JPWO2017163942A1 - 金属を含む層を有する研磨対象物の研磨用組成物 - Google Patents
金属を含む層を有する研磨対象物の研磨用組成物 Download PDFInfo
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- JPWO2017163942A1 JPWO2017163942A1 JP2018507225A JP2018507225A JPWO2017163942A1 JP WO2017163942 A1 JPWO2017163942 A1 JP WO2017163942A1 JP 2018507225 A JP2018507225 A JP 2018507225A JP 2018507225 A JP2018507225 A JP 2018507225A JP WO2017163942 A1 JPWO2017163942 A1 JP WO2017163942A1
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- Prior art keywords
- polishing
- acid
- metal
- polishing composition
- composition
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- 239000011550 stock solution Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
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- 229960002898 threonine Drugs 0.000 description 1
- 229940034208 thyroxine Drugs 0.000 description 1
- XUIIKFGFIJCVMT-UHFFFAOYSA-N thyroxine-binding globulin Natural products IC1=CC(CC([NH3+])C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 XUIIKFGFIJCVMT-UHFFFAOYSA-N 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C09K3/1436—Composite particles, e.g. coated particles
-
- 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
-
- 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]
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/7684—Smoothing; Planarisation
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
Description
本発明に係る研磨対象物は、金属を含む層である。ここで、金属を含む層は、少なくとも研磨対象となる面が金属を含むものであればよい。このため、金属を含む層は、金属から構成される基板、金属を含む層または金属から構成される層を有する基板(例えば、高分子もしくは他の金属の基板上に金属を含む層または金属から構成される層が配置されてなる基板)であってもよい。好ましくは、金属を含む層は、金属から構成される層(例えば、基板)または金属から構成される層を有する研磨対象物(例えば、基板)である。
本発明の研磨用組成物は、砥粒と、酸と、酸化剤と、分散媒と、を含み、この際、酸の酸解離定数(pKa)が研磨用組成物のpHより高い。以下、本発明の研磨用組成物の構成を説明する。
本発明の研磨用組成物は、砥粒を必須に含む。研磨用組成物中に含まれる砥粒は、研磨対象物を機械的に研磨する作用を有し、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。
本発明の研磨用組成物は、当該組成物のpHより高い酸解離定数(pKa)を有する酸を必須に含む。本発明に係る酸は、防食剤として作用する。このため、本発明に係る酸の存在により、研磨対象である金属の溶解(溶出)抑え、金属を含む層(研磨対象物)を平滑に(低い表面粗さ(Ra)で)研磨できる。また、エッチング速度は低く抑えつつ高い研磨速度で金属を含む層(研磨対象物)を研磨できる。
本発明の研磨用組成物は、上記砥粒及び酸に加えて、酸化剤を必須に含む。本発明に係る酸化剤は特に制限されないが、過酸化物が好ましい。すなわち、本発明の好ましい形態によると、酸化剤は過酸化物である。このような過酸化物の具体例としては、以下に制限されないが、過酸化水素、過酢酸、過炭酸塩、過酸化尿素、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム、一過硫酸カリウムおよびオキソンなどが挙げられる。上記酸化剤は、単独でもまたは2種以上混合して用いてもよい。すなわち、本発明の好ましい形態によると、過酸化物は、過酸化水素、過酢酸、過炭酸塩、過酸化尿素、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム、一過硫酸カリウムおよびオキソンからなる群より選択される少なくとも1種である。酸化剤は、過硫酸塩(過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム)および過酸化水素がより好ましく、特に好ましいのは過酸化水素である。
本発明の研磨用組成物は、各成分を分散または溶解するために分散媒を含む。ここで、分散媒は、特に制限されないが、水が好ましい。他の成分の作用を阻害することを抑制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より好ましく、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。
上述したように、本発明の研磨用組成物は、砥粒と、酸と、酸化剤と、分散媒と、を必須に含むが、上記成分に加えて他の添加剤を含んでもよい。ここで、他の添加剤としては、特に制限されず、研磨用組成物に通常に添加される添加剤が使用できる。具体的には、錯化剤、金属防食剤、防腐剤、防カビ剤、還元剤、水溶性高分子、難溶性の有機物を溶解するための有機溶媒等が挙げられる。なお、本発明の研磨用組成物は、例えば特開2013−42131号公報に記載されるジ第4級化合物を実質的に含まない。また、本発明の研磨用組成物は、ヨウ素ガス発生の引き金になりうるヨウ素化合物(例えば、ヨウ素酸カリウム)を実質的に含まない。ここで、「実質的に含まない」とは、対象となる物質が、研磨用組成物に対して、10質量%以下(下限:0質量%)の割合で存在することを意味し、5質量%以下(下限:0質量%)の割合で存在することが好ましい。
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、砥粒、酸、酸化剤、および必要に応じて他の添加剤を、分散媒(例えば、水)中で攪拌混合することにより得ることができる。すなわち、本発明は、前記砥粒、前記酸、および前記酸化剤を混合することを含む、研磨用組成物の製造方法をも提供する。
上述のように、本発明の研磨用組成物は、金属を含む層(研磨対象物)の研磨に好適に用いられる。よって、本発明は、金属を含む層を有する研磨対象物を本発明の研磨用組成物で研磨する研磨方法をも提供する。また、本発明は、金属を含む層を有する研磨対象物を前記研磨方法で研磨する工程を含む、基板の製造方法を提供する。
純水1Lに、砥粒(スルホン酸固定コロイダルシリカ;平均一次粒子径:30nm、平均二次粒子径:60nm、アスペクト比:1.24、D90/D10:2.01)を最終の研磨用組成物に対して2.0質量%の量となるように加え、下記表1に示される酸を加えることで研磨用組成物を調製した。なお、酸は、後述する酸化剤を添加する前の研磨用組成物のpHが2.0になるように加えた。また、タングステンウェーハを研磨する直前に、酸化剤として過酸化水素水(30質量%)を最終の研磨用組成物に対して0.45質量%の量となるように攪拌しながら、上記研磨用組成物に加えた。酸化剤を加えた後の最終研磨用組成物のpHを表1に合わせて示す。研磨用組成物(液温:25℃)のpHは、pHメーター(株式会社堀場製作所製 型番:LAQUA)により確認した。
砥粒を未修飾コロイダルシリカ(平均一次粒子径:30nm、平均二次粒子径:60nm、アスペクト比:1.24、D90/D10:2.01)に変更したこと以外は、実施例12と同様にして研磨用組成物を調製した。
各研磨用組成物を用いて、研磨対象物を以下の研磨条件で研磨する。研磨前後の研磨対象物の厚み(膜厚)を、手動シート抵抗器(VR−120、株式会社日立国際電気製)によって測定する。下記(研磨速度の算出方法)により、研磨前後の研磨対象物の厚み(膜厚)の差を研磨時間で除することによって、研磨速度(Removal Rate)(Å/min)を求める。なお、研磨対象物としては、タングステンウェーハ(大きさ:32mm×32mm)を使用する。
研磨速度(研磨レート)(Å/min)は、下記式(1)により計算する。
下記操作によりエッチング試験を行う。すなわち、各研磨用組成物300mLを300rpmで攪拌させたサンプル容器に、研磨対象物を10分間浸漬することで行なう。浸漬後ウェーハは、純水で30秒洗浄し、エアーガンによるエアブロー乾燥で乾燥させる。エッチング試験前後の研磨対象物の厚み(膜厚)を、手動シート抵抗器(VR−120、株式会社日立国際電気製)によって測定する。下記(エッチング速度の算出方法)により、エッチング試験前後の研磨対象物の厚み(膜厚)の差をエッチング試験時間で除することによって、エッチング速度(Etching Rate)(Å/min)を求める。なお、研磨対象物としては、タングステンウェーハ(大きさ:32mm×32mm)を使用する。
エッチング速度(エッチングレート)(Å/min)は、下記式(2)により計算する。
上記[研磨速度(Removal Rate)の測定]と同様にして、研磨用組成物を用いて、研磨対象物を研磨する。研磨後の研磨対象物の研磨面における表面粗さ(Ra)を、走査型プローブ顕微鏡(SPM)を用いて測定する。なお、SPMとして、株式会社日立ハイテクノロジーズ製のNANO−NAVI2を使用する。カンチレバーは、SI−DF40P2を使用する。測定は、走査周波数0.86Hz、X:512pt、Y:512ptで3回行い、これらの平均値を表面粗さ(Ra)とする。
Claims (10)
- 金属を含む層を有する研磨対象物の研磨に用いられる研磨用組成物であって、
砥粒と、酸と、酸化剤と、分散媒と、を含み、
前記酸の酸解離定数(pKa)が前記組成物のpHより高い、研磨用組成物。 - 前記金属がタングステンである、請求項1に記載の研磨用組成物。
- 前記酸の酸解離定数(pKa)と前記組成物のpHとの差[=(酸の酸解離定数(pKa))−(組成物のpH)]が、0.9以上である、請求項1または2に記載の研磨用組成物。
- 前記酸の酸解離定数(pKa)が、2.9以上5.0未満である、請求項1〜3のいずれか1項に記載の研磨用組成物。
- 前記酸化剤が過酸化物である、請求項1〜4のいずれか1項に記載の研磨用組成物。
- 前記過酸化物は、過酸化水素、過酢酸、過炭酸塩、過酸化尿素、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム、一過硫酸カリウムおよびオキソンからなる群より選択される少なくとも1種である、請求項5に記載の研磨用組成物。
- 前記砥粒は、有機酸を固定化したコロイダルシリカである、請求項1〜6のいずれか1項に記載の研磨用組成物。
- 前記砥粒、前記酸、および前記酸化剤を混合することを含む、請求項1〜7のいずれか1項に記載の研磨用組成物の製造方法。
- 金属を含む層を有する研磨対象物を、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ことを含む、研磨方法。
- 金属を含む層を有する研磨対象物を、請求項9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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