JP5590501B2 - Method for producing metal microspheres - Google Patents
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- JP5590501B2 JP5590501B2 JP2010069860A JP2010069860A JP5590501B2 JP 5590501 B2 JP5590501 B2 JP 5590501B2 JP 2010069860 A JP2010069860 A JP 2010069860A JP 2010069860 A JP2010069860 A JP 2010069860A JP 5590501 B2 JP5590501 B2 JP 5590501B2
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- 239000002184 metal Substances 0.000 title claims description 79
- 239000004005 microsphere Substances 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 239000011261 inert gas Substances 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000007711 solidification Methods 0.000 description 26
- 230000008023 solidification Effects 0.000 description 26
- 239000007789 gas Substances 0.000 description 16
- 239000013078 crystal Substances 0.000 description 8
- 238000007747 plating Methods 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011805 ball Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000011806 microball Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009429 electrical wiring Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Description
本発明は、電子部品の接続端子部等に用いるＣｕ微小球の製造方法に関するものである。 The present invention relates to a method for producing Cu microspheres used for connection terminal portions of electronic components.
近年、電子部品の実装密度の高密度化要求に対応するために、パッケージオンパッケージ（ＰＯＰ）やマルチチップモジュール（ＭＣＭ）などの３次元高密度実装の検討が進んでいる。この問題を解決するために、はんだよりも融点が高い、たとえばＣｕからなるコアボールに、はんだを被覆した複合マイクロボールを用いた実装が提案されている。（特許文献１） In recent years, in order to meet the demand for higher mounting density of electronic components, studies on three-dimensional high-density mounting such as package-on-package (POP) and multichip module (MCM) have been advanced. In order to solve this problem, mounting using a composite microball in which a core ball made of, for example, Cu having a melting point higher than that of solder is coated with solder has been proposed. (Patent Document 1)
一方、上述した複合マイクロボールのコアボールとしてのＣｕ微小球の製造には、たとえば本出願人が特許文献２に提案するように、Ｃｕ金属粉末を熱プラズマ中に投入して溶融し、球状凝固させる、所謂熱プラズマ法が提案されている。
特許文献２には、熱プラズマ法を用いて金属微小球の表面酸化層を含む酸素含有量を５０ｐｐｍ以下とすることにより、電気伝導性に優れ、変形抵抗の小さい金属微小球を製造し、電気的な接続信頼性を改善した提案がなされている。この提案は、大量の金属微小球を短時間に製造するという点で優れたものである。
On the other hand, in the manufacture of Cu microspheres as the core ball of the above-described composite microball, for example, as proposed by the present applicant in Patent Document 2, Cu metal powder is put into thermal plasma and melted, and spherical solidification is performed. A so-called thermal plasma method has been proposed.
In Patent Document 2, a metal microsphere having excellent electrical conductivity and low deformation resistance is manufactured by setting the oxygen content including the surface oxide layer of the metal microsphere to 50 ppm or less using a thermal plasma method. Proposals have been made to improve general connection reliability. This proposal is excellent in that it produces a large amount of metal microspheres in a short time.
また、特許文献３には、コアボールに用いるＣｕ微小球の製造方法として、Ｃｕの溶湯をオリフィスから噴出して分散させてＣｕ微小球を形成する、所謂均一液滴噴霧法が提案されている。 Patent Document 3 proposes a so-called uniform droplet spraying method in which a Cu microsphere is formed by ejecting a Cu melt from an orifice and dispersing it as a method for producing a Cu microsphere used for a core ball. .
上述した特許文献２あるいは特許文献３に開示される製造方法は、金属微小球の変形抵抗を下げる点では有利であるものの、金属微小球の表面平滑性の点では、Ｃｕの凝固収縮に起因する引け巣が発生して凹みが生じるという問題があった。この金属微小球の表面に現れる凹みは、その表面にはんだめっき処理を実施する際、ボイドの発生、めっき密着不良などの問題を起こす可能性が高く、金属微小球を接続端子部として用いた電子部品を実用化する上で、電気的な接続信頼性を損なう大きな問題となる。
本発明の目的は、金属微小球の表面に生じる凹みを低減し、表面平滑性の特性を具備した金属微小球の製造方法を提供することである。
Although the manufacturing method disclosed in Patent Document 2 or Patent Document 3 described above is advantageous in reducing the deformation resistance of the metal microspheres, the surface smoothness of the metal microspheres is caused by solidification shrinkage of Cu. There was a problem that a dent occurred due to the formation of shrinkage nests. The dent appearing on the surface of the metal microsphere is highly likely to cause problems such as voids and poor plating adhesion when solder plating is applied to the surface. In putting parts into practical use, this is a major problem that impairs electrical connection reliability.
An object of the present invention is to provide a method for producing metal microspheres having reduced surface dents on the surface of the metal microspheres and having surface smoothness characteristics.
本発明者は、金属微小球の表面凹みの問題を検討し、金属微小球製造時において、Ｃｕ液滴が球状凝固する雰囲気中の酸素濃度を所定の範囲に調整する構成を採用することで、金属微小球の表面凹みが低減でき、表面平滑性を大きく改善できることを見出し本発明に到達した。 The present inventor examines the problem of the surface dent of the metal microsphere, and adopts a configuration that adjusts the oxygen concentration in the atmosphere in which the Cu droplet is solidified into a predetermined range at the time of manufacturing the metal microsphere, The inventors have found that the surface dents of metal microspheres can be reduced and the surface smoothness can be greatly improved, and the present invention has been achieved.
すなわち本発明は、Ｃｕ液滴を、酸素：１０〜８００体積ｐｐｍ、残部不活性ガス雰囲気で球状凝固させる金属微小球の製造方法である。
また、前記酸素は、１２０〜８００体積ｐｐｍであることが好ましい。
また、前記酸素は、２００〜７６０体積ｐｐｍであることが好ましい。
また、前記不活性ガスは、アルゴンであることが好ましい。
また、前記不活性ガスは、窒素であることが好ましい。
また、前記Ｃｕ液滴は、圧力と振動を付与したＣｕ溶湯をオリフィスより滴下して形成することが好ましい。
That is, the present invention is a method for producing metal microspheres in which Cu droplets are spherically solidified in an atmosphere of oxygen: 10 to 800 ppm by volume and the remaining inert gas.
Moreover, it is preferable that the said oxygen is 120-800 volume ppm.
Moreover, it is preferable that the said oxygen is 200-760 volume ppm.
The inert gas is preferably argon.
The inert gas is preferably nitrogen.
The Cu droplet is preferably formed by dropping a molten Cu imparted with pressure and vibration from an orifice.
本発明によれば、金属微小球の表面凹みを低減させ、表面平滑性を飛躍的に改善することができ、金属微小球を接続端子として用いた電子部品の実用化にとって欠くことのできない技術となる。 According to the present invention, the surface dent of the metal microsphere can be reduced, the surface smoothness can be remarkably improved, and the technology indispensable for the practical use of the electronic component using the metal microsphere as the connection terminal. Become.
上述したように、本発明の重要な特徴は、金属微小球の製造時において、Ｃｕ液滴が球状凝固する雰囲気中の酸素濃度を所定の範囲に調整する構成を採用したことにある。 As described above, an important feature of the present invention is that a configuration in which the oxygen concentration in the atmosphere in which the Cu droplets are spherically solidified is adjusted to a predetermined range when the metal microspheres are manufactured.
本発明におけるＣｕ液滴が球状凝固する雰囲気中の酸素濃度は、１０〜８００体積ｐｐｍである。酸素濃度が１０体積ｐｐｍより低い場合、Ｃｕ液滴の凝固収縮時の引け巣により、金属微小球の表面に顕著な凹みが現れる。この表面に現れる凹みは、金属微小球の表面にはんだめっき処理を実施する際、ボイドの発生、めっき密着不良などの問題を起こす原因となる。
また、金属微小球毎の結晶粒サイズにばらつきが生じると、金属微小球毎の機械的特性（強さ、硬さ、靭性など）のばらつきが懸念される。酸素濃度が１２０体積ｐｐｍより低いときには、金属微小球毎の結晶粒サイズにばらつきが生じる場合があり、大きな結晶粒から構成される金属微小球と、小さな結晶粒から構成される金属微小球が混在する場合がある。このため、金属微小球毎の結晶粒サイズのばらつきを低減し、結晶粒サイズを均一微細化するためには、酸素濃度は１２０体積ｐｐｍ以上が好ましい。より好ましくは、２００体積ｐｐｍ以上である。
In the present invention, the oxygen concentration in the atmosphere in which the Cu droplet is solidified spherically is 10 to 800 ppm by volume. When the oxygen concentration is lower than 10 ppm by volume, a noticeable dent appears on the surface of the metal microsphere due to the shrinkage nest at the time of solidification shrinkage of the Cu droplet. The dents appearing on the surface cause problems such as generation of voids and poor plating adhesion when solder plating is performed on the surface of the metal microspheres.
In addition, when the crystal grain size varies for each metal microsphere, there is concern about variations in mechanical properties (strength, hardness, toughness, etc.) for each metal microsphere. When the oxygen concentration is lower than 120 ppm by volume, the crystal size of each metal microsphere may vary, and metal microspheres composed of large crystal grains and metal microspheres composed of small crystal grains are mixed. There is a case. For this reason, the oxygen concentration is preferably 120 ppm by volume or more in order to reduce the variation in crystal grain size for each metal microsphere and make the crystal grain size uniform. More preferably, it is 200 ppm by volume or more.
一方、酸素濃度が８００体積ｐｐｍを超えると、Ｃｕ液滴が球状凝固する際、液滴の表面全体が酸化膜で厚く覆われて自由表面でなくなるため、Ｃｕ液滴が持つ表面張力により真球になる作用が損なわれ、良好な真球度を持つ金属微小球が得られなくなる。したがって、本発明ではＣｕ液滴が球状凝固する雰囲気中の酸素濃度を１０〜８００体積ｐｐｍに調整することで、金属微小球表面の凹みを抑制し、良好な真球度を持つ金属微小球が得られる。また、好ましい酸素濃度は、１２０〜８００体積ｐｐｍであり、より好ましくは２００〜７６０体積ｐｐｍである。 On the other hand, when the oxygen concentration exceeds 800 ppm by volume, when the Cu droplet is solidified spherically, the entire surface of the droplet is thickly covered with an oxide film and is not a free surface. Thus, metal microspheres having good sphericity cannot be obtained. Therefore, in the present invention, by adjusting the oxygen concentration in the atmosphere in which the Cu droplets are spherically solidified to 10 to 800 ppm by volume, dents on the surface of the metal microspheres are suppressed, and metal microspheres having good sphericity are obtained. can get. Moreover, preferable oxygen concentration is 120-800 volume ppm, More preferably, it is 200-760 volume ppm.
また、本発明では、Ｃｕ液滴が球状凝固する雰囲気中における酸素以外の残部ガスを不活性ガスとする。本発明でいう不活性ガスの種類は、アルゴン等の希ガスや窒素をいい、これらを単体もしくは混合して用いることが好ましい。これにより、Ｃｕ液滴の表面酸化を抑制することができ、良好な真球度を持つ金属微小球を得ることが可能となる。本発明でいう不活性ガス以外のガスは、雰囲気中の汚染や酸素と反応する可能性があるため、好ましくない。 In the present invention, the remaining gas other than oxygen in the atmosphere in which Cu droplets are spherically solidified is an inert gas. The kind of the inert gas referred to in the present invention is a rare gas such as argon or nitrogen, and these are preferably used alone or in combination. Thereby, surface oxidation of Cu droplets can be suppressed, and metal microspheres having good sphericity can be obtained. Gases other than the inert gas referred to in the present invention are not preferable because they may react with contamination in the atmosphere and oxygen.
本発明では、Ｃｕ溶湯に圧力と振動を付与してオリフィスより滴下して形成したＣｕ液滴を凝固させることが好ましい。Ｃｕ溶湯を蓄えた坩堝底面にオリフィスを配置し、坩堝内部のＣｕ溶湯に圧力と振動を付与することにより、Ｃｕ溶湯をオリフィスの孔を通して坩堝下部に位置する酸素を適量含有したガス雰囲気内に安定して噴出することができ、所望の体積を持つＣｕ液滴を形成することが可能となる。 In the present invention, it is preferable to solidify Cu droplets formed by applying pressure and vibration to the molten Cu and dropping from the orifice. By placing an orifice on the bottom of the crucible where the molten Cu is stored and applying pressure and vibration to the molten Cu inside the crucible, the molten Cu is stabilized in a gas atmosphere containing an appropriate amount of oxygen located at the bottom of the crucible through the hole in the orifice. Thus, Cu droplets having a desired volume can be formed.
また、本発明でＣｕ溶湯に振動を付与する場合は、Ｃｕ溶湯のオリフィス通過方向への縦振動が好ましい。Ｃｕ溶湯に縦振動を付与することで、一定体積のＣｕ液滴を連続して滴下することが可能となる。また、本発明は、オリフィスの孔径、Ｃｕ溶湯を滴下させるガス圧力、Ｃｕ溶湯に付与する縦振動の振動数をそれぞれ適宜選定することにより、より均一な直径の金属微小球を量産的に得ることが可能となる。 Moreover, when giving a vibration to Cu molten metal by this invention, the longitudinal vibration to the orifice passage direction of Cu molten metal is preferable. By applying longitudinal vibration to the molten Cu, it is possible to continuously drop a certain volume of Cu droplets. In addition, according to the present invention, metal microspheres having a more uniform diameter can be mass-produced by appropriately selecting the orifice hole diameter, the gas pressure for dropping the Cu molten metal, and the frequency of the longitudinal vibration applied to the Cu molten metal. Is possible.
本発明の金属微小球の製造方法の一例を図１に基づいて説明する。図１において、加熱ユニット５を用いて坩堝１内で溶解したＣｕ溶湯６は、坩堝用ガス７により発生させた坩堝１内の圧力と、凝固雰囲気８の圧力の差圧によりオリフィス９を通って凝固チャンバ３内に噴出し、Ｃｕ溶湯からなるジェットを形成する。Ｃｕ溶湯がオリフィス９を通過する前に、振動部材１０を用いてＣｕ溶湯にオリフィス通過方向への縦振動を付与することで、前記Ｃｕ溶湯からなるジェットは層流から脈流に変遷する。脈流として生じたくびれは、Ｃｕ溶湯が持つ表面張力の作用により発達し、最終的に一つのＣｕ液滴１１として、Ｃｕ溶湯に付与した縦振動の振動数に応じた周期で分断される。分断されたＣｕ液滴１１は、凝固チャンバ３内を落下しながら、自身が持つ表面張力の作用により球状化した後凝固し、金属微小球４として回収缶１３に回収される。 An example of the manufacturing method of the metal microsphere of this invention is demonstrated based on FIG. In FIG. 1, the molten Cu 6 melted in the crucible 1 using the heating unit 5 passes through the orifice 9 due to the differential pressure between the pressure in the crucible 1 generated by the crucible gas 7 and the pressure in the solidified atmosphere 8. Jets into the solidification chamber 3 to form a jet made of molten Cu. Before the molten Cu passes through the orifice 9, the vibrating member 10 is used to impart longitudinal vibration to the molten Cu in the direction of passing the orifice, whereby the jet made of the molten Cu changes from laminar flow to pulsating flow. The constriction produced as a pulsating flow develops due to the action of the surface tension of the molten Cu, and finally is divided into a single Cu droplet 11 at a period corresponding to the frequency of the longitudinal vibration applied to the molten Cu. The divided Cu droplet 11 falls into the solidification chamber 3 while being spheroidized by the action of its own surface tension and then solidified, and is collected in the collection can 13 as metal microspheres 4.
本発明では、ガス雰囲気内をＣｕ液滴が落下し、球状凝固して金属微小球が得られる。Ｃｕ液滴が完全に凝固する前に互いに衝突すると、複数の液滴からなる体積を持つ凝集球や、球形が連なった異形球が発生する。この衝突を避けるため、Ｃｕ液滴に電荷を与えて互いに反発させ、分散した状態で落下させても良い。また、ファンによる風力、ガス注入による噴出圧力によりＣｕ液滴を分散させ、衝突を回避しても良い。 In the present invention, Cu droplets fall in the gas atmosphere and solidify spherically to obtain metal microspheres. When the Cu droplets collide with each other before being completely solidified, agglomerated spheres having a volume composed of a plurality of droplets and deformed spheres having a series of spherical shapes are generated. To avoid this collision, the Cu droplets may be repelled by being charged and dropped in a dispersed state. Further, the collision of the Cu droplets may be avoided by dispersing the Cu droplets by the wind force generated by the fan or the jet pressure generated by gas injection.
Ｃｕ液滴が球状凝固するガス雰囲気の圧力については、大気圧が妥当であるが、大気圧プラス０．２ＭＰａからマイナス０．０５ＭＰａの範囲で適宜調整することが好ましい。ガス雰囲気の圧力が大気圧プラス０．２ＭＰａを超えると、このような圧力に耐え得る凝固チャンバが必要となり、装置重量の増大、装置製作コストの増大を招くため、大気圧プラス０．２ＭＰａ以下が好ましい。 As for the pressure of the gas atmosphere in which Cu droplets solidify spherically, atmospheric pressure is appropriate, but it is preferable to appropriately adjust in the range of atmospheric pressure plus 0.2 MPa to minus 0.05 MPa. If the pressure of the gas atmosphere exceeds atmospheric pressure plus 0.2 MPa, a coagulation chamber that can withstand such pressure is required, leading to an increase in the weight of the apparatus and an increase in the cost of manufacturing the apparatus. preferable.
また、ガス雰囲気の圧力が大気圧マイナス０．０５ＭＰａより低いと、Ｃｕ液滴を冷却凝固させるために必要な不活性ガスの分子が不足し、凝固には長い凝固チャンバが必要となり、装置重量の増大、装置製作コストの増大を招くため、大気圧マイナス０．０５ＭＰａ以上が好ましい。 In addition, if the pressure of the gas atmosphere is lower than atmospheric pressure minus 0.05 MPa, the inert gas molecules necessary for cooling and solidifying the Cu droplets are insufficient, and a long solidification chamber is required for solidification. An atmospheric pressure minus 0.05 MPa or more is preferable because it causes an increase in apparatus manufacturing cost.
図１は、本発明の金属微小球の製造方法に適用する製造装置の一例を示す断面模式図である。
図１の製造装置を用いて、純度が９９．９９質量％以上のＣｕ片を坩堝１内に投入し、加熱ユニット５を用いて坩堝１内で溶解したＣｕ溶湯６を、坩堝用ガス７により発生させた坩堝１内の圧力と凝固雰囲気８の圧力の差圧によりオリフィス９から凝固チャンバ３内に噴出させた。このとき、Ｃｕ溶湯６がオリフィス９を通過する前に、振動部材１０を用いてＣｕ溶湯６にオリフィス９通過方向への縦振動を付与してＣｕ液滴１１を滴下した。
そして、ガス置換装置２により凝固チャンバ３内の凝固雰囲気を調整し、目標直径が２００μｍの金属微小球４を以下に示す製造条件で作製した。このとき、オリフィス９より滴下して形成されたＣｕ液滴１１を、ファン１２により風力を与えて分散させながら凝固チャンバ３内を落下させ、自身が持つ表面張力の作用により球状化・凝固した金属微小球４を回収缶１３に回収した。
FIG. 1 is a schematic cross-sectional view showing an example of a manufacturing apparatus applied to the method for manufacturing metal microspheres of the present invention.
Using the manufacturing apparatus of FIG. 1, a Cu piece having a purity of 99.99% by mass or more is charged into the crucible 1, and the molten Cu 6 melted in the crucible 1 using the heating unit 5 is added to the crucible gas 7. The generated pressure in the crucible 1 and the pressure in the coagulation atmosphere 8 were jetted from the orifice 9 into the coagulation chamber 3. At this time, before the Cu melt 6 passed through the orifice 9, the vibration member 10 was used to apply longitudinal vibration in the direction of passage of the orifice 9 to the Cu melt 6 to drop the Cu droplet 11.
And the solidification atmosphere in the solidification chamber 3 was adjusted with the gas displacement apparatus 2, and the metal microsphere 4 with a target diameter of 200 micrometers was produced on the manufacturing conditions shown below. At this time, the Cu droplet 11 formed by dropping from the orifice 9 is dropped in the coagulation chamber 3 while being dispersed by applying wind force from the fan 12, and is spheroidized and solidified by the action of its own surface tension. The microspheres 4 were collected in the collection can 13.
（製造条件）
Ｃｕ金属片投入重量：４００ｇ
凝固雰囲気：アルゴン
凝固雰囲気の酸素濃度：２３９体積ｐｐｍ
凝固雰囲気の圧力：大気圧プラス０．０２ＭＰａ
坩堝内の圧力：大気圧プラス０．２ＭＰａ
坩堝内の温度：１３００℃
(Production conditions)
Cu metal piece input weight: 400 g
Solidification atmosphere: Argon Oxygen concentration in solidification atmosphere: 239 ppm by volume
Solidification atmosphere pressure: atmospheric pressure plus 0.02 MPa
Pressure in the crucible: atmospheric pressure plus 0.2 MPa
Temperature in crucible: 1300 ° C
図２に、上述の製造条件により得られた金属微小球について、走査型電子顕微鏡を用いてその表面の状態を観察した写真を示す。 FIG. 2 shows a photograph of the surface state of the metal microspheres obtained under the above-described manufacturing conditions using a scanning electron microscope.
実施例１と同様の製造装置を用いて、目標直径が２００μｍの金属微小球を以下に示す製造条件で作製した。 Using the same production apparatus as in Example 1, metal microspheres having a target diameter of 200 μm were produced under the production conditions shown below.
（製造条件）
Ｃｕ金属片投入重量：５０９ｇ
凝固雰囲気：アルゴン
凝固雰囲気の酸素濃度：６５６体積ｐｐｍ
凝固雰囲気の圧力：大気圧プラス０．０１ＭＰａ
坩堝内の圧力：大気圧プラス０．２ＭＰａ
坩堝内の温度：１３３０℃
(Production conditions)
Cu metal piece input weight: 509 g
Solidification atmosphere: Argon Oxygen concentration in solidification atmosphere: 656 volume ppm
Solidification atmosphere pressure: atmospheric pressure plus 0.01 MPa
Pressure in the crucible: atmospheric pressure plus 0.2 MPa
Temperature in crucible: 1330 ° C
図３に、上述の製造条件により得られた金属微小球について、走査型電子顕微鏡を用いてその表面の状態を観察した写真を示す。 FIG. 3 shows a photograph of the surface state of the metal microspheres obtained under the manufacturing conditions described above, using a scanning electron microscope.
実施例１と同様の製造装置を用いて、目標直径が２００μｍの金属微小球を以下に示す製造条件で作製した。 Using the same production apparatus as in Example 1, metal microspheres having a target diameter of 200 μm were produced under the production conditions shown below.
（製造条件）
Ｃｕ金属片投入重量：２７００ｇ
凝固雰囲気：アルゴン
凝固雰囲気の酸素濃度：１５、５０、１２０、２００、２４０、３１０体積ｐｐｍ
凝固雰囲気の圧力：大気圧プラス０．０１ＭＰａ
坩堝内の圧力：大気圧プラス０．２ＭＰａ
坩堝内の温度：１２５０℃
(Production conditions)
Cu metal piece input weight: 2700 g
Solidification atmosphere: Argon Oxygen concentration in solidification atmosphere: 15, 50, 120, 200, 240, 310 volume ppm
Solidification atmosphere pressure: atmospheric pressure plus 0.01 MPa
Pressure in the crucible: atmospheric pressure plus 0.2 MPa
Temperature in crucible: 1250 ° C
図４に、上述の製造条件により得られた金属微小球について、走査型電子顕微鏡を用いてその表面の状態を観察した写真を示す。 FIG. 4 shows a photograph of the surface state of the metal microspheres obtained under the manufacturing conditions described above, using a scanning electron microscope.
実施例１と同様の製造装置を用いて、目標直径が２００μｍの金属微小球を以下に示す製造条件で作製した。 Using the same production apparatus as in Example 1, metal microspheres having a target diameter of 200 μm were produced under the production conditions shown below.
（製造条件）
Ｃｕ金属片投入重量：２０００ｇ
凝固雰囲気：窒素
凝固雰囲気の酸素濃度：１６、５１体積ｐｐｍ
凝固雰囲気の圧力：大気圧プラス０．０２ＭＰａ
坩堝内の圧力：大気圧プラス０．１ＭＰａ
坩堝内の温度：１２５０℃
(Production conditions)
Cu metal piece input weight: 2000 g
Solidification atmosphere: Nitrogen Oxygen concentration in solidification atmosphere: 16, 51 volume ppm
Solidification atmosphere pressure: atmospheric pressure plus 0.02 MPa
Pressure in the crucible: atmospheric pressure plus 0.1 MPa
Temperature in crucible: 1250 ° C
図５に、上述の製造条件により得られた金属微小球について、走査型電子顕微鏡を用いてその表面の状態を観察した写真を示す。 FIG. 5 shows a photograph of the surface state of the metal microspheres obtained under the manufacturing conditions described above, using a scanning electron microscope.
比較例として、実施例１と同様の製造装置を用いて、凝固雰囲気の酸素濃度を本発明の範囲より低く設定して目標直径が２００μｍの金属微小球を以下に示す製造条件で作製した。 As a comparative example, using the same production apparatus as in Example 1, metal microspheres having a target diameter of 200 μm were produced under the production conditions shown below, with the oxygen concentration in the solidification atmosphere set lower than the range of the present invention.
（製造条件）
Ｃｕ金属片投入重量：４８２ｇ
凝固雰囲気：アルゴン
凝固雰囲気の酸素濃度：７体積ｐｐｍ
凝固雰囲気の圧力：大気圧プラス０．０１ＭＰａ
坩堝内の圧力：大気圧プラス０．２ＭＰａ
坩堝内の温度：１３３０℃
(Production conditions)
Cu metal piece input weight: 482 g
Solidification atmosphere: Argon Oxygen concentration in solidification atmosphere: 7 ppm by volume
Solidification atmosphere pressure: atmospheric pressure plus 0.01 MPa
Pressure in the crucible: atmospheric pressure plus 0.2 MPa
Temperature in crucible: 1330 ° C
図６に、上述の製造条件により得られた金属微小球について、走査型電子顕微鏡を用いてその表面の状態を観察した写真を示す。 FIG. 6 shows a photograph of the surface state of the metal microspheres obtained under the manufacturing conditions described above, using a scanning electron microscope.
図２から図５に示すように、本発明を適用した金属微小球においては、比較例である図６に対し、金属微小球の表面に現れる凹みが大幅に低減されている。したがって、本発明の金属微小球の製造方法を適用することにより、金属微小球の表面に生じる凹みを低減し、表面平滑性の特性を具備した金属微小球を作製することが可能である。
また、図４中の試料番号４から６は、酸素濃度が２００体積ｐｐｍ以上の凝固雰囲気で製造された金属微小球であり、試料番号１から３と比較すると、金属微小球毎の結晶粒サイズのばらつきが低減され、結晶粒サイズも均一微細化されており、より好ましい表面形態を有していることが確認できた。
このように、表面平滑性の特性を具備した金属微小球は、その表面にはんだめっき処理を実施する際、ボイドの発生、めっき密着不良などの問題を起こす可能性を低減でき、金属微小球を接続端子部として用いた電子部品を実用化する上で、電気的な接続信頼性を大いに向上することが可能となる。
As shown in FIGS. 2 to 5, in the metal microsphere to which the present invention is applied, the dent appearing on the surface of the metal microsphere is greatly reduced compared to FIG. 6 which is a comparative example. Therefore, by applying the method for producing metal microspheres of the present invention, it is possible to reduce the dents generated on the surface of the metal microspheres and to produce metal microspheres having surface smoothness characteristics.
Sample numbers 4 to 6 in FIG. 4 are metal microspheres manufactured in a solidified atmosphere with an oxygen concentration of 200 ppm by volume or more. Compared with sample numbers 1 to 3, the crystal grain size for each metal microsphere is shown in FIG. It was confirmed that the variation in the thickness was reduced, the crystal grain size was uniformly refined, and the surface morphology was more favorable.
Thus, metal microspheres with surface smoothness characteristics can reduce the possibility of problems such as voids and poor plating adhesion when solder plating is applied to the surface. The electrical connection reliability can be greatly improved when the electronic component used as the connection terminal portion is put into practical use.
Ｃｕ液滴が球状凝固する雰囲気中の酸素濃度を所定の範囲に調整する構成を採用することで、表面平滑性を大きく改善した本発明の金属微小球の製造方法は、電子部品の接続端子部に適した金属微小球を提供するものであり、配線基板の多層化や接続端子部の微小化において、電気的な接続信頼性、多層化後の配線基板における寸法精度を向上することが可能となる。
また、金属液滴をガス雰囲気で球状凝固させる金属球の製造方法において、球状凝固する雰囲気中の酸素濃度を調整することによって、表面平滑性に優れたＣｕ以外の金属球の製造にも適用できる。
By adopting a configuration in which the oxygen concentration in the atmosphere in which the Cu droplets are spherically solidified is adjusted to a predetermined range, the method for producing the metal microspheres of the present invention, in which the surface smoothness is greatly improved, Metal microspheres suitable for use in electrical wiring, and it is possible to improve the electrical connection reliability and the dimensional accuracy in the multilayered wiring board when the wiring board is multi-layered and the connection terminal part is miniaturized. Become.
In addition, in the method for producing a metal sphere in which metal droplets are spherically solidified in a gas atmosphere, the method can be applied to the production of metal spheres other than Cu having excellent surface smoothness by adjusting the oxygen concentration in the atmosphere to be spherically solidified. .
１．坩堝、２．ガス置換装置、３．凝固チャンバ、４．金属微小球、５．加熱ユニット、６．Ｃｕ溶湯、７．坩堝用ガス、８．凝固雰囲気、９．オリフィス、１０．振動部材、１１．Ｃｕ液滴、１２．ファン、１３．回収缶 1. Crucible, 2. 2. gas displacement device; Coagulation chamber; 4. 4. metal microspheres; 5. heating unit; 6. Cu melt, Gas for crucible, 8. 8. solidification atmosphere; Orifice, 10. 10. vibration member; Cu droplet, 12. Fan, 13. Collection can
Claims (5)
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