TW200532009A - Abrasives and compositions for chemical mechanical planarization of tungsten and titanium - Google Patents
Abrasives and compositions for chemical mechanical planarization of tungsten and titanium Download PDFInfo
- Publication number
- TW200532009A TW200532009A TW094108885A TW94108885A TW200532009A TW 200532009 A TW200532009 A TW 200532009A TW 094108885 A TW094108885 A TW 094108885A TW 94108885 A TW94108885 A TW 94108885A TW 200532009 A TW200532009 A TW 200532009A
- Authority
- TW
- Taiwan
- Prior art keywords
- fumed silica
- water
- acid
- concentration
- titanium
- Prior art date
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- 239000010936 titanium Substances 0.000 title claims abstract description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 31
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 26
- 239000010937 tungsten Substances 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 title claims description 28
- 239000003082 abrasive agent Substances 0.000 title claims description 7
- 239000000126 substance Substances 0.000 title claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000002253 acid Substances 0.000 claims abstract description 45
- 238000005498 polishing Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000004065 semiconductor Substances 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims description 25
- 239000006185 dispersion Substances 0.000 claims description 21
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- 239000000377 silicon dioxide Substances 0.000 claims description 18
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- QGWNDRXFNXRZMB-UHFFFAOYSA-N guanidine diphosphate Natural products C1=2NC(N)=NC(=O)C=2N=CN1C1OC(COP(O)(=O)OP(O)(O)=O)C(O)C1O QGWNDRXFNXRZMB-UHFFFAOYSA-N 0.000 description 1
- UALVSYSEFNVPJT-UHFFFAOYSA-N guanidine;phosphono dihydrogen phosphate Chemical compound NC(N)=N.OP(O)(=O)OP(O)(O)=O UALVSYSEFNVPJT-UHFFFAOYSA-N 0.000 description 1
- GCWKPPGPWZXRJG-UHFFFAOYSA-N guanidine;phosphoric acid Chemical compound NC(N)=N.OP(O)(O)=O.OP(O)(O)=O GCWKPPGPWZXRJG-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 229940049918 linoleate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006166 lysate Substances 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
- 229960002510 mandelic acid Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- NQQWFVUVBGSGQN-UHFFFAOYSA-N phosphoric acid;piperazine Chemical compound OP(O)(O)=O.C1CNCCN1 NQQWFVUVBGSGQN-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229960005141 piperazine Drugs 0.000 description 1
- 229960001954 piperazine phosphate Drugs 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 235000019828 potassium polyphosphate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229960000948 quinine Drugs 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- OKQKDCXVLPGWPO-UHFFFAOYSA-N sulfanylidenephosphane Chemical compound S=P OKQKDCXVLPGWPO-UHFFFAOYSA-N 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 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
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- VUDJAFZYSMINQA-UHFFFAOYSA-L zinc metaphosphate Chemical compound [Zn+2].[O-]P(=O)=O.[O-]P(=O)=O VUDJAFZYSMINQA-UHFFFAOYSA-L 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 1
- CZPRKINNVBONSF-UHFFFAOYSA-M zinc;dioxido(oxo)phosphanium Chemical compound [Zn+2].[O-][P+]([O-])=O CZPRKINNVBONSF-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
- F21S8/00—Lighting devices intended for fixed installation
- F21S8/04—Lighting devices intended for fixed installation intended only for mounting on a ceiling or the like overhead structures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V17/00—Fastening of component parts of lighting devices, e.g. shades, globes, refractors, reflectors, filters, screens, grids or protective cages
- F21V17/10—Fastening of component parts of lighting devices, e.g. shades, globes, refractors, reflectors, filters, screens, grids or protective cages characterised by specific fastening means or way of fastening
- F21V17/12—Fastening of component parts of lighting devices, e.g. shades, globes, refractors, reflectors, filters, screens, grids or protective cages characterised by specific fastening means or way of fastening by screwing
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V5/00—Refractors for light sources
- F21V5/06—Hanging lustres for chandeliers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V17/00—Fastening of component parts of lighting devices, e.g. shades, globes, refractors, reflectors, filters, screens, grids or protective cages
- F21V17/10—Fastening of component parts of lighting devices, e.g. shades, globes, refractors, reflectors, filters, screens, grids or protective cages characterised by specific fastening means or way of fastening
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21W—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO USES OR APPLICATIONS OF LIGHTING DEVICES OR SYSTEMS
- F21W2121/00—Use or application of lighting devices or systems for decorative purposes, not provided for in codes F21W2102/00 – F21W2107/00
-
- 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
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S362/00—Illumination
- Y10S362/806—Ornamental or decorative
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
200532009 九、發明說明: 【發明所屬之技術領域】 本杳明係關於半導體晶圓材料之化學機械平整化或拋光 (CMP)’更特別關於用於使半導體晶圓上的鎢和鈦拋光之 CMP研磨劑及方法。本發明進一步關於用於使半導體晶圓 上的4烏和欽抛先之組合物。 【先前技術】 由於對單獨晶片上有源裝置密度增加之需要不斷升級,對 晶圓有源表面上更大平坦度之需要同時增加。對下層的改良 互連金屬化及改良填充通路孔和線之能力需要平表面。 CMP為達到所需平坦度的最重要技術。CMp促進表面材 料移除’機械磨損表面,同時化學組合物(1料,,)選擇性侵 蝕表面。因此,習知CMP漿料對晶圓表面上的至少兩種不 同材料展示不同移除速率(”選擇性,,)(例如,相對於間層電 介質對金屬展示不同拋光速率)。 目剷CMP為形成鎢接觸/通路插塞期間使鎢和鈦拋光之 較佳方法。通常’對於此應帛…般使制/料孔餘刻通 過介電層,以暴露下面裝置之區域(對於第-級金屬化)或金 屬互連(對於更高級金屬化)。使鈦"膠"層沈積於接觸/通路 孔之側部和底部,且在其上沈積嫣。用CMP自晶圓表面移 :戶:沈積的鎢和鈦,在接觸/通路孔中留下具有與所暴露電 "枭八平面之表面之鎢插塞。因此,與電介質比較,用於 嫣處理的CMP毁料對鶴和欽為高度選擇性。此選擇性顧及 過度拋光,同時仍獲得平鎢插塞表面。 100298.doc 200532009 賽蘇若曼(Sethuraman)等人在美國專利第6,〇〇1,269號揭 示種使半導體裝置拋光的已知氧化鋁研磨劑組合物,該 組合物包含以碘酸鹽為基礎之氧化劑。一般用硬氧化鋁研 磨劑達到足夠金屬移除速率,尤其對於如鈦之金屬。很遺 撼’氧化铭研磨劑產生有害的增加缺陷。此外,氧化鋁趨 向於提供不良選擇性速率,特別為鈦對氧化物之選擇性。
因此,需要具有改良選擇性的鎢和鈦之化學_機械拋光之 研磨劑。特別需要提供改良鈦層移除同時抑制介電層移除 之研磨知彳及方法。更需要提供改良鈦層移除同時抑制介電 層移除的具有改良缺陷之組合物。 【發明内容】 第一方面,本發明提供一種製造用於使半導體晶圓上的 鎢和鈦拋光之煙霧矽石之方法,該方法包括,提供預定體 積之水;提供預定濃度之煙霧矽石,其中該濃度為其至少 35重篁%,將酸混入該體積水,以使水酸化,其中該酸之 浪度為該濃度煙霧矽石之〇 〇〇1〇至〇·5重量% ;使煙霧矽石 分散進入經酸化的水;稀釋該濃度煙霧矽石,其中該水具 有1至7之pH;並收集該煙霧矽石。 第二方面,本發明提供一種用於使半導體晶圓上的鎢和 鈦拋光之煙霧矽石,其中該煙霧矽石具有大於9〇米2/克之表 面積,且已完全於酸性pH分散及稀釋。 第三方面,本發明提供一種用於使半導體晶圓上的鎢和 鈦拋光之組e物,5亥組合物包含研磨劑,其中該研磨劑為 具有大於90米2/克之表面積且已完全於酸性pH分散及稀釋 100298.doc 200532009 之煙霧矽石。 【實施方式】 該研磨劑和方法相對於介電層對銘 %曰对移除鎢和鈦提供意外選 擇性。該研磨劑有利在酸性pH處理,H目士一士 且吳有面表面積,以
抑制介電層移除。特別i也,該研磨冑為僅於酸性pH處理的 煙霧矽石,以相對於介電層選擇性使鎢和鈦拋光。此外, 該僅經酸性pH處理的煙霧矽石研磨劑具有大於9〇米v克之 表面積,以相對於介電層選擇性使鎢和鈦拋光。 在本文中,"僅經酸性pH處理的研磨劑”、"僅經酸性?11 處理的煙霧矽石酸性研磨劑,,及,,酸性煙霧矽石,,係界定 為僅於酸性pH處理之研磨劑。換言之,該研磨劑未在任何 點包括最終調配於鹼性溶液中分散或稀釋。 本發明之酸性煙霧矽石最佳藉由初始用預定體積去離子 水填充混合而製備。所用混合器較佳為高剪切混合器, 例如’由加利福尼亞州,貝爾的梅耶工程公司(Meyers Engineering,Inc. 〇f Beii,CA)製造之梅耶混合器(Myers
Mixer)。煙霧矽石,例如Aerosil 130(,,A 130”),自新澤西州, 帕悉潘尼,迪古薩公司(Degussa,of Parsippany,NJ)購得。 隨後,以所需pH為基礎將預定量酸加入水。將酸加入水後, 混合器運轉,以將酸和水混合成酸性水溶液。酸可為礦物 酸或有機酸,如鹽酸、硫酸、墙酸、麟酸、乙酸或馬來酸。 酸較佳為鹽酸。 加入水的酸之量有利為加入水的煙霧矽石之0.001 〇和 0·50重量%間之量。加入水的酸之量較佳為加入水的煙霧矽 100298.doc 200532009 石之0.0015和0.15重量。/〇間之量。
所選擇的水之初始量係基於欲加入的煙霧矽石之量以及 含水分散液中煙霧矽石之所需最終濃度。例如,如果煙霧 石夕石之含水分散液之所需最終濃度為35重量%之煙霧矽 石’則水之初始量為在混合器中產生大於35重量。/〇之煙霧 矽石之量或濃度。在本發明中,分散液將具有大於煙霧矽 石之含水分散液中煙霧矽石所需最終濃度約5重量%之煙 霧矽石濃度。隨後,藉由加入額外量水稀釋混合器中的含 水分散液’以達到煙霧矽石的所需最終濃度。 下一步’在混合器中,使煙霧矽石在水-酸溶液中分散到 預疋濃度。溶液溫度有利地保持在小於6〇〇c,較佳係小於 3 5 C。可將煙霧矽石加入水-酸混合物,同時混合器運轉, 或將煙霧矽石加入水_酸混合物,然後使混合器運轉,由此 加入煙霧石夕石。煙霧矽石亦可在一系列步驟增量加入,且 混合器在各步驟之間運轉。在含水分散液中煙霧矽石之濃 度升到南於煙霧矽石所需最終濃度之點後,使混合器運 轉’直到混合器中的分散液達到所需黏度。高剪切混合破 壞乾燥煙霧矽石之附聚結構,導致黏度下降。因此,高剪 切/%合在整個製程保持,以產生解聚。如果混合器停止, 則分散液可能膠凝並鎖住混合器,在分散液中產生不需要 的較大顆粒。如前討論,在稀釋前,混合器中的分散液具 有大於煙霧矽石所需最終濃度約5%之煙霧矽石濃度。 含水分散液有利包含至少35重量%之煙霧矽石。含水分 散液較佳包含40至65重量%間之煙霧矽石。此外,煙霧矽 100298.doc 200532009 石有利具有大於90米2/克之表面積。煙霧矽石較佳具有大於 130米/克之表面積。 下一步,藉由加入去離子水稀釋分散液。然後將額外水 混入混合器中的含水分散液。所加水之量為足以使含水分 散液中煙霧矽石之濃度降低到所需最終濃度之量。注意, 在稀釋期間,溶液之pH始終保持於丨至7之間。溶液之?11較 佳為1.5至5.5。
隨後’視需要離心或潷析煙霧矽石之含水分散液。此外, 可使煙霧矽石之含水分散液通過濾器,以移除粗粒及任何 附聚的煙霧矽石顆粒。特別過濾具有大於丨微米直徑的任何 不需要顆粒。隨後,視需要包裝經過濾的煙霧矽石,用於 將來使用。 本發明之方法允許製造用於使半導體晶圓中的鎢和鈦拋 光之煙霧矽石。特別地,該方法提供具有至少35重量%之 煙霧矽石濃度之酸性含水分散液。含水分散液更佳具有 % 和65重量%間之煙霧矽石。加入水的酸之量為加入水的煙 霧石夕石之0.0010和0.50重量%間之量。在稀釋期間,溶液之 pH始終保持於1至7之間。pH較佳為ι·5至5.5。此外,煙霧 石夕石有利具有大於90米2/克之表面積。煙霧矽石較佳具有大 於130米2/克之表面積。 本發明之酸性研磨劑有利用於使半導體晶圓上的鎢和鈦 . 拋光所用之組合物。除酸性研磨劑外,組合物可有利包含 0.5至9重量%之氧化劑。氧化劑較佳在1至4重量%之範圍 内。氧化劑最佳在2.5至3.5重量%之範圍内。氧化劑可為至 100298.doc •10- 200532009 夕 些氣化性化合物之一,如〆 鹽、峨酸鹽、過酞酸鎮、氣化氫(H2〇2)、單過硫酸 漠酸鹽、高峨酸鹽、;B肖酸鹽 ”匕過I、過硫酸鹽、 V, Λ/Γ ^ 、取幾、飾鹽、Mn(III)、Mn(IV) 及Mn(Vl)鹽、銀鹽、銅鹽、 nUV) 芨苴、、日入札σ L 视、始鹽、鹵素、次氣酸鹽 舍 吏用氧化劑化合物之混合物。 S拋光桌料包含一種不穩定氧 化Μ時,如過氧化氫,經常 最佳在使用點將氧化劑混入喈 水抖。較佳氧化劑為碘酸鹽, 包括其酸、鹽、混合酸鹽、酿 偏s曰、混合酯及其混合物。 溶液可有利包含0·1至5重量% 至里/。之錯合劑,以軟化鎢上的鈍
化層。錯合劑較佳在0.5至3重量%之範圍内。錯合劑最佳在 1至2重量%之範圍内。溶液有利包含"含碟"化合物作為錯合 劑。含磷化合物為任何含磷原子之化合物。例如,較佳含 磷化合物為磷酸鹽、焦磷酸鹽、偏磷酸鹽、連二磷酸鹽、 多磷酸鹽、膦酸鹽,包括其酸、鹽、混合酸鹽、酯、偏酯、 混合酯及其混合物。特別地,較佳含水拋光組合物可用(例 如)以下含磷化合物調配:磷酸鋅、焦磷酸鋅、偏磷酸鋅、 連二麟酸鋅、多碟酸鋅、膦酸鋅、填酸銨、焦填酸錄、偏 麟酸按、連二填酸錢、多鱗酸按、麟酸按、填酸二錄;、焦 磷酸二銨、偏磷酸二銨、連二磷酸二銨、多磷酸二銨、膦 酸二銨、磷酸胍、焦磷酸胍、偏磷酸胍、連二磷酸胍、多 磷酸胍、膦酸胍、磷酸鐵、焦磷酸鐵、偏磷酸鐵、連二磷 酸鐵、多磷酸鐵、膦酸鐵、碟酸鈽、焦鱗酸鈽、偏填酸鈽、 連二磷酸鈽、多磷酸鈽、膦酸鈽、磷酸乙二胺、磷酸哌嗓、 焦磷酸旅嗪、偏碟酸哌嗪、連二填酸哌唤、膦駿旅嗪、填 -11 - 100298.doc 200532009
酸密胺、磷酸二密胺、焦磷酸密胺、偏磷酸密胺、連二磷 酸密胺、多鱗酸後胺、鱗酸密胺、碟酸密白胺、焦填酸密 白胺、偏填酸密白胺、連二磷酸密白胺、多填酸密白胺、 膦酸密白胺、磷酸密勒胺、焦磷酸密勒胺、偏磷酸密勒胺、 連二構酸密勒胺、多磷酸密勒胺、膦酸密勒胺、磷酸舒、 焦鱗酸鉀、偏鱗酸鉀、連二填酸鉀、多磷酸鉀、膦酸鉀、 磷酸雙亂胺、磷酸脲,包括其酸、鹽、混合酸鹽、醋、偏 6旨、混合酯及其混合物。亦可使用氧化膦、硫化膦及膦酸 鹽、亞磷酸鹽及次膦酸鹽之磷雜環己烷(ph〇sph〇Hnane),包 括其酸、鹽、混合酸鹽、酯、偏酯及混合酯。較佳含構化 合物為焦磷酸鉀。 除錯合劑外,組合物可有利包含〇」至5重量%之螯合劑, 以使自墊上積累的氧化鶴抛光碎屑降到最少。組合物較佳 包含0.5至3重量。/❶之螯合劑。組合物最佳包含丨至2重量%之 螯合劑。實例螯合劑為羧酸,包括其金屬及非金屬鹽。螯 % 合劑可具有結合到開鏈烷(或其衍生物)結構或連接到環結 構的單、一、二或多羧基。羧酸之實例包括乙酸、丙酸、 丁酸、新戊酸、草酸、丙二酸、琥5白酸、戍二酸、己二酸、 本甲酸、丁二酸、天冬胺酸、五倍子酸、葡糖酸、鞣酸和 酞酸及其混合物。較佳螯合劑為“_羥基羧酸(aha),包括 /、孟屬及非金屬鹽。AHA為在與羧基直接相鄰的碳原子上 . 含一每基之有機酸。AHA之實例包括輕基乙酸、乳酸、酒 石酸、檸檬酸、蘋果酸、扁桃酸和水楊酸及其混合物。較 佳AHA為乳酸。 100298.doc -12- 200532009 於夜的;l ^在水之溶液中於寬PH範圍提供效力。兮 〉合液的有用PH範圍自至少 ^ 餘量去離子水W伸此外,溶液有利依賴 佳自2至5丄;?至叫 為(例如 _ 皿I、磷酸及類似者。 溶液可視需要包含〇 ; 々 ·至5重$%抑制氧化物移除之添加 二浴讀佳/含0.5至3重量%之氧化物抑制劑。溶液最佳 匕31至2重量%之氧化物抑制齊I。實例添加劑包括乙二胺 四乙酸及其鹽、乙-胺、〗4 6故 一^ 胺i,4_二氮雜雙環辛烷、乙二醇、冠
醚、鄰苯二盼和掊盼、轉樣酸、乳酸、丙二酸、酒石酸、 琥轴酸、蘋果酸、乙酸和草酸、胺基酸、胺續酸、胺基硫 酸、碌酸、膦酸、2-喹琳叛酸及其鹽。此外,實例添加劑 包括敦化物、I硼酸、氣鈦酸、氫氟酸、氟矽酸及其鹽。 此外’亦可加入聚合添加劑’如聚丙稀酸、環氧丙烧、聚 口比洛烧酮(Polypyrilid()ne)、聚氧化乙稀及聚乙稀醇。 因此,本發明提供一種製造用於使半導體晶圓上的鎢和 鈦拋光之煙霧石夕石之方法。該方法包括提供預定體積水及 提供預定濃度煙霧石夕石之操作,其中該煙霧石夕石之濃度為 忒體積水之至少35重量%。另外,本發明提供以下操作, 將酸混入該體積水,以使水酸化,其中該酸之濃度為該濃 度煙霧矽石之0.001 〇至〇·5重量%,並使煙霧矽石分散進入 經酸化的水。此外,本發明提供稀釋該濃度煙霧矽石,其 中該水之pH為1至7,並收集該煙霧矽石。注意,本發明之 煙霧矽石為純矽石。換言之,該煙霧矽石不包含微量(例如) 100298.doc -13- 200532009 至屬離子或聚合物,以在酸性pH給予碎石電荷。 實例 在貫例中’數字代表本發明之實例,字母代表比較實例。 斤有實例〉谷液包含3重量%之換酸鉀、1.5重量%之焦磷酸卸 及1.5重量%之乳酸。 實例1
本試驗檢驗鎢和鈦相對於半導體晶圓上TEOS之選擇性。 特別檢測僅於酸性pH處理的煙霧矽石相對於te〇s對鶴和 欽之選擇性之影響。換言之,試驗1之煙霧矽石研磨劑未在 製程期間於任何點於鹼性溶液中分散或稀釋。特別地,煙霧 石夕石研磨劑由以下方法製備:1)初始用6531克去離子水和 6.8克鹽酸填充夾套混合容器。使pH保持在2。打開冷卻,將 容器中的溫度控制到低於35°C。開動混合器,使混合器在 6 1 58轉/分運轉。混合器為加利福尼亞州,貝爾的梅耶工程 公司製造之梅耶混合器;2)為允許減黏裂化及防止馬達高電 流牵引,緩慢計量送入煙霧二氧化矽(A 130)。矽石之總填 充量為4540克。用去離子水(272克)喷容器下側,以壓制矽 石粉末。在此點的總填充量為1 1350克,且矽石濃度為4〇% 固體,3)然後使混合器運轉6 0分鐘,保持溫度低於3 $。〇 ; 4) 用足夠去離子水填充一第二容器,以使固體下降到2〇%,並 開動葉輪式混合器。將自夾套槽的分散液快速加入該第二容 器;5)檢驗pH、固體%及顆粒大小,並準備使用。
實例1之溶液包含3重量%具有大於丨3〇米 '克表面積之煙 霧石夕石研磨劑。IPEC 472 DE 200毫米拋光機利用Icl000TM 100298.doc 14 200532009 聚胺基甲酸酯拋光塾[羅姆-哈斯電子材料CMP技術公司 (Rohm and Haas Electronic Materials CMP Technologies)]在 約5磅/平方英寸之下壓力條件下於15〇立方釐米/分之拋光 溶液流速、65轉/分之台板速度及65轉/分之載體速度使樣品 平整化。拋光溶液具有用硝酸調節的4.0之pH。所有溶液均 包含去離子水。 試驗 研磨劑完全 在酸性p Η處 理? TEOS (埃/分) W (埃/分) Ti (埃/分) 選擇性 (W/TEOS) 選擇性 (Ti/TEOS) A 否 273 2023 4190 7.41 15.35 1 是 79 2340 4328 29.62 54.78
如以上表1中所示,加入酸性研磨劑改良組合物之選擇 性。特別地,加入酸性煙霧矽石使試驗1之組合物相對於 TEOS對鶴之選擇性自比較試驗A中的7 41改良到29 62。類 似地’加入酸性煙霧矽石使試驗1之組合物相對於TE〇s對 欽之選擇性自比較試驗A中的15.35改良到54.78。在試驗A 至試驗1中’加入酸性煙霧矽石使TE〇s移除自273埃/分有效 抑制到79埃/分。 實例2 本试驗檢驗鶴和鈦相對於半導體晶圓上TEOS之選擇 性。特別檢測僅於酸性pH處理的煙霧矽石之表面積相對於 TEOS對鶴和鈦之選擇性之影響。換言之,實例2之煙霧石夕 石研磨劑未在製程期間於任何點於鹼性溶液中分散或稀 釋。實例2之溶液包含3重量%之煙霧矽石研磨劑。所有其 他試驗條件與實例1者相同。 100298.doc 200532009
、表2中所示,僅經酸性pH處理的研磨劑之表面積影 響組合物之選擇性。特別地,加入具有大於90米V克表面積
之S义〖生煙霧矽石改良組合物相對於TE〇s對鎢和鈦之選擇 性。例如’當表面積自9〇米2/克增加到U0米2/克時,試驗2 刀别對鶴和鈦提供23.26和49.19之增加的選擇性,在比較試 驗B中分別對鎢和鈦提供3.4〇和7 37之選擇性。同樣,在試 驗B至試驗2中自90米2/克到130米V克的增加表面積使 TEOS移除速率自㈣埃/分抑制到崎/分。此外,在試驗B 至試驗3中自90米V克到米2/克的增加表面積使te〇s移 除速率自61G埃/分抑制到47埃/分。試驗2和3提供優良鈦移 除0 因此,本發明提供一種製造用於使半導體晶圓上的鎢和 钦拋光之煙霧_石之方法。該方法包括提供預定體積水及 提供預定濃度煙霧石夕石之操作,丨中該煙霧石夕石之濃度為 該體積水之至少35重量%。另外,本發明提供以下操作, 將酸混入該體積水,以使水酸化,其中該酸之濃度為該濃 度煙務矽石之0.001 〇至〇 5重量%,並使煙霧矽石分散進入 經酸化的水。此外’本發明提供稀釋㈣度煙霧石夕石,其 中孩水之pH為1至7,並收集該煙霧矽石。 100298.doc -16-
Claims (1)
- 200532009 十、申請專利範圍: 1· 種製造用於使半導體晶圓上的鶴和鈇拋光之煙霧石夕石 之方法,該方法包括: 提供預定體積水; 提供預定濃度之煙霧矽石,其中該濃度為該水體積之 至少35重量% ;將酸混入該體積水,以使該水酸化,其中該酸之濃度 為該濃度煙霧矽石之0.001 〇至0.5重量〇/〇 ; 使該煙霧矽石分散於該經酸化的水中; 稀釋該濃度煙霧矽石,其中該水具有丨至7之pH ;及 收集該煙霧石夕石。 2·如請求項1之方法,其中該水之pH為1.5至5 ·5。 3·如請求項}之方法,其中該分散係於小於6〇它之溫度進 行0 4·如明求項1之方法,其中該煙霧矽石之濃度係於該體積水 之4 0至6 〇重量%之間。 5·如明求項1之方法,其中該酸之濃度為該濃度煙霧矽石之 〇·〇2至 〇·ΐ5 重量 〇/〇。 6·如請求们之方法,其中該煙霧石夕石具有大於9〇米2/克之 ° 如請求項6之方法’其中該煙霧矽石具有大於咖米"克之 表面積。 8. 一種用於使半導體晶圓上的 中該煙霧矽石具有大於90米 鎢和鈦拋光之煙霧矽石,其 /克之表面積且已完全於酸 100298.doc 200532009 性PH分散及稀釋。 其中該煙霧矽石具有大於130米' 9·如請求項8之煙霧矽石 克之表面積。 1 〇·—種用於使半導體晶圓上的鶴和鈦拋光之組合物,該組 合物包含—種研磨劑,其中該研磨劑為具有大於90米2/ 克之表面積且已完全於酸性pH分散及稀釋之煙霧矽石。100298.doc 200532009 七、指定代表圖: (一) 本案指定代表圖為:(無)。 (二) 本代表圖之元件符號簡單說明: ^ 八、本案若有化學式時,請揭示最能顯示發明特徵的化學式: (無)100298.doc 200532009 kw 明專利說明書 (本說明書格式 '順序及^^字,請勿任意更動,※記號部分請勿填寫) ※申請案號: ※申請曰期: · · xipc分類匕L 9 一、 發明名稱:(中文/英文) 上c/ B》 用於鎢及鈦之化學機械平整化之研磨劑及組合物 ABRASIVES AND COMPOSITIONS FOR CHEMICAL MECHANICAL PLANARIZATION OF TUNGSTEN AND TITANIUM 二、 申請人··(共1人) 姓名或名稱··(中文/英文) 羅門哈斯電子材料CMP控股公司 ROHM AND HAAS ELECTRONIC MATERIALS CMP HOLDINGS, INC. 代表人:(中文/英文) 班德門布萊克T BIEDERMAN, BLAKE T. 住居所或營業所地址:(中文/英文) 美國•德拉瓦州19899 ·威明頓•北區市集街1105號1300室 ^105 North Market Street, Suite 1300, Wilmington, DE 19899, U. S. A. 國籍:(中文/英文) 美國 / U.S.A. ] 930S2L
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US8125018B2 (en) * | 2005-01-12 | 2012-02-28 | Spansion Llc | Memory device having trapezoidal bitlines and method of fabricating same |
WO2007024556A2 (en) | 2005-08-19 | 2007-03-01 | Houghton Metal Finishing Company | Methods and compositions for acid treatment of a metal surface |
JP5084134B2 (ja) | 2005-11-21 | 2012-11-28 | 日本電気株式会社 | 表示装置及びこれらを用いた機器 |
US7732393B2 (en) * | 2006-03-20 | 2010-06-08 | Cabot Microelectronics Corporation | Oxidation-stabilized CMP compositions and methods |
US20080096385A1 (en) * | 2006-09-27 | 2008-04-24 | Hynix Semiconductor Inc. | Slurry composition for forming tungsten pattern and method for manufacturing semiconductor device using the same |
US8974655B2 (en) * | 2008-03-24 | 2015-03-10 | Micron Technology, Inc. | Methods of planarization and electro-chemical mechanical polishing processes |
US20150156519A1 (en) * | 2012-07-10 | 2015-06-04 | Sharp Kabushiki Kaisha | Playing device, playing method, delivery device, delivery method, delivery program, playing program, recording medium, and metadata |
CN103146307B (zh) * | 2013-03-28 | 2014-12-10 | 天津理工大学 | 一种化学机械抛光用纳米抛光液 |
KR200482628Y1 (ko) | 2016-07-22 | 2017-02-14 | 하승원 | 애완동물 견인기 |
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US5246624A (en) * | 1989-03-21 | 1993-09-21 | Cabot Corporation | Aqueous colloidal dispersion of fumed silica, acid and stabilizer |
US5340370A (en) * | 1993-11-03 | 1994-08-23 | Intel Corporation | Slurries for chemical mechanical polishing |
US5958288A (en) * | 1996-11-26 | 1999-09-28 | Cabot Corporation | Composition and slurry useful for metal CMP |
US5916855A (en) * | 1997-03-26 | 1999-06-29 | Advanced Micro Devices, Inc. | Chemical-mechanical polishing slurry formulation and method for tungsten and titanium thin films |
US5993685A (en) * | 1997-04-02 | 1999-11-30 | Advanced Technology Materials | Planarization composition for removing metal films |
US6001269A (en) * | 1997-05-20 | 1999-12-14 | Rodel, Inc. | Method for polishing a composite comprising an insulator, a metal, and titanium |
TW510917B (en) * | 1998-02-24 | 2002-11-21 | Showa Denko Kk | Abrasive composition for polishing semiconductor device and method for manufacturing semiconductor device using same |
US6313246B1 (en) * | 1999-07-07 | 2001-11-06 | Nalco Chemical Company | High molecular weight zwitterionic polymers |
JP3721497B2 (ja) * | 1999-07-15 | 2005-11-30 | 株式会社フジミインコーポレーテッド | 研磨用組成物の製造方法 |
US20050211952A1 (en) * | 2004-03-29 | 2005-09-29 | Timothy Mace | Compositions and methods for chemical mechanical planarization of tungsten and titanium |
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