CN1676566A - 用于钨和钛的化学机械平坦化的研磨剂和组合物 - Google Patents
用于钨和钛的化学机械平坦化的研磨剂和组合物 Download PDFInfo
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- CN1676566A CN1676566A CNA2005100624716A CN200510062471A CN1676566A CN 1676566 A CN1676566 A CN 1676566A CN A2005100624716 A CNA2005100624716 A CN A2005100624716A CN 200510062471 A CN200510062471 A CN 200510062471A CN 1676566 A CN1676566 A CN 1676566A
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- Prior art keywords
- fumed silica
- acid
- water
- concentration
- titanium
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- 239000010936 titanium Substances 0.000 title claims abstract description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 36
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 36
- 239000010937 tungsten Substances 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims description 34
- 239000000126 substance Substances 0.000 title description 3
- 239000003082 abrasive agent Substances 0.000 title 1
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- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 100
- 239000002253 acid Substances 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000005498 polishing Methods 0.000 claims abstract description 24
- 239000004065 semiconductor Substances 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims description 21
- 235000012431 wafers Nutrition 0.000 claims description 17
- 239000003651 drinking water Substances 0.000 claims description 4
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- 239000000243 solution Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
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- 150000001875 compounds Chemical class 0.000 description 8
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- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 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 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
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- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
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- 239000003112 inhibitor Substances 0.000 description 2
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 2
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- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
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- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 description 2
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- RILFGEIJJMTZLZ-UHFFFAOYSA-J tetrapotassium;dioxido-oxo-phosphonato-$l^{5}-phosphane Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)P([O-])([O-])=O RILFGEIJJMTZLZ-UHFFFAOYSA-J 0.000 description 1
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- CZPRKINNVBONSF-UHFFFAOYSA-M zinc;dioxido(oxo)phosphanium Chemical compound [Zn+2].[O-][P+]([O-])=O CZPRKINNVBONSF-UHFFFAOYSA-M 0.000 description 1
Classifications
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- 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
- 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
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- 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
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- 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]
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- 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
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Landscapes
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- 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)
Abstract
本发明提供了制造用于抛光半导体晶片上的钨和钛的气相法氧化硅的方法。该方法包括提供预定体积的水和提供预定浓度的气相法氧化硅的过程，其中该气相法氧化硅的浓度至少为该体积的水的35wt％。此外，本发明提供了向该体积的水中混入酸以便将水酸化，其中酸的浓度是气相法氧化硅浓度的0.0010至0.5wt％，然后将气相法氧化硅分散到酸化水中的过程。此外，本发明提供了稀释该气相法氧化硅的浓度，其中该水具有1至7的pH和收集该气相法氧化硅。
Description
技术领域
本发明涉及半导体晶片材料的化学机械平坦化或抛光(CMP)，且更具体地涉及抛光半导体晶片上的钨和钛的CMP研磨剂和方法。此外，本发明涉及抛光半导体晶片上的钨和钛的组合物。
背景技术
随着对于增加单个芯片上的有源器件密度的要求的逐步提高，对晶片有源表面上更大平整度的要求同时提高。需要平坦的表面来改善与下部层的互连金属镀覆和提高填充导孔和线路的能力。
CMP是达到期望平整度的最重要的技术。CMP可增强表面材料的去除，在化学组合物(“浆料”)选择性侵蚀表面的同时对表面进行机械研磨。因此，传统的CMP浆料对于晶片表面上的至少两种不同材料表现出不同的去除速率(“选择性”)(例如，金属相对于中间层电介质的不同抛光速率)。典型地，浆料包含研磨剂成分以便促进表面去除。
目前，在形成钨接触/导孔接头时CMP是抛光钨和钛的优选方法。通常，对于这种应用，穿过电介质层腐蚀出接触/导孔以便暴露下层器件(对于第一级金属镀覆)或金属互连(对于更高级的金属镀覆)的区域。在该接触/导孔的侧面或底部沉积钛“粘合”层，然后在其上沉积钨。使用CMP从晶片表面上除去沉积的钨和钛，并在该接触/导孔中留下具有与暴露电介质共面的表面的钨接头。因此，相比电介质，用于钨处理的CMP浆料应具有高的钨和钛选择性。这种选择性允许过度抛光然而仍可达到平坦的钨接头表面。
Sethuraman等人在美国专利第6,001,269号中公开了用于抛光半导体器件且包含碘酸盐基氧化剂的已知的氧化铝研磨剂组合物。典型利用硬的氧化铝研磨剂来获得足够的金属去除速率，特别是对于例如钛的金属。遗憾的是，该氧化铝研磨剂会产生有害，增加的缺陷。另外，氧化铝研磨剂倾向于提供不良的选择性比率，特别是钛相对于氧化物的选择性。
因此，需要具有改良的选择性的用于钨和钛的化学机械抛光的研磨剂。特别地，需要可提供改良的钛层去除同时可抑制电介质层去除的研磨剂和方法。此外，需要可提供改良的钛层去除同时可抑制电介质层去除并具有改良缺陷的组合物。
发明内容
第一方面，本发明提供了制造用于抛光半导体晶片上的钨和钛的气相法氧化硅的方法，该方法包括：提供预定体积的水；提供预定浓度的气相法氧化硅，其中该浓度至少为该体积的水的35wt％；向该体积的水中混入酸以便将水酸化，其中酸的浓度是气相法氧化硅浓度的0.0010至0.5wt％；将气相法氧化硅分散到酸化的水中；稀释该气相法氧化硅的浓度，其中该水具有1至7的pH；和收集该气相法氧化硅。
第二方面，本发明提供了用于抛光半导体晶片上的钨和钛的气相法氧化硅，其中该气相法氧化硅具有大于90m2/g的表面积并且完全分散并稀释在酸性pH中。
第三方面，本发明提供了用于抛光半导体晶片上的钨和钛的组合物，该组合物包含研磨剂，其中该研磨剂是具有大于90m2/g表面积且完全分散并稀释于酸性pH中的气相法氧化硅。
具体实施方式
该研磨剂和方法提供了意想不到的钨和钛相对于电介质层的去除选择性。优选在酸性pH中对该研磨剂进行处理而且该研磨剂具有高的表面积以便抑制电介质层的去除。特别地，该研磨剂是仅在酸性pH中处理的气相法氧化硅，以便相对电介质层选择性抛光钨和钛。此外，该仅以酸性pH处理的气相法氧化硅研磨剂具有大于90m2/g的表面积，以便相对于电介质层选择性抛光钨和钛。
这里所使用的“仅以酸性pH处理的研磨剂”，“仅以酸性pH处理的气相法氧化硅”，“酸性研磨剂”，和“酸性气相法氧化硅”是指仅在酸性pH中处理过的研磨剂。换言之，在包括最后配置的任何时候，该研磨剂不会分散或稀释于碱性溶液。
优选地，通过最初将预定体积的去离子水装入混合机来制造本发明的酸性气相法氧化硅。所用的混合机优选为高剪切混合机，例如Meyers Engineering，Inc of Bell，CA制造的Myers混合机。气相法氧化硅例如是购自Degussa，of Parsippany，NJ的Aerosil 130(“A130”)。随后，根据需要的pH向水中加入预定量的酸。向水中加入酸之后，混合机运转使酸和水混合从而形成酸性水溶液。该酸可以是无机酸或有机酸例如盐酸，硫酸，硝酸，磷酸，乙酸或顺丁烯二酸。该酸优选为盐酸。
优选地，加入到水中的酸量是将加入水中的气相法氧化硅的0.0010至0.50wt％。优选地，加入到水中的酸量是将加入水中的气相法氧化硅的0.0015至0.15wt％。
最初水量的选择是基于待加入的气相法氧化硅的量，以及水性分散体中气相法氧化硅的期望最终浓度。例如，如果气相法氧化硅的水性分散体的期望最终浓度是35wt％的气相法氧化硅，这时最初的水量是可导致混合机中气相法氧化硅的浓度大于35wt％的水量。在本发明中，该分散体可具有比该气相法氧化硅的水性分散体中的气相法氧化硅的期望最终浓度高大约5wt％的气相法氧化硅浓度。然后，通过加入额外量的水对混合机中的水性分散体进行稀释以便达到气相法氧化硅的期望最终浓度。
接着，将气相法氧化硅分散到混合机内的水-酸溶液中达到预定的浓度。优选地，将该溶液的温度维持在小于60℃，优选小于35℃。可以通过在混合机运转的同时将气相法氧化硅混入水-酸混合物将气相法氧化硅加入，或者通过将气相法氧化硅加入水-酸混合物然后运转混合机。也可以在一系列步骤中逐步加入该气相法氧化硅，并使混合机在每个步骤之间运转。将水性分散体中气相法氧化硅的浓度提高到期望的气相法氧化硅最终浓度之上以后，允许混合机继续运转直到该混合机中的分散体达到要求的粘度。该高剪切搅拌可破碎干态气相法氧化硅的团聚结构从而使粘度降低。因此，在整个过程中维持该高剪切搅拌以引起解团聚。如果混合机停止，该分散体可能会发生凝胶化并塞住(lock up)混合机从而在分散体中产生有害，较大的颗粒。正如所讨论的，混合机中的分散体在稀释之前将具有比气相法氧化硅的期望最终浓度高大约5wt％的气相法氧化硅浓度。
优选地，该水性分散体包含至少35wt％的气相法氧化硅。优选地，该水性分散体包含40至65wt％的气相法氧化硅。另外该气相法氧化硅优选具有大于90m2/g的表面积。优选地，该气相法氧化硅优选具有大于130m2/g的表面积。
然后，通过加入去离子水稀释该分散体。然后将附加的水混入混合机中的水性分散体。加入水的量应足够将水性分散体中的气相法氧化硅的浓度降低到期望的最终浓度。注意，在稀释期间将溶液的pH始终维持在1至7之间。优选地，该溶液的pH是1.5至5.5。
随后，可以根据需要将气相法氧化硅的水性分散体离心或倾析。另外，可以使气相法氧化硅的水性分散体通过过滤器以便除去砂砾和任何团聚的气相法氧化硅颗粒。特别是过滤具有大于1微米直径的任何不需要的颗粒。随后，可以根据需要将过滤的气相法氧化硅包装起来以备将来使用。
本发明的方法允许生产用于抛光半导体晶片上的钨和钛的气相法氧化硅。特别地，本方法可提供具有至少35wt％的气相法氧化硅浓度的酸性水性分散体。更优选地，该水性分散体具有40至65wt％之间的气相法氧化硅浓度。加入水中的酸量是将加入到水中的气相法氧化硅的0.0010至0.50wt％。在稀释过程中，始终保持溶液的pH在1至7。pH优选为1.5至5.5。另外，该气相法氧化硅优选具有大于90m2/g的表面积。优选地，该气相法氧化硅优选具有大于130m2/g的表面积。
优选在用于抛光半导体晶片上的钨和钛的组合物中利用本发明的酸性研磨剂。除该酸性研磨剂以外，该组合物可优选包含0.5至9wt％的氧化剂。该氧化剂优选在1至4wt％的范围之内。最优选地，该氧化剂在2.5至3.5wt％的范围之内。该氧化剂可以是许多氧化性化合物中的至少一种，例如过氧化氢(H2O2)，单过硫酸盐，碘酸盐(酯)，过邻苯二甲酸镁，过乙酸和其它过酸，过硫酸盐，溴酸盐，高碘酸盐，硝酸盐，铁盐，铈盐，Mn(III)盐，Mn(IV)盐和Mn(VI)盐，银盐，铜盐，铬盐，钴盐，卤素，次氯酸盐及其混合物。此外，通常优选使用氧化剂化合物的混合物。当该抛光浆料包含不稳定氧化剂例如过氧化氢时，通常最优选在使用时将该氧化剂混入该浆料。优选的氧化剂是碘酸盐(酯)，包括它的酸，盐，混合酸盐，酯，偏酯，混合酯，及其混合物。
优选地，该溶液可以包含0.1至5wt％的配位剂以便软化钨上的钝化层。该配位剂优选在0.5至3wt％的范围内。最优选地，该配位剂在1至2wt％的范围内。该溶液优选包含“含磷”化合物作为配位剂。“含磷”化合物是包含磷原子的任何化合物。优选的含磷化合物是，例如磷酸盐(酯)，焦磷酸盐(酯)，偏磷酸盐(酯)，连二磷酸盐(酯)，多磷酸盐(酯)，膦酸盐(酯)，包括他们的酸，盐，混合酸盐，酯，偏酯，混合酯，及其混合物。特别地，可以使用例如下列含磷化合物配置优选的水性抛光组合物：磷酸锌，焦磷酸锌，偏磷酸锌，连二磷酸锌，多磷酸锌，膦酸锌，磷酸铵，焦磷酸铵，偏磷酸铵，连二磷酸铵，多磷酸铵，膦酸铵，磷酸二铵，焦磷酸二铵，偏磷酸二铵，连二磷酸二铵，多磷酸二铵，膦酸二铵，磷酸胍，焦磷酸胍，偏磷酸胍，连二磷酸胍，多磷酸胍，膦酸胍，磷酸铁，焦磷酸铁，偏磷酸铁，连二磷酸铁，多磷酸铁，膦酸铁，磷酸铈，焦磷酸铈，偏磷酸铈，连二磷酸铈，多磷酸铈，膦酸铈，磷酸乙二胺，磷酸哌嗪，焦磷酸哌嗪，偏磷酸哌嗪，连二磷酸哌嗪，膦酸哌嗪，磷酸蜜胺，磷酸二蜜胺，焦磷酸蜜胺，偏磷酸蜜胺，连二磷酸蜜胺，多磷酸蜜胺，膦酸蜜胺，磷酸蜜白胺，焦磷酸蜜白胺，偏磷酸蜜白胺，连二磷酸蜜白胺，多磷酸蜜白胺，膦酸蜜白胺，磷酸蜜勒胺，焦磷酸蜜勒胺，偏磷酸蜜勒胺，连二磷酸蜜勒胺，多磷酸蜜勒胺，膦酸蜜勒胺，磷酸钾，焦磷酸钾，偏磷酸钾，连二磷酸钾，多磷酸钾，膦酸钾，磷酸双氰胺，磷酸脲，包括它们的酸，盐，混合酸盐，酯，偏酯，混合酯，及其混合物。此外，可以使用氧化膦，硫化膦和磷烷(phosphorinane)，以及膦酸盐(酯)，亚磷酸盐(酯)和亚膦酸盐(酯)，包括它们的酸，盐，混合酸盐，酯，偏酯和混合酯。优选的含磷混合物是焦磷酸钾。
除配位剂之外，该组合物可优选包含0.1至5wt％的螯合剂以便最大程度上减小氧化钨抛光碎屑在垫上的积累。优选地，该组合物包含0.5至3wt％的螯合剂。最优选地，该组合物包含1至2wt％的螯合剂。螯合剂的实例是羧酸，包括它们的金属和非金属盐。该螯合剂可以具有与开链烷烃(或其衍生物)结构相连，或者与环结构结合的一个，两个，三个，或多个羧基。羧酸的实例包括乙酸，丙酸，丁酸，新戊酸，草酸，丙二酸，丁二酸，戊二酸，己二酸，苯甲酸，丁二酸，天冬氨酸，棓酸，葡糖酸，丹宁酸和邻苯二甲酸，及其混合物。优选的螯合剂是α-羟基羧酸(AHA)，包括它们的金属和非金属盐。AHA是在与羧基直接相邻的碳原子上包含羟基的有机酸。AHA的实例包括羟基乙酸，乳酸，酒石酸，柠檬酸，苹果酸，扁桃酸和水杨酸，及其混合物。优选的AHA是乳酸。
在包含余量水的溶液中该组合物可以在宽的pH范围上提供效力。该溶液的有效pH范围可以扩展到至少1至7。另外，该溶液优选依靠余量的去离子水来限制附带的杂质。本发明的抛光流体的pH优选为2至5，更优选3.5至4.5的pH。用来调节本发明组合物的pH的酸是例如硝酸，硫酸，盐酸，磷酸等等。
该溶液可选包含0.1至5wt％的添加剂以便抑制氧化物的去除。优选地，该溶液包含0.5至3wt％的氧化物抑制剂。最优选地，该溶液包含1至2wt％的氧化物抑制剂。添加剂的实例包括乙二胺四乙酸和它的盐，乙二胺，1，4-二氮杂双环辛烷，乙二醇，冠醚，苯邻二酚和棓酚，柠檬酸，乳酸，丙二酸，酒石酸，丁二酸，苹果酸，乙酸和草酸，氨基酸，氨基磺酸，氨基硫酸磷酸，膦酸，2-喹啉羧酸，和它们的盐。此外，典型的添加剂包括氟化物，氟硼酸，氟钛酸，氢氟酸，氟硅酸，和它们的盐。另外，也可以使用聚合添加剂例如聚丙烯酸，环氧丙烷，聚吡咯烷酮(polypyrilidone)，聚环氧乙烷和聚乙烯醇。
因此，本发明提供了制造用于抛光半导体晶片上的钨和钛的气相法氧化硅的方法。该方法包括提供预定体积的水和提供预定浓度的气相法氧化硅的过程，其中该气相法氧化硅的浓度至少为该体积的水的35wt％。此外，本发明提供了向水中混入酸以便将水酸化，其中酸的浓度是气相法氧化硅浓度的0.0010至0.5wt％，然后将气相法氧化硅分散到酸化水中的过程。此外，本发明提供了稀释该气相法氧化硅的浓度，其中该水具有1至7的pH和收集该气相法氧化硅。注意，本发明的气相法氧化硅是纯净的氧化硅。换言之，该气相法氧化硅不包含例如会在酸性pH中将电荷赋给氧化硅的微量金属离子或聚合物。
实施例
在实施例中，数字代表本发明的实施例而字母代表对照实施例。所有的实施例溶液均包含3wt％的碘酸钾，1.5wt％的焦磷酸钾和1.5wt％的乳酸。
实施例1
本实验测量半导体晶片上的钨和钛相对于TEOS的选择性。特别地，测试了仅在酸性pH中处理过的气相法氧化硅对钨和钛相对TEOS的选择性的影响。换言之，在制备过程的任何时候，没有将测试1的气相法氧化硅分散或稀释到碱性溶液中。具体地，通过下列方法制备该气相法研磨剂：1)最初向夹套式混合容器中装入6531克去离子水和6.8克盐酸。该pH维持在2。开启冷却并控制容器中的温度低于35℃。启动混合机并使其运转在6158rpm下。该混合机是Meyers Engineering，Inc.ofBell，CA制造的Myers Mixer；2)将该气相法二氧化硅(A 130)缓慢定量加入以便允许粘度降低并防止在电机上产生高电流。总的氧化硅装料是4540克。使用去离子水(272g)喷淋容器侧壁将氧化硅粉末冲下。这时总的装料是11350克并具有40％固体的氧化硅浓度；3)然后使混合机运转60分钟，维持温度低于35℃；4)将第二个容器装入足量的去离子水以便使固体下降到20％并开启叶轮式混合机。将夹套容器中的分散体迅速加入第二个容器；5)测量pH，固体％和颗粒尺寸并准备使用。
实施例1的溶液包含3wt％具有130m2/g表面积的气相法氧化硅研磨剂。利用IPEC 472 DE 200mm抛光机，使用IC1000TM聚氨酯抛光垫(Rohmand Haas Electronic Materials CMP Technologies)在约5psi的下压力条件，150cc/min的抛光溶液流速，65RPM的工作台转速和65RPM的托盘转速下对样品进行平坦化。该抛光溶液具有用硝酸调节至4.0的pH。所有的溶液均包含去离子水。
表1
| 测试 | 完全在酸性pH中处理研磨剂？ | TEOS(/min) | W(/min) | Ti(/min) | 选择性(W/TEOS) | 选择性(Ti/TEOS) |
| A | 否 | 273 | 2023 | 4190 | 7.41 | 15.35 |
| 1 | 是 | 79 | 2340 | 4328 | 29.62 | 54.78 |
如上表1所示，酸性研磨剂的添加可提高该组合物的选择性。具体地，该酸性气相法氧化硅的添加可以将测试1的组合物的钨相对TEOS的选择性从对照测试A中的7.41提高到29.62。类似地，该酸性气相法氧化硅的添加可以将测试1的组合物的钛相对TEOS的选择性从对照测试A中的15.35提高到54.78。该酸性气相法氧化硅的添加可将TEOS的去除从测试A中的273/min有效抑制到测试1的79/min。
实施例2
本实验测量半导体晶片上的钨和钛相对于TEOS的选择性。特别地，测量了完全在酸性pH中处理的气相法氧化硅的表面积对钨和钛相对于TEOS的选择性的影响。换言之，在制备过程的任何时候，没有将实施例2的气相法氧化硅研磨剂分散或稀释到碱性溶液中。实施例2的溶液包含3wt％的气相法氧化硅研磨剂。所有的其它测试条件与实施例1相同。
表2
| 测试 | 研磨剂表面积(m2/g) | TEOS(/min) | W(/min) | Ti(/min) | 选择性(W/TEOS) | 选择性(Ti/TEOS) |
| B | 90 | 610 | 2072 | 4497 | 3.40 | 7.37 |
| 2 | 130 | 86 | 1989 | 4230 | 23.26 | 49.19 |
| 3 | 200 | 47 | 2442 | 4509 | 51.95 | 95.94 |
如上表2所示，仅以酸性pH处理的研磨剂的表面积会影响该组合物的选择性。特别地，具有大于90m2/g表面积的酸性气相法氧化硅的添加可提高该组合物的钨和钛相对TEOS的选择性。例如，测试2提供了提高的钨和钛选择性，当表面积从90m2/g增加到130m2/g时，钨和钛的选择性分别从对照测试B中的3.40和7.37提高到23.26和49.19。除此之外，测试B至测试2中表面积从90m2/g增加到130m2/g可以将TEOS的去除速率从610/min抑制到86/min。此外，测试B至测试3中表面积从90m2/g增加到200m2/g可以将TEOS的去除速率从610/min抑制到47/min。测试2和3提供了优异的钛去除。
因此，本发明提供了制造用于抛光半导体晶片上的钨和钛的气相法氧化硅的方法。该方法包括提供预定体积的水和提供预定浓度的气相法氧化硅的过程，其中该气相法氧化硅的浓度至少为该体积的水的35wt％。此外，本发明提供了向该体积的水中混入酸以便将水酸化，其中酸的浓度是气相法氧化硅浓度的0.0010至0.5wt％，然后将气相法氧化硅分散到酸化水中的过程。此外，本发明提供了稀释该气相法氧化硅的浓度，其中该水具有1至7的pH和收集该气相法氧化硅。
Claims (10)
1.制造用于抛光半导体晶片上的钨和钛的气相法氧化硅的方法，该方法包括：
提供预定体积的水；
提供预定浓度的气相法氧化硅，其中该浓度至少为该体积的水的35wt％；
向该体积的水中混入酸以便将水酸化，其中酸的浓度是气相法氧化硅浓度的0.0010至0.5wt％；
将气相法氧化硅分散到酸化的水中；
稀释该气相法氧化硅的浓度，其中该水具有1至7的pH；和
收集该气相法氧化硅。
2.权利要求1的方法，其中该水的pH是1.5至5.5
3.权利要求1的方法，其中在低于60℃的温度下进行该分散。
4.权利要求1的方法，其中该气相法氧化硅的浓度是该体积的水的40至60wt％。
5.权利要求1的方法，其中该酸的浓度是气相法氧化硅浓度的0.02至0.15wt％。
6.权利要求1的方法，其中该气相法氧化硅具有大于90m2/g的表面积。
7.权利要求6的方法，其中该气相法氧化硅具有大于130m2/g的表面积。
8.用于抛光半导体晶片上的钨和钛的气相法氧化硅，其中该气相法氧化硅具有大于90m2/g的表面积且完全分散并稀释在酸性pH中。
9.权利要求8的气相法氧化硅，其中该气相法氧化硅具有大于130m2/g的表面积。
10.用于抛光半导体晶片上的钨和钛的组合物，该组合物包含研磨剂，其中该研磨剂是具有大于90m2/g表面积并且完全分散并稀释在酸性pH中的气相法氧化硅。
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| CN103146307A (zh) * | 2013-03-28 | 2013-06-12 | 天津理工大学 | 一种化学机械抛光用纳米抛光液 |
| CN113122148A (zh) * | 2021-04-07 | 2021-07-16 | 云南合义德新材料有限公司 | 一种晶体硅碱抛光添加剂及使用方法 |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8125018B2 (en) * | 2005-01-12 | 2012-02-28 | Spansion Llc | Memory device having trapezoidal bitlines and method of fabricating same |
| EP1931817A2 (en) * | 2005-08-19 | 2008-06-18 | 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 |
| WO2014010501A1 (ja) * | 2012-07-10 | 2014-01-16 | シャープ株式会社 | 再生装置、再生方法、配信装置、配信方法、配信プログラム、再生プログラム、記録媒体およびメタデータ |
| KR200482628Y1 (ko) | 2016-07-22 | 2017-02-14 | 하승원 | 애완동물 견인기 |
| CN109728158B (zh) * | 2017-10-27 | 2023-07-07 | 华邦电子股份有限公司 | 电阻式存储器及其制造方法与化学机械研磨制程 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| ES2216490T3 (es) * | 1998-02-24 | 2004-10-16 | Showa Denko Kabushiki Kaisha | Composicion abrasiva para pulir un dispositivo semiconductor y procedimiento para producir un dispositivo semiconductor con la misma. |
| 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 |
-
2004
- 2004-03-29 US US10/811,640 patent/US20050214191A1/en not_active Abandoned
-
2005
- 2005-03-23 TW TW094108885A patent/TW200532009A/zh unknown
- 2005-03-28 KR KR1020050025398A patent/KR20060044831A/ko not_active Application Discontinuation
- 2005-03-28 CN CNA2005100624716A patent/CN1676566A/zh active Pending
- 2005-03-29 JP JP2005093375A patent/JP2005286336A/ja active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146307A (zh) * | 2013-03-28 | 2013-06-12 | 天津理工大学 | 一种化学机械抛光用纳米抛光液 |
| 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 |
| CN113122148A (zh) * | 2021-04-07 | 2021-07-16 | 云南合义德新材料有限公司 | 一种晶体硅碱抛光添加剂及使用方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20050214191A1 (en) | 2005-09-29 |
| JP2005286336A (ja) | 2005-10-13 |
| KR20060044831A (ko) | 2006-05-16 |
| TW200532009A (en) | 2005-10-01 |
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