CN1169202C - 半导体元件连接用金线及半导体元件的连接方法 - Google Patents
半导体元件连接用金线及半导体元件的连接方法 Download PDFInfo
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- CN1169202C CN1169202C CNB011213205A CN01121320A CN1169202C CN 1169202 C CN1169202 C CN 1169202C CN B011213205 A CNB011213205 A CN B011213205A CN 01121320 A CN01121320 A CN 01121320A CN 1169202 C CN1169202 C CN 1169202C
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- gold
- semiconductor element
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- gold thread
- electrode
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- 238000000034 method Methods 0.000 title claims abstract description 46
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- 239000010931 gold Substances 0.000 claims abstract description 41
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- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 abstract description 16
- 229910052745 lead Inorganic materials 0.000 abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 3
- 239000011324 bead Substances 0.000 description 42
- 239000000203 mixture Substances 0.000 description 12
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- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
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Abstract
提供一种半导体元件连接用金线和半导体元件的连接方法。该金线中包含5~100质量ppm的Ca、5~100质量ppm的Gd、1~100质量ppm的Y,优选还含有1~100质量ppm的Eu、La、Ce和Lu中的至少一种,更优选地还含有1~100质量ppm的Mg、Ti、Pb中的至少一种,这些元素的总量在200质量ppm以下,其余为金和不可避免的杂质。该半导体元件的连接方法用该金线进行球键合和凸点键合。
Description
技术领域
本发明涉及为把半导体元件上的电极和外部引线等电气连接而使用的半导体元件连接用金线。更具体地涉及适合小间距连接或薄电极连接用的半导体元件连接用金线。
背景技术
现在,在半导体装置的安装中,作为将半导体元件的电极和外部引线连接的方法,用金线进行球键合而布线的方法和用金线形成凸点并通过该凸点进行连接的方法已经十分普及。
在用球键合布线的方法中,是将重复的金线导入作为键合工具的毛细管中,然后将从该工具的出口侧导出的金属细线的前端形成球,之后把球压在Al电极上,在XYZ方向(前后、左右、上下方)上移动毛细管,形成预定的鼓起形状,将外部引线键合后,切断金属细线的引线键合法(下称“球键合”)。
通过凸点进行连接的方法,是在把上述球压按在上述Al电极上之后,在球附着的根部附近将金线切断,通过该球进行连接的方法(下称“凸点连接”)。
另一方面,伴随着最近的半导体装置的高性能化和小型化,为了半导体元件的多间距化,需要进一步小间距化。为此对金线的要求的性能也提高,在这些要求的性能中,按压上述球后的挤压球的外径是布线直径的两倍左右,提高挤压球的圆形度是非常重要的特性。
以前曾尝试对上述球形成时的压接前的球的球形度进行管理。但是现在发现,在适合小间距连接的压接后的球的圆形度与压接前的球的球形度不必一致。
为此开始尝试提高压接后的球的圆形度。例如日本专利特开平11-163016号公报中公开了加入Cu、Pt、Pd中的一种以上总量为0.03~5wt%,特开平10-172998号公报公开了加入Be和Ca,特开平10-303239号和10-83716公报公开了在Mn、Pd中加入Ca等。
但是在小间距的布线中,球采用比以前还小的球,进行压接,在更小的压接直径下要求维持压接后的圆形度。即使在上述尝试中,特开平10-172998号公报公开的情况具有小球的压接圆形度不够,得不到预定的布线强度的缺点。在此,在引线键合的小间距连接中为了防止布线倒转引起的接触事故,特别要求提高布线强度。
而其它的尝试也具有小球的压接圆形度不够,而且由于为提高该圆形度而大量增加添加元素含量导致电阻增大的缺点。
而且,要求半导体元件的Al电极的膜厚为薄的;伴随该电极膜厚的薄型化,尤其在凸点连接中会生成因压接球产生电极开裂导致半导体元件即IC芯片开裂(下称“芯片开裂”)的问题。大幅度增加上述添加元素的含量也会产生该芯片开裂问题。
而且,在通过凸点进行连接的场合,是把球压接到半导体元件的Al电极上之后,从上方引出金线伸开,在球附着根部附近切割的方法。此时要求附着于压接球的残余线长度(下称“线尾长度)均匀。
本发明正是鉴于上述现有的问题而提出的。其目的在于提供这样的半导体元件连接用金线,即,为了抑制电阻上升,采用添加元素含量在200质量ppm以下的特定的金合金成分,同时提高小球压接后的圆形度,增大布线强度,即使在半导体元件的Al电极膜厚为薄的场合也不会产生压接球导致的芯片开裂问题,而且在凸点连接时以均匀的线尾长度引出来。
发明内容
为了实现上述目的,本发明提供下述的发明:
(1).一种半导体元件连接用金线,其中含有5~100质量ppm的Ca、5~100质量ppm的Gd、1~100质量ppm的Y,这些元素的总量为200质量ppm以下,其余为金和不可避免的杂质。
(2).如(1)所述的半导体元件连接用金线,其中还含有1~100质量ppm的Mg、Ti、Pb中的至少一种,且全部添加元素的总量在200质量ppm以下。
(3).一种半导体元件连接用金线,其中含有5~100质量ppm的Ca、5~100质量ppm的Gd、1~100质量ppm的Y,以及1~100质量ppm的Eu、La、Ce和Lu中的至少一种,这些元素的总量为200质量ppm以下,其余为金和不可避免的杂质。
(4).如(3)所述的半导体元件连接用金线,其中还含有1~100质量ppm的Mg、Ti、Pb中的至少一种,且全部添加元素的总量在200质量ppm以下。
(5).一种半导体元件的连接方法,其中包括下列工序:
(A)将金线插入毛细管,加热熔化金线的前端形成金球的工序;
(B)使毛细管下降,将金球压接到半导体元件的电极上,将金线与电极接合的工序;
(C)将含有接合到电极上的上述金线的毛细管描画预定轨迹,在被连接部件上移动,将该金线的侧面压接到被连接部件上的工序;以及
(D)在把压接到被连接部件上的金线弯曲成突起的状态下提升,切断金线,完成半导体元件的电极和被连接部件间的金线的布线的工序,而且
上述金线是如(1)~(4)中任一项所述的金线。
(6).如(5)所述的方法,其中在上述工序(A)和/或工序(C)中,包括通过毛细管向金线的前端部分施加超声波振动,同时用加热器单元对半导体元件或被连接件加热,将上述金球热压接。
(7).如(5)所述的方法,其中半导体元件的邻接电极的间距为70μm以下。
(8).如(5)所述的方法,其中半导体元件的邻接电极的间距为60μm以下。
(9).一种半导体元件的连接方法,包括下列工序:
(A)将金线插入毛细管,加热熔化金线的前端以形成金球的工序;
(B)使毛细管下降,将金球压接到半导体元件的电极上以形成压接金球的工序;以及
(C)在把压接到半导体元件的电极上形成压接金球的上述金线弯曲成突起的状态下提升,在压接金球的附着根部附近切断金线,在电极上形成凸点的工序,而且
上述金线是如(1)~(4)中任一项所述的金线。
(10).如(9)所述的方法,其中还包括把在半导体元件的电极上形成的凸点压接到被连接部件上的工序。
(11).如(9)所述的方法,其中:在上述工序(A)中包括通过毛细管向金线前端施加超声波振动,同时用加热器单元加热半导体元件,热压接上述金球。
(12).如(9)所述的方法,其中:上述半导体元件电极是铝电极膜,其厚度为0.5μm以下。
(13).如(9)所述的方法,其中:上述半导体元件电极是铝电极膜,其厚度为0.1μm以下。
附图说明
图1A~1D是用球键合法布线连接的方法的工序图;
图2A~2D是凸点连接法的工序图;
图3A和3B是用凸点连接法把半导体元件和引线或布线基板连接起来的状态;
图4是凸点的放大图。
具体实施方式
一、成分
(1)厚料金
作为原料金,优选采用至少99.99wt%以上的精制的高纯金。更优选为99.995wt%以上,最优选为99.999wt%以上。用高纯金最好除去有害成分的影响。
(2)[Ca]
本发明用的金合金线有预定量的Gd和Y共存时,使Ca含量为5~100ppm质量可以实现上述目的。
若Ca的含量在该范围内,与Ca含量小于5质量ppm的场合相比,可以提高小球的压接圆形度和破断强度,提高形成凸点时的线尾长度的均匀性。与Ca含量大于100质量ppm的场合相比,可以提高小球的压接圆形度,不产生薄膜电极造成的芯片开裂。因此在有预定量的Gd和Y共存时Ca的含量为5~100质量ppm。
(3)[Gd]
本发明用的金合金线有预定量的Ca和Y共存时,使Gd含量为5~100ppm质量可以实现上述目的。
若Gd的含量在该范围内,与Gd含量小于5质量ppm的场合相比,可以提高小球的压接圆形度,提高形成凸点时的线尾长度的均匀性。与Gd含量大小100质量ppm的场合相比,可以提高小球的压接圆形度,不产生薄膜电极造成的芯片开裂。因此在有预定量的Ca和Y共存时Gd的含量为5~100质量ppm。
(4)[Y]
本发明用的金合金线有预定量的Gd和Ca共有时,使Y含量为1~100ppm质量可以实现上述目的。
若Y的含量在该范围内,与Y含量小于1质量ppm的场合相比,可以提高小球的压接圆形度,提高形成凸点时的线尾长度的均匀性。与Y含量大小100质量ppm的场合相比,可以提高小球的压接圆形度,不产生薄膜电极造成的芯片开裂。因此在有预定量的Gd和Ca共存时Ca的含量为5~100质量ppm。
(5)[除Gd、Y之外的稀土元素](下称“第一组元素”)
在本发明用的金合金线有预定量的Ca、Gd和Y共存时通过添加1~100质量ppm的第一组元素中的至少一个,与不添加的场合相比,可以提高小球的压接圆形度和形成凸点时的线尾长度的均匀性,所以是优选的。第一组元素中优选采用Eu、La、Ce、Lu。
因此在有预定量的Ca、Gd和Y共存时,优选地添加1~100质量ppm的第一组元素中的至少一个。
(6)[Mg、Ti、Pb](下称“第二组元素”)
在本发明用的金合金线有预定量的Ca、Gd和Y共存时或者与向其又添加的预定量的第一组元素共存时,通过添加1~10质量ppm的第二组元素中的至少一个,与不添加的场合相比,有同等的性能。第二组元素中优选采用Mg、Ti、Pb。
(7)添加量的总量
若本发明用的金合金线中添加量的总量超过200质量ppm,会生成薄膜电极引起的芯片开裂。而且电阻会增大,也是不好的。因此添加量的总量必须为200质量ppm以下。
二、金线的制造工艺
对本发明用的半导体元件连接用金线的制造工艺的一例进行说明。首先,将预定成分的金属熔化铸成锭,然后用沟型轧机轧制,交叉进行中间退火,经最终冷加工成为直径10~100μm的细线后,进行最终退火以得到4~6%的延伸率,然后在线的表面涂敷润滑防锈剂。最后将加工结束的线以预定张力在外径50.3mm的卷轴上反复卷绕成预定长度,得到制品。作为预定长度,根据需要在100~3000m中选择。
三、用途
本发明的金线用于半导体元件电极和外部引线(或布线基板)之间的连接。作为连接方法,用金线通过球键合进行布线连接的方法和用金线形成凸点,并通过该凸点进行连接的方法已经普及开来。下面用图1~4说明这些方法。
(1)通过球键合进行连接的方法
在图1A所示的状态中,金线2插入毛细管1,其前端与电火焰3对置,通过与金线2之间发生放电,加热金线2的前端,熔化形成球4。
接着,在图1B所示的状态中,使毛细管1下降,把该球4按压接合在半导体元件6的Al电极5上。此时通过毛细管1施加未图示的超声波振动,同时用加热器单元加热半导体元件6,对上述球4热压,形成压接球4′。
接着,如图1C所示,毛细管1描画预定的轧迹,在外部引线8上移动、下降。此时通过毛细管1施加未图示的超声波振动,用加热器单元加热外部引线8,将金线2的侧面热压在外部引线8上。
然后,如图1D所示,通过弯曲金线2形成突起7并原样上升,切断金线2完成布线。接着用树脂密封该布线部分,成为半导体装置。作为半导体装置,除了树脂密封型之外,还可以是陶瓷封装型等各种形态,没有特殊限制。因此,半导体元件的电极和布线侧用各种引线或电极等都是可以的。
此时邻接的压接球4′的中心间的距离(下称“间距长度”)是现有的80μm左右,但要求70μm以下甚至是60μm以下的小的间距长度。
由于本发明的金线,强度高,且提高了压接球的圆形度,在半导体元件电极和引线部用金线布线连接,用树脂密封布线部的半导体装置中,可优选用于间距长度在70μm以下的半导体装置。
(2)通过凸点进行连接的方法
用与图1A、图1B同样的方法将球4按压接合在半导体元件6上的Al电极5上,形成球4′(图2A,图2A)。
接着,如图2C所示,在半导体元件6被固定的状态下,通过在被弯曲的突起7上方移动金线2,使金线2在压接球4′根部附近残存有线尾部分的状态下破断。此时,金线2受形成球时的热影响,球的附着根部附近变弱,所以在如上所述金线因张力而断裂时,球的附着根部附近也破断。
然后如图2D或3D所示,通过在引线8上压接压接球4′而形成凸点14,半导体元件6的电极5和引线8通过凸点14直接起来。然后用树脂密封该连接部分形成半导体装置。对于利用凸点的半导体元件的连接状态并不限于与引线连接,例如,如图3B所示将具有凸点14的半导体元件16与布线基板21等的电极22用凸点14连接起来的类型和其它类型都是可以的。因此,通过凸点连接的一侧即使是各种引线、电极等都是可以的。
图4示出图2c中金线破断的压接球的放大图。高度a是通过毛细管1的外底部压接的高度,高度b是通过毛细管1的内底部压接的高度,高度c是线尾部分。其中高度a、b的偏差小,而高度c易于产生偏差。如果高度c的偏差大,凸点的大小产生偏差,同时高度c变长,则如图2D所示形成压接球4′时,从布线端部引出的邻接的凸点会发生短路。为此要求抑制高度c的偏差。而且虽然半导体元件Al电极5的膜厚现在为1μm左右,但要求压接在0.5μm以下,或0.3μm以下,甚至0.1μm以下的薄的电极膜上。这样的板薄的电极膜与球压接时,容易产生电极破损,因其影响导致芯片破损。
如果用本发明的金线形成凸点,由于可减小线尾长度的偏差,即使压接在极薄电极膜上也可以防止芯片开裂,所以在半导体元件电极和引线部分用金凸点连接,且用树脂密封连接部分的半导体装置中,适合用于半导体元件Al电极的膜最为0.5μm以下的半导体装置。
实施例
(试验A)
在纯度99.999wt%的高纯金中添加预定量的表1所示的元素,且真空炉熔化后,铸造得到表1所示的A1-A11成分的金合金锭,用沟辊和拉丝机对其进行冷加工和中间退火,经最终冷加工得到直径25μm,并进行最终退火使延伸率为4%,并在表面上覆盖润滑剂,提供供加工测量的金合金线。
第一,进行圆形度试验。首先用高速自动键合机UTC-200型(株式会社新川制造),用电火焰电弧放电在金合金前端形成球。在电弧放电的条件中调整电流和时间形成直径55μm(是线直径的2.2倍的现有球)和直径45μm(是线直径的1.8倍的小球)两种。然后用压接工具在200℃的模子温度下,并且超声波和热压方式把各个球热压接到半导体元件Al电极上。
测量现有球和小球压接前和压接后的圆形度。压接前的球测量任意直角方向的直径,以小直径/大直径的值作为圆形度。压接后的圆形度是分别测量与超声波施加方向垂直方向的压接直径(下称“X)”和平行方向的压接直径(下称“Y”),以X/Y作为小球的压接圆形度。作为各圆形度,取50个球的平均值示于表1中。
第二,进行芯片破损试验。用凸点键合机SBB-1型(株式会社新川制造),同样地,通过电火焰电弧放电在金合金线的前端形成球。球的大小是现有的球(直径55μm)的大小。然后用压接工具在200℃的模子温度下,并用超声波和热压方式把该球热压接到半导体元件Al电极上。作为该半导体元件Al电极,采用通用膜厚(1μm)和小膜厚(0.1μm)。作为热压接条件,有超声波输出为0.5W~1.5W范围内的4个水平,负荷为0.4N~0.8N范围内的3个水平,共计12种。在各个条件下进行400个凸点试验,在全部条件下没有芯片开裂的为合格品,即使有1个有芯片开裂也是不合格品。合格品用“O”表示,不合格品用“X”表示,测量结果示于表1。
第三,进行线尾长度的均匀性试验。除了Al电极采用通用膜厚(1μm)之外,与第二试验同样地进行热压接。然后按图2(c)所示的要领从上方拉引金合金线,形成凸点4′。测量在凸点的放大图即图3中的a+b+c的高度。对每一个成分条件用金属显激镜测量50个凸点,取最大值和最小值的差作为线尾长度的均匀性,示于表1。
第四,在室温下进行拉伸试验,测量断裂负荷。结果示于表1。
(实验例)
除了成分如表2~3所示以外,与试验A同样地制作实验例1~45所示的直径25μm的金合金线,供测量用。
除了在小球的压接圆形度试验中,作为球大小是形成小球(直径45μm)之外,与试验A的圆形度试验同样地测量球压接后的圆形度,其结果示于表2~3。
进行所供材料的拉伸试验,测量断裂负荷,结果示于表2~3。
除了在芯片破损试验中作为半导体元件Al电极的膜厚采用小膜厚(0.1μm)之外,与试验A的芯片破损试验同样地测量芯片破损,结果示于表2~3。
除了在线尾长度均匀性试验中作为半导体元件Al电极的膜厚,采用小膜厚(0.1μm)之外,与试验A的线尾长度均匀性试验同样地测量线尾长度均匀性,结果示于表2~3。
(试验结果)
试验A
用表1所示的成分(试样A1~A11),进行了用来探索实现本发明的目的所必需的元素的试验A。
一、圆形度试验
进行小球的压接后的测量,有下列结论。
(1)不含Ca、Gd、Y中Ca的试样A7,不含Gd的试样A3、A4、A11,不含Y的试样A5、A6、A10,和含0.5%Ag或Co的试样A8、A9的小球压接后圆形度为0.94以下,不够充分。
(2)可看出,上述试样A3~A11的压接前球圆形度或现有球的压接后圆形度为0.97以上,良好,但小球压接后圆形度不够充分。
(3)含有Ca、Gd、Y各20质量ppm的试样A1的小球压接后圆形度为0.97,良好。
(4)在试样A1的成分中含有20质量ppm的作为第一组元素的Eu的试样A2的小球压接后圆形度为1.00,更好。
二、芯片破损试验
测量厚度0.1μm的小电板的芯片破损,有下列结论。
(1)含有0.5%Ag或Co的试样A8、A9发生芯片开裂。
可以由此判定这是添加元素的量的上限值。
三、线尾长度的偏差
(1)不含Ca、Gd、Y中的Ca的试样A7,不含Gd的试样A3、A4、A11,和不含Y的试样A5、A6、A10的线尾长度的偏差在56μm以上,不好。
(2)含有Ca、Gd、Y各20质量ppm的试样A1的线尾长度的偏差为40μm,良好。
(3)在试样A1的成分中含有20质量ppm的作为第一组元素的Eu的试样A2,线尾长度的偏差为19μm,更好。
四、破断负荷
(1)至少含Gd、Ca、Y各20质量ppm的试样A1、A2、A8、A9,破断负荷为129~140mN,良好。
(2)即使含有20质量ppm的Gd、Y但不含Ca的试样A7,和有Be和Gd共存的试样A10,破断负荷为124~127mN,比较低。
五、结论
对于小球压接后圆形度、芯片破损、线尾长度的偏差这些问题,含有Ca、Gd、Y或向其中加入Eu可以得到优良的效果。可以判定,若向其添加的量多,则对小球压接后圆形度和芯片破坏的效果减小。
实验例1~45
为了实现本发明的目的,作为对试验A的追加试验,用表2~3所示的成分进行了实验例1~45。
一、试验I(试验A和实施例1~7)
由改变Ca添加量的表2的试验I可得出下列结论。
(1)可以看出,在有Gd和Y共存时,Ca添加量在5~100质量ppm范围内对本发明的目的有良好的效果。即,小球压接后圆形度为0.96~0.97,破断负荷为133~145mN,没有芯片破损,线尾长度的偏差为31~48μm。
(2)Ca添加量小于5质量ppm时,小球压接后圆形度为0.93,破断负荷为127mN,线尾长度的偏差为78μm,都不好。
(3)Ca添加量超过100质量ppm时,小球压接后圆形度0.91,发生芯片破损,也不好。
(4)若在Ca、Gd、Y中添加Eu,Ca添加量为5~100质量ppm范围内时对本发明的目的有良好的效果。即,小球压接后圆形度为0.99~1.00,线尾长度的偏差为13~27μm,是很好的。
二、试验II(试验A和实验例8-13)
由改变Gd添加量的表2的试验II可得出下列结论。
(1)可以看出,在有Ca和Y共存时,Gd添加量在5~100质量ppm范围内对本发明的目的有良好的效果。即,小球压接后圆形度为0.95~0.97,破断负荷为138~140mN,没有芯片破损,线尾长度的偏差为33~45μm。
(2)Gd添加量小于5质量ppm时,小球压接后圆形度为0.92,线尾长度的偏差为75μm,都不好。
(3)Gd添加量超过100质量ppm时,小球压接后圆形度0.90,发生芯片破损,也不好。
(4)若在Ca、Gd、Y中添加Eu,Gd添加量为5~100质量ppm范围内时对本发明的目的有良好的效果。即,小球压接后圆形度为0.99~1.00,线尾长度的偏差为15~29μm,是很好的。
三、试验III(试验A和实验例14~19)
由改变Y添加量的表2的试验III可得出下列结论。
(1)可以看出,在有Ca和Gd共存时,Y添加量在1~100质量ppm范围内对本发明的目的有良好的效果。即,小球压接后圆形度为0.95~0.97,破断负荷为137~142mN,没有芯片破损,线尾长度的偏差为35~50μm。
(2)Y添加量小于1质量ppm时,小球压接后圆形度为0.93,线尾长度的偏差为82μm,都不好。
(3)Y添加量超过100质量ppm时,小球压接后圆形度0.91,发生芯片破损,也不好。
(4)若在Ca、Gd、Y中添加Eu,Y添加量为1~100质量ppm范围内时对本发明的目的有良好的效果。即,小球压接后圆形度为0.98~1.00,线尾长度的偏差为16~29μm,是很好的。
四、试验IV(试验A及实验例20~31)
由改变第一组元素(Gd、Y以外的稀土元素)的添加量的表3的试验IV可得出下列结果。
(1)可以看出,在有Ca、Gd、Y共存时第一组元素的添加量1~100质量ppm的范围内的实验例20~30和试验A2,对于本发明的目的都有最好的效果。即,小球压接后圆形度为0.98~1.0,破断负荷为136~141mN,无芯片破损,线尾长度的偏差为15~29μm,最好。
(2)第一组元素的添加量大于100质量ppm的实验例31的小球压接后圆形度为0.91,有芯片破损发生,不好。
五、试验V(试验A及实验例32~45)
由改变第二组元素(Mg、Ti、Pb)的添加量的表3的试验V可得出下列结果。
(1)可以看出,在有Ca、Gd、Y和第一组元素共存时,第二组元素中的至少一种的添加量1~100质量ppm的范围内的实验例32~42,对于本发明的目的都有和试验IV同样的最好的效果。即,小球压接后圆形度为0.98~1.0,破断负荷为137~141mN,无芯片破损,线尾长度的偏差为9~18μm,最好。
(2)第二组元素的添加总量大于200质量ppm的实验例43的小球压接后圆形度为0.96,有芯片破损发生,不好。
(3)虽含有预定量的第二组元素,但不含Ca、Gd、Y、第一组元素中的Gd或Y的实验例44、45,小球压接后圆形度为0.91~0.92,线尾长度的偏差为37~43μm。可以看出,在添加有预定量的第二组元素时全部添加了Ca、Gd、Y、第一组元素的实验例32~42非常好。
表1
成分 | 试验结果 | ||||||||||||||||
破断负荷(mN) | 延伸率(%) | 圆形度试验 | 芯片破损试验 | 线尾长度偏差(μm) | |||||||||||||
质量% | 质量ppm | 现有球(直径55μm) | 小球(直径45μm) | 现有膜厚(1μm) | 微小膜厚(0.1μm) | ||||||||||||
Ag | Co | Ca | Be | Gd | Y | Eu | Au | 压着前 | 压着后 | 压着前 | 压着后 | ||||||
试验A1 | 20 | 20 | 20 | 其余 | 140 | 4 | 1.00 | 0.98 | 0.98 | 0.97 | ○ | ○ | 40 | ||||
A2 | 20 | 20 | 20 | 20 | 其余 | 139 | 4 | 1.00 | 0.99 | 1.00 | 1.00 | ○ | ○ | 19 | |||
A3 | 20 | 20 | 其余 | 134 | 4 | 1.00 | 0.99 | 0.98 | 0.92 | ○ | ○ | 75 | |||||
A4 | 20 | 20 | 20 | 其余 | 132 | 4 | 0.99 | 0.98 | 0.97 | 0.91 | ○ | ○ | 57 | ||||
A5 | 20 | 20 | 其余 | 133 | 4 | 1.00 | 0.97 | 0.98 | 0.93 | ○ | ○ | 82 | |||||
A6 | 20 | 20 | 20 | 其余 | 134 | 4 | 0.99 | 0.96 | 0.98 | 0.94 | ○ | ○ | 56 | ||||
A7 | 20 | 20 | 其余 | 127 | 4 | 0.99 | 0.94 | 0.98 | 0.93 | ○ | ○ | 78 | |||||
A8 | 0.5 | 20 | 20 | 20 | 其余 | 140 | 4 | 0.99 | 0.90 | 0.96 | 0.90 | ○ | × | 26 | |||
A9 | 0.5 | 20 | 20 | 20 | 其余 | 140 | 4 | 0.99 | 0.90 | 0.95 | 0.89 | ○ | × | 32 | |||
A10 | 20 | 10 | 20 | 其余 | 124 | 4 | 1.00 | 0.98 | 0.97 | 0.94 | ○ | ○ | 60 | ||||
A11 | 20 | 10 | 20 | 其余 | 135 | 4 | 1.00 | 0.97 | 0.98 | 0.91 | ○ | ○ | 65 |
表2
成分(质量ppm) | |||||||||||||
添加元素 | Au和不可避免的杂质 | ||||||||||||
Ca | Gd | Y | 第1组元素 | 第2组元素 | 计 | ||||||||
Eu La | Ce | Lu | 小计 | Mg | Ti | Pb | |||||||
试验I | 试验A7 | - | 20 | 20 | - - | - | - | - | - | - | - | 40 | 其余 |
实验例1 | 5 | 20 | 20 | - - | - | - | - | - | - | - | 45 | 其余 | |
试验A1 | 20 | 20 | 20 | - - | - | - | - | - | - | - | 60 | 其余 | |
实验例2 | 100 | 20 | 20 | - - | - | - | - | - | - | - | 140 | 其余 | |
实验例3 | 150 | 20 | 20 | - - | - | - | - | - | - | - | 190 | 其余 | |
实验例4 | - | 20 | 20 | 20 - | - | - | 20 | - | - | - | 60 | 其余 | |
实验例5 | 5 | 20 | 20 | 20 - | - | - | 20 | - | - | - | 65 | 其余 | |
试验A2 | 20 | 20 | 20 | 20 - | - | - | 20 | - | - | - | 80 | 其余 | |
实验例6 | 100 | 20 | 20 | 20 - | - | - | 20 | - | - | - | 160 | 其余 | |
实验例7 | 150 | 20 | 20 | 20 - | - | - | 20 | - | - | - | 210 | 其余 | |
试验II | 试验A3 | 20 | - | 20 | - - | - | - | - | - | - | - | 40 | 其余 |
实验例8 | 20 | 5 | 20 | - - | - | - | - | - | - | - | 45 | 其余 | |
试验A1 | 20 | 20 | 20 | - - | - | - | - | - | - | - | 60 | 其余 | |
实验例9 | 20 | 100 | 20 | - - | - | - | - | - | - | - | 140 | 其余 | |
实验例10 | 20 | 150 | 20 | - - | - | - | - | - | - | - | 190 | 其余 | |
实验A4 | 20 | - | 20 | 20 - | - | - | 20 | - | - | - | 60 | 其余 | |
实验例11 | 20 | 5 | 20 | 20 - | - | - | 20 | - | - | - | 65 | 其余 | |
试验A2 | 20 | 20 | 20 | 20 - | - | - | 20 | - | - | - | 80 | 其余 | |
实验例12 | 20 | 100 | 20 | 20 - | - | - | 20 | - | - | - | 160 | 其余 | |
实验例13 | 20 | 150 | 20 | 20 - | - | - | 20 | - | - | - | 210 | 其余 | |
实验III | 试验A5 | 20 | 20 | - | - - | - | - | - | - | - | - | 40 | 其余 |
实验例14 | 20 | 20 | 1 | - - | - | - | - | - | - | - | 41 | 其余 | |
试验A1 | 20 | 20 | 20 | - - | - | - | - | - | - | - | 60 | 其余 | |
实验例15 | 20 | 20 | 100 | - - | - | - | - | - | - | - | 140 | 其余 | |
实验例16 | 20 | 20 | 150 | - - | - | - | - | - | - | - | 190 | 其余 | |
实验A6 | 20 | 20 | - | 20 - | - | - | 20 | - | - | - | 60 | 其余 | |
实验例17 | 20 | 20 | 1 | 20 - | - | - | 20 | - | - | - | 65 | 其余 | |
试验A2 | 20 | 20 | 20 | 20 - | - | - | 20 | - | - | - | 80 | 其余 | |
实验例18 | 20 | 20 | 100 | 20 - | - | - | 20 | - | - | - | 160 | 其余 | |
实验例19 | 20 | 20 | 150 | 20 - | - | - | 20 | - | - | - | 210 | 其余 |
表2(续)
* | 试验结果 | |||||
评价 | 小球压接后的圆形度 | 破断负荷(mN) | 芯片破损 | 线尾长度偏差(μm) | ||
试验I | 实验A7 | × | 0.93 | 127 | ○ | 78 |
实验例1 | △ | 0.96 | 133 | ○ | 48 | |
试验A1 | △ | 0.97 | 140 | ○ | 40 | |
实验例2 | △ | 0.96 | 145 | ○ | 31 | |
实验例3 | × | 0.91 | 150 | × | 25 | |
实验例4 | × | 0.94 | 125 | ○ | 54 | |
实验例5 | ○ | 0.99 | 136 | ○ | 27 | |
试验A2 | ○ | 1.00 | 139 | ○ | 19 | |
实验例6 | ○ | 0.99 | 146 | ○ | 13 | |
实验例7 | × | 0.93 | 149 | × | 10 | |
试验II | 实验A3 | × | 0.92 | 134 | ○ | 75 |
实验例8 | △ | 0.95 | 138 | ○ | 45 | |
试验A1 | △ | 0.97 | 140 | ○ | 40 | |
实验例9 | △ | 0.96 | 140 | ○ | 33 | |
实验例10 | × | 0.90 | 139 | × | 30 | |
试验A4 | × | 0.91 | 132 | ○ | 57 | |
实验例11 | ○ | 1.00 | 138 | ○ | 29 | |
试验A2 | ○ | 1.00 | 139 | ○ | 19 | |
实验例12 | ○ | 0.99 | 139 | ○ | 15 | |
实验例13 | × | 0.93 | 132 | × | 13 | |
试验III | 实验A5 | × | 0.93 | 133 | ○ | 82 |
实验例14 | △ | 0.95 | 137 | ○ | 50 | |
试验A1 | △ | 0.97 | 140 | ○ | 40 | |
实验例15 | △ | 0.95 | 142 | ○ | 35 | |
实验例16 | × | 0.91 | 143 | × | 32 | |
试验A6 | × | 0.94 | 134 | ○ | 56 | |
实验例17 | ○ | 0.98 | 138 | ○ | 29 | |
试验A2 | ○ | 1.00 | 139 | ○ | 19 | |
实验例18 | ○ | 0.99 | 141 | ○ | 16 | |
实验例19 | × | 0.91 | 141 | × | 15 |
表3
成分(质量ppm) | ||||||||||||||
添加元素 | Au和不可避免的杂质 | |||||||||||||
Ca | Gd | Y | 第1组元素 | 第2组元素 | 计 | |||||||||
Eu | La | Ce | Lu | 小计 | Mg | Ti | Pb | |||||||
试验IV | 试验A1 | 20 | 20 | 20 | - | - | - | - | - | - | - | - | 60 | 其余 |
实验例20 | 20 | 20 | 20 | 1 | - | - | - | 1 | - | - | - | 61 | 其余 | |
试验A2 | 20 | 20 | 20 | 20 | - | - | - | 20 | - | - | - | 80 | 其余 | |
实验例21 | 20 | 20 | 20 | 100 | - | - | - | 100 | - | - | - | 160 | 其余 | |
实验例22 | 20 | 20 | 20 | - | 1 | - | - | 1 | - | - | - | 61 | 其余 | |
实验例23 | 20 | 20 | 20 | - | 20 | - | - | 20 | - | - | - | 80 | 其余 | |
实验例24 | 20 | 20 | 20 | - | 100 | - | - | 100 | - | - | - | 160 | 其余 | |
实验例25 | 20 | 20 | 20 | - | - | 20 | - | 20 | - | - | - | 80 | 其余 | |
实验例26 | 20 | 20 | 20 | - | - | - | 20 | 20 | - | - | - | 80 | 其余 | |
实验例27 | 20 | 10 | 10 | 1 | 1 | - | - | 2 | - | - | - | 42 | 其余 | |
实验例28 | 20 | 20 | 10 | 1 | 1 | - | - | 2 | - | - | - | 52 | 其余 | |
实验例29 | 20 | 40 | 40 | 40 | 40 | - | - | 100 | - | - | - | 180 | 其余 | |
实验例30 | 20 | 50 | 50 | 20 | 20 | 20 | 20 | 80 | - | - | - | 200 | 其余 | |
实验例31 | 20 | 20 | 20 | 150 | - | - | - | 150 | - | - | - | 210 | 其余 | |
试验V | 试验A2 | 20 | 20 | 20 | 20 | - | - | - | 20 | - | - | - | 80 | 其余 |
实验例32 | 20 | 20 | 20 | 20 | - | - | - | 20 | 1 | - | - | 81 | 其余 | |
实验例33 | 20 | 20 | 20 | 20 | - | - | - | 20 | 20 | - | - | 100 | 其余 | |
实验例34 | 20 | 20 | 20 | 20 | - | - | - | 20 | 100 | - | - | 180 | 其余 | |
实验例35 | 20 | 20 | 20 | 20 | - | - | - | 20 | - | 1 | - | 81 | 其余 | |
实验例36 | 20 | 20 | 20 | 20 | - | - | - | 20 | - | 20 | - | 100 | 其余 | |
实验例37 | 20 | 20 | 20 | 20 | - | - | - | 20 | - | 100 | - | 180 | 其余 | |
实验例38 | 20 | 20 | 20 | 20 | - | - | - | 20 | - | - | - | 81 | 其余 | |
实验例39 | 20 | 20 | 20 | 20 | - | - | - | 20 | - | - | 2 | 100 | 其余 | |
实验例40 | 20 | 20 | 20 | 20 | - | - | - | 20 | - | - | 10 | 180 | 其余 | |
实验例41 | 20 | 20 | 20 | 20 | - | - | - | 20 | 20 | 20 | - | 120 | 其余 | |
实验例42 | 20 | 20 | 20 | 20 | - | - | - | 20 | 20 | 20 | 2 | 140 | 其余 | |
实验例43 | 20 | 20 | 20 | 20 | - | - | - | 20 | 50 | 50 | 3 | 210 | 其余 | |
实验例44 | 20 | - | 20 | 10 | - | - | - | 10 | 20 | - | - | 70 | 其余 | |
实验例45 | 20 | 20 | - | 10 | - | - | - | 10 | 20 | - | - | 70 | 其余 |
表3(续)
* | 试验结果 | |||||
评价 | 小球压接后的圆形度 | 破断负荷(mN) | 芯片破损 | 线尾长度偏差(μm) | ||
试验IV | 实验A1 | △ | 0.97 | 138 | ○ | 40 |
实验例20 | ○ | 0.98 | 140 | ○ | 27 | |
试验A2 | ○ | 1.00 | 139 | ○ | 19 | |
实验例21 | ○ | 0.99 | 137 | ○ | 13 | |
实验例22 | ○ | 0.99 | 138 | ○ | 29 | |
实验例23 | ○ | 1.00 | 141 | ○ | 24 | |
实验例24 | ○ | 0.99 | 140 | ○ | 20 | |
实验例25 | ○ | 0.99 | 138 | ○ | 26 | |
实验例26 | ○ | 0.98 | 141 | ○ | 27 | |
实验例27 | ○ | 0.99 | 136 | ○ | 28 | |
实验例28 | ○ | 0.99 | 137 | ○ | 25 | |
实验例29 | ○ | 1.00 | 138 | ○ | 18 | |
实验例30 | ○ | 0.99 | 141 | ○ | 15 | |
实验例31 | × | 0.91 | 135 | × | 26 | |
试验V | 实验A2 | △ | 1.00 | 140 | ○ | 19 |
实验例32 | ○ | 0.99 | 139 | ○ | 17 | |
实验例33 | ○ | 0.98 | 141 | ○ | 14 | |
实验例34 | ○ | 0.99 | 140 | ○ | 9 | |
实验例35 | ○ | 0.99 | 140 | ○ | 18 | |
实验例36 | ○ | 1.00 | 140 | ○ | 15 | |
实验例37 | ○ | 0.99 | 141 | ○ | 12 | |
实验例38 | ○ | 0.99 | 139 | ○ | 18 | |
实验例39 | ○ | 0.99 | 137 | ○ | 14 | |
实验例40 | ○ | 0.98 | 138 | ○ | 13 | |
实验例41 | ○ | 0.99 | 140 | ○ | 13 | |
实验例42 | ○ | 0.98 | 139 | ○ | 10 | |
实验例43 | × | 0.96 | 140 | × | 25 | |
实验例44 | × | 0.92 | 132 | ○ | 37 | |
实验例45 | × | 0.91 | 134 | ○ | 43 |
Claims (15)
1.一种半导体元件连接用金线,其中含有5~100质量ppm的Ca、5~100质量ppm的Gd、1~100质量ppm的Y,这些元素的总量为200质量ppm以下,其余为金和不可避免的杂质。
2.如权利要求1所述的半导体元件连接用金线,其中还含有1~100质量ppm的Mg、Ti、Pb中的至少一种,且全部添加元素的总量在200质量ppm以下。
3.一种半导体元件连接用金线,其中含有5~100质量ppm的Ca、5~100质量ppm的Gd、1~100质量ppm的Y,以及1~100ppm质量的Eu、La、Ce和Lu中的至少一种,这些元素的总量为200质量ppm以下,其余为金和不可避免的杂质。
4.如权利要求3所述的半导体元件连接用金线,其中还含有1~100质量ppm的Mg、Ti、Pb中的至少一种,且全部添加元素的总量在200质量ppm以下。
5.一种半导体元件的连接方法,其中包括下列工序:
(A)将金线插入毛细管,加热熔化金线的前端形成金球的工序;
(B)使毛细管下降,将金球压接到半导体元件的电极上,将金线与电极接合的工序;
(C)将含有接合到电极上的上述金线的毛细管描画预定轨迹,在被连接部件上移动,将该金线的侧面压接到被连接部件上的工序;以及
(D)在把压接到被连接部件上的金线弯曲成突起的状态下提升,切断金线,完成半导体元件的电极和被连接部件间的金线的布线的工序,而且
上述金线中含有5~100质量ppm的Ca、5~100质量ppm的Gd、1~100质量ppm的Y,这些元素的总量为200质量ppm以下,其余为金和不可避免的杂质。
6.一种半导体元件的连接方法,其中包括下列工序:
(A)将金线插入毛细管,加热熔化金线的前端形成金球的工序;
(B)使毛细管下降,将金球压接到半导体元件的电极上,将金线与电极接合的工序;
(C)将含有接合到电极上的上述金线的毛细管描画预定轨迹,在被连接部件上移动,将该金线的侧面压接到被连接部件上的工序;以及
(D)在把压接到被连接部件上的金线弯曲成突起的状态下提升,切断金线,完成半导体元件的电极和被连接部件间的金线的布线的工序,而且
上述金线中含有5~100质量ppm的Ca、5~100质量ppm的Gd、1~100质量ppm的Y,以及1~100ppm质量的Eu、La、Ce和Lu中的至少一种,这些元素的总量为200质量ppm以下,其余为金和不可避免的杂质。
7.如权利要求5或6所述的方法,其中在上述工序(A)和/或工序(C)中,包括通过毛细管向金线的前端部分施加超声波振动,同时用加热器单元对半导体元件或被连接件加热,将上述金球热压接。
8.如权利要求5或6所述的方法,其中半导体元件的邻接电极的间距为70μm以下。
9.如权利要求5或6所述的方法,其中半导体元件的邻接电极的间距为60μm以下。
10.一种半导体元件的连接方法,包括下列工序:
(A)将金线插入毛细管,加热熔化金线的前端以形成金球的工序;
(B)使毛细管下降,将金球压接到半导体元件的电极上以形成压接金球的工序;以及
(C)在把压接到半导体元件的电极上形成压接金球的上述金线弯曲成突起的状态下提升,在压接金球的附着根部附近切断金线,在电极上形成凸点的工序,而且
上述金线中含有5~100质量ppm的Ca、5~100质量ppm的Gd、1~100质量ppm的Y,这些元素的总量为200质量ppm以下,其余为金和不可避免的杂质。
11.一种半导体元件的连接方法,包括下列工序:
(A)将金线插入毛细管,加热熔化金线的前端以形成金球的工序;
(B)使毛细管下降,将金球压接到半导体元件的电极上以形成压接金球的工序;以及
(C)在把压接到半导体元件的电极上形成压接金球的上述金线弯曲成突起的状态下提升,在压接金球的附着根部附近切断金线,在电极上形成凸点的工序,而且
上述金线中含有5~100质量ppm的Ca、5~100质量ppm的Gd、1~100质量ppm的Y,以及1~100ppm质量的Eu、La、Ce和Lu中的至少一种,这些元素的总量为200质量ppm以下,其余为金和不可避免的杂质。
12.如权利要求10或11所述的方法,其中还包括把在半导体元件的电极上形成的凸点压接到被连接部件上的工序。
13.如权利要求10或11所述的方法,其中:在上述工序(A)中包括通过毛细管向金线前端施加超声波振动,同时用加热器单元加热半导体元件,热压接上述金球。
14.如权利要求10或11所述的方法,其中:上述半导体元件电极是铝电极膜,其厚度为0.5μm以下。
15.如权利要求10或11所述的方法,其中:上述半导体元件电极是铝电极膜,其厚度为0.1μm以下。
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JP2000166524A JP3382918B2 (ja) | 2000-05-31 | 2000-05-31 | 半導体素子接続用金線 |
JP166524/2000 | 2000-05-31 |
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CN1326224A CN1326224A (zh) | 2001-12-12 |
CN1169202C true CN1169202C (zh) | 2004-09-29 |
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CNB011213205A Expired - Fee Related CN1169202C (zh) | 2000-05-31 | 2001-05-31 | 半导体元件连接用金线及半导体元件的连接方法 |
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US (1) | US6492593B2 (zh) |
EP (1) | EP1160344B1 (zh) |
JP (1) | JP3382918B2 (zh) |
KR (1) | KR100692495B1 (zh) |
CN (1) | CN1169202C (zh) |
DE (1) | DE60140778D1 (zh) |
MY (1) | MY117233A (zh) |
SG (1) | SG90251A1 (zh) |
TW (1) | TW569361B (zh) |
Cited By (1)
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CN111485131A (zh) * | 2020-04-17 | 2020-08-04 | 烟台招金励福贵金属股份有限公司 | 一种键合金丝及其制备方法 |
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US7271497B2 (en) * | 2003-03-10 | 2007-09-18 | Fairchild Semiconductor Corporation | Dual metal stud bumping for flip chip applications |
KR100618052B1 (ko) * | 2003-04-14 | 2006-08-30 | 엠케이전자 주식회사 | 반도체 소자 본딩용 금 합금세선 |
JP4462864B2 (ja) * | 2003-07-18 | 2010-05-12 | フィガロ技研株式会社 | ガスセンサの製造方法 |
JP4513440B2 (ja) * | 2004-07-15 | 2010-07-28 | 住友ベークライト株式会社 | 半導体装置 |
KR100899322B1 (ko) * | 2004-09-30 | 2009-05-27 | 타나카 덴시 코오교오 카부시키가이샤 | Au 합금 본딩·와이어 |
JP2006324553A (ja) * | 2005-05-20 | 2006-11-30 | Renesas Technology Corp | 半導体装置及びその製造方法 |
JP5166738B2 (ja) | 2006-03-24 | 2013-03-21 | 新日鉄住金マテリアルズ株式会社 | 半導体素子接続用金線 |
CN101332477B (zh) * | 2007-06-28 | 2010-09-29 | 山东华宏微电子材料科技有限公司 | 半导体器件硅铝键合线制造方法 |
JP4134261B1 (ja) * | 2007-10-24 | 2008-08-20 | 田中電子工業株式会社 | ボールボンディング用金合金線 |
JP4195495B1 (ja) * | 2007-11-06 | 2008-12-10 | 田中電子工業株式会社 | ボールボンディング用金合金線 |
JP2010123817A (ja) * | 2008-11-21 | 2010-06-03 | Fujitsu Ltd | ワイヤボンディング方法および電子装置とその製造方法 |
CN101626006B (zh) * | 2009-07-09 | 2012-06-20 | 烟台一诺电子材料有限公司 | 柔性键合铜丝及其制备方法 |
KR20130026805A (ko) * | 2011-09-06 | 2013-03-14 | 삼성전자주식회사 | 반도체 패키지의 와이어 본딩 시스템 |
US8540136B1 (en) | 2012-09-06 | 2013-09-24 | Taiwan Semiconductor Manufacturing Company, Ltd. | Methods for stud bump formation and apparatus for performing the same |
JP6455037B2 (ja) * | 2014-09-12 | 2019-01-23 | 富士電機株式会社 | 半導体装置の製造方法 |
CN110718526A (zh) * | 2019-10-22 | 2020-01-21 | 烟台一诺电子材料有限公司 | 一种超细线距电子封装用稀土铜合金键合丝及其制备方法 |
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-
2000
- 2000-05-31 JP JP2000166524A patent/JP3382918B2/ja not_active Expired - Fee Related
-
2001
- 2001-05-29 DE DE60140778T patent/DE60140778D1/de not_active Expired - Lifetime
- 2001-05-29 EP EP01250190A patent/EP1160344B1/en not_active Expired - Lifetime
- 2001-05-29 SG SG200103210A patent/SG90251A1/en unknown
- 2001-05-30 TW TW090113064A patent/TW569361B/zh not_active IP Right Cessation
- 2001-05-30 KR KR1020010030074A patent/KR100692495B1/ko not_active IP Right Cessation
- 2001-05-30 MY MYPI20012572A patent/MY117233A/en unknown
- 2001-05-31 US US09/872,651 patent/US6492593B2/en not_active Expired - Fee Related
- 2001-05-31 CN CNB011213205A patent/CN1169202C/zh not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111485131A (zh) * | 2020-04-17 | 2020-08-04 | 烟台招金励福贵金属股份有限公司 | 一种键合金丝及其制备方法 |
CN111485131B (zh) * | 2020-04-17 | 2021-12-24 | 烟台招金励福贵金属股份有限公司 | 一种键合金丝及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
MY117233A (en) | 2004-05-31 |
EP1160344A1 (en) | 2001-12-05 |
JP3382918B2 (ja) | 2003-03-04 |
CN1326224A (zh) | 2001-12-12 |
KR100692495B1 (ko) | 2007-03-09 |
KR20010110133A (ko) | 2001-12-12 |
US20020007957A1 (en) | 2002-01-24 |
JP2001345342A (ja) | 2001-12-14 |
SG90251A1 (en) | 2002-07-23 |
TW569361B (en) | 2004-01-01 |
DE60140778D1 (de) | 2010-01-28 |
EP1160344B1 (en) | 2009-12-16 |
US6492593B2 (en) | 2002-12-10 |
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