JP2013187508A - Silver bonding wire and method of manufacturing the same - Google Patents
Silver bonding wire and method of manufacturing the same Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229910052709 silver Inorganic materials 0.000 title abstract description 6
- 239000004332 silver Substances 0.000 title description 3
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 238000005491 wire drawing Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000005266 casting Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- 150000001247 metal acetylides Chemical class 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 239000010931 gold Substances 0.000 description 23
- 239000012298 atmosphere Substances 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 4
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- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 238000005275 alloying Methods 0.000 description 1
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- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
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- 239000011261 inert gas Substances 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
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- H01L2224/451—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
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- H01L2924/1025—Semiconducting materials
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- H01L2924/12—Passive devices, e.g. 2 terminal devices
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Abstract
Description
本発明は、半導体素子の電極と基板の電極とを接続するＡｇボンディングワイヤに関し、特にＬＥＤ素子上の電極と基板の電極とを接続するのに好適なＬＥＤパッケージ用Ａｇボンディングワイヤに関するものである。 The present invention relates to an Ag bonding wire for connecting an electrode of a semiconductor element and an electrode of a substrate, and more particularly to an Ag bonding wire for an LED package suitable for connecting an electrode on an LED element and an electrode of a substrate.
一般に半導体素子上の電極と、基板の電極との結線に用いられるボンディングワイヤの直径は２０〜３０μｍと非常に細く、そのため、導電性が良く、加工性に優れた金属材料が用いられている。特に、化学的な安定性や大気中での取り扱いやすさから、従来はＡｕ製のボンディングワイヤ（以下、Ａｕボンディングワイヤと称す）が用いられてきた。
しかし、Ａｕボンディングワイヤは重量の９９％から９９．９９％がＡｕであるため非常に高価であり、コスト面からボンディングワイヤ用の材料として安価な材料に替えたいという強い要請が成されていた。
In general, the diameter of a bonding wire used for connection between an electrode on a semiconductor element and an electrode on a substrate is as very thin as 20 to 30 μm. Therefore, a metal material having good conductivity and excellent workability is used. In particular, an Au bonding wire (hereinafter referred to as an Au bonding wire) has been used because of its chemical stability and ease of handling in the atmosphere.
However, the Au bonding wire is very expensive because 99 to 99.99% of the weight is Au, and there has been a strong demand to replace the bonding wire with an inexpensive material in terms of cost.
さらに近年、ＬＥＤ素子をマウントしたＬＥＤパッケージは低消費電力という長所を活かして表示用から照明用としての用途が活発に検討されてきていた。その検討に当たり、投入電力あたりの発光効率を高めるためには、ＬＥＤパッケージ内に使用する金属、たとえば光反射板の反射率を高めるために、その材質を光反射率が約７１％のＡｌから約９５％のＡｕへ、さらには約９７％のＡｇへと変更されてきている。 Furthermore, in recent years, LED packages mounted with LED elements have been actively studied for applications from display to lighting, taking advantage of the low power consumption. In the examination, in order to increase the luminous efficiency per input power, in order to increase the reflectance of the metal used in the LED package, for example, the light reflector, the material is changed from Al having a light reflectance of about 71%. It has been changed to 95% Au, and further to about 97% Ag.
このような状況の中、素子の電極と基板の電極を結線するボンディングワイヤの材質を「Ａｕ」から「Ａｇ」へ変更することによって、ＬＥＤパッケージとしての明るさが数パーセント向上することが知見された。そのため、早急なＡｇボンディングワイヤへの変更が求められているが、Ａｇは光反射率は高いものの、高温環境下での強度が低い、あるいは熱サイクルによる疲労に弱いという機械的特性上の欠点があり、パーソナルコンピューターや液晶テレビのディスプレイ用のバックライトあるいは照明用としてはまだ実用化に至っていない。 Under such circumstances, it has been found that the brightness of the LED package is improved by several percent by changing the material of the bonding wire connecting the element electrode and the substrate electrode from “Au” to “Ag”. It was. For this reason, there is a demand for an immediate change to an Ag bonding wire, but Ag has a high light reflectivity, but has a disadvantage in mechanical properties such as low strength in high temperature environments or weakness against fatigue due to thermal cycling. Yes, it has not yet been put to practical use as a backlight or lighting for personal computers and LCD TV displays.
ところで、ＬＥＤパッケージの封止材に使用される従来タイプの透明シリコーン樹脂の熱膨張係数は、ＩＣやＬＳＩパッケージに使用されるエポキシ樹脂が６〜１９ｐｐｍ／Ｋであるのに対して２００〜４００ｐｐｍ／Ｋと非常に大きい。
また、ＩＣやＬＳＩパッケージではパッケージの熱膨張率をシリコンチップに近い値まで下げるために無機微小シリコーンフィラーの充填が行われているが、ＬＥＤパッケージでは光透過性が重要であるため、熱膨張率の調製に無機微小シリコーンフィラーを充填することは難しく、そのため、ＬＥＤパッケージはＩＣに比べて熱膨張変化が大きく、封止されているボンディングワイヤは大きな熱ストレスを受けやすく、従ってボンディングワイヤに使用する金属材料には繰り返し応力による疲労耐性が要求されるが、Ａｇボンディングワイヤにおいては、この疲労耐性向上と光反射率とのトレードオフが実用化に際しての難しい大きな理由である。
By the way, the thermal expansion coefficient of the conventional type transparent silicone resin used for the sealing material of the LED package is 200 to 400 ppm / k compared with 6 to 19 ppm / K for the epoxy resin used for the IC or LSI package. K and very large.
In addition, in IC and LSI packages, inorganic fine silicone filler is filled to reduce the thermal expansion coefficient of the package to a value close to that of a silicon chip. However, in LED packages, light transmission is important. It is difficult to fill with inorganic fine silicone filler in the preparation of the LED, so that the LED package has a large thermal expansion change compared with the IC, and the sealed bonding wire is easily subjected to a large thermal stress, and therefore is used for the bonding wire. A metal material is required to have fatigue resistance due to repeated stress. However, in the case of an Ag bonding wire, the trade-off between this improvement in fatigue resistance and light reflectivity is a major reason for practical use.
そこで、その機械的特性の改善を目指して、原料の結晶粒を微細化して機械的特性を改善したＡｇボンディングワイヤとして、Ｃｕ、Ｐｄ、Ａｕなどを合計で５００〜３０００重量ｐｐｍ（０．０５〜０．３重量％）添加したＡｇ合金ボンディングワイヤが提案されている（例えば、特許文献１など参照）。しかし、このＡｇボンディングワイヤでは、ボンディング時に５％水素を含む還元雰囲気中でなければ真球状のボールを得ることが出来ず、設備インフラの投資を必要としない窒素ガス雰囲気でも真球状のボールが形成できるＡｇボンディングワイヤが求められた。 Therefore, with the aim of improving the mechanical properties, Cu, Pd, Au, etc. are added in a total of 500 to 3000 ppm by weight (0.05 to 0.05) as an Ag bonding wire in which the crystal grains of the raw material are refined to improve the mechanical properties. A 0.3 wt%) added Ag alloy bonding wire has been proposed (see, for example, Patent Document 1). However, with this Ag bonding wire, a spherical ball cannot be obtained unless it is in a reducing atmosphere containing 5% hydrogen during bonding, and a spherical ball is formed even in a nitrogen gas atmosphere that does not require investment in equipment infrastructure. A possible Ag bonding wire was sought.
そのような窒素ガス中でボールが形成できるＡｇボンディングワイヤとして、Ａｕが４〜１０重量％、Ｐｄが２〜５重量％、酸化性非貴金属添加元素が１５〜７０質量ｐｐｍのＡｇ合金ボンディングワイヤが提案されている（例えば、特許文献２や３など参照）が、特許文献３に記載のＡｇボンディングワイヤでは窒素ガス中でのボール形成性、高温環境下での機械的特性、さらにはアルミニウム電極との接合信頼性は良好であったが、ＬＥＤ市場が要求するＬＥＤパッケージとしての明るさは、従来のＡｇボンディングワイヤに劣ってしまっている。
そこで、ＬＥＤ市場ではＬＥＤパッケージとしての明るさがより得られるＡｇボンディングワイヤの光反射率の向上が強く求められている。
As an Ag bonding wire capable of forming a ball in such nitrogen gas, an Ag alloy bonding wire having 4 to 10% by weight of Au, 2 to 5% by weight of Pd, and 15 to 70 ppm by mass of an oxidizing non-noble metal additive element is available. Proposed (see, for example, Patent Documents 2 and 3), however, the Ag bonding wire described in Patent Document 3 has ball-forming properties in nitrogen gas, mechanical properties in a high-temperature environment, and an aluminum electrode. However, the brightness of the LED package required by the LED market is inferior to that of conventional Ag bonding wires.
Thus, in the LED market, there is a strong demand for improvement in the light reflectance of Ag bonding wires that can provide more brightness as an LED package.
本発明は、素子上の電極との接合信頼性や、ＬＥＤパッケージに対して、実際に行われるマイナス４０℃からプラス１２５℃などの温度を交互に印加して行う熱サイクル試験を満足すると共に、ＬＥＤパッケージとしての明るさ改善するＡｇボンディングワイヤを提供することを目的とする。 The present invention satisfies the thermal cycle test performed by alternately applying a temperature of minus 40 ° C. to plus 125 ° C., which is actually performed, to the LED package and the reliability of bonding with the electrode on the element. An object of the present invention is to provide an Ag bonding wire that improves brightness as an LED package.
上記課題を解決するために、本発明に係る第１の発明のＡｇボンディングワイヤは、Ａｕを１．０質量％以上、３．０質量％以下、Ｐｄを０．０５質量％以上、１．０質量％以下、Ｂｅを１質量ｐｐｍ以上、８質量ｐｐｍ以下、Ｃａを１質量ｐｐｍ以上、２０質量ｐｐｍ以下含有し、残部がＡｇ及び不可避不純物からなることを特徴とするものである。 In order to solve the above-mentioned problems, the Ag bonding wire according to the first aspect of the present invention includes Au in an amount of 1.0 mass% to 3.0 mass%, Pd in an amount of 0.05 mass% to 1.0 mass%. It is characterized in that it contains 1 mass ppm or more, 8 mass ppm or less, Ca 1 mass ppm or more and 20 mass ppm or less, and the balance is made of Ag and inevitable impurities.
本発明の第２の発明に係るＡｇボンディングワイヤは、Ａｕを１．０質量％以上、３．０質量％以下、Ｐｄを０．０５質量％以上、１．０質量％以下、Ｂｅを１質量ｐｐｍ以上、８質量ｐｐｍ以下、Ｃａを１質量ｐｐｍ以上、２０質量ｐｐｍ以下含有し、Ｃｅ、Ｌａをいずれか又は両者を合計で１質量ｐｐｍ以上、２０質量ｐｐｍ以下含有し、残部がＡｇ及び不可避不純物からなることを特徴とするものである。 In the Ag bonding wire according to the second aspect of the present invention, Au is 1.0% by mass or more and 3.0% by mass or less, Pd is 0.05% by mass or more and 1.0% by mass or less, and Be is 1% by mass. Contains at least ppm and at most 8 mass ppm, contains at least 1 mass ppm and at most 20 mass ppm of Ca, contains either Ce or La or a total of at least 1 mass ppm and at most 20 mass ppm, with the balance being Ag and inevitable It consists of impurities.
本発明の第３の発明に係るＬＥＤパッケージ用Ａｇボンディングワイヤは、第１及び第２の発明におけるＡｇボンディングワイヤのワイヤ表面に、酸化物または炭化物などの介在物が存在しないことを特徴とするものである。 An Ag bonding wire for an LED package according to a third aspect of the present invention is characterized in that inclusions such as oxides or carbides are not present on the surface of the Ag bonding wire in the first and second aspects. It is.
本発明の第４の発明は、第３の発明におけるＬＥＤパッケージ用Ａｇボンディングワイヤの製造方法であって、溶解鋳造工程で得られたインゴットを、伸線工程に供する前に、皮剥ダイス加工による表面研削を行い、インゴットの表面介在物を除去することを特徴とするものである。 A fourth invention of the present invention is a method for producing an Ag bonding wire for an LED package according to the third invention, wherein the ingot obtained in the melt casting process is subjected to a surface by peeling dies before being subjected to the wire drawing process. Grinding is performed to remove surface inclusions from the ingot.
本発明の第５の発明は、第４の発明における溶解鋳造工程により所定の径に形成されたインゴットに、複数回の皮剥ダイス加工を施し、次いで伸線加工と、材料の軟化を目的とした熱処理を繰り返し少なくとも１回施して、最終線径に加工した後、伸び率を調整する仕上げ熱処理を施すことを特徴とするＬＥＤパッケージ用Ａｇボンディングワイヤの製造方法である。 The fifth invention of the present invention aims at subjecting the ingot formed to a predetermined diameter by the melt casting process in the fourth invention to a plurality of stripping dies, followed by wire drawing and softening of the material. A method for producing an Ag bonding wire for an LED package, characterized in that after heat treatment is repeated at least once and processed to a final wire diameter, a finish heat treatment is performed to adjust elongation.
本発明に係るＡｇボンディングワイヤは、ＬＥＤパッケージ用ボンディングワイヤとして好適なもので、Ａｕを１．０質量％以上、３．０質量％以下含むことにより、１００％窒素ガス中でもボール形成が容易で、Ｐｄを０．０５質量％以上、１．０質量％以下含むことにより、ＬＥＤパッケージ内に設置される場合があるツェナーダイオード素子上のアルミニウム電極との接合信頼性にも優れ、Ｂｅを１質量ｐｐｍ以上、８質量ｐｐｍ以下、且つＣａを１質量ｐｐｍ以上、２０質量ｐｐｍ以下含むことによって、細線でもワイヤ強度が高いためボンディング後のボールシア強度やワイヤプル強度も高く、またＣｅ、Ｌａのいずれか又は両者を合計で１質量ｐｐｍ以上、２０質量ｐｐｍ以下含むことによって、熱サイクル試験における疲労耐性が高いという優れた効果を奏するもので、ＬＥＤパッケージ用のボンディングワイヤとして好適なものである。 The Ag bonding wire according to the present invention is suitable as a bonding wire for an LED package. By containing Au in an amount of 1.0% by mass or more and 3.0% by mass or less, ball formation is easy even in 100% nitrogen gas, By including 0.05 mass% or more and 1.0 mass% or less of Pd, it is excellent in bonding reliability with an aluminum electrode on a Zener diode element that may be installed in an LED package, and Be is 1 mass ppm. As described above, by including 8 mass ppm or less and Ca by 1 mass ppm or more and 20 mass ppm or less, the wire strength is high even in a thin wire, so that the ball shear strength and wire pull strength after bonding are also high, and either or both of Ce and La Containing 1 mass ppm or more and 20 mass ppm or less in total, In which excellent effects of high, is suitable as a bonding wire for an LED package.
さらに、ＡｇはＡｕよりも溶解鋳造時に酸化物や炭化物の介在物の巻き込みが発生しやすく、溶解鋳造時の酸化物介在物はインゴット表面に偏析して縮径のための伸線工程において破砕されてボンディングワイヤ表面に残留し、大きいものでは５μｍ程度の介在物が観察される場合もあって、接合性不良の原因となったり光反射率低下の原因となり、特に０．１μｍ以上の介在物は著しく接合性を低下させるが、本発明では、それらの介在物を製造工程の初期で除去することにより、接合性が非常に良好で光反射率の高いＡｇボンディングワイヤとなり、ＬＥＤパッケージの光度を高める効果を奏するものである。 Further, Ag is more likely to involve oxide and carbide inclusions during melting casting than Au, and oxide inclusions during melting casting segregate on the ingot surface and are crushed in the wire drawing process for diameter reduction. In some cases, inclusions of about 5 μm are observed on the surface of the bonding wire, which may cause poor bonding or decrease in light reflectivity. In particular, inclusions of 0.1 μm or more In the present invention, by removing these inclusions at the initial stage of the manufacturing process, an Ag bonding wire having very good bonding properties and high light reflectance is obtained, and the luminous intensity of the LED package is increased. There is an effect.
本発明に係るＡｇボンディングワイヤに用いる原料のＡｇは、電気比抵抗の上昇や溶解鋳造後の酸化性介在物の低減を図る目的のため、純度９９．９９質量％以上の高純度のＡｇを使用するのが好ましい。
その溶解鋳造は、介在物除去に適する下抜きの真空溶解連続鋳造炉を用いて、純度９９．９９９％以上のカーボン製ルツボを使用し、酸化を防止するために雰囲気を真空度１×１０−４Ｐａ以下にした高周波溶解法にて行い、発生するガス成分の除去のために、溶湯温度を１１００℃以上、溶湯での保持時間を１０分以上の条件で行い、十分に脱ガスした後に、窒素ガスなどの不活性ガスを注入して大気圧に戻して鋳造すると良い。
The raw material Ag used in the Ag bonding wire according to the present invention uses high-purity Ag with a purity of 99.99% by mass or more for the purpose of increasing electrical resistivity and reducing oxidative inclusions after melt casting. It is preferable to do this.
The melting casting uses a carbon crucible having a purity of 99.999% or more using a vacuum melting continuous casting furnace suitable for removing inclusions, and the atmosphere is 1 × 10 − in order to prevent oxidation. Performed by a high-frequency melting method at 4 Pa or less, and in order to remove the generated gas components, the molten metal temperature was 1100 ° C. or higher, the holding time in the molten metal was 10 minutes or longer, and after sufficient degassing, An inert gas such as nitrogen gas may be injected to return to atmospheric pressure and cast.
さらに、鋳造に際しては銀表面の酸化や添加した合金化元素の酸化を抑制するため、水冷による鋳型部の一次冷却のみならず、大気中に引き出す前に室温まで冷却するために二次冷却を行うのが好ましい。 Furthermore, in order to suppress the oxidation of the silver surface and the added alloying elements during casting, not only the primary cooling of the mold part by water cooling but also the secondary cooling to cool to the room temperature before drawing it into the atmosphere. Is preferred.
また、含有量が微量なＢｅ、Ｃａ、Ｃｅ、Ｌａなどは、予めＡｇあるいはＡｕとの固溶限内での合金を調合用母材として用いるのが添加元素の均一分散化あるいは酸化物あるいは炭化物介在物の除去といった理由から好ましい。 In addition, for Be, Ca, Ce, La, etc. with a small amount of content, it is possible to use an alloy within the solid solubility limit of Ag or Au in advance as a base material for blending, or to uniformly disperse the additive elements or oxides or carbides. It is preferable for reasons such as removal of inclusions.
本発明におけるＡｇボンディングワイヤにおいて、Ａｕ含有量が１．０質量％未満では、１００％窒素中でのプラズマ放電加熱によるボール形成で真球状のボールが得られず、３．０質量％を超えると光反射率が低下するために、Ａｕ含有量は、１．０質量％以上３．０質量％以下と限定した。 In the Ag bonding wire of the present invention, when the Au content is less than 1.0% by mass, a spherical ball cannot be obtained by ball formation by plasma discharge heating in 100% nitrogen, and when it exceeds 3.0% by mass. In order to reduce the light reflectance, the Au content was limited to 1.0 mass% or more and 3.0 mass% or less.
一方、Ｐｄの含有量を０．０５質量％以上１．０質量％以下と限定するのは、ＬＥＤパッケージ内にアルミニウム電極を備える素子、例えばツェナーダイオード素子などを収納した場合、そのアルミニウム電極との接合信頼性を確保するためで、Ｐｄ含有量が０．０５質量％未満では効果が見られず、１．０質量％を越えると光反射率の顕著な低下を招くため、Ｐｄ含有量は０．０５質量％以上、１．０質量％以下とするものである。 On the other hand, the content of Pd is limited to 0.05% by mass or more and 1.0% by mass or less when an element having an aluminum electrode, such as a Zener diode element, is accommodated in the LED package. In order to ensure the bonding reliability, if the Pd content is less than 0.05% by mass, no effect is observed. If the Pd content exceeds 1.0% by mass, the light reflectivity is significantly reduced, so the Pd content is 0%. 0.05 mass% or more and 1.0 mass% or less.
さらに含有量が微量なＢｅでは、１質量ｐｐｍ以上、８質量ｐｐｍ以下、且つＣａでは１質量ｐｐｍ以上、２０質量ｐｐｍ以下と限定するのは、それぞれ１質量ｐｐｍ未満で含有しても、強度の向上は認められないが、Ｂｅを８質量ｐｐｍ以下かつＣａを２０質量ｐｐｍ以下の範囲で含むことによって、高温及び熱間での強度が向上する上、大気中における加熱によってもワイヤ表面の含有元素による酸化を抑制するためである。Ｂｅが８質量ｐｐｍを超えても、Ｃａが２０質量ｐｐｍを超えても、大気中における加熱によってワイヤ表面での含有元素の酸化が発生し、肉眼での変色は認められないが光反射率の低下が生じる。そのためにＢｅの含有量は１質量ｐｐｍ以上、８質量ｐｐｍ以下、且つＣａの含有量は１質量ｐｐｍ以上、２０質量ｐｐｍ以下とする。 Furthermore, in the case of a very small amount of Be, it is limited to 1 mass ppm or more and 8 mass ppm or less, and Ca is limited to 1 mass ppm or more and 20 mass ppm or less. Although no improvement is observed, the inclusion of Be in the range of 8 ppm by mass or less and Ca in the range of 20 ppm by mass or less improves the strength at high temperature and heat, and the elements contained on the wire surface by heating in the atmosphere. This is to suppress oxidation due to oxidization. Even if Be exceeds 8 mass ppm or Ca exceeds 20 mass ppm, oxidation of the contained elements on the surface of the wire occurs due to heating in the atmosphere, and no discoloration is observed with the naked eye. A decrease occurs. Therefore, the content of Be is 1 mass ppm or more and 8 mass ppm or less, and the content of Ca is 1 mass ppm or more and 20 mass ppm or less.
Ｃｅ、Ｌａのいずれか又は両者を合計で１質量ｐｐｍ以上、２０質量ｐｐｍ以下含有するのは、疲労耐性の向上が目的であり、１質量ｐｐｍ未満では効果が無く、２０質量ｐｐｍを超えると大気中における加熱によってワイヤ表面に酸化が発生し、光反射率が低下するため、合計で１質量ｐｐｍ以上２０質量ｐｐｍ以下とする。 Containing one or both of Ce and La in a total of 1 mass ppm or more and 20 mass ppm or less is for the purpose of improving fatigue resistance, and if it is less than 1 mass ppm, there is no effect, and if it exceeds 20 mass ppm, the atmosphere Since oxidation occurs on the surface of the wire due to heating inside, and the light reflectance decreases, the total content is set to 1 mass ppm or more and 20 mass ppm or less.
さらに、酸化物や炭化物の介在物は、溶解鋳造時に形成されたインゴット表面に発生するため、そのまま伸線を行うと介在物をインゴット内部へめり込ませるのみならずダイス磨耗を促進するため、発生した介在物は伸線工程前に除去することが望ましく、溶解鋳造工程と伸線工程との間で表面研削を行い、介在物を除去する。
その表面研削の方法としては、化学研摩法やブラスト処理もあるが、伸線加工機を用いて線材表面をダイヤモンドや超鋼合金の内周刃によってそぎ落とす皮剥ダイス加工が簡易で好ましい。
Furthermore, since oxide and carbide inclusions are generated on the surface of the ingot formed at the time of melt casting, not only do inclusions squeeze into the ingot but also promote die wear. The generated inclusions are desirably removed before the wire drawing step, and the inclusions are removed by performing surface grinding between the melt casting step and the wire drawing step.
As the surface grinding method, there are a chemical polishing method and a blasting method, but a stripping die processing in which the surface of the wire is scraped off with an inner peripheral blade of diamond or super steel alloy using a wire drawing machine is simple and preferable.
また、連続伸線加工の途中で軟化熱処理を行う場合には、窒素ガス中で熱処理を行ったり、酸化防止剤あるいは変色防止剤などがワイヤ表面に塗布された状態で行ったり、ワイヤの酸化を抑制することが好ましい。ただしワイヤ表面の薄い酸化層は介在物と異なり伸線加工中に自然に剥離除去されるので、伸線潤滑剤は常時フィルタリングして用いることが望ましい。
以上のような介在物の除去作業や表面の酸化防止策により、０．１μｍ以上の介在物は除去され、その線肌は全面が金属面となって、ＬＥＤパッケージ組立後には安定した光度を得ることができる。
以下、本発明に係るＡｇボンディングワイヤについて実施例を用いて詳細に説明する。
When softening heat treatment is performed in the middle of continuous wire drawing, heat treatment is performed in nitrogen gas, an antioxidant or a discoloration inhibitor is applied to the wire surface, or the wire is oxidized. It is preferable to suppress. However, since the thin oxide layer on the wire surface is peeled and removed naturally during wire drawing unlike the inclusions, it is desirable to always use the wire drawing lubricant after filtering.
Due to the above-described removal of inclusions and anti-oxidation measures on the surface, inclusions of 0.1 μm or more are removed, and the entire surface of the line becomes a metal surface to obtain a stable luminous intensity after the assembly of the LED package. be able to.
Hereinafter, the Ag bonding wire according to the present invention will be described in detail using examples.
表１に、実施例で用いたＡｇボンディングワイヤの各種添加元素、添加量、皮剥加工有無を示す。
表１で「皮剥加工あり」と記された試料は、溶解鋳造された８ｍｍ径のインゴットを４回に分けて皮剥ダイスを用いて表面切削してから伸線加工を行った。
Table 1 shows various additive elements, additive amounts, and presence / absence of stripping of the Ag bonding wire used in the examples.
The samples marked “with skinning” in Table 1 were subjected to wire drawing after the melt-cast 8 mm diameter ingot was divided into 4 portions and surface-cut using a skinning die.
４回の皮剥ぎを通して、トータルでの切削厚みは約０．４ｍｍであり、インゴット表面に換算すると約０．３７ｍｍの深さまでの研削にあたる。これによってインゴットは介在物の無いインゴットとなり、この後伸線加工によって約１ｍｍ径まで縮径し、表面に介在物の無い素線とした。 The total cutting thickness is about 0.4 mm through four times of skinning, which corresponds to grinding to a depth of about 0.37 mm in terms of the ingot surface. As a result, the ingot became an ingot having no inclusions, and thereafter the diameter was reduced to about 1 mm by wire drawing to form a strand having no inclusions on the surface.
次に、連続伸線加工によって一気に約０．２ｍｍまで縮径し、引き続いて長さ８００ｍｍの窒素雰囲気炉で連続熱処理を行い約２０％の伸び率まで軟化させ、次に連続伸線によって２５μｍまで縮径し、引き続いて長さ５００ｍｍの窒素雰囲気炉で連続熱処理を行い約１０％の伸び率まで軟化させ、試料とした。 Next, the diameter is reduced to about 0.2 mm at a stretch by continuous wire drawing, and subsequently subjected to continuous heat treatment in a nitrogen atmosphere furnace having a length of 800 mm to soften to an elongation of about 20%, and then to 25 μm by continuous wire drawing. The sample was reduced in diameter and subsequently subjected to continuous heat treatment in a nitrogen atmosphere furnace having a length of 500 mm to soften it to an elongation of about 10%, thereby preparing a sample.
各試料の評価は、銀ボンディングワイヤ先端に窒素ガスを吹き付けながら放電プラズマ加熱によってボール形成できる株式会社新川製「ＵＴＣ−１０００」を使い、ボンディングして評価した。
放電条件は窒素ガス流量を０．５リットル／分とし、直径５０μｍのボールが得られるように放電電流を調整し、潰しボールの直径が７５μｍで厚みが１０μｍとなるようにＬＥＤ素子上の金電極面にボールボンディングを行った。
また、アルミニウム電極との接合信頼性については、シリコンチップ上のＡｌ−０．５質量％Ｃｕ電極面に同様にボールボンディングを行った。
ボール形状については顕微鏡にて球形か鏃形か、さらにボール底部への尖りの発生有無を観察し、球形で尖りの無い場合を○、鏃形もしくは尖りが発生した場合には×と判断した。
Each sample was evaluated by bonding using “UTC-1000” manufactured by Shinkawa Co., Ltd., which can form a ball by discharge plasma heating while blowing nitrogen gas to the tip of the silver bonding wire.
The discharge conditions are such that the nitrogen gas flow rate is 0.5 liter / min, the discharge current is adjusted so that a ball with a diameter of 50 μm is obtained, and the gold electrode on the LED element is such that the diameter of the crushed ball is 75 μm and the thickness is 10 μm. Ball bonding was performed on the surface.
For bonding reliability with the aluminum electrode, ball bonding was similarly performed on the Al-0.5 mass% Cu electrode surface on the silicon chip.
With respect to the ball shape, it was determined whether it was spherical or saddle-shaped with a microscope, and whether or not the ball bottom was sharpened. A spherical shape with no sharpness was judged as ◯, and a saddle shape or sharpness was judged as x.
プル強度は、Ｄａｇｅ社製の「Ｄａｇｅ−ＳＥＲＩＥＳ−５０００」を用いて測定した。
その評価は、従来ＬＥＤ用ワイヤで広く使用されているＡｕ線のプル強度９．２ｇｆよりも１０％以上高い場合を良（○印）、１０％未満で高い場合を可（△印）、Ａｕ線のプル強度９．２ｇｒｆより低い場合を不良（×印）と判断した。
シア強度もＤａｇｅ社製の「Ｄａｇｅ−ＳＥＲＩＥＳ−５０００」を用いて測定し、従来ＬＥＤ用ワイヤで広く使用されているＡｕ線のシア強度４８．８ｇｆよりも１０％以上高い場合を良（○印）、１０％未満で高い場合を可（△印）、Ａｕ線のシア強度４８．８ｇｒｆより低い場合を不良（×印）と判断した。
The pull strength was measured using “Dage-SERIES-5000” manufactured by Dage.
The evaluation is good when the pull strength of the Au wire widely used in LED wires is 9.2 gf by 10% or more (◯ mark), and when it is less than 10% (△ mark). The case where the pull strength of the line was lower than 9.2 grf was judged as defective (x mark).
The shear strength is also measured using “Dage-SERIES-5000” manufactured by Dage, and the case where the shear strength is 10% or more higher than the shear strength of 48.8 gf of Au wire widely used in LED wires in the past is acceptable (marked with ○) ) It was judged that the case of less than 10% and high was acceptable (Δ mark), and the case where it was lower than the shear strength of Au wire 48.8grf was judged as defective (× mark).
接合信頼性は、ヤマト科学株式会社製の「オーブンＤＫＭ６００」を用い、１７５℃で２４０時間で高温放置した後、シア強度を測定し、単位面積当たりシア強度が７．０ｋｇ／ｍｍ２以上を良（○印）、７．０ｋｇ／ｍｍ２未満を不良（×印）と判断した。 The bonding reliability was measured by using “Oven DKM600” manufactured by Yamato Scientific Co., Ltd., left at 175 ° C. for 240 hours, and then measuring the shear strength. If the shear strength per unit area was 7.0 kg / mm 2 or higher (Circle mark) and less than 7.0 kg / mm < 2 > were judged to be bad (* mark).
ＬＥＤパッケージ組み立てメーカーが行う疲労耐性試験は、ＬＥＤパッケージの熱サイクル試験における樹脂の膨張収縮によるワイヤの疲労破壊試験であるが、簡易的に行える代理特性として、室温におけるワイヤの繰り返し引っ張り試験による破断までの引張回数を、株式会社オリエンテック製の「万能引張圧縮試験機 テンシロンＲＴＣ−１１５０Ａ」を用いて測定した。
具体的には試料ワイヤを引張り、試料の破断強度の９５％の張力となったところで一旦元に戻すという繰り返し引張試験を行い、破断までの平均引張回数を測定するもので、従来ＬＥＤ用ワイヤで広く使用されているＡｕ線の破断までの平均引張回数１５５回よりも低い場合を不良（×印）、１５５回以上２００回未満を可（△印）、２００回以上３００回未満を良（○印）、３００回以上を優（◎印）と評価した。
The fatigue resistance test conducted by the LED package assembly manufacturer is a fatigue test of the wire due to the expansion and contraction of the resin in the thermal cycle test of the LED package. Was measured using “Universal Tension / Compression Tester Tensilon RTC-1150A” manufactured by Orientec Co., Ltd.
Specifically, the sample wire is pulled and a tensile test is performed in which the tensile strength is 95% of the breaking strength of the sample. The case where the average number of times of tension until the break of the widely used Au wire is lower than 155 times is poor (x mark), 155 times or more and less than 200 times are acceptable (Δ mark), and 200 times or more and less than 300 times are good (○ ) And more than 300 times were evaluated as excellent (（).
光度は、ボンディング後にフェニル系透明シリコーン樹脂でＬＥＤパッケージに組み立てた後、ケイエルブイ株式会社製「分光放射測定システム ＯＬ７７０−ＬＥＤ」を用いて光度を測定して評価した。
従来のＡｕ線を使用したパッケージの光度を１００％としたとき、１００％以上１０２％未満で明るい場合を可（△印）、１０２％以上１０３％未満で明るい場合を良（○印）、１０３％以上で明るい場合を優（◎印）と評価した。
以上の測定結果を纏めて表２に示す。
The luminous intensity was evaluated by measuring the luminous intensity by using a “spectroscopic radiation measurement system OL770-LED” manufactured by KL Buoy Co., Ltd. after assembling the LED package with a phenyl-based transparent silicone resin after bonding.
When the luminous intensity of a package using a conventional Au wire is 100%, it can be bright when it is 100% or more and less than 102% (Δ mark), and can be bright when it is 102% or more and less than 103% (◯ mark). The case where it was brighter than% was evaluated as excellent (（).
The above measurement results are summarized in Table 2.
［評価］
皮剥加工を行った実施例の試料番号１から１０のワイヤを光学顕微鏡で観察したところ、非常に金属光沢があり、任意の５箇所の表面をそれぞれ５ｍｍ長にわたって走査電子顕微鏡で観察したところ、０．１μｍ以上の大きさの介在物は観察されなかった。
一方、皮剥加工を行わなかった実施例の試料番号１１から１９のワイヤでは、同様の走査電子顕微鏡による観察で０．１μｍ以上の介在物が５箇所すべてで観察された。
また、皮剥加工を行った比較例の試料番号２５から２８のワイヤについては、走査電子顕微鏡による観察では０．１μｍ以上の介在物は観察されなかったものの、ＥＣＩテクノロジ社製「酸化膜測定装置 ＱＣ−２００」を用いた連続電気化学還元法による酸化膜測定の結果、厚み数ナノメートル以下の酸化膜が観察された。
実施例の試料番号１から１９、及び比較例の試料番号２０から２４、２９、３０では酸化膜は観察されなかった。（これらの評価も合わせて表２に示す。）
[Evaluation]
When the wires of Sample Nos. 1 to 10 of the example where skinning was performed were observed with an optical microscope, they had a very metallic luster, and when the surface of any five locations was observed with a scanning electron microscope over a length of 5 mm, it was 0. No inclusions larger than 1 μm were observed.
On the other hand, in the wires of Sample Nos. 11 to 19 of the Examples that were not stripped, inclusions of 0.1 μm or more were observed at all five locations by observation with the same scanning electron microscope.
Further, regarding the wires of sample numbers 25 to 28 of the comparative example subjected to skinning, inclusions of 0.1 μm or more were not observed by observation with a scanning electron microscope, but “Oxide film measuring device QC” manufactured by ECI Technology Co., Ltd. As a result of measuring the oxide film by the continuous electrochemical reduction method using “−200”, an oxide film having a thickness of several nanometers or less was observed.
No oxide film was observed in the sample numbers 1 to 19 of the example and the sample numbers 20 to 24, 29, and 30 of the comparative example. (These evaluations are also shown in Table 2.)
表２に示される結果から明らかなように、本発明のＡｇボンディングワイヤは、１００％窒素ガス雰囲気での放電プラズマ加熱によるボール形成でも真球状のボールが得られ、プル強度、シア強度、接合信頼性は従来の金線と同等以上であり、その光度はＡｕ線の場合を１００％として１０２％以上と明るくなっているにもかかわらず、より良好な疲労耐性を示すものである。また、皮剥ぎ加工を行わなかった場合であっても同等以上の光度が得られるが、皮剥ぎ加工を施すことによって、さらなる光度の向上が得られている。 As is apparent from the results shown in Table 2, the Ag bonding wire of the present invention can obtain a true spherical ball even when ball is formed by discharge plasma heating in a 100% nitrogen gas atmosphere, and pull strength, shear strength, and bonding reliability are obtained. The properties are equal to or better than those of conventional gold wires, and the light intensity is 102% or more when the Au wire is 100%, but it exhibits better fatigue resistance. Further, even when the skinning process is not performed, a luminous intensity equal to or higher than that can be obtained. However, by performing the skinning process, a further improvement in luminous intensity is obtained.
Claims (5)
溶解鋳造工程で得られたインゴットを、伸線工程に供する前に、皮剥ダイス加工による表面研削を行い、前記インゴットの表面介在物を除去することを特徴とするＬＥＤパッケージ用Ａｇボンディングワイヤの製造方法。 It is a manufacturing method of Ag bonding wire for LED packages according to claim 3,
A method for producing an Ag bonding wire for an LED package, wherein the ingot obtained in the melt casting process is subjected to surface grinding by a peeling die process before being subjected to a wire drawing process to remove surface inclusions of the ingot. .
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| CN117133852A (en) * | 2023-07-20 | 2023-11-28 | 贵研半导体材料(云南)有限公司 | Low-light-attenuation anti-color-change bonding silver wire and preparation method thereof |
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| WO2016030050A1 (en) * | 2014-08-27 | 2016-03-03 | Heraeus Deutschland GmbH & Co. KG | Silver bonding wire and method of manufacturing the same |
| CN106663642A (en) * | 2014-08-27 | 2017-05-10 | 贺利氏德国有限两合公司 | Silver bonding wire and method of manufacturing the same |
| US20170256517A1 (en) * | 2014-08-27 | 2017-09-07 | Heraeus Deutschland GmbH & Co. KG | Silver bonding wire and method of manufacturing the same |
| TWI601834B (en) * | 2014-08-27 | 2017-10-11 | 賀利氏德國有限責任兩合公司 | Bonding wire and method of manufacturing the same |
| CN117133852A (en) * | 2023-07-20 | 2023-11-28 | 贵研半导体材料(云南)有限公司 | Low-light-attenuation anti-color-change bonding silver wire and preparation method thereof |
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