GB2220956A - Copper alloy bonding wire - Google Patents

Copper alloy bonding wire Download PDF

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Publication number
GB2220956A
GB2220956A GB8911485A GB8911485A GB2220956A GB 2220956 A GB2220956 A GB 2220956A GB 8911485 A GB8911485 A GB 8911485A GB 8911485 A GB8911485 A GB 8911485A GB 2220956 A GB2220956 A GB 2220956A
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United Kingdom
Prior art keywords
ppm
alloy
wire
copper
group
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GB8911485A
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GB8911485D0 (en
GB2220956B (en
Inventor
Toshiaki Ono
Makoto Kinoshita
Toshinori Ishii
Kiyoaki Tsumura
Hitoshi Fujimoto
Syuichi Osaka
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Mitsubishi Metal Corp
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Mitsubishi Metal Corp
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Priority claimed from JP63121477A external-priority patent/JPH01291435A/en
Priority claimed from JP63121476A external-priority patent/JPH01290231A/en
Application filed by Mitsubishi Metal Corp filed Critical Mitsubishi Metal Corp
Publication of GB8911485D0 publication Critical patent/GB8911485D0/en
Publication of GB2220956A publication Critical patent/GB2220956A/en
Application granted granted Critical
Publication of GB2220956B publication Critical patent/GB2220956B/en
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    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
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Abstract

An ultrafine copper alloy wire, comprising (a) a base material composed essentially of an oxygen-free copper containing not higher than 1.0 ppm in total of at least one member selected from the group consisting of S, Se and Te and balance copper, and (b) at least one alloy element selected from the group consisting of Si, Al, Cr, Fe, Mn, Ni, P, Sn and Zn in a total amount in the range of 1.0 to 500 ppm, and a semiconductor device comprising a bonding wire made of the ultrafine copper alloy wire.

Description

ULTRAFINE WIRES MADE OF COPPER ALLOY AND SEMICONDUCTOR DEVICES USING SAME
BACKGROUND OF THE INVENTION Field of the Invention
The present invention relates to ultrafine wires made of copper alloy f or use in semiconductor devices and semiconductor devices including such wires. Prior Art
Heretofore, various semiconductor devices such as transistors, integrated circuits (IC1s) and large scale integrated circuits (LSI1s) have been known. The semiconductor devices are produced in many steps, For example, one of conventional methods in which IC's are produced mainly include the following steps: (a) at first copper (Cu) alloy strips of 0.1 to 0.3 mm in thickness are provided as a_lead frame material; (b) lead frames having a shape adapted to a IC to be produced are produced from the lead frame material by etching or punching with a press; (c) then, Si chips are bonded to the lead frames at predetermined positions thereof by thermo-bonding the Si chips using a conductive resin such as Ag paste, or soft soldering the Si chips via plating layers made of Au, Ag, Ni, Cu or alloys thereof formed on one surface of Si and that of lead frame or hard soldering them with Au; 22-120956 - 1) - (d) ball bonding is performed over the Si chip and the lead frame using ultrafine an Au wire of 20 to 50 Mm in diameter as a bonding wire; (e) subsequently, the Si chip, the bonding wire and the lead frame are sealed with a resin in order to protect them; and (f) finally, connecting portions of the lead frames are cut to produce IC's.
As stated above, ultrafine gold (Au) wires have been used as a bonding wire in the Production of semiconductor devices and therefore the semiconductor devices have been expensive. Recently, attention is increasingly directed to ultrafine, highly pure oxygen-free copper wires which contain substantially no oxygen and are highly pure and less expensive.
Usually, thermocompression bonding is employed in combination with ultrasonic wave when ultrafine, highly pure oxygen-free copper wires are 1 used as a bonding wire in semiconductor devices. These wires are disadvantageous in that upon thermocompression bonding, ball portions formed at the tip of the wires would cause deterioration, e.g., generation of micro-cracks in Si chips provided with the device to which they are bonded. For this reason, it has _been believed in the art that addition of various elements to increase the hardness of bonding materials is undesirable.
3 However, recent developments in the bonding technique has provided Si chips which can be bonded and are hardly destroyed even when the hardness of the ball portion changed to some extent, which has enabled the incorporation of additional or alloy elements in larger amounts than ever.
Furthermore, there is increasing tendency that semiconductors and semiconductor devices must be used under severer conditions such as high temperatures in accordance with recent increasing demands for enhanced reliability. This causes new problems such as corrosion of junction or bonding between the wire and an aluminum (Al) alloy wiring sheath which occurs as a result of the generation of a local electric cell between the two, resulting in the occurrence of breaking of wire or disconnection.
'-,TJMMARY OF-JHE TNVENTION As the result of intensive research with view to obviating the above- described defects of the,prior art and developing copper bonding wires, it has now been found that (a) when the total content.of sulfur (S), selenium (Se) and tellurium (Te) in the copper exceeds 1.0 ppm, adverse influences are observed on the corrosion resistance of the junction between the wire and Al alloy wiring sheath; (b) incorporation, into the above base material, of at least one member selected from the group consisting of Si, Al, Cr, Fe, Mn, Ni, P, Sn and Zn in amounts in the range of 1.C to 500 ppm in total considerably increases the corrosion resistance of the junction between the wire and the witing sheath; (c) incorporation of the above-described element or elements in a base material containing S, Se and/or Te in total amounts exceeding 1A0 ppm results in not only a disadvantage of increased hardness.of the base material itself but also failure to obtain improvement in the corrosion resistance of the junction.
The present invention is based on the above discovery and provides an ultrafine wire comprising (a) a base material composed essentially of an oxygen-free copper containing not higher than 1.0 ppm in total of at least one member selected from the group consisting of S, Se and Te and balance copper, and (b) at least one alloy element selected from the group consisting of Si, Al, Cr, Fe, Mn, Ni, P, Sn and Zn in a total amount in the range of 1.0 to 500 ppm.
The present invention also provides a semiconductor device comprising the above-described highly pure, ultrafine oxygen-free copper alloy wiring as a bonding wire.
The ultraf ine copper alloy wiring according to the. present invention can reduce the hardness without deteriorating-the corrosion resistance by adjusting total content of S, Se and Te in the highly pure oxygen-free copper to a level of 1.0 ppm or less, and can prevent the formation of local electric cell on the junction and - improve the corrosion resistance at high temperatures when heat bonded to Si chips or on the surface of lead frames by incorporating at least one member selected from the group consisting of Si, Al, Cr, Fe, Mn, Ni, P, Sn and Zn in an amount of 1.0 to 500 ppm, thereby ensuring the co rrosion resistance of the bonding junction with increase in the hardness being in, a range in which bonding is possible.
Furthermore, in semiconductor device using the ultrafine copper wiring according to the present invention, it is possible to prevent the occurrence of accidents such as breakage of wiring due to corrosion as a result of the formation of a local electric cell in the junction between the wiring and A1 alloy coating, and therefore the device shows highly resistant to undesirable environment such as high temperatures.
DETAILED DESCRIPTION OF THE INVENTION
In the ultrafine copper alloy wire of the present invention, the total content of the alloy components, i.e., at least one member selected from the group consisting of Si, Al, Cr, Fe, Mn, Ni, P, Sn and Zn, is 1.0 to 500 ppm. When the total content of the alloy components is below 1.0 ppm, no effect is obtained for improving corrosion resistance in the junction between the wire and Al alloy wiring sheath or coating upon use of the semiconductor device at high temperatures. On the other hand, when the content is above 500 ppm, processing hardening accompanied by the deformation of the ball portion formed on the tip of the wiring at the time of wire bonding occurs abruptly and therefore it becomes difficult to effect wire bonding to Si chips which have a construction difficult to break. The upper limit of the total content of S, Se and Te as unavoidable impurities is determined empirically. When the content is above the upper limit, not only the hardness increases but also reduction in the corrosion resistance in the conventional copper bonding wire cannot be avoided.
Preferably, the ultrafine copper bonding wire contains Si in an amount of not lower than 1.0 ppm, and also at least one member selected from the group consisting of Al, Cr, Fe, Mn, Ni, P, Sm and Zn in a total amount of 1.0 to 500 ppm taken together with Si.
EXAMPLES
The-ultrafine copper alloy wire according to the present invention will be described in greater detail with reference to examples which are mere examples and the present invention should not be construed as-being limited thereto. EXAMPLE 1 After ordinary electric copper used as a starting material was subjected to electrolytic purification repeatedly, an element apt to form a compound with S, Se or Te such as La was added, and the mixture was subjected to zone refining to produce highly pure oxygen-free copper containing S, Se and Te in a total amount of not higher than 1.0 ppm. Subsequently, the highly pure oxygen-free copper was melted in a vacuum smelting furnace and at least one member selected from the group consisting of Al, Cr, Fe, Mn, Ni, P, Sn and Zn was added in a total amount of 1.0 to 500 ppm as shown in Table 1, and the mixture was cast. The copper product thus obtained was subjected to hot and cool drawing steps under ordinary conditions to produce ultrafine wire sample Nos. 1 to 15 each having a diameter of 25 Mm.
For comparison, comparative samples Nos. 1 to 4 were produced in which at least one member selected from the group consisting of Al, Cr, Fe, Mn, Ni, P, Sn and Zn was contained in a total amount below 1.0 ppm or above 500 ppm.
Then, using the thus-obtained various ultrafine copper wires, ball bonding was effected to Si chips having Al alloy wiring sheath which were resistant to ball bonding,and the number of microcracks formed was measured.
Furthermore, semiconductor devices produced using such wires were left to stand at a high temperature as high as 2500C for 30 hours and then the number of portions of poor junction was meas-ured. The results obtained are shown in Table 1.
Table 1 n=1,400 n=50 n=50 Number of Number of Poor Junction Poor Junction Alloy Component Number of After Standing After 500 Cycles Examnle --- and CQntent Mjerorrack at 25CC for 30 li.r.s at -650C to 1500C (Ppm) 1-1 Al 23 0 0 0 1-2 Al 276 0 0 0 1-3 Cr 7.4 0 2 0 1-4 Fe 1.3 0 3 0 1-5 Mn 4 0 0 0 1-6 Ni 376 0 0 0 1 1-7 Ni 55 0 0 0 OD 1-8 p 6.4 0 2 0 1-9 Sn 242 0 0 0 1-10 Zn 471 0 0 0 1-11 Al 33 Fe 73 0 0 0 1-12 Al 79 Ni 209 0 0 0 Table-l-ICQntinued) n=1,400 n=50 Numn=50 Number of ber of Poor Junction Poor Junction Alloy Component Number of After Standing After 500 Cycles Examle and Content MiQrocrack at 2502C for 30 hrs at -65C Lo 1500C (Ppm) 1-13 Ni 7.5 Sn 10.3 0 1 0 1-14 Ni 26 Zn 105 0 0 0 1-15 p 59 Sn 25 0 0 0 Comparative (0 E xamD 1 e_ 1-1 A 0.8 0 32 38 1-2 Ni 0.9 0 40 25 1-3 Zn 536 72 0 0 1-4 Al 337 Ni 320 154 0 0 f - The results in Table 1 show that the ultrafine copper alloy wires of the present invention excepting sample Nos. 3, 4, 8 and 13 showed no corrosion fracture in the junction between the wire and Al alloy wiring sheath, and that samples Nos. 3, 4, 8 and 13 showed fractures to a lesser extent as compared with comparative samples Nos. 1 and 2 in which no improvement in corrosion resistance was obtained due to low content of the alloy element. In the comparative samples Nos. 3 and 4, the bail hardness was high due to high content of the alloy element, and therefore the occurrence of damages or microcracks was not prevented even when bonded to Si chips having a construction resistant to fracture. ExamDle 2 The highly pure oxygen-free copper containing S, Se and Te in a total amount of hot higher than 1.0 ppm was produced in the same manner as in Example 1, and melted in a vacuum smelting furnace. Si was added to the molten copper in amounts shown in Table 2 as an alloy component, and the mixture was cast. The cast products thus obtained were subjected to hot and cold drawing steps to obtain ultrafine copper alloy wires of the present invention having a diameter of 25 Mm (sample Nos. 2-1 to 2-11) For comparison, comparative samples Nos. 2-1 to 2-3 were also produced in which the content of Si was below 1.0 ppm or above 500 ppm.
- 1 1 - Various ultrafine copper alloy wires thus-obtained were bonded by ball bonding to Si chips which had an Al alloy wiring sheath and were resistant to breakage due to bonding, and number-of the occurrence of microcracks was measured.
Furthermore, semiconductor devices produced using such wires were left to stand at a high temperature as high as 2500C for 30 hours and then the number of portions of poor junction was measured. The results obtained are shown in Table 2.
12 - Table 2 n=1,400 n=50 n=50 Number of Number.of Poor Junction Poor Junction Example Si Content Number of After Standing After 500 Cycles (Ppm) Mici:ocrack at 2500C for 30 hrs at -65C to 15CC 2-1 1.2 0 3 0 2-2 5.1 0 2 0 2-3 10.4 0 1 0 2-4 18.6 0 1 0 2-5 24.9 0 0 0 2-6 103 0 0 0 2-7 148 0 0 0 2-8 202 0 2 0 2-9 257 0 0 0 2-10 344 0 0 0 2-11 450 0 0 0 Comparative -- Examole 2-1 0.5 0 38 25 2-2 0.8 0 21 11 2-3 538 98 0 0 Note: Total content of S, Se and Te being not higher than 1.0 ppm.
1 1 1 F--W 1 The results in Table 2 show that the ultrafine copper alloy wires of the present invention excepting sample Nos. 2-1 to 2-4 showed no corrosion fracture in the junction between the wire and Al alloy wiring sheath, while comparative samples Nos. 2-1 and-2-2 showed no improvement in corrosion resistance due to low content of Si. In the comparative sample No. 3 the ball hardness was high due to high content of Si and therefore the occurrence of damages of the wiring sheath or of microcracks was not prevented even when bonded to Si chips having a construction resistant to fracture. Example 3 The highly pure oxygen-free copper containing S, Se and Te in a total amount of not higher than 1 ppm was produced in the same manner as in Example 1, and melted in a vacuum smelting furnace. -Si was added to the molten copper in an amount not lower than 1 ppm, and also at least one member selected from the group consisting of Al, Cr, Fe, Mn, Ni, P, Sn and Zn was added as-an alloy component in a total amount of 1.0 to 500 ppm taken together with Si, and the mixture was cast. The cast products thus obtained were subjected to hot and cold drawing steps to obtain ultrafine copper alloy wires of the present invention having a diameter of 25 Mm (sample Nos. 3-1 to 3-18) For comparison, comparative samples Nos. 3-1 to 3-4 were also produced in which the total content of Si and other alloy component(s) was below 1.0 ppm or above 500 PPM- The same experiments as in Example 1 were repeated using these ultrafine wires. The results obtained are shown in Table 3.
1 Table 3
P=1,400 n=50 n=50 Number of Number of Poor Junction Poor Junction Alloy Component Number of After Standing After 500 Cycles --ExamDle and-Content Microcrack at 2500C for 30 hrs at -652C to 1500C (Ppm) 3-1 si 7.7 Al: 7.5 0 1 0 3-2 si 6.7 Al 46 0 0 0 3-3 si 1.1 Cr 0.3 0 3 0 3-4 si 10 Cr 72 0 0 0 3-5 si 92 Fe 144 0 0 0 3-6 si 98 Fe 336 0 0 0 3-7 si 12 Mn 86 0 0 0 3-8 si 125 Mn 353 0 0 0 Table 3--(Continued) n=1,400 n=50 n=50 Number of Number of Poor Junction Poor Junction Alloy Component Number of After Standing After 500 Cycles ExamDle and Content MicrQcrack at 2500C for 30 hrs at -650C to 1500C (Ppm) 0 3-9 si ' 54 Ni 46 0 0 0 3-10 si 74 Ni 353 0 0 0 3-11 si 403 p 15 0 0 0 3-12 si 243 p 237 0 0 0 3-13 si 98 Sn 250 0 0 0 3-14 si 57 Sn 374 0 0 0 3-15 si 54 Zn 149 0 0 0 3-16 si 9.2 A1 13 Fe 25 0 0 0 Table 3 (Continued) n=1,400 n=50 n=50 Number of Number of Poor Junction Poor Junction Alloy Component Number of After Standing After 500 Cycles ExamDle -and Content Microcrack at 2500C for 30 hrs at -650C-to 1500C (ppm) 3-17 Si 132 Ni 28 P 76 0 0 0 3-18 Si 321 Ni 81 Zn 49 0 0 0 Comparative -Example 3-1 Si 0.3 Al 0.5 0 33 46 3-2 si 89 Ni 660 280 0 0 3-3 si 573 Sn 15 132 0 0 3-4 si 56 Ni 320 Zn 202 193 0 0 The results shown in Table 3 show that the ultrafine copper alloy wires of the present invention excepting sample Nos. 3-1 and 3-3 showed no corrosion fracture in the junction between the wire and A1 alloy wiring sheath, while comparative sample No. 3-1 showed no improvement in corrosion resistance due to low content of Si and Al. In the comparative sample No. 3-2 to 3-4, the ball hardness was high due to high content of Si and other alloy component, and therefore the occurrence of damages of the wiring sheath or of microcracks was not prevented even when bonded to Si chips having a construction resistant to fracture.
WHAT IS CLATMRn TS 1. An ultrafine copper alloy wire, comprising (a) a base material composed essentially of an oxygen-free copper containing not higher than 1.0 ppm in total of at least one member selected from the group consisting of S, Se and Te and balance copper, and (b) at least one alloy element selected from the group consisting of Si, Al, Cr, Fe, Mn, Ni, P, Sn and Zn in a total amount in the range of 1. 0 to 500 ppm.

Claims (1)

  1. 2. An ultrafine copper alloy wire as claimed in Claim 1, wherein said
    alloy element is Si.
    3. An ultrafine copper alloy wire as claimed in Claim 1, wherein said alloy element is Si and at least one member selected from the group consisting of Al, Cr, Fe, Mn, Ni, P, Sn and Zn, the.total amount of the alloy element being in the range of 1.0 to 500 ppm.
    4. In a semiconductor device comprising a semiconductor circuit, a lead frame and a bonding wire,- the improvement wherein said bonding wire is an ultrafine copper alloy wire comprising (a) a base material composed essentially of an oxygen-free copper containing not higher than 1.0 ppm in total of at least one member selected from the group consisting of S, Se and Te and balance copper, and (b) at least one alloy element selected from the group consisting of Si, Al, Cr, Fe, Mn, Ni, P, Sn and Zn in a total amount in the range of 1. 0 to 500 ppm.
    5. A semiconductor device as claimed in Claim 4, wherein said alloy element is Si.
    6. A semiconductor device as claimed in Claim 4, wherein said alloy element is Si and at least one member selected from the group consisting of Al, Cr, Fe, Mn, Ni, P, Sn and Zn, the total amount of the alloy element being in the range of 1.0 to 500 ppm.
    Published 1990at7!4ePatexitOMee,StateHouse.6671 High Ho1born, LondonWClR4TP.Further copies maybe obtained from The Patent Office. Sales Branoh. St Mary Cray, Orpington, Kent BR5 3RD. Printed by Multiplex techniques ltd. St Mary Cray. Kent, Con. V87 1
GB8911485A 1988-05-18 1989-05-18 Ultrafine wires made of copper alloy and semiconductor devices using same Expired - Fee Related GB2220956B (en)

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JP63121477A JPH01291435A (en) 1988-05-18 1988-05-18 Extrafine copper alloy wire for semiconductor device and semiconductor device
JP63121476A JPH01290231A (en) 1988-05-18 1988-05-18 Semiconductor device and copper allow extremely fine wire therefor

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GB2220956A true GB2220956A (en) 1990-01-24
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Cited By (5)

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GB2264306B (en) * 1992-02-21 1995-01-18 Furukawa Electric Co Ltd Electroconductive material for liquid fuel supply instruments
EP1571232A2 (en) * 2004-03-02 2005-09-07 Norddeutsche Affinerie Aktiengesellschaft Copper wire and method and apparatus for making a copper wire
US20080061440A1 (en) * 2006-08-31 2008-03-13 Nippon Steel Materials Co., Ltd. Copper alloy bonding wire for semiconductor device
CN102422404A (en) * 2009-07-30 2012-04-18 新日铁高新材料株式会社 Bonding wire for semiconductor
CN102859672A (en) * 2010-03-25 2013-01-02 田中电子工业株式会社 High-purity Cu bonding wire

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Publication number Priority date Publication date Assignee Title
WO2017221434A1 (en) 2016-06-20 2017-12-28 日鉄住金マイクロメタル株式会社 Bonding wire for semiconductor device

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GB2073250A (en) * 1980-04-09 1981-10-14 Amax Inc Copper alloys with small amounts of manganese and selenium
GB2210061A (en) * 1985-03-27 1989-06-01 Mitsubishi Metal Corp Copper wire for bonding a semiconductor device

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Publication number Priority date Publication date Assignee Title
GB2073250A (en) * 1980-04-09 1981-10-14 Amax Inc Copper alloys with small amounts of manganese and selenium
GB2210061A (en) * 1985-03-27 1989-06-01 Mitsubishi Metal Corp Copper wire for bonding a semiconductor device

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2264306B (en) * 1992-02-21 1995-01-18 Furukawa Electric Co Ltd Electroconductive material for liquid fuel supply instruments
EP1571232A2 (en) * 2004-03-02 2005-09-07 Norddeutsche Affinerie Aktiengesellschaft Copper wire and method and apparatus for making a copper wire
EP1571232A3 (en) * 2004-03-02 2005-12-21 Norddeutsche Affinerie Aktiengesellschaft Copper wire and method and apparatus for making a copper wire
US8610291B2 (en) * 2006-08-31 2013-12-17 Nippon Steel & Sumikin Materials Co., Ltd. Copper alloy bonding wire for semiconductor device
US20080061440A1 (en) * 2006-08-31 2008-03-13 Nippon Steel Materials Co., Ltd. Copper alloy bonding wire for semiconductor device
US8742258B2 (en) * 2009-07-30 2014-06-03 Nippon Steel & Sumikin Materials Co., Ltd. Bonding wire for semiconductor
US20130306352A2 (en) * 2009-07-30 2013-11-21 Nippon Steel & Sumikin Materials Co., Ltd. Bonding wire for semiconductor
US20120118610A1 (en) * 2009-07-30 2012-05-17 Nippon Micrometal Corporation Bonding wire for semiconductor
CN102422404A (en) * 2009-07-30 2012-04-18 新日铁高新材料株式会社 Bonding wire for semiconductor
CN102422404B (en) * 2009-07-30 2015-08-12 新日铁住金高新材料株式会社 Bonding wire for semiconductor
CN105023902A (en) * 2009-07-30 2015-11-04 新日铁住金高新材料株式会社 Bonding wire for semiconductor
CN105023902B (en) * 2009-07-30 2018-01-30 新日铁住金高新材料株式会社 Bonding wire for semiconductor
CN102859672A (en) * 2010-03-25 2013-01-02 田中电子工业株式会社 High-purity Cu bonding wire

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DE3916168A1 (en) 1989-11-30

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