WO2013146504A1 - ダイボンド用導電性ペースト及び該導電性ペーストによるダイボンド方法 - Google Patents

ダイボンド用導電性ペースト及び該導電性ペーストによるダイボンド方法 Download PDF

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Publication number
WO2013146504A1
WO2013146504A1 PCT/JP2013/057985 JP2013057985W WO2013146504A1 WO 2013146504 A1 WO2013146504 A1 WO 2013146504A1 JP 2013057985 W JP2013057985 W JP 2013057985W WO 2013146504 A1 WO2013146504 A1 WO 2013146504A1
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Prior art keywords
bonding
conductive paste
die bonding
powder
die
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PCT/JP2013/057985
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English (en)
French (fr)
Inventor
俊典 小柏
晶和 塩屋
正幸 宮入
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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 KR1020147030165A priority Critical patent/KR20140139104A/ko
Priority to EP13767655.7A priority patent/EP2833393A4/en
Priority to US14/375,362 priority patent/US20150014399A1/en
Priority to CN201380017110.2A priority patent/CN104205312A/zh
Publication of WO2013146504A1 publication Critical patent/WO2013146504A1/ja

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    • 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
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
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    • H01L2924/30—Technical effects
    • H01L2924/35—Mechanical effects
    • H01L2924/351—Thermal stress

Definitions

  • the present invention relates to a conductive paste applied to die bonding and flip chip bonding of a semiconductor chip to a substrate and a bonding method using the same.
  • the present invention relates to a conductive paste having excellent durability that does not cause voids in a joint even when a long time elapses at high temperatures.
  • a method using a brazing material As a method of die bonding various semiconductor chips to a substrate, a method using a brazing material has been widely known.
  • this die bonding method after the brazing material is fused to either the semiconductor chip or the substrate, the semiconductor chip is placed on the substrate and heated to a temperature equal to or higher than the melting point of the brazing material to melt and solidify the brazing material. Yes.
  • the heating temperature (joining temperature) at this time is set in consideration of the melting point of the brazing material to be used.
  • an AuSn brazing material is known as a brazing material generally used in recent years for die bonding, but its melting point is about 280 ° C., so that the bonding temperature is set to a temperature of 300 ° C. or higher. There are many cases.
  • the bonding temperature during die bonding is preferably low. This is because if the bonding temperature is high, the thermal stress generated during cooling after bonding increases, and the electrical characteristics of the semiconductor chip may vary. In addition, heating during bonding may affect the characteristics of the semiconductor chip. Therefore, in order to lower the temperature of die bonding of semiconductor chips, a die bonding method using a conductive paste containing a metal powder made of a conductive metal such as silver is known as an alternative to the conventional die bonding method by brazing. (Patent Documents 1 and 2).
  • the die-bonding method using these conductive pastes can be bonded at a lower temperature than the conventional solder-bonding die-bonding method, and the bonding strength is sufficient, and the handling property of the paste is also good. It is a method that is being used. *
  • defects may occur in the joint portion in a high temperature environment.
  • This defect is a void generated in the cured conductive paste, which is a joint between the materials to be joined.
  • This void tends to occur particularly in an environment where the bonded member is exposed to a high temperature, and it may grow over time and eventually lead to peeling. Such defects do not always occur, but of course should be eliminated.
  • the present invention is based on the above problem, and provides a conductive paste for die-bonding a semiconductor element or the like to a substrate that can suppress the occurrence of defects as described above.
  • FIG. 1 illustrates the joint immediately after joining in a conventional joining process and the state of the joined part when heated at a high temperature.
  • a joining portion is formed by proceeding with densification accompanying rearrangement of metal particles with pressurization during joining and then densification accompanying plastic deformation (shear deformation).
  • the joint at this time is in a relatively dense state as shown in FIG. 1A, but the metal particles are not completely integrated, but voids remain between the particles.
  • the generation of voids as described above occurs when the joint is heated to a high temperature, and is a phenomenon that occurs remarkably in a semiconductor device used in such an environment. Further, if the cause of non-uniform bonding of metal particles is an oxide or sulfide on the surface of the metal particles, it can be said that non-uniform bonding is unlikely to occur if the conductive paste is made of metal powder having excellent corrosion resistance.
  • the range of use of the semiconductor element cannot be limited due to the occurrence of defects in the junction.
  • the above-mentioned defects do not occur for the constituent material of the metal particles of the conductive paste as long as it has excellent corrosion resistance.
  • the present inventors have confirmed this point.
  • a metal such as silver is easy to oxidize and sulfide, but has excellent conductivity and is superior to gold in terms of cost, and it is necessary to use such a metal. Accordingly, the present inventors have arrived at the present invention on the assumption that a predetermined metal conductive paste has improved the corrosion resistance of metal particles and suppressed the generation of voids due to high-temperature heating after joining.
  • the present invention is a conductive paste for bonding comprising a metal powder and an organic solvent, wherein the metal powder is a silver powder having a purity of 99.9% by mass or more and an average particle diameter of 0.01 ⁇ m to 1.0 ⁇ m.
  • a conductive paste comprising one or more metal particles selected from palladium powder and copper powder, and a coating layer made of gold covering at least a part of the metal particles.
  • the present invention suppresses oxidation and sulfidation of metal powder by forming a metal powder by forming a coating layer made of gold for improving corrosion resistance on the surface of metal particles made of silver, palladium, and copper.
  • the inter-particle joining at the joint when subjected to high temperature heating later is made uniform. The present invention will be described in detail below.
  • the metal particles constituting the metal powder in the present invention are made of one or more metals selected from silver powder, palladium powder, and copper powder having a purity of 99.9% by mass or more and an average particle diameter of 0.01 ⁇ m to 1.0 ⁇ m.
  • the reason why a high purity of 99.9% by mass or more is required as the purity of the metal particles is that if the purity is low, the hardness of the powder increases, and plastic deformation is less likely to occur during the formation of the joint during die bonding.
  • the lower limit of 0.01 ⁇ m is taken into consideration that when the particle size is less than this particle size, it tends to agglomerate when used as a paste, making it difficult to handle.
  • the reason why the constituent metal is silver, palladium, or copper is that these metals have good conductivity. And these metals are comparatively easy to corrode, and the effect of the coating layer by this invention expresses.
  • the thickness of the coating layer is preferably 0.002 ⁇ m to 0.3 ⁇ m. This is because if the thickness is less than 0.002 ⁇ m, the effect is not obtained, and if it exceeds 0.3 ⁇ m, there is no difference in the effect and the price of the metal particles is increased.
  • the coating layer is effective when it covers at least a part of the metal particles, and it does not only require that all the metal particles be coated on the entire surface.
  • a thin film forming method such as a plating method or a sputtering method can be applied. It is preferable to control the thickness of the coating layer as described above within a very thin range. For this purpose, it is appropriate to employ a thin film forming method such as a plating method. Particularly preferred is a plating method such as an electroless plating method.
  • the conductive paste according to the present invention is formed by dispersing the above metal powder in an organic solvent.
  • organic solvent for the conductive paste ester alcohol, terpineol, pine oil, butyl carbitol acetate, butyl carbitol and carbitol are preferable.
  • 2,2,4-trimethyl-3-hydroxypentaisobutyrate (C 12 H 24 O 3 ) can be given as a preferred ester alcohol organic solvent. This is because the present solvent can be dried at a relatively low temperature.
  • the content of the metal powder in the conductive paste is preferably 70 to 99% by mass. If it is less than 70% by mass, the metal necessary for bonding is insufficient and a dense bonded part cannot be formed. On the other hand, if it exceeds 99 mass%, the viscosity of the paste becomes so high that the handling property is hindered.
  • the conductive paste according to the present invention may contain one or more selected from acrylic resins, cellulose resins, and alkyd resins in addition to the organic solvent. When these resins and the like are further added, the metal powder in the conductive paste is prevented from agglomerating and becomes more uniform, and a joint can be formed.
  • acrylic resins include methyl methacrylate polymers
  • examples of cellulose resins include ethyl cellulose
  • examples of alkyd resins include phthalic anhydride resins. Of these, ethyl cellulose is particularly preferable.
  • the die bonding method according to the present invention is basically the same as the method using the above-described conventional conductive paste. That is, in a method of die-bonding a semiconductor element or the like that is a bonding member on a substrate, a step of applying the conductive paste according to the present application to the substrate or the bonding member, and after arranging the bonding member on the substrate, A die bonding method including a step of heating and bonding while applying pressure from both directions.
  • the conductive paste application process is not particularly limited, and various methods can be used depending on the size of the member to be joined, such as a spin coat method, a screen printing method, an ink jet method, and a method of spreading the paste with a spatula after dropping. Can be used.
  • the other joining member is placed and heated and pressurized.
  • the heating temperature is preferably 80 to 300 ° C. This is because point contact does not occur below 80 ° C.
  • the temperature is higher than 300 ° C., the bonding between the metal powders proceeds excessively, the necking between the metal powders occurs, and the metal powders are firmly bonded and become too hard. Further, heating exceeding 300 ° C. may cause deformation of the substrate or thermal effects.
  • the pressure during joining is preferably 0.5 MPa to 50 MPa. This is because the conductive paste cannot be adhered to the entire surface to be bonded in the region lower than 0.5 MPa, and no further improvement in the bonding state is observed in the region higher than 50 MPa.
  • ultrasonic waves may be applied in addition to heating.
  • the conditions are preferably an amplitude of 0.5 to 5 ⁇ m and an application time of 0.5 to 3 seconds. This is because application of excessive ultrasonic waves damages the joining member.
  • the heating and ultrasonic wave application in the die bonding step may be performed on at least the bonding portion for the purpose, but may be performed on the entire bonding member.
  • a heating method it is easy to use heat transfer from a tool when pressurizing the joining member.
  • the soundness of the joint can be maintained without generating and growing voids even under high-temperature heating, and the durability is improved. be able to.
  • the present invention can bond various bonding members at a relatively low temperature, and can protect the bonding members from thermal stresses in the cooling process after bonding. Is useful when bonding to a substrate, and can be applied to die bonding, flip chip bonding, and the like. And since a junction part is stable even under high temperature, it is particularly useful for die bonding of power devices and the like.
  • Silver powder (average particle size: 0.3 ⁇ m) having a purity of 99.9% by mass produced by a wet reduction method was coated with gold as a coating layer.
  • the coating layer was formed by an electroless plating method. Specifically, a non-cyan substitutional electroless gold plating solution was used as the plating solution.
  • As the gold source a plating solution containing 5 g / L of gold sulfite as a gold concentration was used.
  • oxides and sulfides on the surface of the silver powder are removed with diluted sulfuric acid, and the plating condition is set to a plating temperature of 70 ° C., the silver powder is poured into the plating solution, and the treatment is performed for 1 hour.
  • Gold layer formation was performed.
  • the average thickness of the coating layer was 0.01 ⁇ m.
  • the calculation of the thickness of the coating layer was based on the result of measuring the gold film thickness when the silver plate was plated under the same conditions by the fluorescent X-ray film thickness method (XRF).
  • the metal powder thus produced is mixed with ester alcohol (2,2,4-trimethyl-3-hydroxypentaisobutyrate (C 12 H 24 O 3 )) as an organic solvent to obtain a conductive paste.
  • ester alcohol 2,2,4-trimethyl-3-hydroxypentaisobutyrate (C 12 H 24 O 3 )
  • a 0.6C-thick DBC substrate (Direct Bonding Copper substrate) obtained by bonding a copper foil (0.15 mm) onto a ceramic, and a Si chip as a bonding member were prepared. Sputtered films of Ti (50 nm), Pt (50 nm), and Au (200 nm) are formed in advance on the surface of the copper foil on the DBC substrate and the Si chip.
  • junction evaluation test (heating cycle test) : The DBC substrate with Si chip die-bonded in the first embodiment and the comparative example was subjected to a heating cycle test to investigate the presence or absence of void generation and peeling. In this test, the operation of holding the substrate at ⁇ 40 ° C. for 5 minutes and then holding at 200 ° C. for 5 minutes was repeated 1000 cycles, and the substrate surface before and after the test was subjected to ultrasonic flaw detection observation (SAT). Further, the cross section of the chip / substrate junction after 1000 cycles was observed.
  • SAT ultrasonic flaw detection observation
  • FIG. 2 shows the results of SAT observation of the first embodiment and the comparative example after the heating cycle.
  • linear voids were observed from the initial cycle (zero times) of the cycle, and peeling occurred from the outer periphery of the Si chip after 1000 cycles.
  • the generation of linear voids was small at the initial stage of the cycle, and only a slight peeling from the outer periphery of the Si chip was observed after 1000 cycles.
  • FIG. 3 is an SEM photograph taken of a cross section of a comparative example after 1000 cycles. As shown in FIG. 3, the crack from the outer periphery of the Si chip propagates inside the bonding material, which seems to lead to peeling of the chip. In addition, since there are many voids near the crack tip, it was speculated that these voids induce cracks.
  • Joint evaluation test (continuous heating test) : Next, the presence or absence of voids when heated for a long time (200 hours) was confirmed for the DBC substrate with Si chip die-bonded in the first embodiment and the comparative example. In this test, each substrate was heated at 300 ° C. for 200 hours, and SAT observation and cross-sectional observation were performed on the heated substrate.
  • FIG. 4 shows the results of SAT observation after the continuous heating test.
  • peeling occurred in the lower half of the chip after 200 hours had elapsed.
  • no peeling was observed in the substrate of the first embodiment.
  • FIG. 5 is an observation result of the junction part cross section of the comparative example after a heating. It was found that continuous voids were formed as a result of separation of the silver powders that should be in the center of the joint.
  • the thickness of the coating layer was changed by changing the plating conditions, setting the gold concentration of the plating solution to 2 to 10 g / L, setting the plating temperature to 60 to 90 ° C., and the plating time to 1 to 2 hours.
  • the conductive paste was manufactured in the same manner as in the first embodiment.
  • a Si chip was bonded on the DBC substrate.
  • the shear strength of the joint was measured using a bonding tester for the substrate before and after heating at 300 ° C. for 200 hours (pressure applied 5 MPa). The measurement results are shown in Table 1.
  • the thickness of the coating layer is preferably 0.002 ⁇ m to 0.3 ⁇ m, more preferably 0.00. It is considered to be 002 ⁇ m to 0.05 ⁇ m.
  • the conductive paste for die bonding according to the present invention, it is possible to form a joint that is difficult to generate and grow voids even when subjected to high temperature heating.
  • the present invention can be applied to die bonding of semiconductor chips and the like, flip chip bonding, and the like, and is particularly useful for bonding of power devices used in a high temperature environment.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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  • Die Bonding (AREA)
  • Powder Metallurgy (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

　本発明は、金属粉末と有機溶剤とからなるダイボンド用の導電性ペーストであって、前記金属粉末は、純度９９．９質量％以上、平均粒径０．０１μｍ～１．０μｍである銀粉、パラジウム粉、銅粉から選択される一種以上の金属粒子と、前記金属粒子の少なくとも一部を覆う金からなる被覆層と、からなる導電性ペーストである。本発明に係る導電性ペーストによれば、半導体素子等を基板へダイボンドする際に、接合部におけるボイド等の欠陥発生を抑制するができる。

Description

ダイボンド用導電性ペースト及び該導電性ペーストによるダイボンド方法
　本発明は、半導体チップの基板へのダイボンド、フリップチップ接合に適用される導電性ペースト及びこれを用いた接合方法に関する。特に、高温下で長時間経過しても接合部内にボイドを生じさせない耐久性にすぐれた導電性ペーストに関する。
　各種半導体チップの基板へのダイボンド方法としては、従来からろう材を用いたものが広く知られている。このダイボンド法においては、半導体チップ又は基板のいずれかにろう材を融着した後に半導体チップを基板に載置して、ろう材の融点以上の温度に加熱してろう材を溶融・凝固させている。このときの加熱温度（接合温度）は、使用するろう材の融点を考慮して設定される。例えば、近年ダイボンドで一般的に用いられているろう材として、ＡｕＳｎ系ろう材が知られているが、その融点は約２８０℃であることから、接合温度は３００℃以上の温度に設定されることが多い。
　ダイボンドの際の接合温度は低温とすることが好ましい。これは、接合温度を高温とすると、接合後の冷却時に生じる熱応力が大きくなり半導体チップの電気的特性に変動が生じるおそれがあることによる。また、接合時の加熱そのものが半導体チップの特性に影響を及ぼすおそれもある。そこで、半導体チップのダイボンディングの低温化を図るため、従来のろう付けによるダイボンド法に替わる方法として、銀等の導電性金属からなる金属粉末を含有する導電性ペーストを使用するダイボンド法が知られている（特許文献１、２）。
特開平１１－２６４８０号公報 特開２００２－１５８３９０号公報
　これらの導電性ペーストによるダイボンド法は、従来のろう材によるダイボンド法よりも低温で接合が可能であり接合強度も十分であることに加え、ペーストの取扱い性も良好であることから、近年より広く利用されつつある方法である。　
　しかし、本発明者等の検討によると、上記従来の導電性ペーストを用いたダイボンド法においては、高温環境で接合部に欠陥が生じることがある。この欠陥とは、被接合材間の接合部である硬化後の導電性ペーストにおいて生じるボイドである。このボイドは、特に、被接合部材が高温に晒される環境で発生する傾向があり、経時的に成長し最終的には剥離に繋がるおそれもある。かかる欠陥は常に生じるものではないが、当然に排除されるべきものである。　
　本発明は、上記課題を背景とするものであり、半導体素子等を基板へダイボンドするための導電性ペーストについて、上記のような欠陥発生を抑制することのできるものを提供する。
　本発明者等は、上記課題を解決すべく、まず、従来の導電性ペーストによる接合プロセスで生じる上記欠陥の性状及びその発生原因について検討した。まずこの検討結果について、図１と共に説明する。図１は、従来の接合プロセスにおける接合直後の接合部と、これが高温加熱されたときの接合部の状態を説明するものである。導電性ペーストによる接合プロセスにおいては、接合時の加圧に伴い金属粒子に再配列に伴う緻密化と、次いで塑性変形（せん断変形）に伴う緻密化が進むことで接合部を形成する。このときの接合部は、図１（ａ）のように、比較的緻密な状態ではあるが、各金属粒子が完全に一体化するものではなく粒子間に空隙が残った状態である。
　そして、この接合部が高温加熱を受けると、金属粒子間の拡散が進行し、金属粒子がより密に接合することとなるが、これが全ての金属粒子の間で均一に生じるのであれば、接合部はより緻密化され問題はないが、実際は必ずしもそうはならない。これは、金属粒子表面に酸化物や硫化物からなる皮膜が形成されていることによる。金属粒子表面に酸化物等の皮膜がある場合、金属粒子間の接合状態は不均一なものとなり、図１（ｂ）のように、局所的にボイドができる。本発明者等は、この高温環境下で発生する金属粒子間の接合状態のばらつきがボイドの要因であることを見出した。
　上記の検討結果から次の点が確認される。即ち、上記のようなボイド発生は、接合部が高温に加熱されて発生するものであり、そのような環境で使用される半導体素子で顕著に生じる現象である。また、金属粒子の接合が不均一となる要因が金属粒子表面に酸化物や硫化物にあるのであれば、耐食性に優れる金属粉からなる導電性ペーストであれば不均一接合は生じ難いといえる。
　もっとも、接合部の欠陥発生を理由として半導体素子の利用範囲を限定することはできない。また、導電性ペーストの金属粒子の構成材料についても、耐食性に優れる金であれば上記欠陥は生じない。この点は本発明者等も確認している。だが、例えば、銀のような金属は、酸化・硫化しやすいものの導電性に優れると共にコスト面で金より優れており、こうした金属の活用も必要である。そこで、本発明者等は、所定の金属の導電性ペーストについて、金属粒子の耐食性を改善し、接合後の高温加熱によるボイド発生が抑制されたものとして本発明に想到した。
　即ち、本発明は、金属粉末と有機溶剤とからなる接合用の導電性ペーストであって、前記金属粉末は、純度９９．９質量％以上、平均粒径０．０１μｍ～１．０μｍである銀粉、パラジウム粉、銅粉から選択される一種以上の金属粒子と、前記金属粒子の少なくとも一部を覆う金からなる被覆層と、からなる導電性ペーストである。
　本発明は、銀、パラジウム、銅からなる金属粒子の表面に耐食性向上のための金からなる被覆層を形成して金属粉末を構成することで、金属粉末の酸化や硫化等を抑制し、ダイボンド後に高温加熱を受けたときの接合部における粒子間接合を均一にするものである。以下、本発明につきより詳細に説明する。
　本発明における金属粉末を構成する金属粒子は、純度９９．９質量％以上、平均粒径０．０１μｍ～１．０μｍである銀粉、パラジウム粉、銅粉から選択される一種以上の金属からなる。金属粒子の純度として９９．９質量％以上の高純度を要求するのは、純度が低いと粉末の硬度が上昇し、ダイボンドの際の接合部形成時に塑性変形が生じ難くなるからである。また、金属粉の平均粒径については、１．０μｍを超える粒径の金属粉では、ダイボンドの際の再配列が生じたときに好ましい近接状態を発現させ難くなるからである。一方、０．０１μｍを下限とするのはこの粒径未満の粒径では、ペーストとしたときに凝集しやすく、取扱いが困難となることを考慮するものである。そして、その構成金属を銀、パラジウム、銅のいずれかとするのは、これらの金属は導電性が良好でだからである。そして、これらの金属は比較的腐食し易く、本発明による被覆層の効果が発現するからである。
　そして、この金属粒子を被覆する材料として金を選択したのは耐食性に優れ金属粒子の腐食抑制に有効だからである。ここで、被覆層の厚さは、０．００２μｍ～０．３μｍとするのが好ましい。０．００２μｍ未満ではその効果がないからであり、０．３μｍを超えても効果に差はなく、金属粒子の価格を上昇させるからである。また、被覆層は金属粒子の少なくとも一部を被覆すれば効果が出現し、全ての金属粒子に対してその全面を被覆することを要求するものばかりではない。部分的な被覆であっても、金属粒子同士の拡散を可能とする接触点が増えることとなり、結果として金属粒子間の接合状態のばらつきを低減することができるからである。具体的には、金属粉末全体の体積に対して０．５～３０ｖｏｌ％の金が存在することが好ましい。
　被覆層の形成方法としては、メッキ法、スパッタリング法等の薄膜形成方法を適用することができる。上記通りの被覆層はきわめて薄い範囲で厚さ制御することが好ましく、そのためにはメッキ法等の薄膜形成方法の採用が的確である。特に好ましいのは、無電解メッキ法等のメッキ法によるものである。
　本発明に係る導電性ペーストは、上記の金属粉末を有機溶剤に分散して形成される。導電性ペーストの有機溶剤としては、エステルアルコール、ターピネオール、パインオイル、ブチルカルビトールアセテート、ブチルカルビトール、カルビトールが好ましい。例えば、好ましいエステルアルコール系の有機溶剤として、２，２，４－トリメチル－３－ヒドロキシペンタイソブチレート（Ｃ１２Ｈ２４Ｏ３）を挙げることができる。本溶剤は、比較的低温で乾燥させることができるからである。
　導電性ペースト中の金属粉末の含有量は、７０～９９質量％とするのが好ましい。７０質量％未満では接合に必要な金属が不足し緻密な接合部を形成することができない。また、９９質量％を超えるとペーストの粘性が高くなりすぎ取扱い性に支障が生じるからである。
　また、本発明に係る導電性ペーストは、上記有機溶剤に加えて、アクリル系樹脂、セルロース系樹脂、アルキッド樹脂から選択される一種以上を含有していても良い。これらの樹脂等を更に加えると導電性ペースト中の金属粉の凝集が防止されてより均質となり、接合部が形成できる。尚、アクリル系樹脂としては、メタクリル酸メチル重合体を、セルロース系樹脂としては、エチルセルロースを、アルキッド樹脂としては、無水フタル酸樹脂を、それぞれ挙げることができる。そして、これらの中でも特にエチルセルロースが好ましい。
　次に、本発明に係る導電性ペーストによるダイボンド法について説明する。本発明に係るダイボンド法は、基本的に上記した従来の導電性ペーストを用いる方法と同様である。即ち、基板上へ接合部材である半導体素子等をダイボンドする方法において、前記基板又は前記接合部材に、本願に係る導電性ペーストを塗布する工程、基板上に接合部材を配置した後、一方向又は双方向から加圧しながら加熱して接合する工程、を含むダイボンド方法である。
　導電性ペーストの塗布工程は特に限られるものはなく、例えば、スピンコート法、スクリーン印刷法、インクジェット法、ペーストを滴下後にヘラ等で広げる方法等、被接合部材のサイズに対応させて種々の方法を用いることができる。
　そして、導電性ペーストを塗布後、他方の接合部材を載せて加熱及び加圧する。加熱及び加圧により、ペースト中の金属粒子同士、及び、接合部材の接合面と金属粒子との間に、互いに点接触した近接状態が形成され、接合部としての形状が安定する。この加熱温度は、８０～３００℃とするのが好ましい。８０℃未満では点接触が生じないからである。一方、３００℃を超える温度とすると、金属粉末同士の結合が過度に進行し金属粉末間のネッキングが生じて強固に結合し、硬すぎる状態となるからである。また、３００℃を超える加熱は基板の変形や熱影響が生じる恐れがある。そして、接合時の加圧は、０．５ＭＰａ～５０ＭＰａとするのが好ましい。０.５ＭＰａより低い領域では被接合面全体に導電性ペーストを密着させることが出来ないこと、５０ＭＰａより高い領域では接合状態の更なる改善が見られないからである。
　また、このダイボンド方法においては、加熱に加えて超音波を印加しても良い。加熱又は加熱と超音波との組合せにより、金属粉末の塑性変形及び結合を促進し、より強固な接合部を形成することができる。超音波を印加する場合、その条件は、振幅０．５～５μｍとし、印加時間を０．５～３秒とするのが好ましい。過大な超音波印加は接合部材を損傷させるからである。ダイボンド工程における上記加熱及び超音波印加は、その目的から少なくとも接合部に対して行なえばよいが、接合部材全体に行っても良い。加熱の方法としては、接合部材を加圧する際の工具からの伝熱を利用するのが簡易である。同様に、超音波の印加は、接合部材を加圧する工具から超音波発振させるのが簡易である。
　以上説明したように、本発明に係るダイボンド用の導電性ペーストによれば、高温加熱下でもボイドを発生・成長させることなく接合部の健全性を維持することができ、その耐久性を向上させることができる。本発明は、各種の接合部材を比較的低温で接合することができると共に、接合後の冷却過程における熱応力から接合部材を保護することができることから、熱応力の影響が懸念される半導体チップ等を基板へ接合する際に有用であり、そのダイボンディング、フリップチップ接合等へ適用することができる。そして、高温下でも接合部が安定していることから、パワーデバイス等についてのダイボンディングに特に有用である。
従来の導電性ペーストを使用する接合プロセスの接合部の状態を説明する模式図。 第１実施形態及び比較例の接合部のＳＡＴ観察写真。 １０００サイクル後の比較例の接合部断面のＳＥＭ写真。 ２００時間熱処理後の比較例の接合部のＳＡＴ観察写真。 ２００時間熱処理後の比較例の接合部の断面観察のＳＥＭ写真。
［第１実施形態］：ここでは、金属粒子に金からなる被覆層を形成した金属粉末を分散させた導電性ペーストを製造し、これを用いてＳｉチップを半導体基板へダイボンドして接合部の健全性を検討した。
導電性ペーストの製造：湿式還元法により製造された純度９９．９質量％の銀粉（平均粒径：０．３μｍ）に被覆層として金を被覆した。被覆層の形成は、無電解メッキ法にて行った。具体的には、メッキ液として、非シアン系の置換型無電解金メッキ液を使用した。金源は亜硫酸金を金濃度として、５ｇ／Ｌ含有させたメッキ液を使用した。前処理として、希釈硫酸により銀粉表面の酸化物や硫化物の除去を行い、メッキ条件として、メッキ温度７０℃に設定してメッキ液へ銀粉を投入して１時間の処理を行い、銀粉表面に金層形成を行った。被覆層平均厚さは０．０１μｍであった。この被覆層の厚さの算出は、銀板に同条件でメッキした際の金膜厚を蛍光Ｘ線膜厚法(ＸＲＦ)で測定した結果を基準とした。
　そして、このようにして製造した金属粉末を、有機溶剤としてエステルアルコール（２，２，４－トリメチル－３－ヒドロキシペンタイソブチレート（Ｃ１２Ｈ２４Ｏ３））に混合して導電性ペーストを製造した（金属粉末の含有量９０質量％）。
接合試験：セラミック上に銅箔（０．１５ｍｍ）を接合した厚さ０．６ｍｍのＤＢＣ基板（Ｄｉｒｅｃｔ　Ｂｏｎｄｉｎｇ　Ｃｏｐｐｅｒ基板）と、接合部材としてＳｉチップを用意した。ＤＢＣ基板上銅箔及びＳｉチップには表面に、Ｔｉ（５０ｎｍ）、Ｐｔ（５０ｎｍ）、Ａｕ（２００ｎｍ）のスパッタ膜を予め形成している。
　ＤＢＣ基板上に上記導電性ペーストを塗布後にＳｉチップ(２ｍｍ角)を載置し、５ＭＰａで加圧したところで１℃/分で３００℃まで昇温、１０分保持して接合した。
［比較例］：第１実施形態における導電性ペースト製造工程で、銀粉末に金をメッキすることなくそのまま有機溶剤と混合して導電性ペーストを製造した。そして、第１実施形態と同様の工程で、ＤＢＣ基板にＳｉチップを接合した。
接合部評価試験（加熱サイクル試験）：第１実施形態及び比較例でダイボンディングしたＳｉチップ付ＤＢＣ基板について、加熱サイクル試験を行いボイド発生・剥離の有無を調査した。この試験では、基板を－４０℃に５分保持した後に２００℃に５分保持する操作を１サイクルとして１０００サイクル繰返し、試験前後の基板面を超音波探傷観察（ＳＡＴ）を行った。また、１０００サイクル後のチップ／基板接合部の断面観察を行った。
　図２は、加熱サイクル後の第１実施形態及び比較例のＳＡＴ観察の結果を示す。比較例においては、サイクル初期（ゼロ回）の段階から線状のボイド発生が認められており、１０００サイクル後にはＳｉチップの外周から剥離が生じていた。これに対し、第１実施形態では、サイクル初期の段階で線状のボイド発生が少なく、１０００サイクル後にはＳｉチップの外周から剥離もごく僅か観察されたのみであった。
　図３は、１０００サイクル後の比較例の接合部断面について撮影したＳＥＭ写真である。図３のように、Ｓｉチップ外周からのクラックは接合材内部を伝播しており、これがチップの剥離に繋がっているものと思われる。また、クラック先端付近にはボイドが多数存在することから、これらボイドがクラックを誘因するものと推測された。
接合部評価試験（継続加熱試験）：次に、第１実施形態及び比較例でダイボンディングしたＳｉチップ付ＤＢＣ基板について、長時間（２００時間）加熱したときのボイドの発生有無を確認した。この試験では、各基板について３００℃で２００時間加熱し、加熱後の基板に対してＳＡＴ観察、断面観察を行った。
　図４は、継続加熱試験後のＳＡＴ観察の結果を示す。比較例では、２００時間経過後にチップ下側半分に剥離が生じていた。一方、第１実施形態の基板では、剥離は見られなかった。また、図５は、加熱後の比較例の接合部断面の観察結果である。接合部中央にあるべき銀粉末同士が離れた結果、連続的なボイドが形成されていたことが判った。
以上の接合部に対する２つの加熱試験の結果から、金層を形成し銀粉末同士の密着性を向上させることでボイドの発生を抑制し、接合部の健全性を保つといえる。比較例におけるボイドの発生は、図１（ｂ）に示したモデルに類似しており、金属粒子表面に酸化物等の皮膜が形成されている場合は、金属粒子間の接合状態が不均一なものとなり、結果として高温環境下でボイドを発生せしめることが確認された。
［第２実施形態］：ここでは、被覆層の厚さを調整した２種の金属粉末（銀粉末、銅粉末）を用意して導電性ペーストを製造し、被覆層の割合による接合部健全性について検討した。金属粉末の製造は第１実施形態と同様とし、被覆層である金メッキの条件を変更しつつ、厚さ０．００１μｍ、０．００２μｍ、０．００５μｍ、０．０５μｍ、０．１μｍ、０．３μｍ、となるようにした。被覆層の厚さはメッキ条件を変更し、メッキ液の金濃度を２～１０ｇ／Ｌとし、メッキ温度６０～９０℃、メッキ時間を１～２時間に設定して処理を行った。また、導電性ペーストの製造も第１実施形態と同様とした。また、同様にＳｉチップをＤＢＣ基板上に接合した。ＳｉチップとＤＢＣ基板との接合部の健全性評価は、３００℃で２００時間加熱前後の基板について、ボンディングテスタを用いて接合部のシェア強度を測定した（加圧力５ＭＰａ）。この測定結果を表１に示す。
Figure JPOXMLDOC01-appb-T000001
　表１から、被覆層（金層）の厚さが０．００１μｍの銀粉末においては、加熱により接合部のシェア強度大きく低下する。一方、金膜厚が０．００２μｍ以上の銀粉末においてはシェア強度の低下はみられない。むしろ、０．００５μｍ以上ではシェア強度が上昇する傾向がみられる。これは、高温加熱により結合部がより緻密なものとなったためと考えられ、このような緻密化は被覆層形成により達成されるものと考えられる。以上の傾向は、銅粉末についても同じ傾向が得られており、一定膜厚以上の金膜を形成することにより、安定性の優れた接合状態を確保できたと言える。尚、金膜を厚く形成すれば金属粒子の価格の上昇になることから、コスト面を考慮すると、被覆層の厚さは０．００２μｍ～０．３μｍであることが好ましく、より好ましくは０．００２μｍ～０．０５μｍであると考えられる。
　本発明に係るダイボンド用の導電性ペーストによれば、高温加熱を受けてもボイドを発生・成長が生じがたい接合部を形成することができる。本発明は、半導体チップ等のダイボンディング、フリップチップ接合等へ適用することができ、特に、高温環境下で使用されるパワーデバイスのボンディングに有用である。
 

Claims (5)

  1. 　金属粉末と有機溶剤とからなるダイボンド用の導電性ペーストであって、
    　前記金属粉末は、純度９９．９質量％以上、平均粒径０．０１μｍ～１．０μｍである銀粉、パラジウム粉、銅粉から選択される一種以上の金属粒子と、前記金属粒子の少なくとも一部を覆う金からなる被覆層と、からなる導電性ペースト。
  2. 　被覆層の厚さが０．００２μｍ～０．３μｍである請求項１記載のダイボンド用の導電性ペースト。
  3. 　被覆層を構成する金属粒子の含有量は、ペースト重量に対して７０～９９質量％の割合である請求項１又は請求項２記載のダイボンド用の導電性ペースト。
  4. 　基板上へ接合部材をダイボンドする方法において、
    　前記基板又は前記接合部材に、請求項１～請求項３のいずれかに記載の導電性ペーストを塗布する工程、
    　基板上に接合部材を配置した後、一方向又は双方向から加圧しながら加熱して接合する工程、を含むダイボンド方法。
  5. 　接合時の加熱温度は、８０～３００℃の温度である請求項４記載のダイボンド方法。
     
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