TWI521070B - Noble metal thin silver alloy wire for ball bonding - Google Patents

Noble metal thin silver alloy wire for ball bonding Download PDF

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Publication number
TWI521070B
TWI521070B TW103111911A TW103111911A TWI521070B TW I521070 B TWI521070 B TW I521070B TW 103111911 A TW103111911 A TW 103111911A TW 103111911 A TW103111911 A TW 103111911A TW I521070 B TWI521070 B TW I521070B
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Taiwan
Prior art keywords
silver alloy
noble metal
wire
bonding
metal silver
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TW103111911A
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Chinese (zh)
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TW201446980A (en
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安原和彥
安徳優希
陳煒
前田菜那子
千葉淳
岡崎純一
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田中電子工業股份有限公司
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Publication of TW201446980A publication Critical patent/TW201446980A/en
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Publication of TWI521070B publication Critical patent/TWI521070B/en

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  • Engineering & Computer Science (AREA)
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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Wire Bonding (AREA)

Description

球焊用貴金屬薄銀合金絲 Precious metal thin silver alloy wire for ball bonding

本發明涉及適用於半導體裝置中使用的IC晶片電極與外部引線等電路板連接的鍵合用貴金屬銀合金絲，特別是指第二次鍵合性優良的球焊用貴金屬銀合金絲。 The present invention relates to a noble metal silver alloy wire for bonding which is used for connecting an IC chip electrode used in a semiconductor device to a circuit board such as an external lead, and particularly to a noble metal silver alloy wire for ball bonding excellent in second bonding property.

一直以來，作為連接半導體裝置的IC晶片電極與外部引線的球焊鍵合絲，因連接可靠性優良而大量使用在質量百分比純度99.99%以上的金(Au)中只添加了不到100質量比ppm其他金屬元素的純金絲。這種純金絲在其一端形成熔球後，通過熱壓超聲波鍵合法被連接至IC晶片電極上的鋁焊盤，另一端被連接至印刷電路板、引線框架及器件等外部引線等。然後，連接好的純金絲被模製樹脂(molded resin)密封，形成半導體裝置。此外，鋁焊盤由純鋁(Al)、Al-1%Si(質量百分比)合金、Al-0.5%Cu(質量百分比)合金、Al-1%Si(質量百分比)-0.5%Cu(質量百分比)合金等構成，一般採用真空蒸鍍等乾式塗佈成形。 Conventionally, as a ball bond wire for connecting an IC wafer electrode and an external lead of a semiconductor device, a large amount of gold (Au) having a mass percent purity of 99.99% or more is added in an amount of less than 100 by mass because of excellent connection reliability. Pure gold wire of other metal elements. After forming a molten ball at one end, the pure gold wire is connected to the aluminum pad on the IC chip electrode by hot pressing ultrasonic bonding, and the other end is connected to an external lead such as a printed circuit board, a lead frame, and a device. Then, the joined pure gold wire is sealed with a molded resin to form a semiconductor device. In addition, the aluminum pad is made of pure aluminum (Al), Al-1% Si (mass percent) alloy, Al-0.5% Cu (mass percent) alloy, Al-1% Si (mass percent) - 0.5% Cu (mass percentage) The alloy or the like is generally formed by dry coating such as vacuum vapor deposition.

銀合金來代替這種純金絲在很早以前就一直被考慮使用。例如，特開2012-99577號公報(後述的“專利文獻1”)中披露了“特徵為以銀(Ag)為主要成分；至少含有一種以上從10000~90000質量比ppm的金(Au)、10000~50000質量比ppm的鈀(Pd)、10000~30000質量比ppm的銅(Cu)、10000~20000質量比ppm的鎳(Ni)中選出的成分；且氯(Cl)含量不到1質量比ppm的鍵合絲”的發明。該發明“旨在廉價提供鍵合絲表面不施加金屬塗層、波長380 ~560nm處的光反射率高、提高了化學穩定性的鍵合絲，從而提高發光裝置的光特性(該公報0008段落)”。 Silver alloys have been used in place of this pure gold wire for a long time. For example, JP-A-2012-99577 (hereinafter referred to as "Patent Document 1") discloses "characterized by using silver (Ag) as a main component; and containing at least one kind of gold (Au) in a mass ratio of 10,000 to 90,000 ppm by weight, 10,000 to 50,000 mass ppm of palladium (Pd), 10,000 to 30,000 mass ppm of copper (Cu), 10,000 to 20,000 mass ppm of nickel (Ni) selected components; and chlorine (Cl) content of less than 1 mass Invention of bonding wire than ppm. The invention "is intended to provide a bond wire surface at a low cost without applying a metal coating, wavelength 380 The light reflectance at ~560 nm is high, and the chemically stable bond wire is improved, thereby improving the light characteristics of the light-emitting device (paragraph 0008 of this publication).

與純銀鍵合絲相比，該銀合金絲因鈀(Pd)等的耐氯性、耐硫性的相互作用，在氯(Cl)、硫(S)等大氣及特殊環境下的污染均比純銀絲大致有了改善。但是，與純金絲相比，合金成分的貴金屬含量為6%以下的所謂貴金屬銀合金絲依然存在鍵合絲表面易髒、硫化程度易加深的缺點。因此，也存在如下缺點：即使是在使用鍵合絲的一般潔淨室內，如果將貴金屬銀合金絲放置30天左右，鍵合絲表面就會因從室外氣體引入的空氣中存在的硫(S)而形成硫化銀(Ag2S)，該硫化銀(Ag2S)會妨礙良好的第二次鍵合，降低採用超聲波時與外部引線的鍵合强度。 Compared with the pure silver bonded wire, the silver alloy wire is contaminated by chlorine (Cl), sulfur (S) and other atmospheric and special environments due to the interaction of chlorine resistance and sulfur resistance of palladium (Pd) or the like. The sterling silver wire has generally improved. However, compared with pure gold wire, the so-called noble metal silver alloy wire having a precious metal content of 6% or less of the alloy component has a drawback that the surface of the bonding wire is easily soiled and the degree of vulcanization is easily deepened. Therefore, there is also a disadvantage that even in a general clean room using a bonding wire, if the noble metal silver alloy wire is left for about 30 days, the surface of the bonding wire is due to sulfur (S) present in the air introduced from the outdoor gas. The formation of silver sulfide (Ag2S), which hinders a good second bond, reduces the bonding strength with external leads when ultrasonic waves are used.

另一方面，為了提高與鍵合工具間的滑動已知的還有“以Au、Al、Cu中的任意一種為主要元素，拉絲加工成10~50μm左右的極細絲，在線軸上捲繞規定長度，並以這種狀態安裝在鍵合機上使用(特開平6-151497號公報(後述的“專利文獻2”)0002段落)”的鍵合絲，和熔鑄後對鑄塊進行酸洗等“特徵為表面的總有機碳量為50~1500μg/m2的半導體器件鍵合絲(該公報請求項1)”。關於該方法，記載如下：“經一般製程，即溶解、鑄造、拉絲、退火、捲繞製程所製造的鍵合絲表面已可發現超過1500μg/m2的總有機碳量，因此，製造表面總有機碳量為50~1500μg/m2的鍵合絲的方法之一就是採用…酸洗…等方法對其進行沖洗，使表面總有機碳量在50~1500μg/m2範圍內(請求項2)。該方法的特徵在於，於一般製程的退火製程前或後適當提供沖洗製程，容易實施。(該公報0010段落)”，而且，“潤滑劑成分有石蠟烴、環烷烴、芳烴等礦物油類；聚烯烴、烷基苯、脂肪酸、高級醇、脂肪酸皂、聚乙二醇、聚苯醚、脂肪酸二酯、多元醇酯、聚氧乙烯烷基醚、磺酸鹽、胺、胺鹽、矽酮、磷酸酯、碳氟化合物、氟聚醚、氟乙二醇等合成 油類；牛油、猪油、棕櫚油、豆油、菜油、蓖麻油、松油等天然油脂類，可以使用任何一種。此外，也可以使用上述多種成分的混合(該公報0012段落)”。 On the other hand, in order to improve the sliding between the bonding tool and the bonding tool, it is known that "the main element is made of any of Au, Al, and Cu, and the wire is processed into a filament of about 10 to 50 μm. In this state, the bonding wire is attached to the bonding machine in the state of the bonding machine (Japanese Patent Laid-Open No. Hei 6-151497 (hereinafter referred to as "Patent Document 2") 0002), and the ingot is pickled after casting. "Semiconductor device bonding wire characterized by a total organic carbon amount of the surface of 50 to 1500 μg/m 2 (Request No. 1 of the publication)". Regarding the method, it is described as follows: "The total organic carbon amount exceeding 1500 μg/m 2 has been found on the surface of the bonding wire produced by the general process, that is, dissolution, casting, drawing, annealing, and winding processes, and therefore, the total surface area is manufactured. One of the methods for bonding wires having an organic carbon amount of 50 to 1500 μg/m 2 is to wash them by a method such as pickling, so that the total organic carbon content in the surface is in the range of 50 to 1500 μg/m 2 (request 2). The method is characterized in that the rinsing process is appropriately provided before or after the annealing process of the general process, which is easy to implement (paragraph 0010 of the publication), and "the lubricant component is a mineral oil such as paraffin hydrocarbon, naphthene or aromatic hydrocarbon. Polyolefin, alkylbenzene, fatty acid, higher alcohol, fatty acid soap, polyethylene glycol, polyphenylene ether, fatty acid diester, polyol ester, polyoxyethylene alkyl ether, sulfonate, amine, amine salt, hydrazine Synthetic oils such as ketones, phosphates, fluorocarbons, fluoropolyethers, and fluoroethylene glycols; and natural fats and oils such as tallow, lard, palm oil, soybean oil, vegetable oil, castor oil, and pine oil can be used. In addition, you can also use the above Min mixing (paragraph 0012 of the Publication). "

但是，該有機碳是作為潤滑劑成分使用，並非以隔離大氣中的硫(S)成分為目的。儘管本發明之貴金屬銀合金絲不是質量百分比純度99.9%以上的純銀絲，但仍具有容易吸收大氣中的硫(S)成分的性質。因此，如果碳層薄，則具有銀(Ag)成分容易與大氣中存在的硫(S)成分結合，在鍵合絲表面形成硫化銀的性質。於是存在如下缺點，即一旦在鍵合絲表面形成牢固的硫化銀(Ag2S)後，該硫化銀(Ag2S)繼續向鍵合絲內部深入，形成不均一的硫化銀(Ag2S)膜，使得第二次鍵合不穩定，而使第二次鍵合的鍵合面不穩定。而且，在對貴金屬銀合金絲進行第二次鍵合時，一般都會將電路板、引線框架、器件等加熱到高溫(100℃~250℃左右)狀態，因此，由於其周圍環境的熱氣，存在於鍵合面的由鍵合絲衍生的硫(S)就更容易與大氣中存在的硫(S)成分結合。因此，還存在第二次鍵合後鍵合面的硫化程度進一步加深，鍵合面變得更容易剝離的缺點。而且，如果鍵合前硫化銀(Ag2S)膜進一步向鍵合絲內部深入，則第一次鍵合前就會發生晶片開裂、鍵合不良等不良影響。 However, this organic carbon is used as a lubricant component, and is not intended to isolate sulfur (S) components in the atmosphere. Although the noble metal silver alloy wire of the present invention is not a pure silver wire having a mass percent purity of 99.9% or more, it has a property of easily absorbing a sulfur (S) component in the atmosphere. Therefore, if the carbon layer is thin, the silver (Ag) component is easily bonded to the sulfur (S) component existing in the atmosphere, and the silver sulfide is formed on the surface of the bonding wire. Therefore, there is a disadvantage that once a strong silver sulfide (Ag2S) is formed on the surface of the bonding wire, the silver sulfide (Ag2S) continues to penetrate into the interior of the bonding wire to form a non-uniform silver sulfide (Ag2S) film, so that the second The secondary bonding is unstable, and the bonding surface of the second bonding is unstable. Moreover, when the precious metal silver alloy wire is subjected to the second bonding, the circuit board, the lead frame, the device, and the like are generally heated to a high temperature (about 100 ° C to 250 ° C), and therefore, due to the heat of the surrounding environment, there is The sulfur (S) derived from the bonding wire on the bonding surface is more easily combined with the sulfur (S) component present in the atmosphere. Therefore, there is a disadvantage that the degree of vulcanization of the bonding surface is further deepened after the second bonding, and the bonding surface becomes more easily peeled off. Further, if the silver sulfide (Ag2S) film before bonding is further penetrated into the inside of the bonding wire, adverse effects such as wafer cracking and bonding failure occur before the first bonding.

【早期技術文獻】 [early technical literature]

【專利文獻】 [Patent Literature]

【專利文獻1】特開2012-99577號公報 [Patent Document 1] JP-A-2012-99577

【專利文獻2】特開平6-151497號公報 [Patent Document 2] Japanese Patent Publication No. 6-151497

本發明是為了解決上述第二次鍵合的課題所開發，旨在提供一個鍵合絲，而該鍵合絲可使貴金屬銀合金絲達到即使其 為貴金屬銀合金仍可防止大氣中的硫所引起的硫化之效果。 The present invention has been developed to solve the above-mentioned problem of the second bonding, and aims to provide a bonding wire which can make a precious metal silver alloy wire even if it The noble metal silver alloy can still prevent the effect of vulcanization caused by sulfur in the atmosphere.

本發明人等著眼於熔鑄後的貴金屬銀合金表面的活性(與大氣中的硫(S)的化學反應性)比純銀合金小此點，旨在實現下列目的：首先通過採用貴金屬銀合金減弱大氣中的硫(S)與鍵合絲表面的銀(Ag)成分的化學反應性；繼而通過對該表面實施縮徑、減小表面積、降低表面活性；然後通過在貴金屬銀合金絲的整體表面上設置極薄的碳層，利用該碳(C)的還原作用防止大氣對貴金屬銀合金的硫化和氧化；而且，即使不是如第一次鍵合時的熔化熱般的强大熱能，而是第二次鍵合時超聲波的低熱能，也能從鍵合面上去除與銀合金絲表面鬆散結合的硫化銀(Ag2S)膜等。 The present inventors have focused on the activity of the surface of the noble metal silver alloy after casting (the chemical reactivity with sulfur (S) in the atmosphere) is smaller than that of the pure silver alloy, and aims to achieve the following purposes: firstly, the atmosphere is attenuated by using a noble metal silver alloy. The chemical reactivity of the sulfur (S) with the silver (Ag) component of the surface of the bonding wire; and then by reducing the diameter of the surface, reducing the surface area, reducing the surface activity; and then passing over the entire surface of the noble metal silver alloy wire Providing an extremely thin carbon layer, using the reduction of the carbon (C) to prevent vulcanization and oxidation of the noble metal silver alloy by the atmosphere; and, even if it is not the strong heat energy like the heat of fusion at the first bonding, but the second The low thermal energy of the ultrasonic waves at the time of the secondary bonding can also remove the silver sulfide (Ag 2 S) film which is loosely bonded to the surface of the silver alloy wire from the bonding surface.

用以解決本發明之課題的球焊用貴金屬銀合金絲的表面結構，其特徵在於：，在質量百分比純度99.9%以上的鈀(Pd)佔質量百分比0.1~6%，且其餘部分由質量百分比純度99.99%以上的銀(Ag)構成的球焊用貴金屬銀合金絲的表面結構中，鈀(Pd)占質量百分比3.0~4.8%，且其餘部分由銀(Ag)構成的鍵合絲表面是連續鑄造面經金剛石模具縮徑後的拉絲加工面，該拉絲加工面的整體表面形成總有機碳量(TOC值)為50~3,000μg/m2且由沸點比上述貴金屬銀合金的熔點低的水溶性非硫系有機高分子衍生的有機碳層。 The surface structure of the noble metal silver alloy wire for ball bonding for solving the problem of the present invention is characterized in that palladium (Pd) having a mass percentage purity of 99.9% or more accounts for 0.1 to 6% by mass, and the balance is by mass percentage In the surface structure of the noble metal silver alloy wire for ball bonding composed of silver (Ag) having a purity of 99.99% or more, palladium (Pd) accounts for 3.0 to 4.8% by mass, and the remaining portion of the bonding wire composed of silver (Ag) is The continuous casting surface is subjected to a wire-cut surface after the diameter reduction of the diamond mold, and the entire surface of the wire-cut surface forms a total organic carbon amount (TOC value) of 50 to 3,000 μg/m 2 and has a boiling point lower than a melting point of the noble metal silver alloy. A water-soluble non-sulfur-based organic polymer-derived organic carbon layer.

在本發明之貴金屬銀合金絲的表面結構中，以連續鑄造面狀態保存該鍵合絲表面，是為了使鍵合絲表面不形成新的活性面。此外，通過金剛石模具對該連續鑄造面進行拉絲加工，是因為金剛石模具對貴金屬銀合金的滑動性好，能在保存連續鑄造面的狀態下進行縮徑。利用金剛石模具的縮徑至少需要最終的拉絲模具是金剛石模具。一般的縮徑是在水中或採用噴淋的濕式連續拉絲方式進行的。藉由使本發明之貴金屬銀合金絲表面變成連續鑄造面經縮徑後的惰性拉絲加工面，並在該表面上設置有機碳層，可以防止大氣中的硫 (S)與鍵合絲表面的銀(Ag)成分的結合。 In the surface structure of the noble metal silver alloy wire of the present invention, the surface of the bonding wire is stored in a continuous casting surface state so that a new active surface is not formed on the surface of the bonding wire. Further, the continuous casting surface is subjected to the wire drawing by the diamond die because the diamond mold has good slidability to the noble metal silver alloy, and the diameter can be reduced in a state in which the continuous casting surface is stored. The reduction in diameter of the diamond mold requires at least that the final wire drawing die is a diamond die. The general diameter reduction is carried out in water or by wet continuous drawing using spray. The sulfur in the atmosphere can be prevented by changing the surface of the noble metal silver alloy wire of the present invention into an inert drawn surface of the continuous casting surface after the diameter reduction, and by providing an organic carbon layer on the surface. (S) bonding to the silver (Ag) component of the surface of the bonding wire.

在本發明之貴金屬銀合金絲的表面結構中，上述貴金屬銀合金為質量百分比純度99.9%以上的鈀(Pd)佔質量百分比0.1~6%且其餘部分為質量百分比純度99.99%以上的銀(Ag)，是因為考慮到與鋁焊盤的鍵合性及可靠性壽命。即，如果事先不將貴金屬銀合金絲本身的硬度降低一定程度，則熔球與純鋁(Al)焊盤及Al合金焊盤等連接時，會更容易發生晶片損傷。此外，這也是為了讓第一次鍵合的鍵合面上銀(Ag)與鋁(Al)的鍵合面沒有硫(S)成分殘留。鈀(Pd)具有在第一次鍵合時，在無空氣焊球(FAB)的氮環境中不與鋁焊盤形成金屬間化合物(intermetallic compound)且以正球體形狀連接熔球的效果。令合金元素的含量為質量百分比6%以下，是因為超過質量百分比6%後，在無空氣焊球(FAB)中形成的熔球會過硬，更容易發生晶片損傷。此外，合金元素的含量為質量百分比0.1%以上，是因為合金元素的含量過少，就不能獲得抗硫化性，即使表層形成了有機碳膜，也不能抑制連續鑄造面上硫化程度的加深。貴金屬銀合金絲的連續鑄造面上形成硫化銀(Ag2S)膜後，就會形成熔球，即使有機碳層高溫裂解，熔球也會變硬，更容易發生晶片損傷。 In the surface structure of the noble metal silver alloy wire of the present invention, the above-mentioned noble metal silver alloy is silver (Ag) having a mass percentage purity of 99.9% or more of palladium (Pd) of 0.1 to 6% by mass and the remainder being 99.99% by mass or more. ) is because of the bonding and reliability life with aluminum pads. In other words, if the hardness of the noble metal silver alloy wire itself is not lowered to some extent in advance, when the molten ball is connected to a pure aluminum (Al) pad or an Al alloy pad or the like, wafer damage is more likely to occur. Further, this is also to prevent the sulfur (S) component from remaining on the bonding surface of silver (Ag) and aluminum (Al) on the bonding surface of the first bonding. Palladium (Pd) has an effect of not forming an intermetallic compound with an aluminum pad and connecting the molten ball in a positive spherical shape in a nitrogen atmosphere without air ball (FAB) at the time of the first bonding. The content of the alloying element is 6% by mass or less because the melting ball formed in the airless solder ball (FAB) is too hard after exceeding 6% by mass, and wafer damage is more likely to occur. Further, the content of the alloying element is 0.1% by mass or more because the content of the alloying element is too small, and the vulcanization resistance cannot be obtained. Even if the surface layer forms an organic carbon film, the degree of vulcanization on the continuous casting surface cannot be suppressed. When a silver sulfide (Ag 2 S) film is formed on the continuous casting surface of the noble metal silver alloy wire, a molten ball is formed, and even if the organic carbon layer is pyrolyzed at a high temperature, the molten ball hardens and wafer damage is more likely to occur.

銀(Ag)成分的純度為質量百分比99.99%以上，是為了使金屬雜質不到100質量比ppm，避免金屬雜質在貴金屬銀合金絲的連續鑄造面上發生內部氧化。為了形成優質的貴金屬銀合金絲，銀(Ag)成分的純度應為質量百分比99.999%以上。同樣，為了形成優質的貴金屬銀合金絲，鈀(Pd)、鉑(Pt)及金(Au)等各合金元素的純度應為質量百分比99.99%以上。 The purity of the silver (Ag) component is 99.99% by mass or more in order to prevent the metal impurities from being less than 100 ppm by mass, and to prevent internal oxidation of metal impurities on the continuous casting surface of the noble metal silver alloy wire. In order to form a high quality precious metal silver alloy wire, the purity of the silver (Ag) component should be 99.999% by mass or more. Similarly, in order to form a high-quality precious metal silver alloy wire, the purity of each alloying element such as palladium (Pd), platinum (Pt), and gold (Au) should be 99.99% by mass or more.

在本發明之貴金屬銀合金絲的合金元素中，最佳為鈀(Pd)。這是因為易於分解第二次鍵合時貴金屬銀合金絲表面形成的硫化物。此外，鈀(Pd)不僅可阻礙於第一次鍵合時，銀(Ag)與鋁(Al)在鍵合面上形成金屬間化合物，亦 可有效防止銀(Ag)與鋁(Al)的金屬間化合物在高溫高濕條件下所造成的鍵合面劣化。此外，本發明之貴金屬銀合金應為：質量百分比純度99.99%以上的鈀(Pd)佔質量百分比0.1~5%、鈦(Ti)佔5~60質量比ppm、且其他部分由質量百分比純度99.99%以上的銀(Ag)所構成。鈦(Ti)是為了抑製熔球形成時鈀(Pd)帶來的催化活性。另一方面，鈦(Ti)存在使貴金屬銀合金熔球變硬的傾向，因此，應為5~60質量比ppm。 Among the alloying elements of the noble metal silver alloy wire of the present invention, palladium (Pd) is most preferred. This is because it is easy to decompose the sulfide formed on the surface of the noble metal silver alloy wire at the time of the second bonding. In addition, palladium (Pd) can not only hinder the formation of intermetallic compounds on the bonding surface between silver (Ag) and aluminum (Al) during the first bonding. The deterioration of the bonding surface caused by the intermetallic compound of silver (Ag) and aluminum (Al) under high temperature and high humidity conditions can be effectively prevented. In addition, the noble metal silver alloy of the present invention should be: palladium (Pd) having a mass percentage purity of 99.99% or more, 0.1 to 5% by mass, titanium (Ti) accounting for 5 to 60 mass ppm, and other portions having a mass percentage purity of 99.99. More than % of silver (Ag). Titanium (Ti) is used to suppress the catalytic activity of palladium (Pd) when the molten sphere is formed. On the other hand, titanium (Ti) tends to harden the noble metal silver alloy melting ball, and therefore should be 5 to 60 mass ppm.

在本發明之球焊用貴金屬銀合金絲的表面結構中，該拉絲加工面的整體表面上形成總有機碳量(TOC值)為50~3,000μg/m2的有機碳層，是為了降低鍵合絲活性，避免貴金屬銀合金絲與大氣中的硫(S)等結合。本發明之有機碳層指的是成分元素中不含硫(S)的非硫系有機高分子化合物衍生物。由於貴金屬銀合金絲的熔點比純金絲低，因此，有機碳層應為沸點比貴金屬銀合金熔點低的水溶性非硫系有機高分子衍生物，如非離子表面活性劑、陰離子表面活性劑、陽離子表面活性劑、兩性表面活性劑。表面活性劑中，最佳為非離子表面活性劑。例如，和光純藥工業株式會社產的商品名NCW-1001等。此外，也可以是沸點比貴金屬銀合金熔點低的水溶性醇衍生物。可以是總分子量小的乙醇、甲醇或異丙醇衍生物。 In the surface structure of the noble metal silver alloy wire for ball bonding of the present invention, an organic carbon layer having a total organic carbon amount (TOC value) of 50 to 3,000 μg/m 2 is formed on the entire surface of the wire-cut surface to reduce the bond. The wire is active, and the precious metal silver alloy wire is prevented from being combined with sulfur (S) in the atmosphere. The organic carbon layer of the present invention refers to a non-sulfur-based organic polymer compound derivative containing no sulfur (S) as a component element. Since the melting point of the noble metal silver alloy wire is lower than that of the pure gold wire, the organic carbon layer should be a water-soluble non-sulfur organic polymer derivative having a boiling point lower than that of the noble metal silver alloy, such as a nonionic surfactant, an anionic surfactant, Cationic surfactant, amphoteric surfactant. Among the surfactants, the most preferred is a nonionic surfactant. For example, trade name NCW-1001 manufactured by Wako Pure Chemical Industries, Ltd., etc. Further, it may be a water-soluble alcohol derivative having a boiling point lower than that of the noble metal silver alloy. It may be an ethanol, methanol or isopropanol derivative having a small total molecular weight.

本發明之拉絲加工面的整體表面上形成有機碳層，是因為如果存在未形成有機碳層的部位，即使只有一部分，大氣中的硫(S)也會經此與貴金屬銀合金絲的表面結合，形成硫化銀(Ag2S)膜。此外，有機碳層的厚度為總有機碳量(TOC值)50~3,000μg/m2，是因為球焊用鍵合絲的線徑一般為15~25μm，可以根據總有機碳量(TOC值)通過計算簡單地算出有機碳層的有效厚度。50~3,000μg/m2的範圍可以通過純水高溫燙洗及超聲波沖洗、或者有機高分子化合物超稀溶液浸漬來控制，按照控制的容易度，應採用超稀溶液 浸漬。此外，上限為3,000μg/m2，是為了減少鍵合工具上的碳粉粘附/堆積量。因為，雖然本發明之貴金屬銀合金絲的熔點比純金鍵合絲低，但即便如此，碳粉也會粘附、堆積在鍵合工具上。如果考慮鍵合工具更換頻率等操作性，則應為2,400μg/m2，1,800μg/m2則更佳。 The organic carbon layer is formed on the entire surface of the wire-finished surface of the present invention because if there is a portion where the organic carbon layer is not formed, even if only a part, the sulfur (S) in the atmosphere is bonded to the surface of the noble metal silver alloy wire. Forming a silver sulfide (Ag 2 S) film. In addition, the thickness of the organic carbon layer is a total organic carbon amount (TOC value) of 50 to 3,000 μg/m 2 because the wire diameter of the bonding wire for ball bonding is generally 15 to 25 μm, which can be based on the total organic carbon amount (TOC value). The effective thickness of the organic carbon layer is simply calculated by calculation. The range of 50 to 3,000 μg/m 2 can be controlled by high-temperature hot washing and ultrasonic washing, or ultra-dilute solution of organic polymer compound, and should be impregnated with an ultra-dilute solution according to the ease of control. Further, the upper limit is 3,000 μg/m 2 in order to reduce the amount of toner adhesion/deposition on the bonding tool. Because, although the melting point of the noble metal silver alloy wire of the present invention is lower than that of the pure gold bonding wire, even if the toner adheres and accumulates on the bonding tool. If operability such as the frequency of replacement of the bonding tool is considered, it should be 2,400 μg/m 2 and more preferably 1,800 μg/m 2 .

水溶性非硫系有機高分子化合物中，如果是非離子表面活性劑、或者乙醇、甲醇或異丙醇等的水溶性醇衍生物，即使表面的總有機碳量超過1,800μg/m2，只要在3,000μg/m2範圍內，在一般鍵合次數為50萬次的連續鍵合作業中不會因碳粉積累而引起毛細管堵塞及夾持器污染等。 In the water-soluble non-sulfur-based organic polymer compound, if it is a nonionic surfactant or a water-soluble alcohol derivative such as ethanol, methanol or isopropyl alcohol, even if the total organic carbon amount on the surface exceeds 1,800 μg/m 2 , In the range of 3,000 μg/m 2 , in the continuous bonding industry in which the number of bonding times is 500,000 times, capillary clogging and gripper contamination are not caused by toner accumulation.

如果採用本發明之球焊用貴金屬銀合金絲，則由於縮徑後的惰性連續鑄造面上已形成有機碳層，因此，貴金屬銀合金絲不會立即與大氣中的硫(S)結合而形成牢固的硫化銀。因此，即使將本發明之球焊用貴金屬銀合金絲長期放置於室溫下，鍵合絲表面也不會產生大氣中存在的硫(S)成分所造成的牢固硫化銀(Ag2S)膜。即，本發明之球焊用貴金屬銀合金絲除了成分組成帶來的優良鍵合特性之外，利用超聲波的第二次鍵合性也很卓越，因此，可以保證開始使用前的鍵合絲產品壽命。此外，如果採用本發明之貴金屬銀合金絲，即使反復鍵合，毛細管也不會發生污染。 If the noble metal silver alloy wire for ball bonding of the present invention is used, since the organic carbon layer is formed on the inert continuous casting surface after the diameter reduction, the noble metal silver alloy wire does not immediately combine with the sulfur (S) in the atmosphere to form. Strong silver sulfide. Therefore, even if the noble metal silver alloy wire for ball bonding of the present invention is left at room temperature for a long period of time, the surface of the bonding wire does not produce a strong silver sulfide (Ag 2 S) film due to the sulfur (S) component present in the atmosphere. . That is, the noble metal silver alloy wire for ball bonding of the present invention has excellent second bonding properties by ultrasonic waves in addition to the excellent bonding characteristics of the component composition, and therefore, the bonding wire product before the start of use can be secured. life. Further, if the noble metal silver alloy wire of the present invention is used, the capillary does not become contaminated even if it is repeatedly bonded.

將具有表1所示之成分組成的貴金屬銀合金(貴金屬成分的純度為：銀(Ag)質量百分比99.999%以上，其他合金成分分別為質量百分比99.99%以上)熔化均勻後進行連續鑄造，得到直徑5mm的粗絲。不對該粗絲進行酸洗處理，而是採用濕式通過金剛石模具連續拉絲，為獲得規定的機械 特性而進行調質熱處理(quenching and tempering treatments)，得到保留了連續鑄造面的直徑為20μm的鍵合絲。然後，連續浸漬於表2所示之各種濃度的非硫系有機化合物水溶液中，得到本發明之球焊用貴金屬銀合金絲(實施品1~實施品15)。此處，實施品9顯示將鍵合絲浸漬於乙醇濃度為1%的水溶液中後，乾燥時的有機碳量為2,800μg/m2。實施品15是在製造Ag-3%Pd合金鍵合絲後，浸漬於乙醇稀溶液中，再以純水高溫沖洗之物。 A noble metal silver alloy having a composition shown in Table 1 (purity of the precious metal component: silver (Ag) by mass of 99.999% or more, and other alloy components of 99.99% by mass or more) is uniformly melted and continuously cast to obtain a diameter. 5mm thick wire. Instead of pickling the thick yarn, it is continuously drawn by a wet diamond die, and quenching and tempering treatments are performed to obtain predetermined mechanical properties, and a key having a diameter of 20 μm in which the continuous casting surface is retained is obtained. Wire. Then, it was continuously immersed in an aqueous solution of a non-sulfur-based organic compound of various concentrations shown in Table 2 to obtain a noble metal silver alloy wire for ball bonding of the present invention (Examples 1 to 15). Here, in the embodiment 9, after the bonding wire was immersed in an aqueous solution having an ethanol concentration of 1%, the amount of organic carbon at the time of drying was 2,800 μg/m 2 . The article 15 was obtained by immersing in an ethanol-diluted solution after the Ag-3% Pd alloy bonding wire was produced, and then rinsing it with pure water at a high temperature.

此外，表2所示之非離子表面活性劑為BLUEBELL株式會社銷售的服裝用液體洗滌劑(商品名：Natural)。陰離子表面活性劑為日油株式會社產的商品名：PERSOFT(注册商標)。陽離子表面活性劑為日油株式會社產的 商品名：NISSANCATION(注册商標)。兩性表面活性劑為日油株式會社產的商品名：NISSANANON(注册商標)BD。 Further, the nonionic surfactant shown in Table 2 is a liquid detergent for clothing (trade name: Natural) marketed by BLUEBELL Co., Ltd. The anionic surfactant is a trade name of Nippon Oil Co., Ltd.: PERSOFT (registered trademark). Cationic surfactant is produced by Nippon Oil Co., Ltd. Product name: NISSANCATION (registered trademark). The amphoteric surfactant is a trade name of Nissin Oil Co., Ltd.: NISSANANON (registered trademark) BD.

按照潔淨室環境(溫度25℃、濕度50%)將該貴金屬銀合金絲在實驗室放置30天後，進行硫化銀(Ag2S)膜厚測量、第二次鍵合鍵合性試驗及毛細管堵塞試驗，得到表3的結果。 The precious metal silver alloy wire was placed in the laboratory for 30 days in a clean room environment (temperature: 25 ° C, humidity: 50%), and silver sulfide (Ag 2 S) film thickness measurement, second bond bonding test, and capillary plugging were performed. Test, the results of Table 3 were obtained.

【比較例】 [Comparative example]

將具有表1所示之成分組成的貴金屬銀合金熔化均勻後進行連續鑄造，得到直徑5mm的粗絲。對於用稀硝酸對該粗絲進行表面酸洗和未進行酸洗之物進行與實施例一樣的操作，得到比較例之球焊用貴金屬銀合金絲(比較品16~比較品18)。此處，比較品16是在對Ag-2.5%Pd合金進行連續鑄造，得到直徑5mm的粗絲後，用稀硝酸進行表面酸洗，連續拉絲，製造鍵合絲，然後浸漬於乙醇超稀溶液中，不放置30天，而是在當天開始試驗之物。比較品17是在對Ag-4%Pt合金進行連續鑄造，得到直徑5mm的粗絲後，用稀硝酸進行表面酸洗，連續拉絲，製造鍵合絲，然後形成非離子表面活性劑衍生的有機碳膜，放置30天后，進行膜厚測量及試驗之物。比較品18是在製造超出金(Au)含量下限的Ag-0.07%Au合金鍵合絲後，形成了超出有機碳量上限之兩性表面活性劑衍生的有機碳膜之物。 The noble metal silver alloy having the composition shown in Table 1 was melted uniformly and then continuously cast to obtain a thick yarn having a diameter of 5 mm. The material which was subjected to surface pickling and pickling with the dilute nitric acid was subjected to the same operation as in the example to obtain a noble metal silver alloy wire for ball bonding of Comparative Example (Comparative Product 16 to Comparative Product 18). Here, the comparative product 16 is obtained by continuously casting an Ag-2.5% Pd alloy to obtain a thick wire having a diameter of 5 mm, and then performing surface pickling with dilute nitric acid, continuously drawing, producing a bonding wire, and then immersing in an ultra-dilute ethanol solution. In the middle, it is not placed for 30 days, but the test is started on the same day. Comparative product 17 is a continuous casting of Ag-4% Pt alloy to obtain a thick wire having a diameter of 5 mm, followed by surface pickling with dilute nitric acid, continuous drawing to produce a bonding wire, and then forming a nonionic surfactant-derived organic After the carbon film was allowed to stand for 30 days, the film thickness measurement and the test were carried out. Comparative article 18 is an amphoteric surfactant-derived organic carbon film which is formed beyond the upper limit of the amount of organic carbon after the production of Ag-0.07% Au alloy bonding wire which exceeds the lower limit of the gold (Au) content.

對於該貴金屬銀合金絲(比較品17~18)，進行了以室溫在實驗室放置30天後的硫化銀(Ag2S)膜厚測量、第二次鍵合鍵合性試驗及毛細管堵塞試驗，得到表3的結果。但是，如上所述，比較品16沒有放置，而是在當天開始了膜 厚測量及試驗。 For the noble metal silver alloy wire (Comparative Products 17 to 18), the silver sulfide (Ag 2 S) film thickness measurement, the second bonding bond test, and the capillary plugging test were carried out after being left at room temperature for 30 days in the laboratory. , get the results of Table 3. However, as described above, the comparative product 16 was not placed, but the film thickness measurement and test were started on the same day.

[總有機碳量(TOC)的測量] [Measurement of Total Organic Carbon (TOC)]

總有機碳量的測量為，分別稱量1000m貴金屬銀合金絲，加入200g的0.1N-NaOH水溶液，用水浴煮沸30分鐘，進行萃取，冷却後加入2.5ml的8N-HCl，輕輕振蕩，在高純度空氣下起泡15分鐘。將其放入株式會社島津製作所產TOC-5000型有機碳分析儀中，測量有機碳濃度，根據該值計算總有機碳重量，除以20μm直徑的貴金屬銀合金絲的表面積，作為表面的非離子表面活性劑的總有機碳量。 The total organic carbon amount was measured by weighing 1000 m of precious metal silver alloy wire, adding 200 g of 0.1 N-NaOH aqueous solution, boiling in a water bath for 30 minutes, extracting, cooling, adding 2.5 ml of 8N-HCl, and gently shaking. Foaming under high purity air for 15 minutes. This was placed in a TOC-5000 organic carbon analyzer manufactured by Shimadzu Corporation, and the organic carbon concentration was measured. Based on this value, the total organic carbon weight was calculated and divided by the surface area of the noble metal silver alloy wire of 20 μm diameter as the surface non-ion. The total amount of organic carbon in the surfactant.

[硫化銀(Ag2S)膜厚的測量] [Measurement of film thickness of silver sulfide (Ag 2 S)]

形成於鍵合絲表面的硫化銀(Ag2S)的測量使用膜厚測量儀(ECI公司產、型號QC200)進行。實施品1~實施品15、以及比較品16的硫化銀(Ag2S)膜厚均為10nm以下。而比較品17~18均為20nm以上。 The measurement of silver sulfide (Ag 2 S) formed on the surface of the bonding wire was carried out using a film thickness measuring instrument (manufactured by ECI Corporation, model QC200). The film thickness of the silver sulfide (Ag 2 S) of the product 1 to the product 15 and the comparative product 16 was 10 nm or less. The comparative products 17 to 18 are all 20 nm or more.

[經過30天後的第二次鍵合鍵合性試驗] [Second bonding bond test after 30 days]

第二次鍵合之鍵合性試驗是使用株式會社新川產鍵合機，使環長為2mm、環高為200μm，用規定的拉鈎對距第二鍵合點20%的位置進行拉伸試驗時的鍵合强度。實施品1~實施品15、以及比較品16的結果優良，但與比較品16對比的比較品17的結果不理想。這是因為硫化銀(Ag2S)形成所致。 In the bonding test of the second bonding, a ring length of 2 mm and a ring height of 200 μm were used, and a predetermined hook was used to stretch the position from the second bonding point by 20%. Bond strength at the time of the test. The results of the products 1 to 15 and the comparative product 16 were excellent, but the results of the comparative product 17 compared with the comparative product 16 were not preferable. This is due to the formation of silver sulfide (Ag 2 S).

[毛細管堵塞試驗] [Capillary plugging test]

毛細管堵塞試驗使用新毛細管開始鍵合，計算鍵合次數，直到毛細管堵塞、不能鍵合為止。結果如表3所示。 The capillary occlusion test uses a new capillary to initiate bonding and counts the number of bonds until the capillary is clogged and cannot be bonded. The results are shown in Table 3.

從經過30天後的第二次鍵合鍵合性試驗可以明確知道，本發明之球焊用貴金屬銀合金絲實施品1~實施品15、以及比較品16的斷裂强度均為4.0克力(gf)以上，優良；而比較例之球焊用貴金屬銀合金絲(比較品17~18)則不理想。 It is clear from the second bonding bond test after 30 days that the breaking strength of the noble metal silver alloy wire for ball bonding 1 to 15 and the comparative product 16 of the present invention are both 4.0 gram (gf). The above is excellent; and the precious metal silver alloy wire for ball bonding of the comparative example (Comparative Products 17 to 18) is not preferable.

從毛細管堵塞試驗可以明確知道，本發明之球焊 用貴金屬銀合金絲(實施品1~8及10~15、比較品16及17)均在鍵合次數超過100萬次後也沒有發生毛細管堵塞，優良；而比較例之球焊用貴金屬銀合金絲(特別是比較品18)在25萬次時就發生了毛細管堵塞。 It is clear from the capillary plugging test that the ball welding of the present invention The precious metal silver alloy wire (the implementation products 1-8 and 10-15, the comparative products 16 and 17) did not cause capillary clogging after the number of bonding times exceeded 1 million times, and was excellent; and the noble metal silver alloy for ball bonding of the comparative example The capillary (especially the comparative product 18) caused capillary blockage at 250,000 times.

從上述實施例及比較例可以明確知道，本發明之相關實施品不僅沒有發生毛細管堵塞，而且以室溫在實驗室中放置30天後的鍵合特性優良。具體可知，就比較品而言，儘管鍵合絲剛製造後，第二次鍵合特性優良(比較品16)，但經過30天後，硫化銀(Ag2S)膜深入，第二拉伸强度變得極低(比較品17~18)；而本發明的相關實施品1~15在放置30天後也未產生或基本上未產生硫化銀(Ag2S)膜，第二拉伸强度高。此外還得知，TOC值越高則毛細管堵塞發生越快(比較品18)使得操作性變差。 As is clear from the above examples and comparative examples, the related embodiment of the present invention is excellent in bonding characteristics after not only blocking capillary clogging but also standing at room temperature for 30 days in the laboratory. Specifically, in the comparative product, although the second bonding property is excellent immediately after the bonding wire is produced (Comparative product 16), after 30 days, the silver sulfide (Ag 2 S) film is deep, and the second tensile strength is deep. It becomes extremely low (Comparative Products 17 to 18); and the related embodiments 1 to 15 of the present invention do not produce or substantially produce a silver sulfide (Ag 2 S) film after being left for 30 days, and the second tensile strength is high. . Further, it is also known that the higher the TOC value, the faster the capillary clogging occurs (Comparative Product 18), which deteriorates the operability.

【產業利用性】 [Industry Utilization]

本發明之球焊用貴金屬銀合金絲除了應用於通用IC、離散式IC(discrete IC)、記憶體IC外，還具有既要求高溫高濕用途又要求低成本的LED用IC封裝、汽車半導體用IC封裝、難以使用銅(Cu)鍵合絲的防禦、航天、航空產業用IC封裝、或醫療用途及光電耦合器等半導體用途。 In addition to general-purpose ICs, discrete ICs, and memory ICs, the noble metal silver alloy wire for ball bonding of the present invention has an IC package for LEDs requiring high temperature and high humidity and low cost, and is used for automotive semiconductors. IC packaging, difficulty in using copper (Cu) bonding wire, IC packaging for aerospace and aerospace industries, or semiconductor applications such as medical applications and optocouplers.

Claims (5)

一種球焊用貴金屬銀合金絲，其特徵在於：在質量百分比純度99.9%以上的鈀(Pd)佔質量百分比0.1~6%，且其餘部分由質量百分比純度99.99%以上的銀(Ag)構成的球焊用貴金屬銀合金絲的表面結構中，鈀(Pd)佔質量百分比3.0~4.8%，且其餘部分由銀(Ag)構成的鍵合絲表面是連續鑄造面經金剛石模具縮徑後的拉絲加工面，該拉絲加工面的整體表面上係形成總有機碳量(TOC值)為50~3,000μg/m2且由沸點比上述貴金屬銀合金的熔點低的水溶性非硫系有機高分子衍生的有機碳層；其中該貴金屬銀合金絲經連續鑄造後並未酸洗。 A noble metal silver alloy wire for ball bonding, characterized in that palladium (Pd) having a mass percentage purity of 99.9% or more accounts for 0.1 to 6% by mass, and the balance is composed of silver (Ag) having a mass percentage purity of 99.99% or more. In the surface structure of the noble metal silver alloy wire for ball bonding, palladium (Pd) accounts for 3.0 to 4.8% by mass, and the remaining portion of the bonding wire composed of silver (Ag) is the drawing of the continuous casting surface after the diameter reduction of the diamond die. a processing surface, the entire surface of the wire-cut surface is formed by a water-soluble non-sulfur organic polymer having a total organic carbon amount (TOC value) of 50 to 3,000 μg/m 2 and a boiling point lower than a melting point of the noble metal silver alloy. The organic carbon layer; wherein the precious metal silver alloy wire is not pickled after continuous casting. 如請求項第1項所述之球焊用貴金屬銀合金絲，其中，該鈀(Pd)的純度為質量百分比99.99%以上。 The noble metal silver alloy wire for ball bonding according to claim 1, wherein the purity of the palladium (Pd) is 99.99% by mass or more. 如請求項第1項所述之球焊用貴金屬銀合金絲，其中，該貴金屬銀合金係質量百分比純度99.99%以上的鈀(Pd)佔質量百分比3.0~4.8%、鈦(Ti)佔5~60質量比ppm、且其他部分由質量百分比純度99.99%以上的銀(Ag)所構成。 The precious metal silver alloy wire for ball bonding according to claim 1, wherein the precious metal silver alloy has a mass percentage purity of 99.99% or more of palladium (Pd) accounting for 3.0 to 4.8% by mass, and titanium (Ti) accounting for 5~. 60 parts by mass and other parts are composed of silver (Ag) having a mass percentage purity of 99.99% or more. 如請求項第1項所述之球焊用貴金屬銀合金絲，其中，該有機碳層為沸點比該貴金屬銀合金熔點低之水溶性醇的衍生物。 The noble metal silver alloy wire for ball bonding according to claim 1, wherein the organic carbon layer is a derivative of a water-soluble alcohol having a boiling point lower than a melting point of the noble metal silver alloy. 請求項第1項所述之球焊用貴金屬銀合金絲，其中，該有機碳層為乙醇、甲醇或異丙醇的衍生物。 The noble metal silver alloy wire for ball bonding according to Item 1, wherein the organic carbon layer is a derivative of ethanol, methanol or isopropanol.
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