KR101568479B1 - Bonding wire for high speed signal - Google Patents

Bonding wire for high speed signal Download PDF

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KR101568479B1
KR101568479B1 KR1020130138234A KR20130138234A KR101568479B1 KR 101568479 B1 KR101568479 B1 KR 101568479B1 KR 1020130138234 A KR1020130138234 A KR 1020130138234A KR 20130138234 A KR20130138234 A KR 20130138234A KR 101568479 B1 KR101568479 B1 KR 101568479B1
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South Korea
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bonding wire
mass
silver
gold
layer
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KR1020130138234A
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Korean (ko)
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KR20140134593A (en
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유키 안토쿠
가즈히코 야스하라
준 치바
웨이 첸
준이치 오카자키
나나코 마에다
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타나카 덴시 코오교오 카부시키가이샤
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Abstract

<과제>
본딩 와이어의 표면에 불안정한 황화은층을 형성해도, 강고한 황화은(Ag2S)막이 없고, 안정한 수GHz대 등의 초고주파 신호를 보낼 수가 있는 Ag－Pd－Au기 합금의 고속 신호선용 본딩 와이어를 제공하는 것을 목적으로 한다.
<해결 수단>
팔라듐(Pd)을 2.5~4.0질량%, 금(Au)을 1.5~2.5질량% 및 잔부가 순도 99.99질량% 이상의 은(Ag)으로 이루어지는 3원 합금으로서, 그 본딩 와이어의 단면은 표피막과 심재로 이루어지고, 그 표피막은 연속 주조 후에 축경된 연주면과 표면 편석층으로 이루어지고, 그 표면 편석층은, 심재보다도 은(Ag)의 함유량이 점증하고 또 금(Au)의 함유량이 점감하고 있는 합금 영역으로 이루어지는 것을 특징으로 하는 고속 신호선용 본딩 와이어이다.<Task>
Provides a bonding wire for high-speed signal lines of Ag-Pd-Au-based alloy capable of transmitting a very high frequency signal of several GHz band without a strong silver sulfide (Ag 2 S) film even if an unstable silver sulfide layer is formed on the surface of the bonding wire .
[Solution]
Wherein the bonding wire is made of a ternary alloy comprising 2.5 to 4.0 mass% of palladium (Pd), 1.5 to 2.5 mass% of gold (Au) and silver (Ag) of a purity of 99.99 mass% The surface layer consists of a concave surface and a surface segregated layer after the continuous casting. The surface segregation layer has a larger content of silver (Ag) and a smaller content of gold (Au) than the core material Alloy region of the second conductivity type.

Description

고속 신호용 본딩 와이어{BONDING WIRE FOR HIGH SPEED SIGNAL}BONDING WIRE FOR HIGH SPEED SIGNAL [0002]

본 발명은 반도체 소자의 패드 전극과 배선 기판 상의 리드 전극을 접속하는 고속 신호선용 본딩 와이어에 관한 것으로서, 특히 1~15GHz의 주파수를 이용하는 고속 신호선용 본딩 와이어에 관한 것이다.The present invention relates to a bonding wire for a high-speed signal line connecting a pad electrode of a semiconductor device and a lead electrode on a wiring board, and more particularly to a bonding wire for a high-speed signal line using a frequency of 1 to 15 GHz.

근년, 반도체 장치의 제조 기술의 발전에 수반하여, 수GHz대를 넘는 초고주파를 이용하는 고속 신호선용의 반도체 집적회로 장치를 휴대전화기 등에 조립해 넣는 경우가 많아졌다. 고주파 전송에는 종래부터 순도 99.99질량% 이상의 고순도 금 본딩 와이어가 일반적으로 사용되어 왔다. 그러나, 수 내지 수십GHz대에 통상의 본딩 와이어를 사용하여 초고주파를 이용하는 고속·초고속 신호선용의 반도체 소자와 배선 전극 등을 접속하면, 초고주파 신호가 본딩 와이어의 표피층을 흐르므로, 초고주파 신호에 의한 고주파 저항이 한층 커진다. 따라서, 고순도 금 본딩 와이어를 이용한 것은 수신 감도나 송신 출력 등을 저하시키는 원인으로 된다.2. Description of the Related Art In recent years, with the development of semiconductor device manufacturing technology, semiconductor integrated circuit devices for high-speed signal lines using microwaves exceeding several GHz have been incorporated into mobile phones and the like. High-purity gold bonding wires having a purity of 99.99 mass% or more have conventionally been used for high-frequency transmission. However, when a semiconductor element for a high-speed / high-speed signal line using a very high frequency and a wiring electrode and the like are connected using a common bonding wire in several to several tens of GHz band, a very high frequency signal flows through the skin layer of the bonding wire, The resistance becomes larger. Therefore, the use of a high-purity gold bonding wire causes a decrease in the reception sensitivity and the transmission output.

이 때문에 전기 비저항치가 고순도 금(Au)의 2.4μΩcm에 대해, 전기 비저항치가 1.6μΩcm인 순도 99.99%의 고순도 은(Ag) 등의 와이어가 검토되었다. 그러나, 용해·주조 후 세정하고 나서 연속 신선(伸線)을 거쳐 본딩 와이어가 제조되는 과정에 있어서, 벌크(bulk)의 고순도 은(Ag) 와이어는 너무 부드러워 실용화에 적합하지 않다. 또, 대기 중에서 은(Ag)이 황화하여 본딩 와이어의 표피층에 황화은(Ag2S) 막이 형성되어 용융볼을 단단하게 해 버리므로, 프리에어볼(FAB: free air ball)에 의한 볼본딩 특성을 손상시켜 버린다고 하는 결점이 있다. 따라서, 순은 본딩 와이어가 직접 수㎛의 표피층을 흐르는 고주파 전송용으로 사용되는 일은 없고, 일본 특허공개 1982－21830호 공보에서 Ag－Pd 합금 와이어가 제안되었지만, 일본 특허공개 2003－59963호 공보(후술하는 특허문헌 1)에서 보여지듯이, 순금 도금을 한 순은 본딩 와이어가 실용화되어 있음에 지나지 않았다. 이와 같이, 순은 본딩 와이어가 실용화되지 않은 것은 초고주파를 이용하는 고속 신호선으로서 이용하기 이전에, 안정한 용융볼을 형성할 수가 없었기 때문이다. 즉, 프리에어볼(FAB)에 의한 볼본딩에 이용하려고 하여 용융볼을 형성했을 때, 와이어 표면에 형성된 강고한 황화은(Ag2S)이 용융볼을 단단하게 하기 때문에, 제1본딩에 있어서 칩깨짐 등을 일으키고 있었다.For this reason, a wire of high purity silver (Ag) having an electrical resistivity of 1.6 mu OMEGA cm and a purity of 99.99% with respect to 2.4 mu OMEGA cm of high purity gold (Au) was studied. However, in the process of manufacturing the bonding wire after cleaning after dissolution / casting and then through continuous drawing, the bulk of the high purity Ag silver wire is too soft to be suitable for practical use. In addition, silver (Ag) is sulphided in the atmosphere and silver sulphide (Ag 2 S) film is formed on the skin layer of the bonding wire to make the molten ball hard, so that the ball bonding property by free air ball There is a drawback that it is damaged. Therefore, Ag-Pd alloy wire has been proposed in Japanese Patent Application Laid-Open No. 198-2-21830, but Japanese Patent Laid-Open Publication No. 2003-59963 As shown in Patent Document 1), a pure silver bonding wire with pure gold plating is merely practically used. The reason why the pure silver bonding wire is not put to practical use is that stable melting balls could not be formed before using the pure silver bonding wire as a high-speed signal line using a very high frequency. That is, when the molten ball is formed for use in ball bonding by the pre-air ball (FAB), since strong silver sulfide (Ag 2 S) formed on the wire surface makes the molten ball hard, And cracking.

한편, 전기 전도성이 높은 Ag의 전기 비저항을 이용하는 것을 목적으로 하여, 현재 널리 사용되고 있는 순도 99%의 Au 와이어와 같은 3.1μΩcm 이하로 그다지 저하시키지 않고, Ag에 10000~55000질량ppm(1~5.5질량%)의 Au 및 1~100질량ppm의 Bi를 첨가하는 Ag－Au 2원계 합금의 본딩 와이어가 개발되고, 또한 이 와이어에 Pd를 20000질량ppm 이하 첨가한 Ag－Au－Pd 3원계 합금의 본딩 와이어도 개발되어 있다(일본 특허공개 2012－49198호 공보(후술하는 특허문헌 2)). 여기서, Pd의 첨가량을 20000질량ppm(2질량%) 이하로 하는 것은, 「20000질량ppm를 넘어 첨가하면 볼의 경도가 높아져 볼본딩시의 패드 손상이 발생한다(동 공보 0021 단락 참조)」는 것 때문이다.On the other hand, for the purpose of utilizing the electrical resistivity of Ag which has high electrical conductivity, it is preferable to use Ag with an amount of 10000 to 55000 mass ppm (1 to 5.5 mass Au) and 1 to 100 mass ppm of Bi were added to the wire, and bonding of the Ag-Au-Pd ternary system alloy in which Pd was added in an amount of 20,000 mass ppm or less to the wire was developed. Wire has also been developed (Japanese Patent Laid-Open Publication No. 2012-49198 (Patent Document 2 to be described later)). The reason why the amount of Pd added is 20,000 mass ppm (2 mass%) or less is that when the amount of Pd added exceeds 20000 mass ppm, the hardness of the ball becomes high and pad damage occurs during ball bonding (see paragraph It is because.

또, Ca, Cu, Gd, Sm으로부터 선택되는 2종 이상의 원소를 합계로 5~500중량ppm 포함하고, Pd, Au로부터 선택되는 1종 이상의 원소를 합계로 0.5~5.0중량% 포함하고, 그 이외가 Ag 및 불가피 불순물로 이루어지는 것을 특징으로 하는 볼본딩용 와이어(일본 특허공개 2012－151350호 공보(후술하는 특허문헌 3))도 개시되어 있다. 그렇지만, 이 본딩 와이어는 반도체 소자의 Ni/Pd/Au 피복된 전극과 회로 배선 기판의 도체 배선을 볼본딩법에 의해 접속하기 위한 본딩용 와이어(W)로서, Al 합금(Al－Si－Cu 등) 패드 전극을 접합하는 것은 아니다. 「Al과 Ag의 접합 개소는 부식하기 쉽다(일본 특허공개 2012－151350호 공보(후술하는 특허문헌 3) 0015 단락 참조)」는 것 때문이다.　Also, it is preferable that a total of 5 to 500 ppm by weight of at least two elements selected from Ca, Cu, Gd and Sm is contained, 0.5 to 5.0% by weight in total of at least one element selected from Pd and Au, (Japanese Unexamined Patent Application Publication No. 2012-151350 (Patent Document 3 to be described later)) which is characterized in that the wire is made of Ag and inevitable impurities. However, this bonding wire is a bonding wire (W) for connecting a Ni / Pd / Au coated electrode of a semiconductor element and a conductor wiring of a circuit wiring board by a ball bonding method, and an Al alloy (Al-Si-Cu ) The pad electrode is not bonded. Quot; Al &quot; and &quot; Ag &quot; are susceptible to corrosion (see Japanese Patent Laid-Open Publication No. 2012-151350 (Patent Document 3 to be described later).

또한, 「은(Ag)을 주성분으로 하고, 10000~90000질량ppm의 금(Au), 10000~50000질량ppm의 팔라듐(Pd), 10000~30000질량ppm의 동(Cu), 10000~20000질량ppm의 니켈(Ni)로부터 선택된 적어도 1종 이상의 성분을 포함하고, 염소(Cl) 함유량이 1질량ppm 미만」인 본딩 와이어도 개시되어 있다(일본 특허공개 2012－99577호 공보(후술하는 특허문헌 4)). 그렇지만, 이 본딩 와이어는 「파장 380~560nm의 광의 반사율이 95% 이상이기 때문에, 청색계의 발광을 사용하는 백색 LED에도 유효하다(동 공보 0010 단락 참조)」라고 하듯이, LED용으로서 고속 신호선용 본딩 와이어와는 목적·효과가 다르다.In addition, "gold (Au)", "gold (Au)", "gold" (Au), and gold (Au) Nickel (Ni), and a chlorine (Cl) content of less than 1 mass ppm "(JP-A-2012-99577 (Patent Document 4) ). However, this bonding wire is effective for a white LED using blue light emission (refer to paragraph [0010]) since the reflectance of light having a wavelength of 380 to 560 nm is 95% or more, The purpose and effect are different from the wire bonding wire.

일본 특허공개 2003－59963호 공보Japanese Patent Application Laid-Open No. 2003-59963 일본 특허공개 2012－49198호 공보Japanese Patent Application Laid-Open No. 2012-49198 일본 특허공개 2012－151350호 공보Japanese Patent Laid-Open Publication No. 2012-151350 일본 특허공개 2012－99577호 공보Japanese Patent Application Laid-Open No. 1995-77577

본 발명은 Ag－Pd－Au기 합금의 본딩 와이어의 표면에, 고농도의 순은층 및 저농도의 금 합금화층(이하 「고농도 순은층」이라고 약한다)을 편석시킴으로써, 그 편석한 균일한 두께의 고농도 순은층의 형성에 의해 프리에어볼(FAB)에 의한 본딩 특성을 양호하게 함과 동시에, 대기 중에 방치해도 일정 기간 황화은의 형성 내지 내부 진행을 저지하여, 안정한 수GHz대 등의 초고주파 신호를 보낼 수가 있는 Ag－Pd－Au기 합금의 고속 신호선용 본딩 와이어를 제공하는 것을 목적으로 한다.The present invention segregates a high-concentration pure silver layer and a low-concentration gold alloy layer (hereinafter referred to as &quot; high-concentration pure silver layer &quot;) on the surface of a bonding wire of an Ag-Pd- The formation of the pure silver layer improves the bonding property by the pre-air ball (FAB). In addition, even if it is left in the air, it can prevent formation of silver sulfide and progress of the silver sulfide for a certain period of time, And an Ag-Pd-Au-based alloy bonding wire for a high-speed signal line.

본 발명의 과제를 해결하기 위한 고속 신호선용 본딩 와이어의 하나는, 반도체 소자의 패드 전극과 배선 기판 상의 리드 전극을 프리에어볼(FAB)에 의해 접속하기 위한 미량 첨가 원소를 함유하는 Ag－Pd－Au기 합금 본딩 와이어로서, 당해 본딩 와이어는 팔라듐(Pd)을 2.5~4.0질량%, 금(Au)을 1.5~2.5질량% 및 잔부가 순도 99.99질량% 이상의 은(Ag)으로 이루어지는 3원 합금으로서, 그 본딩 와이어의 표면은 연속 주조 후에 축경(縮徑)된 연주면(連鑄面)으로 이루어지고, 그 본딩 와이어의 단면은 표면 편석층과 심재로 이루어지고, 그 표면 편석층은, 심재보다도 은(Ag)의 함유량이 점증하고 또 금(Au)의 함유량이 점감하고 있는 합금 영역으로 이루어지는 고농도 순은층이다.One of the bonding wires for high-speed signal lines for solving the problems of the present invention is an Ag-Pd-Pb alloy containing a trace additive element for connecting a pad electrode of a semiconductor element and a lead electrode on a wiring board by means of a pre- Wherein the bonding wire is a ternary alloy comprising 2.5 to 4.0 mass% of palladium (Pd), 1.5 to 2.5 mass% of gold (Au), and silver (Ag) having a purity of 99.99 mass% , The surface of the bonding wire is made of a concave surface having a reduced diameter after continuous casting, the cross section of the bonding wire is composed of a surface segregation layer and a core material, Is a high-concentration pure silver layer composed of an alloy region where the content of silver (Ag) is increasing and the content of gold (Au) is decreasing.

또, 본 발명의 과제를 해결하기 위한 고속 신호선용 본딩 와이어의 하나는, 반도체 소자의 패드 전극과 배선 기판 상의 리드 전극을 프리에어볼(FAB)에 의해 접속하기 위한 미량 첨가 원소를 함유하는 Ag－Pd－Au기 합금 본딩 와이어로서, 당해 본딩 와이어는 팔라듐(Pd)을 2.5~4.0질량%, 금(Au)을 1.5~2.5질량%, 및 로듐(Rh), 이리듐(Ir), 루테늄(Ru), 동(Cu), 니켈(Ni), 철(Fe), 마그네슘(Mg), 아연(Zn), 알루미늄(Al), 인듐(In), 실리콘(Si), 게르마늄(Ge), 베릴륨(Be), 비스무트(Bi), 셀렌(Se), 세륨(Ce), 이트륨(Y), 란탄(La), 칼슘(Ca) 또는 유로퓸(Eu) 중 적어도 1종 이상의 가(加)미량 원소를 그 합계로 5~300질량ppm, 및 잔부가 순도 99.99질량% 이상의 은(Ag)으로 이루어지는 3원계 합금으로서, 그 본딩 와이어의 표면은 연속 주조 후에 축경된 연주면으로 이루어지고, 그 본딩 와이어의 단면은 표면 편석층과 심재로 이루어지고, 그 표면 편석층은, 심재보다도 은(Ag)의 함유량이 점증하고 또 금(Au)의 함유량이 점감하고 있는 합금 영역으로 이루어지는 고농도 순은층이다.In addition, one of the bonding wires for high-speed signal lines for solving the problems of the present invention is a wiring board for a high-speed signal line, in which Ag-Pb containing a trace additive element for connecting a pad electrode of a semiconductor element and a lead electrode on a wiring board by means of a pre- Wherein the bonding wire comprises 2.5 to 4.0 mass% of palladium (Pd), 1.5 to 2.5 mass% of gold (Au), and at least one of rhodium (Rh), iridium (Ir), ruthenium (Ru) Cu, Ni, Fe, Mg, Zn, Al, In, Si, Ge, Ber, At least one or more of trace elements such as bismuth (Bi), selenium (Se), cerium (Ce), yttrium (Y), lanthanum (La), calcium (Ca) or europium (Eu) 5 to 300 mass ppm, and the remainder being silver (Ag) having a purity of 99.99 mass% or more, wherein the surface of the bonding wire is a concave surface after the continuous casting, Made of a segregation phase and the core material, the surface of the segregation phase is, the core material than is the high density layer Silver increasing the content of (Ag) and formed of an alloy zone, which again diminishes the content of gold (Au).

또, 본 발명의 과제를 해결하기 위한 고속 신호선용 Ag－Pd－Au기 합금 본딩 와이어의 바람직한 태양의 하나는, 상기 고속 신호가 1~15GHz의 주파수인 것이다.One of the preferred embodiments of the Ag-Pd-Au-based alloy bonding wire for high-speed signal lines for solving the problems of the present invention is that the high-speed signal has a frequency of 1 to 15 GHz.

또, 본 발명의 과제를 해결하기 위한 고속 신호선용 Ag－Pd－Au기 합금 본딩 와이어의 바람직한 태양의 하나는, 상기 패드 전극이 순도 99.9질량% 이상의 알루미늄(Al) 금속 또는 0.5~2.0질량%의 실리콘(Si) 또는 동(Cu) 및 잔부 순도 99.9질량% 이상의 알루미늄(Al) 합금인 것이다.One of the preferred embodiments of the Ag-Pd-Au-based alloy bonding wire for high-speed signal lines for solving the problems of the present invention is that the pad electrode is made of aluminum (Al) metal having a purity of 99.9 mass% or more or 0.5 to 2.0 mass% (Si) or copper (Cu) and an aluminum (Al) alloy having a purity of 99.9 mass% or more.

또, 본 발명의 과제를 해결하기 위한 고속 신호선용 Ag－Pd－Au기 합금 본딩 와이어의 바람직한 태양의 하나는, 상기 패드 전극이 금(Au), 팔라듐(Pd) 또는 백금(Pt)의 표층으로 이루어지는 전극 패드인 것이다.One preferred embodiment of the Ag-Pd-Au-based alloy bonding wire for high-speed signal lines for solving the problems of the present invention is that the pad electrode is a surface layer of gold (Au), palladium (Pd) .

또한, 본 발명의 과제를 해결하기 위한 고속 신호선용 Ag－Pd－Au기 합금 본딩 와이어는, 순금 본딩 와이어와 마찬가지로, 다이아몬드 다이스에 의해 단면 감소율이 99% 이상 축경되고, 연속하여 냉간 신선 가공되고, 그 후 조질(調質) 열처리에 의해 본딩 와이어의 기계적 특성이 갖춰진다. 이 조질 열처리는 온도가 낮고 처리 시간도 짧으므로, 고농도 순은층의 표면 편석층은 소멸하지 않는다.Further, the Ag-Pd-Au-based alloy bonding wire for high-speed signal lines for solving the problems of the present invention is characterized in that, similarly to the pure gold bonding wire, the cross-sectional reduction ratio is reduced by 99% or more by diamond dies, The mechanical properties of the bonding wire are then provided by a tempering heat treatment. Since this tempering treatment is low in temperature and the treatment time is short, the surface segregation layer of the high-concentration pure silver layer does not disappear.

(주첨가 원소)(Added element)

본 발명에 있어서, 잔부의 은(Ag)에 순도 99.99질량% 이상의 것을 이용하는 것은, 은(Ag)의 함유량이 많은 합금의 표면 편석층을 와이어의 전주연(全周緣)에 균일하게 발생시키기 때문이다. 순도가 낮으면, 불순물의 영향에 의해 은(Ag)의 함유량이 많은 합금의 표면 편석층의 두께가 고르지 않을 우려가 있기 때문이다.In the present invention, the use of a silver (Ag) having a purity of 99.99% by mass or more in the balance causes a surface segregation layer of an alloy having a large amount of silver (Ag) to uniformly occur on the entire periphery of the wire. If the purity is low, there is a possibility that the thickness of the surface segregation layer of the alloy containing a large amount of silver (Ag) may be uneven due to the influence of the impurities.

순은 본딩 와이어의 경우, 황화물이 산화물보다 안정하므로, 이 황화물이 형성되는 것을 꺼린다. 지금까지의 순은 본딩 와이어에서는 대기 중의 고순도 은(Ag) 표면에서 표면의 은(Ag)이 이온으로 되어, 대기 중의 황화수소와 결합하여 황화물로 된다. 이 황화물은 처음에는 순은 와이어 표면에서 불안정한 황화은층이 형성되지만, 이 황화은층이 순은 본딩 와이어의 내부로 나아가고, 이윽고 황화은층이 성장하여 수nm 정도의 강고한 황화은(Ag2S)막이 순은 본딩 와이어의 표면에 확보되어 버린다. 또한, 이 표피층에 존재하는 유황 화합물은 결정립계를 타고 더 순은 본딩 와이어의 내부로 들어가 강고한 황화은(Ag2S)막이 퍼지는 것이라고 생각된다.In the case of a pure silver bonding wire, the sulfide is more stable than the oxide, so that the formation of this sulfide is reluctant. In the pure silver bonding wires so far, silver (Ag) on the surface at the surface of silver (Ag) in high purity becomes ions, and bonds with hydrogen sulfide in the atmosphere to form sulfides. This sulfide initially forms an unstable silver sulfide layer on the surface of the pure silver wire, but the silver sulfide layer moves into the inside of the silver bonding wire, and the silver sulfide layer grows to form a strong silver sulfide (Ag 2 S) As shown in FIG. In addition, the sulfur compound present in the skin layer is thought to be a strong silver sulfide (Ag 2 S) film spreading inside the bonding wire in a grain boundary system.

순은(Ag)에 팔라듐(Pd) 및 금(Au)을 합금화한 벌크의 Ag－Pd－Au 합금의 경우, 고농도 순은층의 황화은층의 형성은 순은 본딩 와이어보다도 약해진다. 또한, 본 발명의 Ag－Pd－Au기 합금의 경우, 금(Au) 농도가 표층으로부터 심재 내부로 갈수록 점증하여, 심재 쪽은 팔라듐(Pd) 및 금(Au)이 4.0~6.5질량%의 함유량이 있으므로, 표면에 형성된 황화은(Ag2S)막이 내부로 들어가는 것을 시간적으로 지연시킬 수가 있다.In the case of a bulk Ag-Pd-Au alloy in which palladium (Pd) and gold (Au) are alloyed with pure silver (Ag), formation of a silver sulfide layer in a high-concentration pure silver layer becomes weaker than a pure silver bonding wire. In the case of the Ag-Pd-Au based alloy of the present invention, the concentration of gold (Au) gradually increases from the surface layer to the inside of the core, and the content of palladium (Pd) and gold (Au) It is possible to delay in time the silver sulfide (Ag 2 S) film formed on the surface into the inside.

Ag－Pd－Au기 합금으로 이루어지는 본딩 와이어의 팔라듐(Pd) 함유량을 금(Au)의 함유량보다도 많게 한 것은, 은(Ag) 매트릭스보다도 내황화성에 대해서 귀한 Ag－Pd 매트릭스를 구성하고, 그 Ag－Pd 매트릭스 내에 더 귀한 금(Au)에 의한 표면 편석층을 형성하기 때문이다.The reason why the content of palladium (Pd) in the bonding wire made of the Ag-Pd-Au based alloy is larger than the content of gold (Au) is that it constitutes a valuable Ag-Pd matrix for resistance to sulfidation, (Au) in the Pd matrix.

본 발명에 있어서, 팔라듐(Pd)을 소정량 첨가하는 것은 황화의 진행을 늦추기 때문이다. 습기가 많은 환경하에서 본딩 와이어를 사용하는 경우 등은, 본딩 와이어 표면이 황화하기 쉬워지므로, 와이어 자체에 내황화성이 있는 Ag－Pd－Au기 합금으로 이루어지는 와이어가 필요하게 된다. 팔라듐(Pd) 함유량이 2.5질량%이면, 순은 본딩 와이어의 표면에 강고한 황화은(Ag2S)막이 형성되어 버리는 것을 지연시킬 수가 있다. 한편, 팔라듐(Pd)이 2.5질량%를 넘어가면, 은 농도가 저하하기 때문에 고주파 특성은 다소 나빠져, 초고주파 신호선으로서는 부적합하게 되지만, 고농도 순은층이 형성되어 있으므로, 실용상 4.0질량%까지는 지장 없다.In the present invention, adding a predetermined amount of palladium (Pd) slows the progress of sulphide. In the case of using a bonding wire under a humid environment, since the surface of the bonding wire is likely to be sulphided, a wire made of an Ag-Pd-Au based alloy having resistance to sulfidization is required for the wire itself. When the palladium (Pd) content is 2.5% by mass, it is possible to delay the formation of a strong silver sulfide (Ag 2 S) film on the surface of the pure silver bonding wire. On the other hand, if palladium (Pd) exceeds 2.5 mass%, the silver concentration is lowered and the high-frequency characteristics are somewhat deteriorated, making it unsuitable as a very high frequency signal line. However, practically 4.0 mass% is not encountered.

또, 팔라듐(Pd)은 현저하게 경도를 증가시키는 합금화 원소이고, 팔라듐(Pd) 함유량이 2.5질량% 이상 존재하면, 프리에어볼(FAB)을 형성했을 때, 용융볼의 경도가 높아져 볼본딩시의 칩깨짐이 염려되지만(특허문헌 2 제0021단락 참조), 금(Au)의 함유량을 많게 하여 저융점의 고농도 순은층을 설치함으로써, 팔라듐(Pd) 함유량이 4.0질량% 이내의 범위이면 이 문제는 해결할 수 있었다. 또한, 팔라듐(Pd)의 농도는 고농도 순은층 내에서도 심재 내에서도 거의 일정하다.When the content of palladium (Pd) is 2.5% by mass or more, the hardness of the molten ball is increased when the pre-air ball (FAB) is formed, (Pd) content is in the range of 4.0 mass% or less by providing a high-concentration pure silver layer having a low melting point by increasing the content of gold (Au). However, Could be solved. Also, the concentration of palladium (Pd) is almost constant in the core layer as well as in the high-concentration pure silver layer.

본 발명에 있어서 금(Au)의 합금화 원소는 은(Ag) 및 팔라듐(Pd)보다도 비중이 높고, Ag－Pd기 합금 매트릭스에 대해서 표면 편석 효과를 발휘한다. 표면 편석한 고농도 순은층은 희박 합금의 고상·기상간의 표면 현상을 이용하는 것이므로, 이 고농도 순은층은 일정한 폭의 층을 본딩 와이어의 전주(全周)에 걸쳐 균일하게 형성할 수가 있다. 이 고농도 순은층에 있어서, 와이어의 표면으로부터 중심을 본 경우, 은(Ag) 농도가 점감하여 낮아지면(도 1의 상측의 곡선), 역으로 금(Au)의 합금화 원소의 농도는 점증하여 높아진다(도 1의 하측의 곡선). 그리고, 와이어 내에는 은(Ag)이 상대적으로 고농도인 고농도 순은층의 영역과 상대적으로 저농도인 심재의 영역의 2 영역이 존재하게 된다. 이 때문에 고농도의 와이어 표면에서 불안정한 황화은층이 형성되어도, 은(Ag)보다도 귀한 합금화 원소(팔라듐(Pd) 및 금(Au))가 존재함과 아울러, 실온 대기 중에서 본딩 와이어가 제조 후 신호선으로서 사용될 때까지의 방치 기간 중에는, 은합금 표면의 유황 화합물이 내부로 진행하는 것을 지연시킴과 아울러, 은합금 표면에서 강고한 황화은(Ag2S)막이 형성되는 것도 지연시킬 수가 있다.In the present invention, the alloying element of gold (Au) has a specific gravity higher than that of silver (Ag) and palladium (Pd) and exerts a surface segregation effect on the Ag-Pd based alloy matrix. Since the surface-segregated high-concentration pure silver layer utilizes the surface phenomenon between the solid phase and the vapor phase of the lean alloy, the high-concentration pure silver layer can uniformly form a layer having a constant width over the entire circumference of the bonding wire. In the high concentration pure silver layer, when the center is viewed from the surface of the wire, the concentration of the silver (Ag) concentration decreases gradually (lower curve of FIG. 1) (Lower curve in Fig. 1). In the wire, there are two regions: a region of a high-concentration pure silver layer having a relatively high concentration of silver (Ag) and a region of a core material having a relatively low concentration. Therefore, even if an unstable silver sulfide layer is formed on the surface of the wire of high concentration, silver (Ag) is more precious alloying elements (palladium (Pd) and gold (Au)) are present and the bonding wire is used as a signal line , It is possible to delay the advance of the sulfur compound on the surface of the silver alloy and to delay the formation of a strong silver sulfide (Ag 2 S) film on the surface of the silver alloy.

고순도의 Ag－Pd 합금 매트릭스에 대해 고순도의 금(Au)은 표면 편석하므로, 팔라듐(Pd)과 금(Au)을 고순도의 은(Ag)에 첨가하여 연속 주조하면, 표피층 근방에 은(Ag)의 고농도 영역과 금(Au)의 저농도 영역의 고농도 순은층이 도넛상으로 형성된다. 본딩 와이어의 제조 공정에 있어서, 이 고농도층을 보지(保持)한 채 물로 냉각 등 하여 냉간으로 연속 신선하면, 이 고농도층은 세선의 선직경에 비례하여 축경된다. 따라서, 이 고농도 순은층은 수GHz 이상의 고주파 신호용으로 이용할 수가 있다.Pd and Au are added to high-purity silver (Ag) by continuous casting, and silver (Ag) is added in the vicinity of the skin layer when high purity gold (Au) And a high-concentration pure silver layer of a low-concentration region of gold (Au) are formed in a donut phase. In the manufacturing process of the bonding wire, when the high-concentration layer is kept cold while being cold-drawn by cooling with water or the like, the high-concentration layer is reduced in size in proportion to the wire diameter of the fine wire. Therefore, this high-concentration pure silver layer can be used for high-frequency signals of several GHz or more.

직경 8mm의 연속 주조 와이어를 20㎛의 본딩 와이어까지 축경하는 경우(단면 감소율 99.9% 이상), 본딩 와이어의 표피에는 이론적으로는 표면으로부터 수nm 이하의 은(Ag)의 고농도층이 남아, 실제로 직경 8mm의 연속 주조 와이어로부터 직경 20㎛의 와이어의 신선 단계에서, 도 1과 같은 은(Ag)의 고농도 영역(도 1의 상측의 곡선)과 금(Au)의 저농도 영역(도 1의 하측의 곡선)의 고농도 순은층이 관찰되었다.When the continuous casting wire having a diameter of 8 mm is shrunk to a bonding wire of 20 m (with a sectional reduction rate of 99.9% or more), a high concentration layer of silver (Ag) (A curve on the upper side in Fig. 1) of silver (Ag) and a low-concentration region of gold (Au) on the lower side of Fig. 1 ) Were observed.

일반적으로 수GHz의 고주파 신호는 1㎛ 정도의 표층을 흐르고, 주파수가 높아지면 과연 보다 표면 근방을 흐른다고 되어 있으므로, 고농도의 은(Ag)층이 표층에 존재하면, 고농도층이 없는 종래의 본딩 와이어에 비해 신호량이 증가하고, 또한 신호 파형을 안정시킬 수가 있다.　In general, a high frequency signal of several GHz flows through the surface layer of about 1 mu m and flows near the surface beyond the surface when the frequency becomes high. Therefore, if a high concentration silver (Ag) layer exists in the surface layer, The signal amount is increased and the signal waveform can be stabilized as compared with the wire.

팔라듐(Pd)의 범위가 2.5~4.0질량%일 때 금(Au)의 범위가 1.5~2.5질량%이면, FAB의 용융볼이 칩깨짐을 일으키는 일도 없이 안정한 본딩 특성을 얻을 수 있다.When the range of the palladium (Pd) is 2.5 to 4.0 mass%, the range of the gold (Au) is 1.5 to 2.5 mass%, so that the bonding balls of the FAB do not cause cracking of the chip and stable bonding characteristics can be obtained.

(미량 첨가 원소)(Trace added element)

본 발명의 Ag－Pd－Au기 합금은 로듐(Rh), 루테늄(Ru), 이리듐(Ir), 동(Cu), 니켈(Ni), 철(Fe), 마그네슘(Mg), 아연(Zn), 알루미늄(Al), 망간(Mn), 인듐(In), 규소(Si), 게르마늄(Ge), 주석(Sn), 베릴륨(Be), 비스무트(Bi), 셀렌(Se), 세륨(Ce), 티탄(Ti), 이트륨(Y), 칼슘(Ca), 란탄(La), 유로퓸(Eu) 또는 안티몬(Sb)의 적어도 1종이 합계로 5~300질량ppm 첨가될 수가 있다. 이들 미량 첨가 원소는 Ag－Pd－Au기 합금의 표면 편석층을 변화시키는 일은 없지만, 고농도 순은층이 없는 Ag－Pd－Au기 합금 본딩 와이어에 있어서 본딩 특성에 효과가 있으므로, 본 발명의 Ag－Pd－Au기 합금 본딩 와이어에 있어서도 채택하였다. 구체적으로는 용융볼과 알루미늄(Al) 금속 또는 알루미늄(Al) 합금의 패드 전극의 접합성, 특히 장기간의 안정성에 효과가 있다. 또, Ag－Pd－Au기 합금에 로듐(Rh), 루테늄(Ru), 이리듐(Ir), 동(Cu), 니켈(Ni), 철(Fe), 마그네슘(Mg), 아연(Zn), 알루미늄(Al), 망간(Mn), 인듐(In), 규소(Si), 게르마늄(Ge), 주석(Sn), 베릴륨(Be), 비스무트(Bi), 셀렌(Se), 세륨(Ce), 티탄(Ti), 이트륨(Y), 칼슘(Ca), 란탄(La), 유로퓸(Eu) 또는 안티몬(Sb)의 원소를 소정 범위 내에서 첨가하면, FAB의 형상을 손상시키지 않고 본딩 와이어의 낭창낭창함을 증가시킨다. 그러나, 이들 원소의 합계가 5질량ppm 미만에서는 첨가 효과가 없고, 300질량ppm를 넘으면 FAB를 형성했을 때의 용융볼의 결정립이 너무 단단해져 칩깨짐을 일으킨다. 따라서, 로듐(Rh), 루테늄(Ru), 이리듐(Ir), 동(Cu), 니켈(Ni), 철(Fe), 마그네슘(Mg), 아연(Zn), 알루미늄(Al), 망간(Mn), 인듐(In), 규소(Si), 게르마늄(Ge), 주석(Sn), 베릴륨(Be), 비스무트(Bi), 셀렌(Se), 세륨(Ce), 티탄(Ti), 이트륨(Y), 칼슘(Ca), 란탄(La), 유로퓸(Eu) 또는 안티몬(Sb) 중 적어도 1종을 합계로 5~300질량ppm의 범위로 하였다. 통상의 본딩 와이어는 이들 미량 첨가 원소는 합계로 100질량ppm 이하로 사용되는 일이 많으므로, 이들 미량 첨가 원소는 5~100질량ppm이 바람직하다.The Ag-Pd-Au-based alloy of the present invention can be formed of a metal such as rhodium Rh, ruthenium Ru, iridium, copper, nickel Ni, iron Fe, magnesium Mg, Bi, Se, Ce, Al, Mn, In, Si, Ge, Sn, Ber, At least one of titanium (Ti), yttrium (Y), calcium (Ca), lanthanum (La), europium (Eu) or antimony (Sb) may be added in a total amount of 5 to 300 mass ppm. Although these minute additive elements do not change the surface segregation layer of the Ag-Pd-Au based alloy, since Ag-Pd-Au based alloy bonding wires free from a high concentration pure silver layer have an effect on bonding characteristics, Pd-Au-based alloy bonding wires. Specifically, it has an effect on bonding properties, particularly long-term stability, of a pad electrode made of a molten ball and an aluminum (Al) metal or an aluminum (Al) alloy. In addition, it is also possible to use a metal such as Rh, Ru, Ir, Cu, Ni, Fe, Mg, Zn, A metal such as aluminum, manganese, indium, silicon, germanium, tin, beryllium, bismuth, selenium, cerium, When the elements of titanium (Ti), yttrium (Y), calcium (Ca), lanthanum (La), europium (Eu) or antimony (Sb) are added within a predetermined range, Increases lupus. However, when the total amount of these elements is less than 5 mass ppm, there is no addition effect, and when it exceeds 300 mass ppm, the crystal balls of the molten ball at the time of forming FAB become too hard and chip breakage occurs. Therefore, it is preferable to use at least one selected from the group consisting of rhodium (Rh), ruthenium (Ru), iridium (Ir), copper (Cu), nickel (Ni), iron (Fe), magnesium (Mg), zinc (Zn) ), Indium (In), silicon (Si), germanium (Ge), tin (Sn), beryllium (Be), bismuth (Bi), selenium (Se), cerium (Ce) ), Calcium (Ca), lanthanum (La), europium (Eu) or antimony (Sb) in a total amount of 5 to 300 mass ppm. In the case of ordinary bonding wires, these minute additive elements are often used in a total amount of 100 mass ppm or less, so that these trace additive elements are preferably 5 to 100 mass ppm.

또한, 패드 전극은 금(Au), 팔라듐(Pd) 또는 금(Au) 또는 백금(Pt)의 표층으로 이루어지는 전극 패드인 것이 바람직하다. 본 발명의 Ag－Pd－Au 3원 합금 및 Ag－Pd－Au 3원계 합금의 본딩 와이어는, 저융점의 고농도 순은층이 있으므로 이들 전극 패드와 FAB에 의한 접합성이 좋기 때문이다.The pad electrode is preferably an electrode pad composed of a surface layer of gold (Au), palladium (Pd), gold (Au), or platinum (Pt). The bonding wires of the Ag-Pd-Au ternary alloy and the Ag-Pd-Au ternary alloy of the present invention have a high-concentration pure silver layer with a low melting point, and the bonding strength between these electrode pads and the FAB is good.

본 발명의 Ag－Pd－Au 3원 합금 및 Ag－Pd－Au 3원계 합금의 Ag－Pd－Au기 합금 본딩 와이어는 고속 신호의 전달에 적합한 고농도의 은(Ag)의 고농도 순은층을 확실히 형성할 수가 있고, 고농도 순은층 및 저농도 금(Au)층이 Ag－Pd－Au 3원 합금 및 Ag－Pd－Au 3원계 합금의 심재에 부가되어 있으므로, 종래의 본딩 와이어보다도 패드와의 접합성도 좋고, 수 내지 수십GHz의 고주파 신호의 전송에 적합한 안정한 부은(富銀)합금의 신호층을 형성할 수 있다.The Ag-Pd-Au ternary alloy wire of the present invention and the Ag-Pd-Au ternary alloy bonding wire of the Ag-Pd-Au ternary alloy alloy firmly form a high-concentration pure silver layer of high concentration of Ag suitable for high- And since the high-concentration pure silver layer and the low-concentration gold (Au) layer are added to the core material of the Ag-Pd-Au ternary alloy and the Ag-Pd-Au ternary alloy, bonding properties to the pad are better than those of the conventional bonding wires , And can form a stable signal layer of a rich silver alloy suitable for transmission of a high frequency signal of several to several tens of GHz.

또, 본 발명의 Ag－Pd－Au기 합금 본딩 와이어는 고농도 순은층의 두께가 얇으므로, 와이어 자체의 벌크의 기계적 강도가 있어, 지금까지의 본딩 와이어와 마찬가지의 뛰어난 루프 특성을 가진다.Further, since the Ag-Pd-Au-based alloy bonding wire of the present invention is thin in thickness of the high-concentration pure silver layer, the bulk of the wire itself has mechanical strength and has excellent loop characteristics as in the conventional bonding wires.

또, FAB 특성 등의 본딩 특성은, 저융점의 고농도 순은층이 표층에 있으므로, 용융볼과 패드 전극의 접합성 및 세컨드 접합성에 대해서는 고농도 순은층이 없는 본딩 와이어보다도 뛰어나다고 하는 추가적 효과가 있다. 특히, 패드 전극의 표층이 금(Au), 팔라듐(Pd) 또는 금(Au) 또는 백금(Pt)으로 이루어지는 전극 패드인 경우는 접합 강도가 안정하다.In addition, the bonding characteristics such as the FAB characteristics have a further effect of excelling in the bonding property and the second bonding property between the molten ball and the pad electrode and the bonding wire without the high-concentration pure silver layer because the high-concentration pure silver layer having a low melting point exists in the surface layer. Particularly, when the surface layer of the pad electrode is an electrode pad made of gold (Au), palladium (Pd), gold (Au), or platinum (Pt), the bonding strength is stable.

또, 본 발명의 Ag－Pd－Au기 합금 본딩 와이어는 본딩 와이어의 기계적 강도에 영향을 주는 팔라듐(Pd)의 첨가량이 4.0질량% 이하 및 금(Au)의 첨가량이 2.5질량% 이하이므로, 저융점의 표면 편석층에 의해 FAB를 형성했을 때의 용융볼의 결정립이 너무 단단해지는 일도 없다. 또, 본 발명의 Ag－Pd－Au기 합금 본딩 와이어는 순도 99.9질량% 이상의 알루미늄(Al) 금속 또는 0.5~2.0질량%의 실리콘(Si) 또는 동(Cu) 및 잔부 순도 99.9질량% 이상의 알루미늄(Al) 합금으로 이루어지는 부드러운 알루미늄 패드를 이용한 경우라도, 저융점의 표면 편석층에 의해 칩깨짐이나 패드 벗겨짐이 생기는 일은 없다. 이 결과 일정 기간 실온 대기 중에서 방치해도, 접합계면에 마이그레이션(migration)이 발생하지 않고, 고주파 신호를 안정하게 전송할 수 있는 효과가 있다.The Ag-Pd-Au based alloy bonding wire according to the present invention is characterized in that the addition amount of palladium (Pd) is 4.0 mass% or less and the amount of gold (Au) is 2.5 mass% or less, which affects the mechanical strength of the bonding wire. The crystal grains of the molten ball when the FAB is formed by the surface segregation layer of the melting point do not become too hard. The Ag-Pd-Au based alloy bonding wire of the present invention is preferably made of an aluminum (Al) metal having a purity of 99.9 mass% or more, silicon (Si) or copper (Cu) of 0.5 to 2.0 mass% Even if a soft aluminum pad made of Al alloy is used, cracking of the chip and peeling of the pad do not occur due to the surface segregation layer having a low melting point. As a result, even if left in a room temperature atmosphere for a certain period of time, migration does not occur at the junction interface, and high-frequency signals can be stably transmitted.

도 1은 본 발명의 고농도 순은층의 분포를 나타내는 단면 모식도로, 상방의 곡선은 은(Ag) 농도를 나타내고, 하방의 곡선은 금(Au) 농도를 나타낸다.
도 2는 실시품 1 및 비교품 22의 시간에 수반하는 전압 변화를 그래프(L자형 곡선 및 계단형 곡선)로 한 도이다.
도 3은 실시품 1의 최표면 근방을 정성 분석한 결과를 나타낸다.FIG. 1 is a schematic cross-sectional view showing the distribution of the high-concentration pure silver layer of the present invention, in which the upper curve represents the silver (Ag) concentration and the lower curve represents the gold (Au) concentration.
Fig. 2 is a graph showing the voltage change accompanying the time of the product 1 and the comparative product 22 as a graph (L-shaped curve and stepped curve).
Fig. 3 shows the result of qualitative analysis of the vicinity of the outermost surface of the product 1.

<실시예><Examples>

표 1에 나타내는 성분 조성을 가지는 Ag－Pd－Au 3원 합금 및 Ag－Pd－Au 3원계 합금(모두 팔라듐(Pd) 및 금(Au)의 순도는 99.99질량% 이상으로 하고, 은(Ag)의 순도는 99.999질량% 이상으로 하고, 미량 첨가 원소로서 로듐(Rh), 루테늄(Ru), 이리듐(Ir), 동(Cu), 니켈(Ni), 철(Fe), 마그네슘(Mg), 아연(Zn), 알루미늄(Al), 망간(Mn), 인듐(In), 규소(Si), 게르마늄(Ge), 주석(Sn), 베릴륨(Be), 비스무트(Bi), 셀렌(Se), 세륨(Ce), 티탄(Ti), 이트륨(Y), 칼슘(Ca), 란탄(La), 유로퓸(Eu), 안티몬(Sb)의 합계를 5~300ppm으로 하였다. 또, 그 제조 방법은 통상의 순금 본딩 와이어와 마찬가지로 용해하고, 불활성 분위기 중에서 8mm 직경까지 연속 주조하였다. 계속해서, 이 연속 주조한 굵은 선을 다이아몬드 다이스에 의해 연속하여 20㎛의 최종 선직경까지 습식으로 단면 감소율이 99.99% 이상인 연속 냉간 신선을 하고, 소정의 조질 열처리를 하여, 20㎛의 선직경을 가지는 본 발명에 관계되는 본딩 와이어(이하 「실시품」이라고 한다) 1~21을 제조하였다.Purity of the Ag-Pd-Au ternary alloy and the Ag-Pd-Au ternary alloy (both palladium (Pd) and gold (Au) having a composition shown in Table 1 was 99.99% by mass or more, (Cu), nickel (Ni), iron (Fe), magnesium (Mg), zinc (Zn), or the like as a trace additive element with a purity of 99.999 mass% (Al), Mn (Mn), In, Si, Ge, Sn, Ber, Bismuth, Se, The total amount of Ce, Ti, Y, Ca, La, Eu, and Sb is 5 to 300 ppm. Then, the continuous casting was carried out continuously by means of a diamond dice to a final wire diameter of 20 μm in a continuous manner in a continuous cold state having a section reduction rate of 99.99% or more Freshness And, to prepare a 1-21 to the desired temper heat treatment (hereinafter referred to as "exemplary width") the bonding wire according to the present invention having the wire diameter of the 20㎛.

실시예 1~9가 청구항 1에 관계되는 실시품이고 실시예 10~21이 청구항 2에 관계되는 실시품이다.Examples 1 to 9 are the products according to claim 1, and examples 10 to 21 are the products according to claim 2.

Figure 112013103717456-pat00001
Figure 112013103717456-pat00001

<비교예><Comparative Example>

실시예와 마찬가지로 하여, 본 발명의 조성 범위에 들어가지 않는 표 1에 나타내는 성분 조성의 비교품의 본딩 와이어 22~25(이하 「비교품」이라고 한다)를 제조하였다.Bonding wires 22 to 25 (hereinafter, referred to as &quot; comparative products &quot;) of comparative products having the compositional compositions shown in Table 1 which did not fall within the composition range of the present invention were prepared.

또한, 비교품 25는 실시예와 마찬가지로 하여 연속 주조한 8mmφ의 굵은 선을 80℃의 희질산으로 산세한 소선(素線)을 연속 신선(축경)하여, 표층에 표면 편석층이 없는 본딩 와이어를 형성한 것이다. 따라서, 비교품 25는 조성 범위는 본 발명의 범위 내에 있지만, 산세되어 있는 점에서 실시품과 다르다.In the comparative product 25, a wire having a thickness of 8 mm? Obtained by continuous casting and a thin line pickled with a dilute acid at 80 占 폚 was continuously drawn (diameter-reduced) to form a bonding wire having no surface segregation layer on the surface layer It is. Therefore, the comparative product 25 has a composition range that is within the range of the present invention, but differs from the product in that it is pickled.

또한, 본 발명 및 비교예에 있어서의 조질 열처리는, 금선의 경우와 마찬가지로, 관상 노에 있어서, 온도 및 스피드를 조정한 후, 인장파단 시험기에 의한 측정으로 신장이 소정의 값으로 되도록 조정하기 위한 열처리이고, 이 조질 열처리에서는 실시품의 표면에 편석한 도넛상의 고농도 순은층이 소실되는 일은 없었다.The tempering heat treatment in the present invention and the comparative example is carried out in the same manner as in the case of the gold wire so as to adjust the temperature and the speed in the tubular furnace so that the elongation becomes a predetermined value measured by a tensile rupture tester In this tempering heat treatment, there was no loss of the highly concentrated pure silver layer on the donut-shaped surface that was segregated on the surface of the product.

[고농도 순은층의 확인] [Identification of high-concentration pure silver layer]

실시품 1의 조성을 가지는 Ag－Pd－Au기 합금을 불활성 분위기하에서 직경 8mm의 굵은 선으로 연속 주조하였다. 이 굵은 선을 수랭으로 연속 신선하고, 신장률이 4%로 되도록 조질 열처리하여 직경 20㎛의 본딩 와이어를 얻었다. 이 본딩 와이어의 은(Ag) 및 금(Au) 원소에 대해서 표층으로부터 중심 방향에의 깊이 방향의 오제 분석을 하였다. 그 결과는 도 1 상측의 모식도에서 나타내는 곡선 및 하측의 곡선과 같이 되었다.An Ag-Pd-Au based alloy having the composition of the product of Example 1 was continuously cast in an inert atmosphere in a thick line of 8 mm in diameter. This bold line was continuously drawn by water cooling and subjected to a tempering treatment so as to have an elongation of 4% to obtain a bonding wire having a diameter of 20 탆. For this silver and gold (Au) element of the bonding wire, the ocher analysis was performed in the depth direction from the surface layer to the center direction. The result was as shown in the schematic diagram on the upper side of Fig. 1 and the curve on the lower side.

도 1의 모식도에서 나타내는 대로, 실시품은 표면으로부터 10nm 부근까지 고농도의 은(Ag)의 점감층이 존재하고, 대조적으로 금(Au)의 합금화 원소는 역의 저농도의 점증층이 존재한다. 또한, 팔라듐(Pd)의 농도는, 도시하고 있지 않지만, 고농도 순은층 내에서도 심재 내에서도 거의 일정하였다.As shown in the schematic diagram of Fig. 1, the embodiment exhibits a high-concentration silver (Ag) gradient layer from about 10 nm to about 10 nm from the surface, and in contrast, there exists an increasingly low-concentration increment layer of gold (Au) alloying elements. The concentration of palladium (Pd) is not shown but is almost constant in the core material as well as in the high-concentration pure silver layer.

［황화은의 확인］[Confirmation of silver sulphate]

실시품 1의 본딩 와이어를 실온의 대기 중에 30일간 방치하여, 황화막 두께 측정기(서마트로닉스사제 QC－200)를 이용하여, 최표면을 연속 전기 화학 환원법에 의한 황화은(Ag2S)의 막 두께를 측정하였다. 그 결과 황화은(Ag2S)막은 검출되지 않았다. 이것을 도 2의 적선(L자상 곡선)으로 나타낸다.The bonding wire of the product 1 was allowed to stand in the atmosphere at room temperature for 30 days and the thickness of the silver sulfide (Ag 2 S) film on the outermost surface was measured by a continuous film electrochemical reduction method using a sulfide film thickness meter (QC-200 manufactured by Sumitronics) Were measured. As a result, silver sulfide (Ag 2 S) film was not detected. This is indicated by the solid line (L-shaped curve) in Fig.

비교품 22의 본딩 와이어를 실시품 1과 마찬가지로, 실온의 대기 중에 30일간 방치하여 황화은(Ag2S)의 막 두께를 측정하였다. 그 결과 황화은(Ag2S)막이 검출되었다. 이것을 도 2의 녹선(계단상 곡선)으로 나타낸다.The bonding wire of the comparative article 22 was left in the air at room temperature for 30 days in the same manner as in the product 1, and the film thickness of silver sulfide (Ag 2 S) was measured. As a result, silver sulfide (Ag 2 S) film was detected. This is represented by the rust line (step-like curve) in Fig.

상술하면, 도 2는 시간에 수반하는 전압 변화를 그래프화한 것이다. 황화은(Ag2S)을 형성한 비교품 22의 경우, 전압이 -0.25~－0.80V의 구간에 있어서 시간이 변화한 경우라도, 도 2의 녹선(계단상 곡선)으로 나타내듯이, 황화은(Ag2S)막이 존재하는 범위에서 전압은 변화하지 않는 현상이 생긴다. 한편, 실시품 1의 본딩 와이어는, 상술한 전압의 구간에 있어서, 상술한 계단상 현상은 보이지 않고, 도 2의 적선(L자상 곡선)으로 나타내듯이, 시간의 경과에 수반하여 전압이 변화하였다. 전압이 변화하지 않은 영역이 없었던 것으로부터, 실시품 1의 본딩 와이어의 최표면은 황화은(Ag2S)막을 형성하고 있지 않는 것을 알 수 있다.In detail, FIG. 2 is a graph of the voltage change with time. In the case of the comparative product 22 in which silver sulfide (Ag 2 S) is formed, even when the time varies in a section where the voltage is in the range of -0.25 to -0.80 V, silver sulfide (Ag 2 S) film, the voltage does not change. On the other hand, in the bonding wire of Practical Example 1, the above-mentioned stepwise phenomenon was not observed in the above-mentioned voltage range, and the voltage was changed with the lapse of time as indicated by the solid line (L-shaped phase curve) . It can be seen that the outermost surface of the bonding wire of Practical Example 1 does not form a silver sulfide (Ag 2 S) film.

또, 실시품 1의 최표면을 주사형 오제 분석 장치(VG사제 MICROLAB-310D)에 의해 정성 분석한 바, 유황(S)이 검출되었다. 이 정성 분석 결과를 도 3에 나타낸다.Further, when the outermost surface of the product 1 was subjected to qualitative analysis by a scanning type Ogen analyzer (MICROLAB-310D manufactured by VG Co.), sulfur (S) was detected. The result of this qualitative analysis is shown in Fig.

도 3에 나타내듯이, 실시품 1의 본딩 와이어의 최표면에는 유황(S)이 존재하고 있는 것을 알 수 있다. 그러나, 도 2의 결과로부터 황화은(Ag2S)막이 검출되지 않은 것으로부터, 실시품 1의 본딩 와이어의 유황(S)은 최표면에 존재하는 은(Ag)과 반응하고 있지만, 강고한 황화은(Ag2S)막을 형성하고 있지 않는 것으로부터, 물리적으로 흡착한 불안정한 황화은의 결합 상태인 것을 알 수 있다. 또, 도 3으로부터 분명한 바와 같이, 실시품 1의 본딩 와이어의 최표면의 금속 원소에는, 은(Ag) 이외의 팔라듐(Pd)과 금(Au)이 검출되지 않고, 실질적으로 고농도의 은(Ag)층뿐이므로, 고속 신호층으로서 최적인 구성인 것을 알 수 있다.As shown in Fig. 3, it can be seen that sulfur (S) is present on the outermost surface of the bonding wire of the product (1). However, since the silver sulfide (Ag 2 S) film was not detected from the results of FIG. 2, the sulfur S of the bonding wire of the product 1 reacted with the silver (Ag) present on the outermost surface, Ag 2 S) film is not formed, it can be seen that unstable silver sulfide that is physically adsorbed is in a bonding state. 3, palladium (Pd) and gold (Au) other than silver (Ag) are not detected in the metal element on the outermost surface of the bonding wire of Practical Example 1, and substantially silver (Ag ) Layer, it is understood that the structure is optimal as a high-speed signal layer.

［알루미늄 스플래시 시험］[Aluminum splash test]

이들 실시품 1~21 및 비교품 22~25를 범용의 와이어 본더에 세트하고, 더미의 반도체 IC(테스트 패턴을 웨이퍼에 매립한 것, 약칭 「TEG」) 표면의 Al－1.0질량% Si－0.5질량% Cu 합금으로 이루어지는 70㎛×70㎛ 알루미늄 패드(표면에 20nm의 금(Au)층을 증착한 것)에, 분사 질소 분위기하에서 38㎛ 목표로 프리에어볼(FAB)을 제작하고, 기재의 가열 온도： 200℃, 루프 길이： 5mm, 루프 높이： 220㎛, 압착볼 직경： 50㎛, 압착볼 높이： 10㎛의 조건으로 볼본딩을 행하였다. 알루미늄 스플래시량의 측정 방법은, 범용의 주사형 전자현미경(SEM)을 이용하여 각 와이어의 압착볼을 바로 위로부터 관찰하여, 압착볼의 외주부를 기점으로 하여 압착볼로부터 가장 불거진 알루미늄의 위치를 계측하였다. 불거진 알루미늄량이 2㎛ 미만인 경우를 ○로 하고, 2㎛ 이상 4㎛ 미만인 경우를 △, 4㎛ 이상을 ×로 판정하였다. 이 알루미늄 스플래시 시험에 대해서 평가 결과를 표 2에 나타낸다.These products 1 to 21 and the comparative products 22 to 25 were set in a general-purpose wire bonder and Al-1.0 mass% Si-0.5 (abbreviated as &quot; TEG &quot; Air ball (FAB) with a target of 38 mu m under a spray nitrogen atmosphere was formed on a 70 mu m x 70 mu m aluminum pad (a 20 nm thick gold (Au) layer was deposited on the surface) Ball bonding was performed under the conditions of a heating temperature of 200 占 폚, a loop length of 5 mm, a loop height of 220 占 퐉, a compression ball diameter of 50 占 퐉, and a compression ball height of 10 占 퐉. The aluminum splash amount was measured by observing the compression balls of each wire directly from above using a general-purpose scanning electron microscope (SEM), measuring the position of the most bulged aluminum from the compression ball with the outer peripheral portion of the compression ball as a starting point Respectively. A case where the amount of aluminum exposed was less than 2 mu m was evaluated as &amp; cir &amp;, a case of 2 mu m or more and less than 4 mu m was evaluated as DELTA, and a case of 4 mu m or more was evaluated as x. The evaluation results are shown in Table 2 for this aluminum splash test.

Figure 112013103717456-pat00002
Figure 112013103717456-pat00002

［칩 손상 시험］[Chip Damage Test]

또한, 이 시료에 대해서 칩 손상을 보았다. 칩 손상 시험은 수산화나트륨 수용액으로 상기의 기재의 알루미늄 패드를 녹인 후에 칩을 실체 현미경으로 관찰한 결과이다. 표 2 중의 「칩 손상 시험」은 흠이나 크랙(crack)이 조금이라도 들어가 있는 경우는 ×로 하고, 흠이나 크랙이 전혀 없는 경우를 ○로 하여 각각 표 2에 나타낸다.In addition, we observed chip damage to this sample. The chip damage test is a result of observing the chip with a stereoscopic microscope after dissolving the above-mentioned aluminum pad with an aqueous solution of sodium hydroxide. &Quot; Chip damage test &quot; in Table 2 indicates &quot; x &quot; when scratches or cracks are contained even slightly, and &quot;

［신호 파형의 열화 시험］[Degradation test of signal waveform]

다음에, 신호 파형의 열화 시험은 4단자법을 이용하여 측정하였다. 시료는 실시품·비교품의 와이어(각각 선직경 20㎛, 길이 100mm)를 사용하였다. 측정에는 범용성 펑션 제너레이터(function generator)를 이용하여 10GHz, 2V의 펄스 파형을 실시품 와이어 및 비교품 와이어에 전파시키고, 10GHz 대역의 펄스 파형이 측정 가능한 소정의 범용 디지털 오실로스코프 및 프로브를 이용하여 신호 파형을 측정하였다. 측정용 프로브 간격은 50mm로 하였다. 신호 파형의 열화의 정도는 와이어에 전파하는 출력 신호 파형이 입력 전압치에 이를 때까지의 지연 시간을 측정하였다. 여기서, 실험 결과로부터 종래의 순금 와이어(Ca 15ppm, Eu 20ppm 및 잔부 99.999질량% Au)의 신호 지연 시간은 20%인 것을 확인하였다. 따라서, 신호 지연 시간의 판정은 지연 시간이 종래의 와이어와 비교하여 20% 미만인 경우는 ○, 20%보다 지연이 큰 경우는 ×로 하였다. 이 신호 파형의 열화 시험에 대해서 실시품·비교품의 와이어의 평가 결과를 표 2에 나타낸다.Next, the deterioration test of the signal waveform was carried out by the four-terminal method. As a sample, wire of the product of the comparative product and the wire of the comparative product (each having a wire diameter of 20 μm and a length of 100 mm) were used. A 10 GHz, 2 V pulse waveform was propagated to the product wire and the comparative product wire using a universal function generator, and the signal waveform was measured using a predetermined general-purpose digital oscilloscope and probe capable of measuring pulse waveforms in the 10 GHz band. Were measured. The measurement probe spacing was 50 mm. The degree of deterioration of the signal waveform was measured as the delay time until the waveform of the output signal propagating on the wire reached the input voltage value. From the experimental results, it was confirmed that the signal delay time of the conventional pure gold wire (Ca 15 ppm, Eu 20 ppm and the rest 99.999 mass% Au) was 20%. Therefore, the determination of the signal delay time is made when the delay time is less than 20%, compared with the conventional wire, and when the delay time is longer than 20%, the signal delay time is judged as x. The deterioration test of this signal waveform is shown in Table 2 with the evaluation results of the wire for the product and the comparative product.

［압착볼의 전단 강도 시험］[Shear Strength Test of Compression Ball]

알루미늄 스플래시 시험과 마찬가지의 부재 및 평가 장치를 이용하여, 실시품 와이어 및 비교품 와이어에 대해, 전용의 IC 칩에 와이어 본더로 본딩을 행하고, 100점에 대해서 데이지사제의 제품명 「만능 본드 테스터(BT)(형식 4000)」를 이용하여 볼본딩시의 압착볼의 전단(shear) 강도 평가를 행하였다. 이 압착볼의 전단 평가 결과를 표 2에 나타낸다.Using a member and an evaluating device similar to those of the aluminum splash test, a dedicated IC chip was bonded to a dedicated IC chip by a wire bonder, and 100 points of the product wire and the comparative article were bonded with a product name &quot; BT (Model 4000) &quot; was used to evaluate the shear strength of the pressed balls at the time of ball bonding. Table 2 shows the shear evaluation results of the compression balls.

표 2 중 「볼 전단」은 제1본드에 있어서의 전단 하중치를 나타내고, ○는 12kg/mm2 이상, △는 10kg/mm2 이상 12kg/mm2 미만, 그리고 ×는 10kg/mm2 미만 혹은 볼 벗겨짐이 발생한 경우를 나타낸다.Table 2 "ball shear" denotes values shear load in the first bond from, ○ is 12kg / mm 2 or more, △ is 10kg / mm 2, more than 12kg / mm 2 or less, and × is 10kg / mm 2 is less than or see Indicates the occurrence of peeling.

표 2의 결과로부터 분명하듯이, 신호 파형의 열화 시험에 대해서 본 발명의 실시품 1~21은 모두 열화가 보이지 않는데 반해, 비교품 22~25는 모두 뒤떨어져 있는 것을 알 수 있다.As apparent from the results of Table 2, it can be seen that all of the comparative products 22 to 25 are inferior to the deterioration test of the signal waveform, while the degradation tests of the products 1 to 21 of the present invention are not observed.

또, 알루미늄 스플래시 시험, 칩 손상 시험 및 압착볼의 전단 강도 시험에 대해서는, 본 발명의 실시품 1~21은 모두 양호한데 반해, 비교품 22는 압착볼의 전단 강도 시험이 뒤떨어져 있고, 비교품 23과 24는 알루미늄 스플래시 시험 및 칩 손상 시험이 뒤떨어져 있는 것을 알 수 있다.As for the aluminum splash test, the chip damage test and the shear strength test of the press-contact ball, the products 1 to 21 of the present invention are all good, whereas the comparative article 22 is inferior to the shear strength test of the press- And 24 show that the aluminum splash test and the chip damage test are inferior.

본 발명의 본딩 와이어는 수 내지 수십GHz의 초고주파 신호의 전송에 최적인 본딩 와이어이고, 널리 고주파 신호의 전송에 적합한 신호용 본딩 와이어의 용도가 있다.
The bonding wire of the present invention is a bonding wire best suited for transmission of a very high frequency signal of several to several tens of GHz and is widely used for signal bonding wires suitable for transmission of a high frequency signal.

Claims (6)

반도체 소자의 패드 전극과 배선 기판 상의 리드 전극을 프리에어볼(FAB)에 의해 접속하기 위한 Ag－Pd－Au기 합금 본딩 와이어로서, 당해 본딩 와이어가 팔라듐(Pd)을 2.5~4.0질량%, 금(Au)을 1.5~2.5질량% 및 잔부가 순도 99.99질량% 이상의 은(Ag)으로 이루어지는 3원 합금으로서, 그 본딩 와이어의 표면은 연속 주조 후에 축경된 연주면(連鑄面)으로 이루어지고, 그 본딩 와이어의 단면은 표면 편석층과 심재로 이루어지고, 그 표면 편석층은, 최표면으로부터 심재를 향해 은(Ag)의 함유량이 점감하고 또 금(Au)의 함유량이 점증하고 있는 합금 영역으로 이루어지는 것을 특징으로 하는 고속 신호선용 본딩 와이어로서, 팔라듐(Pd)의 함유량이 금(Au)의 함유량보다도 많은 것을 특징으로 하는 고속 신호선용 본딩 와이어.An Ag-Pd-Au based alloy bonding wire for connecting a pad electrode of a semiconductor element and a lead electrode on a wiring board by means of a pre-air ball (FAB), wherein the bonding wire comprises 2.5 to 4.0 mass% of palladium (Pd) (Au) in an amount of 1.5 to 2.5 mass% and the balance of silver (Ag) in a purity of 99.99 mass% or more. The surface of the bonding wire has a concave surface, The cross section of the bonding wire is composed of a surface segregation layer and a core material. The surface segregation layer is an alloy region in which the content of silver (Ag) is gradually decreased from the outermost surface toward the core material and the content of gold Wherein the content of palladium (Pd) is greater than the content of gold (Au). 반도체 소자의 패드 전극과 배선 기판 상의 리드 전극을 프리에어볼(FAB)에 의해 접속하기 위한 미량 첨가 원소를 함유하는 Ag－Pd－Au기 합금 본딩 와이어로서, 당해 본딩 와이어가 팔라듐(Pd)을 2.5~4.0질량%, 금(Au)을 1.5~2.5질량%, 및 로듐(Rh), 이리듐(Ir), 루테늄(Ru), 동(Cu), 니켈(Ni), 철(Fe), 마그네슘(Mg), 아연(Zn), 알루미늄(Al), 인듐(In), 실리콘(Si), 게르마늄(Ge), 베릴륨(Be), 비스무트(Bi), 셀렌(Se), 세륨(Ce), 이트륨(Y), 란탄(La), 칼슘(Ca) 또는 유로퓸(Eu) 중 적어도 1종 이상을 포함하고 있고, 첨가 미량 원소의 합계가 5~300질량ppm 및 잔부가 순도 99.99질량% 이상의 은(Ag)으로 이루어지는 3원계 합금으로서, 그 본딩 와이어의 표면은 연속 주조 후에 축경된 연주면(連鑄面)으로 이루어지고, 그 본딩 와이어의 단면은 표면 편석층과 심재로 이루어지고, 그 표면 편석층은, 최표면으로부터 심재를 향해 은(Ag)의 함유량이 점감하고 또 금(Au)의 함유량이 점증하고 있는 합금 영역으로 이루어지는 것을 특징으로 하는 고속 신호선용 본딩 와이어로서, 팔라듐(Pd)의 함유량이 금(Au)의 함유량보다도 많은 것을 특징으로 하는 고속 신호선용 본딩 와이어.An Ag-Pd-Au based alloy bonding wire containing a trace amount of additive element for connecting a pad electrode of a semiconductor element and a lead electrode on a wiring board by a pre-air ball (FAB), wherein the bonding wire is palladium (Pd) (Ni), iron (Fe), magnesium (Mg), copper (Cu), and copper (Cu) in an amount of 0.5 to 4.0 mass%, gold (Au) in an amount of 1.5 to 2.5 mass%, and at least one element selected from the group consisting of rhodium, iridium, ruthenium, ), Zinc (Zn), aluminum (Al), indium (In), silicon (Si), germanium (Ge), beryllium (Be), bismuth (Bi), selenium (Se), cerium (Ag) containing at least one of lanthanum (La), calcium (Ca) and europium (Eu), the total amount of added trace elements being 5 to 300 mass ppm and the remainder being 99.99 mass% Wherein the surface of the bonding wire is composed of a concave surface after the continuous casting and the cross section of the bonding wire is composed of a surface segregation layer and a core material, Wherein a content of palladium (Pd) is higher than that of gold (Au), wherein the content of palladium (Pd) is higher than that of gold (Au) ) Of the bonding wire for high-speed signal lines. 제1항 또는 제2항에 있어서,
상기 본딩 와이어의 은(Ag)이 순도 99.999질량% 이상인 것을 특징으로 하는 고속 신호선용 본딩 와이어.3. The method according to claim 1 or 2,
Wherein the silver (Ag) of the bonding wire has a purity of 99.999 mass% or more. 제1항 또는 제2항에 있어서,
상기 고속 신호가 1~15GHz의 주파수인 것을 특징으로 하는 고속 신호선용 본딩 와이어.3. The method according to claim 1 or 2,
Wherein the high-speed signal has a frequency of 1 to 15 GHz. 제1항 또는 제2항에 있어서,
상기 패드 전극이 순도 99.9질량% 이상의 알루미늄(Al) 금속 또는 0.5~2.0질량%의 실리콘(Si) 또는 동(Cu) 및 잔부 순도 99.9질량% 이상의 알루미늄(Al) 합금인 것을 특징으로 하는 고속 신호선용 본딩 와이어.3. The method according to claim 1 or 2,
Wherein the pad electrode is made of an aluminum (Al) metal having a purity of 99.9 mass% or more, a silicon (Si) or copper (Cu) having a purity of 0.5 to 2.0 mass%, and an aluminum (Al) alloy having a purity of 99.9 mass% Bonding wire. 제1항 또는 제2항에 있어서,
상기 패드 전극이 금(Au), 팔라듐(Pd) 또는 백금(Pt)의 표층으로 이루어지는 전극 패드인 것을 특징으로 하는 고속 신호선용 본딩 와이어.3. The method according to claim 1 or 2,
Wherein the pad electrode is an electrode pad composed of a surface layer of gold (Au), palladium (Pd), or platinum (Pt).
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