,且最差球展露出0.0009μm。 In the case of an average joined ball concentricity, 12 edges are marked along the outer circle. The e-max software predicts the theoretical circle by the least squares method and finds the center of the outer circle. Similarly, it predicts the inner circle and its center. Calculate the center difference between the outer circle and the inner circle in both the X direction and the Y direction, according to which the center difference is To calculate concentricity. The bonded balls with good concentricity exhibited 0.0001 μm, and the worst shot exhibited 0.0009 μm.
F.對連續鑄造桿之鹽溶液浸泡測試: F. Soaking test for salt solution of continuous casting rod:
分出長度為10mm之連續鑄造8mm桿並在85℃下將其浸泡於鹽溶液中達4天,使用DI水沖洗且稍後用丙酮沖洗。該鹽溶液含有溶於去離子(DI)水中之20wt.-%NaCl。在較低倍率鏡(立體鏡-SZX16)下以10X至100X放大率觀察該等桿之表面變色。自原始銅紅色變換至暗黑色之桿表面表明若干處縫隙腐蝕。對暗黑色表面進行之SEM-EDX展露氯峰、氧峰及銅峰。 A continuously cast 8 mm rod of length 10 mm was dispensed and immersed in a salt solution for 4 days at 85 ° C, rinsed with DI water and later rinsed with acetone. The salt solution contained 20 wt.-% NaCl dissolved in deionized (DI) water. The surface discoloration of the rods was observed at a magnification of 10X to 100X under a low magnification mirror (stereoscopic-SZX16). The transition from the original copper red to the dark black rod surface indicates corrosion at several locations. The SEM-EDX on the dark black surface reveals the peaks of chlorine, oxygen and copper.
評估: Evaluation:
+,100%鑄造桿表面自原始銅紅色變換至暗黑色,表明若干處縫隙腐蝕 +, 100% of the cast rod surface changed from the original copper red to dark black, indicating a number of crevice corrosion
++,<70%鑄造桿表面自原始銅紅色變換至黑色,表明縫隙腐蝕 ++, <70% cast rod surface changed from original copper red to black, indicating crevice corrosion
+++,<40%鑄造桿表面自原始銅紅色變換至黑色,表明輕微縫隙腐蝕 +++, <40% cast rod surface changed from original copper red to black, indicating slight crevice corrosion
++++,<10%鑄造桿表面自原始銅紅色變換至暗黑色,表明縫隙腐蝕較不顯著或不存在 ++++, <10% cast rod surface changed from original copper red to dark black, indicating that crevice corrosion is less significant or non-existent
G.對經接合球之鹽溶液浸泡測試: G. Soaking test on the salt solution of the bonded ball:
將線球接合至Al-0.5wt.-%Cu接合墊。將帶有如此接合之線之測試裝置在25℃下浸泡於鹽溶液中達2、4、6、8及10分鐘,用DI水沖洗且稍後用丙酮沖洗。該鹽溶液含有溶於去離子(DI)水中之30wt.-ppm NaCl。在較低倍率鏡(立體鏡-SZX16)下以10X至100X放大率檢查經剝離球之數目。觀察到較高數目個經剝離球表明若干處界面電化腐蝕。 The ball was bonded to an Al-0.5 wt.-% Cu bond pad. The test device with the wire thus joined was immersed in the salt solution at 25 ° C for 2, 4, 6, 8 and 10 minutes, rinsed with DI water and later rinsed with acetone. The salt solution contained 30 wt.-ppm NaCl dissolved in deionized (DI) water. The number of peeled balls was examined at a magnification of 10X to 100X under a lower magnification mirror (stereoscopic mirror-SZX16). A higher number of peeled balls were observed to indicate some interface galvanic corrosion.
H.對連續鑄造桿之耐濕性測試: H. Test for moisture resistance of continuous casting rods:
分出長度為10mm之連續鑄造8mm桿並將其在130℃溫度、85%相對濕度(RH)下儲存於高度加速之應力測試(HAST)室中達4天。在低倍率鏡(立體鏡-SZX16)下以10X至100X放大率檢查經HAST測試樣品以查看表面變色。類似於鹽溶液浸泡測試,自原始銅紅色變換至暗黑色之桿表面表明若干處縫隙腐蝕。對暗黑色表面進行之SEM-EDX展露氧峰及銅峰。 A continuously cast 8 mm rod of 10 mm length was dispensed and stored in a highly accelerated stress test (HAST) chamber at 130 ° C temperature, 85% relative humidity (RH) for 4 days. The HAST test samples were examined at a magnification of 10X to 100X under a low magnification mirror (stereoscopic-SZX16) to see surface discoloration. Similar to the salt solution soak test, the change from the original copper red to the dark black rod surface indicates corrosion at several locations. The SEM-EDX on the dark black surface reveals oxygen peaks and copper peaks.
評估: Evaluation:
+,100%鑄造桿表面自原始銅紅色變換至暗黑色,表明若干處縫隙腐蝕 +, 100% of the cast rod surface changed from the original copper red to dark black, indicating a number of crevice corrosion
++,<70%鑄造桿表面自原始銅紅色變換至黑色,表明縫隙腐蝕 ++, <70% cast rod surface changed from original copper red to black, indicating crevice corrosion
+++,<40%鑄造桿表面自原始銅紅色變換至黑色,表明輕微縫隙腐蝕 +++, <40% cast rod surface changed from original copper red to black, indicating slight crevice corrosion
++++,<10%鑄造桿表面自原始銅紅色變換至暗黑色,表明縫隙腐蝕較不顯著或不存在 ++++, <10% cast rod surface changed from original copper red to dark black, indicating that crevice corrosion is less significant or non-existent
I.對經接合球之耐濕性測試: I. Test for moisture resistance of bonded balls:
將線球接合至Al-0.5wt.-%Cu接合墊。將帶有如此接合之線之測試裝置在130℃溫度、85%相對濕度(RH)下儲存於高度加速之應力測試(HAST)室中達20小時,且稍後在較低倍率鏡(立體鏡-SZX16)下以10X至100X放大率檢查經剝離球之數目。觀察到較高數目個經剝離球表明若干處界面電化腐蝕。 The ball was bonded to an Al-0.5 wt.-% Cu bond pad. The test device with such a bonded wire was stored in a highly accelerated stress test (HAST) chamber at 130 ° C temperature, 85% relative humidity (RH) for 20 hours, and later at a lower magnification mirror (stereoscopic mirror) -SZX16) The number of peeled balls is checked at a magnification of 10X to 100X. A higher number of peeled balls were observed to indicate some interface galvanic corrosion.
J.維氏硬度: J. Vickers hardness:
使用具有維氏壓頭(Vickers indenter)之費氏(Fischer)鏡H110C測試設備來量測硬度。對測試線試樣施加10mN之力達5s之停留時間。該測試係對經退火線芯之中心執行。 The hardness was measured using a Fischer mirror H110C test apparatus with a Vickers indenter. A force of 10 mN was applied to the test line sample for a residence time of 5 s. This test is performed on the center of the annealed core.
實例1-10 Example 1-10
將一定量之至少99.99%純度之銅材料(「4N銅」)在坩堝中熔化。將少量母合金添加至銅熔體並藉由攪拌來確定所添加組分之均勻分佈。使用以下母合金。 A certain amount of at least 99.99% pure copper material ("4N copper") is melted in the crucible. A small amount of the master alloy is added to the copper melt and the uniform distribution of the added components is determined by stirring. The following master alloys were used.
對於表1及表2之合金,添加母合金Cu-5wt.-%Ni、Cu-15wt.-%Ag及Cu-0.5wt.-%P之對應組合。然後,自熔體連續鑄造呈8mm桿形式之線前驅物。 For the alloys of Tables 1 and 2, a corresponding combination of the parent alloys Cu-5wt.-%Ni, Cu-15wt.-%Ag, and Cu-0.5wt.-%P was added. Then, a wire precursor in the form of a rod of 8 mm was continuously cast from the melt.
以6個主要拉製階段(每一階段中具有22個程序步驟)拉製該等8mm桿,以形成圓形形狀且平均直徑為18μm之線,其中在每一程序步驟中對前驅物執行自6%至18%之長度伸長。在本文中所呈現之實例中,針對階段1實踐17%伸長,針對階段2至階段5實踐11%伸長,且針對階段6實踐8%伸長。在拉製期間採用增滑劑。 The 8 mm rods were drawn in 6 main draw stages (22 program steps in each stage) to form a line of circular shape with an average diameter of 18 μm, wherein the precursors were self-executed in each of the program steps. 6% to 18% of the length is elongated. In the examples presented herein, 17% elongation was practiced for stage 1, 11% elongation was practiced for stage 2 to stage 5, and 8% elongation was practiced for stage 6. A slip agent is used during drawing.
藉助於此種程序,製造銅-鎳及銅-鎳-銀合金線及一個比較性線線(Ref)之樣品。 By means of this procedure, samples of copper-nickel and copper-nickel-silver alloy wires and a comparative wire (Ref) were produced.
使用Perkin Elmer ICP-OES 7100DV型號藉由ICP(電感耦合電漿)分析來控制銅、銅-鎳及銅-鎳-銀合金線之化學組成。將線溶於濃硝酸中且將溶液用於ICP分析。 The chemical composition of copper, copper-nickel and copper-nickel-silver alloy wires was controlled by ICP (inductively coupled plasma) analysis using a Perkin Elmer ICP-OES 7100DV model. The line was dissolved in concentrated nitric acid and the solution was used for ICP analysis.
表1展示平均直徑為18μm之發明性銅-鎳合金線之樣品1至6之組 成。線之鎳含量如所指示的那樣而變化,磷之量亦如所指示的那樣變化。比較性線(Ref)由4N銅組成。 Table 1 shows groups 1 to 6 of the inventive copper-nickel alloy wire having an average diameter of 18 μm. to make. The nickel content of the line changes as indicated, and the amount of phosphorus also changes as indicated. The comparative line (Ref) consists of 4N copper.
表2展示各自具有18μm平均直徑之樣品線7至10之組成。該等線之銀、鎳及磷含量如所指示的那樣而變化。比較性線(Ref)由4N銅組成。 Table 2 shows the composition of sample lines 7 to 10 each having an average diameter of 18 μm. The silver, nickel and phosphorus contents of the lines vary as indicated. The comparative line (Ref) consists of 4N copper.
該等線係在最終退火程序步驟中被退火。該退火係藉由使該等線以1m/s之速度通過長度為30cm且退火溫度為560℃(線1-6)或650℃(線7-10)之管式退火爐而作為股線退火被動態地執行。在離開該爐之後,將該等線纏繞於捲軸上以供封裝。 The wires are annealed in the final annealing step. The annealing is performed as a strand annealing by passing the wires at a speed of 1 m/s through a tube annealing furnace having a length of 30 cm and an annealing temperature of 560 ° C (line 1-6) or 650 ° C (line 7-10). It is executed dynamically. After exiting the furnace, the wires are wound onto a reel for packaging.
在本發明實例中,退火時間係一段給定移動線在經加熱爐內之 曝露時間,其為0.3s。在爐區內,調整恆定溫度。 In the example of the present invention, the annealing time is a given moving line in the heating furnace Exposure time, which is 0.3 s. In the furnace zone, adjust the constant temperature.
量測線樣品1至10之平均晶粒大小。對於樣品1至6,結果處於3μm至6μm之範圍中,且對於樣品7至10,結果處於1.5μm至6μm之範圍中。 The average grain size of the sample 1 to 10 was measured. For samples 1 to 6, the results were in the range of 3 μm to 6 μm, and for samples 7 to 10, the results were in the range of 1.5 μm to 6 μm.
下表3展示以樣品1至6之8mm桿及經接合線獲得之測試結果。 Table 3 below shows the test results obtained with the 8 mm rods of Samples 1 through 6 and the bonded wires.
以下表4展示以8mm桿及樣品7至10之經接合線獲得之測試結果。 Table 4 below shows the test results obtained with the 8 mm rod and the bonded wires of samples 7 to 10.
線1-6及7-10產生非常適合於工業應用之程序窗。至少對於處於0.5wt.-%至5wt.-%之範圍中之鎳含量或對於處於0.1wt.-%至0.5wt.-%之範圍中之銀與處於0.1wt.-%至0.5wt.-%之範圍中之鎳之組合,可觀察到所鑄造桿及經接合球之耐腐蝕性及耐濕性之顯著改良。 Lines 1-6 and 7-10 produce a program window that is well suited for industrial applications. At least for the nickel content in the range of 0.5 wt.-% to 5 wt.-% or for the silver in the range of 0.1 wt.-% to 0.5 wt.-% and between 0.1 wt.-% and 0.5 wt.- A significant improvement in the corrosion resistance and moisture resistance of the cast rod and the joined ball can be observed in the combination of nickel in the range of %.
圖1係展示根據樣品3(表1)之鎳合金化之18μm銅線的實例性退火曲線。 Figure 1 is a graph showing an exemplary annealing curve for a nickel alloyed 18 μm copper wire according to Sample 3 (Table 1).
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TW202138572A (en) | 2020-02-21 | 2021-10-16 | 日商日鐵新材料股份有限公司 | Copper bonding wire |
CN115836384B (en) | 2021-06-25 | 2024-06-11 | 日铁新材料股份有限公司 | Bonding wire for semiconductor device |
JPWO2022270077A1 (en) | 2021-06-25 | 2022-12-29 | ||
KR20240026929A (en) | 2021-06-25 | 2024-02-29 | 닛데쓰마이크로메탈가부시키가이샤 | Bonding wire for semiconductor devices |
JP7157279B1 (en) | 2021-06-25 | 2022-10-19 | 日鉄マイクロメタル株式会社 | Bonding wire for semiconductor equipment |
KR20240026927A (en) | 2021-06-25 | 2024-02-29 | 닛데쓰마이크로메탈가부시키가이샤 | Bonding wire for semiconductor devices |
WO2022270050A1 (en) | 2021-06-25 | 2022-12-29 | 日鉄マイクロメタル株式会社 | Bonding wire for semiconductor devices |
WO2023248491A1 (en) | 2022-06-24 | 2023-12-28 | 日鉄ケミカル&マテリアル株式会社 | Bonding wire for semiconductor device |
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