CN107086210A - 接合用银片及其制造方法,以及电子部件接合方法 - Google Patents
接合用银片及其制造方法,以及电子部件接合方法 Download PDFInfo
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- CN107086210A CN107086210A CN201710263360.4A CN201710263360A CN107086210A CN 107086210 A CN107086210 A CN 107086210A CN 201710263360 A CN201710263360 A CN 201710263360A CN 107086210 A CN107086210 A CN 107086210A
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- silver
- silver strip
- engagement
- temperature
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 127
- 239000004332 silver Substances 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 43
- 238000005245 sintering Methods 0.000 claims abstract description 24
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- 238000009792 diffusion process Methods 0.000 description 9
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- 230000000996 additive effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/006—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of flat products, e.g. sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3006—Ag as the principal constituent
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
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- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B23K2103/12—Copper or alloys thereof
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- H01L2224/29338—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/29339—Silver [Ag] as principal constituent
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Abstract
本发明涉及接合用银片及其制造方法,以及电子部件接合方法。本发明提供一种接合用银片,其是粒径1~250nm的银粒子通过烧结而一体化的银片,具有升温至满足下述(1)式的某个温度范围“TA(℃)以上TB(℃)以下”进行保持时进一步进行烧结的性质:270≤TA<TB≤350 ···(1)。
Description
本发明是申请号为201480056727.X(国际申请号为PCT/JP2014/076660),申请日为2014年10月06日、发明名称为“接合用银片及其制造方法,以及电子部件接合方法”的发明申请的分案申请。
技术领域
本发明涉及作为接合材料使用的金属银的片及其制造方法。另外,涉及使用上述片来接合电子部件与基板的方法。
背景技术
作为半导体芯片等电子部件于基板上接合的方法,已知除使用软钎料等焊锡材料的方法外,使用含金属微粉末的糊的方法。由于粒径约100nm以下的金属钠米粒子,用比该金属的熔点大幅低的温度进行烧结是可能的,因此把这样的烧结用糊在被接合构件彼此之间涂布后,于所定温度进行烧成,利用烧结现象,能够进行上述被接合构件的接合。例如,专利文献1已公开了配合银微粉末的结合材料(糊)。
现有技术文献
专利文献
专利文献1:国际公开WO2012/169076号
发明内容
发明要解决的课题
专利文献1的接合材料,对安装电子部件的基板等来说,按照部件配置的电路图案,采用印刷进行涂布的方法等是有用的。然而,由于在最终制品所用的构件上(例如安装电子部件的基板)直接涂布,因此必需对涂布、干燥、烧成的全部工序,根据各个制品构件设定设备规格,所以,为了与多种制品迅速对应,希望采用更合理的方法。
另一方面,如果采用在制品构件上不涂布结合材料,把预先制作的片状接合材料插入被接合构件彼此之间进行烧成的接合方法,则可以省去涂布上述结合材料的工序,使制作制品构件的工序达到合理化。作为这样的接合用片,以软钎料为代表的焊锡材料片已达到实用化,另外,可以考虑,利用固相扩散为前提的金属片、以及利用烧结为前提的金属微粉末粒子用粘合剂加以结合的片等。
采用软钎料等焊锡材料片时,由于焊锡材料金属的熔点低,根据用途,接合部的耐热性不足。另外,被接合构件之一,如适用放热板等比较厚的金属构件时,在接合时,容易产生构件的“弯曲”。
在利用固相扩散的金属片时,此软钎料接合,可以形成耐热性高的接合部。然而,为了利用固相扩散,必须在高温下,在被接合构件彼此之间赋予高的压力。因此,不适于电子部件的接合。
在通过粘合剂结合金属微粉末粒子的片时,可比固相扩散于低温进行接合,但为了确保被接合构件之间有充分的接触面积,必须施加高达10MPa以上的高加压力。当加压力低时,接合部的强度降低。对电子部件等赋予高的加压力未必容易,其用途受很大限制。另外,用于接合的烧成,由于在含粘合剂树脂的状态下进行,接合部易生成空隙,该空隙也成为确保接合部强度的不利因素。另外,还要考虑挥发的粘合剂树脂,对电子部件的不良影响。
本发明的目的是提供以低加压力得到高接合强度的接合用银片。本发明又一目的是提供采用该银片的电子部件的接合方法。
用于解决课题的手段
本发明人的详细研究结果发现,通过银微粉预先烧结而一体化的片,当采用具有进一步可进行烧结现象的性质的银片时,能在低的加压力下通过固相扩散进行接合。
即,上述目的可通过接合用银片达到,该银片是粒径1~250nm的银粒子、更优选粒径20~120nm的银粒子通过烧结而一体化的银片,升温至满足下述(1)式的某个温度范围“TA(℃)以上TB(℃)以下”而保持时具有进一步进行烧结的性质。片表面的算术平均粗糙度Ra,两面均为0.10μm以下是有效果的。
270≤TA<TB≤350···(1)
上述银片,烧结体中存在特有的空隙。“进一步进行烧结的性质”,通过该银片升温至处在TA(℃)以上TB(℃)以下的温度范围内的温度T3(℃)进行实验时,可根据调查空隙的形状是否变化来确认。当温度T3的加热保持时间在5分钟以内时,优选在可观测到加热前后的空隙的形状变化的程度,具有进行烧结的性质。具体的是,具有“在赋予1MPa面压的状态下,升温至处在上述温度范围内的温度T3(℃),保持5分钟时的进一步进行烧结的性质”是优选的。还有,在270~350℃的范围内,存在进一步进行烧结的温度范围“TA(℃)以上TB(℃)以下”即可,但在270~350℃的全部温度范围内未必可以观察到该性质。
空隙的形状变化的观测,例如,在加热实验前后,通过放大30000倍的SEM图像的对比来进行。由此可以确认在空隙发生明显的形状变化时,则明确具有“进一步进行烧结的性质”。作为严谨的调查方法,在产生圆锥状压痕的位置做记号,对同一位置加热前后的上述SEM图像进行对比的方法是有效的。在该方法中,空隙的形状变化是否产生而真伪不明时,则判断为不具有“进一步进行烧结的性质”,而其他的场合,则判断为具有“进一步进行烧结的性质”。
该银片的厚度,两平面测微计测定的片厚度,例如希望在10~120μm的范围。两平面测微计意指基准面及主轴测定面的任何一面均为平面状的测微计。关于该银片的形状,不限于把银微粉的烧结形成一体化的形状,包含各种形状。例如,在厚度方向观察到的投影形状,呈现通过印刷形成的图案形状,也作为本发明的对象。这里所谓“投影形状”,意指作为对象的物体从无限远的一方向观察时,由该物体的轮廓决定的形状。
作为上述银片的制造方法,提供具有以下工序的制造方法:
涂布的工序:将包含粒径1~250nm的银粒子的银粉、与在200℃以下的温度区域有下述(A)定义的25%挥发温度T25(℃)的分散介质混合的银糊,于基板上涂布;
进行分散介质挥发的工序:把上述涂布后的涂膜,在上述T25(℃)以上且不产生银粒子烧结的温度区域进行加热处理,使上述分散介质进行挥发;以及
得到银片的工序:将上述加热处理后的涂膜,在赋予5~35MPa的加压力状态下,于170~250℃的温度进行烧成,得到银粒子通过烧结而一体化的银片。上述银糊于基板上涂布时,也可通过印刷而涂布成图案形状。
(A)上述银糊供给于大气中从常温以10℃/min进行升温的热重量分析(TG)时,由下述(2)式确定的分散介质的重量减少率成为25%的温度作为25%挥发温度T25(℃)。
[分散介质的重量减少率(%)]=[通过热重量分析的升温而已挥发的分散介质的累计质量(g)]/[供给热重量分析前的银糊试样中存在的分散介质总质量(g)]×100···(2)
在此,银粒子粒径,用一次粒子的长径表示。如是包含粒径1~250nm的银粒子的银粉,则将具有各种平均粒径的银微粉混合也可以。使用平均粒径20~120nm的银粉是更优选的。
另外,本发明中提供电子部件接合方法,其将上述银片插在电子部件与接合它的基板之间,一边在电子部件与基板之间赋予加压力以使上述电子部件与银片的接触面压成为0.5~3MPa、更优选1~3MPa,一边加热至上述TA(℃)以上TB(℃)以下的温度范围。
发明的效果
按照本发明,采用片状的接合材料,以所谓3MPa以下的低加压力,使被接合构件彼此接合成为可能。本发明,作为电子部件于基板上接合的手段是特别有用的。
附图说明
[图1]实施例1得到的银片表面的SEM相片。
[图2]实施例5得到的银片表面的SEM相片。
[图3]实施例6得到的银片表面的SEM相片。
[图4]实施例7得到的银片表面的SEM相片。
[图5]实施例8得到的银片表面的SEM相片。
[图6]比较例1得到的预加热处理后的银涂膜表面的SEM相片。
[图7]比较例2得到的预热处理后的银涂膜表面的SEM相片。
[图8]实施例1得到的银片采用加压力1MPa、300℃×5min的条件进行加热试验后的银片表面的SEM相片。
[图9]适于本发明使用的银糊(实施例中的银糊A)的TG-DTA曲线。
具体实施方式
将按照本发明的银片,插在被接合材料之间,利用升温至满足下述(1)式的某个温度范围“TA(℃)以上TB(℃)以下”时产生的银片固相扩散,使两侧的被接合材料彼此接合。
270≤TA<TB≤350···(1)
其特征在于,尽管利用了固相扩散,但赋予的加压力仍设定低至0.5~3MPa左右。
按照本发明的银片,是银粉末通过烧结而形成的烧结片。如上所述,可用低的加压力进行接合,这是由于银片处在上述“TA(℃)以上TB(℃)以下”的温度范围内接合时的加热温度T3,具有“进一步进行烧结的性质”所致。即,在制作银片的阶段进行的烧结以不完全的状态终止。这样状态的银片,内部存在大量空隙。接合时的加热温度,由于进行进一步烧结,仅赋予低的加压力,空隙的形状及数量就发生大的变化,可活泼地进行银原子的移动(扩散)。因此,两侧的被接合材料,构筑成紧密接合的接合部。
究竟是否具有“进一步进行烧结的性质”,如上所述,把该银片供给加热至满足上述(1)式的某温度范围“TA(℃)以上TB(℃)以下”的实验来确定。
用低的加压力进行接合时,为了得到稳定而高的接合强度,使片表面的表面粗糙度变小是有效的。各种探讨的结果表明,当特别重视接合强度时,片表面的算术平均粗糙度Ra,希望表里的两面均在0.10μm以下。通过使后述的加压烧成时施加的加压力成为8MPa以上,能够得到Ra在0.10μm以下的银片。
银片的厚度,通过两平面测微计测定的厚度,希望在10~120μm。为了稳定得到高的接合强度,确保10μm以上的银片厚度是更有效的。达到20μm以上的厚度是更优选的。另一方面,即使达到120μm以上的厚度,接合强度的稳定性提高效果达到了饱和,是不经济的。达到100μm以下的厚度是更优选的,50μm以下是尤其优选的。
〔原料银粉〕
作为银片原料的银粉,由粒径1~250nm的银粒子构成是优选的。由这样的微细粒子构成的银粉,在低于250℃的低温产生烧结现象,对于制得以不完全的状态终止烧结的银片,即具有“进一步进行烧结的性质”的银片,是极有用的。当综合考虑操作性、成本、可开始烧结的温度等时,使用平均粒径20~120nm的银粉是更实用的。在这里,粒径意指粒子的最长部分的直径(长径)。粒子形状为球状是更优选的。
使用的原料银粉的表面,用有机保护材料被覆。该有机保护材料,在供给制作银片的加压烧成前残留是优选的。即,供给加压烧成前的过程中也可多少有些挥发,但希望不要完全消失。更具体地说,在预加热处理终止时,有机保护材料的残留率(相对当初的有机保护材料的总质量之比例)在30%以上是优选的。作为这样有机保护材料,可以举出山梨酸、己酸、丁酸、苹果酸等脂肪酸。对原料银粉的制造法本身未作特别限定,可以使用通过公知的方法得到的银粉。
〔银糊〕
把分散介质与上述原料银粉进行混合,制成银糊。此时,为了进行粘度调节等也可混合添加剂。本发明人的详细研究结果发现,在供给制作银片时的加压烧成之前,必需充分挥发除去构成分散介质的物质,由于是通过低温下的加压烧成而使形成银片成为可能,故其是极重要的。即,在银粒子的周围,分散介质大量存在的状态下进行加压烧成时,阻碍相邻的各个银粒子之间产生的烧结现象,使难以形成银片。但是,已知在充分除去分散介质的的状态下进行加压烧成时,其烧成温度即使低于250℃,优选低于200℃,仍可能构成银片。
采用低于250℃、优选低于200℃的烧成温度进行烧结前,为了充分除去分散介质,必需采用在不发生烧结的低温进行热处理时不挥发的物质,作为分散介质。但是,希望分散介质被充分除去后,供给加压烧成前,各个银粒子表面用有机保护材料被覆。因此,作为分散介质使用的物质,选择在银粒子的有机保护材料残留的低温的热处理时具有挥发性质的物质。具体地说,希望采用在200℃以下的温度区域具有上述(A)定义的25%挥发温度T25(℃)的分散介质。T25处在超过200℃的温度区域的分散介质,在不产生烧结的低温区域,难以充分挥发除去。T25处在100℃以上的温度区域更优选的。当T25低于100℃时,即使在保管环境中也容易挥发,因此,必需严格进行银糊的保管管理。
作为25%挥发温度T25(℃)在200℃以下、更优选在100℃以上200℃以下范围的分散介质,可以举出2-乙基-1,3-己二醇。另一方面,作为用于粘度调节等加入糊的添加剂,例如,可以举出2-丁氧基乙氧基醋酸、2-甲氧基乙氧基醋酸等有机物质。添加剂在糊中的含量为2.0质量%以下是优选的,1.0质量%以下是更优选的。
〔在基板上涂布〕
上述银糊在基板上涂布,形成涂膜。作为基板,可以适用能剥离形成的银片的材料。例如,可以适用平滑性良好的玻璃基板、氧化铝基板等。根据用途,表面为曲面形状的基板、及凹凸形状的基板也可以采用。涂膜厚度,调节以使加压烧成后得到的银片厚度使达所定的范围(上述)。考虑接合的电子部件等的配置,也可采用印刷来涂布成图像形状。
〔预加热处理〕
在供给加压烧成前,把基板上涂布的上述涂膜进行加热,得到使分散介质充分挥发的涂膜。该加热处理,在本说明书中称作“预加热处理”。预加热处理,使分散介质挥发,并且,在不发生银粒子烧结的温度区域中进行。从促进分散介质挥发的观点考虑,达到上述的25%挥发温度T25(℃)以上的加热温度是有效的。当比此加热温度低时,为使分散介质充分进行挥发,需要长时间,有损生产效率,或不可能充分达到分散介质的挥发。从不使银粒子发生烧结的观点考虑,当不赋予加压力时,最好在200℃以下的范围选择适当的温度。当使用的银粉的平均粒径,例如超过120nm时,易选择即使在超过200℃的温度区域也不发生烧结的温度。希望预加热处理温度在250℃以下的范围。当设定比此温度高时,易产生部分烧结。当在预加热处理的阶段产生烧结时,则在加压烧成中,难以实现稳定的片。
分散介质,希望在加压烧成前尽可能除去,即使有多少残留,只要加压烧成时可以形成片也无妨。根据使用的原料银粉及添加剂的种类、后工序的加压烧成条件等,可通过预先实验来确定形成银片的预加热处理条件(保持温度、保持时间等)。当用于挥发除去分散介质的预加热时间过短时,来自分散介质的有机物质大量残留,往往难以形成片。当分散介质为2-乙基-1,3-己二醇时,例如,在加热温度130~170℃、加热时间5~30min的范围内,可以找到适当的预加热处理条件。
〔加压烧成〕
对上述预加热处理终止后,对已充分挥发除去分散介质物质的银糊的涂膜,在对表面赋予加压力的状态下实施烧成,制得银片。加压力,例如玻璃材料及陶瓷材料等,采用具有与银片不接合性质的一对材料,夹住涂膜的两侧表面而赋予加压力。夹住涂膜一侧的材料,也可原样使用涂布了上述银糊的基板。
希望加压力处在5~35MPa的范围,8~35MPa的范围是更优选的。通过提高加压力,能够得到平滑性高的银片。片表面的算术平均粗糙度Ra在0.10μm以下的银片,对于得到被接合材料之间的高接合强度是极有用的。通过使加压力成为8MPa以上,容易形成Ra在0.10μm以下的银片。另一方面,如加压力过高,则使加压烧成的工序负荷增大,也是不优选的。各种探讨的结果表明,在35MPa以下范围设定加压力是优选的。也可管理在25MPa以下或20MPa以下的范围。
在该加压烧成时,银粒子彼此的烧结于不完全的状态下终止,得到银片。加压烧成的温度,当比使用的原料银粉的开始烧结温度过高时,难以在烧结不完全的状态下终止,不能稳定制造具有“进一步进行烧结的性质”的银片。各种探讨的结果表明,使用由粒径250nm以下的银粒子构成的原料银粉时,加压烧成的温度希望在250℃以下。特别是使用平均粒径120nm以下的原料银粉时,可以成为200℃以下的温度。通过赋予加压力,烧结变得容易,因此,采用与预加热处理温度相同的温度或比其低的温度,也可实现加压烧成。
通常,加压烧成的加热温度可在170~250℃、更优选在170~220℃的范围内,加热时间可在3~30min、更优选在3~10min的范围内,设定适当条件。
〔采用银片的接合〕
把按上述操作得到的银片,通过插在被接合材料之间,在赋予所定的加压力的状态下加热至所定的接合温度,而产生固相扩散,发挥作为接合材料的功能。
接合,在满足下述(1)式的TA(℃)以上TB(℃)以下的温度范围内进行。该“TA(℃)以上TB(℃)以下”的温度范围,如上所述,意指可进一步进行银片烧结的温度区域。
270≤TA<TB≤350···(1)
接合时赋予的加压力,处于0.5~3MPa的范围即可。处于0.8~2MPa的范围是更优选的。原来,插入片状的接合材料,例如在270~350℃左右的低温下通过固相扩散进行接合时,必需达到所谓10MPa以上的高加压力。这样高的加压力,施加于电子部件等是不优选的,用途上的限制增多。按照本发明的银片,因为利用了“进一步进行烧结的性质”,引起固相扩散,故能用非常低的加压力的接合。接合时,在上述TA(℃)以上TB(℃)以下温度范围的加热时间,设定在3~30min的范围即可、更优选在3~15min的范围。
实施例
作为原料银粉,准备银粒子凝集体干燥粉,其包含有机保护材料的山梨酸被覆的平均一次粒径约100nm的球状银粒子。该银粉中所含的金属银的量为99.2质量%。作为添加剂,准备用于调节粘度、触变性的2-丁氧基乙氧基醋酸。准备作为分散介质的辛二醇(2-乙基-1,3-己二醇)。
把上述原料银粉90.5g(内含金属银89.776g)、上述添加剂0.95g与上述分散介质的8.55g混合后,用混炼脱泡机(EME社制;V-mini 300型),在转数:1400rpm、旋转:700rpm的条件下进行混炼,得到的混炼物,用三辊轧机(EXAKT Apparatebaus社制;22851Norderstedt型),边调整间隙边通过5~10次,得到银糊。将其称作“银糊A”。
为了进行比较,作为原料银粉,准备银粒子凝集体干燥粉,其包含用有机保护材料油酸被覆的、平均一次粒径约0.8μm的球状银粒子。该银粉中所含的金属银量为99.62质量%。该银粉90.5g(内含金属银90.156g)、上述添加剂0.95g、与上述分散介质8.55g混合之后,采用与上述同样的方法制得银糊。将其称作“银糊B”。
用这些的任何一种银糊,在平板玻璃构成的基板上,使用金属掩膜,采用通过金属涂刷器的手工印刷,进行涂布,使形成13mm正方形、厚度70μm,采用表1、表2中所示的条件,于大气中实施预加热处理。预加热处理,除一部分例子外,采用温度水平不同的2阶段加热处理。表1、表2中所示的预加热处理温度T1(℃),意指预加热处理中采用的处理温度之中,相当于上述的“25%挥发温度T25(℃)以上且银粒子不发生烧结的温度区域”的处理温度。T1栏中的短划线表示:不采用相当于“25%挥发温度T25(℃)以上且银粒子不发生烧结的温度区域”的处理温度进行的预加热处理。预加热处理终止的涂膜的两面,用1对平板玻璃夹住,形成赋予加压力的状态,采用表1、表2中所示的条件实施加压烧成。加压烧成后,取下一侧的平板玻璃,测定加压烧成后涂膜表面的表面粗糙度Ra。其结果示于表1、表2中。
表1、表2中的“片形成评价”栏中,已经确认加压烧成后的银粒子的烧结,从平板玻璃取下涂膜,涂膜不发生破裂时用○表示、其他情况用×表示。对片形成可能的片,取出该银片时,对与上述Ra测定面与相反侧的表面测定Ra。其结果表明,与表1中所示的一侧Ra为几乎未发生变化的值。
可以片化的例子中,从得到的银片切出的样品,用1对平板玻璃夹住,形成赋予加压力1MPa的状态,于大气中、300℃下保持5min,实施加热实验,对加热实验前后的放大30000倍的SEM图像进行对比。其结果表明,任何一种银片,已确认空隙发生明显变化,还确认具有“进一步进行烧结的性质”。
作为被接合材料,准备厚度0.3mm的硅芯片(12.5mm正方形)与厚度1mm的铜板(30mm正方形)。对这些材料在表面实施镀银。在可以片化的例子中,在这些被接合材料之间插入上述银片,采用表1中所示的条件进行接合试验。对得到的接合体,铜板的两端用钳子夹住,进行弯曲,以使30mm正方形铜板中央部分弯曲成约90°。然后,把铜板的形状弯曲恢复成原来状态。测定弯曲恢复后的铜板中剩余的硅芯片的面积比率,用以下的基准评价接合强度,○评价以上判定为合格。
◎:硅芯片的剩余面积比率为100%
○:硅芯片的剩余面积比率为80%以上至低于100%
×:硅芯片的剩余面积比率为低于80%
作为参考,一部分的例子,将银片表面的SEM相片示于图1~图5。另外,对不能形成片的对一部分比较例,加压烧成后的涂膜表面的SEM相片示于图6、图7。表1、表2中,标出对应的SEM相片的图号。另外,对实施例1的银片,赋予1MPa的加压力,大气中于300℃实施5min加热试验后的片,表面的SEM相片示于图8。另外,关于银糊A,于大气中或氮氛围气中,从常温(25℃)至500℃,以10℃/min升温时的TG-DTA曲线示于图9。由于银糊A中分散介质的含量为8.55质量%,因此上述(2)式的[分散介质的重量减少率(%)]成为25%时的分散介质的挥发量,银糊每100g成为8.55×(25/100)≒2.14g。图9的TG曲线中,约170℃以下的区域的重量变化,相当于分散介质的的挥发,故银糊A的25%挥发温度T25明确地处在100℃与150℃之间。
各实施例中,用25%挥发温度T25(℃)以上且银粒子不发生烧结的温度区域中的某温度T1(℃)进行预加热处理。可以认为:通过该预加热处理,糊的分散介质几乎挥发除去。该结果表明,能形成片。另外,在加压烧成的温度T2(℃),银粒子表面的有机保护材料及添加剂的有机物质已几乎被挥发除去。因此,所得到的银片,可以判断已具有上述的“进一步进行烧结的性质”。这些银片,已确认可在低加压力扩散接合时使用。另外,已确认提高银片表面的平滑性,对得到高的接合强度是有效的(实施例8与其他实施例的对比)。
反之,比较例1、2,未在25%挥发温度T25(℃)以上的温度下进行预加热处理,糊的分散介质挥发除去不充分,通过加压烧成而不能形成片。比较例3、4,由于未进行加压烧成,因此,不能形成片。比较例5、6,使用包含粒径超过250nm的银粒子的原料银粉,但未采用按照本发明的加压烧成温度进行烧结,因此,不能形成片。
Claims (6)
1.接合用银片,其是粒径1~250nm的银粒子通过烧结而一体化的银片,具有升温至满足下述(1)式的某个温度范围“TA(℃)以上TB(℃)以下”进行保持时进一步进行烧结的性质:
270≤TA<TB≤350···(1)。
2.按照权利要求1所述的接合用银片,其中,片表面的算术平均粗糙度Ra,两面均在0.10μm以下。
3.按照权利要求1或2所述的接合用银片,其中,通过两平面测微计测定的片厚度为10~120μm。
4.按照权利要求1或2所述的接合用银片,其中,厚度方向见到的投影形状,呈现通过印刷而形成的图案形状。
5.按照权利要求3所述的接合用银片,其中,厚度方向见到的投影形状,呈现通过印刷而形成的图案形状。
6.电子部件接合方法,其把按照权利要求1或2记载的银片插在电子部件与接合它的基板之间,在电子部件与基板之间一边赋予加压力以使上述电子部件与银片的接触面压成为0.5~3MPa,一边加热至上述TA(℃)以上TB(℃)以下的温度范围。
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