JP2012122097A - 電気めっき方法 - Google Patents
電気めっき方法 Download PDFInfo
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- JP2012122097A JP2012122097A JP2010273658A JP2010273658A JP2012122097A JP 2012122097 A JP2012122097 A JP 2012122097A JP 2010273658 A JP2010273658 A JP 2010273658A JP 2010273658 A JP2010273658 A JP 2010273658A JP 2012122097 A JP2012122097 A JP 2012122097A
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- 238000009713 electroplating Methods 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims description 26
- 238000007747 plating Methods 0.000 claims abstract description 233
- 239000000758 substrate Substances 0.000 claims abstract description 219
- 229910052751 metal Inorganic materials 0.000 claims abstract description 177
- 239000002184 metal Substances 0.000 claims abstract description 177
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052802 copper Inorganic materials 0.000 claims abstract description 92
- 239000010949 copper Substances 0.000 claims abstract description 92
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 238000003756 stirring Methods 0.000 description 18
- 230000004888 barrier function Effects 0.000 description 15
- 238000005406 washing Methods 0.000 description 14
- 238000001994 activation Methods 0.000 description 13
- 230000004913 activation Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005240 physical vapour deposition Methods 0.000 description 11
- 239000000654 additive Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005192 partition Methods 0.000 description 5
- 239000011800 void material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- LMPMFQXUJXPWSL-UHFFFAOYSA-N 3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCSSCCCS(O)(=O)=O LMPMFQXUJXPWSL-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- -1 halogen ions Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000003115 supporting electrolyte Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L21/18—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 the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
- H01L21/2885—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition using an external electrical current, i.e. electro-deposition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76898—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics formed through a semiconductor substrate
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
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- Condensed Matter Physics & Semiconductors (AREA)
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- Microelectronics & Electronic Packaging (AREA)
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- Electrochemistry (AREA)
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- Electroplating Methods And Accessories (AREA)
- Electrodes Of Semiconductors (AREA)
Abstract
【解決手段】表面にビアホールが形成された基板を前処理液に浸漬させて前処理を行い、基板とアノードとの間に電圧を印加することなく、基板をめっき液に浸漬させてビアホール内の前処理液をめっき液に置換し、基板とアノードとの間に印加される電圧を、ビアホール内にめっき金属を埋込むのに適した電流が基板とアノードとの間を安定して流れるのに必要な電圧または該電圧より高い電圧に制御して第1段電気めっきを行い、基板とアノードとの間を流れる電流を、ビアホール内にめっき金属を埋込むのに適した電流に制御して第2段電気めっきを行う。
【選択図】図9
Description
例えばビアホールを銅シード層で覆っている基板の場合、基板とアノードとの間に電圧を印加することなく基板をめっき液に浸漬させる時間が長いと、銅シード層がめっき液によってダメージを受ける。このため、基板とアノードとの間に電圧を印加することなく基板をめっき液に浸漬させる時間は、サイズの小さなビアホール(例えば10〜50μm)を有する基板に対しては10〜20秒程度、サイズの大きなビアホール(例えば100μm)を有する基板に対しては、20〜60秒程度であることが好ましい。
これにより、第1段電気めっきで、例えばRuからなる補助金属層の表面にめっき金属を均一に析出させて、基板とアノードとの間を流れる電流を安定させることができる。
電気めっきの進行に伴って、ビアホール内にめっき金属が徐々に析出すると、ビアホールの未充填部のアスペクト比が変化する。ここに、アスペクト比が小さい程、高い電流で安定したボトムアップ成長を伴う埋込みめっきが可能となる。このため、めっき金属の埋め込み状態の変化、すなわちビアホールの未充填部におけるアスペクト比の変化に合わせて、基板と前記アノードとの間を流れる電流を段階的に変化させることで、めっき時間を短縮して生産性を向上させることができる。
これにより、表面の少なくとも一部にRuまたはCo、またはこれらの合金が露出しているビアホールの内部に、内部にボイド等の欠陥のない銅からなるめっき金属を埋込むことができる。
シリコンウェーハに、直径7μm、深さ85μmの複数のビアホールを形成し、ビアホールを含む全表面に、バリア層としてTiをPVDで100nm成膜し、次いでバリア層の表面に、補助金属層としてRuをCVDで10nm成膜し、更に補助金属層の表面に、銅シード層をPVDで100nm成膜した試料を用意した。めっき液の組成は下記の通りである。
硫酸銅五水和物:200g/L
硫 酸:50g/L
塩 素:50mg/L
添加剤:適量
シリコンウェーハに、直径7μm、深さ85μmの複数のビアホールを形成し、ビアホールを含む全表面に、バリア層としてTiをPVDで100nm成膜し、次いでバリア層の表面に、補助金属層としてRuをCVDで10nm成膜した試料を用意した。めっき液の組成は実施例1と同様である。
実施例1と同様の試料を用意し、実施例1と同様な組成のめっき液を使用した。そして、試料を溶在酸素が2mg/L以下の純水(脱気DIW)に1〜10分間浸漬させて、試料の前処理(プリウェット処理)を行った。そして、前処理後の試料を、試料の銅シード層(及び補助金属層)とアノードとの間に電圧を印加することなく、めっき液中に30秒浸漬させた。次に、試料をめっき液中に浸漬させたまま、試料の銅シード層(及び補助金属層)とアノードとの間に0.3A/dm2(ASD)の電流を流す、CCモードによる電気めっきを120分間にわたって行った。
実施例2と同様な試料を用意し、実施例1と同様な組成のめっき液を使用した。そして、試料を溶在酸素が2mg/L以下の純水(脱気DIW)に1〜10分間浸漬させて、試料の前処理(プリウェット処理)を行った。そして、前処理後の試料を、試料の補助金属層とアノードとの間に電圧を印加することなく、めっき液中に30秒浸漬させた。次に、試料をめっき液中に浸漬させたまま、試料の補助金属層とアノードとの間に0.3A/dm2(ASD)の電流を流す、CCモードによる電気めっきを120分間にわたって行った。
14 バリア層
16,22 銅シード層
18 めっき金属
20 補助金属層
124 洗浄・乾燥装置
126 前処理装置
160 基板ホルダ
164 ストッカ
166 活性化処理装置
168a,168b 水洗装置
170 めっき装置
172 ブロー装置
186 めっき槽
220 アノード
224 調整板
232 攪拌パドル(攪拌具)
250 めっき電源
252 制御部
Claims (6)
- 表面にビアホールが形成された基板を用意し、
基板を前処理液に浸漬させて前処理を行い、
基板と該基板と対向する位置に配置されるアノードとの間に電圧を印加することなく、基板をめっき液に浸漬させて前記ビアホール内の前処理液をめっき液に置換し、
基板と前記アノードとの間に印加される電圧を、前記ビアホール内にめっき金属を埋込むのに適した電流が基板と前記アノードとの間を安定して流れるのに必要な電圧または該電圧より高い電圧に制御して第1段電気めっきを行い、しかる後、
基板と前記アノードとの間を流れる電流を、前記ビアホール内にめっき金属を埋込むのに適した電流に制御して第2段電気めっきを行うことを特徴とする電気めっき方法。 - 前記基板とアノードとの間に電圧を印加することなく基板をめっき液に浸漬させる時間は、10〜60秒であることを特徴とする請求項1記載の電気めっき方法。
- 前記第1段電気めっきのめっき時間は、1秒〜10分であることを特徴とする請求項1または2記載の電気めっき方法。
- 前記第2段電気めっきを、基板と前記アノードとの間を流れる電流を段階的に変化させて行うことを特徴とする請求項1乃至3のいずれかに記載の電気めっき方法。
- 前記めっき金属は銅で、前記ビアホールの表面の少なくとも一部には、銅以外の金属が露出していることを特徴とする請求項1乃至4のいずれかに記載の電気めっき方法。
- 前記銅以外の金属は、ルテニウムまたはコバルト、またはこれらの合金であることを特徴とする請求項5記載の電気めっき方法。
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JP2010273658A JP2012122097A (ja) | 2010-12-08 | 2010-12-08 | 電気めっき方法 |
US13/313,154 US20120145552A1 (en) | 2010-12-08 | 2011-12-07 | Electroplating method |
TW100145238A TWI541388B (zh) | 2010-12-08 | 2011-12-08 | 電鍍方法 |
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JP2010273658A JP2012122097A (ja) | 2010-12-08 | 2010-12-08 | 電気めっき方法 |
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Cited By (4)
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---|---|---|---|---|
JP2014201835A (ja) * | 2013-04-09 | 2014-10-27 | 株式会社荏原製作所 | 電気めっき方法 |
JP2015200029A (ja) * | 2014-01-17 | 2015-11-12 | 株式会社荏原製作所 | めっき方法およびめっき装置 |
KR101750665B1 (ko) * | 2013-08-08 | 2017-07-03 | 상하이 신양 세미컨덕터 메테리얼즈 씨오., 엘티디. | 고종횡비에서 3d 구리 인터커넥션을 위한 실리콘 관통전극 기술을 구비한 구리 전기도금에 의해 마이크로비아 필링하는 방법 |
WO2018074883A1 (ko) * | 2016-10-20 | 2018-04-26 | 한국생산기술연구원 | 실리콘 관통전극의 무결함 충전방법 및 충전방법에 사용되는 구리 도금액 |
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US20120145552A1 (en) | 2012-06-14 |
TWI541388B (zh) | 2016-07-11 |
TW201229328A (en) | 2012-07-16 |
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