TWI589713B - 具埃（å）級表面氧化層厚度之銅接合線 - Google Patents

具埃（å）級表面氧化層厚度之銅接合線 Download PDF

Info

Publication number
TWI589713B
TWI589713B TW104120028A TW104120028A TWI589713B TW I589713 B TWI589713 B TW I589713B TW 104120028 A TW104120028 A TW 104120028A TW 104120028 A TW104120028 A TW 104120028A TW I589713 B TWI589713 B TW I589713B
Authority
TW
Taiwan
Prior art keywords
copper
wire
vol
copper wire
range
Prior art date
Application number
TW104120028A
Other languages
English (en)
Other versions
TW201615851A (zh
Inventor
穆拉利 薩蘭加帕尼
兮 張
平熹 楊
歐根 米爾克
Original Assignee
賀利氏德國有限責任兩合公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 賀利氏德國有限責任兩合公司 filed Critical 賀利氏德國有限責任兩合公司
Publication of TW201615851A publication Critical patent/TW201615851A/zh
Application granted granted Critical
Publication of TWI589713B publication Critical patent/TWI589713B/zh

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L24/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C1/00—Manufacture of metal sheets, metal wire, metal rods, metal tubes by drawing
    • B21C1/003—Drawing materials of special alloys so far as the composition of the alloy requires or permits special drawing methods or sequences
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C1/00—Manufacture of metal sheets, metal wire, metal rods, metal tubes by drawing
    • B21C1/02—Drawing metal wire or like flexible metallic material by drawing machines or apparatus in which the drawing action is effected by drums
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/76—Adjusting the composition of the atmosphere
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/525—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/43—Manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/43—Manufacturing methods
    • H01L2224/432—Mechanical processes
    • H01L2224/4321—Pulling
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/43—Manufacturing methods
    • H01L2224/438—Post-treatment of the connector
    • H01L2224/43848—Thermal treatments, e.g. annealing, controlled cooling
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/43—Manufacturing methods
    • H01L2224/43985—Methods of manufacturing wire connectors involving a specific sequence of method steps
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/4501—Shape
    • H01L2224/45012—Cross-sectional shape
    • H01L2224/45015—Cross-sectional shape being circular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • 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
    • H01L2224/45138—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 the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45144—Gold (Au) as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • 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
    • H01L2224/45138—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 the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45147—Copper (Cu) as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/4554—Coating
    • H01L2224/45565—Single coating layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/4554—Coating
    • H01L2224/45599—Material
    • H01L2224/45686—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01046—Palladium [Pd]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01047—Silver [Ag]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/053—Oxides composed of metals from groups of the periodic table
    • H01L2924/0541—11th Group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/20—Parameters
    • H01L2924/207—Diameter ranges
    • H01L2924/20751—Diameter ranges larger or equal to 10 microns less than 20 microns
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/20—Parameters
    • H01L2924/207—Diameter ranges
    • H01L2924/20752—Diameter ranges larger or equal to 20 microns less than 30 microns
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/20—Parameters
    • H01L2924/207—Diameter ranges
    • H01L2924/20753—Diameter ranges larger or equal to 30 microns less than 40 microns
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/20—Parameters
    • H01L2924/207—Diameter ranges
    • H01L2924/20754—Diameter ranges larger or equal to 40 microns less than 50 microns
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/20—Parameters
    • H01L2924/207—Diameter ranges
    • H01L2924/20755—Diameter ranges larger or equal to 50 microns less than 60 microns
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/20—Parameters
    • H01L2924/207—Diameter ranges
    • H01L2924/20756—Diameter ranges larger or equal to 60 microns less than 70 microns
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/20—Parameters
    • H01L2924/207—Diameter ranges
    • H01L2924/20757—Diameter ranges larger or equal to 70 microns less than 80 microns
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/20—Parameters
    • H01L2924/207—Diameter ranges
    • H01L2924/20758—Diameter ranges larger or equal to 80 microns less than 90 microns

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Wire Bonding (AREA)

Description

具埃(Å)級表面氧化層厚度之銅接合線
本發明係關於一種具有僅0.5nm至<6nm之圓周表面銅氧化物薄層之銅線。
在電子及微電子應用中使用接合線係該技術中熟知之情形。儘管起初接合線係由金製造，但現在使用較便宜之材料例如銅。儘管銅線提供極好之導電及導熱性，但銅線之接合具有其挑戰。另外，銅線易於發生線之氧化。
存在各種方法以防止銅接合線表面氧化。實例包含用抗氧化貴金屬塗層、玻璃塗層或聚合物塗層塗布銅線。
用於線接合應用之未經塗布之銅線通常具有表面銅氧化物層，其層厚度通常位於(例如)6nm至20nm之範圍內。
術語“銅氧化物”係在本文中使用。其應意指CuO及/或Cu2O。
作為廣泛研發努力之結果，本申請者已研製出具有10μm至80μm、較佳地15μm至50μm之直徑及0.5nm至<6nm、較佳地0.5nm至4nm、尤其0.5nm至3.5nm之圓周表面銅氧化物薄層之銅線。該銅線基體材料係99.99wt.-%(重量-%)之純銅或銅合金，該銅合金由10wt.-ppm至1000wt.-ppm(重量-ppm)、較佳地100wt.-ppm至300wt.-ppm、尤其200wt.-ppm至250wt.-ppm之銀及/或0.1wt.-%至3wt.-%、較佳地0.5wt.-%至2wt.-%、尤其1.2wt.-%至1.3wt.-%之鈀及作為補 足100wt.-%之剩餘部分之銅所組成。
術語“銅線”係在本文中使用。為避免誤解，其應意指呈任何形式之銅線，即如未經處理之銅線及如經處理之銅線，即球-或楔-接合之銅線。
術語“0.5nm至<6nm之圓周表面銅氧化物薄層”係在本文中使用。其應意指0.5nm至<6nm之圓周表面銅氧化物薄層係銅氧化物或其包括銅氧化物。換言之，該0.5nm至<6nm之圓周表面銅氧化物薄層可由銅氧化物組成或其可包括濃度位於(例如)50wt.-%至100wt.-%範圍內之銅氧化物。在實施例中，其在自線外表面至線中心之垂直方向上在該0.5nm至<6nm之深度中展現銅氧化物之濃度梯度。此銅氧化物濃度在線外表面處可係高的，例如90wt.-%至100wt.-%之銅氧化物，且其在該深度中快速地減小至0wt.-%。
在下文中，“由10wt.-ppm至1000wt.-ppm之銀及/或0.1wt.-%至3wt.-%之鈀及作為補足100wt.-%之剩餘部分之銅所組成之銅合金”亦簡稱為“銅合金”。
片語“作為補足100wt.-%之剩餘部分之銅”係在本文中使用。其應意指銅係該銅合金中之主要組份。為避免誤解，此不應理解為排除未明確命名之其他元素，且該等其他元素可由於佔優之技術條件而已發現進入銅合金之途徑，例如由於在製造期間無意地但不可避免之併入。換言之，此等其他元素可作為不可避免之雜質存在於合金中，然而僅以例如>0wt.-ppm至100wt.-ppm之極小總量存在。在任何情況下，皆未將此等不可避免之雜質故意地添加至或引入銅合金形成組合物中。就此而言，該片語“作為補足100wt.-%之剩餘部分之銅”意指，補足100wt.-%之銅合金所遺漏之wt.-%比例由銅加上該等不可避免之雜質組成(若後者存在)。
該銅合金可藉由熟習金屬合金技術者已知之習用方法來製備， 例如藉由將期望比率之銅及銀及/或鈀熔化在一起。在此過程中，使用習用之銅-銀或銅-鈀母合金係可能的。該熔化方法可(例如)使用感應電爐來實施且在真空或在惰性氣體氛圍下實施係合適的。所用材料可具有例如99.99wt.-%及以上之純度級別。該銅合金熔體通常在室溫模具中鑄型，其中其冷卻且固化。
銅或銅合金線之表面銅氧化物層之性質及厚度可藉由飛行時間二次離子質譜(ToF-SIMS；使用鉍離子分析正極性分子)測定或表徵。
銅或銅合金線之表面銅氧化物層之厚度亦可藉由以下等效方法量測：
-經一段時間在多個步驟中使用Ar離子濺射進行深度剖析，直到觀測到100%銅(Cu)為止。此方法為熟習此項技術者所熟知且不需要進一步解釋。
-藉由使用標準方法之深度剖析進行X-射線光電子光譜法(XPS)。此方法為熟習此項技術者所熟知且不需要進一步解釋。
-序貫電化學還原分析(SERA)。對於SERA可使用來自ECI Technology之Surface-Scan QC200裝置。ECI Technology在其網站 http：//www.ecitechnology.com/sites/default/files/downloads/eci-surfacescan-qc200.pdfcan 揭示細節，據此可使用SERA作為品質控制工具來界定銅線表面氧化層厚度之公差。基本上，藉由使用約8.5 pH之硼酸鹽電解質溶解銅氧化層使用法拉第定律(Faraday’s principle)來量測銅氧化物之厚度。SERA能夠分析銅線表面上與基體銅相似之Cu2O、CuO及Cu2S。SERA記錄Cu2O、CuO及Cu2S對時間之反應電位。在-0.4V至-0.6V、-0.8V至-0.9V、-0.9V至-1.0V及-1.1V至-1.2V範圍內之反應電位分別對應於Cu2O、CuO、Cu2S之還原及H2之釋出。表面氧化物/硫化物之還原時間係與層厚度(T)之存在成比例，如根據法拉第方程式所計算：
其中，I係以安培計之電流，t係以秒量測之還原時間，M係以g計之分子量，F係法拉第常數(96498庫侖)，n係電子數，S係以cm2計之經浸沒銅截面之表面積且d係以g/cm3計之膜密度。
SERA方法係申請者量測銅或銅合金線之表面銅氧化物層之層厚度之較佳方法。
在特定實施例中，本發明之銅線展現在其表面(即在表面銅氧化物層之頂部)之自由碳(元素碳)，及/或作為在自線外表面至線中心之垂直方向上在(例如)0.6nm至5nm之深度中之濃度梯度之自由碳。此自由碳濃度在線外表面處可係高的，例如90wt.-%至<100wt.-%之自由碳，且其在該深度中快速地減小至0wt.-%。該自由碳之濃度梯度可與前文所提及之銅氧化物之濃度梯度重疊。
該自由碳梯度之深度可藉由ToF-SIMS(用鉍離子來分析正極性分子)或藉由使用標準方法之深度剖析之XPS來測定或表徵。
本發明亦係關於用於製造本發明銅線之方法。本發明之銅線可藉由包括以下步驟之方法來製備：(a)提供99.99wt.-%純銅或銅合金之銅前體，(b)拉製該前體直到達到該線10μm至80μm、較佳地15μm至50μm之最終直徑為止；(c)在580℃至750℃之目標溫度(峰值溫度)下，在90vol.-%至96vol.-%(體積-%)惰性氣體：4vol.-%至10vol.-%氫氣氛圍中，使該經拉製線退火0.2秒至0.4秒，及(d)使該經退火線在水中淬火，其中該vol.-%總計為100vol.-%。
在本發明方法之步驟(a)中提供99.99wt.-%純銅或銅合金之銅 前體。
通常，此銅前體係呈棒之形式，其具有(例如)2mm至25mm之直徑及(例如)5m至100m之長度。此棒可類似地製備或根據前文所揭示之製備銅合金之方法製備，即藉由在合適之室溫模具中使該銅或銅合金熔體鑄型，隨後冷卻且固化。
在本發明方法之步驟(b)中，在若干步驟中拉製該銅前體直到達到該線10μm至80μm、較佳地15μm至50μm之最終直徑為止。此線拉製方法為熟習此項技術者熟知。可利用習用之鎢及金剛石拉製模具且可利用習用之拉製潤滑劑來支持該拉製。通常，在完成步驟(b)後獲得之該銅線具有層厚度在(例如)6nm至20nm範圍內之圓周表面銅氧化物層。
在本發明方法之步驟(c)中，在570℃至750℃之目標溫度下，在90vol.-%至96vol.-%惰性氣體：4vol.-%至10vol.-%氫氣氛圍中使該經拉製線退火(最終退火，分股退火)0.2秒至0.4秒，其中該vol.-%總計為100vol.-%。
在99.99wt.-%純銅線之情況下，選擇570℃至630℃之目標溫度係較佳的，但在銅合金線之情況下，較佳目標溫度係在620℃至750℃、尤其650℃至710℃之範圍內。
95vol.-%惰性氣體：5vol.-%氫氣氛圍係較佳氛圍。該惰性氣體可係氮及/或氬；通常，其係氮。
該退火係通常藉由牽拉線通過習用退火爐來實施，該退火爐通常呈給定長度之圓柱狀管之形式且以給定速度具有經界定之溫度剖面。在此過程中，可界定並設定退火時間/目標溫度參數。可用90vol.-%至96vol.-%惰性氣體：4vol.-%至10vol.-%氫之混合物吹掃該退火爐。吹掃較佳係以位於43min-1至125min-1、更佳地43min-1至75min-1、最佳地50min-1至63min-1範圍內之氣體交換速率(=氣體流動速 率[公升/min]：內部爐體積[公升])來實施。
在本發明方法之步驟(d)中，使該經退火線在水中淬火，在實施例中該水可含有表面活性劑，例如0.01體積-%至1體積-%之表面活性劑。在水中淬火意指立即地或快速地，即在0.2秒至0.4秒內，將經退火線自其在步驟(c)接受之目標溫度冷卻至室溫。
已發現，特徵為其僅0.5nm至<6nm之圓周表面銅氧化物薄層之本發明之銅線非常適合用作線接合應用中之接合線，同時呈其上文提及之特定實施例之本發明之銅線極其適合於此應用。
線接合技術為熟習此項技術者所熟知。在線接合過程中，通常形成球接合(第1接合)及針腳式接合(stitch bonding)(第2接合，楔接合)。在接合形成期間，施加一定力(通常以克量測)，此係藉由施加超音波能量(通常以mA量測)來支持。在線接合方法中，所施加力之上限與下限之間之差與所施加超音波能量之上限與下限之間之差之數學乘積界定線接合方法窗口：(所施加力之上限-所施加力之下限)．(所施加超音波能量之上限-所施加超音波能量之下限)=線接合方法窗口。
該線接合方法窗口界定允許形成滿足規格之線接合(即其通過習用測試，如習用拉力測試、球剪切測試及球拉力測試，僅舉幾個例子)之力/超音波能量組合之區域。
對於工業應用，出於線接合方法穩固性之原因，期望具有寬廣的線接合方法窗口。本發明之銅線針對銅接合線展現相當寬廣之線接合方法窗口。舉例而言，本發明之直徑20μm之銅線展現對於球接合在(例如)60mA．g至130mA．g範圍內及對於針腳式接合在(例如)2500mA．g至6000mA．g範圍內之線接合方法窗口。
不管線直徑及線類型為何，即99.99wt.-%純銅或銅合金，線接合結果係相同的。進一步相信，僅0.5nm至<6nm之圓周表面銅氧 化物薄層係本發明銅線之寬廣線接合方法窗口的關鍵。可稱<6nm之圓周表面銅氧化物層係獲得良好球及針腳式接合之標準。
咸信在本發明方法之步驟(c)及(d)期間普遍採用之方法參數之獨特組合係獲得本發明銅線與其相當寬廣之線接合方法窗口之必要條件。該等方法參數之較佳組合係：在570℃至750℃(在99.99wt.-%純銅之情況下570℃至630℃；在銅合金之情況下620℃至750℃或更佳地650℃至710℃)之目標溫度下0.2秒至0.4秒，使用氣體交換速率在43min-1至125min-1、更佳地43min-1至75min-1之範圍內之95vol.-%惰性氣體：5vol.-%氫氣混合物作為吹掃氣體，且在0.2秒至0.4秒內快速冷卻至室溫。發現最佳條件具有方法參數之以下組合：在570℃至750℃(在99.99wt.-%純銅之情況下570℃至630℃；在銅合金之情況下620℃至750℃或更佳地650℃至710℃)之目標溫度下0.2秒至0.4秒，使用95vol.-%惰性氣體：5vol.-%氫氣混合物作為氣體交換速率在50min-1至63min-1範圍內之吹掃氣體，且在0.2秒至0.4秒內快速冷卻至室溫。
在完成步驟(d)後，本發明之銅線製成。為了充分地受益於其寬廣的線接合方法窗口，將其立即(即無遲延，例如在完成步驟(d)後不超過7天內)用於線接合應用係合適的。或者，為了保持銅線之寬廣的線接合方法窗口性質且為了防止其受到氧化或其他化學侵蝕，通常在完成步驟(d)後立即(即無遲延，例如在完成步驟(d)後在<1至5小時內)將製成之銅線捲軸並真空密封，且然後儲存用於作為接合線之其他用途。在真空密封條件中之儲存不應超過6個月在打開真空密封後，銅線應在不超過7天內用於線接合。
較佳地，所有方法步驟(a)至(d)以及捲軸及真空密封係在潔淨室條件下(US FED STD 209E潔淨室標準，1k標準)實施。
以下非限制性實例說明本發明。
實例
一般程序：
將99.99wt.-%純度之銅棒熔化於真空感應電爐中且連續鑄型為直徑8mm之棒。在其他實例中，將少量Cu-10wt.-%Ag或Cu-15wt.-%Pd母合金添加至熔體來鑄型Cu-Ag及Cu-Pd合金，其分別具有以下組成：
此外，在室溫(25℃)下冷線拉製此等連續鑄型棒。使用碳化鎢模具來拉製粗線並使用金剛石模具進行進一步壓縮。拉製係在四個步驟中以不同拉製速度來實施：粗線拉製，以0.5m/s之速度自8mm至4mm且以1m/s之速度自4mm至0.8mm；中間線拉製，以4m/s之速度自0.8mm至0.16mm；及細線拉製，以6m/s之速度自0.16mm至0.02mm。拉製藉由使用基於水之潤滑劑來支持。對於粗線(直徑>200μm)模孔壓縮比率係14%，且對於細線(直徑<200μm)為8%。
合金化Cu-Ag及Cu-Pd線在直徑45μm時立即分別在400℃及600℃下退火。99.99wt.-%純銅線未立即退火。
經拉製線具有20μm之最終直徑且展現具有12nm(平均)層厚度之圓周銅氧化物層。
最後藉由將該等線運行通過習用退火爐並使用習用設備(包含捲盤、捲軸、滑車)來對其進行分股退火。退火時間係0.3s。分股退火溫度係600℃(純銅)、630℃(Cu-Ag合金)及700℃(Cu-Pd合金)。用合成氣體(N2：H2，95：5)以如表2所示之氣體交換速率吹掃該爐。
在離開該爐後，立即(即在0.3s內)將熱線在去離子水中淬火。最後，將該經退火線在直徑50mm之潔淨陽極氧化(經鍍敷)鋁捲軸上捲軸，真空包裝並儲存。
使用SERA量測之經退火99.99wt.-%純銅線之典型電化記錄顯示反應電位在-0.4至-0.6V範圍內，此表明在線表面上存在薄Cu2O層。不存在CuO及Cu2S。根據記錄，Cu2O厚度經計算在1.7nm與3nm之間之範圍內。
此外，ToF-SIMS及XPS揭示在線表面上之自由碳(無碳化物之證據)。ToF-SIMS深度剖析鑒別到，在1nm深之前存在強碳，且在約5nm深度進一步降至零。ToF-SIMS深度剖析展示，自由碳可能存在於銅氧化物層之頂部上，此乃因直到1nm為止皆觀測到強自由碳峰，且在1nm之後發現氧及Cu2O之強峰。
藉由球接合(第1接合)至Al接合墊及針腳式接合(第2接合)至銀引線指來測試該等線。在反應性環境下藉由用合成氣體(N2：H2；95：5)吹掃形成自由空氣球(FAB)，且將其接合至Al接合墊，獲得大於0.01g/μm2(6.5g/密耳2)之強球接合及大於8g之球拉力。
下表2顯示線接合方法窗口結果：
USG=超音波能量
++++優良，+++極佳，++良好，+中等
所有發明性線樣品4至8皆產生非常適合於工業應用之方法窗口。具體而言，發明性線樣品7對於第1及第2接合分別顯示119mA．g及5950mA．g之值。

Claims (18)

  1. 一種具有10μm至80μm直徑之銅線，其中該銅線基體材料係99.99wt.-%純銅或由10wt.-ppm至1000wt.-ppm銀及/或0.1wt.-%至3wt.-%鈀及作為補足100wt.-%之剩餘部分之銅所組成之銅合金，其特徵在於該銅線具有0.5nm至4nm之圓周表面銅氧化物薄層。
  2. 如請求項1之銅線，其中其在自線外表面之垂直方向上在0.6nm至5nm深度中展現自由碳之濃度梯度。
  3. 如請求項1或2之銅線，其可藉由包括以下步驟之方法獲得：(a)提供99.99wt.-%純銅或該銅合金之銅前體，(b)拉製該前體直到達到該線10μm至80μm之最終直徑為止；(c)使該經拉製線在570℃至750℃之目標溫度下，在90vol.-%至96vol.-%惰性氣體：4vol.-%至10vol.-%氫氣氛圍中退火0.2秒至0.4秒，及(d)使該經退火線在水中淬火，其中該vol.-%總計為100vol.-%。
  4. 如請求項3之銅線，其中該銅線基體材料係99.99wt.-%純銅且該目標溫度係在570℃至630℃之範圍內。
  5. 如請求項3之銅線，其中該銅線基體材料係該銅合金且該目標溫度係在620℃至750℃之範圍內。
  6. 如請求項3之銅線，其中惰性氣體：氫之體積比率係95：5。
  7. 如請求項3之銅線，其中該惰性氣體係氮及/或氬。
  8. 如請求項3之銅線，其中該退火係藉由牽拉該線通過退火爐來實施，該退火爐係經該惰性氣體/氫混合物以介於43min-1至125min-1範圍內之氣體交換速率來吹掃。
  9. 如請求項8之銅線，其中該氣體交換速率係在43min-1至75min-1、較佳地50min-1至63min-1之範圍內。
  10. 一種產生如請求項1或2之銅線之方法，其包括以下步驟：(a)提供99.99wt.-%純銅或銅合金之銅前體，(b)拉製該前體直到達到該線10μm至80μm之最終直徑為止；(c)使該經拉製線在570℃至750℃之目標溫度下，在90vol.-%至96vol.-%惰性氣體：4vol.-%至10vol.-%氫氣氛圍中退火0.2秒至0.4秒，及(d)使該經退火線在水中淬火，其中該vol.-%總計為100vol.-%。
  11. 如請求項10之方法，其中該銅線基體材料係99.99wt.-%純銅且該目標溫度係在570℃至630℃之範圍內。
  12. 如請求項10之方法，其中該銅線基體材料係該銅合金且該目標溫度係在620℃至750℃之範圍內。
  13. 如請求項10之方法，其中惰性氣體：氫之體積比率係95：5。
  14. 如請求項10之方法，其中該惰性氣體係氮及/或氬。
  15. 如請求項10之方法，其中該退火係藉由牽拉該線通過退火爐來實施，該退火爐係經該惰性氣體/氫混合物以介於43min-1至125min-1範圍內之氣體交換速率來吹掃。
  16. 如請求項15之方法，其中該氣體交換速率係在43min-1至75min-1、較佳地50min-1至63min-1之範圍內。
  17. 一種如請求項1至9中任一項之銅線之用途，其係用於線接合應用中。
  18. 一種藉由請求項10至16中任一項之方法製造之銅線之用途，其係用於線接合應用中。
TW104120028A 2014-06-23 2015-06-22 具埃（å）級表面氧化層厚度之銅接合線 TWI589713B (zh)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
SG10201403532QA SG10201403532QA (en) 2014-06-23 2014-06-23 Copper bonding wire with angstrom (a) thick surface oxide layer

Publications (2)

Publication Number Publication Date
TW201615851A TW201615851A (zh) 2016-05-01
TWI589713B true TWI589713B (zh) 2017-07-01

Family

ID=53404562

Family Applications (1)

Application Number Title Priority Date Filing Date
TW104120028A TWI589713B (zh) 2014-06-23 2015-06-22 具埃（å）級表面氧化層厚度之銅接合線

Country Status (6)

Country Link
US (1) US20170154863A1 (zh)
EP (1) EP3158096B1 (zh)
CN (1) CN106661672B (zh)
SG (1) SG10201403532QA (zh)
TW (1) TWI589713B (zh)
WO (1) WO2015197432A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6600121B2 (ja) * 2017-08-09 2019-10-30 日鉄ケミカル＆マテリアル株式会社 半導体装置用Ｃｕ合金ボンディングワイヤ
CN109811183A (zh) * 2019-03-27 2019-05-28 广东迪奥应用材料科技有限公司 一种用于制备高导电率薄膜的铜基合金及溅射靶材
CN112139278B (zh) * 2020-08-19 2022-05-31 浙江万胜运河钢缆有限公司 一种镀锌钢缆钢丝表面清洁平直工艺

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3918397B2 (ja) * 2000-04-11 2007-05-23 三菱マテリアル株式会社 耐密着性無酸素銅荒引線、その製造方法及び製造装置
MY147995A (en) * 2008-01-25 2013-02-28 Nippon Steel & Sumikin Mat Co Bonding wire semiconductor device
JP2010245390A (ja) * 2009-04-08 2010-10-28 Tatsuta Electric Wire & Cable Co Ltd ボンディングワイヤ
JP4860004B1 (ja) * 2011-02-28 2012-01-25 タツタ電線株式会社 ボンディングワイヤ及びその製造方法
JP5219316B1 (ja) * 2012-09-28 2013-06-26 田中電子工業株式会社 半導体装置接続用銅白金合金細線

Also Published As

Publication number Publication date
WO2015197432A1 (en) 2015-12-30
CN106661672A (zh) 2017-05-10
EP3158096B1 (en) 2018-10-10
US20170154863A1 (en) 2017-06-01
CN106661672B (zh) 2018-09-18
SG10201403532QA (en) 2016-01-28
TW201615851A (zh) 2016-05-01
EP3158096A1 (en) 2017-04-26

Similar Documents

Publication Publication Date Title
KR101742450B1 (ko) 반도체 장치용 본딩 와이어
JP5219316B1 (ja) 半導体装置接続用銅白金合金細線
JP2017163169A (ja) 半導体装置用ボンディングワイヤ
TWI589713B (zh) 具埃（å）級表面氧化層厚度之銅接合線
JP6622415B2 (ja) 被覆ワイヤ
JP6632728B2 (ja) 銀合金化銅ワイヤ
CN113518687B (zh) 经涂覆线材
US11236430B2 (en) Coated wire
TWI818531B (zh) 塗佈圓線及其製造程序
TWI649434B (zh) 合金化銀線
WO2022169407A1 (en) Coated wire
TW201624655A (zh) 球型接合裝置
WO2020101566A1 (en) Coated wire