JPH07502147A - はんだバンプの製造方法および相互接続システム - Google Patents
はんだバンプの製造方法および相互接続システムInfo
- Publication number
- JPH07502147A JPH07502147A JP5506136A JP50613693A JPH07502147A JP H07502147 A JPH07502147 A JP H07502147A JP 5506136 A JP5506136 A JP 5506136A JP 50613693 A JP50613693 A JP 50613693A JP H07502147 A JPH07502147 A JP H07502147A
- Authority
- JP
- Japan
- Prior art keywords
- solder
- bump
- forming
- layer
- contact pad
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 240
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000009825 accumulation Methods 0.000 claims abstract description 29
- 238000005530 etching Methods 0.000 claims abstract description 19
- 239000010409 thin film Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims description 93
- 239000002184 metal Substances 0.000 claims description 93
- 238000000034 method Methods 0.000 claims description 60
- 230000004888 barrier function Effects 0.000 claims description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 31
- 229910052802 copper Inorganic materials 0.000 claims description 31
- 239000010949 copper Substances 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 28
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 27
- 229910000765 intermetallic Inorganic materials 0.000 claims description 23
- 229910052804 chromium Inorganic materials 0.000 claims description 21
- 239000011651 chromium Substances 0.000 claims description 21
- 210000002105 tongue Anatomy 0.000 claims description 17
- 239000003518 caustics Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 239000010408 film Substances 0.000 claims description 13
- 238000004377 microelectronic Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- 230000001143 conditioned effect Effects 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- WSSJONWNBBTCMG-UHFFFAOYSA-N 2-hydroxybenzoic acid (3,3,5-trimethylcyclohexyl) ester Chemical compound C1C(C)(C)CC(C)CC1OC(=O)C1=CC=CC=C1O WSSJONWNBBTCMG-UHFFFAOYSA-N 0.000 claims 1
- 238000005272 metallurgy Methods 0.000 abstract description 6
- 238000009736 wetting Methods 0.000 abstract 1
- 229920002120 photoresistant polymer Polymers 0.000 description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 231100001010 corrosive Toxicity 0.000 description 6
- 238000000059 patterning Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- WWTBZEKOSBFBEM-SPWPXUSOSA-N (2s)-2-[[2-benzyl-3-[hydroxy-[(1r)-2-phenyl-1-(phenylmethoxycarbonylamino)ethyl]phosphoryl]propanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound N([C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)O)C(=O)C(CP(O)(=O)[C@H](CC=1C=CC=CC=1)NC(=O)OCC=1C=CC=CC=1)CC1=CC=CC=C1 WWTBZEKOSBFBEM-SPWPXUSOSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229940126208 compound 22 Drugs 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- ZTXONRUJVYXVTJ-UHFFFAOYSA-N chromium copper Chemical compound [Cr][Cu][Cr] ZTXONRUJVYXVTJ-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910018082 Cu3Sn Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 235000020046 sherry Nutrition 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- ZFXYFBGIUFBOJW-UHFFFAOYSA-N theophylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1NC=N2 ZFXYFBGIUFBOJW-UHFFFAOYSA-N 0.000 description 1
- 238000007736 thin film deposition technique Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
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- 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
- H01L24/10—Bump connectors ; Manufacturing methods related thereto
- H01L24/11—Manufacturing methods
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/60—Attaching or detaching leads or other conductive members, to be used for carrying current to or from the device in operation
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- H01L2224/039—Methods of manufacturing bonding areas involving a specific sequence of method steps
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- H05K3/00—Apparatus or processes for manufacturing printed circuits
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- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3452—Solder masks
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3457—Solder materials or compositions; Methods of application thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49117—Conductor or circuit manufacturing
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- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
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- Arc Welding In General (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
Description
Claims (27)
- 1.基板上の多数の接点パッドにハンダバンプを形成するにあたり: 前記接点パッドおよび前記接点パッドの間の前記基板にバンプ下側金属を形成し ;次いで 前記接点パッド間の前記バンプ下側金属にハンダ障壁を形成し、前記ハンダ障壁 が前記接点パッド上の前記バンプ下側金属を露出し;次いで 前記ハンダ障壁上にハンダ蓄積領域を形成し、前記ハンダ蓄積領域が前記接続パ ッド上の前記バンプ下側金属を露出し次いで 前記ハンダ障壁と前記ハンダ蓄積領域により露出するバンプ下側金属上に、前記 接続パッド上にハンダパッドを形成し次いで; ハンダパッドをリフローイングさせて前記バンプ下側金属と前記接点パッドに隣 接する前記ハンダとの金属間化合物層を有するハンダバンプを形成し;さらに次 に前記ハンダ障壁および前記接点パッドの間の前記バンプ下側金属を、前記金属 間化合物層を前記ハンダ障壁および前記バンプ下側金属より緩徐にエッチングす る少なくとも1つの腐食剤を用いてエッチングして、これにより前記接点パッド に隣接する前記ハンダバンプのアンダーカッティングを減少させる工程を含むこ とを特徴とするハンダバンプの製造方法。
- 2.前記バンプ下側金属を形成する工程が前記接点パッドの間で、前記基板上に 表面安定化層を形成する工程より前にあることを特徴とする請求項1に記載の方 法。
- 3.前記バンプ下側金属を形成する工程が前記基板および前記接点パッドに隣接 するクロム層を有するバンプ下側金属、前記クロム層上の中間のクロム/銅の調 整した層、および前記クロム/銅層上の銅層を形成する工程を含むことを特徴と する請求項1に記載の方法。
- 4.前記ハンダ障壁を形成する工程が:前記基板上の、前記接点パッドの間およ び上で薄膜ハンダ障壁層を形成し;さらに 前記接点パッド上の前記薄膜ハンダ障壁層を除去する工程を含むことを特徴とす る請求項1に記載の方法。
- 5.前記除去工程が前記接点パッド上の前記ハンダ障壁層をリフトオフする工程 を含むことを特徴とする請求項4に記載の方法。
- 6.前記ハンダ堆積工程が前記接点パッド上に、前記ハンダ障壁および前記ハン ダ蓄積領域により露出されるバンプ下側金属上にハンダをメッキする工程を含む ことを特徴とする請求項1に記載の方法。
- 7.前記リフローイング工程が前記ハンダパッドを溶融する工程を含むことを特 徴とする請求項1に記載の方法。
- 8.さらに前記リフローイング工程がハンダパッドをリフローイングさせて前記 金属間化合物層に舌片を形成する工程を含むことを特徴とする請求項1に記載の 方法。
- 9.前記ハンダが鉛/スズハンダを含み、前記バンプ下側金属には銅が含まれ、 さらに前記リフローイング工程がハンダパッドをリフローイングして銅およびス ズの金属間化合物層を有するハンダバンプを形成する工程を含むことを特徴とす る請求項1に記載の方法。
- 10.前記ハンダ蓄積領域を形成する工程が、前記ハンダパッドを形成する工程 中に前記ハンダパッド含ませるための、前記ハンダ障壁上に厚膜ハンダ蓄積領域 を形成する工程を含むことを特徴とする請求項1に記載の方法。
- 11.基板上の多数の接点パッドにハンダバンプを形成するにあたり: 前記接点パッドおよび前記接点パッドの間の前記基板にバンプ下側金属を形成し ;次いで 前記接点パッド上のバンプ下側金属上にハンダを形成し、前記接点パッドの間の バンプ下側金属がハンダを含まず;次に 前記接点パッド上の少なくとも一部の前記バンプ下側金属を、前記ハンダをリフ ローイングさせることにより前記バンプ下側金属および前記ハンダの金属間化合 物層に変換し;さらに次いで 前記接点パッドの間のバンプ下側金属を除去するとともに前記接点パッド上の前 記金属間化合物層を保護し、これによりリフローイングさせたハンダのアンダー カッティングを減少させる工程を含むことを特徴とするハンダバンプの製造方法 。
- 12.前記バンプ下側金属を形成する工程が接点パッドの間で、前記基板上に表 面安定化層を形成する工程より前にあることを特徴とする請求項11に記載の方 法。
- 13.前記バンプ下側金属を形成する工程が前記基板および前記接点パッド、前 記クロム層上の中間のクロム/銅の調整した層、および前記クロム/銅層上の銅 層に隣接するクロム層を有するバンプ下側金属を形成する工程を含むことを特徴 とする請求項11に記載の方法。
- 14.前記ハンダを形成する工程が前記接点パッド上のバンブ下側金属にハンダ をメッキする工程を含むことを特徴とする請求項11に記載の方法。
- 15.前記ハンダを形成する工程が前記接点パッド上のバンプ下側金属にハンダ を形成するとともに、前記接点パッドの間でハンダの形成を制限する工程を含む ことを特徴とする請求項11に記載の方法。
- 16.前記変換工程が前記ハンダを溶融させる工程を含むことを特徴とする請求 項11に記載の方法。
- 17.さらに前記変換工程が前記ハンダをリフローイングさせることにより前記 金属間化合物層に舌片を形成する工程を含むことを特徴とする請求項11に記載 の方法。
- 18.前記ハンダが鉛/スズハンダを含み、前記バンプ下側金属には銅が含まれ 、さらに前記変換工程が前記接点パッド上の少なくとも1部の前記バンプ下側金 属を銅およびスズの金属間化合物層に変換する工程を含むことを特徴とする請求 項11に記載の方法。
- 19.前記ハンダを形成する工程が: 前記接点パッドの間の前記バンプ下側金属上にハンダ蓄積領域を形成し、前記ハ ンダ蓄積領域が前記接点パッド上の前記バンプ下側金属を露出し;次に 前記接点パッド上のバンプ下側金属にハンダを形成し、前記ハンダ蓄積領域が前 記接点パッドの間のハンダの形成を制限する工程を含むことを特徴とする請求項 15に記載の方法。
- 20.さらに前記バンプ下側金属を形成する工程が前記銅層上に第2クロム層を 形成する工程を含み;さらに前記ハンダを形成する工程が: 前記接点パッドの間の前記バンプ下側金属上にハンダ蓄積領域を形成し、前記ハ ンダ蓄積領域が前記接点パッド上で前記バンプ下側金属を露出し;次いで 前記接点パッド上の前記第2クロム層を除去し;さらに次いで 前記接点パッド上で前記バンプ下側金属にハンダを形成し、前記ハンダ蓄積領域 が前記接点パッドの間のハンダの形成を制限する工程を含むことを特徴とする請 求項13に記載の方法。
- 21.超小型電子基板のための相互接続システムであって:前記基板上の多数の 接点パッド; それぞれの前記接点パッド上のハンダバンプ;および各ハンダバンプと接点パッ ドとの間の金属間化合物層、前記金属間化合物層が結合した接点パッド上で前記 ハンダバンプから外見上広がる舌片を含み、これにより接点パッドを保護するこ とを含むことを特徴とするシステム。
- 22.前記ハンダバンプが鉛/スズハンダバンプであり前記金属間化合物層が銅 /スズの金属間化合物舌片であることを特徴とする請求項21に記載の相互接続 システム。
- 23.前記舌片が外見上前記ハンダバンプから数ミクロン広がることを特徴とす る請求項21に記載の相互接続システム。
- 24.前記ハンダバンプが前記それぞれの接点パッド上の回転楕円面伏のハンダ バンプであり前記舌片が外見上結合した接点パッド上で前記ハンダバンプから広 がる円形舌片であることを特徴とする請求項21に記載の相互接続システム。
- 25.超小型電子基板のための相互接続システムであって:前記基板上の多数の 接点パッド; 前記接点パッド上に底部を有する前記それぞれの接点パッド上の回転楕円面伏の ハンダバンプ;および結合した接点パッド上で前記ハンダバンプから外見上広が る、その底部の前記回転楕円面伏のハンダバンプ上の円形舌片を含み、これによ り接点パッドを保護することを特徴とするシステム。
- 26.前記回転楕円面伏のハンダバンプが回転楕円面伏の鉛/スズハンダバンプ であり前記円形舌片が銅/スズ金属間化合物円形舌片であることを特徴とする請 求項25に記載の相互接続システム。
- 27.前記円形舌片が外見上前記ハンダバンプから数ミクロン広がることを特徴 とする請求項25に記載の相互接続システム。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/759,450 US5162257A (en) | 1991-09-13 | 1991-09-13 | Solder bump fabrication method |
US759,450 | 1991-09-13 |
Publications (2)
Publication Number | Publication Date |
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JPH07502147A true JPH07502147A (ja) | 1995-03-02 |
JP2842692B2 JP2842692B2 (ja) | 1999-01-06 |
Family
ID=25055684
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5506136A Expired - Fee Related JP2842692B2 (ja) | 1991-09-13 | 1992-09-11 | はんだバンプの製造方法および相互接続システム |
Country Status (10)
Country | Link |
---|---|
US (2) | US5162257A (ja) |
EP (1) | EP0603296B1 (ja) |
JP (1) | JP2842692B2 (ja) |
KR (1) | KR0186061B1 (ja) |
AT (1) | ATE156935T1 (ja) |
CA (1) | CA2116766C (ja) |
DE (1) | DE69221627T2 (ja) |
ES (1) | ES2106194T3 (ja) |
TW (1) | TW200417B (ja) |
WO (1) | WO1993006620A1 (ja) |
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-
1991
- 1991-09-13 US US07/759,450 patent/US5162257A/en not_active Expired - Lifetime
-
1992
- 1992-08-07 US US07/927,069 patent/US5293006A/en not_active Expired - Lifetime
- 1992-09-11 ES ES92919808T patent/ES2106194T3/es not_active Expired - Lifetime
- 1992-09-11 KR KR1019940700820A patent/KR0186061B1/ko not_active IP Right Cessation
- 1992-09-11 CA CA002116766A patent/CA2116766C/en not_active Expired - Fee Related
- 1992-09-11 DE DE69221627T patent/DE69221627T2/de not_active Expired - Fee Related
- 1992-09-11 AT AT92919808T patent/ATE156935T1/de not_active IP Right Cessation
- 1992-09-11 JP JP5506136A patent/JP2842692B2/ja not_active Expired - Fee Related
- 1992-09-11 WO PCT/US1992/007722 patent/WO1993006620A1/en active IP Right Grant
- 1992-09-11 EP EP92919808A patent/EP0603296B1/en not_active Expired - Lifetime
- 1992-10-01 TW TW081107808A patent/TW200417B/zh active
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JP2842692B2 (ja) | 1999-01-06 |
EP0603296B1 (en) | 1997-08-13 |
TW200417B (ja) | 1993-02-21 |
DE69221627D1 (de) | 1997-09-18 |
KR940702644A (ko) | 1994-08-20 |
DE69221627T2 (de) | 1998-01-08 |
CA2116766A1 (en) | 1993-04-01 |
EP0603296A1 (en) | 1994-06-29 |
CA2116766C (en) | 1999-02-16 |
US5162257A (en) | 1992-11-10 |
KR0186061B1 (ko) | 1999-04-15 |
ES2106194T3 (es) | 1997-11-01 |
WO1993006620A1 (en) | 1993-04-01 |
ATE156935T1 (de) | 1997-08-15 |
US5293006A (en) | 1994-03-08 |
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