JP2014011274A - Method of manufacturing semiconductor device - Google Patents
Method of manufacturing semiconductor device Download PDFInfo
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- JP2014011274A JP2014011274A JP2012146030A JP2012146030A JP2014011274A JP 2014011274 A JP2014011274 A JP 2014011274A JP 2012146030 A JP2012146030 A JP 2012146030A JP 2012146030 A JP2012146030 A JP 2012146030A JP 2014011274 A JP2014011274 A JP 2014011274A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000004065 semiconductor Substances 0.000 title claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 75
- 229910052751 metal Inorganic materials 0.000 claims abstract description 63
- 239000002184 metal Substances 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 50
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 239000010954 inorganic particle Substances 0.000 claims abstract description 20
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 239000004793 Polystyrene Substances 0.000 claims abstract description 6
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 229920002223 polystyrene Polymers 0.000 claims abstract description 6
- 238000005498 polishing Methods 0.000 claims description 68
- 239000010949 copper Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 31
- 238000005260 corrosion Methods 0.000 abstract description 31
- 238000007664 blowing Methods 0.000 abstract description 7
- 230000009918 complex formation Effects 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 69
- 230000000052 comparative effect Effects 0.000 description 17
- 238000002474 experimental method Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 238000007517 polishing process Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- -1 for example Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- 235000004279 alanine Nutrition 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- PLUHAVSIMCXBEX-UHFFFAOYSA-N azane;dodecyl benzenesulfonate Chemical compound N.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 PLUHAVSIMCXBEX-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- KZOSUZIOUKWADV-UHFFFAOYSA-N ethyne-1,2-diol;oxirane Chemical compound C1CO1.OC#CO KZOSUZIOUKWADV-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- PUAGMZJCVWMYIV-UHFFFAOYSA-N pyridine-2,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O.OC(=O)C1=CC=CN=C1C(O)=O PUAGMZJCVWMYIV-UHFFFAOYSA-N 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- UBDIMPWXBMWVTC-UHFFFAOYSA-N quinoline-2-carboxylic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21.C1=CC=CC2=NC(C(=O)O)=CC=C21 UBDIMPWXBMWVTC-UHFFFAOYSA-N 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B53/00—Devices or means for dressing or conditioning abrasive surfaces
- B24B53/017—Devices or means for dressing, cleaning or otherwise conditioning lapping tools
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
Description
実施形態は、半導体装置の製造方法に関する。 Embodiments described herein relate generally to a method for manufacturing a semiconductor device.
半導体装置の製造過程では、多層配線や素子分離などの工程において、ウェーハ表面を平坦化するために化学的機械研磨（Chemical Mechanical Polishing：CMP）法が用いられる。例えば、ウェーハ表面に形成されたシリコン酸化膜、タングステン(W)、銅(Cu)、アルミニウム(Al)膜などを研磨し、配線やコンタクトプラグを形成する。そして、半導体装置の微細化の進展にともない、平坦性の向上、表面欠陥の低減、および、生産性の向上が求められている。特に、コロージョン、金属残渣などの表面欠陥は、製造歩留まりへの影響が大きいため、その低減が強く求められている。 In the manufacturing process of a semiconductor device, a chemical mechanical polishing (CMP) method is used to planarize the wafer surface in processes such as multilayer wiring and element isolation. For example, a silicon oxide film, tungsten (W), copper (Cu), aluminum (Al) film or the like formed on the wafer surface is polished to form wirings and contact plugs. With the progress of miniaturization of semiconductor devices, improvement in flatness, reduction of surface defects, and improvement in productivity are required. In particular, surface defects such as corrosion and metal residues have a great influence on the production yield, and therefore there is a strong demand for their reduction.
実施形態は、コロージョンを抑制しつつ金属残渣を低減し、配線のショートを抑制できる半導体装置の製造方法を提供する。 The embodiment provides a method of manufacturing a semiconductor device that can reduce metal residues while suppressing corrosion and suppress wiring shorts.
実施形態は、研磨パッドにスラリーを供給し、ウェーハの表面に形成された金属層を研磨する半導体装置の製造方法である。前記スラリーは、無機粒子と、前記無機粒子と同極性の官能基を表面に有しポリスチレンを含む樹脂粒子であって０．００１重量％以上０．１重量％以下の濃度で配合され平均粒子径２００ｎｍ以上１μｍ以下の樹脂粒子と、前記金属層を酸化する酸化剤と、前記金属層の表面に有機錯体を形成する錯体形成剤と、前記有機錯体の表面に親水性膜を形成する界面活性剤と、を含有する。そして、前記研磨パッドにガスを吹き付けながら前記金属層を研磨する。 The embodiment is a method for manufacturing a semiconductor device in which slurry is supplied to a polishing pad and a metal layer formed on the surface of a wafer is polished. The slurry is an inorganic particle and a resin particle having a functional group having the same polarity as the inorganic particle on the surface and containing polystyrene, and is blended at a concentration of 0.001 wt% or more and 0.1 wt% or less and has an average particle diameter 200 nm or more and 1 μm or less of resin particles, an oxidizing agent that oxidizes the metal layer, a complex forming agent that forms an organic complex on the surface of the metal layer, and a surfactant that forms a hydrophilic film on the surface of the organic complex And containing. Then, the metal layer is polished while gas is blown onto the polishing pad.
以下、実施の形態について図面を参照しながら説明する。なお、図面中の同一部分には同一番号を付してその詳しい説明は適宜省略し、異なる部分について説明する。 Hereinafter, embodiments will be described with reference to the drawings. In addition, the same number is attached | subjected to the same part in drawing, the detailed description is abbreviate | omitted suitably, and a different part is demonstrated.
本実施形態は、半導体装置の製造方法に関わり、例えば、メモリ、システムＬＳＩ（Large Scale Integrated circuit）、高速ロジックＬＳＩ、メモリ・ロジック混載ＬＳＩなどの配線工程におけるシリコン絶縁膜や金属配線層の研磨方法に関する。 The present embodiment relates to a method for manufacturing a semiconductor device. For example, a method for polishing a silicon insulating film or a metal wiring layer in a wiring process of a memory, a system LSI (Large Scale Integrated circuit), a high-speed logic LSI, a memory / logic mixed LSI, etc. About.
図１は、実施形態に係る研磨装置１０を模式的に表す斜視図である。研磨装置１０は、研磨ステージ３と、ウェーハホルダ１５と、スラリーノズル２３と、ガスノズル２７と、を備える。研磨ステージ３の上面には、研磨パッド７が取り付けられる。一方、ウェーハホルダ１５の研磨パッド７に対向する面には、ウェーハが固定される。そして、研磨ステージ３を研磨面７ａに平行に回転させ、ウェーハホルダ１５を研磨パッド７の表面に当接させることにより、ウェーハ２０の表面に形成された金属層を研磨する。 FIG. 1 is a perspective view schematically showing a polishing apparatus 10 according to the embodiment. The polishing apparatus 10 includes a polishing stage 3, a wafer holder 15, a slurry nozzle 23, and a gas nozzle 27. A polishing pad 7 is attached to the upper surface of the polishing stage 3. On the other hand, the wafer is fixed to the surface of the wafer holder 15 facing the polishing pad 7. Then, the metal layer formed on the surface of the wafer 20 is polished by rotating the polishing stage 3 parallel to the polishing surface 7 a and bringing the wafer holder 15 into contact with the surface of the polishing pad 7.
研磨パッド７の表面には、スラリーノズル２３を介してスラリー２５が供給される。本実施形態に係る研磨過程はＣＭＰであり、スラリー２５は、無機粒子と、樹脂粒子と、酸化剤と、錯体形成剤と、界面活性剤と、を含む。 A slurry 25 is supplied to the surface of the polishing pad 7 via a slurry nozzle 23. The polishing process according to the present embodiment is CMP, and the slurry 25 includes inorganic particles, resin particles, an oxidizing agent, a complex forming agent, and a surfactant.
無機粒子は、例えば、コロイダルシリカ、フュ−ムドシリカ、コロイダルアルミナ、フュ−ムドアルミナ、コロイダルチタニア、およびフュームドチタニアから選択される少なくとも一種を含む。無機粒子は、一次粒子径１０〜５０ｎｍ、二次粒子径１０〜１００ｎｍであることが好ましい。この範囲を逸脱した場合には、コロージョンやスクラッチ等の表面欠陥が発生するおそれがある。ここで言うコロージョンとは、例えば、金属層の表面における局部的な化学反応の進行による表面欠陥を言い、腐食やディッシング等の窪みとして表れる。 The inorganic particles include at least one selected from, for example, colloidal silica, fumed silica, colloidal alumina, fumed alumina, colloidal titania, and fumed titania. The inorganic particles preferably have a primary particle diameter of 10 to 50 nm and a secondary particle diameter of 10 to 100 nm. When deviating from this range, surface defects such as corrosion and scratches may occur. The term “corrosion” as used herein refers to, for example, a surface defect due to the progress of a local chemical reaction on the surface of the metal layer, and appears as a depression such as corrosion or dishing.
無機粒子の粒子径は、例えば、ＴＥＭ（Transmission Electron Microscope）またはＳＥＭ（Scanning Electron Microscope）により直接測定することができる。 The particle diameter of the inorganic particles can be directly measured by, for example, TEM (Transmission Electron Microscope) or SEM (Scanning Electron Microscope).
樹脂粒子は、ポリスチレンを含む樹脂からなり、無機粒子と同極性の官能基を表面に有する。ポリスチレンを加えることにより、樹脂粒子は適切な硬さに形成される。また、樹脂粒子は、その表面に、例えば、カルボキシル基およびスルフォニル基の少なくともいずれか一方を有する。これにより、無機粒子と、樹脂粒子と、の凝集を防ぐ。 The resin particles are made of a resin containing polystyrene and have functional groups having the same polarity as the inorganic particles on the surface. By adding polystyrene, the resin particles are formed to an appropriate hardness. The resin particles have, for example, at least one of a carboxyl group and a sulfonyl group on the surface. Thereby, aggregation of an inorganic particle and a resin particle is prevented.
また、樹脂粒子は、０．００１重量％以上、０．１重量％以下の濃度で配合され、２００ｎｍ以上、１μｍ以下の平均粒子径を有する。樹脂粒子の平均粒子径は、例えば、ＢＥＴ法により粒子の表面積を測定し、この値を球状換算して粒子径を得て、その平均から求めることができる。あるいは、ＴＥＭまたはＳＥＭにより粒子径を測定し、平均粒子径を算出してもよい。 The resin particles are blended at a concentration of 0.001 wt% or more and 0.1 wt% or less, and have an average particle diameter of 200 nm or more and 1 μm or less. The average particle diameter of the resin particles can be obtained from, for example, the particle surface area obtained by measuring the surface area of the particles by the BET method, and obtaining the particle diameter by converting this value into a spherical shape. Alternatively, the average particle size may be calculated by measuring the particle size with TEM or SEM.
酸化剤は、金属層の表面を酸化し、錯体形成剤は、金属酸化物と結合した有機錯体を金属層の表面に形成する。有機錯体は、金属層の表面を保護し、その化学反応を抑制する。界面活性剤は、疎水性の有機錯体の表面に親水性膜を形成する。そして、金属層の表面に形成された有機錯体を、無機粒子と、親水性の樹脂粒子と、が削り取ることにより研磨が進行する。すなわち、ＣＭＰの過程では、有機錯体を形成して金属層の表面を保護しながら、その有機錯体を削り取ることにより研磨が進行する。これにより、コロージョンの発生を抑制し、金属層を均一に研磨することができる。 The oxidizing agent oxidizes the surface of the metal layer, and the complex forming agent forms an organic complex bonded to the metal oxide on the surface of the metal layer. The organic complex protects the surface of the metal layer and suppresses its chemical reaction. The surfactant forms a hydrophilic film on the surface of the hydrophobic organic complex. Polishing proceeds by scraping off the organic complex formed on the surface of the metal layer with inorganic particles and hydrophilic resin particles. That is, in the CMP process, polishing proceeds by scraping off the organic complex while forming the organic complex to protect the surface of the metal layer. Thereby, generation | occurrence | production of corrosion can be suppressed and a metal layer can be grind | polished uniformly.
金属層が銅（Ｃｕ）の場合、酸化剤には、例えば、過硫酸アンモニウムおよび過酸化水素水などを用いることができる。Ｃｕ層の表面の酸化を促進するために、酸化剤の濃度は、少なくとも０．１重量％以上であることが好ましい。一方、酸化剤が過剰に含有された場合、Ｃｕ層の表面に形成された有機錯体の溶解度が高くなり、コロージョンが増加するおそれがある。このため、濃度の上限は５重量％以下にとどめることが好ましい。 When the metal layer is copper (Cu), for example, ammonium persulfate and hydrogen peroxide water can be used as the oxidizing agent. In order to promote the oxidation of the surface of the Cu layer, the concentration of the oxidizing agent is preferably at least 0.1% by weight. On the other hand, when an oxidizing agent is contained excessively, the solubility of the organic complex formed on the surface of the Cu layer is increased, which may increase the corrosion. For this reason, the upper limit of the concentration is preferably limited to 5% by weight or less.
錯体形成剤には、例えば、キナルジン酸（キノリンカルボン酸）、キノリン酸（ピリジン−２，３−ジカルボン酸）、ベンゾートリアゾール（ＢＴＡ）、ニコチン酸（ピリジン−３−ジカルボン酸）、ピコリン酸、マロン酸、シュウ酸、コハク酸、マレイン酸、クエン酸、グリシン、アラニン、アンモニア水などから選ばれる少なくとも一種を用いることができる。 Complex forming agents include, for example, quinaldic acid (quinolinecarboxylic acid), quinolinic acid (pyridine-2,3-dicarboxylic acid), benzotriazole (BTA), nicotinic acid (pyridine-3-dicarboxylic acid), picolinic acid, malon At least one selected from acids, oxalic acid, succinic acid, maleic acid, citric acid, glycine, alanine, aqueous ammonia and the like can be used.
錯体形成剤の濃度は、０．０１〜１重量％程度とすることが好ましい。０．０１重量％未満の場合には、有機錯体の形成が不十分となる。一方、１重量％を越えた場合には、有機錯体が厚くなり、研磨速度が低下する。 The concentration of the complex forming agent is preferably about 0.01 to 1% by weight. If it is less than 0.01% by weight, the formation of the organic complex is insufficient. On the other hand, if it exceeds 1% by weight, the organic complex becomes thick and the polishing rate decreases.
界面活性剤には、ドデシルベンゼンスルホン酸アンモニウム、ドデシルベンゼンスルホン酸カリウム、ポリビニルピロリドン、ポリビニルアルコール、ポリアクリル酸アンモニウム、ヒドロキシセルロース、アセチレンジオール系ノニオン、ポリオキシエチレンアルキレンエーテルなどを挙げることができる。有機錯体の表面に親水性の膜を形成するため、界面活性剤の濃度は、少なくとも０．０１重量％以上とすることが望ましい。また、有機錯体の溶解を避けるために、その上限は０．５重量％とすることが好ましい。 Examples of the surfactant include ammonium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, polyvinylpyrrolidone, polyvinyl alcohol, ammonium polyacrylate, hydroxycellulose, acetylenic diol nonion, polyoxyethylene alkylene ether, and the like. In order to form a hydrophilic film on the surface of the organic complex, the concentration of the surfactant is preferably at least 0.01% by weight. In order to avoid dissolution of the organic complex, the upper limit is preferably 0.5% by weight.
さらに、研磨装置１０は、ガスノズル２７を備え、研磨パッド７の研磨面７ａにガス３３を吹き付けながら金属層を研磨する。ガス３３は、例えば、圧縮空気、窒素などである。 Further, the polishing apparatus 10 includes a gas nozzle 27 and polishes the metal layer while blowing the gas 33 onto the polishing surface 7 a of the polishing pad 7. The gas 33 is, for example, compressed air or nitrogen.
研磨面７ａの温度は、例えば、ウェーハ２０と、研磨面７ａと、の間に生じる摩擦熱もしくは反応熱により上昇する。これにより、金属層の表面の化学反応が進みコロージョンが発生し易くなる。このため、本実施形態では、研磨パッド７にガス３３を吹き付けることによりその温度を下げ、コロージョンの発生を抑制する。 The temperature of the polishing surface 7a rises due to, for example, frictional heat or reaction heat generated between the wafer 20 and the polishing surface 7a. As a result, the chemical reaction on the surface of the metal layer proceeds and corrosion easily occurs. For this reason, in this embodiment, the temperature is lowered by blowing the gas 33 to the polishing pad 7 to suppress the occurrence of corrosion.
次に、図２を参照して、本実施形態に係る半導体装置の製造方法を説明する。図２（ａ）〜図２（ｄ）は、ウェーハ２０の表面に配線を形成する過程を表す模式断面図である。 Next, with reference to FIG. 2, the manufacturing method of the semiconductor device according to this embodiment will be described. 2A to 2D are schematic cross-sectional views showing a process of forming wiring on the surface of the wafer 20.
図２（ａ）に示すように、例えば、図示しないトランジスタ等が形成されたシリコン基板１３の上に、絶縁層４３を形成する。絶縁層４３は、例えば、シリコン酸化膜である。絶縁層４３には、配線溝４１を形成する。配線溝４１は、シリコン基板１３に形成されたコンタクト領域１７に連通するコンタクトホール４２を含む。 As shown in FIG. 2A, for example, an insulating layer 43 is formed on the silicon substrate 13 on which transistors and the like (not shown) are formed. The insulating layer 43 is, for example, a silicon oxide film. A wiring groove 41 is formed in the insulating layer 43. The wiring trench 41 includes a contact hole 42 communicating with the contact region 17 formed in the silicon substrate 13.
次に、図２（ｂ）に示すように、絶縁層４３の上面および配線溝４１の内面を覆う第１の金属層であるバリアメタル（ＢＭ）層４５を形成する。ＢＭ層４５は、例えば、チタン（Ｔｉ）、タンタル（Ｔａ）あるいはこれら窒化物などが用いられる。コンタクトホール４２では、その底面において、ＢＭ層４５がコンタクト領域１７に接する。 Next, as shown in FIG. 2B, a barrier metal (BM) layer 45 that is a first metal layer covering the upper surface of the insulating layer 43 and the inner surface of the wiring groove 41 is formed. For the BM layer 45, for example, titanium (Ti), tantalum (Ta), or a nitride thereof is used. In the contact hole 42, the BM layer 45 is in contact with the contact region 17 on the bottom surface.
続いて、ＢＭ層４５の上に第２の金属層４７（以下、金属層４７）を形成する。金属層４７は、例えば、銅（Ｃｕ）の電界メッキ層であり、配線溝４１の内部を埋め込み、ＢＭ層４５の表面を覆う。 Subsequently, a second metal layer 47 (hereinafter, metal layer 47) is formed on the BM layer 45. The metal layer 47 is, for example, a copper (Cu) electroplating layer, burying the inside of the wiring groove 41 and covering the surface of the BM layer 45.
次に、図２（ｃ）に示すように、ＢＭ層４５の上に形成された金属層４７を、ＣＭＰ法を用いて除去する（メイン研磨）。配線溝４１の内部には、金属層４７を残す。この際、研磨パッド７にガスを吹き付け冷却する。 Next, as shown in FIG. 2C, the metal layer 47 formed on the BM layer 45 is removed using a CMP method (main polishing). The metal layer 47 is left inside the wiring groove 41. At this time, gas is blown onto the polishing pad 7 to cool it.
続いて、図２（ｄ）に示すように、絶縁層４３の上面に形成されたＢＭ層４５を、ＣＭＰ法を用いて除去する（タッチアップ研磨）。これにより、絶縁層４３の上面のＢＭ層４５および金属層４７を除去し、配線溝４１の内部に金属層４７およびＢＭ層４５を含む配線４９が形成される。 Subsequently, as shown in FIG. 2D, the BM layer 45 formed on the upper surface of the insulating layer 43 is removed using a CMP method (touch-up polishing). Thereby, the BM layer 45 and the metal layer 47 on the upper surface of the insulating layer 43 are removed, and the wiring 49 including the metal layer 47 and the BM layer 45 is formed inside the wiring groove 41.
次に、図３および図４を参照して、本実施形態に係る研磨方法について説明する。図３および図４は、ウェーハ２０の表面に設けられた配線層４０〜６０を模式的に表す部分断面図である。なお、研磨過程を表す意味で、図２の上下を逆にしている。 Next, the polishing method according to this embodiment will be described with reference to FIGS. 3 and 4 are partial cross-sectional views schematically showing the wiring layers 40 to 60 provided on the surface of the wafer 20. In addition, the upper and lower sides of FIG. 2 are reversed to represent the polishing process.
図３（ａ）は、層間絶縁膜４３の上面に形成された金属層４７を除去し、層間絶縁膜４３に形成された配線溝４１の中に金属層４７を残す研磨過程を示している。 FIG. 3A shows a polishing process in which the metal layer 47 formed on the upper surface of the interlayer insulating film 43 is removed, and the metal layer 47 is left in the wiring trench 41 formed in the interlayer insulating film 43.
同図に示すように、研磨過程の終盤において、配線層４０の研磨面に薄く残る有機錯体５１は、粒子径の小さな無機粒子５３では完全に削り取ることができず、金属残滓として残る場合がある。配線層の上に残る有機錯体５１は導電性を有するため、隣接する配線間をショートさせる。そこで、スラリー２５に粒子径の大きな樹脂粒子５７を添加し、無機粒子５３では除去できない有機錯体５１を削り取る。これにより、配線層４０の表面に残る金属残渣を低減する。 As shown in the figure, in the final stage of the polishing process, the organic complex 51 that remains thin on the polished surface of the wiring layer 40 cannot be completely scraped off by the inorganic particles 53 having a small particle diameter, and may remain as a metal residue. . Since the organic complex 51 remaining on the wiring layer has conductivity, the adjacent wirings are short-circuited. Therefore, resin particles 57 having a large particle diameter are added to the slurry 25 to scrape off the organic complex 51 that cannot be removed by the inorganic particles 53. Thereby, metal residues remaining on the surface of the wiring layer 40 are reduced.
図３（ｂ）は、配線層５０における研磨過程を示している。層間絶縁膜４３は、横幅の異なる配線溝４１ａおよび４１ｂを有する。同図に示すように、粒子径の大きい樹脂粒子５７を加えたスラリー２５を用いた場合、横幅の広い配線溝４１ａの方が、横幅の狭い配線溝４１ｂよりも深く研磨される。このため、配線溝４１ａの金属面６３の段差ｄＳは、配線溝４１ｂの金属面６５の段差よりも大きくなる。 FIG. 3B shows a polishing process in the wiring layer 50. The interlayer insulating film 43 has wiring grooves 41a and 41b having different widths. As shown in the figure, when the slurry 25 to which the resin particles 57 having a large particle diameter are added is used, the wiring groove 41a having a wider width is polished deeper than the wiring groove 41b having a smaller width. Therefore, step d S of the metal surface 63 of the wiring trench 41a is larger than the step of the metal surface 65 of the wiring groove 41b.
このように、樹脂粒子５７を添加することにより、下地の構造に追従する研磨が可能となる。例えば、配線層は、下層のデバイス構造を反映した凹凸を有する。そして、配線層の表面に形成された金属層４７を除去する際には、凹凸の形状に沿って研磨することが望ましい。 In this manner, by adding the resin particles 57, it is possible to polish following the structure of the base. For example, the wiring layer has irregularities that reflect the underlying device structure. Then, when removing the metal layer 47 formed on the surface of the wiring layer, it is desirable to polish along the uneven shape.
図４（ａ）に示す配線層６０は、その表面に凹部７１を有する。凹部７１の上に形成される金属層４７は、横幅の広い配線溝を埋め込んだ金属層４７と同等であり、その研磨量は、横幅の狭い配線溝４１ｃの研磨面７５よりも多くなる。これにより、例えば、凹部７１における金属面７３の研磨がより進行し、図４（ｂ）に示すように、配線層６０の凹部７１に沿って金属層４７を除去することができる。その結果、凹部７１の表面に残る金属層４７の残渣を減らすことが可能となり、配線間のショートを防ぐことができる。 The wiring layer 60 shown in FIG. 4A has a recess 71 on the surface. The metal layer 47 formed on the recess 71 is equivalent to the metal layer 47 in which the wiring groove having a wide width is embedded, and the amount of polishing is larger than that of the polishing surface 75 of the wiring groove 41c having a narrow width. Thereby, for example, the polishing of the metal surface 73 in the recess 71 further proceeds, and the metal layer 47 can be removed along the recess 71 of the wiring layer 60 as shown in FIG. As a result, it is possible to reduce the residue of the metal layer 47 remaining on the surface of the recess 71, and to prevent a short circuit between wirings.
このように、スラリーに粒子径の大きな樹脂粒子を添加することにより、下地に対する研磨量の追従性を向上させることができる。 In this way, by adding resin particles having a large particle diameter to the slurry, it is possible to improve the followability of the polishing amount with respect to the base.
次に、図５〜図７を参照して、実施例を説明する。本実施例では、研磨パッドとして、ニッタハース製 発泡性パッド（ＩＣ１０００）を用いた。 Next, examples will be described with reference to FIGS. In this example, a foam pad (IC1000) manufactured by Nita Haas was used as the polishing pad.
スラリーの成分は、以下の通りである。
無機粒子：コロイダルシリカ（０．４重量％、平均粒子径３０ｎｍ）、
樹脂粒子：ポリスチレン粒子（０．１重量％、平均粒子径２００ｎｍ、カルボキシル基およびスルフォニル基を表面に有する。）、
酸化剤：過硫酸アンモニウム（１．５重量％）、
錯体形成剤：キナルジン酸（０．１重量％）、ＢＴＡ（０．０００１重量％）、アラニン（０．４重量％）、ドデシルベンゼンスルホン酸アンモニウム（０．０２重量％）、アンモニア水（０．２重量％）、
界面活性剤：アセチレンジオールエチレンオキシド付加物（ＨＬＢ値１８、０．１ｗｔ％）、
ｐＨ調整剤：水酸化カリウム適量（ｐＨ９）、
残部：水。
The components of the slurry are as follows.
Inorganic particles: colloidal silica (0.4% by weight, average particle size 30 nm),
Resin particles: polystyrene particles (0.1% by weight, average particle size 200 nm, having carboxyl group and sulfonyl group on the surface),
Oxidizing agent: ammonium persulfate (1.5% by weight),
Complex forming agent: quinaldic acid (0.1% by weight), BTA (0.0001% by weight), alanine (0.4% by weight), ammonium dodecylbenzenesulfonate (0.02% by weight), aqueous ammonia (0. 2% by weight),
Surfactant: Acetylene diol ethylene oxide adduct (HLB value 18, 0.1 wt%),
pH adjuster: potassium hydroxide appropriate amount (pH 9),
The rest: water.
なお、比較例１として、上記の成分のうちの樹脂粒子を添加しないスラリーを用いた例を示す。また、比較例２として、研磨パッドへのガスの吹きつけない例を示す。 In addition, as Comparative Example 1, an example using a slurry to which resin particles are not added among the above components will be shown. Further, as Comparative Example 2, an example in which gas is not blown onto the polishing pad is shown.
図５は、研磨後の配線層の表面を例示する写真である。図５（ａ）は、樹脂粒子を添加しない比較例１に係る研磨後の表面である。図５（ｂ）は、研磨パッドに空気を吹きつけない比較例２に係る研磨後の表面である。図５（ｃ）は、本実施例による研磨後の表面である。 FIG. 5 is a photograph illustrating the surface of the wiring layer after polishing. FIG. 5A shows the surface after polishing according to Comparative Example 1 in which no resin particles are added. FIG. 5B shows the surface after polishing according to Comparative Example 2 in which air is not blown onto the polishing pad. FIG. 5C shows the surface after polishing according to this example.
図５（ａ）に示す比較例１の表面では、金属層４７の表面、および、それを囲む層間絶縁膜４３の表面に白い金属残渣が多数見られる。これらは、有機錯体４１であり研磨が不足していることを示す。すなわち、比較例１のスラリーは樹脂粒子を含まないため、有機錯体を除去しきれないことを示している。 On the surface of Comparative Example 1 shown in FIG. 5A, many white metal residues are found on the surface of the metal layer 47 and the surface of the interlayer insulating film 43 surrounding it. These are organic complexes 41 and indicate that polishing is insufficient. That is, since the slurry of Comparative Example 1 does not contain resin particles, it indicates that the organic complex cannot be completely removed.
これに対し、図５（ｂ）および図５（ｃ）に示すように、本実施例および比較例２の研磨後の表面に有機錯体４１は残らない。また、図５（ｂ）および図５（ｃ）に示す表面の間に差は見られないことから、樹脂粒子を添加したスラリーを用いた研磨力に、ガスの吹きつけの有無による差は生じないことがわかる。 On the other hand, as shown in FIGS. 5B and 5C, the organic complex 41 does not remain on the polished surfaces of the present example and the comparative example 2. Further, since there is no difference between the surfaces shown in FIG. 5B and FIG. 5C, there is a difference in the polishing force using the slurry to which the resin particles are added depending on whether or not the gas is blown. I understand that there is no.
図６は、金属層４７の平坦性を、配線幅（横幅）に対して示したグラフである。グラフＡは、本実施例の特性を示し、グラフＢは、比較例１、グラフＣは、比較例２の特性をそれぞれ示している。配線の被覆率（Density）は、５０％である。 FIG. 6 is a graph showing the flatness of the metal layer 47 with respect to the wiring width (lateral width). A graph A shows the characteristics of this example, a graph B shows the characteristics of Comparative Example 1, and a graph C shows the characteristics of Comparative Example 2, respectively. The wiring coverage (Density) is 50%.
グラフＣは、配線幅が１０μｍを越えると段差が増加することを示している。一方、グラフＡでは、配線幅が３０μｍを越えると段差が増加する。この差は、研磨パッドへの空気の吹きつけの有無によるものであり、研磨パッドの表面を冷却することにより研磨力が低くなることがわかる。さらに、グラフＢでは、配線幅が５０μｍを越えると段差が増加する。 Graph C shows that the step increases when the wiring width exceeds 10 μm. On the other hand, in the graph A, the step increases when the wiring width exceeds 30 μm. This difference is due to the presence or absence of air blowing to the polishing pad, and it can be seen that the polishing power is lowered by cooling the surface of the polishing pad. Further, in the graph B, the step increases when the wiring width exceeds 50 μm.
グラフＣをグラフＢと比較すると、スラリーに樹脂粒子を加えたことによる段差の増加が顕著である。すなわち、比較例２では、樹脂粒子の効果により、下地の形状に対する追随性が大幅に向上する。一方、本実施例では、比較例２に比べて劣るものの、比較例１に比べると、下地形状に対する追随性は大きいと言える。 When graph C is compared with graph B, the increase in level difference due to the addition of resin particles to the slurry is significant. That is, in Comparative Example 2, the followability with respect to the shape of the base is greatly improved due to the effect of the resin particles. On the other hand, in this example, although it is inferior to the comparative example 2, it can be said that the followability to the base shape is large as compared with the comparative example 1.
さらに、樹脂粒子の種類を変えて実験を行った。表１は、樹脂粒子として、ＰＭＭＡ（ポリメタクリル酸メチル樹脂）とＰＳＴ（ポリスチレン樹脂）とを用いた実験１〜４の結果を示している。表中の○は、Ｃｕ残り無し、Ｃｕコロージョン無し、および、下地追従性が良好であることを示す。ここで、Ｃｕ残り無し、および、Ｃｕコロージョン無しとは、それぞれ、Ｃｕ膜残り及びＣｕコロージョンが発生したとしても実用上問題無いレベルである状態も含む。×は、Ｃｕ残り有り、Ｃｕコロージョン有り、および、下地追従性が悪いことを示す。 Furthermore, the experiment was performed by changing the type of resin particles. Table 1 shows the results of Experiments 1 to 4 using PMMA (polymethyl methacrylate resin) and PST (polystyrene resin) as resin particles. “◯” in the table indicates that there is no Cu residue, no Cu corrosion, and good base followability. Here, “no Cu residue” and “no Cu corrosion” include a state where there is no practical problem even if a Cu film residue and Cu corrosion occur, respectively. X indicates that there is Cu residue, Cu corrosion, and poor base followability.
表１に示すように、いずれの樹脂粒子でも下地追従性は良好である。しかしながら、ＰＭＭＡを用いた実験１の結果では、Ｃｕ残りおよびＣｕコロージョンが発生している。ＰＳＴを用いた実験２の場合は、Ｃｕ残りについては良好であるが、Ｃｕコロージョンが発生している。一方、実験３の結果に示すように、ＰＳＴであっても、無機粒子と官能基の極性が異なる場合にはＣｕ残りが生じる。また、実験４に示すように、ＰＭＭＡにＰＳＴを加えるとＣｕ残りが改善される。 As shown in Table 1, the ground followability is good in any resin particle. However, in the result of Experiment 1 using PMMA, Cu residue and Cu corrosion have occurred. In the case of Experiment 2 using PST, the remaining Cu is good, but Cu corrosion occurs. On the other hand, as shown in the result of Experiment 3, even in the case of PST, when the polarities of the inorganic particles and the functional groups are different, Cu residue is generated. Further, as shown in Experiment 4, when PST is added to PMMA, the remaining Cu is improved.
このように、無機粒子と同極性の官能基を有し、ＰＳＴを含む樹脂粒子を用いれば、下地追従性を向上させ、Ｃｕ残りを低減できることがわかる。 Thus, it can be seen that the use of resin particles having a functional group having the same polarity as that of the inorganic particles and containing PST can improve the base followability and reduce the Cu residue.
次に、ＰＳＴの粒子径および配合濃度を変えて実験した。樹脂粒子の径は、１５０ｎｍ、２００ｎｍおよび５００ｎｍとし、それぞれの配合濃度を０．０００１重量％（ｗｔ％）〜０．１重量％の範囲で変化させた。 Next, the experiment was performed by changing the particle size and blending concentration of PST. The diameters of the resin particles were 150 nm, 200 nm, and 500 nm, and the respective compounding concentrations were changed in the range of 0.0001 wt% (wt%) to 0.1 wt%.
表２に実験の結果を示す。ここで、○および×は、表１と同じ判定を示し、△は、一応の効果が見られるものの、不十分であることを示す。 Table 2 shows the results of the experiment. Here, ◯ and x indicate the same determination as in Table 1, and Δ indicates that although a temporary effect is seen, it is insufficient.
表２に示すように、粒子径１５０ｎｍのＰＳＴを用いた場合（実験５〜６）、Ｃｕ残りおよび下地追従性は、樹脂粒子の濃度を高くするにしたがい向上するが、十分なレベルには至らない。一方、Ｃｕコロージョンは、樹脂粒子の濃度を高くするほど多くなる。粒子径２００ｎｍ、５００ｎｍの場合（実験９〜１６）、０．００１重量％以上の濃度において、Ｃｕ残りが無く、下地追従性が良好な結果が得られる。一方、濃度が高くなるほどＣｕコロージョンが多くなる傾向は変わらない。 As shown in Table 2, when PST having a particle diameter of 150 nm was used (Experiments 5 to 6), the Cu residue and the ground followability improved as the resin particle concentration was increased, but reached a sufficient level. Absent. On the other hand, Cu corrosion increases as the concentration of resin particles increases. In the case of particle diameters of 200 nm and 500 nm (Experiments 9 to 16), at a concentration of 0.001% by weight or more, there is no Cu residue, and a good base followability can be obtained. On the other hand, the tendency for Cu corrosion to increase as the concentration increases does not change.
これらの結果より、粒径２００ｎｍ以上、配合濃度０．００１％以上のＰＳＴを含む樹脂粒子を用いることにより、Ｃｕ残り、および、下地追従性が良好な状態を実現できることが分かる。一方、Ｃｕコロージョンは、樹脂粒子の濃度が高くなるほど多く発生する。 From these results, it can be seen that by using resin particles containing PST having a particle size of 200 nm or more and a blending concentration of 0.001% or more, it is possible to realize a state in which the Cu residue and the ground followability are good. On the other hand, more Cu corrosion occurs as the concentration of resin particles increases.
図７は、研磨後の金属層４７に生じるコロージョンの数を比較したグラフである。同図に示す比較例１のコロージョン数と、比較例２のコロージョン数と、を比べると、樹脂粒子を加えた比較例２に係る研磨方法の方が、コロージョンの発生が多いことがわかる。すなわち、樹脂粒子を含むスラリーにより研磨力が向上するため、有機錯体に覆われない銅表面の露出頻度が高くなり、化学反応が促進されるためと考えられる。 FIG. 7 is a graph comparing the number of corrosion occurring in the metal layer 47 after polishing. Comparing the number of corrosion in Comparative Example 1 and the number of corrosion in Comparative Example 2 shown in the figure, it can be seen that the polishing method according to Comparative Example 2 to which resin particles are added causes more corrosion. That is, it is considered that the polishing power is improved by the slurry containing the resin particles, so that the exposure frequency of the copper surface not covered with the organic complex is increased and the chemical reaction is promoted.
一方、本実施例では、樹脂粒子を含むスラリーを使用するにもかかわらず、比較例２よりもコロージョンの数が少なく、比較例１のコロージョンの数と同じレベルである。すなわち、研磨パッドに空気を吹きつけ冷却することにより、金属層４７の表面における化学反応が抑制され、コロージョンの発生を抑えることができるものと考えられる。 On the other hand, in this example, although the slurry containing resin particles is used, the number of corrosion is smaller than that in Comparative Example 2, and is the same level as the number of corrosion in Comparative Example 1. That is, it is considered that the chemical reaction on the surface of the metal layer 47 is suppressed by blowing air on the polishing pad and cooling, and the occurrence of corrosion can be suppressed.
表３は、樹脂粒子の濃度を０．００１重量％以上とした実験１０〜１２および１４〜１６と同条件において、研磨パッドに空気を吹き付けた場合（圧縮空気５００Ｌ／分）の結果を示している。 Table 3 shows the results when air was blown onto the polishing pad (compressed air: 500 L / min) under the same conditions as in Experiments 10-12 and 14-16 where the concentration of the resin particles was 0.001% by weight or more. Yes.
配合濃度０．００１重量％（実験１０および１４）の結果では、Ｃｕが残り、下地追従性がやや劣化するが、それ以上の濃度では、Ｃｕ残り、下地追従性のいずれも良好な結果が得られている。そして、Ｃｕコロージョンの発生は、０．００１重量％以上のどの濃度においも抑制される。 In the result of the blending concentration of 0.001% by weight (Experiments 10 and 14), Cu remains and the ground followability is slightly deteriorated. However, when the concentration is higher than that, good results are obtained for both the Cu remaining and the ground followability. It has been. The occurrence of Cu corrosion is suppressed at any concentration of 0.001% by weight or more.
上記の結果によれば、樹脂粒子を添加したスラリーを用いることにより研磨力を向上させ、配線層の表面に残る金属残渣（有機錯体）を低減できる。さらに、下地の形状に対する追随性を向上させることが可能であることを示している。しかしながら、樹脂粒子の添加により研磨力が向上すれば、コロージョンが発生し易くなるデメリットも生じる。そして、研磨パッドにガスを吹き付ける冷却方法が、この相反関係を緩和するために有効である。すなわち、スラリーに樹脂粒子を加え、研磨パッドにガスを吹き付けながら研磨を行うことにより、金属残渣の低減（金属残渣のクリア性）と、下地追従性と、を向上させ、且つ、コロージョンの発生を抑制する研磨方法を実現することができる。 According to said result, by using the slurry which added the resin particle, polishing power can be improved and the metal residue (organic complex) which remains on the surface of a wiring layer can be reduced. Further, it is shown that the followability to the shape of the base can be improved. However, if the polishing power is improved by the addition of resin particles, there is a demerit that corrosion is likely to occur. And the cooling method which blows gas on a polishing pad is effective in order to ease this reciprocal relationship. In other words, by adding resin particles to the slurry and polishing while blowing gas to the polishing pad, the reduction of metal residues (clearance of metal residues) and the base followability are improved, and the occurrence of corrosion is also improved. A suppressing polishing method can be realized.
また、金属残渣のクリア性と、下地追従性と、を向上させるため、平均粒子形２００ｎｍ以上の樹脂粒子をスラリーに添加することが望ましい。また、樹脂粒子の平均粒子径は、１μｍを越えないことが望ましい。平均粒子径が１μｍを越えると沈降を生じ、スラリー中に均等に分散させることが難しくなる。 Further, in order to improve the clearness of the metal residue and the base followability, it is desirable to add resin particles having an average particle shape of 200 nm or more to the slurry. Further, it is desirable that the average particle diameter of the resin particles does not exceed 1 μm. When the average particle diameter exceeds 1 μm, sedimentation occurs, and it becomes difficult to uniformly disperse in the slurry.
さらに、樹脂粒子の濃度は、０．００１重量％以上、０．１重量％以下であることが望ましい。樹脂粒子の濃度が０．００１重量％を下回ると、金属残渣のクリア性および下地追従性が低下する。一方、０．１重量％を越えると研磨力が過剰となり、コロージョンが増える。 Furthermore, the concentration of the resin particles is desirably 0.001 wt% or more and 0.1 wt% or less. When the concentration of the resin particles is less than 0.001% by weight, the metal residue clearness and the base followability are deteriorated. On the other hand, if it exceeds 0.1% by weight, the polishing force becomes excessive and corrosion increases.
上記の通り、本実施形態は、金属層の表面におけるコロージョンの発生を抑制しながら、金属残渣のクリア性、および、下地追従性を向上させた研磨方法を実現する。そして、この研磨方法を用いた半導体装置の製造過程では、配線間のショートの発生が抑制され、製造歩留まりを向上させることができる。 As described above, the present embodiment realizes a polishing method that improves the clearness of metal residues and the base followability while suppressing the occurrence of corrosion on the surface of the metal layer. In the manufacturing process of the semiconductor device using this polishing method, the occurrence of a short circuit between wirings is suppressed, and the manufacturing yield can be improved.
上記の実施例では、樹脂粒子を添加したスラリーを用いたＣｕ層のＣＰＭを例に説明したが、これに限定される訳ではない。例えば、アルミ配線の形成過程にも適用可能である。また、研磨パッドの冷却方法は、ガスの吹きつけに限定されるものではなく、例えば、スラリーを冷却して供給しても良い。 In the above embodiment, the CPM of the Cu layer using the slurry added with the resin particles has been described as an example, but the present invention is not limited to this. For example, it can be applied to the formation process of aluminum wiring. Further, the method of cooling the polishing pad is not limited to gas blowing, and for example, the slurry may be cooled and supplied.
本発明のいくつかの実施形態を説明したが、これらの実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら新規な実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。これら実施形態やその変形は、発明の範囲や要旨に含まれるとともに、特許請求の範囲に記載された発明とその均等の範囲に含まれる。 Although several embodiments of the present invention have been described, these embodiments are presented by way of example and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.
３・・・研磨ステージ、 ７・・・研磨パッド、 ７ａ・・・研磨面、 １０・・・研磨装置、 １３・・・シリコン基板、 １５・・・ウェーハホルダ、 １７・・・コンタクト領域、 ２０・・・ウェーハ、 ２３・・・スラリーノズル、 ２５・・・スラリー、 ２７・・・ガスノズル、 ３３・・・ガス、 ４０、５０、６０・・・配線層、 ４１、４１ａ、４１ｂ、４１ｃ・・・ビアホール、 ４３・・・層間絶縁膜、 ４５・・・バリアメタル層、 ４７、４７ａ・・・金属層、 ４９・・・配線、 ５１・・・有機錯体、 ５３・・・無機粒子、 ５７・・・樹脂粒子、 ６３、６５、７３、７５・・・金属面、 ７１・・・凹部、 DESCRIPTION OF SYMBOLS 3 ... Polishing stage, 7 ... Polishing pad, 7a ... Polishing surface, 10 ... Polishing apparatus, 13 ... Silicon substrate, 15 ... Wafer holder, 17 ... Contact area | region, 20 ... wafer, 23 ... slurry nozzle, 25 ... slurry, 27 ... gas nozzle, 33 ... gas, 40, 50, 60 ... wiring layer, 41, 41a, 41b, 41c ... -Via hole, 43 ... Interlayer insulating film, 45 ... Barrier metal layer, 47, 47a ... Metal layer, 49 ... Wiring, 51 ... Organic complex, 53 ... Inorganic particles, 57 ..Resin particles, 63, 65, 73, 75 ... metal surface, 71 ... concave,
Claims (5)
前記スラリーは、無機粒子と、前記無機粒子と同極性の官能基を表面に有しポリスチレンを含む樹脂粒子であって０．００１重量％以上０．１重量％以下の濃度で配合され平均粒子径２００ｎｍ以上１μｍ以下の樹脂粒子と、前記金属層を酸化する酸化剤と、前記金属層の表面に有機錯体を形成する錯体形成剤と、前記有機錯体の表面に親水性膜を形成する界面活性剤と、を含有し、
前記研磨パッドにガスを吹き付けながら前記金属層を研磨する半導体装置の製造方法。 A method of manufacturing a semiconductor device for supplying a slurry to a polishing pad and polishing a metal layer formed on a surface of a wafer,
The slurry is an inorganic particle and a resin particle having a functional group having the same polarity as the inorganic particle on the surface and containing polystyrene, and is blended at a concentration of 0.001 wt% or more and 0.1 wt% or less and has an average particle diameter 200 nm or more and 1 μm or less of resin particles, an oxidizing agent that oxidizes the metal layer, a complex forming agent that forms an organic complex on the surface of the metal layer, and a surfactant that forms a hydrophilic film on the surface of the organic complex And containing
A method of manufacturing a semiconductor device, wherein the metal layer is polished while gas is blown onto the polishing pad.
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| JP2004146582A (en) * | 2002-10-24 | 2004-05-20 | Toshiba Corp | Post cmp (chemical mechanical polishing) processing liquid, and method of manufacturing semiconductor device using the same |
| JP2005159166A (en) * | 2003-11-27 | 2005-06-16 | Toshiba Corp | Slurry for cmp, method of polishing and method of manufacturing semiconductor device |
| US20060175298A1 (en) * | 2005-02-07 | 2006-08-10 | Junzi Zhao | Method and composition for polishing a substrate |
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| JP2009267367A (en) * | 2008-03-31 | 2009-11-12 | Toshiba Corp | Semiconductor device manufacturing method |
| US20100227435A1 (en) * | 2009-03-09 | 2010-09-09 | Joon-Sang Park | Chemical-mechanical polishing method for polishing phase-change material and method of fabricating phase-change memory device using the same |
| JP2012054529A (en) * | 2010-08-04 | 2012-03-15 | Toshiba Corp | Method for manufacturing semiconductor device |
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| JP2004146582A (en) * | 2002-10-24 | 2004-05-20 | Toshiba Corp | Post cmp (chemical mechanical polishing) processing liquid, and method of manufacturing semiconductor device using the same |
| JP2005159166A (en) * | 2003-11-27 | 2005-06-16 | Toshiba Corp | Slurry for cmp, method of polishing and method of manufacturing semiconductor device |
| US20060175298A1 (en) * | 2005-02-07 | 2006-08-10 | Junzi Zhao | Method and composition for polishing a substrate |
| JP2007157841A (en) * | 2005-12-01 | 2007-06-21 | Toshiba Corp | Aqueous dispersion solution for cmp, polishing method, and manufacturing method of semiconductor device |
| JP2009267367A (en) * | 2008-03-31 | 2009-11-12 | Toshiba Corp | Semiconductor device manufacturing method |
| US20100227435A1 (en) * | 2009-03-09 | 2010-09-09 | Joon-Sang Park | Chemical-mechanical polishing method for polishing phase-change material and method of fabricating phase-change memory device using the same |
| JP2012054529A (en) * | 2010-08-04 | 2012-03-15 | Toshiba Corp | Method for manufacturing semiconductor device |
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