WO2012046641A1 - 半導体素子接合用の貴金属ペースト - Google Patents

半導体素子接合用の貴金属ペースト Download PDF

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Publication number
WO2012046641A1
WO2012046641A1 PCT/JP2011/072512 JP2011072512W WO2012046641A1 WO 2012046641 A1 WO2012046641 A1 WO 2012046641A1 JP 2011072512 W JP2011072512 W JP 2011072512W WO 2012046641 A1 WO2012046641 A1 WO 2012046641A1
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WIPO (PCT)
Prior art keywords
noble metal
paste
bonding
metal paste
organic solvent
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PCT/JP2011/072512
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English (en)
French (fr)
Inventor
正幸 宮入
伸之 秋山
克二 稲垣
俊典 小柏
Original Assignee
田中貴金属工業株式会社
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Application filed by 田中貴金属工業株式会社 filed Critical 田中貴金属工業株式会社
Priority to EP11830573.9A priority Critical patent/EP2626893B1/en
Priority to US13/822,334 priority patent/US9539671B2/en
Priority to JP2012537672A priority patent/JP5613253B2/ja
Priority to KR1020137010925A priority patent/KR101522117B1/ko
Priority to CN201180048501.1A priority patent/CN103155126B/zh
Publication of WO2012046641A1 publication Critical patent/WO2012046641A1/ja
Priority to US15/361,666 priority patent/US10366963B2/en

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    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
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    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B23K1/0016—Brazing of electronic components
    • 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
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B23K35/025—Pastes, creams, slurries
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    • 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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    • H01L2924/10251—Elemental semiconductors, i.e. Group IV
    • H01L2924/10253—Silicon [Si]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/30—Technical effects
    • H01L2924/35—Mechanical effects
    • H01L2924/351—Thermal stress

Definitions

  • the present invention relates to a noble metal paste suitable for bonding a substrate and a semiconductor element.
  • a brazing material For joining various members such as die-bonding to a substrate of a semiconductor element, a brazing material is widely used, and an AuSn brazing material that is a fluxless brazing material is generally used.
  • the brazing material After placing a pair of members to be joined via the brazing material, the brazing material is melted by heating to a temperature above the melting point (about 300 ° C or higher) at which the brazing material melts. Methods of wearing are known.
  • a member such as a semiconductor element may have a problem of variation in electrical characteristics due to thermal stress applied to the member after joining.
  • Patent Document 1 includes silver powder and epoxy resin, and includes 100 to 200. A silver paste that can be bonded at a relatively low temperature of ° C. is described.
  • Patent Document 2 the present inventors have provided a gold paste containing gold powder having a predetermined purity and particle size and an organic solvent.
  • the paste containing the resin as described in Patent Document 1 may not be completely decomposed by heating at the time of bonding, and may remain on the member after bonding. For this reason, in a member such as a semiconductor chip, the remaining resin may be a cause of contamination and affect semiconductor performance and the like.
  • the paste of Patent Document 2 can be configured so as not to contain a resin, but in this case, the aggregation of the noble metal particles tends to proceed relatively easily when the paste is applied, and the organic solvent exudes from the applied paste. In some cases, it was difficult to apply uniformly.
  • the paste containing an organic solvent like patent document 2 when heating the paste after application
  • the present invention is a noble metal paste that does not cause member contamination after joining, and can be applied uniformly to the joining member, and the sintered body after the noble metal is sintered by heating during joining is also good
  • the purpose is to provide a noble metal paste.
  • the present inventors examined noble metal pastes that can be uniformly applied to the joining member without using various resins that may cause contamination after joining. As a result, the inventors have conceived the following noble metal paste of the present invention.
  • the present invention is composed of a noble metal powder and an organic solvent, the noble metal powder has a purity of 99.9% by mass or more, an average particle size of 0.1 to 0.5 ⁇ m, and the organic solvent has a boiling point of 200 to 350 ° C.
  • the noble metal paste has a thixotropy index (TI) value calculated from a measured value of viscosity of 4 / s with respect to the viscosity of shear rate of 40 / s at 23 ° C. by a rotational viscometer for joining semiconductor elements of 6.0 or more. Relating to noble metal paste.
  • the noble metal paste of the present invention has good wettability and can be uniformly applied to the joining member without including various resins that can cause contamination of the joining member.
  • the dispersibility of the noble metal particles after coating can be maintained uniformly, so that outgas due to volatilization / decomposition of organic components can be released uniformly during heating during bonding. , The generation of voids can be suppressed.
  • the “TI (thixotropic index) value” defined in the paste of the present invention will be described.
  • the viscosity tends to decrease as the shear rate applied to the paste during measurement increases.
  • the TI value is calculated as the ratio of the two viscosities using the values of the viscosities measured at two rotational speeds having different shear rates.
  • the TI value is a value indicating a change in viscosity with respect to the shear rate, that is, an index representing the high thixotropic property.
  • the noble metal paste of the present invention has a TI value of 6.0 or more and has a reasonably high thixotropic property. For this reason, in addition to being able to maintain the formability when the paste is applied, the sintering of the noble metal by heating at the time of joining is allowed to proceed uniformly, and the sintered body after sintering can be brought into a dense state. . Because of such advantages, the noble metal paste of the present invention is particularly suitable for die bond bonding in which a large area is applied. If the TI value is less than 6.0, the solvent may ooze out (bleed out) when the noble metal paste is applied to the joining member.
  • the upper limit of the TI value is preferably 20 or less. If it exceeds 20, it tends to be difficult to handle at the time of kneading before applying the noble metal paste.
  • the viscosity at a share rate of 4 / s which is a precondition for calculating the TI value, is preferably 100 to 1000 Pa ⁇ s. If it is less than 100 Pa ⁇ s, the precious metal powder tends to settle and easily separate from the solvent, and if it exceeds 1000 Pa ⁇ s, the handling property tends to deteriorate.
  • the noble metal paste in the present invention will be described in detail.
  • the organic solvent in the present invention has a boiling point of 200 to 350 ° C. (under atmospheric pressure).
  • the organic solvent evaporates at a high rate when heated at the time of joining, making it difficult to control the aggregation of the noble metal particles. Therefore, handling during paste application becomes difficult.
  • the organic solvent exceeds 350 ° C., the organic solvent may remain in the joined member. If it is in the range of this boiling point, the organic solvent can contain 1 type, or 2 or more types.
  • boiling point 200 to 350 ° C means that when two or more organic solvents are included, all kinds of organic solvents contained have boiling points 200 to 350, respectively. It means being within the range of ° C.
  • organic solvent that can be used in the present invention, branched saturated aliphatic dihydric alcohols and monoterpene alcohols are preferable.
  • branched saturated aliphatic dihydric alcohol propylene glycol, 1,2-butanediol is preferable.
  • 1,3-butanediol 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol or derivatives thereof are used.
  • citronellol is used as monoterpene alcohol.
  • the organic solvent preferably has 5 to 20 carbon atoms.
  • a saturated aliphatic dihydric alcohol having 5 to 20 carbon atoms 2,4-diethyl-1,5-pentanediol (product name: NISKA MARS Nippon Fragrance Chemicals Co., Ltd., hereinafter referred to as MARS) is particularly suitable.
  • MARS 2,4-diethyl-1,5-pentanediol
  • MARS 2,4-diethyl-1,5-pentanediol
  • two organic solvents it is preferable to use a mixture of a monocyclic monoterpene alcohol having 5 to 20 carbon atoms and a bicyclic monoterpene alcohol.
  • Isobornylcyclohexanol product name: Tersolve MTPH; Japan
  • MTPH Terpen Chemical Co., Ltd.
  • ⁇ -terpineol in a mass ratio of 1/1 to 3/1 is particularly preferred.
  • the precious metal powder constituting the paste of the present invention will be described.
  • the noble metal powder gold powder, silver powder, or a mixed powder thereof can be used. In consideration of electrical and thermal conductivity, it is particularly preferable to use only gold powder.
  • the purity of the precious metal powder that requires a high purity of 99.9% by mass or more is that if the purity is low, the sintering behavior of Au particles becomes unstable and the stability of the bonding strength decreases, or the bonding after bonding This is because the member becomes hard and cracks easily occur due to thermal shock or the like.
  • the average particle diameter of the noble metal powder is 0.1 to 0.5 ⁇ m. In the case of noble metal powder having a particle size exceeding 0.5 ⁇ m, it becomes difficult to maintain the dispersed state in the paste, and the noble metal powder tends to settle. Moreover, even after sintering the noble metal powder by heating at the time of joining, it is difficult to express a preferable proximity state between the noble metal powders. On the other hand, when the average particle size is less than 0.1 ⁇ m, aggregation of the noble metal powder may occur.
  • the content of the noble metal powder in the paste is preferably in the range of 26 to 66% by volume (v / v) in terms of volume content (volume of noble metal powder / volume of the entire noble metal paste). With such a volume content, a noble metal paste having a TI value of 6.0 or more tends to be obtained. In addition, the sintered body after joining is also likely to be in a dense state, and joining with high adhesion can be realized. When the content of the metal powder is less than 26% by volume, it is difficult to obtain the effect of improving adhesion, and the paste is also difficult to knead. On the other hand, when it exceeds 66 volume%, aggregation of the noble metal powder may occur.
  • the precious metal content is more preferably 35 to 55% by volume (v / v).
  • the precious metal paste composed of the precious metal powder and the organic solvent described above can further contain 0.05 to 1% by mass of a surfactant.
  • a surfactant When the surfactant is included, it is easy to maintain a state in which the noble metal powder is uniformly diffused in the noble metal paste.
  • the surfactant When the surfactant is less than 0.05% by mass, the effect of suppressing the aggregation of the noble metal powder is low, and when it exceeds 1% by mass, the surfactant may remain on the member after joining.
  • a cationic surfactant is preferable, for example, dodecyltrimethylammonium salt, hexadecyltrimethylammonium salt, octadecyltrimethylammonium salt, dodecyldimethylammonium salt, octadecenyldimethylethylammonium salt, dodecyldimethylbenzylammonium salt.
  • Quaternary ammonium salts such as salt, hexadecyldimethylbenzylammonium salt, octadecyldimethylbenzylammonium salt, trimethylbenzylammonium salt, triethylbenzylammonium salt, alkyl such as octadecylamine salt, stearylamine salt, N-alkylalkylenediamine salt
  • Pyridinium salt systems such as amine salt systems, hexadecyl pyridinium salts and dodecyl pyridinium salts are used.
  • alkyl (C8-C18) amine acetate product name: Armac C
  • N-alkyl (C14-C18) trimethylenediamine oleate product name: Duomine TDO
  • Polymeric surfactants are not suitable for the present invention because they require high temperatures for decomposition.
  • the precious metal paste of the present invention can be uniformly applied to various joining members without causing contamination of the members after joining, and can be uniformly sintered by heating during joining. Become.
  • Example 1 95% by mass of gold powder (average particle size: 0.3 ⁇ m) having a purity of 99.99% by mass produced by a wet reduction method, 3.75% by mass of isobornylcyclohexanol (MTPH) as an organic solvent, ⁇ - Gold paste was prepared by mixing 1.25% by mass of terpineol. The volume content of the gold powder in this gold paste was 49.6% by volume. The following physical properties were measured for the organic solvent used and the gold paste obtained.
  • MTPH isobornylcyclohexanol
  • the viscosity of the organic solvent and the gold paste was measured at a measurement temperature of 23 ° C. with a cone-type rotational viscometer (HAAKE, Rheoless RS75, cone plate: titanium, 35 mm, ⁇ 1 °, gap measured at 0.050 mm). After holding at a share rate of 0 / s for 30 seconds, the share rates of 4 / s, 20 / s, and 40 / s were held for 30 seconds, respectively, and measurement was continuously performed. The boiling point of the organic solvent was measured at a temperature increase rate of 10 ° C./min in the atmosphere by TG-DTA (thermal weight / differential thermal simultaneous analysis: TG8101D manufactured by Rigaku).
  • TG-DTA thermo weight / differential thermal simultaneous analysis: TG8101D manufactured by Rigaku
  • TI thixotropy index
  • the viscosity of the gold paste of Example 1 at a shear rate of 4 / s was 256 Pa ⁇ s. Further, from TG-DTA, it was confirmed that in the gold paste of Example 1, the evaporation of the organic solvent started at 70 ° C. and the organic components completely disappeared at 190 ° C.
  • Example 2 Using the same gold powder as in Example 1, a gold paste was prepared with the organic solvent and gold content shown in Table 1.
  • gold powder having an average particle size of 0.1 ⁇ m was used.
  • Comparative Example 7 bisalkenyl succinimide (manufactured by King Industries, trade name: KX1223C) was used as the organic solvent.
  • the viscosity and boiling point of the organic solvent and the viscosity and TI value of the gold paste were measured in the same manner as in Example 1. The results are shown in Table 1.
  • a gold paste was prepared in the same manner as in Example 1 using gold powder having an average particle size of 0.7 ⁇ m and 0.05 ⁇ m.
  • the average particle size of the gold powder was 0.7 ⁇ m, the dispersion of the gold powder could not be maintained in the paste, causing sedimentation, and when it was 0.05 ⁇ m, partial aggregation was confirmed in the paste.
  • the silver paste was created similarly to Example 1 using silver powder (86 weight%; 37 volume%) instead of gold powder, and the physical-property measurement was performed.
  • the obtained silver paste had a viscosity at a share rate of 4 / s of 176 Pa ⁇ s, a viscosity at a share rate of 40 / s of 19 Pa ⁇ s, and a TI value of 9.3.
  • the gold pastes of Examples 1 to 5 had moderate wettability and were easy to apply to the substrate, and the gold paste after application maintained sufficient moldability.
  • the solvent tended to ooze out from the applied gold paste, and the paste after application was deformed.
  • the bonding test was performed by placing an Si chip (Ti (20 nm) and Au (200 nm) formed in advance) having an area of 4 mm 2 on the paste after coating, and heating and pressing.
  • the pressure at the time of joining was 20 N (5 MPa) per chip, the heating was 230 ° C. by heat transfer from the tool, and the heating and pressing time was 10 minutes.
  • Example 1 From the results shown in FIG. 1, in the appearance X-ray fluoroscopic image, the white portion derived from voids due to void generation is hardly observed in the joint portion of Example 1 from the gold paste, and the metal powder is point-contacted even in the cross-sectional SEM image. It was close to the state. Moreover, the joining rate of Table 2 was 90% or more. From the above, in Example 1, it was confirmed that the sintering of the gold powder by heating at the time of joining proceeded uniformly.
  • the bonding strength is that the semiconductor chip (heat-resistant Si chip) 30 bonded to the semiconductor substrate 10 via the sintered body 20 is brought into contact with the chip at a constant speed from the lateral direction and advanced to break (chip).
  • the average value (unit: N) of the stress at the time of occurrence of peeling was measured. From this measured value and the joint area after fracture, the average value (unit: MPa) of the joint strength per unit area was calculated. The results are shown in Table 3.
  • the noble metal paste of the present invention is suitable for low-temperature bonding of various bonding members, and is useful when bonding a semiconductor element or the like, which may be affected by thermal stress, to a substrate.

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Abstract

　部材汚染を生じることなく、接合部材に対し均一に塗布可能としつつ、接合後の状態も良好となる貴金属ペーストを提供する。　本発明は、貴金属粉と有機溶剤とから構成される貴金属ペーストにおいて、貴金属粉は純度９９．９質量％以上、平均粒径０．１～０．５μｍ、有機溶剤は沸点２００～３５０℃であり、回転粘度計による２３℃におけるシェアレート４０／ｓの粘度に対する４／ｓの粘度の測定値から算出されるチクソトロピー指数（ＴＩ）値が６．０以上である半導体素子接合用の貴金属ペーストに関する。

Description

半導体素子接合用の貴金属ペースト
　本発明は、基板と半導体素子との接合に好適な貴金属ペーストに関する。
　半導体素子の基板へのダイボンド等、各種部材の接合には、ろう材が広く用いられており、フラックスレスのろう材であるＡｕＳｎ系ろう材が一般に用いられている。ろう材を用いて各種部材を接合する場合、ろう材を介して接合する一対の部材を配置した後、ろう材が溶融する融点以上（約３００℃以上）の温度に加熱してろう材を融着させる方法が知られている。しかしながら、このような高温に加熱すると、接合後に部材に加わる熱応力により、半導体素子等の部材では、電気的特性の変動という問題を生じる場合があった。
　このような理由から、ろう材に替えて、できるだけ低温の加熱により部材を接合できる材料が望まれており、かかる材料として、例えば特許文献１には、銀粉とエポキシ樹脂とを含み、１００～２００℃という比較的低温で接合可能となる銀ペーストが記載されている。また、本発明者等は、特許文献２において、所定の純度及び粒径を有する金粉と有機溶剤とを含む金ペーストを提供している。
特開２００４－３５９８３０号公報 特開２００７－３２４５２３号公報
　しかしながら、上記特許文献１のような樹脂を含むペーストは、接合時の加熱では樹脂が完全に分解せず、接合後の部材に残る場合があった。このため、半導体チップ等の部材では、残存した樹脂が汚染原因となり、半導体性能等に影響することがあった。この点、特許文献２のペーストは、樹脂を含まない構成にもできるが、この場合、ペースト塗布時に貴金属粒子の凝集が比較的進行しやすい傾向や、塗布したペーストから有機溶剤がしみ出てしまうことがあり、均一に塗布することが困難であった。また、特許文献２のように有機溶剤を含むペーストでは、塗布後のペーストを加熱して金を焼結させる際、有機溶剤の揮発等により焼結体にボイドが発生することがあった。
　そこで本発明では、接合後に部材汚染を生じることのない貴金属ペーストであって、接合部材に対し均一に塗布可能としつつ、接合時の加熱により貴金属が焼結した後の焼結体の状態も良好となる貴金属ペーストの提供を目的とする。
　本発明者等は、上記課題を解決すべく、接合後の汚染原因となりうる各種樹脂等を用いることなく、接合部材に対し均一に塗布可能となる貴金属ペーストについて検討した。その結果、以下のような本発明の貴金属ペーストに想到した。
　すなわち、本発明は、貴金属粉と有機溶剤とから構成され、貴金属粉は、純度９９．９質量％以上、平均粒径０．１～０．５μｍ、有機溶剤は、沸点２００～３５０℃であり、貴金属ペーストは、回転粘度計による２３℃におけるシェアレート４０／ｓの粘度に対する４／ｓの粘度の測定値から算出されるチクソトロピー指数（ＴＩ）値が、６．０以上である半導体素子接合用の貴金属ペーストに関する。本発明の貴金属ペーストは、接合部材の汚染原因となりうる各種樹脂を含むことなく、接合部材に対し、濡れ性が良好で均一に塗布可能となる。また、本発明の貴金属ペーストによれば、塗布後の貴金属粒子の分散性を均一に維持できるため、接合時の加熱の際、有機系成分の揮発・分解によるアウトガスを均一に放出することができ、ボイドの発生を抑制できる。
　ここで、本発明のペーストにおいて規定する「ＴＩ（チクソトロピー指数）値」に関し説明する。貴金属等のペーストでは、一般に、測定時にペーストに対して与えるせん断速度が大きくなるに従い、粘度が低下する傾向にある。このような背景の下、ＴＩ値は、せん断速度が異なる２種の回転速度により測定した粘度の値を用いて、両者の粘度の比として算出される。このためＴＩ値は、せん断速度に対する粘度変化を示す値となり、すなわち、チクソトロピー性の高さを表す指標となる。
　本発明の貴金属ペーストはＴＩ値６．０以上であり、チクソトロピー性が適度に高い。このため、ペーストを塗布した際に成形性を維持できることに加え、接合時の加熱による貴金属の焼結を均一に進行させることとなり、焼結後の焼結体を緻密な状態とすることができる。このような利点から、本発明の貴金属ペーストは、特に大面積の塗布を行うダイボンド接合に好適となる。ＴＩ値は６．０未満であると、貴金属ペーストを接合部材に塗布する際に溶剤がしみ出る（ブリードアウト）場合がある。また、ＴＩ値の上限値としては、２０以下であることが好ましい。２０を超えると、貴金属ペースト塗布前の混錬時に取扱い困難な傾向となる。
　また、ＴＩ値を算出する前提となるシェアレート４／ｓにおける粘度については、１００～１０００Ｐａ・ｓであることが好ましい。１００Ｐａ・ｓ未満であると、貴金属粉が沈降して溶剤と分離しやすい傾向があり、１０００Ｐａ・ｓを超えると、ハンドリング性が低下しやすい。以下、本発明における貴金属ペーストについて詳細に説明する。
　まず、本発明の貴金属ペーストを構成する有機溶剤について説明する。本発明における有機溶剤は、沸点２００～３５０℃（大気圧下）のものである。有機溶剤の沸点は、２００℃未満であると、接合時に加熱した際、有機溶剤の蒸発速度が速く、貴金属粒子の凝集制御が困難となる他、場合によっては、常温でも有機溶剤が蒸発してしまうためペースト塗布時の取り扱いが難しくなる。一方、有機溶剤の沸点が３５０℃を超えると、接合後の部材に有機溶剤が残る場合がある。有機溶剤は、かかる沸点の範囲内であれば、１種又は２種以上のものを含むことができる。ここで、本発明の有機溶剤について、「沸点２００～３５０℃」とあるのは、２種以上の有機溶剤が含まれる場合においては、含有する全ての種類の有機溶剤が、それぞれ沸点２００～３５０℃の範囲内にあることを意味する。
　本発明で利用可能な有機溶剤としては、分岐鎖状飽和脂肪族２価アルコール類、モノテルペンアルコール類が好ましく、分岐鎖状飽和脂肪族２価アルコールとしては、プロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，２－ペンタンジオール、１，３－ペンタンジオール、１，４－ペンタンジオール、１，５－ペンタンジオール、２，３－ペンタンジオール、２，４－ペンタンジオール、１，２－ヘキサンジオール、１，３－ヘキサンジオール、１，４－ヘキサンジオール、１，５－ヘキサンジオール、１，６－ヘキサンジオールあるいはそれらの誘導体などが用いられ、モノテルペンアルコールとしては、シトロネロール、ゲラニオール、ネロール、メントール、テルピオール、カルベオール、ツイルアルコール、ピノカンフェオール、β－フェンチルアルコール、ジメチルオクタノール、ヒドロキシシトロネロール、あるいはそれらの誘導体などが用いられる。
　溶剤の沸点を考慮すると、上記有機溶剤の炭素数は５～２０であることが好ましい。特に、１種の有機溶媒のみからなる場合は、炭素数が５～２０の飽和脂肪族２価アルコールを用いることが好ましく、２,４－ジエチル-１，５-ペンタンジオール（製品名　日香ＭＡＲＳ；日本香料薬品（株）、以下、ＭＡＲＳと記載する。）が特に好適である。２種の有機溶媒からなる場合、炭素数が５～２０の単環式モノテルペンアルコールと２環式モノテルペンアルコールを混合して用いることが好ましく、イソボルニルシクロヘキサノール（製品名　テルソルブＭＴＰＨ；日本テルペン化学（株）、以下、ＭＴＰＨと記載する。）とα－テルピネオールとを質量比で１／１～３／１の割合で混合したものが特に好適である。
　次に、本発明のペーストを構成する貴金属粉について説明する。貴金属粉としては、金粉又は銀粉、あるいはその混合粉を用いることができる。電気的、熱的伝導性の面を考慮すると、特に金粉のみを用いることが好適である。
　貴金属粉の純度として９９．９質量％以上の高純度を要求するのは、純度が低いと、Ａｕ粒子の焼結挙動が不安定になり接合強度の安定性が低下したり、接合後の接合部材が硬くなり熱衝撃等によってクラックが入りやすくなるからである。また、貴金属粉の平均粒径は０．１～０．５μｍとする。０．５μｍを超える粒径の貴金属粉では、ペースト中での分散状態の維持が困難となり、貴金属粉が沈降しやすくなる。また、接合時の加熱により貴金属粉を焼結した後も、貴金属粉同士の好ましい近接状態を発現させ難くなる。一方、平均粒径０．１μｍ未満とすると、貴金属粉の凝集を生じる場合がある。
　ペースト中における貴金属粉の含有量は、体積含有率（貴金属粉の体積／貴金属ペースト全体の体積）で２６～６６体積％（ｖ／ｖ）の範囲内であることが好ましい。このような体積含有率であると、ＴＩ値が６．０以上の貴金属ペーストとなりやすい。また、接合後の焼結体も緻密な状態となりやすく、密着性の高い接合を実現できる。金属粉の含有率は、２６体積％未満であると、密着性向上の効果が得られにくく、ペーストも混錬しにくくなる。一方、６６体積％を超えると、貴金属粉の凝集を生じる場合がある。貴金属の含有量は、３５～５５体積％（ｖ／ｖ）であると、より好ましい。
　以上説明した貴金属粉と有機溶剤から構成される貴金属ペーストには、０．０５～１質量％の界面活性剤を更に含むことが可能である。界面活性剤を含むと、貴金属ペースト中に貴金属粉が均一に拡散した状態を維持しやすくなる。界面活性剤は０．０５質量％未満であると貴金属粉の凝集抑制効果が低く、１質量％を超えると接合後の部材に界面活性剤が残ることがある。界面活性剤としては、カチオン性界面活性剤が好ましく、例えば、ドデシルトリメチルアンモニウム塩、ヘキサデシルトリメチルアンモニウム塩、オクタデシルトリメチルアンモニウム塩、ドデシルジメチルアンモニウム塩、オクタデセニルジメチルエチルアンモニウム塩、ドデシルジメチルベンジルアンモニウム塩、ヘキサデシルジメチルベンジルアンモニウム塩、オクタデシルジメチルベンジルアンモニウム塩、トリメチルベンジルアンモニウム塩、トリエチルベンジルアンモニウム塩などの第４級アンモニウム塩系、オクタデシルアミン塩、ステアリルアミン塩、Ｎ－アルキルアルキレンジアミン塩などのアルキルアミン塩系、ヘキサデシルピリジニウム塩、ドデシルピリジニウム塩などのピリジニウム塩系が使用される。その中でも、アルキル（Ｃ８－Ｃ１８）アミン酢酸塩（製品名：アーマックＣ）、Ｎ－アルキル（Ｃ１４－Ｃ１８）トリメチレンジアミンオレイン酸塩（製品名：デュオミンＴＤＯ）が、特に好適である。尚、ポリマー系界面活性剤は、分解に高温を要するため、本発明には好適でない。
　以上説明したように、本発明の貴金属ペーストは、接合後の部材汚染等を生じることなく、各種接合部材に対して均一に塗布可能としつつ、接合時の加熱による焼結も均一に進行可能となる。
接合部の外観Ｘ線透視像及び電子顕微鏡（ＳＥＭ）による断面観察結果。 接合強度の試験方法を示す図。
　以下、本発明の好適な実施形態について説明する。
[実施例１]
湿式還元法により製造した純度９９．９９質量％の金粉（平均粒径：０．３μｍ）を９５質量％と、有機溶剤としてイソボルニルシクロヘキサノール（ＭＴＰＨ）を３．７５質量％と、α－テルピネオール１．２５質量％とを混合して金ペーストを調整した。この金ペースト中における金粉の体積含有率は４９．６体積％であった。使用した有機溶剤及び得られた金ペーストについて、以下の物性測定を行った。
物性測定
　有機溶剤及び金ペーストの粘度は、円錐型回転粘度計（ＨＡＡＫＥ社製、Ｒｈｅｏｓｔｒｅｓｓ　ＲＳ７５、コーンプレート：チタン製　３５ｍｍ、φ１°、ギャップ０．０５０ｍｍにて測定）にて、測定温度２３℃、シェアレート０／ｓで３０秒間保持した後、シェアレート４／ｓ、２０／ｓ、４０／ｓの順でそれぞれ３０秒間保持して連続的に測定した。有機溶剤の沸点は、ＴＧ－ＤＴＡ（熱重量／示差熱同時分析：Ｒｉｇａｋｕ製ＴＧ８１０１Ｄ）により、大気下１０℃/ｍｉｎの昇温レートで測定した。また、チクソトロピー指数（ＴＩ）値は、前記シェアレート４／ｓ及び４０／ｓの粘度測定値から下記式にて算出した。また、実施例１の金ペーストについて、ＴＧ－ＤＴＡ（熱重量／示差熱同時分析）を行った。
　ＴＩ＝（シェアレート４／ｓの粘度）÷（シェアレート４０／ｓの粘度）
　以上の結果、実施例１の金ペーストのシェアレート４／ｓの粘度は２５６Ｐａ・sであった。また、ＴＧ－ＤＴＡより、実施例１の金ペーストでは、７０℃で有機溶剤の蒸発が始まり、１９０℃で有機成分が完全に消失したことを確認できた。
[実施例２～５、比較例１～７]
実施例１と同じ金粉を用いて、表１に示す有機溶剤及び金含有量で金ペーストを作成した。実施例２では、平均粒径０．１μｍの金粉を用いた。比較例７では有機溶剤としてビスアルケニルスクシンイミド（Ｋｉｎｇ　Ｉｎｄｕｓｔｒｉｅｓ社製、商品名：ＫＸ１２２３Ｃ）を使用した。各実施例及び比較例について、有機溶剤の粘度及び沸点と、金ペーストの粘度及びＴＩ値を、実施例１と同様の方法で測定した。結果を表１に示す。
Figure JPOXMLDOC01-appb-T000001
　以上の物性測定の結果より、実施例１～５の貴金属ペーストは、ＴＩ値６．０以上であることが示された。これに対し、比較例１～３、５、７では、ＴＩ値が６．０未満であった。また、比較例４、６では、金粉と有機溶剤とを混合しても、貴金属粉がすぐに沈降して溶剤と分離してしまうか、あるいはハンドリング困難なものとなり、いずれもペースト化することができなかった。
[金粉の平均粒径]
　以上の実施例及び比較例の他、金粉として、平均粒径０．７μｍ及び０．０５μｍのものを用いて、実施例１と同様に金ペーストを作成した。その結果、金粉の平均粒径が０．７μｍの場合、ペースト中で金粉の分散が維持できずに沈降が生じ、０．０５μｍの場合、ペースト中に部分的な凝集が確認された。
[銀ペースト]
　また、金粉の代わりに銀粉（８６重量％；３７体積％）を用いて、実施例１と同様に銀ペーストを作成し、物性測定を行った。その結果、得られた銀ペーストは、シェアレート４／ｓの粘度が１７６Ｐａ・ｓ、シェアレート４０／ｓの粘度が１９Ｐａ・ｓであり、ＴＩ値９．３となった。
基板に対する塗布試験
　次に、上記実施例１～５及び比較例１～３、５の金ペーストを、１００ｍｍ２の半導体基板（Ｓｉ）中央に、面積２５ｍｍ２となるように塗布し、基板への塗布性能を評価した。尚、基板には、表面にＴｉ（５０ｎｍ）、Ａｕ（２００ｎｍ）を予めスパッタリングで製膜したものを用いた。
　上記の結果、実施例１～５の金ペーストは、適度なぬれ性があり基板に塗布しやすく、塗布後の金ペーストも十分な成形性を維持していた。一方、比較例３の金ペーストは、塗布した金ペーストから溶剤がしみ出る傾向となり、塗布後のペーストに変形が生じるものであった。
接合試験
　上記のようにペーストを塗布した後、乾燥及び焼結を行わずに、以下の接合試験を行った。接合試験は、塗布後のペースト上に、面積４ｍｍ２のＳｉチップ（Ｔｉ（２０ｎｍ）とＡｕ（２００ｎｍ）を予め製膜した）を載置し、加熱及び加圧して行った。接合時の加圧は、１つのチップ当り２０Ｎ（５ＭＰａ）とし、加熱は工具からの伝熱により２３０℃となるようにし、加熱及び加圧時間は１０分間とした。
　上記により接合した接合部について、外観Ｘ線透視像（ユニハイトシステム社製）による組織観察を行い、下記式に基づき接合率を算出した。接合率の結果を表２に示す。また、実施例１及び比較例１のＸ線透視像及び、実施例１の断面ＳＥＭ観察結果を図１に示す。Ｘ線透視像では、接合部において、ボイドが発生し空隙が生じた部分は白色、接合部が密着している部分は灰色（黒色）として観察される。
　接合率＝｛密着していた部分（Ｘ線透過画像における灰色部分）の面積｝÷｛接合部全体（Ｘ線透過画像における灰色部分と白い部分の合計）の面積｝
Figure JPOXMLDOC01-appb-T000002
　図１の結果より、実施例１の金ペーストによる接合部は、外観Ｘ線透視像において、ボイド発生による空隙に由来する白色部分はほとんど観察されず、断面ＳＥＭ像においても、金属粉末が点接触に近い状態で近接していた。また、表２の接合率も９０％以上であった。以上より、実施例１では、接合時の加熱による金粉の焼結が、均一に進行したことを確認できた。
　実施例２～５のペーストを用いた場合も、表２より接合率は９０％以上であり、実施例１と同様に、ボイドの発生はほとんど観察されず、焼結が均一に進行したことを確認できた。また、銀ペーストを用いて接合した場合も、外観Ｘ線透視像より、ボイドの発生はほとんど観察されず、銀粉の焼結が均一に進行したことを確認できた。
　一方、比較例１の金ペーストを用いた場合、表２より接合率は９０％未満となり、図１の外観Ｘ線透視像では、ボイド発生による空隙に由来する白色部分が多数観察された。このため、比較例１では、接合時の加熱の際、有機成分由来のアウト（放出）ガスにより、多数のボイドが発生し、金粉の焼結が均一に進行しなかったと考えられる。
　比較例２、３、５のペーストを用いた場合も、表２より接合率９０％未満となり、ボイド発生の空隙に由来する白色部分が、多数観察された。また、比較例７の金ペーストを用いて接合した場合にも、外観Ｘ線透視像より、ボイド発生の空隙に由来する白色部分が、多数観察された。
接合強度試験
　次に、以上で行った接合に関して、図２に従い接合強度試験を行った。接合強度は、半導体基板１０上に焼結体２０を介して接合された半導体チップ（耐熱性Ｓｉチップ）３０に対し、横方向から一定速度でブレードをチップに当接、進行させ、破断（チップの剥離）が生じたときの応力の平均値（単位：Ｎ）を測定した。この測定値と破断後の接合部面積とから、単位面積あたりの接合強度の平均値（単位：ＭＰａ）を算出した。結果を表３に示す。
Figure JPOXMLDOC01-appb-T000003
　表３より、実施例１～５のペーストを用いて接合した場合、接合部はは、電子部品の接合等に十分な接合強度（２０ＭＰａ以上）となったことを確認できた。また、比較例１のペーストを用いた接合では、接合強度については実施例と同程度になったものの、以上説明したように、接合率が低く（表２）、多数のボイド発生が観察された（図１）ため、電子部品の接合に好適なものではなかった。
　本発明の貴金属ペーストは、各種の接合部材の低温接合に好適であり、熱応力の影響が懸念される半導体素子等を基板に接合する際に有用である。

Claims (5)

  1. 貴金属粉と有機溶剤とから構成される貴金属ペーストにおいて、
    貴金属粉は純度９９．９質量％以上、平均粒径０．１～０．５μｍ、
    有機溶剤は沸点２００～３５０℃であり、
    貴金属ペーストは、回転粘度計による２３℃におけるシェアレート４０／ｓの粘度に対する４／ｓの粘度の測定値から算出されるチクソトロピー指数（ＴＩ）値が６．０以上である半導体素子接合用の貴金属ペースト。
  2. 貴金属粉が、金粉又は銀粉のいずれか一種以上からなる請求項１記載の貴金属ペースト。
  3. 貴金属ペースト中における貴金属粉の体積含有率が２６～６６体積％（ｖ／ｖ）である請求項１又は２に記載の貴金属ペースト。
  4. 半導体素子のダイボンド接合に用いられる請求項１～３のいずれかに記載の貴金属ペースト。
  5. 半導体素子を接合した場合の接合部では、Ｘ線透視像において接合部全体の面積に対する接合部のうち密着していた部分の面積の割合より算出される接合率が９０％以上となる請求項１～４のいずれかに記載の貴金属ペースト。
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KR20130073975A (ko) 2013-07-03
US9539671B2 (en) 2017-01-10
EP2626893A4 (en) 2016-08-03
CN103155126A (zh) 2013-06-12
CN103155126B (zh) 2016-03-30
EP2626893B1 (en) 2018-05-30
US20180151531A1 (en) 2018-05-31
US10366963B2 (en) 2019-07-30
TWI484000B (zh) 2015-05-11
JP5613253B2 (ja) 2014-10-22
US20130168437A1 (en) 2013-07-04

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