KR20180003233A - Metal plating compositions and metal plating method using the same - Google Patents
Metal plating compositions and metal plating method using the same Download PDFInfo
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- KR20180003233A KR20180003233A KR1020160082805A KR20160082805A KR20180003233A KR 20180003233 A KR20180003233 A KR 20180003233A KR 1020160082805 A KR1020160082805 A KR 1020160082805A KR 20160082805 A KR20160082805 A KR 20160082805A KR 20180003233 A KR20180003233 A KR 20180003233A
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- Prior art keywords
- metal plating
- metal
- polyalkylene glycol
- acid
- plating composition
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- 238000007747 plating Methods 0.000 title claims abstract description 83
- 239000002184 metal Substances 0.000 title claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 72
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 21
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 14
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 13
- -1 bismaleimide compound Chemical class 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WRBSVISDQAINGQ-UHFFFAOYSA-N 3-(dimethylcarbamothioylsulfanyl)propane-1-sulfonic acid Chemical compound CN(C)C(=S)SCCCS(O)(=O)=O WRBSVISDQAINGQ-UHFFFAOYSA-N 0.000 claims description 2
- REEBJQTUIJTGAL-UHFFFAOYSA-N 3-pyridin-1-ium-1-ylpropane-1-sulfonate Chemical compound [O-]S(=O)(=O)CCC[N+]1=CC=CC=C1 REEBJQTUIJTGAL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 2
- KQFAFFYKLIBKDE-UHFFFAOYSA-M sodium;ethanesulfonate Chemical compound [Na+].CCS([O-])(=O)=O KQFAFFYKLIBKDE-UHFFFAOYSA-M 0.000 claims description 2
- NPAWNPCNZAPTKA-UHFFFAOYSA-M sodium;propane-1-sulfonate Chemical compound [Na+].CCCS([O-])(=O)=O NPAWNPCNZAPTKA-UHFFFAOYSA-M 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 2
- 159000000000 sodium salts Chemical class 0.000 claims 2
- YXEXMVJHQLWNGG-UHFFFAOYSA-N 3-(3,3-disulfopropyldisulfanyl)propane-1,1-disulfonic acid Chemical compound OS(=O)(=O)C(S(O)(=O)=O)CCSSCCC(S(O)(=O)=O)S(O)(=O)=O YXEXMVJHQLWNGG-UHFFFAOYSA-N 0.000 claims 1
- WIYCQLLGDNXIBA-UHFFFAOYSA-L disodium;3-(3-sulfonatopropyldisulfanyl)propane-1-sulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)CCCSSCCCS([O-])(=O)=O WIYCQLLGDNXIBA-UHFFFAOYSA-L 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000009499 grossing Methods 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 150000002366 halogen compounds Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-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
- MRYMYQPDGZIGDM-UHFFFAOYSA-L copper;4-methylbenzenesulfonate Chemical compound [Cu+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 MRYMYQPDGZIGDM-UHFFFAOYSA-L 0.000 description 1
- RIOSFUBRIQHOMS-UHFFFAOYSA-L copper;benzenesulfonate Chemical compound [Cu+2].[O-]S(=O)(=O)C1=CC=CC=C1.[O-]S(=O)(=O)C1=CC=CC=C1 RIOSFUBRIQHOMS-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
- 239000013078 crystal Substances 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
- 230000000694 effects Effects 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 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
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/124—Unsaturated polyimide precursors the unsaturated precursors containing oxygen in the form of ether bonds in the main chain
-
- 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
-
- 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
- C25D5/02—Electroplating of selected surface areas
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
본 발명은 전해 도금에 사용되는 금속 도금 조성물 및 이를 이용하여 기판에 금속을 도금하는 방법에 관한 것이다.The present invention relates to a metal plating composition for use in electroplating and a method for plating metal on a substrate using the same.
반도체 소자 제조 시 배선이 다층화됨에 따라 높은 종횡비(high aspect ratio)를 갖는 피처(feature)(예를 들어, 비아(via), 트렌치(trench))가 기판에 형성되고 있다. 상기 피처는 금속 도금 조성물을 전해 도금하여 충전하게 되는데, 이때, 보이드(void) 및/또는 심(seam) 등과 같은 결합을 최소화하기 위해서는 가속화제, 억제제 등과 같은 첨가제를 사용하는 것이 요구된다.[0003] As semiconductor devices are manufactured in a multilayered structure, features (for example, vias, trenches) having a high aspect ratio are being formed on a substrate. The features are filled by electroplating the metal plating composition. In order to minimize bonding such as voids and / or seams, it is required to use additives such as accelerators, inhibitors and the like.
상기 가속화제는 금속 표면에 흡착하여 금속 이온의 환원을 가속하는 물질로서, 설폰네이트(sulfonate) 계열의 화합물 중 싸이올(-SH), 다이설파이드(S-S)와 같은 작용기를 갖는 물질이 사용되고 있다. 상기 억제제는 금속 표면에 흡착하여 금속 이온의 환원을 방지하는 물질로서, 폴리에틸렌글리콜(polyethylene glycol)(PEG)과 염화이온(Cl-)이 결합된 물질이 사용되고 있다.The accelerator accelerates the reduction of metal ions by adsorbing on the metal surface, and among the sulfonate compounds, a substance having a functional group such as thiol (-SH) or disulfide (S-S) is used. The inhibitor is a substance that adsorbs on a metal surface to prevent the reduction of metal ions, and a substance in which polyethylene glycol (PEG) and chloride ion (Cl < - >) are combined is used.
상기 가속화제를 포함하는 금속 도금 조성물은 가속화제의 영향으로 도금 과정에서 범프(bump)가 형성되고, 도금 과정의 후반에는 범프의 성장으로 인해 하나의 집합체를 형성하게 된다. 이때, 피처와 같이 종횡비가 크고 밀도가 높은 지역은 범프의 형성이 가속화되어 더 큰 집합체가 형성되는데, 이러한 현상을 과전착(overplating)이라고 한다. 상기 과전착이 일어난 부분은 주변 지역과 단차를 형성하게 되며, 형성된 단차는 화학적 기계적 연마 공정에서 공정의 시간을 증가시키고, 표면의 평활성을 떨어뜨리기 때문에 반도체 소자의 결함을 야기하게 된다.The metal plating composition comprising the accelerator forms a bump in the plating process due to the effect of the accelerator and forms a single aggregate due to the growth of the bump in the latter half of the plating process. At this time, in the region where the aspect ratio is large and the density is high like the feature, the formation of the bump is accelerated and a larger aggregate is formed. This phenomenon is referred to as overplating. The over-formed portion forms a step with the peripheral region, and the formed step increases the time of the process in the chemical mechanical polishing process and lowers the smoothness of the surface, thereby causing defects of the semiconductor device.
이에 따라 범프의 형성을 억제하기 위해 상기 억제제가 사용되는데, 억제제의 사용만으로는 범프의 형성을 억제하는데 한계가 있었다. 또한 도금 부위의 평활성을 높이기 위해 평활제가 함께 사용되어야 하는 번거로움도 있었다.Accordingly, the above-mentioned inhibitors are used to suppress the formation of bumps. However, the use of the inhibitors has a limitation in inhibiting the formation of bumps. In addition, there was a problem that a smoothing agent had to be used together to increase the smoothness of the plating part.
따라서 범프의 형성을 억제하면서 보이드 및/또는 심 등과 같은 결함의 발생없이 기판을 균일하게 도금할 수 있는 금속 도금 조성물이 요구되고 있다.Accordingly, there is a demand for a metal plating composition capable of uniformly plating a substrate without generating defects such as voids and / or shims while suppressing the formation of bumps.
본 발명은 상기한 문제점을 해결하기 위해, 범프의 형성을 억제하면서도 결함의 발생없이 기판을 균일하게 충전할 수 있는 금속 도금 조성물을 제공하는 것을 목적으로 한다.In order to solve the above problems, it is an object of the present invention to provide a metal plating composition capable of uniformly filling a substrate without generating defects while suppressing the formation of bumps.
또한 본 발명은 상기 금속 도금 조성물을 이용한 금속 도금 방법을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide a metal plating method using the metal plating composition.
상기한 목적을 달성하기 위해 본 발명은, 폴리알킬렌 글리콜 비스말레이미드계 화합물을 포함하는 금속 도금 조성물을 제공한다.In order to achieve the above object, the present invention provides a metal plating composition comprising a polyalkylene glycol bismaleimide-based compound.
또한, 본 발명은, a) 상기 금속 도금 조성물을 포함하는 금속 도금 조에 기판을 투입하는 단계; 및 b) 상기 금속 도금 조에 전류를 인가하여 상기 기판에 형성된 피처에 금속을 도금하는 단계를 포함하는 금속 도금 방법을 제공한다.The present invention also relates to a method of manufacturing a metal plating composition, comprising the steps of: a) introducing a substrate into a metal plating bath containing the metal plating composition; And b) plating a metal on the feature formed on the substrate by applying an electric current to the metal plating bath.
본 발명의 금속 도금 조성물은 폴리알킬렌 글리콜 비스말레이미드계 화합물을 포함하기 때문에 도금 과정에서 범프의 형성이 억제되고 도금 표면의 평활성을 확보할 수 있다. 따라서 본 발명은 결함이 없으면서도 도금이 균일하게 이루어진 기판을 제공할 수 있으며, 이로 인해 반도체 소자의 신뢰도를 향상시킬 수 있다.Since the metal plating composition of the present invention contains a polyalkylene glycol bismaleimide-based compound, the formation of bumps can be suppressed during the plating process and the smoothness of the surface of the plating can be ensured. Therefore, the present invention can provide a substrate having uniform plating without any defects, thereby improving the reliability of the semiconductor device.
이하 본 발명을 설명한다.Hereinafter, the present invention will be described.
반도체 소자 제조 시, 기판에 배선을 형성하는 과정에는 비아(via), 또는 트렌치(trench)와 같은 피처(feature)를 금속으로 충전하는 과정이 포함되며, 상기 충전에는 금속 도금 조성물을 전해 도금하는 방법이 사용된다. 이때, 보이드(void) 및/또는 심(seam) 등과 같은 결함의 발생없이 상기 피처에 금속을 균일하게 도금하기 위해서는 상기 금속 도금 조성물이 가속화제, 억제제, 평활제와 같은 첨가제를 포함하는 것이 요구된다.In the process of forming a wiring on a substrate in manufacturing a semiconductor device, a process of filling a feature such as a via or a trench with a metal is included. In the filling process, a metal plating composition is electroplated Is used. At this time, it is required that the metal plating composition includes an additive such as an accelerator, an inhibitor, and a smoothing agent in order to uniformly coat the metal with the feature without causing defects such as voids and / or seams .
이에 따라 가속화제, 억제제, 평활제를 포함하는 금속 도금 조성물이 종래에 다수 개시되었지만, 결함의 발생을 방지하면서 금속을 균일하게 도금하는 데는 한계가 있었다.Accordingly, a large number of metal plating compositions including an accelerator, an inhibitor, and a smoothing agent have been conventionally disclosed, but there are limitations in uniformly plating the metal while preventing the occurrence of defects.
특히, 평활제를 포함하는 금속 도금 조성물은 평활한 표면을 가지도록 피처를 도금할 수 있지만, 평활제가 금속 도금 조성물 내에서 불순물로 작용하여 피처의 도금 시 저항이 상승됨에 따라 도금 효율이 저하되는 문제점이 있었다. 또한, 평활제가 금속 도금 조성물 내에서 분해되어 금속 도금 조성물이 오염됨에 따라 금속 도금 조성물 및 반도체 소자의 수명이 저하되는 문제점도 있었다.In particular, although the metal plating composition containing a smoothing agent can be plated so as to have a smooth surface, there is a problem that the plating efficiency is lowered as the smoothing agent acts as an impurity in the metal plating composition, . Also, there is a problem that the lifetime of the metal plating composition and the semiconductor device is lowered as the smoothing agent is decomposed in the metal plating composition and the metal plating composition is contaminated.
이에 본 발명은, 금속 도금 조성물에 특정의 화합물을 포함시켜 평활제를 사용하지 않더라도 도금 과정에서 결함의 발생을 방지함과 동시에, 기판에 금속을 균일하게(평활하게) 도금할 수 있도록 한 것으로, 이에 대해 구체적으로 설명하면 다음과 같다.Accordingly, it is an object of the present invention to prevent the occurrence of defects in the plating process and to uniformly (smoothly) coat metal on the substrate even when a specific compound is included in the metal plating composition, This will be described in detail as follows.
1. 금속 도금 조성물1. Metal plating composition
본 발명의 금속 도금 조성물은 폴리알킬렌 글리콜 비스말레이미드계 화합물을 포함한다.The metal plating composition of the present invention comprises a polyalkylene glycol bismaleimide-based compound.
본 발명의 금속 도금 조성물에 포함되는 상기 폴리알킬렌 글리콜 비스말레이미드계 화합물은 금속의 도금 속도를 억제함과 동시에 금속의 도금이 균일하게(평활하게) 이루어지도록 조절한다. 즉, 상기 폴리알킬렌 글리콜 비스말레이미드계 화합물은 평활제 역할을 하는 말레이미드와 억제제 역할을 하는 폴리알킬렌 글리콜(또는 폴리알킬렌 옥사이드)가 결합되어 있어, 평활제 역할과 억제제 역할을 동시에 수행할 수 있다.The polyalkylene glycol bismaleimide compound contained in the metal plating composition of the present invention is controlled so as to suppress the plating rate of the metal and to uniformly (smoothly) coat the metal. That is, the polyalkylene glycol bismaleimide compound is combined with maleimide serving as a smoothing agent and polyalkylene glycol (or polyalkylene oxide) serving as an inhibitor, so that the polyalkylene glycol bismaleimide compound simultaneously acts as a smoothing agent and an inhibitor can do.
따라서 본 발명의 금속 도금 조성물은, 종래에 공지된 평활제를 비포함하더라도, 평활제 역할과 억제제 역할을 복합적으로 수행할 수 있는 폴리알킬렌 글리콜 비스말레이미드계 화합물을 포함하기 때문에 기판에 형성된 피처의 측벽 및/또는 모서리 부분에서 범프의 형성이 효과적으로 제어되어 결함이 없으면서도 표면이 평활하도록 피처를 도금할 수 있다.Therefore, the metal plating composition of the present invention includes a polyalkylene glycol bismaleimide-based compound that can perform complex functions as a smoothing agent and an inhibitor even though it does not include a conventionally known smoothing agent, The formation of the bumps can be effectively controlled at the side wall and / or the edge portion of the side walls and / or the corner portions of the side walls.
상기 폴리알킬렌 글리콜 비스말레이미드계 화합물의 몰질량은 특별히 한정되지 않으나, 평활성, 도금 효율 등을 고려할 때, 1,000 내지 20,000 g/mol인 것이 바람직하다.The molar mass of the polyalkylene glycol bismaleimide compound is not particularly limited, but is preferably 1,000 to 20,000 g / mol in consideration of smoothness, plating efficiency and the like.
또한 폴리알킬렌 글리콜 비스말레이미드계 화합물의 농도도 특별히 한정되지 않으나, 결함발생, 평활성, 도금 효율 등을 고려할 때, 5 내지 10,000 ppm인 것이 바람직하다.Also, the concentration of the polyalkylene glycol bismaleimide compound is not particularly limited, but it is preferably 5 to 10,000 ppm in view of occurrence of defects, smoothness, plating efficiency and the like.
이러한 폴리알킬렌 글리콜 비스말레이드계 화합물에 결합된 폴리알킬렌 글리콜의 구조는 에틸렌옥사이드, 프로필렌옥사이드, 또는 부틸렌옥사이드 각각이 반복단위로 결합되어 있거나, 에틸렌옥사이드, 프로필렌옥사이드, 또는 부틸렌옥사이드가 랜덤, 교대, 또는 블록 단위로 결합된 구조를 가질 수 있다.The structure of the polyalkylene glycol bonded to such a polyalkylene glycol bismaleade compound may be a structure in which ethylene oxide, propylene oxide, or butylene oxide are each bonded in a repeating unit, or ethylene oxide, propylene oxide, or butylene oxide Random, alternating, or block-by-block structure.
이와 같은 폴리알킬렌 글리콜 비스말레이미드계 화합물은 하기 화학식 1 내지 4로 표시되는 화합물로 이루어진 군에서 선택되는 것이 바람직하다.Such polyalkylene glycol bismaleimide compounds are preferably selected from the group consisting of compounds represented by the following formulas (1) to (4).
[화학식 1][Chemical Formula 1]
[화학식 2](2)
[화학식 3](3)
[화학식 4][Chemical Formula 4]
상기 화학식 1 내지 4에서, n은 10 내지 500의 정수이다.In the general formulas (1) to (4), n is an integer of 10 to 500.
한편, 본 발명의 금속 도금 조성물은 도금 과정에서 금속 이온을 공급하는 금속 이온 공급원을 더 포함할 수 있다. 상기 금속 이온 공급원은 특별히 한정되지 않으나, 구리 염인 것이 바람직하다. 상기 구리 염은 특별히 한정되지 않으나, 구리 설페이트, 구리 클로라이드, 구리 아세테이트, 구리 시트레이트, 구리 니트레이트, 구리 플루오로보레이트, 구리 메탄 설포네이트, 구리 페닐 설포네이트, 구리 p-톨루엔 설포네이트, 또는 이들의 혼합물 등을 들 수 있다.Meanwhile, the metal plating composition of the present invention may further include a metal ion source for supplying metal ions during the plating process. The metal ion source is not particularly limited, but is preferably a copper salt. Examples of the copper salt include, but are not limited to, copper sulfate, copper chloride, copper acetate, copper citrate, copper nitrate, copper fluoroborate, copper methanesulfonate, copper phenylsulfonate, copper p-toluenesulfonate, And the like.
이러한 금속 이온 공급원의 농도는 특별히 한정되지 않으나, 도금 효율을 고려할 때, 10 내지 100 g/L인 것이 바람직하고, 30 내지 70 g/L인 것이 더욱 바람직하다.The concentration of such a metal ion source is not particularly limited, but is preferably 10 to 100 g / L, more preferably 30 to 70 g / L in view of the plating efficiency.
또한, 본 발명의 금속 도금 조성물은 금속 도금 조성물에 전도성이 부여될 수 있도록 전해질을 더 포함할 수 있다. 상기 전해질은 산성인 것이 바람직하다. 구체적으로 전해질로는 황산, 아세트산, 플루오로붕산, 메탄설폰산, 에탄설폰산, 프로판설폰산, 트리플루오로메탄설폰산, 벤젠설폰산, p-톨루엔설폰산, 설파민산, 염산, 브롬화수소산, 과염소산, 질산, 크롬산, 인산, 또는 이들의 혼합물 등을 들 수 있다.In addition, the metal plating composition of the present invention may further include an electrolyte to impart conductivity to the metal plating composition. The electrolyte is preferably acidic. Specific examples of the electrolyte include inorganic acids such as sulfuric acid, acetic acid, fluoroboric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, sulfamic acid, Perchloric acid, nitric acid, chromic acid, phosphoric acid, and mixtures thereof.
이러한 전해질의 농도는 특별히 한정되지 않으나, 도금 효율을 고려할 때, 1 내지 50 g/L인 것이 바람직하고, 5 내지 20 g/L인 것이 더욱 바람직하다.The concentration of such an electrolyte is not particularly limited, but is preferably 1 to 50 g / L, and more preferably 5 to 20 g / L in view of the plating efficiency.
또, 본 발명의 금속 도금 조성물은 금속 도금의 속도를 높여주는 가속화제를 더 포함할 수 있다.In addition, the metal plating composition of the present invention may further include an accelerator for accelerating the metal plating.
상기 가속화제는 특별히 한정되지 않으나, N,N-디메틸-디티오카르밤산-(3-설포프로필)에스테르, 3-머캡토-프로필설폰산-(3-설포프로필)에스테르, 3-머캡토-프로필설폰산 소디움염, 비스-설포프로필 디설파이드, 비스-(소디움 설포프로필)-디설파이드, 3-(벤조티아졸릴-s-티오)프로필 설폰산 소디움염, 피리디늄 프로필 설포베타인, 1-소디움-3-머캡토프로판-1-설포네이트, N,N-디메틸-디티오카르밤산-(3-설포에틸)에스테르, 3-머캡토-에틸 프로필설폰산-(3-설포에틸)에스테르, 3-머캡토-에틸설폰산 소디움염, 비스-설포에틸 디설파이드, 3-(벤조티아졸릴-s-티오)에틸 설폰산 소디움염, 피리디늄 에틸 설포베타인 및 1-소디움-3-머캡토에탄-1-설포네이트로 이루어진 군에서 선택된 1종 이상인 것이 바람직하다.Examples of the accelerator include, but are not limited to, N, N-dimethyl-dithiocarbamic acid- (3-sulfopropyl) ester, 3-mercapto-propylsulfonic acid- (3-sulfopropyl) (Sodium thiosulfopropyl) disulfide, 3- (benzothiazolyl-s-thio) propyl sulfonic acid sodium salt, pyridinium propyl sulfobetaine, 1-sodium- 3-mercaptopropane-1-sulfonate, N, N-dimethyl-dithiocarbamic acid- (3-sulfoethyl) (Benzothiazolyl-s-thio) ethylsulfonate sodium salt, pyridinium ethylsulfobetaine and 1-sodium-3-mercaptoethane-1 - < / RTI > sulfonate.
이러한 가속화제의 농도는 특별히 한정되지 않으나, 도금 효율을 고려할 때, 5 내지 100 ppm인 것이 바람직하다.The concentration of such an accelerator is not particularly limited, but it is preferably 5 to 100 ppm in consideration of the plating efficiency.
또한, 본 발명의 금속 도금 조성물은 도금 속도를 보조적으로 제어(억제)하는 할로겐 화합물을 더 포함할 수 있다. 상기 할로겐 화합물은 특별히 한정되지 않으나, 염산을 들 수 있다.In addition, the metal plating composition of the present invention may further include a halogen compound which additionally controls (suppresses) the plating rate. The halogen compound is not particularly limited, but hydrochloric acid can be mentioned.
이러한 할로겐 화합물의 농도는 특별히 한정되지 않으나. 약 50 ppm인 것이 바람직하다.The concentration of such a halogen compound is not particularly limited. Preferably about 50 ppm.
2. 금속 도금 방법2. Metal plating method
본 발명은 상기 금속 도금 조성물을 이용하여 기판을 금속 도금하는 방법을 제공하는데, 이에 대해 구체적으로 설명하면 다음과 같다.The present invention provides a method of metal plating a substrate using the metal plating composition, which will be described in detail as follows.
a) 금속 도금 조에 기판 투입a) Substrate into metal plating tank
상술한 금속 도금 조성물이 포함된(수용된) 금속 도금 조(bath)에 기판을 투입한다. 상기 기판은 배선의 형성을 위해 비아(via), 또는 트렌치(trench)와 같은 피처(feature)가 형성되어 있는 것으로, 실리콘 기판, 실리콘-게르마늄 기판, SOI(silicon on insulator) 기판, GOI(germanium on insulator) 기판, 금속 산화물 단결정 기판 등을 들 수 있다.The substrate is put into a metal plating bath containing (containing) the above-mentioned metal plating composition. The substrate may be a silicon substrate, a silicon-germanium substrate, a silicon on insulator (SOI) substrate, a germanium on silicon (SOI) substrate, or the like, in which features, such as vias or trenches, insulator substrate, a metal oxide single crystal substrate, and the like.
상기 기판에 형성된 피처의 간극의 크기는 특별히 한정되지 않으나, 100 ㎚ 이하일 수 있으며, 구체적으로는 50 ㎚ 이하일 수 있다. 또한, 피처의 종횡비도 특별히 한정되지 않으나, 3 이상일 수 있으며, 구체적으로는 10 이상일 수 있다.The size of the gap between the features formed on the substrate is not particularly limited, but may be 100 nm or less, specifically 50 nm or less. The aspect ratio of the features is not particularly limited, but may be 3 or more, and may be 10 or more.
b) 도금b) Plating
상기 금속 도금 조에 전류를 인가하여 상기 기판에 형성된 피처에 금속을 도금한다. 구체적으로, 양극이 설치된 금속 도금 조에 전류를 인가하면 기판이 음극으로 작용하여 기판에 형성된 피처에 금속이 도금된다. 이때, 인가되는 전류의 밀도는 특별히 한정되지 않으나, 도금 효율을 고려할 때 1 내지 50 ㎃/㎠인 것이 바람직하다.A current is applied to the metal plating bath to deposit a metal on a feature formed on the substrate. Specifically, when an electric current is applied to a metal plating vessel provided with an anode, the substrate functions as a cathode, and metal is plated on a feature formed on the substrate. At this time, the density of the applied current is not particularly limited, but it is preferably 1 to 50 mA / cm 2 considering the plating efficiency.
3. 금속 도금 첨가제3. Metal plating additive
본 발명은 상술한 폴리알킬렌 글리콜 비스말레이미드계 화합물을 포함하는 금속 도금 첨가제를 제공한다. 구체적으로, 본 발명의 금속 도금 첨가제는 금속 도금 조성물의 평활성 및 도금 속도의 제어를 위해 금속 도금 조성물에 포함되는 것으로, 상술한 폴리알킬렌 글리콜 비스말레이미드계 화합물이 단독으로 사용되거나, 상술한 폴리알킬렌 글리콜 비스말레이미드계 화합물과 당 업계에 공지된 첨가제가 혼합된 것일 수 있다.The present invention provides a metal plating additive comprising the polyalkylene glycol bismaleimide-based compound described above. Specifically, the metal plating additive of the present invention is included in the metal plating composition for controlling the smoothness and the plating rate of the metal plating composition, and the polyalkylene glycol bismaleimide-based compound described above may be used alone, An alkylene glycol bismaleimide-based compound and additives known in the art may be mixed.
Claims (14)
상기 폴리알킬렌 글리콜 비스말레이미드계 화합물이 하기 화학식 1 내지 4로 표시되는 화합물로 이루어진 군에서 선택되는 것인 금속 도금 조성물.
[화학식 1]
[화학식 2]
[화학식 3]
[화학식 4]
상기 화학식 1 내지 4에서,
n은 10 내지 500의 정수이다.The method according to claim 1,
Wherein the polyalkylene glycol bismaleimide-based compound is selected from the group consisting of compounds represented by Chemical Formulas 1 to 4 below.
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
In the above Chemical Formulas 1 to 4,
and n is an integer of 10 to 500.
상기 폴리알킬렌 글리콜 비스말레이미드계 화합물의 몰질량이 1,000 내지 20,000 g/mol인 금속 도금 조성물.The method according to claim 1,
Wherein the polyalkylene glycol bismaleimide-based compound has a molar mass of 1,000 to 20,000 g / mol.
상기 폴리알킬렌 글리콜 비스말레이미드계 화합물의 농도가 5 내지 10,000 ppm인 금속 도금 조성물.The method according to claim 1,
Wherein the concentration of the polyalkylene glycol bismaleimide compound is 5 to 10,000 ppm.
금속 이온 공급원을 더 포함하는 금속 도금 조성물.The method according to claim 1,
A metal plating composition further comprising a metal ion source.
상기 금속 이온 공급원이 구리 염인 금속 도금 조성물.The method of claim 5,
Wherein the metal ion source is a copper salt.
전해질을 더 포함하는 금속 도금 조성물.The method according to claim 1,
A metal plating composition further comprising an electrolyte.
가속화제를 더 포함하는 금속 도금 조성물.The method according to claim 1,
≪ / RTI > further comprising an accelerator.
상기 가속화제는 N,N-디메틸-디티오카르밤산-(3-설포프로필)에스테르, 3-머캡토-프로필설폰산-(3-설포프로필)에스테르, 3-머캡토-프로필설폰산 소디움염, 비스-설포프로필 디설파이드, 비스-(소디움 설포프로필)-디설파이드, 3-(벤조티아졸릴-s-티오)프로필 설폰산 소디움염, 피리디늄 프로필 설포베타인, 1-소디움-3-머캡토프로판-1-설포네이트, N,N-디메틸-디티오카르밤산-(3-설포에틸)에스테르, 3-머캡토-에틸 프로필설폰산-(3-설포에틸)에스테르, 3-머캡토-에틸설폰산 소디움염, 비스-설포에틸 디설파이드, 3-(벤조티아졸릴-s-티오)에틸 설폰산 소디움염, 피리디늄 에틸 설포베타인 및 1-소디움-3-머캡토에탄-1-설포네이트로 이루어진 군에서 선택된 1종 이상인 금속 도금 조성물.The method of claim 8,
The accelerator may be selected from the group consisting of N, N-dimethyl-dithiocarbamic acid- (3-sulfopropyl) ester, 3-mercapto-propylsulfonic acid- (3-sulfopropyl) , Bis-sulfopropyl disulfide, bis- (sodium sulfopropyl) -disulfide, 3- (benzothiazolyl-s-thio) propyl sulfonic acid sodium salt, pyridinium propyl sulfobetaine, 1-sodium- (3-sulfoethyl) ester, N, N-dimethyl-dithiocarbamic acid- (3-sulfoethyl) ester, 3-mercaptoethylpropylsulfonic acid- Consisting of sodium salt, sodium salt, bis-sulfonyl disulfide, 3- (benzothiazolyl-s-thio) ethylsulfonate sodium salt, pyridinium ethylsulfobetaine and 1-sodium-3-mercaptoethane- Lt; RTI ID = 0.0 > 1, < / RTI >
상기 가속화제의 농도가 5 내지 100 ppm인 금속 도금 조성물.The method of claim 8,
Wherein the accelerator has a concentration of 5 to 100 ppm.
b) 상기 금속 도금 조에 전류를 인가하여 상기 기판에 형성된 피처에 금속을 도금하는 단계를 포함하는 금속 도금 방법.A method of manufacturing a metal plating bath, comprising: a) introducing a substrate into a metal plating bath comprising a metal plating composition according to any one of claims 1 to 10; And
b) applying a current to the metal plating bath to deposit a metal on a feature formed on the substrate.
상기 피처의 종횡비가 3 이상인 금속 도금 방법.The method of claim 11,
Wherein the aspect ratio of the feature is 3 or more.
상기 폴리알킬렌 글리콜 비스말레이미드계 화합물이 하기 화학식 1 내지 4로 표시되는 화합물로 이루어진 군에서 선택되는 것인 금속 도금 첨가제.
[화학식 1]
[화학식 2]
[화학식 3]
[화학식 4]
상기 화학식 1 내지 4에서,
n은 10 내지 500의 정수이다.14. The method of claim 13,
Wherein the polyalkylene glycol bismaleimide-based compound is selected from the group consisting of compounds represented by Chemical Formulas 1 to 4 below.
[Chemical Formula 1]
(2)
(3)
[Chemical Formula 4]
In the above Chemical Formulas 1 to 4,
and n is an integer of 10 to 500.
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|---|---|---|---|---|
| US5217599A (en) * | 1991-11-08 | 1993-06-08 | Industrial Technology Research Institute | Bonding of polyimide film |
| KR20040045328A (en) | 2002-11-21 | 2004-06-01 | 쉬플리 캄파니, 엘.엘.씨. | Electroplating bath |
| KR20070037349A (en) * | 2005-09-30 | 2007-04-04 | 롬 앤드 하스 일렉트로닉 머트어리얼즈, 엘.엘.씨. | Leveler compounds |
| KR20140011137A (en) * | 2012-07-17 | 2014-01-28 | 삼성전자주식회사 | Integrated circuit device having through silicon via structure and method of manufacturing the same |
| JP2014017482A (en) * | 2012-07-09 | 2014-01-30 | Rohm & Haas Electronic Materials Llc | Improved method of metal-plating semiconductors |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5217599A (en) * | 1991-11-08 | 1993-06-08 | Industrial Technology Research Institute | Bonding of polyimide film |
| KR20040045328A (en) | 2002-11-21 | 2004-06-01 | 쉬플리 캄파니, 엘.엘.씨. | Electroplating bath |
| KR20070037349A (en) * | 2005-09-30 | 2007-04-04 | 롬 앤드 하스 일렉트로닉 머트어리얼즈, 엘.엘.씨. | Leveler compounds |
| JP2014017482A (en) * | 2012-07-09 | 2014-01-30 | Rohm & Haas Electronic Materials Llc | Improved method of metal-plating semiconductors |
| KR20140011137A (en) * | 2012-07-17 | 2014-01-28 | 삼성전자주식회사 | Integrated circuit device having through silicon via structure and method of manufacturing the same |
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