JP6157151B2 - 微細レジストパターン形成用組成物およびそれを用いたパターン形成方法 - Google Patents
微細レジストパターン形成用組成物およびそれを用いたパターン形成方法 Download PDFInfo
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- JP6157151B2 JP6157151B2 JP2013043177A JP2013043177A JP6157151B2 JP 6157151 B2 JP6157151 B2 JP 6157151B2 JP 2013043177 A JP2013043177 A JP 2013043177A JP 2013043177 A JP2013043177 A JP 2013043177A JP 6157151 B2 JP6157151 B2 JP 6157151B2
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Classifications
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
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- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
- C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
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- G—PHYSICS
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/094—Multilayer resist systems, e.g. planarising layers
-
- G—PHYSICS
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- G—PHYSICS
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
- G03F7/405—Treatment with inorganic or organometallic reagents after imagewise removal
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- 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
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- 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
- H01L21/76801—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 dielectrics, e.g. smoothing
- H01L21/76802—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 dielectrics, e.g. smoothing by forming openings in dielectrics
- H01L21/76816—Aspects relating to the layout of the pattern or to the size of vias or trenches
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Description
(1)形成されたレジストパターンを酸によって架橋しえる組成物でレジストパターンを覆い、加熱によりレジストパターン中に存在する酸を拡散させ、レジストとの界面に架橋層をレジストパターンの被覆層として形成させ、現像液で非架橋部分を取り除くことでレジストパターンを太らせ、レジストパターンのホール径または分離幅が微細化される方法(特許文献1および2参照)。
(2)形成されたレジストパターンに、(メタ)アクリル酸モノマーと水溶性ビニルモノマーとからなるコポリマーの水溶液をレジストパターンに塗布し、熱処理により、レジストパターンを熱収縮させてパターンを微細化させる方法(特許文献3参照)。
(3)アミノ基、特に1級アミンを含むポリマーを含有する、フォトレジストパターンを被覆するための水溶性被覆用組成物(特許文献4参照)。
繰り返し単位中にアミノ基を含むポリマーと、
溶剤と
酸と、
を含んでなることを特徴とするものである。
半導体基板上に化学増幅型フォトレジスト組成物を塗布してフォトレジスト層を形成する工程、
前記フォトレジスト層で被覆された前記半導体基板を露光する工程、
前記露光後に現像液で現像してフォトレジストパターンを形成する工程、
前記フォトレジストパターンの表面に、繰り返し単位中にアミノ基を含むポリマーと、溶剤と、酸とを含んでなる微細パターン形成用組成物を塗布する工程、
塗布済みのフォトレジストパターンを加熱する工程、および
過剰の微細パターン形成用組成物を洗浄して除去する工程
を含んでなることを特徴とするものである。
本発明による微細パターン形成用組成物(以下、簡単のために単に「組成物」ということがある)は、繰り返し単位中にアミノ基を含むポリマーと溶剤と酸を含んでなる。本発明において用いられるポリマーは、アミノ基を含むものである。ここでアミノ基は、第一級アミノ基(−NH2)、第二級アミノ基(−NHR)、および第3級アミノ基(−NRR’)をいう。ここで、アミノ基には、−N=のように窒素が二重結合を介して隣接元素に結合しているものも包含するものとする。これらのアミノ基は、繰り返し単位の側鎖に含まれていてもよいし、ポリマーの主鎖構造中に含まれていてもよい。
脱保護されたアルカリ可溶性樹脂は、アルカリ現像液(例:テトラメチルアンモニウム水溶液)に可溶なため、現像処理によって除去できる。
次に、本発明による微細なレジストパターンの形成方法について説明する。本発明の微細パターン形成用組成物が適用される代表的なパターン形成方法をあげると、次のような方法が挙げられる。
現像処理後、リンス液を用いてレジストパターンのリンス(洗浄)が行われることが好ましい。このとき、リンス液には純水を用いることが好ましい。
そして、本発明による微細化パターン形成用組成物を用いて製造されたレジストパターンは半導体素子の製造に当たって、より微細なパターンを有する半導体素子等の製造に有用なものである。
レジストパターン形成
スピンコーター(東京エレクトロン株式会社製)にて、下層反射防止膜AZ ArF−1C5D(商品名、AZエレクトロニックマテリアルズ株式会社製)を8インチシリコンウェハーに塗布し、200℃にて、60秒間ベークを行い、膜厚37nmの反射防止膜を得た。その上に感光性樹脂組成物AZ AX2110P(商品名、AZエレクトロニックマテリアルズ株式会社製)を、110℃にて60秒間ベークを行い120nmの膜厚を得た。得られたウエハーをArF線(193nm)の露光波長を有する露光装置(株式会社ニコン製)を用いて、マスク(ライン/スペース=1/1)を用いて、1回目のパターン露光を行った。次に、同マスクを、1回目の露光と直交する方向に回転し、2回目の露光を行った。その後110℃にて、60秒間ベークした後、テトラメチルアンモニウムヒドロキシド水溶液(2.38%)にて30秒間現像処理を行い、ピッチ160nm、ホールサイズ80nmのレジストパターンを得た。
微細パターン形成用組成物に用いるポリマーとしてポリスチレン換算重量平均分子量25,000のポリアリルアミンを用意した。このポリマーを純水に溶解し、2重量%の水溶液を得た。さらに界面活性剤として、この水溶液に対して500ppmとなる量のポリオキシエチレンノニルフェニルエーテル(下式(1))をくわえた。これを組成物Aとする。
67,000のポリビニルピロリドンを用意した。このポリマーを純水に溶解し、2重量%の水溶液を得た。さらに界面活性剤として、この水溶液に対して700ppmとなる量のジメチルラウリル―アミンオキシド(下式(5))をくわえた。これを組成物Eとする。
a: 極めて良好
b: 欠陥が見られるものの事実上支障なし
c: 不良
Claims (12)
- 化学増幅型ポジ型フォトレジスト組成物を用いてポジ型レジストパターンを形成させる方法において、レジストパターンを太らせることによってパターンを微細化するために用いられる微細パターン形成用組成物であって、
ポリビニルアミン、ポリアリルアミン、ポリジアリルアミン、ポリエチレンイミン、およびポリ(アリルアミン−co−ジアリルアミン)からなる群から選択される、繰り返し単位中にアミノ基を含むポリマーと、
溶剤と、
前記ポリマーの全重量を基準として、0.5〜50重量%のスルホン酸、カルボン酸、硫酸、硝酸、およびそれらの混合物からなる群から選択される酸と、
を含んでなることを特徴とする微細パターン形成用組成物。 - 前記酸が、硫酸、ペンタフルオロプロピオン酸、p−トルエンスルホン酸、トリフルオロメタンスルホン酸からなる群から選択されるものである、請求項1に記載の組成物。
- 前記酸が、メタンスルホン酸、エタンスルホン酸、2−アミノメタンスルホン酸、トリフルオロメタンスルホン酸、p−トルエンスルホン酸、および10−カンファースルホン酸からなる群から選択されるものである、請求項1に記載の組成物。
- 前記酸が、酢酸、メトキシ酢酸、グリコール酸、グルタル酸、リンゴ酸からなる群から選択されるものである、請求項1に記載の組成物。
- pHが2以上11以下である、請求項1〜4のいずれか1項に記載の組成物。
- 前記溶剤が水を含んでなる、請求項1〜5のいずれか1項に記載の組成物。
- 界面活性剤をさらに含んでなる、請求項1〜6のいずれか1項に記載の組成物。
- 半導体基板上に化学増幅型フォトレジスト組成物を塗布してフォトレジスト層を形成する工程、
前記フォトレジスト層で被覆された前記半導体基板を露光する工程、
前記露光後に現像液で現像してフォトレジストパターンを形成する工程、
前記フォトレジストパターンの表面に、ポリビニルアミン、ポリアリルアミン、ポリジアリルアミン、ポリエチレンイミン、およびポリ(アリルアミン−co−ジアリルアミン)からなる群から選択される、繰り返し単位中にアミノ基を含むポリマーと、溶剤と、前記ポリマーの全重量を基準として、0.5〜50重量%のスルホン酸、カルボン酸、硫酸、硝酸、およびそれらの混合物からなる群から選択される酸とを含んでなる微細パターン形成用組成物を塗布する工程、
塗布済みのフォトレジストパターンを加熱する工程、および
過剰の微細パターン形成用組成物を洗浄して除去する工程
を含んでなることを特徴とするポジ型レジストパターンの形成方法。 - 前記酸が、硫酸、ペンタフルオロプロピオン酸、p−トルエンスルホン酸、トリフルオロメタンスルホン酸からなる群から選択されるものである、請求項8に記載の方法。
- 前記フォトレジスト組成物が、光酸発生剤をさらに含んでなる、請求項8または9に記載の方法。
- 前記溶剤が水を含んでなる、請求項8〜10のいずれか1項に記載の方法。
- 界面活性剤をさらに含んでなる、請求項8〜11のいずれか1項に記載の方法。
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IL240732B (en) | 2018-05-31 |
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US20160011508A1 (en) | 2016-01-14 |
CN105103053B (zh) | 2019-12-27 |
JP2014170190A (ja) | 2014-09-18 |
CN105103053A (zh) | 2015-11-25 |
IL240732A0 (en) | 2015-10-29 |
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