TW201205695A - Bonding wire for semiconductor - Google Patents

Abstract

Disclosed is a bonding wire for semiconductor, which ensures good wedge bonding even of palladium-plated lead frames and has excellent oxidation resistance, and in which copper or a copper alloy is used as a core wire. The bonding wire is characterized by comprising a core wire that comprises copper or a copper alloy, a coating layer that is arranged on the surface of the core wire, has a thickness of 10 to 200 nm and contains palladium, and an alloy layer that is arranged on the surface of the coating layer, has a thickness of 1 to 80 nm and contains a noble metal and palladium, wherein the noble metal is silver or gold, and the noble metal is contained in the alloy layer at a concentration of 10 to 75 vol% inclusive.

Description

201205695 IV. Designation of the representative representative: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. In the case of a chemical formula, please disclose the chemical which best shows the characteristics of the invention. 6. Description of the Invention: Technical Field The present invention relates to a terminal for connecting an electrode on a semiconductor element to an external terminal. Bonding wires for connected semiconductors. [Prior Art] At present, a bonding wire for a semiconductor that connects an electrode on a semiconductor element to an external connection terminal (hereinafter referred to as "joining a wire, mainly used - a wire diameter of 2 〇 -5 () (4) A gold (Au) bonding wire (gold bonding wire) having a high purity of W4-Nine 'purity of 99.99% by mass or more, and a gold bonding wire bonded to a stone wafer as a semiconductor element. In the case of an electrode, generally, ban bonding e is performed by ultrasonic bonding, that is, 'using a universal bonding device, and the gold bonding wire is passed to the inside of a jig called a capillary. The tip end of the wire is heated by the arc input heat, and after the ball portion is formed by the surface tension, the ball which is heated and melted is pressed and joined to the electrode heated in the range of 150 to _t. 201205695 Aspect: When a gold bond wire is connected to an external connection terminal such as a lead or a land, it is generally not necessary to form the ball portion as described above, but to directly bond the gold bond wire to The so-called wedge-shaped joint. In recent years, the structure, material, and connection technology of semiconductor mounting have been rapidly diversified. In the installation structure, in addition to the current QFP (Quad Flat Packaging) using lead frame wood, the substrate or the poly is used. BGA (Ball Grid Array), cSP (Chip Scale)

Novel installation forms such as Packaging are put to practical use, and external connection terminals are also diversified. Therefore, wedge bonding characteristics are more important than ever. In addition, there is a growing demand for miniaturization of semiconductor elements, and in order to perform thin mounting, a low-circuit bonding technique for reducing the height of a circuit (lQQp) for bonding wires, or a wafer for a plurality of layers is stacked, and the reverse of the circuit is terminated by the substrate side. Bonding technology has become widespread. However, with the recent high resource prices, the price of gold, which is the raw material for gold bonding wires, has skyrocketed, and the low-cost wire for the replacement of gold has been reviewed. Copper (Cu) has been reviewed. However, copper is more easily oxidized than gold. Therefore, it is not good to use a simple copper-bonded wire for long-term storage and wedge-lifting. In addition, when the ball portion is formed at the tip end of the simple copper joint 2 as shown above, in order to prevent the ball from being oxidized, it is necessary to form a raw mist. Specifically, a gas obtained by mixing 4 volumes of j right hydrogen (HO) with nitrogen (I) is used to form a gas around the spherical portion as a reducing mist, but even this is not easy to use. , a good ball interface that people are willing to guard against. Based on the 4 reasons, the use of copper bonding wires and

field. LSI 201205695 Therefore, in order to solve the problem of oxidation of copper bonding wires, a copper bonding wire coated with silver (Ag) on the surface of a copper wire has been proposed. For example, in Patent Document 1, a specific example in which silver is coated with a copper wire is not disclosed, but a non-pure precious metal such as IS (A1), copper, iron (Fe), iron, and alloy (jreNi) is used as a joint. The inner metal of the wire, in the case where the surface of the bonding wire is coated with a metal, reveals a metal having corrosion resistance to moisture, salt, alkali, or the like, such as gold or silver. Further, in Patent Document 2, a specific example of coating a copper wire with silver is not disclosed, but a copper-based bonding wire in which a copper-based wire is coated with a noble metal containing gold or silver is exemplified, and it is described that the copper-based wire is applied. Breaking, corrosion resistance will be more enhanced. Patent Document 3 discloses that a bonding wire of a noble metal such as gold or silver is plated on aluminum (A1) or a copper wire, and a copper bonding wire is right on the right side of the copper plating wire. The problem of corrosion resistance and thermal oxidation is solved by the plating described above. The bonding of the leads (4) can also be as reliable as the gold bonded wires. Patent Document 4 discloses a copper bonded wire in which a surface of a high-purity copper ultrafine wire is coated with a noble metal or a corrosion-resistant metal, and silver is used as one of the noble metals covered as described above. By constituting as shown above; suppressing surface oxidation of the copper bonding wire (specifically, placing in the atmosphere ^ day = presence or absence of surface oxidation). Further, in terms of the diameter of the copper thin wire, the film opening is 15 to 80/im', and the coating film to be coated is set to have a thickness of 1 〇 (10) 〜 ^ ^ (in the embodiment, 25/zm diameter) In the patent document 5, it is disclosed in the patent document 5 that the steel is coated with silver at a thickness of NUi times, that is, the copper thin wire of 25# m is formed as 〇〇2 to twist. The silver-covered steel is connected to the vine, and the thick wire is connected to the wire. By coating the silver to suppress the oxidation of the steel, 201205695 and improving the ball forming ability. ^Before solving the problem of oxidation of the copper bonding wire, it is proposed that The second guide: the surface is coated with a noble metal, specifically, copper of gold (Au) is described in Patent Document 1, and the copper wire is covered with gold, but the copper is mainly used for the inner metal of the bonded wire. Non-pure precious metals such as iron (Fe), iron and recorded alloys (FeN1), and the metal coated with metal on the surface of the lunar y-bonded wire reveals a metal that is resistant to moisture, such as alkali, such as gold or Silver. In Patent Document 7: α has carried out a 'copper-type copper alloy containing copper or tin as In the case of the wire, the joint strength of the gold wire is increased, and the fracture strength is improved. Further, as described in Patent Document 2, the specific example of the copper wire covered with gold is not disclosed. Copper joints covering precious metals containing gold and silver 2 If the copper-based wires are coated, the corrosion-resistant surname will be further improved. In Lie 3, it is disclosed that the wires (8) or copper wires are coated with gold or silver. In the case of the copper bonded wire, the problem of thermal oxidation is solved by the above-mentioned mineral deposit, and the reliability of the bonding line with the lead frame is the same. In Patent Document 4, the surface of the high-purity, field line is disclosed. A steel bonded wire coated with a metal or a corrosion-resistant metal, using gold as one of the precious metals covered as described above. By configuring as described above: 'It is possible to suppress surface oxidation of the copper bonded wire (specifically, whether it is placed in the atmosphere in the future) Further, the diameter of the copper thin wire is 15 to 80 (four), and the film to be coated is set to have a thousand-thickness (10) in the embodiment (in the embodiment, &Μ" Thick In the case of Patent Document 8, it is disclosed that the outer circumference of the copper-clad core wire of the skin 201205695 is improved, and the bonding property of the electrode made of aluminum is improved. Patent Document 9 discloses a core material which is not plastically deformed. And a composite conductor composed of a peripheral material which is plastically deformed more softly than the core material, and an example in which gold is used as the core material, and an example in which the copper alloy is used as the outer peripheral material, has an effect of improving the connection strength between the wire and the circuit. In Patent Document 1Q, it is disclosed that the outer side of the copper alloy is coated with gold or a gold alloy, and the defect in which the bonding wires are brought into contact with each other when the semiconductor element resin is sealed is prevented. In Patent Document u, it is disclosed in the case of an oxygen-free copper wire. The surface of the wire is subjected to pure money to remove the bonding wires which are excellent in signal transmission and high in signal transmission rate. Patent Document 12 discloses a bonding of a coating layer made of an oxidation resistant metal having a higher melting point than copper by transmitting a dissimilar metal layer made of a metal other than copper on a core material containing copper as a main component. The wire 'is stable in forming the ball portion of the real ball, and further exhibits excellent adhesion between the coating layer and the core material. However, as described above, in the copper bonded wire in which the surface of the wire is covered with silver or gold, the surface oxidation of copper (especially the progress of oxidation in storage) can be suppressed'. However, most of the ball portion formed at the leading end of the wire at the time of bonding is formed. It does not become a true ball and is deformed to prevent the practical use of the copper bonding wire. If silver is coated, when the front end of the wire is heated and melted by arcing, the silver with a lower melting point (melting point 961 C) will preferentially melt. In contrast, copper with a higher melting point (melting 2 1〇83) 〇 仅有 仅有 仅有 仅有 仅有 仅有 仅有 仅有 仅有 仅有 仅有 仅有 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若) It is not easy to melt. In contrast, the specific heat of gold is smaller than U28 J/kg·Κ), even if it is slightly heat input, it can be melted. As a result, in the complex structure of copper and gold, Kim will give priority to 201205695. Melting is related. Further, as shown in Patent Document 5, when bonding is performed under a reducing atmosphere (10% H2-N2), most of the spherical portions are formed well even if they are coated with silver, but they cannot be obtained under zero encirclement gas containing no hydrogen. Since oxidation at the time of smelting is suppressed, joining is difficult, and formation of a favorable spherical part cannot be achieved. On the other hand, instead of covering silver or gold, it is also considered to cover the surface of the steel wire (10). In fact, in Patent Documents 2 to 4, the metal other than silver or gold is also exemplified in the coating layer. Although the advantages of Ji in the aforementioned literature are not disclosed, since the melting point is higher than silver (refining point 1554C), the specific heat is higher than gold (244 J/kg.K), so if it is coated, Z solves the above. The silver or gold-like copper wire occurs (4) and in the front of the shape, the coating layer melts and the method is opened; {忐古+ ..., the 沄 forms a true spherical ball. Also by covering the surface of the copper wire, I1 is able to simultaneously solve the oxidation of copper and prevent the true sphericality of the ball portion from ensuring two. ^ ( ', ^ _ ° is disclosed in the patent document 6 in the core wire In the 2 waste '2 layer bonding wires of the coating layer (outer peripheral portion), a diffusion layer is provided between the core wire and the coating to cover the cover of the frost layer a. The adhesion of the coating layer is 'but the core wire is connected In the case of the palladium-coated copper wire and the wire shown above, since the oxidation of the copper is suppressed, it is not only long-term storage or wedge-bonding, but also excellent in forming a ball at the tip end of the wire. At the time of the Ministry, the oxidation of the ball Ρ 亦 will also be larger than the hydrogen of the body, and (4) Tian / Therefore, not used is dangerous gas

Pure helium gas forms the periphery of the ball into nitrogen ♦ HI oxygen, which also forms the ball of the true ball. [Patent Document] (Patent Document 1) 曰本特将开昭57-1 2543号 201205695 (Patent Document 2) Japanese Patent Laid-Open No. 59_181〇4〇 (Patent Japanese Patent Laid-Open Publication No. Sho 62-97360 (Patent Document 5) Japanese Laid-Open Patent Publication No. SHO 62-112-57 (Patent Document 6) Japanese Patent Laid-Open Publication No. SHO-63-46738 (Patent Document No. 9) Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei. Japanese Unexamined Patent Application Publication No. JP-A No. No. No. No. No. No. No. Publication No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No As mentioned above, the 'steel-bonded wire system, which is covered on the surface of the copper wire, is more practical as a cheaper joint wire than the gold-bonded wire, but for the nearest lane, the ++ Rapid changes in construction/material/connection technology in the cow-conducting women's clothing π # τ _ Ai Yi's eve of the problem is not necessarily compatible with the problem gradually becoming apparent. W^丨 Green is very sturdy surface is generally ir'j For this, recently it has progressed to the use of the lead frame n to the 'silver-plated lead frame (hereinafter referred to as "silver-plated lead frame, in the lead Before the frame is soldered to the substrate such as the motherboard, the purpose of soldering with the solder material as much as possible is to have the welding material, the 201205695 mineral deposit process (welding material plating process), which becomes a high cost. Compared with silver, the material can ensure high wettability of 18-substituted silver (4) on the lead frame, thereby omitting the welding material ore-laying process to form a low cost. The inventors found that if it is in a copper wire The surface-covered copper-bonded wire, _ although it has not become apparent in the silver-plated lead frame until now, has a problem that the cross-bonding property of the lead-plated lead frame becomes insufficient. Further, the inventors and the like have studied in detail the above-mentioned problems, and found that since the outermost surface of the copper bonding wire is a handle, palladium contacts each other in the wedge bonding of the absolutely plated lead frame. Due to 1 bar The hardness (the Mohs hardness of 4·75 and the Mohs hardness of copper is 3 〇) is high, so that it is not easily deformed, so that the destruction of the scaled oxide layer on the surface is insufficient, which is the cause of the above problem. Further, it has been found that the diffusion between the surface of the wire and the surface of the lead frame is slow, whereby the formation of a sufficient diffusion layer between the two palladium layers is also a cause of the above problem. The oxidation of the wire, considering the surface of the copper wire is covered with a precious metal that is less susceptible to oxidation than copper. Generally speaking, silver, platinum, and gold are known to be more precious metals than copper, "the silver and gold in the ball are as described above. Part (4) has difficulty in its formation. On the other hand, it is a very expensive material, so the industrial use of platinum-bonded copper-bonded wires on the surface of copper wires is easy. As shown above, even on the surface of copper wires. Simply covered expensive:: (Gold, m), it is not easy to satisfy the good wedge bondability, oxidation resistance and sulfidation resistance on the lead frame of the brokerage ore. In addition, the power of a large current such as a motor is high. Component office Required diameter of the core wire with access wire 20 201 205 695 billion large, packets were proud refuse secret engagement pull β m month or so, but this time, since the wire diameter than the

'The combined conductor for semiconductors which is excellent in oxidation and copper or copper alloy as a core. (Means for Solving the Problem) In order to achieve the above object, the gist of the present invention is as follows. A bonding wire for a semiconductor according to claim 1, comprising: a core wire made of copper or a copper alloy; a palladium-containing coating layer formed on the surface of the core wire and having a thickness of 1 to 2 nm; formed in the coating The surface of the layer, the alloy layer having a thickness of 1 to 80 nm and containing a noble metal, wherein the noble metal is gold or silver, and the concentration of the noble metal in the alloy layer is 10% by volume or more and 75% by volume or less. The joint wire for semiconductors of Patent Application No. 2 is a gold. The concentration of gold in the alloy layer is 15% by volume or more: shell volume% or less. b The surface crystal grain of the gold layer is the semiconductor joint guide ramie in the third application of the patent scope _ the above-mentioned combination in the wire, the wire direction of the crystal orientation of the <111> 10 201205695 - the rate is 15 degrees or less The area of the crystal grain is 40% or more and 1% by mass or less. In the semiconductor bonding wire of the fourth aspect of the invention, the concentration of gold in the alloy layer is 40% by volume or more and 75% by volume or less. In the bonding wire for a semiconductor of the invention of claim 5, the noble metal is silver, the alloy layer is formed by a thickness of (10) (10), and the concentration of silver in the alloy layer is 10% by volume or more and 7% by volume or less. In the bonding wire for a semiconductor of the sixth aspect of the invention, the concentration of silver in the alloy layer is 20% by volume or more and 7% by volume or less. In the joint wire for a semiconductor of claim 7 of the invention, in the surface crystal grain of the alloy layer, 'pair' is <1〇. The area of the crystal grain in which the inclination direction of the crystal orientation is 15 degrees or less is 5 % or more and 〇〇 〇〇 % or less. In the bonding wire for a semiconductor of the above-mentioned alloy layer, the area of the crystal grain of the alloy layer in which the slope of the crystal orientation of the alloy layer is 15 degrees or less is 6〇%. Above, 1〇 (10) or less. In the bonding wire for a semiconductor of the invention of claim 4, the surface of the bonding wire has a side hardness of 〇.2 to 2 〇 (^3). The bonding of the semiconductor of the first application of the Japanese Patent Application No. 4 In the wire, the core wire 3 has at least i of 5, 3, and 3 of B, p, and Se. (Effect of the invention) By the present invention, a lead frame is provided even if palladium is plated, t: A bonding wire for an inexpensive semiconductor element which is excellent in wedge bonding property and oxidation resistance and which is made of copper or copper. [Embodiment] 11 201205695 Hereinafter, the configuration of the bonding wire of the present invention will be further described. In the following description, unless otherwise stated, “%” means “% by volume.” In addition, the composition is only the numerical average of the metals obtained when analyzing the complex parts, and the carbon system is natural and mixed (inevitable) The present invention does not include the composition described below. The present inventors have found that good wedge bonding is provided in order to provide a (four) wire frame under the lead frame (7) which ensures palladium plating. Both the oxidation resistance and the inexpensive bonding wire using copper or a copper alloy as a core wire form a coating layer containing a specific thickness on the surface of a core wire made of copper or a copper alloy, and further, in the coating layer It is effective that the surface is formed with a specific thickness of a noble metal having a specific composition and a bonding wire of the alloy layer. The noble metal of the present invention is silver or gold. First, a configuration in which a coating layer of a suitable thickness is formed on the surface of a core wire made of copper or a copper alloy will be described. Since copper or a copper alloy is easily oxidized as described above, the bonding wire made of copper or a copper alloy has long-term storage or poor wedge-bonding property. On the other hand, by forming a coating layer containing palladium on the surface of a core wire made of copper or a copper alloy, oxidation of copper is suppressed, so that not only the long-term storage or the wedge bonding property is excellent, but also a ball is formed at the tip end of the bonding wire. The concern that the ball will oxidize will be greatly improved. The above effect is obtained by the fact that the coating layer contains (4) which is less susceptible to oxidation than copper (i.e., the oxide generates hot crystals are large). Thereby, even if a mixed gas of hydrogen and nitrogen which is a dangerous gas is not used, and only a pure nitrogen gas is used, and the periphery of the ball portion is formed into a nitrogen mist enclosure, a spherical portion of the true ball can be formed. The effect as shown above is obtained when the thickness of the coating layer is 1 〇 2 2 〇〇 1 ^. 12 201205695 On the other hand, if the thickness of the coating layer is less than 1 〇 nm, the oxidation suppressing effect is insufficient. If the thickness of the coating layer exceeds 20 Å, most of the bubbles having a diameter of #m on the surface of the ball portion are less preferable. The elements other than the palladium in the 'specturing coating layer' constitute an element which is an inevitable impurity and an outermost surface of the core wire or the bonding wire. Further, when the content of palladium in the coating layer is 50% or more, a sufficient oxidation inhibiting effect can be obtained. However, in the case of an element other than palladium contained in the coating layer, silver which constitutes the outermost surface to be described later is not contained, or when silver is contained, the concentration of silver is preferably less than 10%. If the concentration of silver in the coating layer is 1% by weight or more, the problem of the silver-coated wire as described above (oxidation at the time of ball formation, etc.) is revealed. In the element other than palladium contained in the coating layer, gold which constitutes the outermost surface to be described later is not contained, or when gold is contained, the concentration of gold is preferably less than 15%. If the concentration of gold in the coating layer is 5% or more, the problem of the gold-coated wire as described above (the case where the ball portion does not become a true ball and deforms) is present. If the above-described configuration of the palladium-containing coating layer is formed only on the surface of the core wire made of copper or a copper alloy, good wedge-shaped bondability cannot be ensured on the palladium-plated lead frame. In order to solve this problem, the inventors of the present invention have found that an alloy layer of silver or gold may be formed on the surface of the coating layer. The alloy layer is formed by the thickness of the other layer (9) (10) on the coating layer. This is based on the fact that the wedge-shaped bondability is governed by the physical property value of the region where the outermost surface of the bonded wire is about 3 (10). Also, the area of the outermost surface of the bonding wire is at least 1 nm, preferably the outer surface of the bonding wire is a metal such as silver or gold and palladium alloy. 'Wedge shape on the palladium plating lead frame 13 201205695 At this time, silver or gold in the alloy layer constituting the outermost surface of the bonding wire preferentially diffuses toward the palladium on the palladium plating lead frame, and a new alloy layer is easily formed between the bonding wire and the palladium plating lead frame. Thereby, the wedge bonding property of the bonding wire of the present invention and the palladium plating lead frame is improved, and for example, the 2nd peel strength becomes good. This is based on the fact that the interdiffusion between silver or gold and palladium is faster than full self-diffusion. However, if the thickness of the alloy layer is less than lmn, the coating layer belonging to the base of the bonding wire affects the aforementioned wedge-shaped bondability, so that the wedge-shaped bonding property with the palladium-plated lead frame cannot be ensured. Further, if the thickness of the alloy layer is less than 3 nm, the risk that the coating layer belonging to the base of the bonding wire adversely affects the wedge-shaped bondability is not zero, and the above effect becomes unstable, so that it is preferable. The thickness is formed to be 3 nm or more. In order to obtain the aforementioned effects, the upper limit of the thickness of the alloy layer of silver or gold and palladium is not particularly limited. In order to shape the thickness of the alloy layer, "the material is 8 〇 nm, # is the electrolysis recorded later, at a large current", if it is an electroless bond for a long time, if the steaming method is for a long time, After silver plating, gold plating, silver vapor deposition, or gold vapor deposition, it is necessary to form a temperature in the furnace to be described later to be more than 74 Å. Since the high temperature of the crucible is difficult to ensure stable quality, the upper limit of the thickness of the alloy is set to 8 nm or less. Among them, the thickness of the alloy layer is preferably set to an upper limit of 5 or less. When the upper limit is made 5 〇 nm or less, the heating temperature can be formed to be 600 C to 650 ° C. Further, in order to obtain the above effects obtained by the above-mentioned alloy layer of silver or gold and palladium, it is necessary that the composition of silver or gold (silver or gold concentration) in the alloy layer is a specific range. Specifically, if the silver or the alloy layer of gold or palladium is used, the silver or gold concentration is ίο% or more, and the wedge bondability of the butyl lead frame is 75%. If °A and the other words are not able to obtain the above 1 L / gold concentration is less than 10%, 75%, when in ίί, if the aforementioned silver or gold inelquality exceeds the above-mentioned silver or gold Priority is given to the fact that the sexuality is increased by =", so it is less good. 1 The risk of the ball... Under the bonding wire, the second =: silver _ mixed eight, ra + AA, # layer silver or gold and palladium will be homogeneous, so when the ball is formed at the tip of the wire, it melts to form a deformed ball. The danger will disappear ^ the true spherical or dimensional accuracy of the part. The bonding wire having a structure including a silver and a gold alloy layer on the surface of the coating layer will be described in more detail without impairing the gold. The alloy layer is additionally on the aforementioned coating layer! ~Edited thickness User: Former. This is based on the fact that the wedge bondability is governed by the physical property values of the area around the outermost surface of the bonded wire. That is, the area of the outermost surface of the bonding wire is at least 1 nm, preferably the area of the outermost surface of the bonding wire is 3, if the alloy is silver and the alloy is formed when the wedge interface is formed on the forged lead frame. The silver in the alloy layer on the outermost surface of the wire preferentially diffuses toward the palladium on the palladium-plated lead frame, and a new alloy layer is easily formed between the bond wire and the palladium-plated lead frame. Thereby, the wedge bonding property of the bonding wire of the present invention and the lead plating frame is improved, for example, the 2nd peel strength becomes good. This is based on the fact that the interdiffusion between silver and Ji is faster than the self-diffusion of saturating. However, if the thickness of the alloy layer is less than 1 nm, the coating layer belonging to the base of the bonding wire affects the bonding property of the wedge 15 201205695, so that the helmet method ensures the properties of the lead frame with palladium plating. In addition, if the poor model is connected to 5 D. The thickness of the crucible is less than 3 nm, and the coating layer belonging to the bonding guide substrate has a risk of not being I for the wedge-shaped joint guiding, and the risk of taking a sputum and sputum is considered to be a risk that the above effect becomes unstable. Therefore, it is more preferable to form the aforementioned thickness to be more preferably 3 nra or more. In order to obtain the above effect, the yttrium-like effect of the alloy layer of silver and palladium is described. The thickness of the alloy layer is formed so that the front opening is "...the bottom is more than 3 〇 nm", and the furnace temperature to be described later must be formed. In addition, it is difficult to ensure a stable quality, and the upper limit of the thickness of the gold is formed to be 3 以下 or less. ▲ In addition, 'in order to obtain the alloy layer by the silver and the nucleus The above-mentioned effect: the composition (silver concentration) of silver in the σ gold layer must be in a specific range. Specifically, if the silver concentration in the alloy layer of the silver and the kiln is ι〇% or more and 70% or less, it is more 9 is preferably 2 (U or more, 70% or less, which can further improve the wedge-shaped bondability with the surface-plated lead frame 1n〇/not. If the silver concentration is less than 〇/0', the above effect cannot be obtained. If the concentration of silver exceeds that of humans. When the wire forms a ball at the end of the wire, only the silver in the above-mentioned 5 gold layers formed by silver and Ming will preferentially melt to form a deformed ball. Poor relative to this, if the silver in the alloy layer is 70 % Below 'In the alloy layer of the bonding wire, silver and the fins will be homogeneously mixed, so when a ball is formed at the tip of the wire, only silver will preferentially melt, and the risk of forming a deformed ball will disappear without In addition, when the silver concentration is m or more and m or less, the true spherical shape or dimensional accuracy of the ball portion is better, which is preferable. In the bonding wire of the invention, a surface of a coating layer formed of a copper or copper alloy 16 201205695 is formed into a suitably thick and smear coating layer, and an alloy screen of a proper thickness and a stack of silver and a layer is applied. , to ensure that the palladium-plated lead frame * is wrong with both, and 1# good wedge-shaped bondability and anti-oxidation r Wang I test, and copper or copper, in addition, if the cheap joint of m Wire. 'The alloy layer of silver and palladium makes the sound: fA 20% or more, 70% or less, can also be sound." The agricultural degree § is also - in general, the effect shown in the hair ... two. In the joint system, the capillary tube and the bonding wire are connected to each other. At this time, avoid! The capillary tube and the bonding wire continuously scratch the bonding wire, so that the inner wall of the capillary is attached to the hair in the aforementioned region, and is processed in the manner of the conventional =. The surface of the wire has only the handle. Covered layer::, - owe you such as buckle, KC guard depth r right repeat most - people such as more than 5mm long span of the soul of the soul of the anchor $ 蛀 迷 迷 毛细管 capillary and the joint contact The area of the capillary is abraded. As a result, sharp concavities and convexities are generated in this area. As a result, the scratch formed by the capillary * ^ ^ will pay attention to the surface of the wire. This is also hardened by the coating of palladium. In the present invention, in the above-mentioned alloy layer provided on the surface of the coating layer, the concentration of silver in the alloy layer is increased, so that suppression can be suppressed. The sharp twins as described above are in the above-mentioned silver and palladium «, and the silver and strontium are homogeneously mixed in a manner called full-rate solid solution. When the concentration is high, the capillary is in contact with the bonding wire. : Domain 1 convex: t priority helps to deform As described above capable of suppressing the sharp "Health. The effect obtained as described above is a case where the silver concentration is 20% to 17 201205695, more preferably 30% or more. Further, if the silver concentration is 7〇% or more, the true sphericality or dimensional accuracy of the ball portion is not sufficiently obtained for the above reasons. Further, it was found that in the above-mentioned silver and alloy layer, if the silver concentration in the alloy layer forms A 20% in _L, the effects as described below are also obtained. Incidentally, if it is a conventional technique in which a bonding wire having only a palladium-containing coating layer is formed on a surface of a core wire made of steel or a copper alloy, if a ball portion having a diameter larger than 30 (four) is formed at the tip end of the bonding wire, There are cases where a number of directly controlled bubbles of the number ^ are generated on the surface of the ball. This system is related to the miniaturization and high functionality of recent electronic devices. In other words, in order to support the miniaturization and high functionality of the electronic device, the semiconductor device is also miniaturized and can be made. However, in the bonding wire, the area of the bonding portion is reduced, and the ball formed at the leading end of the wire is reduced. In the past, even if the ball portion of the diameter is small, the bubble unit of the diameter is recently produced. The micro-β of the number (4) as described above is also formed in the ball portion of the diameter of the two main 〇" m or more, because the ball control is larger, so the joint area is also inevitably larger, as above; So far it has not been specifically regarded as a problem. However, in the recent smaller ball portion having a diameter larger than 3 〇, the joint area (4) is ll A, and B is also reduced in the sag. Therefore, even if it is a joint strength of the upper joint portion which is not problematic Or long-term reliability / ', docking questions. It became known that it was asked to ask the inventor and other regulations such as μ _ interest. That is, the existing portion of the bubble is often the surface of the surface of the ball, which is formed in the deserted region where the wire is segregated to form a new layer in the formation of the ball, and is enclosed by the organic matter in this region by 18 201205695. gas. On the other hand, in the case of silver in a certain concentration or higher, the surface of the coating layer containing the coating layer contains a concentration of palladium which is not formed when the spherical portion is formed. Therefore, in the concentrated bonding wire of the present yttrium silver ternary alloy, if it is the concentrated region, the risk of skin protection and skin encapsulation due to organic matter becomes small, so even if it is formed, for example, more than 30// M-like comparisons, in the case of the ball that is widely recognized by the ancients, can also inhibit the occurrence of gas. That is, if this is 2. More than %, it is possible to obtain the effect of the silver in the alloy of silver and the alloy, and if it is more preferably 30% or more, the effect is more advanced. The method for measuring the thickness and composition of the coating layer and the alloy layer is a method in which one side of the surface of the bonding wire is digging in the depth direction by the bismuth ore method, or a line under the section of the connecting wire to the interface wire. Analysis or point analysis is more effective in the method of measuring the side of the surface. If the depth of the measurement is increased, the measurement time will be too expensive. The latter's line analysis or point analysis is based on the entire section of the section of the Tang Dynasty, the right to the Α - cloth or several. The confirmation of the reproducibility of the niche is more advantageous than Di Yi Fang A. In the section of the joint wire, although the line analysis is more: when the right side of the wire is to be used to improve the analysis accuracy, the analysis interval of the narrow line analysis, or the point analysis after zooming in the area to be analyzed in detail is also effective. The thickness of the alloy layer is grouped by the surface in the depth direction

Into the analysis and the concentration of silver; f! n. / |V u A is the distance (depth) of the part above 10/D. In addition, the thickness of the coating layer is the distance (depth) of the portion which is formed in the depth direction by the interface which is the thickness of the alloy layer, and which is formed into a platen concentration A 5 or more, and the analysis used for the analysis. For example, βρΜA (Electron Probe Micro Analysis, Electron Probe Micro Analysis), EDX (Energy Dispersive X-Ray Analysis), AES ( & Jay Electron Spectrometry, Auger) Electron Spectroscopy, TEM (Transmission Electron Microscope, Transmission Electron ^^ (^〇%〇1) 6), and the like. If the thickness or composition obtained by any of the above methods is within the range of the present invention, the effects of the present invention can be obtained. In order to ensure both the good wedge bondability and the oxidation resistance on the palladium-coated lead frame as described above, and also satisfying the loop characteristics described later, the inventors have found that the crystal orientation of the wire surface, the hardness of the wire surface, It is also effective to use a bonding wire in which the type and composition of the additive element in the core wire are set to a specific range. Regarding the crystal orientation of the surface of the wire, it is on the surface of the aforementioned alloy layer. Among the aB particles, it is more preferable that the slope in the direction of the line direction of the crystal orientation of <1〇〇> is none or less. Specifically, when the slope is 15 degrees or less and the area of the crystal grains is 50% or more and 1% by weight or less, even when the reverse bonding is performed, wrinkles are less likely to occur on the surface of the circuit, which is preferable. More preferably, it is more preferably m or more and 100% or less, and the effect is further improved. Here, the wrinkles are a general term for minute damage or unevenness of the surface generated when the circuit is formed. As a result, for example, the bonding of the electrodes is gradually increased, and the bonding of the electrodes is performed, and the bonding of the electrodes for lst bonding is performed. This suppresses the height of the circuit and makes the thickness of the wafer easier. By the way, in the reverse bonding as described above, first, the ball is joined by the ist bonding electrode, and the ball is joined immediately before the ball to be joined, and the ball is bonded to the 2nd bonding electrode. Finally, the ball portion on the 1st bonding electrode fabricated in the previous 20 201205695 is wedge-bonded. After the ball joint of the 1st bonding electrode is performed, when the bonding wire directly above the ball is cut, if a large impact is applied to the bonding wire, wrinkles are formed on the surface of the bonding wire. Further, when the heating due to the use of the element and the thermal fatigue which is cooled to room temperature with the stop of the element are applied to the element over a long period of time, the wrinkles are accelerated and cracked. The inventors of the present invention have carefully studied the results and found that the crystal orientation of the wire surface (alloy layer) is associated with the wrinkle defect, which is represented by the "丨丨" crystal orientation, and if it is high in strength but lacks ductility. Wrinkles are remarkably observed. As a result of further research by the present inventors, it has been found that in order to suppress the slope, the slope of the wire direction of the <100> crystal orientation is reduced in the surface of the wire, and the slope is desired. When the area of the crystal grains of 15 degrees or less is 50% or more, the ductility sufficient to suppress wrinkles can be ensured. However, if the area of the crystal grains having a slope of 15 degrees or less is less than 5 (10)', the above-described one cannot be obtained. Effect: Here, the slope of the linear direction of the <100> crystal orientation of the crystal grains observed on the surface of the aforementioned alloy layer can be determined by a small-area X-ray method or electron backscattering provided in the viewing device. Diffraction (EBSD, Electron Backscattered D, ffract1〇n) is determined. The EBSD method also has the feature of observing the angular difference of the crystal orientation between adjacent measurement points by observing the orientation of individual crystal grains. The wire-like thin wire 'is also simpler and more accurate to see the slope', so it is ideal. In addition, the slope is 15 degrees or less, and the area is determined by the micro-area $ X-ray method. The crystal grain two::: the X-ray intensity of the orientation is taken as the volume of the crystal orientation, and 21 201205695 can be calculated by the 々EBSD method from the orientation of the individual crystal grains observed as described above. In order to calculate the ratio of the aforementioned area, it is observed that the length of the surface of the wire which is perpendicular to the direction of the wire of the bonding wire is at least 1/4 of the diameter of the wire, and the length of the wire in the direction of the wire. The surface formed into at least 1 GMra, and the observed area thereof is (10) is a percentage of the area occupied by the crystal grains having a slope of 15 degrees or less. If the thickness or composition obtained by any of the methods is within the scope of the present invention, The effect of the present invention is obtained. Regarding the crystal orientation of the surface of the wire, it is preferable that the slope of the surface crystal grain of the alloy layer is not or less than the slope in the direction of the line direction of the crystal orientation of <111>. Specifically, when the area of the crystal grain having the slope of 15 degrees or less is 60% or more and 10 (10) or less, even when special bonding of a high loop height at 3 〇〇 ym & It is preferable that the tilting failure is caused by the fact that the circuit is tilted in a direction perpendicular to the joining direction, and more preferably 70% or more and 1% by weight or less, which is more preferable because the effect is further improved. If the orientation is at or near the crystal orientation of the <1U>, the strength or the modulus of elasticity of the material is increased. As a result of repeated studies, the inventors have found that in order to suppress the incidence of tilt failure, The slope of the pulling direction of the crystal orientation of the <111> is reduced in the surface, and the area of the crystal grain having the slope of 15 degrees or less is formed to be 40% or more, thereby ensuring the strength and elasticity sufficient to suppress the incidence of the tilt failure. rate. However, if the slope is 15 degrees or less and the area of the crystal grains is less than 5 %, the effect of suppressing the incidence of poor tilt is not sufficient. Here, the slope of the linear direction of the <111> crystal orientation of the crystal grains observed on the surface of the alloy layer 22 201205695 can be determined by a micro-region χ line method or electron backscattering provided in the TEM observation apparatus. The measurement was carried out by a diffraction (EBSD, Electron Backscattered Diffracti〇n) method or the like. The EBSD method also has the feature of observing the orientation of individual crystal grains, and can show the difference in the angular difference of the crystal orientation between adjacent measurement points. Even if it is a thin wire such as a bonding wire, the crystal grain can be observed simply and accurately. The slope 'is ideal. Further, the area of the crystal grains having a slope of 15 degrees or less can be obtained by the volume ratio of the ridge line strength of the crystal orientation in the crystal grain as the crystal orientation in the micro area rifling method, and in addition, in the EBSD method. It can be directly calculated from the orientation of the individual crystal pulls observed in the foregoing. When calculating the ratio of the aforementioned area, observing any surface of the surface of the wire, at least 1/4 of the diameter of the bonding wire in a direction perpendicular to the direction of the wire of the bonding wire, at least the length in the direction of the wire of the bonding wire The face is set to 1 〇〇, and the slope is a percentage of the area occupied by the crystal grains of 15 degrees or less. The thickness or composition obtained by the above ten methods is within the scope of the invention: 』^ In this issue, regarding the hardness of the surface of the wire, the U-force of the wire is set to a range of 0.2 to 2 for the surface of the wire, even in the low-circuit junction of the circuit of the re-stage. In addition, it is also preferable to suppress the occurrence of a bad condition called ":". Bell injury The neck injury refers to the damage caused by the ball and the busbar. When the loop is in an extremely low loop, it will cause an excessive burden when the loop is formed. Recently, in order to apply the type of electrons to the electrons, in order to maximize the memory capacity, the memory is as thin as 201205695. In the thinness degree shown above, it has been used in a thin component type device equipped with a plurality of thin-grained wafers. Since it is inevitable that the circuit is liable to reduce the neck damage, the inventors have found that it is clear that the occurrence of the neck injury is closely related to the hardness of the surface of the wire. By reducing the hardness, the neck is supplied at the time of joining. Excessive negative 氐 33 Behe surface can also be plastically deformed, which can be suppressed: neck: injury. Specifically, 'the above effect is transmitted by the side of the surface of the bonding wire from the human body. However, if the above is connected. The surface has a side hardness of more than 2 〇Gpa and is formed to have the same hardness as the usual silver metal. If the neck is subjected to an excessive load during low-circuit bonding, the surface layer cannot be sufficiently plastically deformed. The shape is not able to obtain the aforementioned effect. On the other hand, the surface hardness of the surface of the bonding wire is less than 22 Gpa. Since the hardness is too small, it is easy to damage the surface of the wire during the process of bonding the wire, and there is a treatment. In the case where a plurality of surface damages occur, the term "edge hardness" refers to the hardness measured by the indenter of the steel ball or the super hard alloy ball, and refers to the load when the concave portion is added to the test surface by the indenter. The value obtained by the projected area of the diameter of the permanent recess, which has a stress dimension. If the surface of the material called the nanoindentation method is used, the edge hardness in the depth of about 丨nm can also be measured. Therefore, when confirming the side hardness value of the present invention, it is preferable to use a nanoindentation method. Further, the edge hardness of the surface of the bonding wire is measured by a nanoindentation method to bond the alloy layer and the coating layer. The outermost surface of the wire is obtained. Among them, the side hardness of 0.2~2_〇GPa is equivalent to the Vickers hardness of about 5〇~57〇Hv. 24 201205695 Types and groups of added elements in the heart line In the core wire of the present invention, the core wire is made of copper or a copper alloy. However, the core wire may be added with various additives in a range that does not impair the effects of the present invention. In addition, Ca, Β, Ρ, Al, Ag, Se, and the like are listed. Among the added elements, at least i selected from the group consisting of B, p, and Se is more preferable, and the added element contains 5 to 300 ppm by mass in total. The strength of the bonding wire is further increased. As a result, for example, the straightness of the loop can be ensured even when a long loop of a loop length of more than 5 mm is performed. This is because the addition of 7 liters contributes to the copper crystal grains in the core. The solid solution strengthening or the strengthening of the crystallization boundary. However, if the intrinsic added element does not reach the ppm of 5 masses, the above-mentioned strength is not improved. On the other hand, *When the wave content of the additive element exceeds the mass, the ball portion is excessively hardened, so that the risk of damage to the wafer during ball bonding is increased, which is less desirable. Regarding the method of analyzing the content of the component in the anger line, the method of cutting the joint wire and cutting it in the depth direction by sputtering or the like, or the line analysis or the point analysis under the section is In the method of effectively digging one side of the shaver, if the depth of measurement is increased, the time will be too expensive. The advantage of the latter's line analysis or point analysis is that. The concentration distribution of the entire kneading surface or the reproducibility of several parts is more convenient than that of the grain. In the section of the bonding wire, the line analysis is relatively simple, but if the accuracy of the knife analysis is to be improved, the analysis interval of the narrow line analysis, or the amplification of the area to be analyzed in detail, is also effective. In the analysis device used for the knife analysis, 'the 可, EDX, AES, TEM, etc. can be used. In addition, in the investigation of the average composition, the bonding wire is dissolved by the liquid phase such as acid 25 201205695 in the surface portion. A method of determining the composition of the dissolved portion from the concentration contained in the solution is also possible. If the thickness or composition obtained by any of the above methods is within the scope of the present invention, the effects of the present invention can be obtained. The preferred embodiments of the present invention have been described above, but the present invention can be suitably modified. For example, a diffusion layer may be formed between the core wire and the coating layer. For example, a region containing palladium is connected to the coating layer, and the palladium or copper constituting the core wire is diffused to contain a diffusion layer of less than 50% of palladium. Due to the presence of the diffusion layer as shown above, the bonding wire can improve the adhesion of the coating layer to the core. Next, a bonding wire having a structure in which an alloy layer containing gold and palladium is provided on the surface of the coating layer will be described. The alloy layer has a thickness of 1 to 80 nm on the coating layer. This is because the wedge bondability is governed by the physical property value of the region where the outermost surface of the bonding wire is about 3 nm. That is, a region of at least 1 nm from the outermost surface of the wire, preferably a region of 3 nm from the outermost surface of the bonding wire, if it is an alloy of gold and palladium, is wedge-bonded to the palladium-plated lead frame to form a wire. The gold in the outermost alloy layer preferentially diffuses toward the palladium on the palladium plated leadframe, and a new alloy layer is easily formed between the bond wire and the palladium plated lead frame. Thereby, the bonding property of the bonding wire of the present invention to the palladium-plated lead frame is improved, and for example, the 2nd peel strength becomes good. This is because the interdiffusion between gold and palladium is faster than the self-diffusion of palladium. However, if the thickness of the alloy layer is less than 1 nm, the coating layer which is the base of the bonding wire affects the aforementioned wedge-shaped bondability, so that the wedge-shaped bondability with the coated lead frame cannot be ensured. In addition, if the thickness of the alloy layer is not & 3(10), it belongs to the bonding wire. The coating layer of the substrate has a bad effect on the above-mentioned transverse jointability. The danger of ringing 2012 201295 is not zero, it is dangerous, so it is better to be ahead. It is more preferable that the wind in which the fr effect becomes unstable is set to have a thickness of 4, and the above-mentioned effect of containing gold to horse is particularly limited. In order to combine the above, the electrolysis (4) described later is that when the electric power is more than 8 Gnm', if the right method is a long time, and the gold plating or gold steaming is performed, the heating process will be described later. The high temperature is not easily determined. The degree is formed to a quality exceeding 70 ° C. Therefore, the upper limit δ of the thickness of the alloy is 80 nm or less. And φ everyone, middle,. The thickness of gold is preferably set to an upper limit of 5 〇 nm or less. If the 勹 and the field limit β are 50 nm or less, the twist/sub-degree can be formed to be 600 t to 650 ° C. In addition, in order to obtain the composition (gold concentration) of gold in the upper, the capsule and the σ gold layer obtained from the above-mentioned alloy layer containing gold and gold, it is necessary to be in a specific range, specifically, the aforementioned alloy containing gold and free The degree of gold in the layer is 15% or more, and 75% is more preferably more than 75%, and the wedge-shaped bondability with the 1 bar plating lead frame can be further improved. If the aforementioned gold concentration is less than 15:', the aforementioned effects cannot be obtained. On the other hand, if the gold concentration exceeds 75%, the gold in the alloy layer containing gold and palladium preferentially melts when the ball portion is formed at the tip end of the wire, whereby the risk of forming the deformed ball portion is increased, which is less preferable. As described above, when the tip end of the wire is arc-in, and the heat is melted, gold having a low thermal conductivity (3i7w/m·valley is easily sealed with heat, and gold is preferentially melted. Copper with a high thermal conductivity (4 01 W / m · K ) is easy to remove heat, while copper has only a part of the melting is related. In contrast, if the gold concentration in the alloy layer is 75% or less, at 27 201205695 ==The alloy layer is mixed with gold and 'homogeneously, so it is at the front end of the wire; the material gold is preferentially smelted, and there is no danger of forming a deformed ball portion. · The life will not damage the true sphericality or dimensional accuracy of the ball. In addition, if the gold concentration is 15% or more and less than 4Q%, the true sphericality or dimensional accuracy of the ball portion is further improved, so that it is preferable in the bonding wire of the present invention. Or a palladium-containing coating layer having a specific thickness on the surface of the core of the steel alloy, having a specific thickness and a specific composition of an alloy layer containing gold and palladium on the surface of the coating layer, thereby providing a coating on the lead frame Good (four) bondability to ensure oxidation resistance and resistance Chemically, and copper or copper alloy is used as an inexpensive bonding wire for the core wire. The thickness and composition of the coating layer and the alloy layer are measured by using a surface of the bonding wire by a sputtering method to dig in the depth direction. Or a method of line analysis or point analysis of a cross section of a bonding wire. Here, the thickness of the alloy layer is a distance (depth) of a portion where the concentration of gold is 15% or more from the surface toward the depth direction. The thickness of the coating layer is a distance (depth) of a portion in which the composition of the thickness of the alloy layer is analyzed in the depth direction and the concentration of palladium is 50% or more. The analysis device used for the analysis can be used. EPMA (Electronic Line Microanalysis,

Electron Probe Micro Analysis), EM (Energy Dispersive X-Ray Analysis), AES (Auger Electron Spectroscopy) 'TEM (Transmission Electron Microscope). If the thickness or composition obtained by any of the above methods is within the scope of the present invention, 28 201205695, the effects of the present invention can be obtained. In order to ensure both good wedge-bonding property and oxidation resistance on the palladium-plated lead frame as described above, it also satisfies the loop characteristics described later: People have found the crystal orientation of the wire surface and the hardness of the wire surface. Or, the type and composition of the added elements in the core wire are extremely effective in the bonding guide of a specific range. Regarding the crystal orientation of the surface of the wire, it is preferable that the slope of the direction of the crystal direction of the <111> crystal orientation among the surface crystal grains of the alloy layer is none or less. Specifically, when the area of the crystal grain having the slope of 15 degrees or less is set to 6 G% or more, or less, even when special bonding of the above high circuit height is performed, it is less likely to be called a poor tilt. : A problem occurs in which the circuit is tilted in a direction perpendicular to the joining direction. If it is more preferable to form 4 m or more, the following effect can be further improved: this is because if the orientation is in the vicinity of the <ln> crystal orientation or The intensity or the modulus of elasticity of the material becomes high. The results of the present inventors have further studied and found that in order to suppress the incidence of poor tilt, the direction of the line of the <m> crystal orientation in the surface of the wire is reduced. If the slope of the crystal grain having the slope of u or less is 60% or more, the strength and the modulus of elasticity which are sufficient to suppress the incidence of the pour failure are ensured. However, if the slope is a crystal grain of a degree below the twist The area is less than 60%. The incidence of suppressing the tilting failure is not sufficient. Here, the diagonal direction of the crystal orientation of the crystal grains observed on the surface of the alloy layer is inclined. It can be measured by a small area X-ray method or an electron backscattered diffraction (EBSD, EIectron Backscattered Diffracti〇n) method, etc., which is set in the observation apparatus, and the EBSD method also has an observation of individual crystal grains. The orientation is such that the angular difference of the crystal orientation between adjacent measurement points can be illustrated, and even if it is a thin wire such as a bonding wire, the slope of the crystal grain can be observed easily and accurately, which is preferable. The area of the crystal grains having a slope of 15 degrees or less can be obtained by the micro-area X-ray method based on the X-ray intensity of the crystal orientation in the respective crystal grains as the volume ratio of the crystal orientation, and can be determined by the EBSD method. The calculation is performed directly on the orientation of the individual crystal grains observed as described above. When calculating the ratio of the aforementioned areas, the length of any surface of the wire surface perpendicular to the direction of the wire of the bonding wire is the diameter of the bonding wire. At least 1/4 of the length, the length of the bonding wire in the wire drawing direction is at least 100 (four), and the observation area is H). "Percentage of area occupied by crystal grains below 15 degrees: The thickness or composition obtained by any of the above methods is within the scope of the present invention. The effect of the present invention can be obtained. Regarding the hardness of the surface of the wire, if Luo 1 ^ n 9 . The edge of the wire is 硬度 硬度 〜 2 2 2 2 2 2 2 2 2 2 2 0 0 0 0 0 0 0 0 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线 导线It refers to the bad condition caused by the excessive burden in the ball and the mother's injury in the parental area (neck) of the extremely low circuit & ^, and the type of electronic machine g Φ is applied to the head. In a thin-film machine such as a flash memory, in order to maximize the capacity of the memory (4), a plurality of thin-type twins are used to quantify, and in the type of components, the inevitability is second. In the thinness shown above, it is necessary to reduce the height of the circuit. Therefore, the conventional neck 30 201205695 is prone to the aforementioned neck damage. The inventors have found that it is clear that the occurrence of the above-mentioned negative scallops is closely related to the hardness of the surface of the wire, and by lowering the hardness, even if the surface of the neck is excessively negative, the surface of the neck can be plastically deformed. Can inhibit neck damage. Specifically, the above effect can be sufficiently obtained by setting the edge hardness of the surface of the bonding wire to 2.0 GGPa or less. However, when the side surface hardness of the surface of the bonding wire exceeds 2.0 GPa, it is formed so that the hard surface of the normal silver alloy (four) is excessively applied to the neck when the circuit is joined with a low load. Plastic deformation does not fully achieve the aforementioned effects. On the other hand, if the surface hardness of the surface of the bonding wire is less than GP2 GPa, since the hardness is too small, the valley is liable to be damaged on the surface of the wire during the process of bonding the wire, and there are multiple surface damages depending on the treatment method. The situation. Here, the side hardness refers to the hardness measured by the indenter using a steel ball or a super hard alloy ball, and is obtained by dividing the load when the concave portion is added to the test surface by the indenter by the projected area of the diameter of the permanent concave portion. A value that has a dimension of stress. When the surface of the material called the nanoindentation method is used, the edge hardness in the depth of about 1 nm can be measured. Therefore, when the edge hardness value of the present invention is confirmed, the nano-duplication method is used. It is better. Further, the edge hardness of the surface of the bonding wire was obtained by measuring the outermost surface of the bonding wire having the alloy layer and the coating layer by the nanoindentation method. Wherein '0. 2~2. OGPa's side hardness is equivalent to a Vickers hardness of about 50 to 570Hv. Regarding the type and composition of the additive element in the core wire, the core wire of the present invention is made of copper or a copper alloy. However, the above-mentioned core wire may be added with various additive elements within a range that does not impair the effects of the invention of the present invention. Examples of the elements which can be added to the core wire include Ca, B, P, A1, Ag, Se, and the like. Among these added elements, at least one selected from the group consisting of B, P and Se is more preferable. If the added element contains a total of 5 to 3 Å by mass, the strength of the bonding wire is further enhanced. As a result, for example, the straightness of the loop can be ensured even when the long loop of the loop length of more than 5 minutes is engaged. This is because the added element contributes to solid solution strengthening or strengthening of crystal grain boundaries in the copper crystal grains in the core. However, if the concentration of the aforementioned additive element is less than 5 mass s ppm, the above-mentioned strength is not sufficiently obtained. On the other hand, if the concentration of the additive element exceeds 3 〇〇 mass ppm, the ball 4 is hardened more, so that the risk of damage to the wafer during ball bonding is increased, which is less desirable. When analyzing the content of the component in the core wire, the method of cutting the joint wire, the surface from which the face is cut by the splash or the like, or the line analysis or the point analysis under the profile is used. Method 1 For the analysis device used in the analysis, _, 、, 厅, 葡, etc. can be used. Further, in the analysis of the average composition, it is also possible to use a method in which the bonding wire is dissolved in a surface portion by a chemical solution such as an acid, and the composition of the dissolved portion is determined from the concentration contained in the solution t. If

The thickness or composition obtained by any of the above methods gives the effects of the present invention in the present invention. The preferred embodiment of the present invention is described above, but the present invention can be suitably modified. : ' A diffusion layer may be formed between the core wire and the coating layer. The female area is connected to the coating layer, and the above-mentioned exemption or expansion of the core wire contains an undesired diffusion layer. Due to the presence of the 32 201205695 diffusion layer as described above, the bonding wire can improve the adhesion of the coating layer to the core wire. Hereinafter, a method for producing a bonding wire according to the present invention will be described, and a method of manufacturing a bonding wire having a structure including silver and an octagonal layer on the surface of the coating layer will be described. 5, in order to manufacture the above-mentioned composition of the bonding wire, high purity 99.99% or more, 戋兮 古 古 古 、 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ( ( ( ( ( ( ( ( ( ( ( ( 1 in the high straight _ leaves are the original U with the true two or 虱 or Ar or other heating to dissolve, thereby obtaining the crystal bond of copper or copper alloy. Use: the underarms to pull the crystal bond to the final need The diameter of the core wire is adjusted to the diameter of the wire to the final core wire to form a coating layer containing the coating layer.

In the case of η, electrolytic plating, electroless plating, vapor deposition, or the like can be used. Among them, _ plating number and demineralization are the most ideal in the industry. = The electrical thickness of the film thickness is alloyed by silver and saturating. In the method, the surface of the fracture layer is formed into the coating layer, and in addition, in any method, for example, in the film, the surface of the electric furnace is used as a skin layer to form a silver layer. In the middle, it is preferable to sweep the wire in a continuous manner, thereby promoting the alloying and the thickness of the alloy. Specifically, the gold is gradually vulcanized while the alloying is performed, and in order to prevent oxidation or u at 18 (Tc to 21 (heating of Γρ to 24 hours), in the method of the film of the second layer of the coating layer. In other words, it is preferable to use electroless shovel, sputum, sputum, silver, etc., and it is preferable to use electroless plating or steaming method for electrolytic plating for the above reasons. The method is widely used for vulcanization, and the fog entrainment in the furnace is formed into a t1 valley brittle or inert inert gas such as Ar. This 201205695 is different from the conventional heating method of the bonding wire VII 4 ,. The concentration of sulfur contained in the mist enclosure is set to 900 ΡΡΠ 1 to τ.β 乂. More preferably, if it is mixed with a reducing gas a ^ t emulsion such as 1 ΟΟρρηι hydrogen in an inert gas, 'to prevent the vulcanization of the wire. The effect will be further improved, so it is better. The best ^ ^, horse in order to avoid as much as possible the sulfur and other impurity gases are brought in by the outside of the device, A. y right in the divided gas furnace (first fog gas furnace) On the outside, when another 1 layer of 筮_册第分分分炉炉, The second mist is surrounded by a small amount of miscellaneous impurities. The heavy impurities are not easily reachable to the first atmosphere gas furnace. The surname is a ^ and the text is good. In addition, the proper temperature in the furnace is X. Although it depends on the composition of the wire, the speed of the wire is different from that of the flying wire. However, if it is set to a range of about 2, C to 2, a stable quality bonding wire can be obtained, which is preferable. When the speed of sweeping the wire in the wire drawing process is, for example, about 40 to 80 m/min, it is preferable because it can be stably operated. In the method of manufacturing the bonding wire of the present invention, The area in which the slope of the orientation direction is 15 degrees or less is 50% or more, and the manufacturing method below the service level is difficult to manufacture by a usual manufacturing method, and is manufactured by a special method. Specifically, After obtaining a crystal bond, a palladium-containing coating layer is formed in the same manner as described above, and a silver film is formed in the same manner as described above. A crystal bond of the coating layer and the silver film is formed, and a metal mold is used. Pull the wire to the final core When the diameter of the wire is up to the thickness of 80 (four) or more, the shrinkage ratio of the mold is about u~m, and the wire is not drawn to the wire diameter of 80 &quot; m. The face ratio is drawn at a ratio of about 7 to m, which is usually a larger shrinkage ratio. Thereby, the directional structure of the silver film can be obtained (the crystal orientation is uniform in the direction of the pull line 34 201205695 - the collective organization) It is developed. However, if the risk of breaking the wire is increased when the wire is pulled at a large shrinkage ratio, it is more preferable to prevent the wire breakage speed from being formed, for example, to be 4, for example. In the present bonding wire, heat treatment for promoting alloying is also performed in the same manner as described above after the wire is pulled. The temperature of the heat treatment for promoting the alloying after the wire drawing is a low temperature, and the ratio of the area of the crystal grain of 15 degrees or less in the direction of the line direction of the crystal orientation is increased, and if it is a high temperature, the ratio of the area is high. Will decrease. When the area is lowered, the directionality in the 戍杲〇 ' ', 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Specifically, the temperature in the furnace is 23 〇〇 c to (10). The ratio of the area of the C, ^ is "simplified". If the temperature in the furnace is 68 (the range of TC to 72: C), the ratio of the area is about 50%, and the ratio of the area can be controlled by the temperature of the heat treatment. In the manufacturing method of the bonding wire of the invention, it is difficult to use a usual manufacturing method in a manufacturing method in which the slope of the crystal grain in the direction of the pulling direction of the <(1)> crystal is 15 degrees or less is 50%: upper and lower than 100%. It is made in a special way, and it is manufactured by a special method. σ After the ingot is obtained by the method, the coating layer containing the handle is formed in the same manner as described above, and a silver film is formed in the same manner as described above. When the crystal bond of the coating layer and the silver film is formed and the wire is drawn to the diameter of the final core wire by using a metal mold, the thickness of the mold is set to 20 or more. The shrinkage ratio of the thickness of the mold which is less than 15〇(4) is about 18~19%, and the thickness of the wire is 20,05605695. If the wire diameter is less than 80 // πι, the wire is formed as described above. Reducing the face rate and using 20~22% again The value of the right is high. Thereby, the directional assembly on the silver film (the crystal orientation is uniform in the direction of the pull line. Wei weaving) can be developed. However, if the wire is pulled at a large shrinkage ratio In this case, the risk of disconnection becomes high, and therefore, in order to prevent disconnection of the bonding wires, the wire drawing speed is preferably at a lower speed than, for example, 1 to 3 m/min. In the bonding wire, After the wire is pulled, the heat treatment for promoting alloying is performed in the same manner as described above. The temperature in the heat treatment process for promoting alloying after the wire is pulled, if it is low/orphan, is in the direction of the pull of the &lt;1 〇〇&gt; crystal orientation The ratio of the area of the crystal grain having a slope of 1 deg or less becomes high, and when # is a high temperature, the ratio of the area is lowered. If the decrease in the area is promoted by recrystallization in the process, the aforementioned set The directionality in the structure is easily lost. Specifically, 'If the temperature in the furnace is 68 Gt to 72, the ratio of the area is 50%'. If the temperature in the furnace is 72 〇 &lt; t 〜 74 (rc The range of the aforementioned area becomes more than 5〇 %, less than 7〇%, and the ratio of the aforementioned area in the range of 740 C to 750 C in the furnace is 7 % or more, and the ratio of the area is controlled by the temperature of the heat treatment. In the method of manufacturing the bonding wire, the side of the surface of the coating layer is more 〇. 2~2. The manufacturing method of the bonding wire in the range of 〇GPa is difficult to manufacture. The method is as follows: the alloy of silver and palladium on the surface of the wire is specially softened. Specifically, any of the above methods is drawn to the target wire diameter, and the above-mentioned ',' for the alloying process is finished. In addition, the bonding wires can be placed in an electric furnace controlled by an argon mist, and heated at ~t 36 201205695 for 2 0~2 4 small b#, and then _β j. Manufacturing. If it is a lower temperature than 15CTC or a heating time of more than 20 J, the alloy of silver and palladium cannot be particularly softened to the above hardness. If the ratio is 2. . . . For higher temperatures or for a longer period of time than 24 hours of heating, the diffusion between the adjacent wires is promoted, and there are cases where the wires are in close contact with each other. Next, a method of manufacturing a bonding wire having a structure including gold and a sharp alloy layer on the surface of the coating layer will be described. In order to manufacture the above-mentioned bonding wires, the high-purity copper (purity of 99.99/β or more) or the high-purity copper and the additive element raw materials are used as raw materials, and then they are subjected to high vacuum. Or an inert inert gas such as nitrogen or Ar is heated to solve the problem. Thus, an ingot of copper or copper alloy is obtained. The ingot is drawn to the diameter of the final desired core using a metal mold. The palladium-containing coating layer of the present invention is further added after the wire is pulled to the diameter of the final core. In the method of forming a coating layer containing palladium, electrolytic plating, electroless plating, vapor deposition, or the like can be used. Among them, it is most desirable to use the electrolysis clock which can stably control the film thickness. Thereafter, an alloy layer containing gold and palladium is formed on the surface of the coating layer. The method may be any method, for example, after forming the aforementioned coating layer, forming a gold film on the surface thereof as a skin layer, in order to set the furnace temperature in the electric furnace, and continuously sweeping the wire at a constant speed. This method of promoting alloying can surely control the composition and thickness of the alloy, which is preferable. Specifically, the surface-prevention: the oxidation of the first surface is carried out by alloying, and it is sufficient to heat the film on the surface of the coating layer at 16 (TC to i9). In this case, electrolytic plating, electroless plating, or the like can be used. 31 201205695 At this time, electrolytic plating is also used in the industry for the above-mentioned reason. In consideration of the contamination of the raw material, the atmosphere in the furnace is formed into an inert atmosphere such as nitrogen or Ar. Further, unlike the conventional heating method of the bonding wire, the oxygen concentration in the mist surrounding gas is set to It is more preferably 5000 ppm or less. More preferably, when at least 500 ppm of a reducing gas such as hydrogen is mixed in the inert gas, the effect of preventing contamination of the raw material of the wire is further improved, and it is preferable that the appropriate temperature in the furnace is also dependent on the wire. The speed of composing or sweeping the wire varies, but if it is set to a range of about 21 〜7 〇〇t:, it is better to obtain the bonding wire of the product f. Then, 'sweeping in the wire drawing process The speed of the line is set to, for example, 20 In the method of manufacturing a bonded wire according to the present invention, the slope of the direction of the wire in the direction of the wire is less than 15 degrees, and the area of the crystal grain is less than or equal to 15 degrees. The production method of 50% or more and the following is difficult to manufacture by a usual production method, and is manufactured by a special method. Specifically, after the crystal bond is obtained in the above manner, the crystal bond is formed in the same manner as described above. A coating layer of palladium is formed thereon, and a gold film is formed in the same manner as described above. When the ingot of the coating layer and the gold crucible is formed, and the wire is drawn to the diameter of the final core wire using a gold mold, the wire diameter is 150&quot; The thickness of the mold is such that the shrinkage ratio of the mold is about i2~2i% 2^, and the thickness of the wire is less than 15~, and the length of the wire is greater than usual. The shrinkage rate is used to pull the wire so that the gold I has a directional aggregate structure (the crystal orientation is in the direction of the pull direction). However, if the ratio is larger (4) 38 201205695 when pulling the wire' The risk of disconnection will become paralyzed. In order to prevent disconnection of the bonding wires, the wire drawing speed is preferably, for example, 2 to 411/1, which is lower than usual. In the bonding wire, after the wire is pulled, the alloying is promoted in the same manner as described above. In the heat-receiving section, the temperature in the heat treatment process for promoting alloying after pulling the wire, if it is low temperature, the slope of the crystallographic direction of the crystal orientation of the &lt;111;&gt; The ratio will become high, and if it is high temperature, the ratio of the area will decrease. If the decrease in the area is promoted by recrystallization in the process of heating in the crucible, the directionality in the aggregate structure is easily lost. Specifically, if the temperature in the furnace is 21 〇 &lt; t 260 ° C, the ratio of the area is 1 〇〇 %, and if the range is 峨 战 , , , , , , , , , , , , , , , , , , , , , , , , The ratio can be controlled by the temperature of the heat treatment. In the method for producing a bonding wire according to the present invention, the method for producing a bonding wire having a side edge hardness of 0.2 to 2.0 GPa on the surface of the coating layer is difficult to manufacture by a usual manufacturing method, @ in a special method, The alloy of gold and palladium on the surface of the wire is specially softened. Specifically, after the wire is drawn to the target wire diameter by any of the above methods, after the heat treatment process for alloying is completed, the joint wire can be disposed on each reel at 4% controlled by argon mixing. In an electric furnace of hydrogen atmosphere, it is heated by heating at 130 to 18 rc for 24 to 28 hours. If it is a lower temperature than 13 (TC is a lower temperature or a shorter time than 24 hours, it is not possible to soften the alloy of gold and palladium to a hardness as described above. If it is higher than 1 °C or more than 28 hours For longer periods of heat, the diffusion between adjacent wires is promoted to 'there will be a close relationship between the wires.' Therefore, it is necessary to pay attention to 2012056056. [Examples] Hereinafter, examples will be described. First, a manufacturing example of a bonding wire having a structure including silver and a permanent gold layer on the surface of the coating layer and an evaluation thereof will be described. . In the material of the bonding wire, the material used for the core purity is 99.99% by mass or more, and the copper used for the core wire is added to the B, P, Se ' Ca, A1, and coating layers of the core t. The silver used in the skin layer. The above-mentioned copper or copper and an additive element raw material are used as a starting point; after weighing, it is heated and dissolved under a vacuum of hydrazine to obtain an ingot having a diameter of about 2 nm of copper or a copper alloy. Thereafter, forging, rolling, and drawing are performed to make a wire having a predetermined diameter. Thereafter, a palladium-containing coating layer was formed by electrolytic plating on the surface of each of the wires. Here, the thickness of the coating layer is controlled during the time of electrolytic plating. Thereafter, a silver film is electrically formed on the surface of the coating layer, and is held at 300 to 800. In the furnace, the wire is continuously swept at a speed of /min, thereby forming an alloy layer of silver x and palladium on the surface of the coating layer. Here, the thickness of the alloy layer is determined by the above-mentioned silver film. That is, the electroplating time is controlled. As shown above, a bonding wire having a straight diameter of 20 m is obtained. Among them, in a part of the sample, the slope of the wire direction for controlling the crystal orientation of &lt;10 〇&gt; When the area of the crystal grain of 丨5 degrees or less is the thickness of the wire diameter of 80% or more, the shrinkage ratio of the mold is set to about 13 to 18%, and the wire is pulled, and the wire diameter is less than 8 〇 #m. When the thickness of the wire is pulled, the above-mentioned shrinkage ratio is drawn at a ratio of more than 8 to 12%, which is larger than the normal shrinkage ratio. Further, in some samples, for the control of the surface of the coating layer for 201205695 Hardness, the joint wire is arranged in each coil in an electric furnace controlled by an argon mist, and is heated at 15 〇 2 〇〇 2 〇〇 2 2 〜 2 4 hours. The diameter of the anger line, the thickness of the coating layer and the alloy layer will be bonded On the one side of the surface, the side is destroyed, and the analysis is performed by aes. 'In addition, the jointed wire is subjected to cross-section grinding, and the ^m is divided into the composition-surface to carry out the enthalpy. (4) The concentration &amp; 5_, and the concentration of silver is less than 10%. In the alloy layer containing silver and palladium on the surface of the coating layer, a region having a silver concentration of 10 to 70% is used as the alloy layer. The thickness and composition of the coating layer and the alloy layer are separately described. In Table 1 to 5 °, in order to evaluate the oxidation preventing effect of the bonding wire obtained by the coating layer, the bonding wires were placed on each reel for 72 hours in a high-temperature and high-humidity furnace having a humidity of 85% and a temperature of 85 Å. Accelerate the test to promote the oxidation of the surface of the wire. After heating, remove the bonding wire from the high-temperature and high-humidity furnace and observe the degree of surface oxidation by optical microscopy. At this time, if the surface of the wire is fully oxidized, the surface of the wire is X δ A part of the oxidation is marked with △. If the surface of the wire is not oxidized, the mark of "long-term storage (oxidation)" in the surface of the surface is marked with a mark. In order to evaluate the bond obtained by the coating layer. The vulcanization prevention effect of the wire is maintained in a high temperature furnace at a temperature of 1 9.5 ° C under atmospheric fog, and the bonding wires are placed on each reel for 155 hours to accelerate the test of the surface of the wire. When it is placed at a high temperature in the atmosphere fog as described above, even if it is a very small amount of sulfur contained in the atmosphere, it can accelerate the vulcanization. In the case of heating, the joint wire is taken out from the high temperature furnace to the market. The color meter (Minolta CR-300) sold is used to observe the degree of surface vulcanization. If the brightness is less than 30, it is considered to be vulcanized. If it exceeds 3 〇 and it is 4 〇 or less, it will be a practically unobstructed level. 40 is set to the preferred level. At this time, if the vulcanization part is observed on the surface of the wire, the mark is marked with x, if it is a bit level that is not practically practicable, the mark is △, if the surface of the wire is not vulcanized, the mark is marked with 〇 Marked in the "long-term storage (vulcanization)" position in Tables 1 and 5. A commercially available automatic wire accessor is used for the connection of the bonding wires. A portion was formed at the tip end of the bonding wire by arc discharge before the bonding instant, but the diameter was formed to be 34 // πι so as to be 17 times the diameter of the bonding wire. The mist surrounding gas at the time of production of the ball portion is formed into nitrogen. The actual diameter of the ball portion is measured by SEM to measure 2 各 each of the ball portions. If the difference between the maximum value and the minimum value exceeds the average value of the ball diameter, it is considered to be not intense and is not good. When % is less than or equal to 1%, it is considered to be moderate to Δ, and if it is more than 3% and is 5% or less, there is no practical good condition, 'it is good', and if it is 3% or less, It is a very good place to mark the "FAB true ball" in the air. In addition, when the spheroid is observed by SEM, if bubbles are found in the appearance, the field of "FAB bubble suppression in nitrogen" in the table 5 indicates that the ball is ground for each ball. Observed by an optical microscope, the bubbles were not observed on the face, which was extremely good. If the mark was ◎ ◎, if 10 bubbles were observed in only 12 balls, it was good, and only ◎ was recorded in ◎ 4 (four) is observed (four) bubble, for the use of the problem level level.叩 t t ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The bubble is inferior, and the X mark is described in Table 4, "FAB bubble suppression in nitrogen" (four). The A1 electrode having a thickness of 1/m formed on the Si wafer and the lead having a silver or palladium-plated lead frame were respectively used for bonding the bonding wires. After the prepared ball portion blood is also /, D. &lt;, the electrode to 260 ° C is ball bonded, and the bus bar portion of the bonding wire is heated to Μ. . . The aforementioned lead wire is wedge-joined, and the ball portion is again formed, thereby continuously overlappingly joined. The loop length is 4 · 9 πππ. Among them, the knife is carried out in a part of the sample: the reverse stroke joint with a loop length of about 1 mm, and the loop of the second sample is about 8-12 mils in other samples, and the loop length is about the aforementioned high back. In other samples, the length of the loop was approximately the same, the low loop of the second loop (1) was joined, and the other specimens were elongated with a length of 5.3_(2) 〇ro(1). Regarding the wedge-shaped bonding property of the bonding wire, the square-shaped gripping force MJ is used for the bonding wire of the cancer of the cancer at the interface of the wedge-shaped joint (the fourth interface). Cut off the measurement method to measure the crack load (the peeling (four) peel strength standard deviation exceeds _, must greatly improve the ^ right peel strength over _ and is less than 6mN, so in the actual capacity, therefore X' if it is super 5~, since there is no practical bit level 'in △, it is marked in the table "Ag々F2nd joint two so 〇' frame lead) and "Pd cut (five) two (: silver plate number 5丨) The position of the lead of the wire frame. 〇" (Right palladium plated bow | line 43 201205695 Here, it is observed by optical microscope whether damage is caused by the capillary. The number of loops observed is 2 〇, If there is no damage in one piece, it is extremely good to use ◎ ◎ mark, and when only 1 to 2 loops are observed to be damaged, it is good for 'good mark ◎ mark only when it is observed in 3 to 4 circuits. There is no problem at the bit level, with a 〇 mark, only in 5 When the damage is observed, it is a practically permissible bit level, and the △ mark is used. If six or more circuits are observed to be damaged, it is a poor mark, and the mark is marked as "damage suppression" in Table 丄, 5. The slope of the direction of the crystal orientation of the crystal grain of the <1〇〇> crystal orientation observed on the surface of the coating layer is calculated by observing the orientation of the individual crystal grains by the EBSD method. In the case of having a width of 8 &quot; m in a direction perpendicular to the direction of the wire of the bonding wire, a surface having a length of 150 (four) in the wire drawing direction of the bonding wire is observed, and each sample is observed for three fields of view. Tables 2 to 4 are the fields of "the area of the crystal grain having a slope of the line direction of the crystal orientation of 15 degrees or less". The crystal grains observed on the surface of the coating layer (1) The slope of the drawing direction is observed by the leaking method of the individual crystal grains. The drawing of the material 4 and the bonding wire is carried out in the direction of the straight line 2 = the width of the wire will be in the field of the bonding wire. Face 'each sample is observed 3 times two == 2~4 "The alignment of the crystal orientation, such as the area of the granules of the day". After the reverse bonding, the wrinkles of the surface of the wire are optically perceived. Brother "loop, if there is no wrinkle in one, it is extremely 44 201205695 Good to ◎ ◎ mark 'only when 1~2 loops are observed wrinkles, it is good to @6己号, only in 3~4 When the circuit is observed to be wrinkled, it is a practically problem-free bit level, with a 〇 mark. If the 5 traces are observed, the sensitive mark 'is bad' with the X mark, marked in Table 2~4. The stagnation of the enemy's mark is suppressed. The tilting of the surface of the bonding wire after the high-circuit bonding is performed by observing 2G loops with an optical microscope, and if there is no tilting of one of the samples, it is extremely good to ◎ ◎ mark only When it is observed that the tilt is poor in the two loops, it is good. When the ◎ mark is observed in only 3 to 4 loops, the tilt level is poor, and the bit level is practically no problem. Observed the poor tilt, for the difference, with the χ mark, marked in the surface of the table Elam bit suppression "of. The side hardness of the surface of the wire is measured by the neat (four) mark method, 卩h = accuracy, and the value is described in the field of the side hardness of Tables 3 to 4.扪表:: It is said that there is no damage in the neck after the low-circuit joint is observed. If there is no damage in one of the two loops, it is extremely good that there are 1 to 2 loops in the right 20, and the damage is observed. For - there is a phase level, with a 〇 mark, if the damage is observed, the difference is χ mark, mark the 2:3:: 76.2 / / m (3m (1) level low circuit head damage" position. 4 For the loop after the long joint, the loop 2 of each sample is determined. Here, the value measured by the * camera is set as the wire bending rate: the value of the spoon divided by the length of the loop is less than 4%. The state is extremely good, with 45 201205695 ◎ mark, if it is 4~5%, with 〇 mark, if it exceeds 5%, it is judged to be a bit problem with no problem in practical use, it is judged as bad, "5 of Table 4" The field of 3 mm (210 mil class) long curved" is marked with an X mark, and the plastic phase of the bonding wire formed by the gold layer is ηBη. For the surface of the aforementioned coating layer, there is gold and palladium.

Control during the time of application. After that, „ 卜 ~ The thickness of the heart layer is in electrolytic plating

A gold film was formed by plating, and the wire was continuously swept at a speed of 3 μm/min in a furnace maintained at 300 to 8 Torr to form an alloy layer of gold and palladium on the surface of the coating layer. Here, the thickness of the alloy layer is controlled by the above-mentioned gold film, that is, the electroplating time. A bonding wire having a diameter of 20/m was obtained as shown above. In the sample, in order to control the area of the crystal grain in which the slope of the crystal orientation of the &lt;111 &gt; crystal orientation is 15 degrees or less, the thickness of the wire diameter is 150 &quot; m or more, and the mold is When the shrinkage ratio is formed to be about 16 to 20%, the wire is pulled, and when the wire diameter is less than the thickness of the wire of i5〇&quot;m, the shrinkage ratio is about 13 to 15%, which is larger than the normal shrinkage ratio. Come to pull the line. Further, in a part of the samples, 46 201205695 was used to control the edge hardness of the surface of the coating layer, and the bonding wires were placed in an electric furnace controlled by an argon mist for each reel a at ~2〇〇 〇c under 2 0~2 4 hours of heating. The diameter of the core wire, the thickness of the coating layer and the alloy layer in the bonding wire of the element is analyzed by AES while the surface of the bonding wire is sputtered, and the bonding wire is subjected to cross-section grinding, and the composition is analyzed by ΕΜ The measurement was performed on one side. A region in which the concentration of palladium is 5% by weight or more and the concentration of gold is less than 15% is used as a coating layer, and in the alloy layer containing gold and palladium on the surface of the coating layer, the gold concentration is in the range of 15 to 75%. The area acts as an alloy layer. The thickness and composition of the coating layer and the alloy layer are shown in Tables 6 to 10, respectively. In order to evaluate the oxidation preventing effect of the bonding wire obtained by the coating layer, the bonding wire was placed on each reel for 72 hours in a high-temperature high-humidity furnace having a humidity of 85% and a temperature of 85 t: an accelerated test for promoting surface oxidation of the wire was performed. . After heating, the bonded wires were taken out from the high-temperature and high-humidity furnace, and the degree of surface oxidation was observed by an optical microscope. At this time, if the surface of the wire is completely oxidized, the X mark is used. If the surface of the wire is not oxidized, the column of "long-term storage (oxidation)" in Table 6, i 〇 is marked with a mark. In order to evaluate the vulcanization preventing effect of the bonding wire obtained by the coating layer, the temperature was maintained at 195 t in a high-temperature furnace under atmospheric atmosphere, and the bonding wire was placed on each reel for 155 hours to accelerate the surface vulcanization. . When it is placed at a high temperature in an atmospheric atmosphere as described above, even if it is a trace amount of sulfur contained in the atmosphere, the vulcanization reaction can be accelerated. After heating, the bonding wires are taken out from the two furnaces, and the degree of surface vulcanization is observed by a commercially available color 47 201205695 (Minolta CR-300). If the brightness (L*) is 30 or less, it is regarded as vulcanization. In addition, it is a level of 4 〇 or less that is practically not obstructive, and more than 40 is set to a preferred level. At this time, if the vulcanization portion is observed on the surface of the wire, the mark is marked with x, and if it is a bit level which is not practically practical, the mark is marked with △, and if the surface of the wire is not vulcanized, it is marked with the mark ' in Tables 6, 10 The "long-term storage (vulcanization)" field. A commercially available automatic wire bonder is used in the connection of the bonding wires. The ball portion was formed at the tip end of the bonding wire by arc discharge before the bonding, but the diameter was formed to be 34 / / m so as to be 17 times the straight line of the bonding wire. The mist surrounding gas at the time of production of the ball portion is formed as nitrogen. The actual diameter of the ball portion is measured by SEM to measure each of the two ball portions. If the difference between the large value and the minimum value exceeds the average value of the ball diameter (10), it is considered to be uneven and is not good, and X is exceeded. When 5% is 1% or less, it is regarded as the middle 2, and if Δ' is more than 3% and is 5% or less, there is no practical non-form, and it is considered to be good, and if it is 3% or less, It is considered to be extremely good, 〇, marked in the brackets of “FAB True Ball in Nitrogen” in Tables 6 and 10. That is, the ball portion is observed by sem, and if the bubble is found in the appearance, the field mark of the "FAB bubble suppression in nitrogen" of the 6, 10 towel is marked with an X mark, and when the bubble is not found, the mark is marked. In the case of the bonding object of the thickness of the wire, the wire is formed on the Si wafer. The A1 electrode of 〃m and the surface of the gold or palladium-plated lead frame are joined. The ball portion produced is replaced with the electrode of the heated i 26Gt, and the bus bar portion of the bonding wire is heated to 260 ° C. The aforementioned "joining" is used to make the ball portion again, thereby continuously joining the balls. Circuit 48 201205695 - The long became 4. 9 positions. Among them, the height of each road is about 304. 8 # m (12mi 1), the circuit and the material are carried out: the return loop is joined, and the other height of the loop length 2 in other samples is 76.2#m (3m(1) The low-circuit junction "3_, the loop height is 5.3fflm (2I〇m(1) of the long joint, and the other 4 materials are the wedge-shaped joints of the joint wires, and the joint wires of the wedge-joined state are :::: Department: The so-called stripping::: / shell, 疋 method, for the rupture load obtained at the time of cutting, to determine 40 burst loads (peel strength). If the deviation exceeds 5 mN, the unevenness must be greatly improved. Therefore, if x is more than 3 ιπΝ and 5 mN or less, it is in the tube. ...... Because there is no major problem in the use, the right is more than Μ below. It is good, so the 6 1G ""VF 2nd bonding" β is used as the gold ore for the frame) and the "...(6) bonding" (if (4) when the lead of the lead frame is applied). Observe with an optical microscope whether it is produced in the loop due to capillary Damage: The number of loops observed is 20, and if there is no damage to one, it is very good to ◎ ◎ έ 号, only when i ~ 2 loops are observed to be damaged, it is good to ◎ 5 When only 3 to 4 loops are observed to be damaged, there is no problem with the bit level, and the mark is used, and only 5 loops are observed when the shell is injured. In the case of the △ mark, if six or more circuits are observed to be damaged, they are inferior, and the X mark is used to mark the field of "damage suppression" in Tables 6 and 10. Observed on the surface of the coating layer. &lt;11 1&gt; Crystalline of the crystal grain 201205695 The slope of the orientation direction of the orientation is calculated after the orientation of the individual crystal grains is observed by the EBSD method. When this calculation is performed, it is perpendicular to the direction of the bonding wire. It has a width of 8 mm and will be in the direction of the bonding wire field = 15°... length. Each sample is observed for 3 times. (10) Tables 7 to 9 have a slope of 15 degrees in the direction of the wire direction of the crystal orientation. The rest of the area of the following crystal grains". The bonding after the high loop bonding described above The tilting of the surface of the wire is not good. Γ: Microscopic observation of 2° loops. If no one is observed, no observation is made. (4) No X is good. ◎ ◎ mark 'If only 1 to 2 loops are observed, the skew is observed. When it is bad, it is good for 1 ◎ Ε When the road is observed to be poorly tilted, in the case of 3 to 4 times _, ... no problem, the right level is observed in 5 or more circuits, and the inclination is poor. ::r7, "High loop tilt suppression: 'The two-negative (four) trace method, ... the right side of the booth called "" is shown in Tables 8 to 9 "The wire shows no damage". Each sample is optically 弁, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Marked in the position of "^guan 2_bei injury, low-level circuit neck injury" in Tables 8 to 9. Κ3ΠΠ1) About the loop after the long joint is completed. The loop 2 f of each sample is measured using a hinge machine. Here, the average value is divided by the length of the loop 50 201205695 • The value obtained is set as the wire bending rate, ◎ mark, if..., it is judged as true: upper:] is broken very well, with 〇 mark, if it is one If the level of the problem is exceeded, if it exceeds (10), it is judged to be the bit level used for the bad n, and the position of the 5.3 mark, "5.3_(2) level length X5 唬 ' is marked in the small test piece of Table 8". In the evaluation of the wafer damage, if the crack is generated in the electrode g ' ϋ邛 20 剖面, the stone is cracked, that is, the crack is judged to be bad, and the Χ mark is not observed. And the field marked with 〇 mark. The evaluation results of Table 1 to Table 10 are explained below. The surface of the four lines of Examples 1 to 63 and the examples of Examples 136 to 192 of Table 6 were formed to form a surface of 10 to 200 nm. The surface of the layer additionally had a thickness of silver and chemical properties. In the bonding wire, the 'available surface ensures the anti-oxidation of the FAB (=:))) or the true sphericality of the ball ("Nitrogen, the surface is obtained on the palladium plating lead frame: good Bonding ("Pd cut 2nd joint"). (4) As shown in Example 1, if the coating layer is not specifically provided on the copper wire, the core, ·: long-term storage or 2nd bondability Further, as in Comparative Example 2, when the coating layer on the surface of the copper core wire is formed into silver, the true sphericality of the ball portion in nitrogen is inferior. Further, as shown in Comparative Examples 3 to 5. When only the coating layer is provided on the copper wire 4, the joint shape on the lead frame of the kiln is relatively poor. Further, as shown in Comparative Example 6, even above the copper core wire, l0~ A thickness in the range of 200 nm forms a coating layer of palladium, 51 201205695. Further, when the thickness of the silver and the sharp alloy layer formed on the surface thereof is thinner than that, the ore is applied. In addition, as shown in Comparative Example 7, even if a coating layer of palladium is formed on the copper core wire in a thickness in the range of 10 to 200 nm, silver and palladium are additionally formed on the surface thereof. When the thickness m of the 7 alloy layer is thicker, it becomes not S to ensure a stable buckle. The gold layer is oxidized or vulcanized, thereby making any of the characteristics evaluated poor. Further, as shown in Comparative Example 8. a coating layer in which palladium is formed on the copper core wire in a thickness in the range of 10 to 20 〇 nm, and the silver concentration in the silver and the alloy layer on the surface is less than 10%. The wedge-shaped bondability on the upper side is inferior. Further, as in Comparative Example 9, the coating layer is formed in a thickness of 1 〇 to 2 〇〇 nm over the copper core wire, and silver is additionally formed on the surface thereof. When the silver concentration in the alloy layer is more than 75%, the true sphericality of the ball portion in nitrogen is inferior. 1匕: as shown in Comparative Example 10, if formed on the copper core wire When the thickness of the coated ruthenium of palladium exceeds the range of 10 to 2 〇〇 nm, even if another

The thickness of the alloy layer of the silver iridium on the surface is in the range of 3 to 8 Gnm, and if bubbles are formed in 2, the bubble is generated ("... ΑΒ bubble suppression" field). For example, if you only have a core wire that is not covered with a coating layer on the copper wire, long-term storage or 2nd bonding is poor, as in the case of Comparative Example 12 - #r 2 The coating layer on the surface of the copper core wire is formed into a silver =:::part:: the sphericality is greatly deteriorated, and the cracked layer on the surface is formed as a fork in long-term storage. Also #乱(9)珠. The true sphericality of ruthenium is greatly improved as shown in Examples 14 to 16. If only the copper core wire is provided, the wedge bondability on the palladium-plated lead frame of the coating layer of pour palladium on the surface of the 201205695 is deteriorated. It is shown that even if the coating layer of palladium is formed on the copper core wire in a thickness range of 丨〇 to 200 nm, the thickness of the alloy layer of gold and palladium formed on the surface thereof is also thinner than 3 nm, palladium plating lead The wedge bond on the frame is not sufficient. Further, as shown in Comparative Example 18, even if the coating layer was formed on the copper core wire at a thickness in the range of 1 〇 to 2 〇〇 nm, the thickness of the alloy layer formed on the surface thereof was also When it is thicker than 8〇1^, it becomes a stable quality, and the wedge-shaped bondability ("Pd-L/F 2nd bonding") on the lead frame of the money is inferior. In addition, due to the alloy The layer is oxidized and cannot satisfy the true sphere of the ball (the field of FAB true in the nitrogen). Further, as in Comparative Example 19, it was not on the copper core wire. a coating layer of a thickness-shaped palladium in the range of ~2 〇〇 nm, additionally formed in the alloy layer of the gold and the surface on the surface:: low degree of farming &amp; 15% of the wedge shape on the palladium-plated lead frame Bonding is not divided. Further, 'as shown in Comparative Example 1', the thick U.S. UUnm X in the range above the copper core wire forms a coating layer of palladium, and forms a true spherical shape of the ball portion which is adhered to the alloy φ of gold and palladium. 2T: 75%, in nitrogen... As shown in Comparative Example 21, if the thickness of the coating layer of palladium on the copper 4 line is 4, the thickness of the coating layer is even if it is different. The range of 2 〇〇 nm forms a range of 3 to 80 mn of gold and palladium on the surface of the surface, and if a small diameter sphere is formed in the nitrogen: the 'dry' degree is (the "FAB bubble suppression in nitrogen" is blocked. ). ..., bubbles will occur

An example in which the surface of the coating layer of the gold bismuth layer has a bonding wire having a structure of silver and a gold layer will be described.叼Q 53 201205695 As described in Examples 1 to 12, 16 to 27, 31 to 42, and 46 to 57 of Table 1, 'a coating layer having a thickness of 1 G to nm is formed on the surface of the core wire of copper, and the coating layer is formed on the coating layer. In the bonding wire of the alloy layer of silver and palladium having a thickness of 10 (10), the surface is ensured to have oxidation resistance ("long-term storage (oxidation)" field) or the true sphericality of the ball ("Nitrate The FAB is a true sphere, and a good wedge-shaped bond on the palladium-plated lead frame ("Μ' / F 2nd joint" field) is obtained. With respect to these, as shown in the comparative example, if only the core wire of the coating layer is not provided on the copper wire, the long-term storage or the 2nd bondability is inferior. Further, as shown in Comparative Example 2, when the coating layer on the surface of the copper core wire was made of silver, the true sphericality of the ball portion in nitrogen was inferior. Further, as shown in Comparative Examples 3 to 5, when only the coating layer was provided on the copper core wire, the mold bondability on the cored lead frame was inferior. Further, as shown in Comparative Example 6, even if a coating layer of 1 bar was formed on the copper core wire with a thickness in the circumference of iQ~2_m, the thickness of the alloy layer of the silver and the other formed on the surface thereof was also formed. When it is thinner than lnm, the mold bondability on the lead frame of the ore dressing is inferior. Further, as shown in Comparative Example 7, even if the (four) coating layer was formed on the copper core wire in a thickness in the range of 10 to 20 Å, the thickness of the silver and the alloy layer additionally formed on the surface thereof was also 3 When 〇nm is thicker, it becomes difficult to ensure stable quality, and the alloy layer is oxidized or vulcanized', and thus any characteristic evaluated is also inferior. Further, as shown in Comparative Example 8, the coating layer was formed on the copper core wire in a thickness in the range of 10 to 200 nm, and the silver concentration in the gold layer of the silver ', which is additionally formed on the surface thereof, was low. At j 〇%, the mold bondability on the palladium-plated lead frame is poor. In addition, as shown in Comparative Example 9, above the copper core 54 201205695 line, 10~? The thickness of m is formed outside the surface of the surface to form the coating layer. When the thickness is 70%, the silver concentration in the alloy layer of nitrogen and palladium is higher than that of the ball in the gas. The ball is relatively poor. In addition, as shown in the case of the pregnancy example 1 ,, the thickness of the coating layer of palladium above the 10~9ηη 乂 copper core wire exceeds 10~2〇〇nro, and the palladium is poured into a, even if The thickness of the silver and/or gold layer formed on the surface is 3 to 3 〇, and the u bubble (the inhibition of FAB bubble suppression in nitrogen). In the examples 16 to 63, when the above-mentioned alloy of silver and palladium is formed, the damage caused by the capillary is more suppressed (the "damage suppression" field), and even in the case of Gas shape:,. (4) The part also suppresses the occurrence of bubbles ("the bubble suppression in nitrogen" is as shown in the examples 31 to 63. If the silver concentration is 30% or more, the effect is higher. Example 64 of Table 2 When the slope of the crystal grain direction of the &lt;100&gt; crystal orientation observed on the surface of the above-mentioned bonding wire is 〇5 or less, the area of the crystal grain is 5〇% or more and 1%% or less, Counter-attack: When it is combined, the effect of suppressing wrinkles on the surface of the circuit will become higher ("stop wrinkle suppression"). If the area is 7〇% or more, the effect will be more south. As shown in the fourth to sixth embodiments of Table 2, the area of the crystal grain having a slope of the line direction of the &lt;111&gt; crystal orientation observed on the surface of the bonding wire of 15 degrees or less is 6% or more, When the height is less than 1%, the effect of suppressing the occurrence of the tilting failure is high ("high circuit (four) suppression" field), and if the area is 70% or more, the effect is more effective.言55 201205695 as shown in Examples 92 to 96, 99 to 102, 104 of Table 3, if the surface of the bonding wire is The hardness is 〇. 2~2. The range of 〇GPa, even if the low-circuit joint is additionally performed, the neck damage is also suppressed ("76 2 //m(3mil) low-circuit neck injury" field). In the examples of the examples 109 to 117 and 121 to 124, the core wire is composed of at least one of B, P, and Se, and the copper σ gold of the total amount of B, P, and Se is suppressed even when elongated bonding is performed. Bending of the circuit (paste of 5.3 mm (210 mil) grade bend). 2, as shown in Examples 125 to 135 of Table 5, even if a diffusion layer is formed between the coating layer and the "line", or the core wire is contained The copper can be diffused in the coating layer to ensure the effect of the present invention. Next, an example of a bonding wire having a gold layer on the surface of the coating layer will be described as an example of the examples 136 to 192 of Table 6. The surface of the copper core wire has a palladium coating layer having a thickness of 1 〇 to 200 nm, and the thickness of gold and the nipple having a thickness of 1 to 8 〇 nm outside the surface of the coating layer ensures oxidation resistance (" Long-term storage (oxidation)"_:) = chemical ("long-term storage (vulcanization)" field), or The true ball of the ministry ("the FAB true ball" block), on the one hand, obtains the good wedge-shaped bondability on the lead frame ("Pd cut 2nd joint J"). It is shown that only the core wire which is not provided with a layer on the copper wire is used for long-term storage or poor 2nd bondability.

In the eleventh example, when the coating layer on the surface of the Cubic line is formed into gold, the true sphericality of the I-ball portion in the nitrogen is less, and . Further, as shown in Comparative Example 12, even if the thickness of the coating layer in the range of Π) to 20- above the copper core wire of 56 201205695 is formed, the thickness of the alloy layer of gold and palladium additionally formed on the surface thereof is also formed. When the ratio is thinner, the wedge-shaped bondability on the palladium-plated lead frame is not sufficient. Further, as shown in the comparison of Η3, even if the thickness of the coating layer is formed in the range of the thickness of the copper core wire, the thickness of the alloy layer formed on the surface thereof is thicker than 8_, It is difficult to ensure stable quality, and the wedge-shaped bondability on the palladium-plated lead frame ("pd_L/F2nd access field") is inferior. In addition, since the alloy layer is oxidized, it does not satisfy the true sphericality of the ball portion. ("The interception of FAB true ball in nitrogen"). Further, as shown in the comparative example, the coating layer was formed on the copper core wire in a thickness ranging from 1 Å to 2 Å, and the gold concentration on the surface and the gold concentration in the gold-input layer were formed. When the low force is 15%, the (4) bondability on the lead-plated lead frame is not sufficient. Further, as shown in Comparative Example 15, the gold concentration in the range of 20 to 2 G () nm of the copper core wire was such that the gold concentration in the alloy layer of gold and palladium additionally formed on the surface of the coating layer exceeded 75. When the value is high, the true sphericality of the ball portion in the nitrogen is poor. Further, as in the comparative example, the thickness of the coating layer of palladium formed on the copper core wire exceeds the work. In the range of ~2〇〇nm, even if the thickness of the alloy layer of gold and palladium formed on the surface thereof is in the range of 3 to 8 〇 nm, if a small-diameter ball portion is formed in nitrogen, bubbles may occur in p (" "Field of FAB bubble suppression in nitrogen"). 2. As shown in Examples 136 to 168, 250, 251, 253, and 256, if the gold concentration in the alloy formed by the combination of gold and palladium is not more than the above, the true sphericality of the ball python is further improved ("Nitr In the FAB true ball position"). As shown in Examples 169 to 192, 252, 254, 255, and 257 to 260, 57 201205695, if the gold concentration in the alloy of gold and palladium is 4% or more, the wedge bonding property is further improved ("Pd-L/ F 2nd joint" block). As shown in Examples 193 to 216 of Table 7, the slope of the crystal grain in the direction of the line direction of the <111> crystal orientation observed on the surface of the bonding wire was 50% or more, 1〇. When the area is below 70%, the effect of suppressing the occurrence of the tilt failure is increased ("high circuit tilt 2 suppression"). If the area is 70% or more, the effect is higher. As shown in Examples 217 to 222 and 225 to 228 of Table 8, when the surface of the bonding wire has a side hardness of 0.2 to 2. OGPa, neck damage can be suppressed even if low-circuit bonding is additionally performed (" 76 2 &quot;m(3mii) low loop neck injury" rotten position). As shown in Examples 234 to 242 and 246 to 249 of Table 9, in the case where the core wire contains at least i kinds of copper alloys of 5 to 3 Å by mass in total of B, P, and Se, even when elongated bonding is performed. Also, the bending of the loop is suppressed ("5. 3mm (210mil) grade bend" field). On the other hand, as shown in the embodiment 243, when the core wire is added in excess of 3 〇〇 mass ppm, wafer damage ("wafer damage" field) occurs. As shown in Examples 250 to 260 of Table 10, the effect of the present invention can be ensured even if a diffusion layer is formed between the coating layer and the core wire or copper contained in the core wire is diffused in the coating layer. Core material palladium-coated coating layer Silver and palladium alloy layer long-term storage (oxidation) Long-term storage (vulcanization) Ag-L/F 2nd bonding nitrogen in FAB true spherical Pd-L/F 2nd bonding damage inhibition FAB bubble inhibition Thickness of coating layer (nm) Thickness (nm) of alloy layer alloy layer Example 1 Cu Yd 10 Agl0Pd90 1 〇〇 ◎ Δ 〇〇 58 201205695 Example 2 Cu Pd 10 Agl0Pd90 1 〇Δ 〇 ◎ Δ 〇〇 Example 3 Cu Pd 10 Agl0Pd90 1 〇 △ 〇 ◎ Δ 〇〇 Example 4 Cu Pd 10 Agl0Pd90 3 〇 △ 〇 ◎ Example 5 Cu Pd 100 Agl0Pd90 3 〇Δ 〇 ◎ 〇〇〇 Example 6 Cu Pd 200 Agl0Pd90 3 〇Δ 〇 ◎ 〇〇〇 Example 7 Cu Pd 10 Agl0Pd90 15 〇Δ 〇 ◎ 〇〇〇 Example 8 Cu Pd 100 Agl0Pd90 15 〇 △ 〇 ◎ 〇〇〇 Example 9 Cu Pd 200 Agl0Pd90 15 〇 △ 〇 ◎ 〇〇〇 Example 10 Cu Pd 10 Agl0Pd90 30 〇Δ 〇 ◎ Example 11 Cu Pd 100 Agl0Pd90 30 〇Δ 〇 ◎ 〇〇〇 Example 12 Cu Pd 200 Agl0Pd90 30 〇Δ 〇 ◎ 〇〇〇 Example 13 Cu Pd 10 Agl0Pd90 80 Δ Δ Δ ◎ Δ Δ Δ Example 14 Cu Pd 100 Agl0Pd90 80 Δ Δ Δ ◎ Δ Δ Δ Example 15 Cu Pd 200 Agl0Pd90 80 Δ Δ Δ ◎ Δ Δ Δ Example 16 Cu Pd 10 Ag20Pd80 1 〇Δ 〇 ◎ Δ ◎ ◎ Example 17 Cu Pd 100 Ag20Pd80 1 〇Δ 〇 ◎ Δ ◎ ◎ Example 18 Cu Pd 200 Ag20Pd80 1 〇Δ 〇 ◎ Δ ◎ ◎ Example 19 Cu Pd 10 Ag20Pd80 3 〇 △ 〇 ◎ ◎ ◎ Example 20 Cu Pd 100 Ag20Pd80 3 〇 △ 〇 ◎ ◎ ◎ Example 21 Cu Pd 200 Ag20Pd80 3 〇 Δ 〇 ◎ ◎ ◎ Example 22 Cu Pd 10 Ag20Pd80 15 〇Δ 〇 ◎ 〇 ◎ ◎ Example 23 Cu Pd 100 Ag20Pd80 15 〇 △ 〇 〇 ◎ ◎ Example 24 Cu Pd 200 Ag20Pd80 15 〇Δ 〇 ◎ ◎ ◎ Example 25 Cu Pd 10 Ag20Pd80 30 〇Δ 〇 ◎ ◎ ◎ ◎ Example 26 Cu Pd 100 Ag20Pd80 30 〇Δ 〇 ◎ ◎ ◎ Example 27 Cu Pd 200 Ag20Pd80 30 〇 △ 〇 ◎ ◎ ◎ Example 28 Cu Pd 10 Ag20Pd80 80 Δ Δ Δ ◎ Δ ◎ ◎ Example 29 Cu Pd 100 Ag20Pd80 80 Δ Δ Δ ◎ Δ ◎ ◎ Example 30 Cu Pd 200 Ag20Pd80 80 Δ Δ Δ ◎ Δ ◎ ◎ Example 31 Cu Pd 10 Ag30Pd70 1 〇 △ 〇 ◎ Δ ◎ ◎ ◎ ◎ Example 32 Cu Pd 100 Ag40Pd60 1 〇Δ 〇 ◎ Δ ◎ ◎ ◎ ◎ Example 33 Cu Pd 200 Ag30Pd70 1 〇 Δ 〇 ◎ Δ ◎ ◎ ◎ ◎ Example 34 Cu Pd 10 Ag30Pd70 3 〇 Δ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 35 Cu Pd 100 Ag40Pd60 3 〇 Δ 〇 ◎ ◎ ◎ ◎ ◎ ◎ Example 36 Cu Pd 200 Ag30Pd70 3 〇 Δ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 37 Cu Pd 10 Ag40Pd60 15 〇 △ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 38 Cu Pd 100 Ag30Pd70 15 〇 Δ 〇◎ 〇 ◎ ◎ ◎ ◎ Example 39 Cu Pd 200 Ag40Pd60 15 〇 Δ 〇 ◎ ◎ ◎ ◎ ◎ ◎ Example 40 Cu Pd 10 Ag30Pd70 30 〇 △ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 41 Cu Pd 100 Ag40Pd60 30 〇 Δ 〇 ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Cu 44 Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Δ Δ Δ ◎ Δ ◎ ◎ ◎ ◎ Example 45 Cu Pd 200 Ag30Pd70 80 Δ Δ Δ ◎ Δ ◎ ◎ ◎ ◎ Example 46 Cu Pd 10 Ag50Pd50 1 〇 Δ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 47 Cu Pd 100 Ag60Pd40 1 〇 Δ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu 〇◎ ◎ ◎ ◎ ◎ ◎ Example 51 Cu Pd 200 Ag70Pd30 3 〇 Δ 〇 ◎ ◎ ◎ ◎ ◎ Example 52 Cu Pd 10 Ag70Pd30 15 〇 Δ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 53 Cu Pd 100 Ag60Pd40 15 〇 △ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Ag70Pd30 30 〇Δ 〇 ◎ ◎ ◎ ◎ ◎ Example 57 Cu Pd 200 Ag50Pd50 30 〇 △ 〇 ◎ ◎ ◎ ◎ ◎ Example 58 Cu Pd 10 Ag50Pd50 80 Δ Δ Δ ◎ ◎ ◎ ◎ ◎ ◎ Example 59 Cu Pd 100 Ag50Pd50 80 Δ Δ Δ ◎ ◎ ◎ ◎ ◎ ◎ Example 60 Cu Pd 200 Ag50Pd50 80 △ △ △ ◎ ◎ ◎ ◎ ◎ ◎ Example 61 Cu Pd 10 Ag75Pd25 80 △ △ △ Δ ◎ ◎ ◎ ◎ ◎ ◎ Comparative Example 1 Cu No 0 None 0 X 〇 XXX 〇〇 Comparative Example 2 Cu Ag 200 No 0 〇〇〇X ◎ ◎ ◎ ◎ ◎ Comparative Example 3 Cu Pd 100 No 0 〇〇〇 ◎ XXX Comparative Example 4 Cu Pd 5 No 0 X 〇 XXXXX Comparative Example 5 Cu Pd 210 No 0 〇〇〇 ◎ XXX surface also has bubbles Comparative Example 6 Cu Pd 10 Agl0Pd90 0 〇Δ 〇 ◎ XXX Comparative Example 7 Cu Pd 100 Agl0Pd90 90 X △ XXXXX Comparative Example 8 Cu Pd 200 Ag5Pd95 3 〇△ 〇 ◎ XXX Comparative Example 9 Cu Pd 200 Ag80Pd20 30 〇 △ 〇 X ◎ ◎ ◎ ◎ ◎ Comparative Example 10 Cu Pd 210 Ag20Pd80 15 〇 △ 〇 ◎ 〇 ◎ X surface also has bubbles (Table 2) Core material containing palladium ruthenium coated silver The area of the crystal grain of the alloy layer with palladium in the direction of the linear orientation of the crystal orientation of 15 degrees or less (3⁄4) and the crystal grain of the slope of the crystal direction of the &lt;m&gt; crystal orientation of 15 degrees or less Area (%) Circuit inclination suppression coating layer thickness (nm) Alloy layer alloy layer thickness (nm) Example 4 Cu Pd 10 Agl0Pd90 3 40 60 〇 ◎ Example 5 Cu Pd 100 Agl0Pd90 3 30 70 〇 ◎ ◎ Example 6 Cu Pd 200 Agl0Pd90 3 20 80 〇 ◎ ◎ Example 64 Cu Pd 10 Agl0Pd90 1 50 50 ◎ Example 65 Cu Pd 10 Agl0Pd90 1 60 40 ◎ 〇 Example 66 Cu Pd 10 Agl0Pd90 1 70 30 ◎ ◎ 〇 Example 67 Cu Pd 10 Agl0Pd90 1 100 0 ◎ ◎ Example 68 Cu Pd 10 Agl0Pd90 3 50 50 ◎ Example 69 Cu Pd 10 Agl0Pd90 3 60 40 ◎ 〇 Example 70 Cu Pd 10 Agl0Pd90 3 70 30 ◎ ◎ 〇 Example 71 Cu Pd 10 Agl0Pd90 3 100 0 ◎ ◎ Example 72 Cu Pd 100 Ag20Pd80 15 50 50 ◎ Example 73 Cu Pd 100 Ag20Pd80 15 60 40 ◎ 〇 Example 74 Cu Pd 100 Ag20Pd80 15 70 30 ◎ ◎ Example 75 Cu Pd 100 Ag20Pd80 15 100 0 ◎ ◎ Example 76 Cu Pd 10 Ag30Pd70 30 50 50 ◎ Example 77 Cu Pd 10 Ag30Pd70 30 60 40 ◎ 〇 Example 78 Cu Pd 10 Ag30Pd70 30 70 30 ◎ ◎ 〇 Example 79 Cu Pd 10 A g30Pd70 30 100 0 ◎ ◎ 〇 Example 80 Cu Pd 10 Ag30Pd70 80 50 50 ◎ Example 81 Cu Pd 10 Ag30Pd70 80 60 40 ◎ Example 82 Cu Pd 10 Ag30Pd70 80 70 30 ◎ ◎ Example 83 Cu Pd 10 Ag30Pd70 80 100 0 ◎ ◎ Example 84 Cu Pd 200 Ag70Pd30 15 50 50 ◎ Example 85 Cu Pd 200 Ag70Pd30 15 60 40 ◎ Example 86 Cu Pd 200 Ag70Pd30 15 70 30 ◎ ◎ Example 87 Cu Pd 200 Ag70Pd30 15 100 0 ◎◎ 〇Example 88 Cu Pd 200 Ag75Pd25 15 50 50 ◎ 〇60 201205695

The slope of the linear direction of the &lt;100> crystal orientation is the area of the crystal grain of 15 degrees or less (3⁄4) The thickness of the coating layer (nm) The thickness of the alloy layer alloy layer (nm) The edge hardness of the surface of the wire (GPa ) Anti-wrinkle suppression 76. 2; um (3mil) low loop neck injury

(Table 4) The combination of the palladium-coated palladium coating and palladium is the area (%) of the crystal grain of the slope of the line direction of the crystal orientation of the line (00&gt; (GPa) Anti-wrinkle suppression 76.2jum C3mil) Grade low loop neck damage 5. 3mm (210mil) grade long curved core residue (except for unavoidable impurities) Additive element (mass ppm) in the core material Thickness of layer coating layer (nm) Thickness of alloy layer alloy layer (&quot;nm, Example 4 Cu No Pd 10 Agl〇Pd9〇3 40 0 1 〇〇〇Example 105 Cu 5ppoiCa Pd 10 Agl〇Pd90 3 40 〇 1 〇〇〇 Example 106 Cu lOppm Al Pd 10 Agl〇Pd9〇3 40 0. 1 〇〇〇 Example 107 Cu 20ppm Ag Pd 10 AglOPdfln 3 40 0. 1 〇〇〇 Example 108 Cu 4ppmB Pd 10 Agl〇Pd9 〇3 40 0 1 〇〇〇Example 109 Cu 5ppmB Pd 10 AS10Pd90 3 40 0.1 〇〇 ◎ Example 110 Cu 5ppmP Pd 10 Agl〇Pd90 3 40 η 1 〇〇 ◎ Example 111 Cu 5ppm Se Pd 10 Agl〇Pd90 3 40 0.1 〇〇 ◎ Example 112 Cu lOppmB Pd 10 AglOPdQn 3 40 0.1 〇 ◎ Example 113 Cu lOppmP Pd 10 Agl〇Pd9〇3 40 0.] 〇〇◎ Example 114 Cu 1OppmSe Pd 10 AglOPdiin 3 40 0 1 〇〇 ◎ Example 115 Cu 300ppmB Pd 10 A|]〇Pd9〇3 40 0.1 〇〇 ◎ Example 116 Cu 300 ppm P Pd 10 Agl 〇 Pd9 〇 3 40 0.1 〇〇 ◎ Example 117 Cu 300 ppm Se Pd 10 Agl 〇 Pd9 〇 3 40 0 1 〇〇 ◎ Example 118 Cu 310 ppm P Pd 10 A810 Pd90 3 40 0 1 〇〇 ◎ Example 119 Cu No Pd 10 AglOPd9 〇 3 50 0.2 ◎ ◎ Example 120 Cu 5ppm Al Pd 10 AglOPdgo 3 50 0 2 ◎ ◎ 〇 Example 121 Cu 8ppmB Pd 10 Agi〇Pd9〇3 50 0 5 ◎ ◎ 例 Example 122 Cu 15ppmP Pd 10 AglOPd9〇3 50 1.0 ◎ ◎ ◎ Example 123 Cu 30ppm Se Pd 10 Agl〇Pd9〇3 50 2 0 ◎ ◎ ◎ Example 124 Cu 7ppmP Pd 10 Agl〇_ 3 40 2.2 〇 〇◎ 61 201205695 (Table 5) Diffusion layer palladium-coated coating layer alloy layer of silver and palladium« &lt;b TAR alloy layer damage ILt r/vc core expansion layer is stored in a multi-layer storage Ag-L/F nitrogen in FAB The thickness of the Pd-L/F bubble material diffusion layer is complex Thickness of layer thickness of alloy layer (oxidation) (vulcanization) 2nd bonding true spherical 2nd joint inhibition inhibition (ran) (nm) (nm) Example 125 Cu No 0 Cu50Pd50 40 Agl0Pd90 1 〇Λ Ο ◎ Λ Ο 〇 〇 Example 126 Cu No 0 Cu50Pd50 40 Agl0Pd90 3 〇Δ Ο ◎ Ο ο ο Example 127 Cu No 0 Cu50Pd50 50 Ag20Pd80 3 〇A 〇◎ 〇a Example 128 Cu No 0 Cu30Pd70 50 AglOPd60Cu30 5 〇Δ 〇◎ Ο a ◎ Poor Exception 12 Cu Cu Cu20Pd80 10 Cu8Pd90Ag2 80 Ag30Pd70 10 〇厶〇 ◎ ◎ ◎ ◎ ◎ ◎ Example 130: Cu No 0 Cu9Pd90Agl 100 Ag50Pd50 15 〇 Δ 〇〇 ◎ ◎ ◎ ◎ ◎ Example 131 Cu No 0 Cul0Pd90 200 Agl0Pd90 20 〇 Δ 0 ◎ Ο ο Ο 拖 拖 132 132 Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu9Pd90Agl 90 Ag50Pd50 3 〇Δ 〇〇◎◎ ◎◎ Example 135 Cu No 0 Cu50Pd50 200 Ag50Pd50 20 〇Δ 〇〇◎ ◎◎ ◎◎ (Table 6) Coating layer containing palladium Long-term storage (oxidation) of alloy layer with palladium Long-term storage (vulcanization) Ag-L/F 2nd Bonding of FA in FAB True spherical Pd-L/F 2nd joint damage inhibition FAB in FAB bubble suppression coating layer thickness (nm ) Thickness (nm) of alloy layer alloy layer Example 136 Cu Pd 10 Aul5Pd85 1 〇〇〇 ◎ A 实施 Example 137 Cu Pd 100 Aul5Pd85 1 〇〇〇 ◎ Δ Λ 〇〇 Example 138 Cu Pd 200 Aul5Pd85 1 〇〇 〇 ◎ 实施 Example 139 Cu Pd 10 Aul0Pd90 3 〇〇〇 ◎ Δ ί Example 140 Cu Pd 10 Aul0Pd90 3 〇〇〇 ◎ Δ Λ UD Example 141 Cu Pd 10 Aul0Pd90 3 〇〇〇 ◎ Δ Λ r\ Example 142 Cu Pd 10 Aul0Pd90 3 〇〇〇 ◎ Δ Λ Γ) Example 143 Cu Pd 10 Aul0Pd90 3 〇〇〇 ◎ Δ A Λ 〇 Example 144 Cu Pd 10 Aul0Pd90 3 〇〇〇 ◎ Δ Instance 145 Cu Pd 10 Aul0Pd90 3 〇〇〇 ◎ Δ Λ U 〇 Example 146 Cu Pd 10 Aul0Pd90 3 〇〇〇 ◎ Example 147 Cu Pd 10 Aul0Pd90 3 〇〇〇 ◎ Δ Example 148 Cu Pd 10 Aul5Pd85 3 〇〇〇 ◎ 〇Λ Example 149 Cu Pd 10 0 Aul5Pd85 3 〇〇〇 ◎ 实施 Example 150 Cu Pd 2W Aul5Pd85 3 〇〇〇 ◎ 〇-Δ Λ U 〇 Example 151 Cu Pd 10 Aul5Pd85 40 〇〇〇 ◎ Example 152 Cu Pd 100 Aul5Pd85 40 〇〇 〇 〇Λ 〇Λ 〇 Example 153 Cu Pd 200 Aul5Pd85 40 〇〇〇 ◎ 〇Λ r\ Example 154 Cu Pd 10 Aul5Pd85 80 〇〇〇 ◎ 实施 Example 155 Cu Pd 1U0 Aul5Pd85 80 〇〇〇 ◎ 〇Λ U Example 156 Cu Pd 200 Aul5Pd85 80 〇〇〇 〇Λ 实施 Example 157 Cu Pd 10 Au38Pd62 1 〇〇〇 ◎ Δ Λ D Example 158 Cu Pd 100 Au38Pd62 1 〇〇〇 ◎ Δ 实施 Example 159 Cu Pd 2UU Au38Pd62 I 〇〇〇 Δ AU Example 160 Cu Pd 10 Au38Pd62 3 〇〇〇 ◎ Ο Λ CJ Example 161 Cu Pd 100 Au38Pd62 3 〇〇〇 ◎ 〇Λ 〇Γ \ Example 162 Cu Pd 2UU Au38Pd62 3 〇〇 〇〇Λ U 〇 Example 163 Cu Pd 10 Au38Pd62 40 〇〇〇 ◎ 〇 施 施 164 Cu Pd 100 Au38Pd62 40 〇〇〇 ◎ 实施 Example 165 Cu Pd 200 Au38Pd62 40 〇〇〇 ◎ 〇 〇 Example 16 (i Cu Pd 10 Au38Pd62 80 〇〇〇 〇厶〇 Example 167 Cu Pd 100 Au38Pd62 80 〇〇〇 - - 实施 168 Example 168 Cu Pd 2ϋϋ Au38Pd62 80 〇〇〇 ◎ 〇Λ U r\ Example 169 Cu Pd 10 Au40Pd60 3 〇〇〇〇◎ Λ U 〇62 201205695

Example 170 Cu Pd 100 Au50Pd50 3 〇〇〇〇 ◎ 〇 〇 Example 171 Cu Pd 200 Au40Pd60 3 〇〇〇〇 ◎ Δ 〇 Example 172 Cu Pd 10 Au40Pd60 3 〇〇〇〇 ◎ Δ 〇 Example 173 Cu Pd 100 Au50Pd50 3 〇〇〇〇 ◎ 〇 〇 Example 174 Cu Pd 200 Au40Pd60 3 〇〇〇〇 ◎ Δ 〇 Example 175 Cu Pd 10 Au50Pd50 40 〇〇〇〇 ◎ Δ 〇 Example 176 Cu Pd 100 Au40Pd60 40 〇〇 〇〇 ◎ Δ 〇 Example 177 Cu Pd 200 Au50Pd50 40 〇〇〇〇 ◎ Δ 〇 Example Cu 8 Cu Pd 10 Au40Pd60 80 〇〇〇〇 ◎ Δ 〇 Example 179 Cu Pd 100 Au50Pd50 80 〇〇〇〇 ◎ Δ 〇 Example 180 Cu Pd 200 Au40Pd60 80 〇〇〇〇 Δ 〇 Example 181 Cu Pd 10 Au60Pd40 3 〇〇〇〇 ◎ 〇 〇 Example 182 Cu Pd 100 Au70Pd30 3 〇〇〇〇 ◎ Δ 〇 Example 183 Cu Pd 200 Au75Pd25 3 〇〇〇〇 ◎ 〇 〇 Example 184 Cu Pd 10 Au60Pd40 3 〇〇〇〇 ◎ Δ 〇 Example 185 Cu Pd 100 Au70Pd30 3 〇〇〇〇 ◎ Δ 〇 implementation Example 186 Cu Pd 200 Au75Pd25 3 〇〇〇〇 ◎ Δ o Example 187 Cu Pd 10 Au75Pd25 40 〇〇〇〇 ◎ Δ 〇 Example 188 Cu Pd 100 Au70Pd30 40 〇〇〇〇 ◎ Δ 〇 Example 189 Cu Pd 200 Au60Pd40 40 〇〇〇〇 Δ 〇 Example 190 Cu Pd 10 Au70Pd30 80 〇〇〇〇 Δ 〇 Example 191 Cu Pd 100 Au75Pd25 80 〇〇〇〇 ◎ Δ o Example 192 Cu Pd 200 Au60Pd40 80 〇〇〇 〇 ◎ Δ 〇 Comparative Example 11 Cu Au 200 No 0 〇〇〇 X ◎ X 〇 Comparative Example 12 Cu Pd 10 Aul5Pd85 0 〇〇〇 ◎ X Δ 〇 Comparative Example 13 Cu Pd 100 Aul5Pd85 90 X 〇 XXX Δ 〇 Comparative Example 14 Cu Pd 200 Au5Pd95 3 〇〇〇 ◎ X Δ 〇 Comparative Example 15 Cu Pd 200 Au80Pd20 80 〇〇〇X ◎ Δ 〇 Comparative Example 16 Cu Pd 210 Au38Pd62 40 〇〇〇◎ 〇Δ X (Table 7) Core material containing The area of the crystal layer of the coating layer of gold and Ig in the direction of the line direction of the crystal orientation of the crystal region of 15 degrees or less (%). The slope of the coating layer of the coating layer is suppressed by the thickness of the coating layer (nm). Alloy layer alloy Floor Thickness (nm) Example 148 Cu Pd 10 Aul5Pd85 3 40 〇 Example 193 Cu Pd 10 Aul5Pd85 1 50 ◎ Example 194 Cu Pd 10 Aul5Pd85 1 60 ◎ Example 195 Cu Pd 10 Aul5Pd85 1 70 ◎ ◎ Example 196 Cu Pd 10 Aul5Pd85 1 100 ◎ ◎ Example 197 Cu Pd 10 Aul0Pd90 3 50 ◎ Example 198 Cu Pd 10 Aul0Pd90 3 60 ◎ Example 199 Cu Pd 10 Aul0Pd90 3 70 ◎ ◎ Example 200 Cu Pd 10 Aul0Pd90 3 100 ◎ ◎ Example 201 Cu Pd 10 Aul5Pd85 3 50 ◎ Example 202 Cu Pd 10 Aul5Pd85 3 60 ◎ Example 203 Cu Pd 10 Aul5Pd85 3 70 ◎ ◎ Example 204 Cu Pd 10 Aul5Pd85 3 100 ◎ ◎ Example 205 Cu Pd 100 Au38Pd62 40 50 ◎ Example 206 Cu Pd 100 Au38Pd62 40 60 ◎ Example 207 Cu Pd 100 Au38Pd62 40 70 ◎ ◎ 63 201205695 Example 208 Cu Pd 100 Au38Pd62 40 100, Example 209 Cu Pd 10 Au40Pd60 80 50 — ' Example 210 Cu Pd 10 Au40Pd60 80 60, Example 211 Cu Pd 10 Au40Pd60 80 70 Example 212 Cu Pd 10 Au40Pd60 80 100~ Example 213 Cu Pd 200 Au75Pd25 40 50, Example 214 Cu Pd 200 Au75Pd25 40 60 Example 215 Cu Pd 200 Au75Pd25 40 70~ ΪΤExample 216 Cu Pd 200 Au75Pd25 40 100~ (Table 8) Example 148

Thickness (nm) of Cu-containing palladium-coated coating layer coating layer 10 Gold-palladium alloy layer alloy layer alloy layer thickness (nm) The slope of the line direction of &lt;丨11&gt; crystal orientation is 15 degrees or less Area of crystal grain (%) Edge hardness of the surface of the wire (CPa) 76.2

Aul5Pd85 Example 217

Cu

Pd 10

Aul5Pd85 Example 218

Cu

Pd 10

Aul0Pd90 40 Example 219

Cu

Pd 10

Aul5Pd85 40 Example 220

Cu

Pd 10

Aul5Pd85 40 Embodiment 221 Embodiment 222 Embodiment 223 Embodiment 224 Embodiment 225 Embodiment 226 Embodiment 227 Example 228 Example 229

Cu

Cu

Cu

Cu

Cu

Cu

Cu

Cu

Cu

Pd

Pd

Pd

Pd

Pd

Pd

Pd 10 10 10 50 100 200 60 150 180

Aul5Pd85

Aul5Pd85

Aul5Pd85

Au38Pd62

Au40Pd60

Au50Pd50

Au60Pd40

Au70Pd30

Au75Pd25 40 40 40 10 30 60 70 50 60 70 Neck: {s 100

(Table 9) The core layer of the palladium-containing coating layer and the alloy layer of IE have a bevel of the crystal orientation of the crystal orientation of the &lt;111&gt; crystal orientation of 15 degrees or less (%) of the surface of the wire. Hardness (GPa) High loop tilt suppression 76. 2^ιη (3mil) grade low loop neck damage 5. 3mm (210mil) graded tortuous wafer damage core material residue (except for unavoidable impurities) Additive elements in core material (ppm by mass) Thickness of layer to be laminated (nm) Thickness (nm) of alloy layer alloy layer Example 148 Cu No Pd 10 Aul5Pd85 3 40 0.1 〇〇〇〇 Example 23C Cu 5ppmCa Pd 10 Aul5Pd85 3 40 0.1 Example 231 Cu IOddhiAI Pd 10 Aul5Pd85 3 40 0.1 〇〇. 〇〇 Poor Example 232 Cu 20ρρσιΑε Pd 10 Aul5Pd85 3 40 0.1 〇〇〇〇 Example 233 Cu 4ρ〇ηΒ Pd 10 Aul5Pd85 3 40 0.1 〇 〇〇〇Example 234 Cu 5pmnB Pd 10 Aul5Pd85 3 40 0.1 〇〇 〇 Example 235 Cu 5ppmP Pd 10 Aul5Pd85 3 40 0.1 0 0 ◎ 〇 Example 236 Cu 5〇DinSe Pd 10 Aul5Pd85 3 40 0.1 〇〇◎ 〇 Lean application 237 Cu l〇DDmB Pd 10 Aul5Pd85 3 40 0.1 〇〇 ◎ 〇 施 施 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 Example 240 Cu 300ddi〇B Pd 10 Aul5Pd85 3 40 0.1 〇〇 〇 Example 241 Cu 300ddidP Pd 10 Aul5Pd85 3 40 0.1 0 ο 1 ◎ Example 242 Cu 30〇DDmSe Pd Aul5Pd85 3 40 oi 1 〇〇◎ 〇Implementation Example 243 Cu 310p〇niP Pd 10 Aul5Pd85 3 40 0.1 〇〇 ◎ X Lean Example 244 Cu No Pd 10 Aul5Pd85 3 50 0.2 ◎ ◎ △ 〇 铯 Example 245 Cu 5ppm Al Pd 10 Aul5Pd85 3 50 0.2 Ί ◎ ◎ 〇〇 Implementation Example 246 Cu 8ppmB Pd 10 Aul5Pd85 3 50 0.5 ◎ ◎ 〇 64 201205695 Example 247 Cu 15 ppm P Pd 10 Aul5Pd85 3 50 1.0 ◎ ◎ ◎ Example 248 Cu 30 ppm Se Pd 10 Aul5Pd85 3 50 2.0 ◎ ◎ ◎ 〇 Example 249 Cu 7ppmP Pd 10 Aul5Pd85 3 40 2.2 〇〇◎ 〇 (Table 10) Diffusion layer Palladium-containing coating layer Gold and alloy layer for long-term storage (deuteration) Long-term storage (vulcanization) Nitrogen core diffusion layer coating alloy Layer Ag-L/F Nitrogen FAB Pd-L/F Damage thickness of FAB material diffusion layer Cnm) Thickness of coating layer (nm) Thickness of alloy layer (rnn) 2nd bonding true spherical 2nd joint suppression bubble suppression Example 250 Cu No 0 Cu50Pd50 40 Aul5Pd85 3 〇〇〇 ◎ Δ Δ 〇 Example 251 Cu No 0 Cu50Pd50 40 Aul5Pd85 3 〇〇〇 ◎ 〇 Δ 〇 Example 252 Cu No 0 Cu50Pd50 50 Au40Pd60 3 〇〇〇〇 ◎ Δ 〇 Example 253 Cu no 0 Cu30Pd70 50 Aul5Pd60Cu25 10 〇〇〇 ◎ 〇 Δ 〇 Example 254 Cu Cu20Pd80 10 Cu8Pd90Au2 80 Au45Pd55 30 〇〇〇〇 ◎ 〇 〇 Example 255 Cu No 0 Cu9Pd90Aul 100 Au70Pd30 40 〇〇〇〇 ◎ Δ 〇 Example 256 Cu No 0 Cul0Pd90 200 Aul5Pd85 60 〇〇〇 ◎ 〇 Δ 〇 Example 257 Cu No 0 Cul0Pd90 40 Au40Pd60 70 〇〇〇〇 ◎ △ 〇 Example 258 Cu Cu20Pd80 0 Cu50Pd50 40 Aul5Pd85 3 〇〇〇 ◎ Δ Δ 〇 Example 259 Cu No 0 Cu50Pd50 40 Aul5Pd85 3 〇〇〇 ◎ 〇 Δ 〇 Example 260 Cu No 0 Cu50Pd50 50 Au40Pd60 3 〇〇〇〇 ◎ Δ 〇 [Simple description of the drawing] jfe 〇 4 *»' [Description of main component symbols] Benefits 》", 65

Claims (1)

201205695 VII. Patent application scope: 1. A bonding wire for semiconductor, comprising: a core wire formed of copper or a copper alloy; a coating layer formed on the surface of the core wire and having a thickness of 1〇n; containing precious metal and The alloy layer is formed on the surface of the coating layer and has a thickness of 1 to 80 nm. The noble metal is gold or silver, and the concentration of the noble metal in the alloy layer is 10% by volume or more and 7.55% by volume or less. . 2. If you apply for a patent range! The bonding wire for a semiconductor according to the above aspect, wherein the noble metal is gold, and the alloy layer has a gold concentration of 15% by volume or more and 75% by volume or less. The bonding wire for a semiconductor according to the second aspect of the invention, wherein, in the surface crystal grain of the alloy layer, the slope of the crystal direction of the crystal orientation of the &lt;m&gt; crystal orientation is 15 degrees or less. The area is 4% or more and 100% or less. 4. The bonding wire for a semiconductor according to the third aspect of the invention, wherein the alloy layer has a filling degree of gold of 4 vol% or more and 75 vol% or less. 5. If you apply for a patent range! The bonding wire for a semiconductor according to the invention, wherein the noble metal is silver, 66 201205695, the alloy layer is made of a thick sleeve of 1 to 30 nm, and 70% by volume of the silver in the alloy layer is 1 〇 5% by volume or more. 6. The bonding wire for a semiconductor according to claim 5, wherein a concentration of silver in the alloy layer is 2% by volume or more and 7% by volume or less. 7. The bonding wire for a semiconductor according to the sixth aspect of the invention, wherein the crystal grain of the surface layer of the alloy layer has a slope of a gradient of 15 degrees or less with respect to a crystal orientation of the crystal orientation. The area of the granules is 5Q% or more and 100% or less. 8. The bonding wire for a semiconductor according to the sixth aspect of the invention, wherein the crystal grain of the surface layer of the alloy layer has a slope of a gradient of 15 degrees or less in the direction of the crystal orientation of the film. The area of the granules is 6〇% or more and 100% or less. The semiconductor side hardness of the item is 〇. 2 9. The range of the 〜2. OGPa of the surface of the bonding wire of the bonding wire '. The bonding wire according to any one of claims 1 to 9, wherein the core wire contains β, Ρ, and a total of 5 to 300 ppm by mass. 67 201205695 IV. Designation of Representative Representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. In the case of a chemical formula, please disclose the chemical which best shows the characteristics of the invention. 6. Description of the Invention: Technical Field The present invention relates to a terminal for connecting an electrode on a semiconductor element to an external terminal. Bonding wires for connected semiconductors. [Prior Art] At present, a bonding wire for a semiconductor that connects an electrode on a semiconductor element to an external connection terminal (hereinafter referred to as "joining a wire, mainly used - a wire diameter of 2 〇 -5 () (4) A gold (Au) bonding wire (gold bonding wire) having a high purity of W4-Nine 'purity of 99.99% by mass or more, and a gold bonding wire bonded to a stone wafer as a semiconductor element. In the case of an electrode, generally, ban bonding e is performed by ultrasonic bonding, that is, 'using a universal bonding device, and the gold bonding wire is passed to the inside of a jig called a capillary. The tip end of the wire is heated by the arc input heat, and after the ball portion is formed by the surface tension, the ball portion heated and melted is pressure-bonded to the electrode heated in the range of 150 to _t.