JP7488672B2 - 研磨方法および半導体基板の製造方法 - Google Patents
研磨方法および半導体基板の製造方法 Download PDFInfo
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- JP7488672B2 JP7488672B2 JP2020049610A JP2020049610A JP7488672B2 JP 7488672 B2 JP7488672 B2 JP 7488672B2 JP 2020049610 A JP2020049610 A JP 2020049610A JP 2020049610 A JP2020049610 A JP 2020049610A JP 7488672 B2 JP7488672 B2 JP 7488672B2
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- Prior art keywords
- polishing
- acid
- silicon germanium
- silicon
- abrasive grains
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 48
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
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- 238000005530 etching Methods 0.000 claims description 17
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 15
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 14
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 4
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- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 claims description 3
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
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- 239000004814 polyurethane Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 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
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 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
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
-
- 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
-
- 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
- C09K3/1409—Abrasive particles per se
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
本発明に係る研磨対象物は、シリコンゲルマニウムを含む。研磨対象物であるシリコンゲルマニウム中のゲルマニウム含有量は10質量%以上であることが好ましい。
本発明で用いられる研磨用組成物は、砥粒を含む。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。
本発明で用いられる研磨用組成物は、無機塩を含む。かような無機塩は、研磨用組成物の電気伝導度を高め、シリコンゲルマニウム表面の電気二重層を圧縮する。したがって、シリコンゲルマニウム表面における砥粒の作用が向上し、シリコンゲルマニウムの研磨速度が向上する。
本発明で用いられる研磨用組成物は、酸基を有する研磨促進剤(以下、単に「研磨促進剤」とも称する)を含む。酸基を有する研磨促進剤は、Ge酸化膜の表面に吸着し、Ge酸化膜を部分的に改質する。改質されたGe酸化膜は、加工性に富んでおり研磨速度は高くなるが、溶解は起こり難く、エッチングは抑制されると考えられる。
本発明で用いられる研磨用組成物のpHは、8以上である。pHが8未満の場合、シリコンゲルマニウム膜(Ge酸化膜)への研磨促進剤の作用が十分に進まず、研磨速度が十分に得られない。
上記のpHとするために、本発明で用いられる研磨用組成物は、pH調整剤を含んでもよい。pH調整剤は、pH調整機能を有する化合物であれば特に制限されず、公知の化合物を用いることができる。pH調整剤は、pH調整機能を有するものであれば特に制限されないが、例えば、酸、アルカリ等が挙げられる。
本発明で用いられる研磨用組成物は、各成分を分散するための分散媒を含むことが好ましい。分散媒としては、水;メタノール、エタノール、エチレングリコール等のアルコール類;アセトン等のケトン類等や、これらの混合物などが例示できる。これらのうち、分散媒としては水が好ましい。すなわち、本発明のより好ましい形態によると、分散媒は水を含む。本発明のさらに好ましい形態によると、分散媒は実質的に水からなる。なお、上記の「実質的に」とは、本発明の目的効果が達成され得る限りにおいて、水以外の分散媒が含まれ得ることを意図し、より具体的には、好ましくは90質量%以上100質量%以下の水と0質量%以上10質量%以下の水以外の分散媒とからなり、より好ましくは99質量%以上100質量%以下の水と0質量%以上1質量%以下の水以外の分散媒とからなる。最も好ましくは、分散媒は水である。
本発明の研磨用組成物は、必要に応じて、酸化剤、錯化剤、防腐剤、防カビ剤等の他の成分をさらに含有してもよい。以下、他の成分である、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研磨用組成物は、酸化剤を含むことが好ましい。酸化剤は、シリコンゲルマニウムの表面を酸化する作用を有し、研磨用組成物によるシリコンゲルマニウム膜の研磨速度をより向上させうる。
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、1,2-ベンゾイソチアゾリン-3-オン、2-n-オクチル-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、オルトフェニルフェノール、およ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、砥粒、無機塩、酸基を有する研磨促進剤、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。各成分の詳細は上述した通りである。したがって、本発明は、砥粒、無機塩、および酸基を有する研磨促進剤を混合する工程を含む、本発明の研磨用組成物の製造方法を提供する。
本発明の研磨方法において、研磨装置としては、研磨対象物を有する基板等を保持するホルダーと回転数を変更可能なモータ等とが取り付けてあり、研磨パッド(研磨布)を貼り付け可能な研磨定盤を有する一般的な研磨装置を使用することができる。
砥粒、下記表2に示す無機塩および研磨促進剤を、研磨用組成物全体に対して下記表2に示す含有量となるように添加した。また、酸化剤として過酸化水素水溶液(濃度:31質量%)を準備し、研磨用組成物全体に対して下記表2に示す含有量となるように添加した。さらに、防腐剤として、イソチアゾリン系防腐剤を研磨用組成物全体に対して0.1質量%の含有量となるように添加した。これらの成分を、純水中で攪拌混合し(混合温度:約25℃、混合時間:約10分)、実施例1~13および比較例1~5の研磨用組成物を調製した。研磨用組成物のpHはアンモニアを加えて調整し、pHメーターにより確認した。
研磨対象物として、以下のウェーハを準備した:
シリコンゲルマニウム(SiGe)ウェーハ:表面に厚さ1500Åのシリコンゲルマニウム膜(Si:Ge=50:50質量比)を形成したシリコンウェーハ(300mm、ブランケットウェーハ、アドバンスマテリアルテクノロジー株式会社製)
酸化ケイ素(TEOS)ウェーハ:表面に厚さ10000Åの酸化ケイ素膜を形成したシリコンウェーハ(300mm、ブランケットウェーハ、株式会社アドバンテック製)
窒化ケイ素(SiN)ウェーハ:表面に厚さ3500Åの窒化ケイ素膜を形成したシリコンウェーハ(300mm、ブランケットウェーハ、株式会社アドバンテック製)。
攪拌子を用いて300rpmで回転させている研磨用組成物中に、30mm×30mmの大きさのシリコンゲルマニウムウェーハ(Si:Ge=50:50質量比)を、43℃で1時間浸漬させ、浸漬前後の膜厚の差を基に溶解量(エッチング量)を算出した。
Claims (12)
- 研磨用組成物を用いて、シリコンゲルマニウムを含む研磨対象物を研磨する工程を含む研磨方法であって、
前記研磨用組成物は、砥粒、無機塩、および酸基を有する研磨促進剤を含み、かつpHが8以上であり、
下記方法により測定される前記シリコンゲルマニウムのエッチング量は30Å以下である、研磨方法:
〔エッチング量〕
攪拌子を用いて300rpmで回転させている研磨用組成物中に、30mm×30mmの大きさのシリコンゲルマニウムウェーハ(Si:Ge=50:50質量比)を、43℃で1時間浸漬させ、浸漬前後の膜厚の差を基に溶解量(エッチング量)を算出する。 - 前記研磨促進剤は、N-(2-ヒドロキシエチル)エチレンジアミン-N,N’,N’-三酢酸、N,N,N’,N’-エチレンジアミンテトラキス(メチレンホスホン酸)、2-ホスホノブタン-1,2,4-トリカルボン酸、N,N-ジ(2-ヒドロキシエチル)グリシン、アスパラギン酸、および(S,S)-エチレンジアミン-N,N’-ジコハク酸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1に記載の研磨方法。
- 前記研磨促進剤は、N,N,N’,N’-エチレンジアミンテトラキス(メチレンホスホン酸)である、請求項1または2に記載の研磨方法。
- 前記無機塩は、硝酸アンモニウム、硫酸アンモニウム、硫酸水素アンモニウム、リン酸三アンモニウム、リン酸水素二アンモニウム、およびリン酸二水素アンモニウム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1~3のいずれか1項に記載の研磨方法。
- 前記無機塩は硫酸アンモニウムである、請求項1~4のいずれか1項に記載の研磨方法。
- 前記シリコンゲルマニウムの研磨速度は280Å/min.以上である、請求項1~5のいずれか1項に記載の研磨方法。
- 前記研磨対象物は窒化ケイ素をさらに含む、請求項1~6のいずれか1項に記載の研磨方法。
- 前記窒化ケイ素の研磨速度に対する前記シリコンゲルマニウムの研磨速度の比は15以上である、請求項7に記載の研磨方法。
- 前記研磨対象物は酸化ケイ素をさらに含む、請求項1~6のいずれか1項に記載の研磨方法。
- 前記酸化ケイ素の研磨速度に対する前記シリコンゲルマニウムの研磨速度の比は12以上である、請求項9に記載の研磨方法。
- 半導体基板を、請求項1~10のいずれか1項に記載の研磨方法により研磨する工程を有する、半導体基板の製造方法。
- シリコンゲルマニウムを含む研磨対象物を研磨するために用いられる研磨用組成物であって、
砥粒、無機塩、および酸基を有する研磨促進剤を含み、かつpHが8以上であり、
下記方法により測定される前記シリコンゲルマニウムのエッチング量は30Å以下である、研磨用組成物:
〔エッチング量〕
攪拌子を用いて300rpmで回転させている研磨用組成物中に、30mm×30mmの大きさのシリコンゲルマニウムウェーハ(Si:Ge=50:50質量比)を、43℃で1時間浸漬させ、浸漬前後の膜厚の差を基に溶解量(エッチング量)を算出する。
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