JP5568250B2 - 銅を充填する方法 - Google Patents
銅を充填する方法 Download PDFInfo
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- JP5568250B2 JP5568250B2 JP2009120133A JP2009120133A JP5568250B2 JP 5568250 B2 JP5568250 B2 JP 5568250B2 JP 2009120133 A JP2009120133 A JP 2009120133A JP 2009120133 A JP2009120133 A JP 2009120133A JP 5568250 B2 JP5568250 B2 JP 5568250B2
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- copper
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- copper plating
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- 229910052802 copper Inorganic materials 0.000 title claims description 108
- 239000010949 copper Substances 0.000 title claims description 108
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 105
- 238000007747 plating Methods 0.000 claims description 92
- 239000000758 substrate Substances 0.000 claims description 67
- 238000005868 electrolysis reaction Methods 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 44
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 32
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 32
- 229910052710 silicon Inorganic materials 0.000 claims description 32
- 239000010703 silicon Substances 0.000 claims description 32
- 230000002378 acidificating effect Effects 0.000 claims description 29
- 230000000737 periodic effect Effects 0.000 claims description 17
- 230000002441 reversible effect Effects 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 14
- 238000000813 microcontact printing Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 150000001879 copper Chemical class 0.000 claims description 12
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims 1
- 229940006460 bromide ion Drugs 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229940006461 iodide ion Drugs 0.000 claims 1
- -1 sulfonic acid copper salts Chemical class 0.000 description 10
- 239000002202 Polyethylene glycol Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- 229920006317 cationic polymer Polymers 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000013013 elastic material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 1
- XCENPWBBAXQVCG-UHFFFAOYSA-N 4-phenylpiperidine-4-carbaldehyde Chemical compound C=1C=CC=CC=1C1(C=O)CCNCC1 XCENPWBBAXQVCG-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- UZLVCMCALLIHEI-UHFFFAOYSA-N [P].[Cu]=O Chemical group [P].[Cu]=O UZLVCMCALLIHEI-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical class NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 description 1
- SEGDGYCSRNUBHG-UHFFFAOYSA-N copper;propan-1-ol Chemical compound [Cu].CCCO SEGDGYCSRNUBHG-UHFFFAOYSA-N 0.000 description 1
- NPSDYIWFLLIHOT-UHFFFAOYSA-L copper;propane-1-sulfonate Chemical compound [Cu+2].CCCS([O-])(=O)=O.CCCS([O-])(=O)=O NPSDYIWFLLIHOT-UHFFFAOYSA-L 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
- H01L21/76861—Post-treatment or after-treatment not introducing additional chemical elements into the layer
-
- 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
-
- 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
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Electrodes Of Semiconductors (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Description
すなわち、本発明は、
(1) 基板上に存在する、アスペクト比(深さ/開口径)が5以上の導電処理した非貫通穴に銅を充填する方法であって、酸性銅めっき浴として、水溶性銅塩、硫酸、塩素イオン、ブライトナー及び一般式(I)
(ただし、R1およびR2は独立に水素原子又は炭素数1〜2のアルキル基を示し、X−は塩素イオン、臭素イオン又は沃素イオンである)
で示されるジアリルアミン類構成単位と式(II)
周期的電流反転めっきが、正電解、逆電解の順又は正電解、逆電解、休止の順で繰り返すように設定され、正電解時間が60〜500msec、逆電解時間が正電解時間の1/100〜1/5の時間であり、かつ、休止時間が正電解時間の0〜3倍の時間であることを特徴とする銅充填方法、
(2) 酸性銅めっき浴がさらにキャリアを含む、上記(1)に記載の銅充填方法、
(3) 基板がシリコン層を含む基板である、上記(1)に記載の銅充填方法、
(4) 基板があらかじめマイクロコンタクトプリンティング処理した基板である、上記(1)又は(3)に記載の銅充填方法、
(5) 周期的電流反転銅めっきにおける正電解時の電流密度が3.5mA/cm2以上である上記(1)〜(4)のいずれかに記載の銅充填方法、
(6) 周期的電流反転銅めっきにおける逆電解時の電流密度が正電解の電流密度の1〜5倍である、上記(5)に記載の銅充填方法、
を提供するものである。
本発明において酸性銅めっき浴中の硫酸の濃度は、10g/L〜80g/Lが好ましく、15g/L〜60g/Lがさらに好ましい。
本発明において酸性銅めっき浴中の塩素イオンの濃度は、0.2〜20mmol/Lが好ましく、0.4〜10mmol/Lがさらに好ましい。
で示されるジアリルアミン類構成単位と式(II)
本発明の銅充填方法の対象となる基板は、ビア等の非貫通穴を有するもので導電処理した基板である。
本発明においては、銅めっきする前に、導電処理した非貫通穴を有する基板に、マイクロコンタクトプリンティング処理することが、めっき時間を短縮する点から好ましい。
(1) 導電処理した非貫通穴を有するシリコン基板の作製
基板として、図1に示すように開口径10μm×深さ70μm(アスペクト比7)のビア(非貫通穴)1を形成したシリコン基板2を用いた。この基板に対して銅スパッタリングによる導電処理層3を厚さ31000Åとなるように形成し、導電処理済みのシリコン基板2を作製した。実施例1、比較例1ではこの基板を酸性銅めっきによる銅充填に付した。
図2に示すように、ポリ(ジメチルシロキサン)スタンプ4を、めっき阻止物質であるオクタデカンチオール(ODT)5の濃度5mmol/Lエタノール溶液に1分浸漬させた後、乾燥させて、ODT5が付着したポリ(ジメチルシロキサン)スタンプ4を得、次いでこれを、上記(1)で作製した導電化処理した非貫通穴を有するシリコン基板2に5秒接触させてODTを転写し、エタノールで1分、イオン交換水で1分超音波洗浄し、凸部の表面のみにODT5の自己組織化膜を形成して、マイクロコンタクトプリンティング処理済みの基板6を作製した。実施例2、3、比較例2、3では、この基板を酸性銅めっきによる銅充填に付した。
上記(1)で作製したシリコン基板2および上記(2)で作製したシリコン基板6を酸性銅めっきし、非貫通穴に銅充墳するために用いた装置の概略図を図3に示す。電源には、ポテンショスタット/ガルバノスタット8を用いた。基板2又は6を回転円板電極11の底部に取り付けカソードとして用い、回転制御装置9で回転数を1000rpmで制御しながら酸性銅めっき浴7中で銅めっきを行った。アノード10には含リン銅を用いた。電解条件はパルスジェネレーター12を用いてPR電解(周期的電流反転電解)を以下の条件で行った。
周期的電流反転電解波形
正電解電流値(Ion) −6mA/cm2
逆電解電流値(Ioff) 12mA/cm2
正電解時間(Ton) 200ms
逆電解時間(Trev) 10 ms
休止時間(Toff) 200ms又は100ms
添加剤として 塩酸、ビス−(3−スルホプロピル)ジスルフィド(SPS)、ポリエチレングリコール(PEG)(重量平均分子量Mw10000)、ジアリルジメチルアンモニウムクロリドと二酸化硫黄との1:1共重合体(P(DADMAC/SO2))(分子量 4000)を用い、これらを下記組成と表1の条件で混合して各実施例および比較例に用いる酸性銅めっき浴を調製した。
硫酸銅 200g/L
硫酸 25g/L
塩酸 70mg/L
PEG(Mw10000) 25mg/L(実施例1、比較例1)
又は0mg/L(実施例2、3、比較例2、3)
SPS 2ppm
P(DADMAC/SO2) 1mg/L(実施例1、2、3)
又は0mg/L(比較例1、2、3)
浴温度 室温
攪拌速度 1000rpm (回転円盤電極による)
陽極 含リン銅
酸素置換 0.5L/min、50min
(めっき液300mlに対して)
銅めっき終了後、ビアホール(非貫通穴)への銅充填状態を評価するため、ビアホール開口を切断し断面を鏡面研磨して、走査電子顕微鏡((株)日立製作所製FESEM S−4300)により断面観察を行った。評価結果を表1に示す。また、得られた断面の写真を図4に示す。表1および図4に示すように、カチオン系重合体であるP(DADMAC/SO2)を含む酸性銅めっき浴を用いて周期的電流反転銅めっきをおこなった実施例1〜3では、ボイドがなく銅充填も短時間で進行していることが確認できた。
これに対して、カチオン系重合体であるP(DADMAC/SO2)を含まない酸性銅めっき浴を用いて周期的電流反転銅めっきを行った比較例1〜3では、ボイドの発生が認められることが確認された。
2 シリコン基板
3 導電処理層
4 ポリ(ジメチルシロキサン)スタンプ
5 めっき阻止物質 オクタデカンチオール
6 マイクロコンタクトプリンティング処理基板
7 酸性銅めっき浴
8 ポテンショスタット/ガルバノスタット
9 回転制御装置
10 アノード
11 回転円板電極
12 パルスジェネレーター
Claims (6)
- 基板上に存在する、アスペクト比(深さ/開口径)が5以上の導電処理した非貫通穴に銅を充填する方法であって、酸性銅めっき浴として、水溶性銅塩、硫酸、塩素イオン、ブライトナー及び一般式(I)
で示されるジアリルアミン類構成単位と式(II)
周期的電流反転めっきが、正電解、逆電解の順又は正電解、逆電解、休止の順で繰り返すように設定され、正電解時間が60〜500msec、逆電解時間が正電解時間の1/100〜1/5の時間であり、かつ、休止時間が正電解時間の0〜3倍の時間であることを特徴とする銅充填方法。 - 酸性銅めっき浴がさらにキャリアを含む、請求項1に記載の銅充填方法。
- 基板がシリコン層を含む基板である、請求項1に記載の銅充填方法。
- 基板があらかじめマイクロコンタクトプリンティング処理した基板である、請求項1又は3に記載の銅充填方法。
- 周期的電流反転銅めっきにおける正電解時の電流密度が3.5mA/cm2以上である、請求項1〜4のいずれかに記載の銅充填方法。
- 周期的電流反転銅めっきにおける逆電解時の電流密度が正電解の電流密度の1〜5倍である、請求項5に記載の銅充填方法。
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CN201010183443.0A CN101892501B (zh) | 2009-05-18 | 2010-05-18 | 铜填充方法 |
US12/782,157 US20100307925A1 (en) | 2009-05-18 | 2010-05-18 | Copper filling-up method |
US13/974,113 US9512534B2 (en) | 2009-05-18 | 2013-08-23 | Copper filling-up method |
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KR102192417B1 (ko) * | 2013-04-02 | 2020-12-17 | 가부시키가이샤 아데카 | 전해 구리 도금욕용 첨가제, 그 첨가제를 포함하는 전해 구리 도금욕 및 그 전해 구리 도금욕을 사용한 전해 구리 도금 방법 |
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US20150179555A1 (en) * | 2013-12-20 | 2015-06-25 | Sung Soo Kim | Integrated circuit packaging system with vialess substrate and method of manufacture thereof |
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