JP2014099565A - 研磨用組成物 - Google Patents
研磨用組成物 Download PDFInfo
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- JP2014099565A JP2014099565A JP2012251521A JP2012251521A JP2014099565A JP 2014099565 A JP2014099565 A JP 2014099565A JP 2012251521 A JP2012251521 A JP 2012251521A JP 2012251521 A JP2012251521 A JP 2012251521A JP 2014099565 A JP2014099565 A JP 2014099565A
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- Prior art keywords
- polishing
- acid
- silica
- polishing composition
- polished
- Prior art date
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- 239000000758 substrate Substances 0.000 claims description 11
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- 238000004090 dissolution Methods 0.000 description 2
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- 238000005227 gel permeation chromatography Methods 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
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Classifications
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- 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
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
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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
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
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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
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Mechanical Engineering (AREA)
Abstract
【解決手段】有機酸を表面に固定したシリカと、分子量が2万未満の2価アルコールと、pH調整剤と、を含み、pHが6以下である、研磨用組成物。
【選択図】なし
Description
本発明の第一は、有機酸を表面に固定化したシリカと、分子量が2万未満の2価アルコールと、pH調整剤と、を含み、pHが6以下である研磨用組成物である。このような構成とすることにより、保管安定性が良好であり、化学反応性に乏しい研磨対象物を高速で研磨することができる。
本発明の研磨用組成物中に含まれる有機酸を表面に固定したシリカは、砥粒として用いられる、有機酸を表面に化学的に結合させたシリカである。前記シリカにはフュームドシリカやコロイダルシリカ等が含まれるが、特にコロイダルシリカが好ましい。前記有機酸は、特に制限されないが、スルホン酸、カルボン酸、リン酸などが挙げられ、好ましくはスルホン酸またはカルボン酸である。なお、本発明の研磨用組成物中に含まれる「有機酸を表面に固定したシリカ」の表面には、上記有機酸由来の酸性基(例えば、スルホ基、カルボキシル基、リン酸基など)が(場合によってはリンカー構造を介して)共有結合により固定されていることになる。
本発明で用いられる分子量が2万未満の2価アルコールは、特に制限されないが、下記化学式(1)で表される化合物であることが好ましい。
本発明の研磨用組成物のpHの値は、6以下である。pHがアルカリ性の場合、多結晶シリコンやTEOSは溶解が始まるために、研磨用組成物を用いて多結晶シリコンやTEOS等の研磨速度を抑制することは困難になる。また、pH6を超えると、窒化ケイ素のゼータ電位がマイナス側になり、ゼータ電位がマイナスである砥粒を用いて窒化ケイ素を高速度で研磨することも困難になる。研磨用組成物による窒化ケイ素の研磨速度のさらなる向上という点からは、研磨用組成物のpHの値は5以下であることが好ましく、より好ましくは4.5以下、さらに好ましくは4以下である。
本発明の研磨用組成物は、通常各成分の分散または溶解のための分散媒または溶媒が用いられる。分散媒または溶媒としては有機溶媒、水が考えられるが、その中でも水を含むことが好ましい。他の成分の作用を阻害するという観点から、不純物をできる限り含有しない水が好ましい。具体的には、イオン交換樹脂にて不純物イオンを除去した後フィルタを通して異物を除去した純水や超純水、または蒸留水が好ましい。
本発明の研磨用組成物は、必要に応じて、有機酸を表面に固定したシリカ以外の砥粒、錯化剤、金属防食剤、防腐剤、防カビ剤、酸化剤、還元剤、界面活性剤等の他の成分をさらに含んでもよい。以下、砥粒、酸化剤、防腐剤、防カビ剤について説明する。
本発明で用いられる有機酸を表面に固定したシリカ以外の砥粒は、無機粒子、有機粒子、および有機無機複合粒子のいずれであってもよい。無機粒子の具体例としては、例えばアルミナ、セリア、チタニア等の金属酸化物からなる粒子、窒化ケイ素粒子、炭化ケイ素粒子、窒化ホウ素粒子が挙げられる。有機粒子の具体例としては、例えば、ポリメタクリル酸メチル(PMMA)粒子が挙げられる。該砥粒は、単独でもまたは2種以上混合して用いてもよい。また、該砥粒は、市販品を用いてもよいし合成品を用いてもよい。
研磨用組成物中に含まれる酸化剤は、研磨対象物の表面を酸化する作用を有し、研磨用組成物による研磨対象物の研磨速度を向上させる。
本発明で用いられる防腐剤および防カビ剤としては、例えば、2−メチル−4−イソチアゾリン−3−オンや5−クロロ−2−メチル−4−イソチアゾリン−3−オン等のイソチアゾリン系防腐剤、パラオキシ安息香酸エステル類、及びフェノキシエタノール等が挙げられる。これら防腐剤および防カビ剤は、単独でもまたは2種以上混合して用いてもよい。
本発明の研磨用組成物の製造方法は、特に制限されず、例えば、有機酸を表面に固定したシリカ、分子量が2万未満の2価アルコール、pH調整剤、および必要に応じて他の成分を、攪拌混合して得ることができる。
本発明の被研磨材料は、特に制限されず、例えば、炭化ケイ素、炭化ホウ素などの金属炭化物、窒化ケイ素、窒化ホウ素、窒化ガリウム、窒化チタン、窒化リチウムなどの金属窒化物、またはこれらの複合材料などの研磨対象物を含む被研磨材料が挙げられる。これら研磨対象物は、単独でもまたは2種以上の組み合わせであってもよい。なお、研磨対象物は、単層構造でもよいし2種以上の多層構造であってもよい。多層構造の場合、各層は同じ材料を含んでもよいし、異なる材料を含んでもよい。
上述のように、本発明の研磨用組成物は、研磨対象物と、前記研磨対象物とは異なる材料を含む層と、を有する被研磨材料の研磨に好適に用いられる。よって、本発明の第二は、研磨対象物と、研磨対象物とは異なる材料を含む層と、を有する被研磨材料を本発明の研磨用組成物を用いて研磨する研磨方法である。また、本発明の第三は、研磨対象物と、前記研磨対象物とは異なる材料と、を有する被研磨材料を前記研磨方法で研磨する工程を含む基板の製造方法である。
研磨用組成物は、表2に示す組成で、砥粒、2価アルコール、およびpH調整剤を水中で混合することにより得た(混合温度約25℃、混合時間:約10分)。研磨用組成物のpHは、pHメータにより確認した。
保管安定性は、研磨用組成物を60℃で一週間保管したものと、25℃で一週間保管したものでPoly、SiN、TEOSを研磨し、研磨レートの変化を確認することで評価している。そこで研磨レートの変化が10%以内に収まる場合は保管安定性が良いので、○と記載している。また研磨レートの変化が10%以内に収まらない場合は保管安定性が悪いので、×と記載している。さらに砥粒の沈降や、2価アルコールが固体として析出する等の影響で研磨評価に支障を来たしたものは、××と表記している。
研磨機: 200mm用片面CMP研磨機
パッド: ポリウレタン製パッド
圧力: 1.8psi
定盤回転数: 97rpm
キャリア回転数: 92rpm
研磨用組成物の流量: 200ml/min
研磨時間:1分
研磨速度は、以下の式により計算した。
研磨速度[Å/min]=1分間研磨した時の膜厚の変化量
膜厚測定器:光干渉式膜厚測定装置
研磨速度の測定結果を下記表2に示す。
Claims (9)
- 有機酸を表面に固定したシリカと、
分子量が2万未満の2価アルコールと、
pH調整剤と、
を含み、pHが6以下である、研磨用組成物。 - 前記有機酸は、スルホン酸またはカルボン酸である、請求項1に記載の研磨用組成物。
- 前記2価アルコールの分子量は、5000以下である、請求項1〜3のいずれか1項に記載の研磨用組成物。
- 研磨対象物と、
前記研磨対象物とは異なる材料を含む層と、
を有する被研磨材料を研磨するのに用いられる、請求項1〜4のいずれか1項に記載の研磨用組成物。 - 前記研磨対象物は窒化ケイ素であり、かつ前記研磨対象物とは異なる材料を含む層は、多結晶シリコンおよびオルトケイ酸テトラエチルの少なくとも一方を含む、請求項5に記載の研磨用組成物。
- 前記有機酸を表面に固定したシリカの含有量は、0.005重量%以上1重量%以下である、請求項1〜6のいずれか1項に記載の研磨用組成物。
- 研磨対象物と、
前記研磨対象物とは異なる材料を含む層と、
を有する被研磨材料を、請求項1〜7のいずれか1項に記載の研磨用組成物を用いて研磨する工程を含む、研磨方法。 - 研磨対象物と、
前記研磨対象物とは異なる材料と、
を有する被研磨材料を、請求項8に記載の研磨方法で研磨する工程を含む、基板の製造方法。
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