JP6327481B2 - Resist underlayer film forming composition - Google Patents
Resist underlayer film forming composition Download PDFInfo
- Publication number
- JP6327481B2 JP6327481B2 JP2015512438A JP2015512438A JP6327481B2 JP 6327481 B2 JP6327481 B2 JP 6327481B2 JP 2015512438 A JP2015512438 A JP 2015512438A JP 2015512438 A JP2015512438 A JP 2015512438A JP 6327481 B2 JP6327481 B2 JP 6327481B2
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- JP
- Japan
- Prior art keywords
- group
- resist underlayer
- underlayer film
- film forming
- forming composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 biphenylyl group Chemical group 0.000 claims description 36
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- 125000003118 aryl group Chemical group 0.000 claims description 10
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
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- 125000005843 halogen group Chemical group 0.000 claims description 6
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- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- NHJIDZUQMHKGRE-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetate Chemical compound C1CC2OC2CC1OC(=O)CC1CC2OC2CC1 NHJIDZUQMHKGRE-UHFFFAOYSA-N 0.000 description 1
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
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- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
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- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
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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
- G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1422—Side-chains containing oxygen containing OH groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/342—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3424—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms non-conjugated, e.g. paracyclophanes or xylenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Description
本発明は、リソグラフィープロセス用レジスト下層膜形成組成物に関する。特に、高硬度で、リソグラフィープロセスによって形成されるレジストパターンの曲がり（ｗｉｇｇｌｉｎｇ）が発生しにくい、レジスト下層膜を形成するための組成物に関する。 The present invention relates to a resist underlayer film forming composition for a lithography process. In particular, the present invention relates to a composition for forming a resist underlayer film that has high hardness and is less likely to cause wiggling of a resist pattern formed by a lithography process.
半導体装置の製造において、リソグラフィープロセスによる微細加工が行われる。そのリソグラフィープロセスでは、基板上のレジスト層をＫｒＦエキシマレーザー、ＡｒＦエキシマレーザー等紫外線レーザーで露光する際、基板表面に該紫外線レーザーが反射することに起因し発生する定在波による影響で、所望の形状を有するレジストパターンが形成されない問題が知られている。その問題を解決するため、基板とレジスト層の間にレジスト下層膜（反射防止膜）を設けることが採用されている。そして、レジスト下層膜を形成するための組成物として、ノボラック樹脂を用いることが知られている。例えば、特許文献１及び特許文献２には、ビスフェノール基を有する化合物をノボラック化した繰り返し単位を有する樹脂を含有するフォトレジスト下層膜形成材料が開示されている。さらに、特許文献３には、ポリマーの主鎖中に３つ又はそれ以上縮合した芳香族環を有するポリマーを含む、スピンコート可能な反射防止膜組成物が開示されている。 In manufacturing a semiconductor device, fine processing is performed by a lithography process. In the lithography process, when the resist layer on the substrate is exposed with an ultraviolet laser such as a KrF excimer laser or an ArF excimer laser, the desired effect is caused by the standing wave generated by the reflection of the ultraviolet laser on the substrate surface. There is a known problem that a resist pattern having a shape is not formed. In order to solve the problem, it is adopted to provide a resist underlayer film (antireflection film) between the substrate and the resist layer. And it is known to use a novolak resin as a composition for forming a resist underlayer film. For example, Patent Document 1 and Patent Document 2 disclose a photoresist underlayer film forming material containing a resin having a repeating unit obtained by novolakizing a compound having a bisphenol group. Furthermore, Patent Document 3 discloses a spin-coatable antireflection film composition containing a polymer having an aromatic ring condensed in three or more in the main chain of the polymer.
また、レジストパターンの微細化に伴い求められるレジスト層の薄膜化のため、レジスト下層膜を少なくとも２層形成し、該レジスト下層膜をマスク材として使用する、リソグラフィープロセスも知られている。前記少なくとも２層を形成する材料として、有機樹脂（例えば、アクリル樹脂、ノボラック樹脂）、ケイ素樹脂（例えば、オルガノポリシロキサン）、無機ケイ素化合物（例えば、ＳｉＯＮ、ＳｉＯ２）が挙げられる。上記有機樹脂層から形成されるパターンをマスクとしてドライエッチングする際、該パターンがエッチングガス（例えばフルオロカーボン）に対し耐エッチング性を有することが必要である。このような有機樹脂層を形成するための組成物として、例えば特許文献４には複素環芳香族部分を含む重合体を含有する組成物が開示されている。In addition, a lithography process is also known in which at least two resist underlayer films are formed and used as a mask material in order to reduce the thickness of the resist layer required in accordance with the miniaturization of the resist pattern. Examples of the material forming the at least two layers include organic resins (for example, acrylic resins and novolac resins), silicon resins (for example, organopolysiloxane), and inorganic silicon compounds (for example, SiON, SiO 2 ). When dry etching is performed using a pattern formed from the organic resin layer as a mask, the pattern needs to have etching resistance to an etching gas (for example, fluorocarbon). As a composition for forming such an organic resin layer, for example, Patent Document 4 discloses a composition containing a polymer containing a heterocyclic aromatic moiety.
ところで、上述のリソグラフィープロセスとエッチングプロセスを経て加工すべき基板にレジストパターンを形成する際、形成されるパターン幅が狭くなるにしたがって、不規則なパターンの曲がりが発生しやすくなるという問題があった。これは、具体的には、目的の加工基板をエッチングする際にマスク材として使用されるレジスト下層膜において、特に有機樹脂層から形成されたパターンが、左右に曲がる現象が発生するというものである。 By the way, when forming a resist pattern on a substrate to be processed through the above-described lithography process and etching process, there is a problem that irregular pattern bending tends to occur as the formed pattern width becomes narrower. . Specifically, in a resist underlayer film that is used as a mask material when etching a target processed substrate, a phenomenon that a pattern formed from an organic resin layer, in particular, bends left and right occurs. .
本発明は、上記問題を解決するものである。すなわち本発明は、下記式（１）：
（式中、Ｘ１は、ハロゲノ基、ニトロ基、アミノ基又はヒドロキシ基で置換されていてもよい芳香環を少なくとも１つ有する炭素原子数６乃至２０の二価の有機基を表し、Ｘ２は、ハロゲノ基、ニトロ基、アミノ基又はヒドロキシ基で置換されていてもよい芳香環を少なくとも１つ有する炭素原子数６乃至２０の有機基、又はメトキシ基を表す。）
で表される構造単位を有するポリマー及び溶剤を含むレジスト下層膜形成組成物である。The present invention solves the above problems. That is, the present invention provides the following formula (1):
(Wherein X 1 represents a divalent organic group having 6 to 20 carbon atoms having at least one aromatic ring optionally substituted with a halogeno group, a nitro group, an amino group or a hydroxy group, and X 2 Represents an organic group having 6 to 20 carbon atoms having at least one aromatic ring optionally substituted with a halogeno group, a nitro group, an amino group or a hydroxy group, or a methoxy group.
It is a resist underlayer film forming composition containing the polymer which has a structural unit represented, and a solvent.
上記及び後述するハロゲノ基として、例えばクロロ基、ブロモ基が挙げられる。上記及び後述する芳香環を少なくとも１つ有する炭素原子数６乃至２０の二価の有機基として、例えばフェニレン基、ビフェニリレン基、ターフェニリレン基、フルオレニレン基、ナフチレン基、アントリレン基、ピレニレン基（下記式（ａ−１）及び下記式（ａ−２）で表される基）、カルバゾリレン基（下記式（ｂ）で表される基）及び下記式（ｃ）で表される基（式中、ｎは０又は１を表す。）が挙げられる。上記芳香環を少なくとも１つ有する炭素原子数６乃至２０の有機基として、例えばフェニル基、ビフェニリル基、ターフェニリル基、フルオレニル基、ナフチル基、アントリル基、ピレニル基、カルバゾリル基、下記式（ｄ−１）及び下記式（ｄ−２）で表される基（式中、ｎは０又は１を表す。）が挙げられる。
前記ポリマーは、更に下記式（２）：
（式中、Ｘ１はハロゲノ基、ニトロ基、アミノ基又はヒドロキシ基で置換されていてもよい芳香環を少なくとも１つ有する炭素原子数６乃至２０の二価の有機基を表し、Ｒ３はフェニル基、ナフチル基、アントリル基、ピレニル基、チエニル基又はピリジル基を表し、Ｒ４は水素原子、フェニル基又はナフチル基を表し、Ｒ３及びＲ４がそれぞれフェニル基を表すときＲ３及びＲ４はそれらが結合する同一の炭素原子と一緒になってフルオレン環を形成してもよい。）
で表される構造単位を有してもよい。The polymer is further represented by the following formula (2):
(Wherein X 1 represents a C 6-20 divalent organic group having at least one aromatic ring optionally substituted with a halogeno group, a nitro group, an amino group, or a hydroxy group, and R 3 represents A phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a thienyl group or a pyridyl group; R 4 represents a hydrogen atom, a phenyl group or a naphthyl group; and R 3 and R 4 each represent a phenyl group, R 3 and R 4 may form a fluorene ring together with the same carbon atom to which they are attached.
You may have a structural unit represented by these.
本発明のレジスト下層膜形成組成物は、更に任意成分として、架橋剤、酸性化合物、熱酸発生剤及び界面活性剤のうち少なくとも１つを含有してもよい。 The resist underlayer film forming composition of the present invention may further contain at least one of a crosslinking agent, an acidic compound, a thermal acid generator and a surfactant as an optional component.
本発明のレジスト下層膜形成組成物を用いて形成されるレジスト下層膜は、高硬度であり、しかも該レジスト下層膜を適用することにより、リソグラフィープロセスにおいて形成されるパターンの曲がり（ｗｉｇｇｌｉｎｇ）を抑制することができる。 The resist underlayer film formed by using the resist underlayer film forming composition of the present invention has high hardness, and by applying the resist underlayer film, the bending of the pattern formed in the lithography process is suppressed. can do.
本発明のレジスト下層膜形成組成物に含まれる、上記式（１）で表される構造単位を有するポリマーの構造単位として、例えば下記式（１−１）乃至式（１−１０）で表される構造単位が挙げられる。
更に、上記式（２）で表される構造単位として、例えば下記式（２−１）で表される構造単位が挙げられる。
本発明のレジスト下層膜形成組成物に含まれるポリマーの重量平均分子量は、標準ポリスチレン換算値で例えば２，０００乃至１０，０００である。 The weight average molecular weight of the polymer contained in the resist underlayer film forming composition of the present invention is, for example, 2,000 to 10,000 in terms of standard polystyrene.
前記ポリマーは、２つのヒドロキシフェニル基を有するビフェノール化合物と芳香族化合物又は複素環式化合物と、必要に応じて芳香族アルデヒド又は芳香族ケトンとを、スルホン酸化合物などの酸触媒の存在下で重合反応させて合成することができる。前記ポリマーの合成に用いられる、２つのヒドロキシフェニル基を有するビフェノール化合物として、例えば、３，３’，５，５’−テトラメトキシメチル−４，４’−ジヒドロキシビフェニルが挙げられる。前記ポリマーの合成に用いられる芳香族化合物として、例えば、ベンゼン、ナフタレン、アントラセン、ピレン、フルオレン、ｍ−ターフェニルが挙げられる。前記ポリマーの合成に用いられる複素環式化合物として、例えば、カルバゾールが挙げられる。前記ポリマーの合成に用いられる芳香族アルデヒドとして、例えば、フルフラール、ピリジンカルボキシアルデヒド、ベンズアルデヒド、ナフチルアルデヒド、アントリルアルデヒド、フェナントリルアルデヒド、サリチルアルデヒド、フェニルアセトアルデヒド、３−フェニルプロピオンアルデヒド、トリルアルデヒド、（Ｎ，Ｎ−ジメチルアミノ）ベンズアルデヒド、アセトキシベンズアルデヒド、１−ピレンカルボキシアルデヒド、アニスアルデヒドが挙げられる。また、前記ポリマーの合成に用いられる芳香族ケトンは、ジアリールケトン類であり、例えば、ジフェニルケトン、フェニルナフチルケトン、ジナフチルケトン、フェニルトリルケトン、ジトリルケトン、９−フルオレノンが挙げられる。前記ポリマーの合成に使用されるビフェノール化合物は１種の化合物に限定されず２種以上用いてもよく、芳香族化合物、複素環式化合物、芳香族アルデヒド及び芳香族ケトンも１種の化合物に限定されず２種以上用いてもよい。 The polymer polymerizes a biphenol compound having two hydroxyphenyl groups, an aromatic compound or a heterocyclic compound, and if necessary, an aromatic aldehyde or an aromatic ketone in the presence of an acid catalyst such as a sulfonic acid compound. It can be synthesized by reaction. Examples of the biphenol compound having two hydroxyphenyl groups used for the synthesis of the polymer include 3,3 ', 5,5'-tetramethoxymethyl-4,4'-dihydroxybiphenyl. Examples of the aromatic compound used for the synthesis of the polymer include benzene, naphthalene, anthracene, pyrene, fluorene, and m-terphenyl. Examples of the heterocyclic compound used for the synthesis of the polymer include carbazole. Examples of the aromatic aldehyde used for the synthesis of the polymer include furfural, pyridinecarboxaldehyde, benzaldehyde, naphthylaldehyde, anthrylaldehyde, phenanthrylaldehyde, salicylaldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, tolylaldehyde, ( N, N-dimethylamino) benzaldehyde, acetoxybenzaldehyde, 1-pyrenecarboxaldehyde, anisaldehyde. Moreover, the aromatic ketone used for the synthesis | combination of the said polymer is diaryl ketones, For example, diphenyl ketone, phenyl naphthyl ketone, dinaphthyl ketone, phenyl tolyl ketone, ditolyl ketone, 9-fluorenone is mentioned. The biphenol compound used for the synthesis of the polymer is not limited to one type of compound, and two or more types may be used, and aromatic compounds, heterocyclic compounds, aromatic aldehydes and aromatic ketones are also limited to one type of compound. Two or more of them may be used.
本発明のレジスト下層膜形成組成物は、さらに架橋剤を含有することができる。前記架橋剤としては、少なくとも二つの架橋形成置換基を有する架橋性化合物が好ましく用いられる。例えば、メチロール基、メトキシメチル基等の架橋形成置換基を有する、メラミン系化合物、置換尿素系化合物及びフェノール系化合物が挙げられる。具体的には、メトキシメチル化グリコールウリル、メトキシメチル化メラミンなどの化合物であり、例えば、テトラメトキシメチルグリコールウリル、テトラブトキシメチルグリコールウリル、ヘキサメトキシメチルメラミンを挙げることができる。さらに、置換尿素系化合物として、例えば、テトラメトキシメチル尿素、テトラブトキシメチル尿素を挙げることができる。フェノール系化合物として、例えば、テトラヒドロキシメチルビフェノール、テトラメトキシメチルビフェノール、テトラメトキシメチルビスフェノールを挙げることができる。
前記架橋剤としては、また、少なくとも二つのエポキシ基を有する化合物を用いることもできる。このような化合物として、例えば、トリス（２，３−エポキシプロピル）イソシアヌレート、１，４−ブタンジオールジグリシジルエーテル、１，２−エポキシ−４−（エポキシエチル）シクロヘキサン、グリセロールトリグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、２，６−ジグリシジルフェニルグリシジルエーテル、１，１，３−トリス［ｐ−（２，３−エポキシプロポキシ）フェニル］プロパン、１，２−シクロヘキサンジカルボン酸ジグリシジルエステル、４，４’−メチレンビス（Ｎ，Ｎ−ジグリシジルアニリン）、３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート、トリメチロールエタントリグリシジルエーテル、ビスフェノール−Ａ−ジグリシジルエーテル、（株）ダイセル製のエポリード〔登録商標〕ＧＴ−４０１、同ＧＴ−４０３、同ＧＴ−３０１、同ＧＴ−３０２、セロキサイド〔登録商標〕２０２１、同３０００、三菱化学（株）製の１００１、１００２、１００３、１００４、１００７、１００９、１０１０、８２８、８０７、１５２、１５４、１８０Ｓ７５、８７１、８７２、日本化薬（株）製のＥＰＰＮ２０１、同２０２、ＥＯＣＮ−１０２、同１０３Ｓ、同１０４Ｓ、同１０２０、同１０２５、同１０２７、ナガセケムテックス（株）製のデナコール〔登録商標〕ＥＸ−２５２、同ＥＸ−６１１、同ＥＸ−６１２、同ＥＸ−６１４、同ＥＸ−６２２、同ＥＸ−４１１、同ＥＸ−５１２、同ＥＸ−５２２、同ＥＸ−４２１、同ＥＸ−３１３、同ＥＸ−３１４、同ＥＸ−３２１、ＢＡＳＦジャパン（株）製のＣＹ１７５、ＣＹ１７７、ＣＹ１７９、ＣＹ１８２、ＣＹ１８４、ＣＹ１９２、ＤＩＣ（株）製のエピクロン２００、同４００、同７０１５、同８３５ＬＶ、同８５０ＣＲＰを挙げることができる。前記少なくとも二つのエポキシ基を有する化合物としては、また、アミノ基を有するエポキシ樹脂を使用することもできる。このようなエポキシ樹脂として、例えば、ＹＨ−４３４、ＹＨ−４３４Ｌ（新日化エポキシ製造（株）製）が挙げられる。
前記架橋剤としては、また、少なくとも２つのブロックイソシアネート基を有する化合物を使用することもできる。このような化合物として、例えば、三井化学（株）製のタケネート〔登録商標〕Ｂ−８３０、同Ｂ−８７０Ｎ、エボニックデグサ社製のＶＥＳＴＡＮＡＴ〔登録商標〕Ｂ１３５８／１００が挙げられる。
前記架橋剤としては、また、少なくとも２つのビニルエーテル基を有する化合物を使用することもできる。このような化合物として、例えば、ビス（４−（ビニルオキシメチル）シクロヘキシルメチル）グルタレート、トリ（エチレングリコール）ジビニルエーテル、アジピン酸ジビニルエステル、ジエチレングリコールジビニルエーテル、１，２，４−トリス（４−ビニルオキシブチル）トリメリテート、１，３，５−トリス（４−ビニルオキシブチル）トリメリテート、ビス（４−（ビニルオキシ）ブチル）テレフタレート、ビス（４−（ビニルオキシ）ブチル）イソフタレート、エチレングリコールジビニルエーテル、１，４−ブタンジオールジビニルエーテル、テトラメチレングリコールジビニルエーテル、テトラエチレングリコールジビニルエーテル、ネオペンチルグリコールジビニルエーテル、トリメチロールプロパントリビニルエーテル、トリメチロールエタントリビニルエーテル、ヘキサンジオールジビニルエーテル、１，４−シクロヘキサンジオールジビニルエーテル、テトラエチレングリコールジビニルエーテル、ペンタエリスリトールジビニルエーテル、ペンタエリスリトールトリビニルエーテル及びシクロヘキサンジメタノールジビニルエーテルを挙げることができる。
これらの各種架橋剤から選択された１種類を添加してもよいし、２種以上を組合せて添加することもできる。前記架橋剤の含有割合は、本発明のレジスト下層膜形成組成物から後述する溶剤を除いた固形分に対して、例えば２質量％乃至６０質量％である。The resist underlayer film forming composition of the present invention can further contain a crosslinking agent. As the cross-linking agent, a cross-linkable compound having at least two cross-linking substituents is preferably used. Examples thereof include melamine compounds, substituted urea compounds and phenolic compounds having a crosslink forming substituent such as a methylol group or a methoxymethyl group. Specific examples include compounds such as methoxymethylated glycoluril and methoxymethylated melamine, and examples include tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, and hexamethoxymethylmelamine. Furthermore, examples of the substituted urea compound include tetramethoxymethylurea and tetrabutoxymethylurea. Examples of phenolic compounds include tetrahydroxymethyl biphenol, tetramethoxymethyl biphenol, and tetramethoxymethyl bisphenol.
As the cross-linking agent, a compound having at least two epoxy groups can also be used. Examples of such compounds include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, and diethylene glycol. Diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4 '-Methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, Daipel Co., Ltd. Epolide [registered trademark] GT-401, GT-403, GT-301, GT-302, Celoxide [registered trademark] 2021, 3000, Mitsubishi Chemical Corporation 1001, 1002 1003, 1004, 1007, 1009, 1010, 828, 807, 152, 154, 180S75, 871, 872, EPPN201, 202, EOCN-102, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd. 1025, 1027, Denasel (registered trademark) EX-252, EX-611, EX-612, EX-614, EX-622, EX-622, EX-411, manufactured by Nagase ChemteX Corporation EX-512, EX-522, EX-421, EX-313, EX-314, EX-321, BAS Japan made of (stock) CY175, CY177, CY179, CY182, CY184, CY192, DIC (Ltd.) of Epichlone 200, the 400, the 7015, the 835LV, mention may be made of the same 850CRP. As the compound having at least two epoxy groups, an epoxy resin having an amino group can also be used. Examples of such epoxy resins include YH-434 and YH-434L (manufactured by Nippon Kayaku Epoxy Manufacturing Co., Ltd.).
As the crosslinking agent, a compound having at least two blocked isocyanate groups can also be used. Examples of such compounds include Takenate [registered trademark] B-830 and B-870N manufactured by Mitsui Chemicals, Inc., and VESTANAT [registered trademark] B1358 / 100 manufactured by Evonik Degussa.
As the cross-linking agent, a compound having at least two vinyl ether groups can also be used. Examples of such compounds include bis (4- (vinyloxymethyl) cyclohexylmethyl) glutarate, tri (ethylene glycol) divinyl ether, adipic acid divinyl ester, diethylene glycol divinyl ether, 1,2,4-tris (4-vinyl). Oxybutyl) trimellitate, 1,3,5-tris (4-vinyloxybutyl) trimellitate, bis (4- (vinyloxy) butyl) terephthalate, bis (4- (vinyloxy) butyl) isophthalate, ethylene glycol divinyl ether, 1 , 4-butanediol divinyl ether, tetramethylene glycol divinyl ether, tetraethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether Le, trimethylolethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, and pentaerythritol trivinyl ether, and cyclohexanedimethanol divinyl ether.
One kind selected from these various crosslinking agents may be added, or two or more kinds may be added in combination. The content of the crosslinking agent is, for example, 2% by mass to 60% by mass with respect to the solid content excluding the solvent described later from the resist underlayer film forming composition of the present invention.
本発明のレジスト下層膜形成組成物は、さらに酸性化合物を含有することができる。前記酸性化合物は架橋反応を促進する触媒としてはたらき、例えば、ｐ−トルエンスルホン酸、トリフルオロメタンスルホン酸、ピリジニウム−ｐ−トルエンスルホネート、サリチル酸、カンファースルホン酸、５−スルホサリチル酸、４−クロロベンゼンスルホン酸、４−ヒドロキシベンゼンスルホン酸、ベンゼンジスルホン酸、１−ナフタレンスルホン酸、クエン酸、安息香酸、ヒドロキシ安息香酸等のスルホン酸化合物及びカルボン酸化合物、塩酸、硫酸、硝酸、リン酸等の無機酸を挙げることができる。上記酸性化合物に代えて、又は上記酸性化合物と共に、熱酸発生剤を含有することができる。前記熱酸発生剤も架橋反応を促進する触媒としてはたらき、例えばトリフルオロメタンスルホン酸の第４級アンモニウム塩を挙げることができる。これらの酸性化合物及び熱酸発生剤から選択された１種類を添加してもよいし、２種以上を組合せて添加することもできる。前記酸性化合物又は熱酸発生剤の含有割合は、本発明のレジスト下層膜形成組成物から後述する溶剤を除いた固形分に対して、例えば０．１質量％乃至２０質量％である。 The resist underlayer film forming composition of the present invention can further contain an acidic compound. The acidic compound serves as a catalyst for promoting a crosslinking reaction, such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, Examples include 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, sulfonic acid compounds such as hydroxybenzoic acid, and carboxylic acid compounds, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. be able to. Instead of the acidic compound or together with the acidic compound, a thermal acid generator can be contained. The thermal acid generator also serves as a catalyst for promoting the crosslinking reaction, and examples thereof include quaternary ammonium salts of trifluoromethanesulfonic acid. One kind selected from these acidic compounds and thermal acid generators may be added, or two or more kinds may be added in combination. The content ratio of the acidic compound or thermal acid generator is, for example, 0.1% by mass to 20% by mass with respect to the solid content excluding the solvent described later from the resist underlayer film forming composition of the present invention.
本発明のレジスト下層膜形成組成物は、さらに界面活性剤を含有することができる。前記界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタントリステアレート等のソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリオレエート、ポリオキシエチレンソルビタントリステアレート等のポリオキシエチレンソルビタン脂肪酸エステル類等のノニオン系界面活性剤、エフトップ〔登録商標〕ＥＦ３０１、同ＥＦ３０３、同ＥＦ３５２（三菱マテリアル電子化成（株）製）、メガファック〔登録商標〕Ｆ１７１、同Ｆ１７３、同Ｒ−３０、同Ｒ−３０−Ｎ、同Ｒ−４０、同Ｒ−４０−ＬＭ（ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１（住友スリーエム（株）製）、アサヒガード〔登録商標〕ＡＧ７１０、サーフロン〔登録商標〕Ｓ−３８２、同ＳＣ１０１、同ＳＣ１０２、同ＳＣ１０３、同ＳＣ１０４、同ＳＣ１０５、同ＳＣ１０６（旭硝子（株）製）等のフッ素系界面活性剤、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）を挙げることができる。これらの界面活性剤から選択された１種類を添加してもよいし、２種以上を組合せて添加することもできる。前記界面活性剤の含有割合は、本発明のレジスト下層膜形成組成物から後述する溶剤を除いた固形分に対して、例えば０．０１質量％乃至５質量％である。 The resist underlayer film forming composition of the present invention can further contain a surfactant. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene Polyoxyethylene alkyl aryl ethers such as ethylene nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan Sorbitan fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as rubitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, Ftop [registered trademark] ] EF301, EF303, EF352 (Mitsubishi Materials Electronics Chemical Co., Ltd.), MegaFuck [registered trademark] F171, F173, R-30, R-30-N, R-40, R- 40-LM (manufactured by DIC Corporation), Florard FC430, FC431 (manufactured by Sumitomo 3M Corporation), Asahi Guard [registered trademark] AG710, Surflon [registered trademark] S-382, SC101, SC102, SC103 SC104, SC105, SC10 (Asahi Glass Co., Ltd.) Fluorine-based surfactant and the like can be mentioned organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co.). One kind selected from these surfactants may be added, or two or more kinds may be added in combination. The content rate of the said surfactant is 0.01 mass% thru | or 5 mass% with respect to solid content except the solvent mentioned later from the resist underlayer film forming composition of this invention.
本発明のレジスト下層膜形成組成物は、上記の各成分を適当な溶剤に溶解させることによって調製でき、均一な溶液状態で用いられる。そのような溶剤として、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、メチルセロソルブアセテート、エチルセロソルブアセテート、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、２−ヒドロキシプロピオン酸エチル、２−ヒドロキシ−２−メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２−ヒドロキシ−３−メチルブタン酸メチル、３−メトキシプロピオン酸メチル、３−メトキシプロピオン酸エチル、３−エトキシプロピオン酸エチル、３−エトキシプロピオン酸メチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドンを挙げることができる。これらの有機溶剤は１種、又は２種以上を組合せて使用することができる。前記組成物から有機溶剤を除いた固形分の割合は、例えば０．５質量％乃至３０質量％、好ましくは０．８質量％乃至１５質量％である。 The resist underlayer film forming composition of the present invention can be prepared by dissolving each of the above components in an appropriate solvent, and is used in a uniform solution state. Examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol. Propyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methyl Methyl butanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, lactic acid Examples include butyl, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone. These organic solvents can be used alone or in combination of two or more. The ratio of the solid content excluding the organic solvent from the composition is, for example, 0.5% by mass to 30% by mass, preferably 0.8% by mass to 15% by mass.
本発明のレジスト下層膜形成組成物を塗布しベークする工程は、基材（例えば、シリコンウェハー、該シリコンウェハーは酸化珪素膜、窒化珪素膜、酸化窒化珪素膜、又はアルミニウム、タングステンなどの金属膜で被覆されていてもよい。）の上に、スピナー、コーター等の適当な塗布方法により該組成物を塗布し、その後、ホットプレート等の加熱手段を用いてベークすることにより行われる。ベーク条件としては、ベーク温度１００℃乃至４００℃、ベーク時間０．３分乃至１０分間の中から適宜選択される。 The step of applying and baking the resist underlayer film forming composition of the present invention includes a base material (for example, a silicon wafer, which is a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or a metal film such as aluminum or tungsten). The composition may be coated by a suitable coating method such as a spinner or a coater, and then baked using a heating means such as a hot plate. Baking conditions are appropriately selected from a baking temperature of 100 ° C. to 400 ° C. and a baking time of 0.3 minutes to 10 minutes.
前記工程により形成した第１のレジスト下層膜上にオルガノポリシロキサン膜を第２のレジスト下層膜として形成し、その上にレジストパターンを形成する。この第２のレジスト下層膜は、ＣＶＤ、ＰＶＤなどの蒸着法で形成されるＳｉＯＮ膜又はＳｉＮ膜であってもよい。さらにこの第２のレジスト下層膜上に第３のレジスト下層膜として反射防止膜（ＢＡＲＣ）を形成してもよく、該第３のレジスト下層膜は反射防止能を有しないレジスト形状補正膜であってもよい。前記レジストパターンを形成する工程において、露光は所定のパターンを形成するためのマスク（レチクル）を通して又は直接描画により行なわれる。露光源には、例えば、ｇ線、ｉ線、ＫｒＦエキシマレーザー、ＡｒＦエキシマレーザー、ＥＵＶ、電子線を使用することができる。露光後、必要に応じて露光後加熱（Ｐｏｓｔ ＥｘｐｏｓｕｒｅＢａｋｅ）が行なわれる。その後、現像液（例えば２．３８質量％水酸化テトラメチルアンモニウム水溶液）により現像し、さらにリンス液又は純水ですすぎ、使用した現像液を除去する。その後、レジストパターンの乾燥及び下地との密着性を高めるためポストベークを行う。 An organopolysiloxane film is formed as a second resist underlayer film on the first resist underlayer film formed by the above process, and a resist pattern is formed thereon. The second resist underlayer film may be a SiON film or a SiN film formed by a vapor deposition method such as CVD or PVD. Further, an antireflection film (BARC) may be formed as a third resist underlayer film on the second resist underlayer film, and the third resist underlayer film is a resist shape correction film having no antireflection ability. May be. In the step of forming the resist pattern, exposure is performed through a mask (reticle) for forming a predetermined pattern or by direct drawing. As the exposure source, for example, g-line, i-line, KrF excimer laser, ArF excimer laser, EUV, or electron beam can be used. After the exposure, post-exposure heating (Post Exposure Bake) is performed as necessary. Thereafter, development is performed with a developer (for example, an aqueous 2.38 mass% tetramethylammonium hydroxide solution), and further rinsed with a rinse solution or pure water to remove the used developer. Thereafter, the resist pattern is dried and post-baked in order to improve adhesion to the base.
前記レジストパターン形成後に行われるエッチング工程は、ドライエッチングにより行われる。ドライエッチングに使用するエッチングガスとして、第２のレジスト下層膜（オルガノポリシロキサン膜）に対しては例えばＣＨＦ３、ＣＦ４、Ｃ２Ｆ６が挙げられ、本発明のレジスト下層膜形成組成物から形成された第１のレジスト下層膜に対しては例えばＯ２、Ｎ２Ｏ、ＮＯ２が挙げられ、段差又は凹部及び／又は凸部を有する表面に対しては例えばＣＨＦ３、ＣＦ４、Ｃ２Ｆ６が挙げられる。さらに、これらのガスにアルゴン、窒素又は二酸化炭素を混合して使用することができる。The etching process performed after forming the resist pattern is performed by dry etching. Examples of the etching gas used for dry etching include CHF 3 , CF 4 , and C 2 F 6 for the second resist underlayer film (organopolysiloxane film). From the resist underlayer film forming composition of the present invention, For the formed first resist underlayer film, for example, O 2 , N 2 O, NO 2 can be mentioned, and for the surface having a step or a concave portion and / or a convex portion, for example, CHF 3 , CF 4 , C 2 F 6 is mentioned. Further, argon, nitrogen or carbon dioxide can be mixed with these gases.
以下、本発明について合成例及び実施例を挙げて説明するが、本発明は下記記載によって限定されるものではない。 EXAMPLES Hereinafter, although a synthesis example and an Example are given and demonstrated about this invention, this invention is not limited by the following description.
下記合成例１乃至合成例３、比較合成例１及び比較合成例２に示す重量平均分子量及び多分散度は、ゲルパーミエーションクロマトグラフィー（以下、本明細書ではＧＰＣと略称する。）による測定結果に基づく。測定には、東ソー（株）製ＧＰＣシステムを用い、測定条件は下記のとおりである。
ＧＰＣカラム：ＴＳＫｇｅｌ ＳｕｐｅｒＭｕｌｔｉｐｏｒｅ〔登録商標〕Ｈｚ−Ｎ（東ソー（株））
カラム温度：４０℃
溶媒：テトラヒドロフラン（ＴＨＦ）
流量：０．３５ｍｌ／分
標準試料：ポリスチレン（東ソー（株））The weight average molecular weight and polydispersity shown in the following Synthesis Examples 1 to 3, Comparative Synthesis Example 1 and Comparative Synthesis Example 2 are measured by gel permeation chromatography (hereinafter abbreviated as GPC in this specification). based on. For the measurement, a GPC system manufactured by Tosoh Corporation is used, and the measurement conditions are as follows.
GPC column: TSKgel SuperMultipore [registered trademark] Hz-N (Tosoh Corporation)
Column temperature: 40 ° C
Solvent: tetrahydrofuran (THF)
Flow rate: 0.35 ml / min Standard sample: Polystyrene (Tosoh Corporation)
（合成例１）
２００ｍＬ四口フラスコに３，３’，５，５’−テトラメトキシメチル−４，４’−ジヒドロキシビフェニル（以下、本明細書ではＴＭＯＭ−ＢＰと略称する。）（２３．８３ｇ、０．０６６ｍｏｌ、本州化学工業（株）製）、ピレン（２７．００ｇ、０．１３４ｍｏｌ、東京化成工業（株）製）、パラトルエンスルホン酸一水和物（０．５３ｇ、０．００３ｍｏｌ、東京化成工業（株）製）を加え、さらに１，４−ジオキサン（１１９．８４ｇ、関東化学（株）製）を仕込み、撹拌し、リフラックスが確認されるまで昇温し溶解させ、重合を開始した。６時間後６０℃まで放冷後、メタノール（１０００ｇ、関東化学（株）製）へ再沈殿させた。得られた沈殿物をろ過し、減圧乾燥機で６０℃、１２時間乾燥させ、下記式（３）で表される構造単位を有する、目的とするポリマー（以下、本明細書ではＴＭＯＭ−Ｐｙと略称する。）２８．６ｇを得た。得られたＴＭＯＭ−Ｐｙの、ＧＰＣによるポリスチレン換算で測定される重量平均分子量は２６００であった。
In a 200 mL four-necked flask, 3,3 ′, 5,5′-tetramethoxymethyl-4,4′-dihydroxybiphenyl (hereinafter abbreviated as TMOM-BP) (23.83 g, 0.066 mol, Honshu Chemical Industry Co., Ltd.), pyrene (27.00 g, 0.134 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), p-toluenesulfonic acid monohydrate (0.53 g, 0.003 mol, Tokyo Chemical Industry Co., Ltd.) )) And 1,4-dioxane (119.84 g, manufactured by Kanto Chemical Co., Inc.) was added, stirred, and heated to dissolve until reflux was confirmed, and polymerization was started. Six hours later, the mixture was allowed to cool to 60 ° C. and then reprecipitated into methanol (1000 g, manufactured by Kanto Chemical Co., Inc.). The obtained precipitate was filtered, dried in a vacuum dryer at 60 ° C. for 12 hours, and a target polymer having a structural unit represented by the following formula (3) (hereinafter referred to as TMOM-Py and (Abbreviated) 28.6 g was obtained. The weight average molecular weight of the obtained TMOM-Py measured in terms of polystyrene by GPC was 2600.
（合成例２）
１００ｍＬ四口フラスコにＴＭＯＭ−ＢＰ（２．２１ｇ、０．００６ｍｏｌ、本州化学工業（株）製）、カルバゾール（５．００ｇ、０．０３０ｍｏｌ、東京化成工業（株）製）、１−ピレンカルボキシアルデヒド（５．７６ｇ、０．０２５ｍｏｌ、シグマアルドリッチ社製）、パラトルエンスルホン酸一水和物（０．８９ｇ、０．００６ｍｏｌ、東京化成工業（株）製）を加え、さらに１，４−ジオキサン（２５．７５ｇ、関東化学（株）製）を仕込み、撹拌し、リフラックスが確認されるまで昇温し溶解させ、重合を開始した。７時間後６０℃まで放冷後、メタノール（１０００ｇ、関東化学（株）製）へ再沈殿させた。得られた沈殿物をろ過し、減圧乾燥機で６０℃、１２時間乾燥させ、下記式（４）で表される２種の構造単位を有する、目的とするポリマー（以下、本明細書ではＴＭＯＭ−Ｃｚ−ＰＣＡと略称する。）６．３ｇを得た。得られたＴＭＯＭ−Ｃｚ−ＰＣＡの、ＧＰＣによるポリスチレン換算で測定される重量平均分子量は８９００であった。
In a 100 mL four-necked flask, TMOM-BP (2.21 g, 0.006 mol, manufactured by Honshu Chemical Industry Co., Ltd.), carbazole (5.00 g, 0.030 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pyrenecarboxaldehyde (5.76 g, 0.025 mol, manufactured by Sigma-Aldrich), paratoluenesulfonic acid monohydrate (0.89 g, 0.006 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and 1,4-dioxane ( 25.75 g (manufactured by Kanto Chemical Co., Inc.) was charged, stirred, and heated to dissolve until reflux was confirmed, and polymerization was started. After 7 hours, the mixture was allowed to cool to 60 ° C. and then reprecipitated into methanol (1000 g, manufactured by Kanto Chemical Co., Inc.). The obtained precipitate was filtered, dried in a vacuum dryer at 60 ° C. for 12 hours, and a target polymer having two structural units represented by the following formula (4) (hereinafter referred to as TMOM in the present specification). -Abbreviated as -Cz-PCA.) 6.3 g was obtained. The weight average molecular weight of the obtained TMOM-Cz-PCA measured by polystyrene conversion by GPC was 8,900.
（合成例３）
２００ｍＬ四口フラスコにＴＭＯＭ−ＢＰ（１３．９３ｇ、０．０３８ｍｏｌ、本州化学工業（株）製）、ナフタレン（１０．００ｇ、０．０７８ｍｏｌ、東京化成工業（株）製）、パラトルエンスルホン酸一水和物（０．３１ｇ、０．００２ｍｏｌ、東京化成工業（株）製）を加え、さらに１，４−ジオキサン（５６．５６ｇ、関東化学（株）製）を仕込み、撹拌し、リフラックスが確認されるまで昇温し溶解させ、重合を開始した。５時間後６０℃まで放冷後、メタノール（１０００ｇ、関東化学（株）製）へ再沈殿させた。得られた沈殿物をろ過し、減圧乾燥機で６０℃、１２時間乾燥させ、下記式（５）で表される構造単位を有する、目的とするポリマー（以下、本明細書ではＴＭＯＭ−Ｎａと略称する。）５．９ｇを得た。得られたＴＭＯＭ−Ｎａの、ＧＰＣによるポリスチレン換算で測定される重量平均分子量は５０００であった。
In a 200 mL four-necked flask, TMOM-BP (13.93 g, 0.038 mol, manufactured by Honshu Chemical Industry Co., Ltd.), naphthalene (10.00 g, 0.078 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), p-toluenesulfonic acid Hydrate (0.31 g, 0.002 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and 1,4-dioxane (56.56 g, manufactured by Kanto Chemical Co., Inc.) was further added and stirred. The temperature was raised until dissolution was confirmed, and polymerization was started. After 5 hours, the mixture was allowed to cool to 60 ° C. and then reprecipitated into methanol (1000 g, manufactured by Kanto Chemical Co., Inc.). The obtained precipitate was filtered, dried in a vacuum dryer at 60 ° C. for 12 hours, and a target polymer having a structural unit represented by the following formula (5) (hereinafter referred to as TMOM-Na in this specification). (Abbreviated) 5.9 g was obtained. The weight average molecular weight of the obtained TMOM-Na measured by polystyrene conversion by GPC was 5000.
（比較合成例１）
窒素下、１００mＬ四口フラスコにカルバゾール（６．６９ｇ、０．０４０ｍｏｌ、東京化成工業（株）製）、９−フルオレノン（７．２８ｇ、０．０４０ｍｏｌ、東京化成工業（株）製）、パラトルエンスルホン酸一水和物（０．７６ｇ、０．００４０ｍｏｌ、東京化成工業（株）製）を加え、さらに１，４−ジオキサン（６．６９ｇ、関東化学（株）製）を仕込み、撹拌し、１００℃まで昇温し溶解させ、重合を開始した。２４時間後６０℃まで放冷後、クロロホルム（３４ｇ、関東化学（株）製）を加え希釈し、メタノール（１６８ｇ、関東化学（株）製）へ再沈殿させた。得られた沈殿物をろ過し、減圧乾燥機で８０℃、２４時間乾燥させ、下記式（６）で表される構造単位を有する、目的とするポリマー９．３７ｇを得た。得られたポリマーの、ＧＰＣによるポリスチレン換算で測定される重量平均分子量は２８００であった。
Under nitrogen, carbazole (6.69 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), paratoluene in a 100 mL four-necked flask. Sulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and 1,4-dioxane (6.69 g, manufactured by Kanto Chemical Co., Inc.) was further added and stirred. The temperature was raised to 100 ° C. to dissolve, and polymerization was started. After 24 hours, the mixture was allowed to cool to 60 ° C., diluted with chloroform (34 g, manufactured by Kanto Chemical Co., Inc.), and reprecipitated into methanol (168 g, manufactured by Kanto Chemical Co., Inc.). The obtained precipitate was filtered and dried in a vacuum dryer at 80 ° C. for 24 hours to obtain 9.37 g of a target polymer having a structural unit represented by the following formula (6). The weight average molecular weight of the obtained polymer measured by polystyrene conversion by GPC was 2,800.
（実施例１）
合成例１で得たポリマー２０ｇに、界面活性剤としてメガファックＲ−３０（ＤＩＣ（株）製）０．０６ｇを混合し、シクロヘキサノン８０ｇに溶解させ溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、更に、孔径０．０５μｍのポリエチレン製ミクロフィルターを用いてろ過して、多層膜によるリソグラフィープロセスに用いるレジスト下層膜形成組成物を調製した。Example 1
To 20 g of the polymer obtained in Synthesis Example 1, 0.06 g of Megafac R-30 (manufactured by DIC Corporation) as a surfactant was mixed and dissolved in 80 g of cyclohexanone to obtain a solution. Thereafter, the mixture is filtered using a polyethylene microfilter having a pore size of 0.10 μm, and further filtered using a polyethylene microfilter having a pore size of 0.05 μm to prepare a resist underlayer film forming composition used in a lithography process using a multilayer film. did.
（実施例２）
合成例２で得たポリマー２０ｇに、界面活性剤としてメガファックＲ−３０（ＤＩＣ（株）製）０．０６ｇを混合し、シクロヘキサノン８０ｇに溶解させ溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、更に、孔径０．０５μｍのポリエチレン製ミクロフィルターを用いてろ過して、多層膜によるリソグラフィープロセスに用いるレジスト下層膜形成組成物を調製した。(Example 2)
To 20 g of the polymer obtained in Synthesis Example 2, 0.06 g of Megafac R-30 (manufactured by DIC Corporation) was mixed as a surfactant and dissolved in 80 g of cyclohexanone to obtain a solution. Thereafter, the mixture is filtered using a polyethylene microfilter having a pore size of 0.10 μm, and further filtered using a polyethylene microfilter having a pore size of 0.05 μm to prepare a resist underlayer film forming composition used in a lithography process using a multilayer film. did.
（実施例３）
合成例３で得たポリマー２０ｇに、界面活性剤としてメガファックＲ−３０（ＤＩＣ（株）製）０．０６ｇを混合し、シクロヘキサノン８０ｇに溶解させ溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、更に、孔径０．０５μｍのポリエチレン製ミクロフィルターを用いてろ過して、多層膜によるリソグラフィープロセスに用いるレジスト下層膜形成組成物を調製した。(Example 3)
To 20 g of the polymer obtained in Synthesis Example 3, 0.06 g of Megafac R-30 (manufactured by DIC Corporation) was mixed as a surfactant and dissolved in 80 g of cyclohexanone to obtain a solution. Thereafter, the mixture is filtered using a polyethylene microfilter having a pore size of 0.10 μm, and further filtered using a polyethylene microfilter having a pore size of 0.05 μm to prepare a resist underlayer film forming composition used in a lithography process using a multilayer film. did.
（比較例１）
比較合成例１で得たポリマー２０ｇに、界面活性剤としてメガファックＲ−３０（ＤＩＣ（株）製）０．０６ｇを混合し、シクロヘキサノン８０ｇに溶解させ溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、更に、孔径０．０５μｍのポリエチレン製ミクロフィルターを用いてろ過して、多層膜によるリソグラフィープロセスに用いるレジスト下層膜形成組成物を調製した。(Comparative Example 1)
To 20 g of the polymer obtained in Comparative Synthesis Example 1, 0.06 g of Megafac R-30 (manufactured by DIC Corporation) was mixed as a surfactant and dissolved in 80 g of cyclohexanone to obtain a solution. Thereafter, the mixture is filtered using a polyethylene microfilter having a pore size of 0.10 μm, and further filtered using a polyethylene microfilter having a pore size of 0.05 μm to prepare a resist underlayer film forming composition used in a lithography process using a multilayer film. did.
（比較例２）
比較合成例１で得たポリマー２０ｇに、架橋剤としてＴＭＯＭ−ＢＰ（本州化学工業（株）製）３．０ｇ、触媒としてピリジニウムパラトルエンスルホネート０．６ｇ、界面活性剤としてメガファックＲ−３０（ＤＩＣ（株）製）０．０６ｇを混合し、シクロヘキサノン８０ｇに溶解させ溶液とした。その後、孔径０．１０μｍのポリエチレン製ミクロフィルターを用いてろ過し、更に、孔径０．０５μｍのポリエチレン製ミクロフィルターを用いてろ過して、多層膜によるリソグラフィープロセスに用いるレジスト下層膜形成組成物を調製した。(Comparative Example 2)
To 20 g of the polymer obtained in Comparative Synthesis Example 1, 3.0 g of TMOM-BP (produced by Honshu Chemical Industry Co., Ltd.) as a crosslinking agent, 0.6 g of pyridinium paratoluenesulfonate as a catalyst, and Megafac R-30 (as a surfactant) DIC Co., Ltd.) (0.06 g) was mixed and dissolved in 80 g of cyclohexanone to obtain a solution. Thereafter, the mixture is filtered using a polyethylene microfilter having a pore size of 0.10 μm, and further filtered using a polyethylene microfilter having a pore size of 0.05 μm to prepare a resist underlayer film forming composition used in a lithography process using a multilayer film. did.
（膜の硬度測定）
実施例１乃至実施例３、比較例１及び比較例２で調製したレジスト下層膜形成組成物を、それぞれスピンコーターを用いてシリコンウェハー上に塗布した。塗布されたウェハーをホットプレート上で２４０℃１分間、または４００℃２分間ベークし、レジスト下層膜（膜厚０．２５μｍ）を形成した。これらのレジスト下層膜を、ナノインデンテーション装置Ｇ２００（アジレント・テクノロジー社製）を用いて膜の硬度を測定した。その結果を表１に示す。(Measurement of film hardness)
The resist underlayer film forming compositions prepared in Examples 1 to 3, Comparative Example 1 and Comparative Example 2 were each applied onto a silicon wafer using a spin coater. The applied wafer was baked on a hot plate at 240 ° C. for 1 minute or at 400 ° C. for 2 minutes to form a resist underlayer film (film thickness: 0.25 μm). The hardness of the resist underlayer film was measured using a nanoindentation apparatus G200 (manufactured by Agilent Technologies). The results are shown in Table 1.
上記表１の結果から、本発明に係る実施例１乃至実施例３のレジスト下層膜形成組成物を用い４００℃２分間ベークして形成されたレジスト下層膜は、比較例１及び比較例２のレジスト下層膜形成組成物を用い同条件でベークして形成されたレジスト下層膜よりも、高い硬度を有することがわかった。 From the results of Table 1 above, the resist underlayer films formed by baking at 400 ° C. for 2 minutes using the resist underlayer film forming compositions of Examples 1 to 3 according to the present invention are those of Comparative Example 1 and Comparative Example 2. It was found that the resist underlayer film was harder than the resist underlayer film formed by baking under the same conditions using the resist underlayer film forming composition.
（フォトレジスト溶剤への溶出試験）
実施例１乃至実施例３及び比較例１で調製したレジスト下層膜形成組成物を、それぞれスピンコーターを用いてシリコンウェハー上に塗布した。塗布されたウェハーをホットプレート上で４００℃２分間ベークし、レジスト下層膜（膜厚０．２５μｍ）を形成した。このレジスト下層膜をレジストに使用する溶剤（乳酸エチル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、シクロヘキサノン）に浸漬し、これらの溶剤に不溶であることを確認した。(Elution test for photoresist solvent)
The resist underlayer film forming compositions prepared in Examples 1 to 3 and Comparative Example 1 were each applied onto a silicon wafer using a spin coater. The applied wafer was baked on a hot plate at 400 ° C. for 2 minutes to form a resist underlayer film (film thickness: 0.25 μm). This resist underlayer film was immersed in a solvent (ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone) used for the resist, and it was confirmed that the resist underlayer film was insoluble in these solvents.
（光学パラメータの測定）
実施例１乃至実施例３で調製したレジスト下層膜形成組成物を、それぞれスピンコーターを用いてシリコンウェハー上に塗布した。塗布されたウェハーをホットプレート上で２４０℃１分間または４００℃２分間ベークし、レジスト下層膜（膜厚０．０５μｍ）を形成した。これらのレジスト下層膜を、分光エリプソメーターを用いて波長１９３ｎｍでの屈折率（ｎ値）及び光学吸光係数（ｋ値、減衰係数ともいう）を測定した。その結果を表２に示す。
The resist underlayer film forming compositions prepared in Examples 1 to 3 were each applied on a silicon wafer using a spin coater. The applied wafer was baked on a hot plate at 240 ° C. for 1 minute or 400 ° C. for 2 minutes to form a resist underlayer film (film thickness 0.05 μm). These resist underlayer films were measured for refractive index (n value) and optical absorption coefficient (also referred to as k value or attenuation coefficient) at a wavelength of 193 nm using a spectroscopic ellipsometer. The results are shown in Table 2.
（耐熱性の測定）
実施例１乃至実施例３で調製したレジスト下層膜形成組成物を、それぞれスピンコーターを用いてシリコンウェハー上に塗布した。塗布されたウェハーをホットプレート上で４００℃２分間ベークし、レジスト下層膜（膜厚０．２μｍ）を形成した。これらのレジスト下層膜をシリコンウェハーから削り取り、粉末体を得た。得られた粉末体の４００℃での熱重量現象をＴＧ／ＤＴＡ（ＢＲＵＫＥＲ社製 ＴＧ−ＤＴＡ２０１０ＳＲ）にて測定した。その結果を表３に示す。
The resist underlayer film forming compositions prepared in Examples 1 to 3 were each applied on a silicon wafer using a spin coater. The applied wafer was baked on a hot plate at 400 ° C. for 2 minutes to form a resist underlayer film (film thickness 0.2 μm). These resist underlayer films were scraped from the silicon wafer to obtain a powder. The thermogravimetric phenomenon at 400 ° C. of the obtained powder was measured with TG / DTA (TG-DTA2010SR manufactured by BRUKER). The results are shown in Table 3.
（ドライエッチング速度の測定）
ドライエッチング速度の測定に用いたエッチャー及びエッチングガスは以下のものである。
エッチャー：ＲＩＥ−１０ＮＲ（サムコ（株）製）
エッチングガス：ＣＦ４
実施例１乃至実施例３で調製したレジスト下層膜形成組成物を、それぞれスピンコーターを用いてシリコンウェハー上に塗布した。塗布されたウェハーをホットプレート上で２４０℃１分間または４００℃２分間ベークし、レジスト下層膜（膜厚０．２５μｍ）を形成した。次にエッチングガスとしてＣＦ４ガスを使用して、これらのレジスト下層膜のドライエッチング速度を測定した。また、フェノールノボラック樹脂（市販品、ＧＰＣによるポリスチレン換算で測定される重量平均分子量Ｍｗは２０００、多分散度Ｍｗ／Ｍｎは２．５）の溶液を、スピンコーターを用いてシリコンウェハー上に塗布し、塗布されたウェハーをホットプレート上で２０５℃１分間ベークしてフェノールノボラック樹脂膜（膜厚０．２５μｍ）を形成した。次にエッチングガスとしてＣＦ４ガスを使用して、そのフェノールノボラック樹脂膜のドライエッチング速度を測定した。このフェノールノボラック樹脂膜のドライエッチング速度を１．００とした時の、実施例１乃至実施例３で調製したレジスト下層膜形成組成物から形成したレジスト下層膜のドライエッチング速度を、ドライエッチング速度比として算出した結果を表４に示す。ドライエッチング速度が小さいほど、ＣＦ４ガスに対する耐エッチング性が高いことを示す。
ドライエッチング速度比＝（レジスト下層膜のドライエッチング速度）／（フェノールノボラック樹脂膜のドライエッチング速度）
The etcher and etching gas used for the measurement of the dry etching rate are as follows.
Etcher: RIE-10NR (manufactured by Samco)
Etching gas: CF 4
The resist underlayer film forming compositions prepared in Examples 1 to 3 were each applied on a silicon wafer using a spin coater. The applied wafer was baked on a hot plate at 240 ° C. for 1 minute or 400 ° C. for 2 minutes to form a resist underlayer film (film thickness 0.25 μm). Next, the dry etching rate of these resist underlayer films was measured using CF 4 gas as an etching gas. In addition, a solution of phenol novolac resin (commercial product, weight average molecular weight Mw measured in terms of polystyrene by GPC is 2000, polydispersity Mw / Mn is 2.5) is applied onto a silicon wafer using a spin coater. The applied wafer was baked on a hot plate at 205 ° C. for 1 minute to form a phenol novolac resin film (film thickness: 0.25 μm). Next, CF 4 gas was used as an etching gas, and the dry etching rate of the phenol novolac resin film was measured. When the dry etching rate of this phenol novolac resin film was set to 1.00, the dry etching rate of the resist underlayer film formed from the resist underlayer film forming composition prepared in Examples 1 to 3 was expressed as a dry etching rate ratio. The results calculated as are shown in Table 4. The smaller the dry etching rate, the higher the etching resistance against CF 4 gas.
Dry etching rate ratio = (Dry etching rate of resist underlayer film) / (Dry etching rate of phenol novolac resin film)
（ウィグリング発生パターン幅の確認）
実施例１乃至実施例３及び比較例２で調製したレジスト下層膜形成組成物を、それぞれスピンコーターを用いてそれぞれ酸化ケイ素膜付きシリコンウェハー上に塗布した。塗布されたウェハーをホットプレート上で４００℃２分間ベークし、レジスト下層膜（膜厚２００ｎｍ）を形成した。そのレジスト下層膜上にポリシロキサンを含有する公知のシリコンハードマスク形成組成物を塗布し、それを２４０℃で１分間ベークし、シリコンハードマスク層（膜厚４５ｎｍ）を形成した。さらにその上にレジスト溶液（ＰＡＲ８５５ Ｓ９０（住友化学（株）製））を塗布し、それを１００℃で１分間ベークしレジスト層（膜厚１２０ｎｍ）を形成した。このレジスト層をマスクを用いて波長１９３ｎｍで露光し、露光後加熱（ＰＥＢ、１０５℃で１分間）を行った後、現像してレジストパターンを得た。その後、フッ素系ガス（成分はＣＦ４）でドライエッチングを行い、レジストパターンをハードマスク層に転写した。次いで酸素系ガス（成分はＯ２）でドライエッチングを行い、レジストパターンを上記レジスト下層膜に転写した。その後、さらにフッ素系ガス（成分はＣ４Ｆ８）でドライエッチングを行い、シリコンウェハー上の酸化ケイ素膜の除去を行った。最終的に得られたそれぞれのパターン形状を電子顕微鏡で観察した。(Check wiggling pattern width)
The resist underlayer film forming compositions prepared in Examples 1 to 3 and Comparative Example 2 were each applied onto a silicon wafer with a silicon oxide film using a spin coater. The applied wafer was baked on a hot plate at 400 ° C. for 2 minutes to form a resist underlayer film (film thickness 200 nm). A known silicon hard mask forming composition containing polysiloxane was applied onto the resist underlayer film and baked at 240 ° C. for 1 minute to form a silicon hard mask layer (film thickness: 45 nm). Further, a resist solution (PAR855 S90 (manufactured by Sumitomo Chemical Co., Ltd.)) was applied thereon and baked at 100 ° C. for 1 minute to form a resist layer (film thickness 120 nm). This resist layer was exposed using a mask at a wavelength of 193 nm, post-exposure heating (PEB, 105 ° C. for 1 minute), and then developed to obtain a resist pattern. Thereafter, dry etching was performed with a fluorine-based gas (component is CF 4 ), and the resist pattern was transferred to the hard mask layer. Next, dry etching was performed with an oxygen-based gas (component is O 2 ) to transfer the resist pattern to the resist underlayer film. Thereafter, dry etching was further performed with a fluorine-based gas (component is C 4 F 8 ) to remove the silicon oxide film on the silicon wafer. Each finally obtained pattern shape was observed with an electron microscope.
パターン幅が狭まるにしたがいウィグリング（ｗｉｇｇｌｉｎｇ）と称する不規則なパターンの曲がりが発生しやすくなるため、上記実施例１乃至実施例３で調製したレジスト下層膜形成組成物を用いて上述のパターン形成工程を行い、得られたパターンの曲がり（ｗｉｇｇｌｉｎｇ）が生じ始めるパターン幅を電子顕微鏡で観測した。パターンの曲がり（ｗｉｇｇｌｉｎｇ）が発生することで忠実なパターンに基づく基板加工ができなくなるため、パターンの曲がり（ｗｉｇｇｌｉｎｇ）が発生する直前のパターン幅（限界パターン幅）により基板加工をする必要がある。パターンの曲がり（ｗｉｇｇｌｉｎｇ）が発生し始める限界パターン幅は、その値が狭ければ狭いほど微細な基板の加工が可能となる。解像度の測定には測長走査型電子顕微鏡（（株）日立ハイテクノロジーズ製）を用いた。測定結果を表５に示す。 As the pattern width narrows, irregular pattern bending called wiggling is likely to occur. Therefore, the above-described pattern formation is performed using the resist underlayer film forming composition prepared in Examples 1 to 3. The process was performed, and the pattern width at which the resulting pattern began to wiggle was observed with an electron microscope. Since the processing of the substrate based on the faithful pattern becomes impossible due to the occurrence of pattern bending, it is necessary to process the substrate with the pattern width (limit pattern width) immediately before the occurrence of the pattern bending. The narrower the limit pattern width at which pattern bending starts to occur, the finer the substrate can be processed. A length measurement scanning electron microscope (manufactured by Hitachi High-Technologies Corporation) was used for resolution measurement. Table 5 shows the measurement results.
本発明の多層膜によるリソグラフィープロセスに用いるレジスト下層膜形成組成物は、反射防止膜としての効果も併せ持つことが出来るレジスト下層膜を提供することができる。また、本発明のレジスト下層膜形成組成物は、その上層にＣＶＤ法でハードマスクを形成できる耐熱性を有することが判った。また、パターン幅を狭くした場合でも、パターンの曲がり（ｗｉｇｇｌｉｎｇ）が発生し難く良好なパターンが得られ、少なくとも５０ｎｍ付近のパターン幅では曲がりのない良好なパターンが得られる。 The resist underlayer film forming composition used in the lithography process using the multilayer film of the present invention can provide a resist underlayer film that can also have an effect as an antireflection film. Moreover, it turned out that the resist underlayer film forming composition of this invention has the heat resistance which can form a hard mask in the upper layer by CVD method. Further, even when the pattern width is narrowed, a good pattern is obtained in which pattern bending is difficult to occur, and a good pattern with no bend is obtained at a pattern width of at least about 50 nm.
Claims (6)
（式中、Ｘ１は、ハロゲノ基、ニトロ基、アミノ基又はヒドロキシ基で置換されていてもよい芳香環を少なくとも１つ有する炭素原子数６乃至２０の二価の有機基を表し、Ｘ２は、ハロゲノ基、ニトロ基、アミノ基又はヒドロキシ基で置換されていてもよい芳香環を少なくとも１つ有する炭素原子数６乃至２０の有機基、又はメトキシ基を表す。）
で表される構造単位を有するポリマー及び溶剤を含むレジスト下層膜形成組成物。Following formula (1):
(Wherein X 1 represents a divalent organic group having 6 to 20 carbon atoms having at least one aromatic ring optionally substituted with a halogeno group, a nitro group, an amino group or a hydroxy group, and X 2 Represents an organic group having 6 to 20 carbon atoms having at least one aromatic ring optionally substituted with a halogeno group, a nitro group, an amino group or a hydroxy group, or a methoxy group.
A resist underlayer film forming composition comprising a polymer having a structural unit represented by formula (I) and a solvent.
In the formula (1), the divalent organic group having 6 to 20 carbon atoms having at least one aromatic ring is a phenylene group, biphenylylene group, terphenylylene group, fluorenylene group, naphthylene group, anthrylene group, pyrenylene group, carbazolylene group. Or a group represented by the following formula (c) (wherein n represents 0 or 1), and the organic group having 6 to 20 carbon atoms having at least one aromatic ring is a phenyl group, a biphenylyl group, A terphenylyl group, a fluorenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a carbazolyl group, or a group represented by the following formula (d-1) or the following formula (d-2) (wherein n represents 0 or 1) The composition for forming a resist underlayer film according to claim 1, wherein
（式中、Ｘ１は請求項１に記載の定義と同義であり、Ｒ３はフェニル基、ナフチル基、アントリル基、ピレニル基、チエニル基又はピリジル基を表し、Ｒ４は水素原子、フェニル基又はナフチル基を表し、Ｒ３及びＲ４がそれぞれフェニル基を表すときＲ３及びＲ４はそれらが結合する同一の炭素原子と一緒になってフルオレン環を形成してもよい。）
で表される構造単位を有する請求項１又は請求項２に記載のレジスト下層膜形成組成物。The polymer is further represented by the following formula (2):
Wherein X 1 is as defined in claim 1, R 3 represents a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a thienyl group or a pyridyl group, and R 4 represents a hydrogen atom or a phenyl group. Alternatively, it represents a naphthyl group, and when R 3 and R 4 each represent a phenyl group, R 3 and R 4 together with the same carbon atom to which they are bonded may form a fluorene ring.
The resist underlayer film forming composition of Claim 1 or Claim 2 which has a structural unit represented by these.
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| PCT/JP2014/059633 WO2014171326A1 (en) | 2013-04-17 | 2014-04-01 | Composition for forming resist underlayer film |
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| CN107340688B (en) * | 2016-04-29 | 2022-05-06 | 东友精细化工有限公司 | Composition for hard mask |
| CN117539127A (en) * | 2017-01-13 | 2024-02-09 | 日产化学株式会社 | Composition for forming resist underlayer film containing amide solvent |
| KR102349937B1 (en) * | 2017-03-27 | 2022-01-10 | 동우 화인켐 주식회사 | Composition for hard mask |
| TWI748087B (en) * | 2017-04-25 | 2021-12-01 | 日商日產化學工業股份有限公司 | Resistor underlayer film forming composition using stilbene compound |
| KR102383692B1 (en) * | 2017-06-30 | 2022-04-05 | 동우 화인켐 주식회사 | Composition for hard mask |
| US11248086B2 (en) | 2018-05-01 | 2022-02-15 | Tokyo Ohka Kogyo Co., Ltd. | Hard-mask forming composition and method for manufacturing electronic component |
| TW202039619A (en) * | 2019-01-11 | 2020-11-01 | 日商三菱瓦斯化學股份有限公司 | Composition for forming film, resist composition,radiation-sensitive composition, method forproducing amorphous film, method for formingresist pattern, composition for forming underlayerfilm for lithography, method for producing underlayer film for lithography, and method for forming circuit pattern |
| WO2021112194A1 (en) * | 2019-12-04 | 2021-06-10 | 三菱瓦斯化学株式会社 | Composition for forming underlayer film for lithography, underlayer film for lithography, resist pattern forming method, circuit pattern forming method, oligomer, and purification method |
| CN115136074A (en) | 2020-02-28 | 2022-09-30 | 日产化学株式会社 | Composition for forming resist underlayer film |
| JPWO2021172296A1 (en) | 2020-02-28 | 2021-09-02 | ||
| WO2022107759A1 (en) * | 2020-11-19 | 2022-05-27 | 日産化学株式会社 | Resist underlayer film-forming composition |
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