TWI272152B - Doped alloys for electrical interconnects, methods of production and uses thereof - Google Patents

Doped alloys for electrical interconnects, methods of production and uses thereof Download PDF

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Publication number
TWI272152B
TWI272152B TW093127208A TW93127208A TWI272152B TW I272152 B TWI272152 B TW I272152B TW 093127208 A TW093127208 A TW 093127208A TW 93127208 A TW93127208 A TW 93127208A TW I272152 B TWI272152 B TW I272152B
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Taiwan
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copper
predominantly
solder
phosphorus
ppm
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TW093127208A
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Chinese (zh)
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TW200513337A (en
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Nancy Dean
James Flint
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Honeywell Int Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/50—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor for integrated circuit devices, e.g. power bus, number of leads
    • H—ELECTRICITY
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    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
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    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
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  • Engineering & Computer Science (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Mechanical Engineering (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

Solder materials and dopants described herein comprise at least one solder material, at least one phosphorus-based dopant and at least one copper-based dopant. Methods of forming doped solder materials include: (a) providing at least one solder material; (b) providing at least one phosphorus-based dopant; (c) providing at least one copper-based dopant, and (d) blending the at least one solder material, the at least one phosphorus-based dopant and the at least one copper-based dopant to form a doped solder material. Layered materials are also described herein that comprise: (a) a surface or substrate; (b) an electrical interconnect; (c) a solder material comprising at least one phosphorus-based dopant and at least one copper-based dopant, such as those described herein, and (d) a semiconductor die or package. Electronic and semiconductor components that comprise solder materials and/or layered materials described herein are also contemplated.

Description

1272152 九、發明說明： 【發明所屬之技術領域】 本發明領域為電子兀件，半導體元件及其它相關多層材 質應用之熱互連系統、熱界面系統及界面物質。 【先前技術】 愈來愈多的消費性及商業性電子產品使用電子元件。一 些這些消費性及商業性產品之實例為電視、個人電腦、網 際網路伺服器、行動電路、，叫器、掌上型數位助理器、 手提式收音機、汽車音響，或遙控器。隨著對於這些消費 及商業性電子器件之需求增加，/亦需要適於消費者及商業 之更j更夕^能，及更容易攜帶之此等相同產品。 以2於這些產品之尺寸減少，所以構成產品之元件亦必需 、欠侍更小。需要減少尺寸或按比例縮小之一些此種元件實 Η為p刷私路或線路板、電阻器、配線、鍵盤、觸控板， 及晶片封裝。 ，因此將it件分解並研究以決^是否有可以使其按比例縮 ’::以適合較小電子元件需求之更佳組成材料、中間材料、 =时及方法。決定是否有更佳組成材料、機器及方法之一 方法為研九製造設備及組裝各元件之方法如何操 作。 /、 個二；而要私子互連器之此等元件而言，可使用能夠使兩 70件之間產生電氣互連結構之焊球、焊珠、焊粉、預製 Τ、或某些其它主要含焊料之元件。就BGA焊球而言，該 谭球可以在封裝體與印刷電路板之間形成電氣互連結構及 96033.doc 1272152 /或在半導體晶片及封裝體或板之間形成電氣互連結構。焊 球接觸板、封裝體或晶片之位置稱為銲墊。於焊料回焊時， 焊墊金屬與焊球之交互作用可決定焊點品質，且小的交互 作用或反應會導致焊墊之焊點很容易失效。焊墊金屬性質 之太多反應或交互作用會由於形成過多脆性介金屬化合物 導致相同問題或自所形成介金屬化合物產生不想要的產 物。 有幾種修正及/或減少文中所述焊接問題之方法。例如， 曰本專利（JP07195189A)同時使用鉍、銅及銻作為BGA焊球 之摻質以改良焊點完整性。可或可不添加磷；然而，此專 利之結果顯示添加構之功用很差。與其它組份比較，填係 以高重量％添加。銅含量之範圍自100 ppm至1000 ppm。 在’’Effect of Cu Concentration on the reactions between Sn-Ag-Cu Solders and Niff(Journal of Electronic Materials, Vol· 31，No 6，p584，2002 by C.E. Ho，et· al，）及 Republic of China Patent 149096 I (March 23，2001) ; (C.R· Kao及 C.E. Ho)中，係研究銅添加對於改良ENIG焊墊上之Sn-Pb共晶性 能之影響。並未研究含小於2000 ppm Cu之組合物。1272152 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The field of the invention is thermal interconnect systems, thermal interface systems, and interface materials for electronic components, semiconductor components, and other related multilayer materials. [Prior Art] More and more consumer and commercial electronic products use electronic components. Some examples of such consumer and commercial products are televisions, personal computers, internet servers, mobile circuits, callers, handheld digital assistants, portable radios, car stereos, or remote controls. As the demand for these consumer and commercial electronic devices increases, / there is also a need for consumers and businesses to be able to carry these same products more easily. The size of these products is reduced by 2, so the components that make up the product are also necessary and less servant. Some of these components that need to be reduced in size or scaled down are actually p-blanks or boards, resistors, wiring, keyboards, trackpads, and chip packages. Therefore, the it is decomposed and studied to determine if it can be scaled down:: to better material, intermediate material, time and method suitable for the needs of smaller electronic components. One of the ways to decide whether there are better materials, machines, and methods is how to operate the equipment and how to assemble the components. /, two; and for these components of the private interconnect, a solder ball, solder beads, solder powder, prefabricated crucible, or some other that can create an electrical interconnection between two 70 pieces can be used. Mainly contains solder components. In the case of BGA solder balls, the Tan ball can form an electrical interconnect structure between the package and the printed circuit board and form an electrical interconnect structure between the semiconductor wafer and the package or board. The position of the solder ball contact plate, package or wafer is referred to as a solder pad. During solder reflow, the interaction of the pad metal with the solder balls determines the solder joint quality, and small interactions or reactions can cause solder joint pads to fail easily. Too much reaction or interaction of the metal properties of the pad can result in the same problem or the formation of unwanted products from the formed intermetallic compound due to the formation of too many brittle intermetallic compounds. There are several ways to correct and/or reduce the welding problems described herein. For example, this patent (JP07195189A) uses tantalum, copper and tantalum as binders for BGA solder balls to improve solder joint integrity. Phosphorus may or may not be added; however, the results of this patent show that the additive structure is poorly functioning. The filling is added at a high weight % compared to the other components. Copper content ranges from 100 ppm to 1000 ppm. In ''Effect of Cu Concentration on the reactions between Sn-Ag-Cu Solders and Niff (Journal of Electronic Materials, Vol. 31, No 6, p584, 2002 by CE Ho, et al) and Republic of China Patent 149096 I (March 23, 2001); (CR· Kao and CE Ho) studied the effect of copper addition on the improvement of Sn-Pb eutectic properties on ENIG pads. Compositions containing less than 2000 ppm Cu were not investigated.

Jeon 等人，"Studies of Electroless Nickel Under Bump Metallurgy-Solder Interfacial Reactions and Their Effects on Flip Chip Joint Reliability’’，Journal of Electronic Materials，2002年，Jeon et al., "Studies of Electroless Nickel Under Bump Metallurgy-Solder Interfacial Reactions and Their Effects on Flip Chip Joint Reliability’’, Journal of Electronic Materials, 2002,

第 5期，第 31冊，第 520-528 頁，及 Jeon等人，"Comparison of Interfacial Reactions and Reliabilities of Sn 3.5Ag and Sn4.0Ag0.5Cu and Sn0.7Cu Solder Bumps on Electroless Ni-P 96033.doc 1272152 UBMs” Proceeding of Electronic Components and Technology Conference，IEEE (2003年），第1203頁討論在純錄焊墊上介 金屬化合物之增大比在無電鎳焊墊上介金屬化合物之增大 更快。亦在上述兩篇論文中研究並討論濃度為〇.5%(5000 ppm) 或更高之銅之優點。No. 5, Vol. 31, pp. 520-528, and Jeon et al., "Comparison of Interfacial Reactions and Reliabilities of Sn 3.5Ag and Sn4.0Ag0.5Cu and Sn0.7Cu Solder Bumps on Electroless Ni-P 96033. Doc 1272152 UBMs” Proceeding of Electronic Components and Technology Conference, IEEE (2003), p. 1203 discusses that the increase in the intermetallic compound on a purely recorded pad is faster than the increase in the intermetallic compound on an electroless nickel pad. The advantages of copper at a concentration of 〇.5% (5000 ppm) or higher are studied and discussed in the above two papers.

Zhang 等人，"Effects of Substrate Metallization on Solder/UnderBump Metallization Interfacial Reactions in Flip-Chip Packages during Multiple Reflow Cyclesf,5 Journal of Electronic Materials，2003年，第 3期，第 32冊，第 123-130頁 表示一旦使介金屬化合物之消耗變慢時，麟並不會產生影 響，其與 Jeon 之論文矛盾。ShingYeh，’’Copper Doped Eutectic Tin-Lead Bump for Power Flip Chip Applications”，Proceeding of Electronic Components and Technology Conference, IEEE (2003 年），第33 8頁特別提及1%銅添加可減少鎳層消耗。Zhang et al., "Effects of Substrate Metallization on Solder/UnderBump Metallization Interfacial Reactions in Flip-Chip Packages during Multiple Reflow Cyclesf, 5 Journal of Electronic Materials, 2003, No. 3, Book 32, pp. 123-130 Once the consumption of the intermetallic compound is slowed down, Lin does not have an effect, which contradicts Jeon's thesis. ShingYeh, ''Copper Doped Eutectic Tin-Lead Bump for Power Flip Chip Applications', Proceeding of Electronic Components and Technology Conference, IEEE (2003), p. 33 8 specifically mentions that 1% copper addition can reduce nickel layer consumption.

Niedrich專利及申請案（EP0400363 Al、EP0400363 B1 及 1^501165 8)表示使用銅作為811-?13-111焊料之摻質可以使銅 焊墊或連接器之消耗減至最少（亦即未使用鎳障壁層）。已發 現焊料中之銅可減少銅連接器之溶解。Niedrich使用銅以抑 制鎳障壁層交互作用，因此可避免形成介金屬化合物或 (Cu、Ni)Sn介金屬化合物。在銅的使用方面，Niedrich專利 與美國專利第2671844號很類似，Niedrich專利描述於精細 焊接操作時添加超過0.5重量％含量之銅至焊料内以使銅焊 接鐵尖頭之溶解減至最少。 頒予Ozaki之美國專利第4,938,924號特別提及添加 96033.doc 1272152 2000-4000 ppm銅可改良Sn-36P6-2Ag合金之潤濕性及長期 焊接可靠性。日本專利 JP60166191Af’Solder Alloy Having Excellent Resistance to Fatigue Characteristic”揭示一種已 添加300-5000 ppm銅以改良耐疲乏性之Sn Bi P6合金。 美國頒予之專利第6,307,160號教示使用至少2%銦以改 良無電敷鎳/浸金（ENIG)焊墊上之共晶Sn-Pb合金之黏結強 度。 美國頒予之專利第4,695,428號”Solder Composition”揭示 用以測量焊接處之無Pb焊料組合物。所使用之銅濃度係超 過1000 ppm，且亦添加幾種其它元素作為合金添加物以改 良焊料之液相線、固相線、流動性質及表面光潔度。 美國頒予之專利第2303 193A號教示除了 Cd及Sb外，使用 0.1_1.5%Cu(l，000-15,000 ppm Cu)可增加焊料之抗潛變 力。該專利明確地表示”小於上述含量之銅並不足以實質上 改良普通鉛-錫合金之耐久性π。 因此，有持續必要來：a)研發對於整體焊料性質不會有 不利影響之焊料及焊料摻質，且其可以使鎳障壁層之消耗 及磷富集層之增大變慢，因此於回焊及後回焊熱老化時， 可維持黏結完整性；b)設計及製造可符合顧客規格同時可 以使製造成本減至最低，並使合併電氣互連結構之產物品 質增至最佳之電氣互連結構；及c)研發製備電氣互連結構 及含此等互連結構之元件之可靠方法。 【發明内容】 文中所述及之焊料及摻質包含至少一種焊料、至少一種 96033.doc 1272152 主要3 %之私貝及至少一種主要含銅之摻質。形成摻雜焊 料之方法包括：a)提供至少一種焊料；b)提供至少一主要含 %之払貝，c)提供至少一種主要含銅之摻質，及幻摻合該至 ’烊料該至少一種主要含鱗之摻質及該至少一種主要 含銅之摻質以形成摻雜焊料。 文中亦描述夕層材質，其包含：a) 一表面或基料；七）一電 氣互連結構；C)含有如文中所述至少一種主要含磷之摻質 及至少-種主要含銅之摻質之焊料，及d)半導體晶片或封 衣體文中亦，函盍含有焊料及/或多層材質之電子及半導體 鲁 元件。 【實施方式】 不像前述參考資料，本發明已研發對於整體焊料性質不 會有不利影響，且又會使沁障壁層之消耗及磷富集層之增 大變慢，因此於回焊及後回焊熱老化時可維持焊接完整性 之摻雜焊料及焊料摻質。此種焊料摻質可符合下述目標： a)没叶及製造能符合消費性電子產品之規格同時可以使製 =成本減至最低並使合併電氣互連結構之產物品質增至t · 仫之電氣互連結構；及b)研發製備電氣互連結構及含此等 互連結構之元件之可靠方法。 電氣互連結構（例如，BGA焊球）一般所焊接之基材、封 衣體或板上之金屬化法通常使用之金屬常為銅。銅可以與 大部分焊料（錫）之主要成分快速反應以形成c卜Sn介金屬 化口物，其可快速增大，並可剝裂或與界面斷裂。此種斷 裂現象會減少焊點之強度及完整性。 96033.doc -10- 1272152 為了減少焊墊之消耗，使用障壁層以避免s^cu直接接 觸。這些額外層通常稱為焊塾金屬或凸塊底層金屬 )1而„ BGA焊球之焊塾金屬已包括使用鑛錄 以提供銅之障Μ及薄金塗層以維持可焊性。雖然錄可以 與Sn相互作用以形成介金屬化合物，該介金屬增大率實質 上低於CU_Sn介金屬之增大率。根據過去的資料，已使用電 解鍍鎳法。在此種電鍍法中，鎳沉積很純，僅有很少之不 想要元素（例如，碟）共沉積物。 為了減少製造成本，提供較新的電鍍法，亦即光進行無 電敷錄（EN)’繼而進行浸金（IG)e — m無電敷鎳沉 積浴包括使用次亞磷酸鹽（HJO2—)溶液，其可以使EN塗層 中之磷共沉積物達至7-15個原子％。於IG電鍍及回焊或後‘ 熱處理法時，此額㈣會產生問題。於電鍍阳時，低碟含 量塗層之抗蝕性差，因此使用者希望得到較高含量之磷沉 積物。 於焊料回焊時，薄IG塗層幾乎立刻溶解。然後焊料中之 錫與EN塗層内之鎳反應以形成1^_如介金屬化合物。該介金 屬形成中並不含有磷，因此當介金屬化合物於高溫下增大 日^ ’愈來愈對的填被介金屬界面拒斥。該麟可累積在薄碟_ 富Ni-P層上，其會弱化焊點，或呈結晶狀Ni_p，其亦會弱 化焊點。焊點會因為此種磷富集層而失效。在本工業内這 些失效種類稱為”黑墊”失效，因為由於失效所曝露之磷富 集層可具有稱黑之外觀。由於當焊接點曝露於高溫下時， 甚至呈固態之介金屬化合物可快速增大，所以這些失效可 96033.doc -11 - 1272152 發生在經熱老化之焊點（其在焊料回焊後不久，似乎报好）。 文中涵蓋之焊料及摻質包含至少一種焊料、至少一種主 要δ石夕牛之摻負及至少一種主要含銅之推質。形成文中所述 之摻^焊料之方法包括· a)提供至少—種焊料…提供至少 一種主要含磷之摻質；e)提供至少—種主要含銅之推質， 及句摻合該至少—焊料，該至少_種主要含磷之摻質及該 至少一種主要含銅之摻質以形成摻雜焊料。在涵蓋之具體 貝鉍例中，添加至焊料合金或材質之銅及磷之摻質可減少 無電敷鎳（EN)鍍面障壁層之消耗。藉由此種在共同擁有之 美國頒予專利第6579479號（其全文以引用的方式併入本文 中）中所述之方法’可添加摻質至焊料合金内以製備焊粉、 焊糊、焊鑄錠、焊線、預製件或BGA焊球。 文中涵蓋多層材質，其包含·· a)一表面或基材；b)一電氣 互連結構；c)含，例如，此等文令所述之主要含磷之摻質 及主要含銅之摻質之焊料，及d)半導體晶片《封裝體。所 涵蓋之表面可含有印刷電路板或適合之電子元件。亦涵蓋 5有文中所述之焊料及/或多層材質之電子及半導體元件。 文中所述之涵蓋具體實施例與列舉參考資料不同之處在 於口孟添加物之濃度不同及使用磷作為焊料之添加物不 同且々人馬冴的是其很有效。在多篇論文（例如，文中先 前列舉之Jeon論文）中已表示焊料中之高含量銅可降低介金 屬層之消耗。文中所使用之含量可降低2·5至> 1〇倍。^〇之 著述顯示銅組合物在0·2%(2000 ppm)以下，可以於鎳/焊料 界面處形成不同介金屬。在文中所提之主題含量中，任何 96033.doc -12- 1272152 地方皆未特別提及銅與磷之組合物。 而且’文中前述之Niedrich專利藉由使用銅形成銅介金屬 化合物或（Cu、Ni)Sn介金屬化合物以抑制鎳障壁層。 Niedrich專利與美國專利第2671 844號在銅的使用方面很類 似’於精細焊接操作時，其添加含量大於〇·5重量％之鋼至 焊料中以使銅焊鐵尖頭之溶解減至最低。這些銅添加量皆 必需明顯高於文中涵蓋之數量。〇zaki專利也是如此，其中 銅之添加量明顯高於文中涵蓋之數量。 焊料可含有任何適合焊料、合金或金屬，例如，銦，鉛、 銀、銅、鋁、錫、鉍、鎵及其合金，覆銀之銅、覆銀之鋁 或其組合物。較佳焊料可含有鉛錫合金，其包括鉛（37%)_ 錫（63%)共晶合金、銦錫（InSn)化合物及合金、銦銀（inAg) 化合物及合金、主要含銦之化合物、錫銀銅化合物（其已經 含有銅）及合金（SnAgCu)，錫絲化合物及合金（SnBi)，主要 含铭之化合物與合金及其組合物。如文中使用，該名詞，，金 屬’’意指元素週期表d執域及f執域中之元素，及具有似金屬 性質之元素，例如，矽及鍺。如文中使用，該名詞”4執域，， 意指具有電子填滿包圍元素原子核之3d、4d、5d、及6d軌 域之元素。如文中使用，該名詞”f執域”意指具有電子填滿 包圍元素原子核之4f及5f執域之元素，其包括鑭系及锕系。 較佳金屬包括，例如，銦、鉛、銀、銅、鋁、錫、鉍、嫁 及其合金、覆銀之銅，及覆銀之鋁。該名詞”金屬”亦包括 合金、金屬/金屬複合物、金屬陶瓷複合物、金屬聚合物複 合物’及其它金屬複合物。如文中使用，該名詞”化合物，， 96033.doc -13- 1272152 意指具有恆定組成，且可以藉由化學方法分解成元素之物 質。 所涵蓋之摻質含有至少一主要含磷之化合物/摻質及至 少一主要含銅之化合物/摻質。文中所涵蓋之摻質含量為小 於約100 ppm磷及小於約800 ppm銅。在某些具體實施例 中，所涵蓋之摻質含量為約10_100 ppm磷及約25_8〇〇卯m 銅。在某些具體實施例中，所涵蓋之摻質含量為約1〇_7〇 ppm磷及約25-500 ppm鋼。在其它具體實施例中，所涵蓋之 摻質含量為約20-60 ppm磷及約4〇-6〇〇 ppm銅。在又另外具 體實施例中，所涵蓋之摻質為約3〇-6〇 ppm磷及約3〇〇_5〇〇 ppm 銅。 可以於鑄造時，直接添加摻賞至焊料主成分中。當使用 少里摻質時，可較佳製備一種母合金，並使其經未摻雜焊 料稀釋以便更有效地控制摻雜濃度。 可藉由任可適合方法提供該至少一種焊料、該至少一種 主要含磷之化合物/摻質及/或該至少一種主要含銅之化合 物/摻質，這些方法包括勾向供應商購買應至少一種焊料、 該至少一種主要含磷之化合物/摻質及/或該至少一主要含 銅之化合物/換質；b)供應商在室内使用由其它來源提供之 化予απ製備或生產至少一些該至少一種焊料、該至少一種 主要含鱗之化合物/摻質及/或該至少一種主要含銅之化合 物/摻質，及/或C)供應商在室内使用亦在室内或於所在地產 生或提供之化學品製備或生產該至少一種焊料、該至少一 種主要含磷之化合物/摻質及/或該至少一種主要含銅之化 96033.doc -14- 1272152 合物/摻質。 亦可以使用文中所述之焊料、焊球及其它相關材料以製 備焊糊、聚合物焊料及其它主要含焊料之調配物與材質， 例如，此等在下述Honeywell International Inc. ’s頒予之專利 申請中之專利申請案（美國專利申請案系號09/851 103、 60/357754、60/372525、60/396294、及 09/543628 ;及 PCT 申請中之申請案系號：PCT/US 02/14613，及全部相關接續 申請案、個別申請案、部分接續申請案及外國申請案，其 全文以引用的方式於本文之中）中所找到之焊料及其它相 關材料。亦可使用文中所述之焊料、塗料組合物及其它相 關材料作為組分或構成主要含電子元件之產物、電子元件 及半導體元件。在所涵蓋具體實施例中，可以使用文中揭 示之合金以製備BGA焊球，可以在含BGA焊球之電子組裝 (例如，凸起封裝之晶片或球狀晶片、封裝體或基材）中使用 文中揭示之合金，且可以使用文中揭示之合金作為陽極、 導線或焊糊，或亦可以呈浴型使用文中揭示之合金。 同樣，在涵蓋之具體實施例中，使焊球與封裝物/基材或 晶片連接並以和未摻雜焊球類似之方式回焊。摻質可以使 EN塗層之消耗率變慢，並形成較高完整性（較高強度）之焊 點。 可以’’潤飾’’主要含電子元件之產物，其方式可以使其隨 時可使用在工業中或經由其它消費性電子產品使用。消費 性電子產物成品為電視、電腦、行動電路、呼叫器，掌上 型數位助理器、攜帶式收音機、汽車音響，及遙控器。亦 96033.doc -15- 1272152 月&便用在產物成 盖中間"產物，例如，可 晶片封裝體，及鍵盤。 電子產物亦可包含自概念模型至最終按 物大模型之任-發展階段之原型元件。原型可或可不:; 產物成品備需之實際元件，且原型可具有一些由複合物材 枓所製成之元件以使其對於其它元件之影響 原型係先經測試。 遠 Φ 二中：用，該名詞"電子元件"意指可以使用於電路中 二 ▲所要電乳功用之任何器件或零件。文中涵罢之 可以經許多不同方法分類，其包括可成類成= 1及被動元件。，主動元件為可具有一些動態功用之電子 凡，例如’通常需要電源才能操作之信號放大、 二:::控制。實例為雙載子電晶體、場效應電二 及積體琶路。被動元件為操作時呈靜態之電子 ::不此使“唬放大或振盪之電子元件，且其通需 :力即可進行其特性操作。實例為習知電阻器、電^要 包感器、二極體、整流器及保險絲。 谷口口 亦可以將文中涵蓋之電子元件分類成導體 絕緣體。文中，導體為可以使载子（例如，^:或 很容…、子之間移動之元件。導體元件之實):=般 縱器及含金屬之介層。絕緣體為具有實質上盘路不 抗電流傳導性有關之功用之元件，例如，使用以恭貝^極 它元件之材質，而半導體為其功用實質上與一材:隔離其 電流之性質有關且在導體及絕緣體之間具有天秋:可傳導 96033.doc -16- 1272152 元件。半導體元件之實例為電晶體、二極體、一些雷射光 器、整流器、閘流電晶體及光感測器。 亦可以將文中涵蓋之電子元件分類成電源或功率消耗 器。一般而言，電源元件用以提供其它元件之動力，且其 包括電池、電容器、線圈，及燃料電池。如文中使用，該 名詞π電池”意指可藉由化學反應產生有用量之電功率之器 件。同樣，可再充電或二次電池為可藉由化學反應貯存有 用量之電能之器件。功率消耗元件包括電阻器、電晶體、 Ics、感測器，及諸如此類。 又進一步亦可以將文中涵蓋之電子元件分類成分立元件 或積體元件。分立元件為可提供一特定電性質集中於電路 内之一處之器件。實例為電阻器、電容器、二極體，及電 晶體。積體元件為可提供多種電性質於電路内之一處之元 件組合。實例在Ics，亦即，積體電路，其中係合併多種元 件及連結示縱器以進行多種或複雜功用，例如，邏輯。 實例 文中表示4種代表實例，其含有經下述用量之銅及磷摻質 摻雜之Sn37Pb : > 實例# 1 : 40 ppm+/-10 ppm銅及石粦 > 實例 # 2 : 500 ppm+/-10 ppm銅及30 ppm+/-10 ppm石粦 > 實例 # 3 : 200 ppm+/-10 ppm銅及30 ppm+/-10 ppm石粦 > 實例 # 4 : 200 ppm+/-30 ppm銅及 15 ppm+/-5 ppm填 > 實例# 5 :未摻雜之Sn-37Pb合金（對照物） 96033.doc -17- I272l52 實例號數 ~TENlGif^ 勇斷焊球所吸 ^---- 收之總能量 _ 553'^ 60^^ __ 63^9^^ _ 513 ~ L_5 4L8 失效模式 銅之潤 濕性 芝楚逢性 _185^ TssTi ZII55 此數據顯示自未摻雜材料(實 質會大大減少熔點。全部合金對於:又種曰金摻 剪斷IF ”、；稞鋼之潤濕性依然佳。 J辦與ENIG知墊金屬焊接之焊 换枚 知球所需之總能量高於剪斷 摻雜焊球所需之總能量，且失 门〜斷 ^ _ 权式&摻質含量增加自未 推雜材質之脆性失效至更想要之延性失效模式 因此，已揭示使用摻雜焊料及焊料摻質作為電子互連结 構之特定具體實施例及申請案。 然而，熟悉本項技藝者應 :白只要不違背文中本發明概念，…等在文中已描 :可以有許多修飾。而i ’在解釋本專利說明書時， w忒以和本文一致之最廣泛可用 〜一 用之方式解釋全部名詞。特 ㈣㈣"含有"及”包含"以非限制方式解釋為 :明、70件，或步驟’其表示可以存在，或使用，或合併 :確表示之其它元素、元件’或步驟之上述元素 或步驟。 96033.doc -18-The Niedrich patents and applications (EP0400363 Al, EP 0400363 B1 and 1^501165 8) indicate that the use of copper as a dopant for 811-?13-111 solder minimizes the consumption of copper pads or connectors (ie, no nickel is used). Barrier layer). Copper in the solder has been found to reduce the dissolution of the copper connector. Niedrich uses copper to suppress nickel barrier layer interactions, thus avoiding the formation of intermetallic compounds or (Cu, Ni)Sn intermetallic compounds. In terms of the use of copper, the Niedrich patent is very similar to U.S. Patent No. 2,671,844, which describes the addition of more than 0.5% by weight of copper to the solder during the fine soldering operation to minimize dissolution of the brazed iron tip. U.S. Patent No. 4,938,924 to Ozaki specifically mentions the addition of 96033.doc 1272152 2000-4000 ppm copper to improve the wettability and long-term soldering reliability of the Sn-36P6-2Ag alloy. Japanese Patent JP60166191Af 'Solder Alloy Having Excellent Resistance to Fatigue Characteristic" discloses a Sn Bi P6 alloy which has been added with 300-5000 ppm of copper to improve fatigue resistance. U.S. Patent No. 6,307,160 teaches the use of at least 2% indium to improve electrolessness. The bond strength of a eutectic Sn-Pb alloy on a nickel/immersion gold (ENIG) pad. The "Solder Composition" of U.S. Patent No. 4,695,428 discloses a Pb-free solder composition for measuring solder joints. The concentration is more than 1000 ppm, and several other elements are added as alloy additions to improve the liquidus, solidus, flow properties and surface finish of the solder. US Patent No. 2303 193A teaches in addition to Cd and Sb. The use of 0.1_1.5% Cu (l,000-15,000 ppm Cu) increases the resistance of the solder to latent forces. The patent expressly states that "less than the above content of copper is not sufficient to substantially improve the durability of ordinary lead-tin alloys. Sex π. Therefore, there is a continuing need to: a) develop solder and solder dopants that do not adversely affect the overall solder properties, and which can slow the consumption of the nickel barrier layer and the increase of the phosphorus-rich layer, thus reflowing And after reheating heat aging, maintains bond integrity; b) designs and manufactures electrical interconnects that meet customer specifications while minimizing manufacturing costs and maximizing the quality of the combined electrical interconnect structure Structure; and c) develop a reliable method of fabricating electrical interconnect structures and components containing such interconnect structures. SUMMARY OF THE INVENTION The solder and dopant described herein comprise at least one solder, at least one of 96033.doc 1272152, primarily 3% of the shellfish, and at least one predominantly copper-containing dopant. The method of forming a doped solder includes: a) providing at least one solder; b) providing at least one predominantly containing mussel, c) providing at least one predominantly copper-containing dopant, and phantom blending the to the dip. A primary scaled dopant and the at least one predominantly copper-containing dopant form a doped solder. Also described herein is a layer material comprising: a) a surface or binder; VII) an electrical interconnect structure; C) containing at least one predominantly phosphorus-containing dopant and at least one predominantly copper-containing dopant as described herein. Qualitative solders, and d) semiconductor wafers or closures. The text also contains electronic and semiconductor components of solder and/or multilayer materials. [Embodiment] Unlike the above-mentioned reference materials, the present invention has been developed to have no adverse effect on the overall solder properties, and also to reduce the consumption of the barrier layer and the increase of the phosphorus-rich layer, so that after reflow and after Doped solder and solder dopants that maintain solder integrity during reheat soldering. Such solder dopants can meet the following objectives: a) No leaf and manufacturing can meet the specifications of consumer electronics while minimizing system cost and increasing the quality of the combined electrical interconnect structure to t · 仫Electrical interconnect structure; and b) a reliable method of developing electrical interconnect structures and components containing such interconnect structures. Electrical interconnect structures (e.g., BGA solder balls) are commonly used for metallization of substrates, packages, or boards that are typically soldered. Copper can react rapidly with most of the main components of solder (tin) to form c-Sn intermetallic openings, which can rapidly increase and can be cracked or fractured at the interface. This cracking reduces the strength and integrity of the solder joint. 96033.doc -10- 1272152 To reduce pad consumption, use a barrier layer to avoid direct contact with s^cu. These additional layers are often referred to as solder metal or bump underlying metal)1 and the BGA solder ball solder metal has included the use of minerals to provide copper barriers and thin gold coatings to maintain solderability. Interacting with Sn to form a intermetallic compound, the rate of increase of the intermetallic metal is substantially lower than the increase rate of the CU_Sn intermetallic. According to past data, electrolytic nickel plating has been used. In this electroplating method, nickel deposition is very Pure, there are only a few unwanted elements (eg, discs) co-deposits. In order to reduce manufacturing costs, a newer plating method is provided, that is, light is electrolessly recorded (EN)' followed by immersion gold (IG)e — m electroless nickel deposition bath including the use of a hypophosphite (HJO 2 —) solution which allows the phosphorus co-deposit in the EN coating to reach 7-15 atomic %. IG plating and reflow or post-heat treatment In the case of the law, this amount (4) will cause problems. In the case of electroplating, the low-disc content coating has poor corrosion resistance, so the user desires to obtain a higher content of phosphorus deposit. In the case of solder reflow, the thin IG coating is almost immediately Dissolved. Then the tin in the solder and the EN coating The reaction forms a metal compound such as a metal compound. The metal is formed to contain no phosphorus, so that when the intermetallic compound is grown at a high temperature, it is increasingly repelled by the intervening metal interface. Accumulated on the thin-disk Ni-P layer, which weakens the solder joint or crystallizes Ni_p, which also weakens the solder joint. Solder joints will fail due to this phosphorus-rich layer. These failures in the industry The type is called "black mat" failure because the phosphorus-rich layer exposed due to failure can have a black appearance. Since even when the solder joint is exposed to high temperatures, even the solid intermetallic compound can rapidly increase, these Failure may be 96033.doc -11 - 1272152 occurs in heat-aged solder joints (which appears to be reported shortly after solder reflow). The solder and dopants covered herein contain at least one solder, at least one major δ Shi Xi Niu The method of forming a solder-containing solder as described herein comprises: a) providing at least one solder to provide at least one dopant mainly comprising phosphorus; e) providing at least one of the main Copper-containing push, and Blending at least the solder, the at least one predominantly phosphorus-containing dopant, and the at least one predominantly copper-containing dopant to form a doped solder. In the specific shell examples covered, the copper is added to the solder alloy or material And the phosphorus dopant can reduce the consumption of the electroless nickel (EN) plated barrier layer, as described in the commonly-owned U.S. Patent No. 6,579,479, the disclosure of which is incorporated herein in its entirety by reference. The method 'adds a dopant to the solder alloy to prepare a solder powder, a solder paste, a solder ingot, a bonding wire, a preform, or a BGA solder ball. The present invention encompasses a multilayer material comprising: a) a surface or substrate; b) an electrical interconnect structure; c) containing, for example, the main phosphorus-containing dopants and the predominantly copper-containing dopants described in these publications, and d) the semiconductor wafer "package." The surface covered may contain printed circuit boards or suitable electronic components. It also covers 5 electronic and semiconductor components of the solder and/or multilayer materials described in the text. The specific embodiments described herein differ from the enumerated references in that the concentration of the oral extract is different and that the addition of phosphorus as a solder is different and is effective. It has been shown in a number of papers (e.g., the previously cited Jeon papers) that high levels of copper in the solder can reduce the consumption of the intermetallic layer. The amount used herein can be reduced by 2.5 to > 1 fold. ^〇 The writing shows that the copper composition is below 0.2% (2000 ppm), which can form different intermetallics at the nickel/solder interface. Among the subject matter mentioned in the text, any combination of copper and phosphorus is not specifically mentioned in any of the places of 96033.doc -12- 1272152. Further, the aforementioned Niedrich patent suppresses the nickel barrier layer by using copper to form a copper intermetallic compound or a (Cu, Ni) Sn intermetallic compound. The Niedrich patent is similar to the use of copper in U.S. Patent No. 2,671,844. In the case of a fine welding operation, steel is added in an amount of more than 5% by weight to the solder to minimize the dissolution of the brazing iron tip. These copper additions must be significantly higher than the quantities covered in the text. The same is true for the 〇zaki patent, where the amount of copper added is significantly higher than the amount covered in the text. The solder may comprise any suitable solder, alloy or metal, such as indium, lead, silver, copper, aluminum, tin, antimony, gallium and alloys thereof, silver coated copper, silver coated aluminum or combinations thereof. Preferably, the solder may contain a lead-tin alloy including lead (37%)_tin (63%) eutectic alloy, indium tin (InSn) compound and alloy, indium silver (inAg) compound and alloy, mainly indium-containing compound, Tin-silver-copper compounds (which already contain copper) and alloys (SnAgCu), tin-wire compounds and alloys (SnBi), mainly containing the compounds and alloys and compositions thereof. As used herein, the term "metal" refers to elements of the periodic table d and f, and elements having metal-like properties, such as 矽 and 锗. As used herein, the term "4" means an element that has electrons filling the 3d, 4d, 5d, and 6d orbital domains surrounding the atomic nucleus of the element. As used herein, the term "f domain" means having an electron. Filling the elements of the 4f and 5f domains surrounding the elemental nucleus, including lanthanides and lanthanides. Preferred metals include, for example, indium, lead, silver, copper, aluminum, tin, antimony, marry and alloys thereof, and silver coating. Copper, and silver-coated aluminum. The term "metal" also includes alloys, metal/metal composites, cermet composites, metal polymer composites, and other metal composites. As used herein, the term "compound," , 96033.doc -13- 1272152 means a substance having a constant composition and which can be chemically decomposed into elements. The dopants contemplated comprise at least one predominantly phosphorus-containing compound/doped material and at least one predominantly copper-containing compound/filler. The dopant content encompassed herein is less than about 100 ppm phosphorus and less than about 800 ppm copper. In some embodiments, the dopant content is about 10 to 100 ppm phosphorus and about 25 to 8 angstroms copper. In certain embodiments, the dopant content is about 1 〇 7 〇 ppm phosphorus and about 25-500 ppm steel. In other embodiments, the dopant content is about 20-60 ppm phosphorus and about 4 〇-6 〇〇 ppm copper. In still other embodiments, the dopants contemplated are about 3 -6 -6 ppm phosphorus and about 3 〇〇 5 〇〇 ppm copper. It can be directly added to the main component of the solder during casting. When a lesser doping is used, it is preferred to prepare a master alloy and dilute it with an undoped solder to more effectively control the doping concentration. The at least one solder, the at least one primary phosphorus-containing compound/doped material, and/or the at least one predominantly copper-containing compound/filler may be provided by any suitable method, including at least one of Solder, the at least one predominantly phosphorus-containing compound/dosing and/or the at least one predominantly copper-containing compound/replacement; b) the supplier uses indoors to provide alpha π preparation or production of at least some of the at least a solder, the at least one predominantly scaly compound/dosing and/or the at least one predominantly copper-containing compound/doping, and/or C) chemistry that is produced or provided indoors or at the location of the supplier by the supplier Preparing or producing the at least one solder, the at least one predominantly phosphorus-containing compound/doping and/or the at least one predominantly copper-containing 96033.doc-14-1272152 compound/doping. Solder pastes, solder balls, and other related materials may also be used to prepare solder pastes, polymer solders, and other solder-containing formulations and materials, such as those patented by Honeywell International Inc. 's, as described below. The patent application under application (US Patent Application Nos. 09/851 103, 60/357754, 60/372525, 60/396294, and 09/543628; and PCT Application No. PCT/US 02/ 14613, and all related continuation applications, individual applications, partial continuation applications and foreign applications, the full text of which is found in this article by reference in the solder and other related materials. The solder, coating composition and other related materials described herein may also be used as a component or as a product, electronic component and semiconductor component mainly comprising electronic components. In the specific embodiments covered, the alloys disclosed herein can be used to prepare BGA solder balls, which can be used in electronic assemblies containing BGA solder balls (eg, bump-wrap wafers or ball wafers, packages, or substrates). The alloys disclosed herein may be alloyed as an anode, wire or solder paste, or may be in the form of a bath using the alloys disclosed herein. Also, in the specific embodiment covered, the solder balls are attached to the package/substrate or wafer and reflowed in a similar manner to the undoped solder balls. The dopants can slow the consumption of the EN coating and form a higher integrity (higher strength) solder joint. The product of the electronic component can be 'retouched' in such a manner that it can be used in the industry or via other consumer electronic products at any time. Consumer electronics products are televisions, computers, mobile circuits, pagers, handheld digital assistants, portable radios, car stereos, and remote controls. Also 96033.doc -15- 1272152 Month & used in the middle of the product cover "products, for example, chip package, and keyboard. The electronic product can also include prototype components from the conceptual model to the final-development phase of the final model. The prototype may or may not: The actual component of the finished product, and the prototype may have some components made of composite material to affect its other components. The prototype is tested first. Far Φ 2: Use, the term "electronic component" means any device or part that can be used in the circuit. The text can be classified by many different methods, including the classification of = 1 and passive components. The active component is an electronic device that can have some dynamic functions, such as 'signal amplification that normally requires power to operate, two::: control. Examples are bipolar transistor, field effect electric 2 and integrated circuit. The passive component is a static electron during operation:: This does not cause the electronic component to be amplified or oscillated, and its general purpose: force can perform its characteristic operation. Examples are conventional resistors, electric sensors, Diodes, rectifiers and fuses. Taniguchi can also classify the electronic components covered in the text into conductor insulators. In this paper, the conductors are components that can make carriers (for example, ^: or very... Real): = as a vertical device and a metal-containing interlayer. The insulator is a component that has a function of substantially resisting current conduction, for example, using a material of the component, and the semiconductor The function is essentially related to the material: it is related to the nature of the current and has a connection between the conductor and the insulator: it can conduct 96033.doc -16-1272152 components. Examples of semiconductor components are transistors, diodes, and some laser light. , rectifiers, thyristor transistors, and photosensors. The electronic components covered in this article can also be classified into power supplies or power consumers. In general, power components are used to provide power to other components, and Including batteries, capacitors, coils, and fuel cells. As used herein, the term π cell "means that there can be produced by a chemical reaction of the amount of electric power of the device. Also, a rechargeable or secondary battery is a device that can store a useful amount of electrical energy by a chemical reaction. Power consuming components include resistors, transistors, Ics, sensors, and the like. Further, the electronic components covered in the text may be classified into discrete components or integrated components. A discrete component is a device that provides a specific electrical property concentrated in one of the circuits. Examples are resistors, capacitors, diodes, and transistors. The integrated component is a combination of components that provide a variety of electrical properties at one of the circuits. Examples are in Ics, i.e., integrated circuits, in which multiple elements and associated interleavers are combined for multiple or complex functions, such as logic. In the examples, four representative examples are shown which contain Sn37Pb doped with copper and phosphorus dopants in the following amounts: > Example #1: 40 ppm +/- 10 ppm copper and sarcophagus> Example # 2 : 500 ppm+/ -10 ppm copper and 30 ppm +/- 10 ppm sarcophagus > Example # 3 : 200 ppm +/- 10 ppm copper and 30 ppm +/- 10 ppm sarcophagus > Example # 4 : 200 ppm +/- 30 ppm copper and 15 Ppm +/- 5 ppm filled > Example # 5 : Undoped Sn-37Pb alloy (control) 96033.doc -17- I272l52 Example number ~TENlGif^ Brake ball is sucked ^---- Total Energy _ 553'^ 60^^ __ 63^9^^ _ 513 ~ L_5 4L8 Failure Mode Copper Wettability Zhichu Fengheng _185^ TssTi ZII55 This data shows that the material is undoped (substantially reduces the melting point) All alloys are: 又 掺 掺 掺 IF IF 稞 稞 稞 稞 稞 稞 稞 稞 润湿 润湿 润湿 润湿 润湿 润湿 润湿 润湿 润湿 润湿 润湿 润湿 润湿 润湿 润湿 润湿 润湿 润湿 润湿 润湿 润湿 润湿 润湿 EN EN EN EN EN EN EN EN EN The total energy required for the solder ball, and the loss of the gate ~ break ^ _ weight & the content of the dopant increases from the brittle failure of the undoped material to the more desirable ductile failure mode. Therefore, the use of doped solder and The material dopant is a specific embodiment and application of the electronic interconnection structure. However, those skilled in the art should: white as long as it does not violate the concept of the invention in the text, etc., as described in the text: there may be many modifications. In interpreting this patent specification, w忒 is to be interpreted in its broadest sense and is used in the broadest sense. The terms (4)(4)"include" and "include" are interpreted in a non-limiting manner as: Ming, 70, or The steps 'it' can be used, or used, or combined: the elements or steps described above for other elements, elements' or steps. 96033.doc -18-

Claims (1)

1272152 十、申請專利範圍： 1 · 一種摻雜焊料，其含有·· 至少一種焊料， 至少一種主要含磷之摻質；及 至少一種主要含銅之摻質。 2·如請求項丨之摻雜焊料，其中該至少一種焊料包含銦、 鉛、銀、銅、鋁、錫、鉍、鎵及其合金、覆銀之銅、覆 銀之紹或其組合物。 3·如請求項2之摻雜焊料，其中該至少一種焊料包含鉛錫合 金、銦錫（InSn)化合物及合金、銦銀（ItlAg)化合物及合金， 主要含銦之化合物、錫銀銅化合物及合金（SnAgCu)、錫 絲化合物及合金（SnBi)、主要含鋁之化合物及其合金與組 合物。 4·如請求項3之摻雜焊料，其中該鉛錫合金包含錯（37%)_錫 (63%)共晶合金。 5 ·如請求項1之摻雜焊料，其中該至少一種主要含麟之摻質 係以小於約100 ppm磷之含量存在。 6.如請求項5之摻雜焊料，其中該至少一種主要含鱗之摻質 係以小於約70 ppm磷之含量存在。 7 ·如凊求項6之备雜焊料，其中該至少一種主要含碟之摻質 係以小於約60 ppm磷之含量存在。 8 ·如請求項1之摻雜焊料，其中該至少一種主要含銅之掺質 係以小於800 ppm銅之含量在在。 9 ·如請求項8之摻雜焊料，其中該至少一種主要含銅之摻質 96033.doc 1272152 係以小於約600 ppm銅之含量存在。 1 〇·如請求項9之摻雜焊料，其中該至少一種主要含銅之摻質 係以小於約500 ppm銅之含量存在。 11·如請求項1之摻雜焊料，其中該至少一種主要含磷之摻質 及該至少一主要含鋼之摻質係以約1〇_1〇〇卯m磷及約 25-800 ppm銅之含量存在。 12·如請求項1之摻雜烊料，其中該至少一種主要含磷之摻質 及該至少一主要含銅之摻質係以約1〇_7〇卯m磷及約 25-500 ppm銅之含量存在。 13·如請求項1之摻雜焊料，其中該至少一種主要含磷之摻質 及該至少一主要含銅之摻質係以約2〇_6〇 ppm磷及約 40-600 ppm銅之含量存在。 14·如請求項1之摻雜焊料，其中該至少一種主要含磷之摻質 及該至少一主要含銅之摻質係以約3〇_6() ppm磷及約 300_500 ppm銅之含量存在。 15· —種形成摻雜焊料之方法，其包括： 提供至少一種焊料； 提供至少一種主要含磷之摻質； 提供至少一種主要含銅之摻質，並 摻合該至少一種焊料、該至少一主要含磷之摻質及該 至少一種主要含鋼之摻質以形成摻雜焊料。 κ如請求項15之方法，其中該至少―種焊料包含銦、船、 銀、銅、鋁、錫、鉍、鎵及其合金、覆銀之銅、覆銀之 紹或其組合物。 96033.doc -2 · 1272152 1 7·如請求項16之方法，其中該至少一種焊料包含鉛錫合 金、銦錫（InSn)化合物及合金、銦銀（InAg)化合物及合金、 主要含銦之化合物、錫銀鋼化合物及合金（SnAgCu)、錫 鉍化合物及合金（SnBi)、主要含鋁之化合物及其合金與組 合物。 18·如請求項17之方法，其中該鉛錫合金包含鉛（37%)_錫 (63%)共晶合金。 19·如請求項丨5之方法，其中該至少一種主要含磷之摻質係 以小於約100 ppm填之含量存在。 20·如請求項19之方法，其中該至少一種主要含磷之摻質係 以小於約70 ppm填之含量存在。 21 ·如請求項20之方法，其中該至少一種主要含鱗之摻質係 以小於約60 ppm填之含量存在。 22·如請求項15之方法，其中該至少一種主要含銅之摻質係 以小於約800 ppm銅之含量存在。 23·如請求項22之方法，其中該至少一種主要含銅之摻質係 以小於約600 ppm銅之含量存在。 24·如請求項23之方法，其中該至少一種主要含銅之摻質係 以小於約500 ppm銅之含量存在。 25·如請求項15之方法，其中該至少一種主要含磷之摻質及 該至少一種主要含銅之摻質係以約1〇_1〇〇 磷及約 25-800 ppm銅之含量存在。 26·如請求項15之方法，其中該至少一種主要含磷之摻質及 該至少一種主要含銅之摻質係以約1〇-7〇 磷及約 96033.doc 1272152 25-500 ppm銅之含量存在。 27. 如請求項15之方法，其中該至少一種主要含磷之摻質及 該至少一種主要含銅之摻質係以約20-60 ppm磷及約 40-600 ppm銅之含量存在。 28. 如請求項15之方法，其中該至少一種主要含磷之摻質及 該至少一種主要含銅之摻質係以約30-60 ppm磷及約 300-500 ppm銅之含量存在。 29. —種多層材質，其包含： 一表面或基片； 一電氣互連結構； 含至少一種主要含磷之摻質及至少一種主要含銅之摻 ^ 質；及， 半導體晶片或封裝體。 30. —種電子元件，其含有如請求項1之摻雜焊料。 31. —種半導體元件，其含有如請求項1之摻雜焊料。 96033.doc1272152 X. Patent application scope: 1 . A doped solder comprising at least one solder, at least one dopant mainly comprising phosphorus; and at least one dopant mainly comprising copper. 2. The doped solder of claim 1, wherein the at least one solder comprises indium, lead, silver, copper, aluminum, tin, antimony, gallium and alloys thereof, silver coated copper, silver coated or combinations thereof. 3. The doped solder of claim 2, wherein the at least one solder comprises a lead-tin alloy, an indium tin (InSn) compound and an alloy, an indium silver (ItlAg) compound and an alloy, a compound mainly containing indium, a tin-silver-copper compound, and Alloy (SnAgCu), tin wire compound and alloy (SnBi), mainly aluminum-containing compounds and alloys and compositions thereof. 4. The doped solder of claim 3, wherein the lead-tin alloy comprises a (37%)-tin (63%) eutectic alloy. 5. The doped solder of claim 1, wherein the at least one predominantly lining dopant is present at a level of less than about 100 ppm phosphorus. 6. The doped solder of claim 5, wherein the at least one predominantly scaled dopant is present at a level of less than about 70 ppm phosphorus. 7. The hybrid solder of claim 6, wherein the at least one predominantly disc containing dopant is present at a level of less than about 60 ppm phosphorus. 8. The doped solder of claim 1, wherein the at least one predominantly copper-containing dopant is present at a level of less than 800 ppm copper. 9. The doped solder of claim 8, wherein the at least one predominantly copper-containing dopant 96033.doc 1272152 is present at a level of less than about 600 ppm copper. 1 1. The doped solder of claim 9, wherein the at least one predominantly copper-containing dopant is present at a level of less than about 500 ppm copper. 11. The doped solder of claim 1, wherein the at least one predominantly phosphorus-containing dopant and the at least one predominantly steel-containing dopant are about 1 〇 1 〇〇卯 m phosphorus and about 25-800 ppm copper The content is present. 12. The doped material of claim 1, wherein the at least one predominantly phosphorus-containing dopant and the at least one predominantly copper-containing dopant are about 1 〇 7 μm phosphorus and about 25-500 ppm copper The content is present. 13. The doped solder of claim 1, wherein the at least one predominantly phosphorus-containing dopant and the at least one predominantly copper-containing dopant are between about 2 〇 6 〇 ppm phosphorus and about 40-600 ppm copper. presence. 14. The doped solder of claim 1 wherein the at least one predominantly phosphorus-containing dopant and the at least one predominantly copper-containing dopant are present at a level of about 3 〇 6 (6 ppm) phosphorus and about 300 Å to 500 ppm copper. . A method of forming a doped solder, comprising: providing at least one solder; providing at least one dopant mainly comprising phosphorus; providing at least one dopant mainly comprising copper, and blending the at least one solder, the at least one The primary phosphorus-containing dopant and the at least one predominantly steel-containing dopant form a doped solder. </ RTI> The method of claim 15, wherein the at least one of the solders comprises indium, boat, silver, copper, aluminum, tin, antimony, gallium and alloys thereof, silver coated copper, silver coated or combinations thereof. The method of claim 16, wherein the at least one solder comprises a lead-tin alloy, an indium tin (InSn) compound and an alloy, an indium silver (InAg) compound and an alloy, and a compound mainly containing indium. Tin-silver steel compounds and alloys (SnAgCu), tin-bismuth compounds and alloys (SnBi), mainly aluminum-containing compounds, and alloys and compositions thereof. 18. The method of claim 17, wherein the lead-tin alloy comprises a lead (37%)-tin (63%) eutectic alloy. 19. The method of claim 5, wherein the at least one predominantly phosphorus-containing dopant is present at a level of less than about 100 ppm. The method of claim 19, wherein the at least one predominantly phosphorus-containing dopant is present at a level of less than about 70 ppm. The method of claim 20, wherein the at least one predominantly scaly dopant is present at a level of less than about 60 ppm. The method of claim 15 wherein the at least one predominantly copper-containing dopant is present at a level of less than about 800 ppm copper. The method of claim 22, wherein the at least one predominantly copper-containing dopant is present at a level of less than about 600 ppm copper. The method of claim 23, wherein the at least one predominantly copper-containing dopant is present at a level of less than about 500 ppm copper. The method of claim 15 wherein the at least one predominantly phosphorus-containing dopant and the at least one predominantly copper-containing dopant are present at a level of about 1 〇 1 〇〇 phosphorus and about 25-800 ppm copper. The method of claim 15, wherein the at least one primary phosphorus-containing dopant and the at least one predominantly copper-containing dopant are about 1 〇 -7 〇 phosphorus and about 96033.doc 1272152 25-500 ppm copper The content is present. 27. The method of claim 15 wherein the at least one predominantly phosphorus-containing dopant and the at least one predominantly copper-containing dopant are present at a level of from about 20 to about 60 ppm phosphorus and from about 40 to about 600 ppm copper. 28. The method of claim 15 wherein the at least one predominantly phosphorus-containing dopant and the at least one predominantly copper-containing dopant are present at a level of from about 30 to 60 ppm phosphorus and from about 300 to 500 ppm copper. 29. A multilayer material comprising: a surface or substrate; an electrical interconnect structure; a dopant comprising at least one predominantly phosphorus-containing dopant and at least one predominantly copper-containing dopant; and, a semiconductor wafer or package. 30. An electronic component comprising the doped solder of claim 1. 31. A semiconductor component comprising the doped solder of claim 1. 96033.doc
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US20130045131A1 (en) * 2011-08-17 2013-02-21 Honeywell International Inc. Lead-Free Solder Compositions
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US6348740B1 (en) * 2000-09-05 2002-02-19 Siliconware Precision Industries Co., Ltd. Bump structure with dopants
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