JP5692090B2 - Low molecular weight positive radiation sensitive composition and resist pattern forming method - Google Patents
Low molecular weight positive radiation sensitive composition and resist pattern forming method Download PDFInfo
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- JP5692090B2 JP5692090B2 JP2011545054A JP2011545054A JP5692090B2 JP 5692090 B2 JP5692090 B2 JP 5692090B2 JP 2011545054 A JP2011545054 A JP 2011545054A JP 2011545054 A JP2011545054 A JP 2011545054A JP 5692090 B2 JP5692090 B2 JP 5692090B2
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- 125000000524 functional group Chemical group 0.000 claims description 55
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
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- 125000002993 cycloalkylene group Chemical group 0.000 description 5
- AXUUHWJXDWBCSG-UHFFFAOYSA-L disodium 4,5-dihydroxy-3-[(4-nitrophenyl)diazenyl]naphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].Oc1cc(cc2cc(c(N=Nc3ccc(cc3)[N+]([O-])=O)c(O)c12)S([O-])(=O)=O)S([O-])(=O)=O AXUUHWJXDWBCSG-UHFFFAOYSA-L 0.000 description 5
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- 125000001624 naphthyl group Chemical group 0.000 description 5
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
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- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/30—Compounds having groups
- C07C43/303—Compounds having groups having acetal carbon atoms bound to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/92—Systems containing at least three condensed rings with a condensed ring system consisting of at least two mutually uncondensed aromatic ring systems, linked by an annular structure formed by carbon chains on non-adjacent positions of the aromatic system, e.g. cyclophanes
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- Chemical & Material Sciences (AREA)
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- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Materials For Photolithography (AREA)
Description
本発明は、特定の低分子量化合物を含む有用なポジ型感放射線性組成物およびそれを用いたレジストパターン形成方法に関する。 The present invention relates to a useful positive radiation-sensitive composition containing a specific low molecular weight compound and a resist pattern forming method using the same.
これまでの一般的なレジスト材料は、高分子量ポジ型レジストであった。しかしながら高分子系ポジ型レジスト材料(ポリマー)は分子量が1万〜10万程度と大きく、分子量分布も広いため、高分子系レジストを用いるリソグラフィでは、微細パターン表面にラフネスが生じ、パターン寸法を制御することが困難となり、歩留まりが低下する。従って、従来の高分子系レジスト材料を用いるリソグラフィでは微細化に限界がある。より微細なパターンを作製するために、種々の低分子量ポジ型レジスト材料が提案されている。
従来の低分子量ポジ型レジスト材料(化合物)は、一般的に低分子量ポリフェノールに対し酸解離性官能基導入試剤を反応させて得られた。しかしながらその場合、得られるレジスト材料は保護基の導入数の異なる化合物からなる混合物となり、その生成比の制御が困難であり、品質の安定したポジ型レジストを得ることが困難であり実用的で無かった(特許文献1参照)。また低分子量ポリフェノールの全てのフェノール性水酸基に保護基を導入すれば純物質が得られるが、その場合はそれを用いたポジ型レジストの感度が低下してしまい実用的で無かった(特許文献1参照)。さらには低分子量ポリフェノールにカルボキシル基を導入し、そのカルボキシル基にのみ選択的に保護基を導入して純物質を得る報告もある(特許文献2参照)。しかしながら、その場合はカルボキシル基の導入された低分子量ポリフェノールの製造が煩雑であり、それにより得られる低分子量ポジ型レジスト材料の純度が低いといった問題があり、それらの改善が望まれていた。Conventional general resist materials have been high molecular weight positive resists. However, since the high molecular weight positive resist material (polymer) has a large molecular weight of about 10,000 to 100,000 and a wide molecular weight distribution, in lithography using a high molecular weight resist, roughness is generated on the surface of a fine pattern, and the pattern size is controlled. It becomes difficult to do, and the yield decreases. Therefore, there is a limit to miniaturization in conventional lithography using a polymer resist material. In order to produce a finer pattern, various low molecular weight positive resist materials have been proposed.
Conventional low molecular weight positive resist materials (compounds) are generally obtained by reacting a low molecular weight polyphenol with an acid-dissociable functional group introduction reagent. However, in that case, the resulting resist material is a mixture composed of compounds with different numbers of introduced protective groups, and it is difficult to control the production ratio, and it is difficult to obtain a positive resist with stable quality, which is practical and not necessary. (See Patent Document 1). In addition, a pure substance can be obtained by introducing protective groups into all phenolic hydroxyl groups of low molecular weight polyphenols, but in that case, the sensitivity of a positive resist using the same decreases and is not practical (Patent Document 1). reference). Furthermore, there is a report in which a pure substance is obtained by introducing a carboxyl group into a low molecular weight polyphenol and selectively introducing a protective group only into the carboxyl group (see Patent Document 2). However, in that case, there is a problem that the production of a low molecular weight polyphenol having a carboxyl group introduced therein is complicated and the purity of the resulting low molecular weight positive resist material is low, and improvements have been desired.
本発明の目的は、上記課題を解決するポジ型感放射線性組成物およびそれを用いたレジストパターン形成方法を提供することである。 An object of the present invention is to provide a positive-type radiation-sensitive composition that solves the above problems and a resist pattern forming method using the same.
本発明者らは上記課題を解決するため鋭意検討した結果、特定の低分子量化合物を含む有用なポジ型感放射線性組成物が上記課題の解決に有効であり、かつ、良好なレジストパターン形状を与えることを見出し本発明に到った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a useful positive-type radiation-sensitive composition containing a specific low molecular weight compound is effective in solving the above-mentioned problems, and has a good resist pattern shape. The present invention has been found.
すなわち、本発明はつぎの通りである。
1. 下記a)〜e)のすべての条件を満たす化合物(A)、下記f)〜i)のすべての条件を満たす化合物(B)、可視光線、紫外線、エキシマレーザー、電子線、極端紫外線(EUV)、X線、およびイオンビームからなる群から選ばれるいずれかの放射線の照射により直接的または間接的に酸を発生する酸発生剤(C)、酸拡散制御剤(E)、ならびに溶媒を含むポジ型感放射線性組成物であって、該組成物が固形成分1〜80重量%および溶媒20〜99重量%からなり、該化合物(A)の重量と該化合物(B)の重量との和が固形成分全重量の50〜99重量%であるポジ型感放射線性組成物。
a)分子量:400〜3000
b)アルカリ現像液(テトラメチルアンモニウムヒドロキシド(TMAH)2.38wt%)に不溶
c)酸の作用により、アルカリ現像液(TMAH2.38wt%)に可溶となる
d)分子内に少なくとも1つの酸解離性官能基の導入されたフェノール性水酸基またはカルボキシル基を有する
e)1.00≦Mw/Mn≦1.05 (Mw:数平均分子量、Mw:重量平均分子量)
f)分子量:350〜2500
g)アルカリ現像液(TMAH2.38wt%)に可溶
h)分子内に少なくとも1つのフェノール性水酸基またはカルボキシル基を有する
i)1.00≦Mw/Mn≦1.05
2. 前記化合物(A)が、前記化合物(B)の全てのフェノール性水酸基およびカルボキシル基に、酸解離性官能基を導入した化合物(Aa)である第1項記載のポジ型感放射線性組成物。
3. 前記化合物(B)が、全てのフェノール性水酸基およびカルボキシル基に、酸解離性官能基が導入されていない化合物(Bb)である第1項記載のポジ型感放射線性組成物。
4. 前記化合物(A)が、前記化合物(Aa)であって、下記式(1A)で示される環状化合物(A1)であり、かつ前記化合物(B)が、前記化合物(Bb)であって、下記式(1B)で示される環状化合物(B1)である第1項記載のポジ型感放射線性組成物。
5. 第1項〜第4項のいずれかに記載の感放射線性組成物を用いて、基板上にレジスト膜を形成する工程、該レジスト膜を露光する工程、および該レジスト膜を現像してレジストパターンを形成する工程を含むレジストパターン形成方法。That is, the present invention is as follows.
1. Compound (A) that satisfies all the following conditions a) to e), Compound (B) that satisfies all the following conditions f) to i), visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV) A positive electrode containing an acid generator (C), an acid diffusion controller (E), and a solvent that generate acid directly or indirectly by irradiation with any radiation selected from the group consisting of X-rays, and ion beams Type radiation-sensitive composition, wherein the composition comprises 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent, and the sum of the weight of the compound (A) and the weight of the compound (B) is A positive radiation-sensitive composition that is 50 to 99% by weight of the total weight of solid components.
a) Molecular weight: 400 to 3000
b) Insoluble in alkali developer (tetramethylammonium hydroxide (TMAH) 2.38 wt%) c) Soluble in alkali developer (TMAH 2.38 wt%) by the action of acid d) At least one in the molecule E) 1.00 ≦ Mw / Mn ≦ 1.05 (Mw: number average molecular weight, Mw: weight average molecular weight)
f) Molecular weight: 350-2500
g) Soluble in alkali developer (TMAH 2.38 wt%) h) At least one phenolic hydroxyl group or carboxyl group in the molecule i) 1.00 ≦ Mw / Mn ≦ 1.05
2. The positive radiation sensitive composition according to claim 1, wherein the compound (A) is a compound (Aa) in which an acid-dissociable functional group is introduced into all phenolic hydroxyl groups and carboxyl groups of the compound (B).
3. The positive radiation sensitive composition according to claim 1, wherein the compound (B) is a compound (Bb) in which no acid-dissociable functional group is introduced into all phenolic hydroxyl groups and carboxyl groups.
4). The compound (A) is the compound (Aa), a cyclic compound (A1) represented by the following formula (1A), and the compound (B) is the compound (Bb), The positive radiation-sensitive composition according to item 1, which is a cyclic compound (B1) represented by the formula (1B).
5. A step of forming a resist film on a substrate, a step of exposing the resist film using the radiation-sensitive composition according to any one of items 1 to 4, and developing the resist film to form a resist pattern A resist pattern forming method including a step of forming a film.
本発明により、上記課題を解決するポジ型感放射線性組成物、および該組成物を用いるレジストパターン形成方法を提供することができる。本発明はポジ型感放射線性組成物に有用なレジスト化合物の製造を容易にし、レジスト化合物の純度を高めることができるため、品質管理が容易になる。また、該レジスト化合物を含むポジ型感放射線性組成物は良好なレジストパターンを与える。 According to the present invention, it is possible to provide a positive radiation-sensitive composition that solves the above problems, and a resist pattern forming method using the composition. The present invention facilitates the production of a resist compound useful for a positive radiation-sensitive composition and can increase the purity of the resist compound, thereby facilitating quality control. A positive radiation sensitive composition containing the resist compound gives a good resist pattern.
以下、本発明を詳細に説明する。
[ポジ型感放射線性組成物]
本発明は、
下記a)〜e)のすべての条件を満たす化合物(A)、
下記f)〜i)のすべての条件を満たす化合物(B)、
可視光線、紫外線、エキシマレーザー、電子線、極端紫外線(EUV)、X線、およびイオンビームからなる群から選ばれるいずれかの放射線の照射により直接的または間接的に酸を発生する酸発生剤(C)、酸拡散制御剤(E)、ならびに溶媒を含むポジ型感放射線性組成物であって、
該組成物が固形成分1〜80重量%および溶媒20〜99重量%からなり、
前記化合物(A)の重量と化合物(B)の重量との和が固形成分全重量の50〜99重量%であるポジ型感放射線性組成物に関する。
a)分子量:400〜5000
b)アルカリ現像液(TMAH2.38wt%)に不溶
c)酸の作用により、アルカリ現像液(TMAH2.38wt%)に可溶となる
d)分子内に少なくとも1つの酸解離性官能基の導入されたフェノール性水酸基またはカルボキシル基を有する
e)1.00≦Mw/Mn≦1.05
f)分子量:350〜4000
g)アルカリ現像液(TMAH2.38wt%)に可溶
h)分子内に少なくとも1つのフェノール性水酸基またはカルボキシル基を有する
i)1.00≦Mw/Mn≦1.05Hereinafter, the present invention will be described in detail.
[Positive radiation sensitive composition]
The present invention
Compound (A) that satisfies all the following conditions a) to e):
Compound (B) that satisfies all the following conditions f) to i):
An acid generator that generates an acid directly or indirectly upon irradiation with radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam ( C), a positive radiation sensitive composition comprising an acid diffusion controller (E), and a solvent,
The composition comprises 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent,
The present invention relates to a positive radiation sensitive composition in which the sum of the weight of the compound (A) and the weight of the compound (B) is 50 to 99% by weight of the total weight of the solid component.
a) Molecular weight: 400-5000
b) Insoluble in alkali developer (TMAH 2.38 wt%) c) Soluble in alkali developer (TMAH 2.38 wt%) by the action of acid d) At least one acid-dissociable functional group is introduced into the molecule E) having a phenolic hydroxyl group or carboxyl group e) 1.00 ≦ Mw / Mn ≦ 1.05
f) Molecular weight: 350-4000
g) Soluble in alkali developer (TMAH 2.38 wt%) h) At least one phenolic hydroxyl group or carboxyl group in the molecule i) 1.00 ≦ Mw / Mn ≦ 1.05
ここでアルカリ現像液に可溶とは、該化合物を後述する溶媒に溶解した溶液を用いてスピンコートにより作製したアモルファス膜の溶解速度が10Å/sec以上であることを示す。またアルカリ現像液に不溶とは、該化合物を後述する溶媒に溶解した溶液を用いて、スピンコートにより作製したアモルファス膜の溶解速度が5Å/sec以下であることを示す。 Here, being soluble in an alkaline developer means that the dissolution rate of an amorphous film prepared by spin coating using a solution obtained by dissolving the compound in a solvent described later is 10 Å / sec or more. The term “insoluble in an alkaline developer” means that the dissolution rate of an amorphous film prepared by spin coating using a solution obtained by dissolving the compound in a solvent described later is 5% / sec or less.
Mw/Mnとは多分散度を表わし、Mnが数平均分子量、Mwが重量平均分子量であり、GPC分析等により求めることができる。Mw/Mnは、1.00≦Mw/Mn≦1.05であり、1.00≦Mw/Mn≦1.03が好ましく、1.00≦Mw/Mn≦1.01がより好ましく、Mw/Mn=1.00が単一成分からなり、得られるレジストパターンのラフネスが低減することから特に好ましい。 Mw / Mn represents polydispersity, Mn is the number average molecular weight, Mw is the weight average molecular weight, and can be determined by GPC analysis or the like. Mw / Mn is 1.00 ≦ Mw / Mn ≦ 1.05, preferably 1.00 ≦ Mw / Mn ≦ 1.03, more preferably 1.00 ≦ Mw / Mn ≦ 1.01, Mw / Mn Mn = 1.00 is composed of a single component, and is particularly preferable because the roughness of the resulting resist pattern is reduced.
酸解離性官能基とは、フェノール性水酸基および/またはカルボキシル基に導入されうる、酸の作用により解離し、元のフェノール性水酸基および/またはカルボキシル基を生じる基であり、KrFやArF用の化学増幅型感放射線性組成物に用いられるヒドロキシスチレン系樹脂、(メタ)アクリル酸系樹脂等において提案されているものの中から適宜選択して用いることができる。例えば、置換メチル基、1−置換エチル基、1−置換−n−プロピル基、1−分岐アルキル基、シリル基、アシル基、1−置換アルコキシメチル基、環状エーテル基、およびアルコキシカルボニル基などが好ましく挙げられる。前記酸解離性官能基は、架橋性官能基を有さないことが好ましい。 An acid-dissociable functional group is a group that can be introduced into a phenolic hydroxyl group and / or carboxyl group and dissociates by the action of an acid to produce the original phenolic hydroxyl group and / or carboxyl group. It can be appropriately selected from those proposed for hydroxystyrene-based resins, (meth) acrylic acid-based resins and the like used in the amplified radiation-sensitive composition. For example, a substituted methyl group, 1-substituted ethyl group, 1-substituted-n-propyl group, 1-branched alkyl group, silyl group, acyl group, 1-substituted alkoxymethyl group, cyclic ether group, alkoxycarbonyl group, etc. Preferably mentioned. The acid dissociable functional group preferably has no crosslinkable functional group.
化合物(A)は、化合物(B)の全てのフェノール性水酸基およびカルボキシル基に、酸解離性官能基を導入した化合物(Aa)を用いることが、製造上および品質管理の容易さから好ましい。化合物(B)の全てのフェノール性水酸基およびカルボキシル基に、酸解離性官能基を導入することは、一部のフェノール性水酸基およびカルボキシル基に、酸解離性官能基を導入することよりも容易に、品質管理に有利な高純度の化合物を得ることができる。 As the compound (A), it is preferable to use a compound (Aa) in which an acid-dissociable functional group is introduced into all phenolic hydroxyl groups and carboxyl groups of the compound (B) from the viewpoint of production and ease of quality control. It is easier to introduce an acid dissociable functional group into all phenolic hydroxyl groups and carboxyl groups of the compound (B) than to introduce an acid dissociable functional group into some phenolic hydroxyl groups and carboxyl groups. Thus, a high-purity compound advantageous for quality control can be obtained.
化合物(B)は、全てのフェノール性水酸基およびカルボキシル基に、酸解離性官能基が導入されていない化合物(Bb)を用いることが、製造上および品質管理の容易さから好ましい。アルカリ現像液に可溶である酸解離性官能基の導入された化合物(B)は、一部のフェノール性水酸基およびカルボキシル基に、酸解離性官能基を導入することより得ることができるが、その反応の制御および品質管理は、全てのフェノール性水酸基およびカルボキシル基に、酸解離性官能基が導入されていない化合物(Bb)よりも困難である。 As the compound (B), it is preferable to use a compound (Bb) in which no acid-dissociable functional group is introduced into all phenolic hydroxyl groups and carboxyl groups from the viewpoint of production and quality control. The compound (B) having an acid dissociable functional group that is soluble in an alkali developer can be obtained by introducing an acid dissociable functional group into some phenolic hydroxyl groups and carboxyl groups. Control of the reaction and quality control are more difficult than the compound (Bb) in which no acid-dissociable functional group is introduced into all phenolic hydroxyl groups and carboxyl groups.
上記化合物(Aa)と化合物(Bb)とを組み合わせて用いることが、製造上および品質管理の容易さからより好ましい。その割合は、固形成分の23℃における2.38質量%TMAH水溶液に対する溶解速度により適宜決定されるが、通常、化合物(Aa):化合物(Bb)=10〜90:10〜90(重量%)であり、より好ましくは化合物(Aa):化合物(Bb)=12.5〜50:50〜87.5(重量%)、さらに好ましくは化合物(Aa):化合物(Bb)=15〜30:70〜85(重量%)である。上記配合割合であると、高感度で、高解像度が得られ、ラインエッジラフネスが小さくなる。 It is more preferable to use the compound (Aa) and the compound (Bb) in combination from the viewpoint of production and ease of quality control. The proportion is appropriately determined depending on the dissolution rate of the solid component in the 2.38 mass% TMAH aqueous solution at 23 ° C., but usually compound (Aa): compound (Bb) = 10 to 90:10 to 90 (wt%) More preferably, compound (Aa): compound (Bb) = 12.5-50: 50-87.5 (wt%), more preferably compound (Aa): compound (Bb) = 15-30: 70 -85 (% by weight). With the above blending ratio, high sensitivity and high resolution can be obtained, and the line edge roughness becomes small.
本発明において、化合物(A)は、上記化合物(Aa)であって、下記式(1A)で示される環状化合物(A1)であり、かつ化合物(B)は、上記化合物(Bb)であって、下記式(1B)で示される環状化合物(B1)であることが好ましい。 In the present invention, the compound (A) is the compound (Aa), a cyclic compound (A1) represented by the following formula (1A), and the compound (B) is the compound (Bb) The cyclic compound (B1) represented by the following formula (1B) is preferable.
前記酸解離性官能基は、KrFやArF用の化学増幅型レジスト組成物に用いられるヒドロキシスチレン系樹脂、(メタ)アクリル酸系樹脂等において提案されているものの中から適宜選択して用いることができる。例えば、置換メチル基、1−置換エチル基、1−置換−n−プロピル基、1−分岐アルキル基、シリル基、アシル基、1−置換アルコキシメチル基、環状エーテル基、およびアルコキシカルボニル基などが好ましく挙げられる。前記酸解離性官能基は、架橋性官能基を有さないことが好ましい。 The acid dissociable functional group may be appropriately selected and used from those proposed in hydroxystyrene-based resins, (meth) acrylic acid-based resins and the like used in chemically amplified resist compositions for KrF and ArF. it can. For example, a substituted methyl group, 1-substituted ethyl group, 1-substituted-n-propyl group, 1-branched alkyl group, silyl group, acyl group, 1-substituted alkoxymethyl group, cyclic ether group, alkoxycarbonyl group, etc. Preferably mentioned. The acid dissociable functional group preferably has no crosslinkable functional group.
置換メチル基としては、通常、炭素数2〜20の置換メチル基であり、炭素数4〜18の置換メチル基が好ましく、炭素数6〜16の置換メチル基がさらに好ましい。例えば、メトキシメチル基、メチルチオメチル基、エトキシメチル基、n−プロポキシメチル基、イソプロポキシメチル基、n−ブトキシメチル基、t−ブトキシメチル基、2−メチルプロポキシメチル基、エチルチオメチル基、メトキシエトキシメチル基、フェニルオキシメチル基、1−シクロペンチルオキシメチル基、1−シクロヘキシルオキシメチル基、ベンジルチオメチル基、フェナシル基、4−ブロモフェナシル基、4−メトキシフェナシル基、ピペロニル基、および下記式(7)で示される置換基等を挙げることができる。 The substituted methyl group is usually a substituted methyl group having 2 to 20 carbon atoms, preferably a substituted methyl group having 4 to 18 carbon atoms, and more preferably a substituted methyl group having 6 to 16 carbon atoms. For example, methoxymethyl group, methylthiomethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, t-butoxymethyl group, 2-methylpropoxymethyl group, ethylthiomethyl group, methoxy Ethoxymethyl group, phenyloxymethyl group, 1-cyclopentyloxymethyl group, 1-cyclohexyloxymethyl group, benzylthiomethyl group, phenacyl group, 4-bromophenacyl group, 4-methoxyphenacyl group, piperonyl group, and the following formula ( The substituent etc. which are shown by 7) can be mentioned.
1−置換エチル基としては、通常、炭素数3〜20の1−置換エチル基であり、炭素数5〜18の1−置換エチル基が好ましく、炭素数7〜16の置換エチル基がさらに好ましい。例えば、1−メトキシエチル基、1−メチルチオエチル基、1,1−ジメトキシエチル基、1−エトキシエチル基、1−エチルチオエチル基、1,1−ジエトキシエチル基、n−プロポキシエチル基、イソプロポキシエチル基、n−ブトキシエチル基、t−ブトキシエチル基、2−メチルプロポキシエチル基、1−フェノキシエチル基、1−フェニルチオエチル基、1,1−ジフェノキシエチル基、1−シクロペンチルオキシエチル基、1−シクロヘキシルオキシエチル基、1−フェニルエチル基、1,1−ジフェニルエチル基、および下記式(8)で示される置換基等を挙げることができる。 The 1-substituted ethyl group is usually a 1-substituted ethyl group having 3 to 20 carbon atoms, preferably a 1-substituted ethyl group having 5 to 18 carbon atoms, and more preferably a substituted ethyl group having 7 to 16 carbon atoms. . For example, 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl group, n-propoxyethyl group, Isopropoxyethyl group, n-butoxyethyl group, t-butoxyethyl group, 2-methylpropoxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-cyclopentyloxy Examples thereof include an ethyl group, a 1-cyclohexyloxyethyl group, a 1-phenylethyl group, a 1,1-diphenylethyl group, and a substituent represented by the following formula (8).
1−置換−n−プロピル基としては、通常、炭素数4〜20の1−置換−n−プロピル基であり、炭素数6〜18の1−置換−n−プロピル基が好ましく、炭素数8〜16の1−置換−n−プロピル基がさらに好ましい。例えば、1−メトキシ−n−プロピル基および1−エトキシ−n−プロピル基等を挙げることができる。
1−分岐アルキル基としては、通常、炭素数3〜20の1−分岐アルキル基であり、炭素数5〜18の1−分岐アルキル基が好ましく、炭素数7〜16の分岐アルキル基がさらに好ましい。例えば、イソプロピル基、sec−ブチル基、tert−ブチル基、1,1−ジメチルプロピル基、1−メチルブチル基、1,1−ジメチルブチル基、2−メチルアダマンチル基、および2−エチルアダマンチル基等を挙げることができる。The 1-substituted-n-propyl group is usually a 1-substituted-n-propyl group having 4 to 20 carbon atoms, preferably a 1-substituted-n-propyl group having 6 to 18 carbon atoms, and having 8 carbon atoms. More preferred are ˜16 1-substituted-n-propyl groups. For example, a 1-methoxy-n-propyl group and a 1-ethoxy-n-propyl group can be exemplified.
The 1-branched alkyl group is usually a 1-branched alkyl group having 3 to 20 carbon atoms, preferably a 1-branched alkyl group having 5 to 18 carbon atoms, and more preferably a branched alkyl group having 7 to 16 carbon atoms. . For example, isopropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, 2-methyladamantyl group, 2-ethyladamantyl group, etc. Can be mentioned.
シリル基としては、通常、炭素数1〜20のシリル基であり、炭素数3〜18のシリル基が好ましく、炭素数5〜16のシリル基がさらに好ましい。例えば、トリメチルシリル基、エチルジメチルシリル基、メチルジエチルシリル基、トリエチルシリル基、tert−ブチルジメチルシリル基、tert−ブチルジエチルシリル基、tert−ブチルジフェニルシリル基、トリ−tert−ブチルシリル基およびトリフェニルシリル基等を挙げることができる。
アシル基としては、通常、炭素数2〜20のアシル基であり、炭素数4〜18のアシル基が好ましく、炭素数6〜16のアシル基がさらに好ましい。例えば、アセチル基、フェノキシアセチル基、プロピオニル基、ブチリル基、ヘプタノイル基、ヘキサノイル基、バレリル基、ピバロイル基、イソバレリル基、ラウリロイル基、アダマンチルカルボニル基、ベンゾイル基およびナフトイル基等を挙げることができる。The silyl group is usually a silyl group having 1 to 20 carbon atoms, preferably a silyl group having 3 to 18 carbon atoms, and more preferably a silyl group having 5 to 16 carbon atoms. For example, trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiethylsilyl group, tert-butyldiphenylsilyl group, tri-tert-butylsilyl group and triphenylsilyl Groups and the like.
The acyl group is usually an acyl group having 2 to 20 carbon atoms, preferably an acyl group having 4 to 18 carbon atoms, and more preferably an acyl group having 6 to 16 carbon atoms. Examples include acetyl group, phenoxyacetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, laurylyl group, adamantylcarbonyl group, benzoyl group and naphthoyl group.
1−置換アルコキシメチル基としては、通常、炭素数2〜20の1−置換アルコキシメチル基であり、炭素数4〜18の1−置換アルコキシメチル基が好ましく、炭素数6〜16の1−置換アルコキシメチル基がさらに好ましい。例えば、1−シクロペンチルメトキシメチル基、1−シクロペンチルエトキシメチル基、1−シクロヘキシルメトキシメチル基、1−シクロヘキシルエトキシメチル基、1−シクロオクチルメトキシメチル基および1−アダマンチルメトキシメチル基等を挙げることができる。
環状エーテル基としては、通常、炭素数2〜20の環状エーテル基であり、炭素数4〜18の環状エーテル基が好ましく、炭素数6〜16の環状エーテル基がさらに好ましい。例えば、テトラヒドロピラニル基、テトラヒドロフラニル基、テトラヒドロチオピラニル基、テトラヒドロチオフラニル基、4−メトキシテトラヒドロピラニル基および4−メトキシテトラヒドロチオピラニル基等を挙げることができる。The 1-substituted alkoxymethyl group is usually a 1-substituted alkoxymethyl group having 2 to 20 carbon atoms, preferably a 1-substituted alkoxymethyl group having 4 to 18 carbon atoms, and a 1-substituted alkoxy group having 6 to 16 carbon atoms. More preferred are alkoxymethyl groups. For example, 1-cyclopentylmethoxymethyl group, 1-cyclopentylethoxymethyl group, 1-cyclohexylmethoxymethyl group, 1-cyclohexylethoxymethyl group, 1-cyclooctylmethoxymethyl group, 1-adamantylmethoxymethyl group and the like can be mentioned. .
The cyclic ether group is usually a cyclic ether group having 2 to 20 carbon atoms, preferably a cyclic ether group having 4 to 18 carbon atoms, and more preferably a cyclic ether group having 6 to 16 carbon atoms. Examples thereof include a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group, a 4-methoxytetrahydropyranyl group, a 4-methoxytetrahydrothiopyranyl group, and the like.
アルコキシカルボニル基としては、通常、炭素数2〜20のアルコキシカルボニル基であり、炭素数4〜18のアルコキシカルボニル基が好ましく、炭素数6〜16のアルコキシカルボニル基がさらに好ましい。例えば、メトキシカルボニル基、エトキシカルボニル基、n−プロポキシカルボニル基、イソプロポキシカルボニル基、n−ブトキシカルボニル基、tert−ブトキシカルボニル基または下記式(9)のn=0で示される酸解離性官能基等を挙げることができる。 The alkoxycarbonyl group is usually an alkoxycarbonyl group having 2 to 20 carbon atoms, preferably an alkoxycarbonyl group having 4 to 18 carbon atoms, and more preferably an alkoxycarbonyl group having 6 to 16 carbon atoms. For example, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a tert-butoxycarbonyl group, or an acid dissociable functional group represented by n = 0 in the following formula (9) Etc.
アルコキシカルボニルアルキル基としては、通常、炭素数2〜20のアルコキシカルボニルアルキル基であり、炭素数4〜18のアルコキシカルボニルアルキル基が好ましく、炭素数6〜16のアルコキシカルボニルアルキル基がさらに好ましい。例えば、メトキシカルボニルメチル基、エトキシカルボニルメチル基、n−プロポキシカルボニルメチル基、イソプロポキシカルボニルメチル基、n−ブトキシカルボニルメチル基または下記式(9)のn=1〜4で示される酸解離性官能基等を挙げることができる。 The alkoxycarbonylalkyl group is usually an alkoxycarbonylalkyl group having 2 to 20 carbon atoms, preferably an alkoxycarbonylalkyl group having 4 to 18 carbon atoms, and more preferably an alkoxycarbonylalkyl group having 6 to 16 carbon atoms. For example, a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, an n-propoxycarbonylmethyl group, an isopropoxycarbonylmethyl group, an n-butoxycarbonylmethyl group, or an acid dissociative function represented by n = 1 to 4 in the following formula (9) Groups and the like.
これらの酸解離性官能基のうち、置換メチル基、1−置換エチル基、1−置換アルコキシメチル基、環状エーテル基、アルコキシカルボニル基、およびアルコキシカルボニルアルキル基が好ましく、置換メチル基、1−置換エチル基、アルコキシカルボニル基およびアルコキシカルボニルアルキル基が高感度であるためより好ましく、さらに炭素数3〜12のシクロアルカン、ラクトンおよび炭素数6〜16の芳香族環から選ばれる構造を有する酸解離性官能基がより好ましい。炭素数3〜12のシクロアルカンとしては、単環でも多環でも良いが、多環であることがより好ましい。具体例には、モノシクロアルカン、ビシクロアルカン、トリシクロアルカン、テトラシクロアルカン等が挙げられ、より具体的には、シクロプロパン、シクロブタン、シクロペンタン、シクロヘキサン等のモノシクロアルカンや、アダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロデカン等のポリシクロアルカンが挙げられる。これらの中でも、アダマンタン、トリシクロデカン、テトラシクロデカンが好ましく、特にアダマンタン、トリシクロデカンが好ましい。炭素数3〜12のシクロアルカンは置換基を有しても良い。ラクトンとしては、ブチロラクトンまたはラクトン基を有する炭素数3〜12のシクロアルカン基が挙げられる。炭素数6〜16の芳香族環としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ピレン環等が挙げられ、ベンゼン環、ナフタレン環が好ましく、特にナフタレン環が好ましい。
特に下記式(10)で示される各基からなる群から選ばれる酸解離性官能基が、解像性が高く好ましい。Of these acid dissociable functional groups, a substituted methyl group, a 1-substituted ethyl group, a 1-substituted alkoxymethyl group, a cyclic ether group, an alkoxycarbonyl group, and an alkoxycarbonylalkyl group are preferable. An ethyl group, an alkoxycarbonyl group, and an alkoxycarbonylalkyl group are more preferable because of high sensitivity, and further have an acid dissociation property having a structure selected from a cycloalkane having 3 to 12 carbon atoms, a lactone, and an aromatic ring having 6 to 16 carbon atoms. A functional group is more preferable. The cycloalkane having 3 to 12 carbon atoms may be monocyclic or polycyclic, but is preferably polycyclic. Specific examples include monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane and the like. More specifically, monocycloalkane such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantane, norbornane, Examples include polycycloalkanes such as isobornane, tricyclodecane, and tetracyclodecane. Among these, adamantane, tricyclodecane, and tetracyclodecane are preferable, and adamantane and tricyclodecane are particularly preferable. The cycloalkane having 3 to 12 carbon atoms may have a substituent. Examples of the lactone include butyrolactone or a cycloalkane group having 3 to 12 carbon atoms having a lactone group. Examples of the aromatic ring having 6 to 16 carbon atoms include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring, and a benzene ring and a naphthalene ring are preferable, and a naphthalene ring is particularly preferable.
In particular, an acid dissociable functional group selected from the group consisting of groups represented by the following formula (10) is preferable because of its high resolution.
(式(10)中、R6Aは、水素原子または炭素数1〜4の直鎖または分岐アルキル基であり、R6は、水素原子、炭素数1〜4の直鎖または分岐アルキル基、シアノ基、ニトロ基、複素環基、ハロゲン原子、カルボキシル基であり、n1は0〜4の整数、n2は1〜5の整数、n0は0〜4の整数である。)
また酸解離性官能基R1は、本発明の効果が損なわれない限りで、下記式(11)で示される繰り返し単位と、下記式(12)またはR1(R1は上記と同様)で示される末端基からなる置換基であっても良い。(In the formula (10), R 6A is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, R 6 is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, cyano A group, a nitro group, a heterocyclic group, a halogen atom, and a carboxyl group, n 1 is an integer of 0 to 4, n 2 is an integer of 1 to 5, and n 0 is an integer of 0 to 4.)
The acid dissociable functional group R 1 is a repeating unit represented by the following formula (11) and the following formula (12) or R 1 (R 1 is the same as above) as long as the effects of the present invention are not impaired. It may be a substituent consisting of the terminal group shown.
式(11)および/または(12)において、R1は前記と同様ある。Lは前記と同様であり、好ましくは単結合、メチレン基、エチレン基またはカルボニル基である。複数個のQは、同一でも異なっていても良い。n5は0〜4の整数、n6は1〜3の整数、xは0〜3の整数であり、1≦n5+n6≦5を満たす。複数個のn5、n6、xは、同一でも異なっていても良い。R3は、ハロゲン原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルコキシ基、アリールオキシ基、アルケニル基、アシル基、アルコキシカルボニル基、アルキロイルオキシ基、アリーロイルオキシ基、シアノ基、およびニトロ基からなる群から選ばれる置換基である。ハロゲン原子としては、塩素原子、臭素原子およびヨウ素原子が挙げられ;アルキル基としてはメチル基、エチル基、プロピル基、n−プロピル基、n−ブチル基、イソブチル基、sec−ブチル基、tert−ブチル基等の炭素原子数1〜4のアルキル基が挙げられ;シクロアルキル基としてはシクロヘキシル基、ノルボルニル基、アダマンチル基等が挙げられ;アリール基としてはフェニル基、トリル基、キシリル基、ナフチル基等が挙げられ;アラルキル基としてはベンジル基、ヒドロキシベンジル基、ジヒドロキシベンジル基等が挙げられ;アルコキシ基としてはメトキシ基、エトキシ基、ヒドロキシエトキシ基、プロポキシ基、ヒドロキシプロポキシ基、イソプロポキシ基、n−ブトキシ基、イソブトキシ基、sec−ブトキシ基、tert−ブトキシ基等の炭素原子数1〜4のアルコキシ基が挙げられ;アリールオキシ基としてはフェノキシ基等が挙げられ;アルケニル基としてはビニル基、プロペニル基、アリル基、ブテニル基等の炭素原子数2〜4のアルケニル基が挙げられ;アシル基としてはホルミル基、アセチル基、プロピオニル基、ブチリル基、バレリル基、イソバレリル基、ピバロイル基等の炭素原子数1〜6の脂肪族アシル基、およびベンゾイル基、トルオイル基等の芳香族アシル基が挙げられ;アルコキシカルボニル基としてはメトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、イソプロポキシカルボニル基、n−ブトキシカルボニル基、イソブトキシカルボニル基、sec−ブトキシカルボニル基、tert−ブトキシカルボニル基等の炭素原子数2〜5のアルコキシカルボニル基が挙げられ;アルキロイルオキシ基としてはアセトキシ基、プロピオニルオキシ基、ブチリルオキシ基、イソブチリルオキシ基バレリルオキシ基、イソバレリルオキシ基、ピバロイルオキシ基等が挙げられ;アリーロイルオキシ基としてはベンゾイルオキシ基等が挙げられる。複数個のR3は、同一でも異なっていても良い。In the formula (11) and / or (12), R 1 is the same as described above. L is as defined above, and preferably a single bond, a methylene group, an ethylene group or a carbonyl group. A plurality of Q may be the same or different. n 5 is an integer of 0 to 4, n 6 is an integer of 1 to 3, x is an integer of 0 to 3, satisfying a 1 ≦ n 5 + n 6 ≦ 5. A plurality of n 5 , n 6 and x may be the same or different. R 3 is a halogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, alkenyl group, acyl group, alkoxycarbonyl group, alkyloyloxy group, aryloyloxy group, cyano group, And a substituent selected from the group consisting of nitro groups. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom; examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples thereof include alkyl groups having 1 to 4 carbon atoms such as butyl group; examples of cycloalkyl groups include cyclohexyl group, norbornyl group and adamantyl group; examples of aryl groups include phenyl group, tolyl group, xylyl group and naphthyl group. Aralkyl groups include benzyl group, hydroxybenzyl group, dihydroxybenzyl group, etc .; alkoxy groups include methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, isopropoxy group, n -Butoxy group, isobutoxy group, sec-butoxy group Examples thereof include alkoxy groups having 1 to 4 carbon atoms such as tert-butoxy group; examples of aryloxy groups include phenoxy groups; examples of alkenyl groups include carbon atoms such as vinyl, propenyl, allyl, and butenyl groups. An acyl group having 1 to 6 carbon atoms such as formyl group, acetyl group, propionyl group, butyryl group, valeryl group, isovaleryl group, pivaloyl group, and the like. And aromatic acyl groups such as benzoyl group and toluoyl group; examples of alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec- Butoxycarbonyl group, tert-butoxycar An alkoxycarbonyl group having 2 to 5 carbon atoms such as an nyl group; the alkyloyloxy group includes an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovaleryloxy group, and a pivaloyloxy group. An aryloyloxy group includes a benzoyloxy group and the like. A plurality of R 3 may be the same or different.
本発明において、酸解離性官能基とは、酸の存在下で開裂して、アルカリ可溶性基を生じる特性基をいう。アルカリ可溶性基としては、フェノール性水酸基、カルボキシル基、スルホン酸基、ヘキサフルオロイソプロパノール基などが挙げられ、フェノール性水酸基およびカルボキシル基が好ましく、フェノール性水酸基が特に好ましい。前記酸解離性官能基は、更に高感度・高解像度なパターン形成を可能にするために、酸の存在下で連鎖的に開裂反応を起こす性質を有することが好ましい。 In the present invention, the acid dissociable functional group means a characteristic group that is cleaved in the presence of an acid to generate an alkali-soluble group. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group. A phenolic hydroxyl group and a carboxyl group are preferable, and a phenolic hydroxyl group is particularly preferable. The acid-dissociable functional group preferably has a property of causing a chain-breaking reaction in the presence of an acid in order to enable pattern formation with higher sensitivity and higher resolution.
上記式(1)で示される化合物(A)は、芳香族カルボニル化合物(A11)からなる群より選ばれる1種以上,およびフェノール類(A12)を縮合反応し、その後、酸解離性官能基導入試剤を反応させて得られる。 The compound (A) represented by the above formula (1) is subjected to a condensation reaction of at least one selected from the group consisting of the aromatic carbonyl compound (A11) and a phenol (A12), and then introduced with an acid-dissociable functional group. Obtained by reacting reagents.
芳香族カルボニル化合物(A11)は、ベンズアルデヒドおよびその誘導体であり、例えば、ベンズアルデヒド、メチルベンズアルデヒド、ジメチルベンズアルデヒド、エチルベンズアルデヒド、プロピルベンズアルデヒド、ブチルベンズアルデヒド、エチルメチルベンズアルデヒド、イソプロピルメチルベンズアルデヒド、ジエチルベンズアルデヒド、アニスアルデヒド、ナフトアルデヒド、アントラアルデヒド、シクロプロピルベンズアルデヒド、シクロブタンベンズアルデヒド、シクロペンタンベンズアルデヒド、シクロヘキサンベンズアルデヒド、フェニルベンズアルデヒド、ナフチルベンズアルデヒド、アダマンチルベンズアルデヒド、ノルボルニルベンズアルデヒド、ラクチルベンズアルデヒド、イソプロピルベンズアルデヒド、ノルマルプロピルベンズアルデヒド、ブロモベンズアルデヒド、ジメチルアミノベンズアルデヒド、シクロプロピルベンズアルデヒド、シクロブタンベンズアルデヒド、シクロペンタンベンズアルデヒド、シクロヘキサンベンズアルデヒド、フェニルベンズアルデヒド、ナフチルベンズアルデヒド、アダマンチルベンズアルデヒド、ノルボルニルベンズアルデヒド、ラクチルベンズアルデヒド、ヒドロキシベンズアルデヒドおよびジヒドロキシベンズアルデヒド等が挙げられ、プロピルベンズアルデヒド、ブチルベンズアルデヒド、ヒドロキシベンズアルデヒド、シクロヘキシルベンズアルデヒド、フェニルベンズアルデヒドが好ましく、プロピルベンズアルデヒド、ブチルベンズアルデヒド、シクロヘキシルベンズアルデヒドおよびフェニルベンズアルデヒドがより好ましく、プロピルベンズアルデヒドおよびシクロヘキシルベンズアルデヒドがさらに好ましい。芳香族カルボニル化合物(A11)は本発明の効果を損ねない範囲で炭素数1〜4の直鎖または分岐アルキル基、シアノ基、水酸基、ハロゲン原子等を有していても良い。芳香族カルボニル化合物(A11)は、単独でまたは二種以上組み合わせて使用してもよい。 The aromatic carbonyl compound (A11) is benzaldehyde and derivatives thereof, such as benzaldehyde, methylbenzaldehyde, dimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, ethylmethylbenzaldehyde, isopropylmethylbenzaldehyde, diethylbenzaldehyde, anisaldehyde, naphthoaldehyde. Aldehyde, anthraldehyde, cyclopropylbenzaldehyde, cyclobutanebenzaldehyde, cyclopentanebenzaldehyde, cyclohexanebenzaldehyde, phenylbenzaldehyde, naphthylbenzaldehyde, adamantylbenzaldehyde, norbornylbenzaldehyde, lactylbenzaldehyde, isopropylbenzaldehyde N-propylbenzaldehyde, bromobenzaldehyde, dimethylaminobenzaldehyde, cyclopropylbenzaldehyde, cyclobutanebenzaldehyde, cyclopentanebenzaldehyde, cyclohexanebenzaldehyde, phenylbenzaldehyde, naphthylbenzaldehyde, adamantylbenzaldehyde, norbornylbenzaldehyde, lactylbenzaldehyde, hydroxybenzaldehyde and dihydroxybenzaldehyde And propyl benzaldehyde, butyl benzaldehyde, hydroxy benzaldehyde, cyclohexyl benzaldehyde, and phenyl benzaldehyde are preferable, and propyl benzaldehyde, butyl benzaldehyde, cyclohexyl benzaldehyde and More preferably Le benzaldehyde, more preferably propyl benzaldehyde and cyclohexyl benzaldehyde. The aromatic carbonyl compound (A11) may have a linear or branched alkyl group having 1 to 4 carbon atoms, a cyano group, a hydroxyl group, a halogen atom or the like as long as the effects of the present invention are not impaired. The aromatic carbonyl compound (A11) may be used alone or in combination of two or more.
フェノール類(A12)は、後述する置換基を有していても良いフェノール、カテコール、レゾルシノール、ハイドロキノン、ピロガロール等が挙げられ、4−置換フェノール、レゾルシノール、ピロガロールが好ましく、レゾルシノール、ピロガロールがより好ましく、レゾルシノールが更に好ましい。フェノール類(A12)は本発明の効果を損ねない範囲で炭素数1〜20の直鎖または分岐アルキル基、炭素数1〜20の環状アルキル基、炭素数6〜20のアリール基、シアノ基、水酸基、ハロゲン原子等を有していても良い。フェノール類(A12)は、単独でまたは二種以上組み合わせて使用してもよい。 Phenols (A12) include phenol, catechol, resorcinol, hydroquinone, pyrogallol and the like, which may have a substituent described later, 4-substituted phenol, resorcinol, pyrogallol are preferred, resorcinol, pyrogallol are more preferred, Resorcinol is more preferred. Phenols (A12) are linear or branched alkyl groups having 1 to 20 carbon atoms, cyclic alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, cyano groups, and the like within a range not impairing the effects of the present invention. It may have a hydroxyl group, a halogen atom or the like. The phenols (A12) may be used alone or in combination of two or more.
上記式(1B)で示される化合物は、公知の方法によって製造できる。例えば、メタノール、エタノール等の有機溶媒中、芳香族カルボニル化合物(A11)1モルに対し、フェノール類(A12)を0.1〜10モル量、酸触媒(塩酸、硫酸またはパラトルエンスルホン酸等)を使用し、60〜150℃で0.5〜20時間程度反応させ、濾過後、メタノール等のアルコール類で洗浄後、水洗し、濾過を行い分離し、乾燥させることにより得られる。酸触媒の代わりに、塩基性触媒(水酸化ナトリウム、水酸化バリウムまたは1,8−ジアザビシクロ[5.4.0]ウンデセン−7等)を使用し、同様に反応することによっても得られる。さらに上記式(1B)で示される化合物は、上記芳香族カルボニル化合物(A11)をハロゲン化水素若しくはハロゲンガスでジハロゲン化物とし、単離したジハロゲン化物とフェノール類(A12)を反応させて製造することも出来る。 The compound represented by the above formula (1B) can be produced by a known method. For example, in an organic solvent such as methanol or ethanol, 0.1 to 10 moles of phenols (A12) and acid catalyst (hydrochloric acid, sulfuric acid, paratoluenesulfonic acid, etc.) per 1 mole of aromatic carbonyl compound (A11) It is obtained by reacting at 60 to 150 ° C. for about 0.5 to 20 hours, filtering, washing with an alcohol such as methanol, washing with water, filtering, separating and drying. Instead of the acid catalyst, a basic catalyst (such as sodium hydroxide, barium hydroxide or 1,8-diazabicyclo [5.4.0] undecene-7) may be used and reacted in the same manner. Further, the compound represented by the formula (1B) is produced by converting the aromatic carbonyl compound (A11) into a dihalide with hydrogen halide or a halogen gas, and reacting the isolated dihalide with a phenol (A12). You can also.
化合物(A)は、化合物(B)の少なくとも1つのフェノール性水酸基またはカルボキシル基に酸解離性官能基を導入することで得られる。化合物(B)の少なくとも1つのフェノール性水酸基またはカルボキシル基に酸解離性官能基を導入する方法は公知である。例えば以下のようにして、化合物(B)の少なくとも1つのフェノール性水酸基またはカルボキシル基に酸解離性官能基を導入することができる。酸解離性官能基を導入するための化合物(酸解離性官能基導入試剤)は、公知の方法で合成もしくは容易に入手でき、例えば、酸クロライド、酸無水物、ジカーボネートなどの活性カルボン酸誘導体化合物、アルキルハライド、ビニルアルキルエーテル、ジヒドロピラン、ハロカルボン酸アルキルエステルなどが挙げられるが特に限定はされない。 Compound (A) can be obtained by introducing an acid dissociable functional group into at least one phenolic hydroxyl group or carboxyl group of compound (B). A method for introducing an acid-dissociable functional group into at least one phenolic hydroxyl group or carboxyl group of the compound (B) is known. For example, an acid dissociable functional group can be introduced into at least one phenolic hydroxyl group or carboxyl group of the compound (B) as follows. A compound for introducing an acid-dissociable functional group (acid-dissociable functional group-introducing reagent) can be synthesized or easily obtained by a known method. For example, an active carboxylic acid derivative such as acid chloride, acid anhydride, dicarbonate, etc. Compounds, alkyl halides, vinyl alkyl ethers, dihydropyrans, halocarboxylic acid alkyl esters and the like can be mentioned but are not particularly limited.
例えば、アセトン、テトラヒドロフラン(THF)、プロピレングリコールモノメチルエーテルアセテート等の非プロトン性溶媒に化合物(B)を溶解または懸濁させる。続いて、エチルビニルエーテル等のビニルアルキルエーテルまたはジヒドロピランを加え、ピリジニウム p−トルエンスルホナート等の酸触媒の存在下、常圧で、20〜60℃、6〜72時間反応させる。反応液をアルカリ化合物で中和し、蒸留水に加え白色固体を析出させた後、分離した白色固体を蒸留水で洗浄し、乾燥することにより化合物(A)を得ることができる。 For example, the compound (B) is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like. Subsequently, a vinyl alkyl ether such as ethyl vinyl ether or dihydropyran is added, and the reaction is carried out at 20 to 60 ° C. for 6 to 72 hours at atmospheric pressure in the presence of an acid catalyst such as pyridinium p-toluenesulfonate. The reaction solution is neutralized with an alkali compound and added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and dried to obtain compound (A).
また、アセトン、THF、プロピレングリコールモノメチルエーテルアセテート等の非プロトン性溶媒に化合物(B)を溶解または懸濁させる。続いて、エチルクロロメチルエーテル等のアルキルハライドまたはブロモ酢酸メチルアダマンチル等のハロカルボン酸アルキルエステルを加え、炭酸カリウム等のアルカリ触媒の存在下、常圧で、20〜110℃、6〜72時間反応させる。反応液を塩酸等の酸で中和し、蒸留水に加え白色固体を析出させた後、分離した白色固体を蒸留水で洗浄し、乾燥することにより化合物(A)を得ることができる。 Further, the compound (B) is dissolved or suspended in an aprotic solvent such as acetone, THF, propylene glycol monomethyl ether acetate or the like. Subsequently, an alkyl halide such as ethyl chloromethyl ether or a halocarboxylic acid alkyl ester such as methyl adamantyl bromoacetate is added, and the reaction is carried out in the presence of an alkali catalyst such as potassium carbonate at 20 to 110 ° C. for 6 to 72 hours. . The reaction solution is neutralized with an acid such as hydrochloric acid and added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and dried to obtain compound (A).
2種以上の芳香族カルボニル化合物(A11)を用いることがより好ましい。2種以上の芳香族カルボニル化合物(A11)を用いることにより、得られる環状化合物の半導体安全溶媒に対する溶解性が向上する。 It is more preferable to use two or more aromatic carbonyl compounds (A11). By using two or more aromatic carbonyl compounds (A11), the solubility of the resulting cyclic compound in a semiconductor safety solvent is improved.
上記式(1A)で示される化合物の分子量は990〜2900であり、好ましくは1040〜2650、より好ましくは1080〜2400、さらに好ましくは1150〜2200である。上記式(1B)で示される化合物の分子量は790〜2000であり、好ましくは840〜1750、より好ましくは880〜1500、さらに好ましくは950〜1300である。上記範囲であるとレジスト材料に必要な製膜性を保持しつつ、耐熱性を有することができる。 The molecular weight of the compound represented by the formula (1A) is 990 to 2900, preferably 1040 to 2650, more preferably 1080 to 2400, and further preferably 1150 to 2200. The molecular weight of the compound represented by the formula (1B) is 790 to 2000, preferably 840 to 1750, more preferably 880 to 1500, and further preferably 950 to 1300. Within the above range, it is possible to have heat resistance while maintaining the film forming property required for the resist material.
上記式(1A)で表される化合物(A)としては、好ましくは下記式(2A)で示される化合物があげられる。
上記式(1A)で表される化合物(A)としては、より好ましくは下記式(3A)で示される化合物があげられる。
上記式(1A)で表される化合物(A)としては、さらに好ましくは下記式(4A)で示される化合物があげられる。
上記式(1A)で表される化合物(A)としては、特に好ましくは下記式(5A)で示される化合物があげられる。
上記式(1B)で表される化合物(B)としては、好ましくは下記式(2B)で示される化合物があげられる。
上記式(1B)で表される化合物(B)としては、より好ましくは下記式(3B)で示される化合物があげられる。
上記式(1B)で表される化合物(B)としては、さらに好ましくは下記式(4B)で示される化合物があげられる。
上記式(1B)で表される化合物(B)としては、特に好ましくは下記式(5B)で示される化合物があげられる。
上記化合物(A)は耐熱性が高く、アモルファス性を有するため製膜性にも優れ、昇華性を持たず、アルカリ現像液溶解抑止性、エッチング耐性等に優れ、レジスト材料、特にレジスト材料の主成分(基材)として好適に用いられる。
また、製造面においても工業的に製造されている芳香族アルデヒドをはじめとする各種アルデヒド類とレゾルシノール、ピロガロール等のフェノール類を原料として、塩酸等の非金属触媒により脱水縮合反応させ、その後、工業的に製造されている酸解離性官能基導入試剤を、塩酸やアミン類等の非金属触媒により反応させることにより、高収率で製造できることから、実用性にも極めて優れる。The compound (A) has high heat resistance and is amorphous so that it is excellent in film-forming properties, does not have sublimation properties, is excellent in alkali developer dissolution deterrence, etching resistance, and the like. It is suitably used as a component (base material).
Also, in terms of production, various aldehydes including industrially produced aromatic aldehydes and phenols such as resorcinol and pyrogallol are used as raw materials to undergo a dehydration condensation reaction with a nonmetallic catalyst such as hydrochloric acid, and then industrial Since the acid-dissociable functional group-introducing reagent that has been produced in general is reacted with a nonmetallic catalyst such as hydrochloric acid or amines, it can be produced in a high yield, so that it is extremely excellent in practicality.
上記化合物(B)は耐熱性が高く、アモルファス性を有するため製膜性にも優れ、昇華性を持たず、アルカリ現像液溶解性、エッチング耐性等に優れ、レジスト材料、特にレジスト材料の主成分(基材)として好適に用いられる。
また、製造面においても工業的に製造されている芳香族アルデヒドをはじめとする各種アルデヒド類とレゾルシノール、ピロガロール等のフェノール類を原料として、塩酸等の非金属触媒により脱水縮合反応させることにより、高収率で製造できることから、実用性にも極めて優れる。The compound (B) has high heat resistance and is amorphous so that it has excellent film-forming properties, no sublimation, excellent alkali developer solubility, etching resistance, and the like. It is suitably used as (base material).
Also, in terms of production, various aldehydes including industrially produced aromatic aldehydes and phenols such as resorcinol and pyrogallol are used as raw materials to cause a dehydration condensation reaction with a nonmetallic catalyst such as hydrochloric acid. Since it can be produced in a yield, it is extremely excellent in practicality.
化合物(A)または化合物(B)の残存金属量を低減するために、必要に応じて精製してもよい。また酸触媒が残存すると、一般に、ポジ型感放射線性組成物の保存安定性が低下する、または塩基性触媒が残存すると、一般に、ポジ型感放射線性組成物の感度が低下するので、その低減を目的とした精製を行ってもよい。精製は、化合物(A)または化合物(B)が変性しない限り公知の方法により行うことができ、特に限定されないが、例えば、水で洗浄する方法、酸性水溶液で洗浄する方法、塩基性水溶液で洗浄する方法、イオン交換樹脂で処理する方法、シリカゲルカラムクロマトグラフィーで処理する方法などが挙げられる。これら精製方法は2種以上を組み合わせて行うことがより好ましい。酸性水溶液、塩基性水溶液、イオン交換樹脂およびシリカゲルカラムクロマトグラフィーは、除去すべき金属、酸性化合物および/または塩基性化合物の量や種類、精製する溶解抑止剤の種類などに応じて、最適なものを適宜選択することが可能である。例えば、酸性水溶液として、濃度が0.01〜10mol/Lの塩酸、硝酸、酢酸水溶液、塩基性水溶液として、濃度が0.01〜10mol/Lのアンモニア水溶液、イオン交換樹脂として、カチオン交換樹脂、例えばオルガノ製Amberlyst 15J−HG Dryなどが挙げられる。精製後に乾燥を行っても良い。乾燥は公知の方法により行うことができ、特に限定されないが、化合物(A)または化合物(B)が変性しない条件で真空乾燥、熱風乾燥する方法などが挙げられる。 You may refine | purify as needed in order to reduce the residual metal amount of a compound (A) or a compound (B). Further, when the acid catalyst remains, generally the storage stability of the positive radiation sensitive composition is lowered, or when the basic catalyst remains, generally the sensitivity of the positive radiation sensitive composition is lowered. Purification for the purpose may be performed. The purification can be performed by a known method as long as the compound (A) or the compound (B) is not denatured, and is not particularly limited. For example, the method is washed with water, washed with an acidic aqueous solution, washed with a basic aqueous solution. A method of treating with an ion exchange resin, a method of treating with silica gel column chromatography, and the like. These purification methods are more preferably performed in combination of two or more. Acidic aqueous solution, basic aqueous solution, ion exchange resin, and silica gel column chromatography are optimal depending on the metal to be removed, the amount and type of acidic compound and / or basic compound, the type of dissolution inhibitor to be purified, etc. Can be selected as appropriate. For example, as acidic aqueous solution, hydrochloric acid, nitric acid, acetic acid aqueous solution having a concentration of 0.01 to 10 mol / L, aqueous ammonia solution having a concentration of 0.01 to 10 mol / L as basic aqueous solution, cation exchange resin as ion exchange resin, For example, Amberlyst 15J-HG Dry made by Organo can be mentioned. You may dry after refinement | purification. Drying can be performed by a known method, and is not particularly limited, and examples thereof include a method of vacuum drying and hot air drying under conditions where the compound (A) or the compound (B) is not denatured.
本発明における化合物(A)および化合物(B)は、シス体およびトランス体を取りうるが、いずれかの構造若しくは混合物でもよい。感放射線性組成物のレジスト成分として用いる場合は、シス体およびトランス体のいずれかの構造のみを有する方が、純物質化合物となり、レジスト膜中成分の均一性が高いので好ましい。シス体およびトランス体のいずれかの構造のみを有する環状化合物を得る方法は、カラムクロマトや分取液体クロマトグラフィによる分離や製造時における反応溶媒および反応温度等の最適化等、公知の方法で行うことができる。 The compound (A) and the compound (B) in the present invention can take a cis isomer and a trans isomer, but may have any structure or mixture. When used as a resist component of a radiation-sensitive composition, it is preferable to have only a cis- or trans-structure because it is a pure substance compound and the uniformity of the components in the resist film is high. A method for obtaining a cyclic compound having only a cis- or trans-structure is performed by a known method such as separation by column chromatography or preparative liquid chromatography or optimization of a reaction solvent and reaction temperature during production. Can do.
本発明における化合物(A)および化合物(B)のガラス転移温度は、好ましくは100℃以上、より好ましくは120℃以上、さらに好ましくは140℃以上、特に好ましくは150℃以上である。ガラス転移温度が上記範囲内であることにより、半導体リソグラフィープロセスにおいて、パターン形状を維持しうる耐熱性を有し、高解像度などの性能が付与しうる。
本発明における化合物(A)および化合物(B)のガラス転移温度の示差走査熱量分析により求めた結晶化発熱量は20J/g未満であるのが好ましい。また、(結晶化温度)−(ガラス転移温度)は好ましくは70℃以上、より好ましくは80℃以上、さらに好ましくは100℃以上、特に好ましくは130℃以上である。結晶化発熱量が20J/g未満、または(結晶化温度)−(ガラス転移温度)が上記範囲内であると、感放射線性組成物をスピンコートすることにより、アモルファス膜を形成しやすく、かつレジストに必要な成膜性が長期に渡り保持でき、解像性を向上することができる。The glass transition temperature of the compound (A) and the compound (B) in the present invention is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher. When the glass transition temperature is within the above range, the semiconductor lithography process has heat resistance capable of maintaining the pattern shape and can provide performance such as high resolution.
In the present invention, the calorific value of crystallization determined by differential scanning calorimetry of the glass transition temperatures of the compound (A) and the compound (B) in the present invention is preferably less than 20 J / g. Further, (crystallization temperature) − (glass transition temperature) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, further preferably 100 ° C. or higher, and particularly preferably 130 ° C. or higher. When the crystallization heat generation amount is less than 20 J / g, or (crystallization temperature) − (glass transition temperature) is within the above range, an amorphous film can be easily formed by spin-coating the radiation-sensitive composition, and The film formability required for the resist can be maintained for a long time, and the resolution can be improved.
本発明において、前記結晶化発熱量、結晶化温度およびガラス転移温度は、島津製作所製DSC/TA−50WSを用いて次のように測定および示差走査熱量分析により求めることができる。試料約10mgをアルミニウム製非密封容器に入れ、窒素ガス気流中(50ml/min)昇温速度20℃/minで融点以上まで昇温する。急冷後、再び窒素ガス気流中(30ml/min)昇温速度20℃/minで融点以上まで昇温する。さらに急冷後、再び窒素ガス気流中(30ml/min)昇温速度20℃/minで400℃まで昇温する。ベースラインに不連続部分が現れる領域の中点(比熱が半分に変化したところ)の温度をガラス転移温度(Tg)、その後に現れる発熱ピークの温度を結晶化温度とする。発熱ピークとベースラインに囲まれた領域の面積から発熱量を求め、結晶化発熱量とする。 In the present invention, the crystallization calorific value, crystallization temperature and glass transition temperature can be determined by measurement and differential scanning calorimetry as follows using DSC / TA-50WS manufactured by Shimadzu Corporation. About 10 mg of a sample is put in an aluminum non-sealed container and heated to a melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (50 ml / min). After the rapid cooling, the temperature is again raised to the melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (30 ml / min). Further, after rapid cooling, the temperature is increased again to 400 ° C. at a rate of temperature increase of 20 ° C./min in a nitrogen gas stream (30 ml / min). The temperature at the midpoint where the discontinuity appears in the baseline (where the specific heat has changed to half) is the glass transition temperature (Tg), and the temperature of the exothermic peak that appears thereafter is the crystallization temperature. The calorific value is obtained from the area of the region surrounded by the exothermic peak and the baseline, and is defined as the crystallization calorific value.
化合物(A)および化合物(B)は、常圧下、100℃以下、好ましくは120℃以下、より好ましくは130℃以下、さらに好ましくは140℃以下、特に好ましくは150℃以下において、昇華性が低いことが好ましい。昇華性が低いとは、熱重量分析において、所定温度で10分保持した際の重量減少が10%、好ましくは5%、より好ましくは3%、さらに好ましくは1%、特に好ましくは0.1%以下であることが好ましい。昇華性が低いことにより、露光時のアウトガスによる露光装置の汚染を防止することができる。また低LERで良好なパターン形状を与えることができる。 Compound (A) and Compound (B) have low sublimation properties under normal pressure at 100 ° C. or lower, preferably 120 ° C. or lower, more preferably 130 ° C. or lower, further preferably 140 ° C. or lower, particularly preferably 150 ° C. or lower. It is preferable. The low sublimation property means that, in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10%, preferably 5%, more preferably 3%, still more preferably 1%, particularly preferably 0.1. % Or less is preferable. Since the sublimation property is low, it is possible to prevent exposure apparatus from being contaminated by outgas during exposure. Moreover, a favorable pattern shape can be given with low LER.
化合物(A)および化合物(B)は、好ましくはF<3.0(Fは、全原子数/(全炭素原子数−全酸素原子数)を表す)、より好ましくはF<2.5を満たす。上記条件を満たしていることにより、耐ドライエッチング性が優れる。 Compound (A) and Compound (B) are preferably F <3.0 (F represents the total number of atoms / (total number of carbon atoms−total number of oxygen atoms)), more preferably F <2.5. Fulfill. By satisfying the above conditions, the dry etching resistance is excellent.
化合物(A)および化合物(B)は、プロピレングリコールモノメチルエーテルアセテート(PGMEA)、プロピレングリコールモノメチルエーテル(PGME)、シクロヘキサノン(CHN)、シクロペンタノン(CPN)、2−ヘプタノン、アニソール、酢酸ブチル、プロピオン酸エチル、および乳酸エチルから選ばれ、かつ、化合物(A)および化合物(B)に対して最も高い溶解能を示す溶媒に、23℃で、好ましくは1重量%以上、より好ましくは5重量%以上、さらに好ましくは10重量%以上、特に好ましくは、PGMEA、PGME、CHNから選ばれ、かつ、化合物(A)および化合物(B)に対して最も高い溶解能を示す溶媒に、23℃で、20重量%以上溶解する。上記条件を満たしていることにより、実生産における半導体製造工程での使用が可能となり、保存安定性も良好となる。 Compound (A) and Compound (B) are propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-heptanone, anisole, butyl acetate, propion A solvent selected from ethyl acid and ethyl lactate and having the highest solubility in compound (A) and compound (B) at 23 ° C., preferably 1% by weight or more, more preferably 5% by weight Or more, more preferably 10% by weight or more, particularly preferably a solvent selected from PGMEA, PGME, and CHN and having the highest solubility in the compound (A) and the compound (B) at 23 ° C., Dissolves 20% by weight or more. By satisfying the above conditions, use in a semiconductor manufacturing process in actual production is possible, and storage stability is also improved.
本発明の効果を損ねない範囲で、化合物(B)の少なくとも1つのフェノール性水酸基および/またはカルボキシル基に非酸解離性官能基を導入しても良い。非酸解離性官能基とは、酸の存在下で開裂せず、アルカリ可溶性基を生じない特性基をいう。例えば、酸の作用により分解することの無い、C1〜20のアルキル基、C3〜20のシクロアルキル基、C6〜20のアリール基、C1〜20のアルコキシル基、シアノ基、ニトロ基、水酸基、複素環基、ハロゲン原子、カルボキシル基、C1〜20のアルキルシリル基、これらの誘導体からなる群から選択される官能基等が挙げられる。 A non-acid-dissociable functional group may be introduced into at least one phenolic hydroxyl group and / or carboxyl group of the compound (B) within a range not impairing the effects of the present invention. The non-acid-dissociable functional group refers to a characteristic group that does not cleave in the presence of an acid and does not generate an alkali-soluble group. For example, C1-20 alkyl group, C3-20 cycloalkyl group, C6-20 aryl group, C1-20 alkoxyl group, cyano group, nitro group, hydroxyl group, Examples thereof include a cyclic group, a halogen atom, a carboxyl group, a C1-20 alkylsilyl group, and a functional group selected from the group consisting of these derivatives.
上記化合物(A)および化合物(B)は、スピンコートによりアモルファス膜を形成することができる。また一般的な半導体製造プロセスに適用することができる。 The compound (A) and the compound (B) can form an amorphous film by spin coating. Further, it can be applied to a general semiconductor manufacturing process.
本発明のポジ型感放射線性組成物は、スピンコートによりアモルファス膜を形成することができる。本発明のポジ型感放射線性組成物をスピンコートして形成したアモルファス膜の23℃における2.38質量%TMAH水溶液に対する溶解速度は、5Å/sec以下が好ましく、0.05〜5Å/secがより好ましく、0.0005〜5Å/secがさらに好ましい。溶解速度が5Å/sec以下であるとアルカリ現像液に不溶で、レジストとすることができる。またアモルファス膜が0.0005Å/sec以上の溶解速度を有すると、解像性が向上する場合もある。これは、環状化合物の露光前後の溶解性の変化により、アルカリ現像液に溶解する未露光部と、アルカリ現像液に溶解しない露光部との界面のコントラストが大きくなるからと推測される。またLERの低減、ディフェクトの低減効果がある。 The positive radiation sensitive composition of the present invention can form an amorphous film by spin coating. The dissolution rate of the amorphous film formed by spin-coating the positive radiation-sensitive composition of the present invention in a 2.38 mass% TMAH aqueous solution at 23 ° C. is preferably 5 Å / sec or less, and 0.05 to 5 Å / sec. More preferably, 0.0005-5 g / sec is still more preferable. When the dissolution rate is 5 Å / sec or less, it is insoluble in an alkali developer and can be used as a resist. In addition, when the amorphous film has a dissolution rate of 0.0005 K / sec or more, resolution may be improved. This is presumed to be due to the increase in the contrast of the interface between the unexposed portion dissolved in the alkali developer and the exposed portion not dissolved in the alkali developer due to the change in solubility of the cyclic compound before and after exposure. Further, there is an effect of reducing LER and reducing defects.
本発明のポジ型感放射線性組成物の固形成分をスピンコートして形成したアモルファス膜のKrFエキシマレーザー、極端紫外線、電子線またはX線等の放射線により露光した部分の23℃における2.38質量%TMAH水溶液に対する溶解速度は、10Å/sec以上が好ましく、10〜10000Å/secがより好ましく、100〜1000Å/secがさらに好ましい。溶解速度が10Å/sec以上であると、アルカリ現像液に溶解し、レジストとすることができる。また露光した部分が10000Å/sec以下の溶解速度を有すると、解像性が向上する場合もある。これは、前記環状化合物のミクロの表面部位が溶解し、LERを低減するからと推測される。またディフェクトの低減効果がある。 2.38 mass at 23 ° C. of a portion exposed by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray of an amorphous film formed by spin-coating the solid component of the positive radiation-sensitive composition of the present invention. The dissolution rate in the% TMAH aqueous solution is preferably 10 が / sec or more, more preferably 10 to 10000 Å / sec, and still more preferably 100 to 1000 Å / sec. When the dissolution rate is 10 Å / sec or more, it can be dissolved in an alkali developer to form a resist. In addition, when the exposed portion has a dissolution rate of 10000 kg / sec or less, resolution may be improved. This is presumed to be because the micro surface portion of the cyclic compound is dissolved and LER is reduced. There is also an effect of reducing defects.
本発明のポジ型感放射線性組成物は、固形成分1〜80重量%および溶媒20〜99重量%からなる。好ましくは固形成分1〜50重量%および溶媒50〜99重量%、さらに好ましくは固形成分2〜40重量%および溶媒60〜98重量%であり、特に好ましくは固形成分2〜10重量%および溶媒90〜98重量%である。
前記化合物(A)の重量と化合物(B)の重量との和は、固形成分全重量の50〜99重量%であり、好ましくは65〜80重量%、より好ましくは60〜70重量%である。上記配合割合であると、高解像度が得られ、ラインエッジラフネスが小さくなる。The positive radiation sensitive composition of the present invention comprises 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent. The solid components are preferably 1 to 50% by weight and the solvent 50 to 99% by weight, more preferably 2 to 40% by weight of the solid component and 60 to 98% by weight of the solvent, and particularly preferably 2 to 10% by weight of the solid component and the solvent 90. ~ 98 wt%.
The sum of the weight of the compound (A) and the weight of the compound (B) is 50 to 99% by weight, preferably 65 to 80% by weight, more preferably 60 to 70% by weight of the total weight of the solid component. . When the blending ratio is as described above, high resolution is obtained and the line edge roughness is reduced.
前記酸発生剤(C)としては、下記式(7−1)〜(7−8)で表される化合物からなる群から選択される少なくとも一種類であることが好ましい。
前記式(7−1)で示される化合物は、トリフェニルスルホニウムトリフルオロメタンスルホネート、トリフェニルスルホニウムノナフルオロ−n−ブタンスルホネート、ジフェニルトリルスルホニウムノナフルオロ−n−ブタンスルホネート、トリフェニルスルホニウムパーフルオロ−n−オクタンスルホネート、ジフェニル−4−メチルフェニルスルホニウムトリフルオロメタンスルホネート、ジ−2,4,6−トリメチルフェニルスルホニウムトリフルオロメタンスルホネート、ジフェニル−4−t−ブトキシフェニルスルホニウムトリフルオロメタンスルホネート、ジフェニル−4−t−ブトキシフェニルスルホニウムノナフルオロ−n−ブタンスルホネート、ジフェニル−4−ヒドロキシフェニルスルホニウムトリフルオロメタンスルホネート、ビス(4−フルオロフェニル)−4−ヒドロキシフェニルスルホニウムトリフルオロメタンスルホネート、ジフェニル−4−ヒドロキシフェニルスルホニウムノナフルオロ−n−ブタンスルホネート、ビス(4−ヒドロキシフェニル)−フェニルスルホニウムトリフルオロメタンスルホネート、トリ(4−メトキシフェニル)スルホニウムトリフルオロメタンスルホネート、トリ(4−フルオロフェニル)スルホニウムトリフルオロメタンスルホネート、トリフェニルスルホニウムp−トルエンスルホネート、トリフェニルスルホニウムベンゼンスルホネート、ジフェニル−2,4,6−トリメチルフェニル−p−トルエンスルホネート、ジフェニル−2,4,6−トリメチルフェニルスルホニウム−2−トリフルオロメチルベンゼンスルホネート、ジフェニル−2,4,6−トリメチルフェニルスルホニウム−4−トリフルオロメチルベンゼンスルホネート、ジフェニル−2,4,6−トリメチルフェニルスルホニウム−2,4−ジフルオロベンゼンスルホネート、ジフェニル−2,4,6−トリメチルフェニルスルホニウムヘキサフルオロベンゼンスルホネート、ジフェニルナフチルスルホニウムトリフルオロメタンスルホネート、ジフェニル−4−ヒドロキシフェニルスルホニウム−p−トルエンスルホネート、トリフェニルスルホニウム10−カンファースルホネート、ジフェニル−4−ヒドロキシフェニルスルホニウム10−カンファースルホネートおよびシクロ(1,3−パーフルオロプロパンジスルホン)イミデートからなる群から選択される少なくとも1種類であることが好ましい。 The compound represented by the formula (7-1) includes triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, diphenyltolylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-. Octanesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, di-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenyl Sulfonium nonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethanes Phonate, bis (4-fluorophenyl) -4-hydroxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, tri ( 4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (4-fluorophenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, diphenyl-2,4,6-trimethylphenyl-p-toluene Sulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2-trifluoromethylben Zensulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-4-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6 -Trimethylphenylsulfonium hexafluorobenzenesulfonate, diphenylnaphthylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate and cyclo (1,3-perfluoropropanedisulfone) at least selected from the group consisting of imidates It is preferable that the type.
前記式(7−2)で示される化合物は、ビス(4−t−ブチルフェニル)ヨードニウムトリフルオロメタンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウムノナフルオロ−n−ブタンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウムパーフルオロ−n−オクタンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウム p−トルエンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウムベンゼンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウム−2−トリフルオロメチルベンゼンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウム−4−トリフルオロメチルベンゼンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウム−2,4−ジフルオロベンゼンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウムヘキサフルオロベンゼンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウム10−カンファースルホネート、ジフェニルヨードニウムトリフルオロメタンスルホネート、ジフェニルヨードニウムノナフルオロ−n−ブタンスルホネート、ジフェニルヨードニウムパーフルオロ−n−オクタンスルホネート、ジフェニルヨードニウム p−トルエンスルホネート、ジフェニルヨードニウムベンゼンスルホネート、ジフェニルヨードニウム10−カンファースルホネート、ジフェニルヨードニウム−2−トリフルオロメチルベンゼンスルホネート、ジフェニルヨードニウム−4−トリフルオロメチルベンゼンスルホネート、ジフェニルヨードニウム−2,4−ジフルオロベンゼンスルホネート、ジフェニルヨードニウムへキサフルオロベンゼンスルホネート、ジ(4−トリフルオロメチルフェニル)ヨードニウムトリフルオロメタンスルホネート、ジ(4−トリフルオロメチルフェニル)ヨードニウムノナフルオロ−n−ブタンスルホネート、ジ(4−トリフルオロメチルフェニル)ヨードニウムパーフルオロ−n−オクタンスルホネート、ジ(4−トリフルオロメチルフェニル)ヨードニウム p−トルエンスルホネート、ジ(4−トリフルオロメチルフェニル)ヨードニウムベンゼンスルホネートおよびジ(4−トリフルオロメチルフェニル)ヨードニウム10−カンファースルホネートからなる群から選択される少なくとも一種類であることが好ましい。 The compound represented by the formula (7-2) includes bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t -Butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodoniumbenzenesulfonate, bis (4-t-butylphenyl) Iodonium-2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-2,4-difluorobenzenesulfonate, bis ( 4-t Butylphenyl) iodonium hexafluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, Diphenyliodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium10-camphorsulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-4-trifluoromethylbenzenesulfonate, diphenyliodonium-2,4-difluorobenzene Sulfonate, diphenyl Iodonium hexafluorobenzenesulfonate, di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, di (4-trifluoromethylphenyl) iodonium per From fluoro-n-octanesulfonate, di (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, di (4-trifluoromethylphenyl) iodoniumbenzenesulfonate and di (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate Preferably, at least one selected from the group consisting of:
前記式(7−3)で示される化合物は、N−(トリフルオロメチルスルホニルオキシ)スクシンイミド、N−(トリフルオロメチルスルホニルオキシ)フタルイミド、N−(トリフルオロメチルスルホニルオキシ)ジフェニルマレイミド、N−(トリフルオロメチルスルホニルオキシ)ビシクロ[2.2.1]へプト−5−エン−2,3−ジカルボキシイミド、N−(トリフルオロメチルスルホニルオキシ)ナフチルイミド、N−(10−カンファースルホニルオキシ)スクシンイミド、N−(10−カンファースルホニルオキシ)フタルイミド、N−(10−カンファースルホニルオキシ)ジフェニルマレイミド、N−(10−カンファースルホニルオキシ)ビシクロ[2.2.1]へプト−5−エン−2,3−ジカルボキシイミド、N−(10−カンファースルホニルオキシ)ナフチルイミド、N−(n−オクタンスルホニルオキシ)ビシクロ[2.2.1]へプト−5−エン−2,3−ジカルボキシイミド、N−(n−オクタンスルホニルオキシ)ナフチルイミド、N−(p−トルエンスルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド、N−(p−トルエンスルホニルオキシ)ナフチルイミド、N−(2−トリフルオロメチルベンゼンスルホニルオキシ)ビシクロ[2.2.1]へプト−5−エン−2,3−ジカルボキシイミド、N−(2−トリフルオロメチルベンゼンスルホニルオキシ)ナフチルイミド、N−(4−トリフルオロメチルベンゼンスルホニルオキシ)ビシクロ[2.2.1]へプト−5−エン−2,3−ジカルボキシイミド、N−(4−トリフルオロメチルベンゼンスルホニルオキシ)ナフチルイミド、N−(パーフルオロベンゼンスルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド、N−(パーフルオロベンゼンスルホニルオキシ)ナフチルイミド、N−(1−ナフタレンスルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド、N−(1−ナフタレンスルホニルオキシ)ナフチルイミド、N−(ノナフルオロ−n−ブタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド、N−(ノナフルオロ−n−ブタンスルホニルオキシ)ナフチルイミド、N−(パーフルオロ−n−オクタンスルホニルオキシ)ビシクロ[2.2.1]へプト−5−エンー2,3−ジカルボキシイミドおよびN−(パーフルオロ−n−オクタンスルホニルオキシ)ナフチルイミドからなる群から選択される少なくとも一種類であることが好ましい。 The compound represented by the formula (7-3) includes N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- ( Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) Succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2 , 3-Dicarboximide, N- 10-camphorsulfonyloxy) naphthylimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) Naphthylimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide, N- (2 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Perfluorobenzenesulfonyloxy) naphthylimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) Naphthylimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept It is preferably at least one selected from 5-En 2,3-dicarboximide, and N- (perfluoro--n- C1-12alkyl oxy) group consisting naphthylimide.
前記式(7−4)で示される化合物は、ジフェニルジスルフォン、ジ(4−メチルフェニル)ジスルフォン、ジナフチルジスルフォン、ジ(4−tert−ブチルフェニル)ジスルフォン、ジ(4−ヒドロキシフェニル)ジスルフォン、ジ(3−ヒドロキシナフチル)ジスルフォン、ジ(4−フルオロフェニル)ジスルフォン、ジ(2−フルオロフェニル)ジスルフォンおよびジ(4−トルフルオロメチルフェニル)ジスルフォンからなる群から選択される少なくとも1種類であることが好ましい。 The compound represented by the formula (7-4) is diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone. , Di (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone and di (4-trifluoromethylphenyl) disulfone It is preferable.
前記式(7−5)で示される化合物は、α−(メチルスルホニルオキシイミノ)−フェニルアセトニトリル、α−(メチルスルホニルオキシイミノ)−4−メトキシフェニルアセトニトリル、α−(トリフルオロメチルスルホニルオキシイミノ)−フェニルアセトニトリル、α−(トリフルオロメチルスルホニルオキシイミノ)−4−メトキシフェニルアセトニトリル、α−(エチルスルホニルオキシイミノ)−4−メトキシフェニルアセトニトリル、α−(プロピルスルホニルオキシイミノ)−4−メチルフェニルアセトニトリルおよびα−(メチルスルホニルオキシイミノ)−4−ブロモフェニルアセトニトリルからなる群から選択される少なくとも一種類であることが好ましい。 The compound represented by the formula (7-5) is α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino). -Phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile And at least one selected from the group consisting of α- (methylsulfonyloxyimino) -4-bromophenylacetonitrile.
式(7−7)および(7−8)中、R19およびR20はそれぞれ独立に、メチル基、エチル基、n−プロピル基、イソプロピル基等の炭素原子数1〜3のアルキル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基、メトキシ基、エトキシ基、プロポキシ基等の炭素原子数1〜3のアルコキシル基、またはフェニル基、トルイル基、ナフチル基等アリール基、好ましくは、炭素原子数6〜10のアリール基である。L19およびL20はそれぞれ独立に1,2−ナフトキノンジアジド基を有する有機基である。1,2−ナフトキノンジアジド基を有する有機基としては、具体的には、1,2−ナフトキノンジアジド−4−スルホニル基、1,2−ナフトキノンジアジド−5−スルホニル基、1,2−ナフトキノンジアジド−6−スルホニル基等の1,2−キノンジアジドスルホニル基を好ましいものとして挙げることができる。特に、1,2−ナフトキノンジアジド−4−スルホニル基および1,2−ナフトキノンジアジド−5−スルホニル基が好ましい。pは1〜3の整数、qは0〜4の整数、かつ1≦p+q≦5である。J19は単結合、炭素原子数1〜4のポリメチレン基、シクロアルキレン基、フェニレン基、下記式(7−7−1)で表わされる基、カルボニル基、エステル基、アミド基またはエーテル基であり、Y19は水素原子、アルキル基またはアリール基であり、X20は、それぞれ独立に下記式(7−8−1)で示される基である。In the formulas (7-7) and (7-8), R 19 and R 20 are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or cyclopentyl. Group, cycloalkyl group such as cyclohexyl group, alkoxyl group having 1 to 3 carbon atoms such as methoxy group, ethoxy group and propoxy group, or aryl group such as phenyl group, toluyl group and naphthyl group, preferably 6 carbon atoms -10 aryl groups. L 19 and L 20 are each independently an organic group having a 1,2-naphthoquinonediazide group. Specific examples of the organic group having a 1,2-naphthoquinonediazide group include a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, and a 1,2-naphthoquinonediazide- A 1,2-quinonediazidosulfonyl group such as a 6-sulfonyl group can be mentioned as a preferable one. In particular, 1,2-naphthoquinonediazido-4-sulfonyl group and 1,2-naphthoquinonediazide-5-sulfonyl group are preferable. p is an integer of 1 to 3, q is an integer of 0 to 4, and 1 ≦ p + q ≦ 5. J 19 is a single bond, a polymethylene group having 1 to 4 carbon atoms, a cycloalkylene group, a phenylene group, a group represented by the following formula (7-7-1), a carbonyl group, an ester group, an amide group or an ether group. , Y 19 is a hydrogen atom, an alkyl group or an aryl group, and X 20 is independently a group represented by the following formula (7-8-1).
その他の酸発生剤として、ビス(p-トルエンスルホニル)ジアゾメタン、ビス(2,4-ジメチルフェニルスルホニル)ジアゾメタン、ビス(tert-ブチルスルホニル)ジアゾメタン、ビス(n-ブチルスルホニル)ジアゾメタン、ビス(イソブチルスルホニル)ジアゾメタン、ビス(イソプロピルスルホニル)ジアゾメタン、ビス(n-プロピルスルホニル)ジアゾメタン、ビス(シクロヘキシルスルホニル)ジアゾメタン、ビス(イソプロピルスルホニル)ジアゾメタン、1、3−ビス(シクロヘキシルスルホニルアゾメチルスルホニル)プロパン、1、4−ビス(フェニルスルホニルアゾメチルスルホニル)ブタン、1、6−ビス(フェニルスルホニルアゾメチルスルホニル)ヘキサン、1、10−ビス(シクロヘキシルスルホニルアゾメチルスルホニル)デカンなどのビススルホニルジアゾメタン類、2-(4-メトキシフェニル)-4,6-(ビストリクロロメチル)-1,3,5-トリアジン、2-(4-メトキシナフチル)-4,6-(ビストリクロロメチル)-1,3,5-トリアジン、トリス(2,3-ジブロモプロピル)-1,3,5-トリアジン、トリス(2,3-ジブロモプロピル)イソシアヌレートなどのハロゲン含有トリアジン誘導体等が挙げられる。 Other acid generators include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) ) Diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, 1,3-bis (cyclohexylsulfonylazomethylsulfonyl) propane, 1, 4 -Bis (phenylsulfonylazomethylsulfonyl) butane, 1,6-bis (phenylsulfonylazomethylsulfonyl) hexane, 1,10-bis (cyclohexylsulfonyla) Bissulfonyldiazomethanes such as methylsulfonyl) decane, 2- (4-methoxyphenyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6 Halogen-containing triazine derivatives such as-(bistrichloromethyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3,5-triazine, tris (2,3-dibromopropyl) isocyanurate Etc.
上記酸発生剤のうち、芳香環を有する酸発生剤が好ましく、式(7−1)または(7−2)で示され酸発生剤がより好ましい。式(7−1)または(7−2)のX−が、アリール基もしくはハロゲン置換アリール基を有するスルホン酸イオンを有する酸発生剤がさらに好ましく、アリール基を有するスルホン酸イオンを有する酸発生剤が特に好ましく、ジフェニルトリメチルフェニルスルホニウム p−トルエンスルホネート、トリフェニルスルホニウム p−トルエンスルホネート、トリフェニルスルホニウム トリフルオロメタンスルホナート、トリフェニルスルホニウム ノナフルオロメタンスルホナートが特に好ましい。該酸発生剤を用いることで、LERを低減することができる。
上記酸発生剤(C)は、単独で、または2種以上を使用することができる。Among the acid generators, acid generators having an aromatic ring are preferable, and an acid generator represented by formula (7-1) or (7-2) is more preferable. An acid generator having a sulfonate ion having an aryl group or a halogen-substituted aryl group as X − in formula (7-1) or (7-2) is more preferred, and an acid generator having a sulfonate ion having an aryl group Are particularly preferable, and diphenyltrimethylphenylsulfonium p-toluenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, and triphenylsulfonium nonafluoromethanesulfonate are particularly preferable. LER can be reduced by using the acid generator.
The acid generator (C) can be used alone or in combination of two or more.
本発明においては、放射線照射により酸発生剤から生じた酸のレジスト膜中における拡散を制御して、未露光領域での好ましくない化学反応を阻止する作用等を有する酸拡散制御剤(E)を感放射線性組成物に配合しても良い。この様な酸拡散制御剤(E)を使用することにより、感放射線性組成物の貯蔵安定性が向上する。また解像度が向上するとともに、電子線照射前の引き置き時間、電子線照射後の引き置き時間の変動によるレジストパターンの線幅変化を抑えることができ、プロセス安定性に極めて優れたものとなる。このような酸拡散制御剤(E)としては、窒素原子含有塩基性化合物、塩基性スルホニウム化合物、塩基性ヨードニウム化合物等の電子線放射分解性塩基性化合物が挙げられる。酸拡散制御剤は、単独でまたは2種以上を使用することができる。
上記酸拡散制御剤としては、例えば、含窒素有機化合物や、露光により分解する塩基性化合物等が挙げられる。上記含窒素有機化合物としては、例えば、下記一般式(10): In the present invention, an acid diffusion control agent (E) having an action of controlling undesired chemical reaction in an unexposed region by controlling diffusion of an acid generated from an acid generator by irradiation in a resist film. You may mix | blend with a radiation sensitive composition. By using such an acid diffusion controller (E), the storage stability of the radiation-sensitive composition is improved. Further, the resolution is improved, and a change in the line width of the resist pattern due to fluctuations in the holding time before electron beam irradiation and the holding time after electron beam irradiation can be suppressed, and the process stability is extremely excellent. Examples of such an acid diffusion controller (E) include electron beam radiation decomposable basic compounds such as a nitrogen atom-containing basic compound, a basic sulfonium compound, and a basic iodonium compound. The acid diffusion controller can be used alone or in combination of two or more.
Examples of the acid diffusion controller include nitrogen-containing organic compounds and basic compounds that decompose upon exposure. Examples of the nitrogen-containing organic compound include the following general formula (10):
上記一般式(10)中、R61、R62およびR63は相互に独立に水素原子、直鎖状、分岐状若しくは環状のアルキル基、アリール基、またはアラルキル基を示す。また、上記アルキル基、アリール基、またはアラルキル基は、非置換でもよく、ヒドロキシル基等の他の官能基で置換されていてもよい。ここで、上記直鎖状、分岐状若しくは環状のアルキル基としては、例えば、炭素数1〜15、好ましくは1〜10のものが挙げられ、具体的には、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、sec−ブチル基、t−ブチル基、n−ペンチル基、ネオペンチル基、n−ヘキシル基、テキシル基、n−へプチル基、n−オクチル基、n−エチルヘキシル基、n−ノニル基、n−デシル基等が挙げられる。また、上記アリール基としては、炭素数6〜12のものが挙げられ、具体的には、フェニル基、トリル基、キシリル基、クメニル基、1−ナフチル基等が挙げられる。更に、上記アラルキル基としては、炭素数7〜19、好ましくは7〜13のものが挙げられ、具体的には、ベンジル基、α−メチルベンジル基、フェネチル基、ナフチルメチル基等が挙げられる。In the general formula (10), R 61 , R 62 and R 63 each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group, or aralkyl group may be unsubstituted or substituted with another functional group such as a hydroxyl group. Here, examples of the linear, branched or cyclic alkyl group include those having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, specifically, methyl group, ethyl group, n- Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group , N-ethylhexyl group, n-nonyl group, n-decyl group and the like. Moreover, as said aryl group, a C6-C12 thing is mentioned, Specifically, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, 1-naphthyl group, etc. are mentioned. Furthermore, examples of the aralkyl group include those having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, and specific examples include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
上記含窒素化合物(I)として具体的には、例えば、n−ヘキシルアミン、n−ヘプチルアミン、n−オクチルアミン、n−ノニルアミン、n−デシルアミン、n−ドデシルアミン、シクロヘキシルアミン等のモノ(シクロ)アルキルアミン類;ジ−n−ブチルアミン、ジ−n−ペンチルアミン、ジ−n−ヘキシルアミン、ジ−n−ヘプチルアミン、ジ−n−オクチルアミン、ジ−n−ノニルアミン、ジ−n−デシルアミン、メチル−n−ドデシルアミン、ジ−n−ドデシルメチル、シクロヘキシルメチルアミン、ジシクロヘキシルアミン等のジ(シクロ)アルキルアミン類;トリエチルアミン、トリ−n−プロピルアミン、トリ−n−ブチルアミン、トリ−n−ペンチルアミン、トリ−n−ヘキシルアミン、トリ−n−ヘプチルアミン、トリ−n−オクチルアミン、トリ−n−ノニルアミン、トリ−n−デシルアミン、ジメチル−n−ドデシルアミン、ジ−n−ドデシルメチルアミン、ジシクロヘキシルメチルアミン、トリシクロヘキシルアミン等のトリ(シクロ)アルキルアミン類;モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン類;アニリン、N−メチルアニリン、N,N−ジメチルアニリン、2−メチルアニリン、3−メチルアニリン、4−メチルアニリン、4−ニトロアニリン、ジフェニルアミン、トリフェニルアミン、1−ナフチルアミン等の芳香族アミン類等を挙げることができる。 Specific examples of the nitrogen-containing compound (I) include mono-cyclohexane such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine and cyclohexylamine. ) Alkylamines; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine , Methyl-n-dodecylamine, di-n-dodecylmethyl, cyclohexylmethylamine, dicyclohexylamine and the like di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n- Pentylamine, tri-n-hexylamine, tri-n-heptylamine, -Tri (cyclo) alkylamines such as n-octylamine, tri-n-nonylamine, tri-n-decylamine, dimethyl-n-dodecylamine, di-n-dodecylmethylamine, dicyclohexylmethylamine, tricyclohexylamine; Alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine , Aromatic amines such as triphenylamine and 1-naphthylamine.
上記含窒素化合物(II)として具体的には、例えば、エチレンジアミン、N,N,N’,N’−テトラメチルエチレンジアミン、N,N,N’,N’−テトラキス(2−ヒドロキシプロピル)エチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、4,4’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルエーテル、4,4’−ジアミノベンゾフェノン、4,4’−ジアミノジフェニルアミン、2,2−ビス(4−アミノフェニル)プロパン、2−(3−アミノフェニル)−2−(4−アミノフェニル)プロパン、2−(4−アミノフェニル)−2−(3−ヒドロキシフェニル)プロパン、2−(4−アミノフェニル)−2−(4−ヒドロキシフェニル)プロパン、1,4−ビス[1−(4−アミノフェニル)−1−メチルエチル]ベンゼン、1,3−ビス[1−(4−アミノフェニル)−1−メチルエチル]ベンゼン等を挙げることができる。 Specific examples of the nitrogen-containing compound (II) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, Tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) ) Propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl)- 2- (4-Hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and the like.
上記含窒素化合物(III)として具体的には、例えば、ポリエチレンイミン、ポリアリルアミン、N−(2−ジメチルアミノエチル)アクリルアミドの重合体等を挙げることができる。
上記アミド基含有化合物として具体的には、例えば、ホルムアミド、N−メチルホルムアミド、N,N−ジメチルホルムアミド、アセトアミド、N−メチルアセトアミド、N,N−ジメチルアセトアミド、プロピオンアミド、ベンズアミド、ピロリドン、N−メチルピロリドン等を挙げることができる。Specific examples of the nitrogen-containing compound (III) include polyethyleneimine, polyallylamine, N- (2-dimethylaminoethyl) acrylamide polymer, and the like.
Specific examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N- And methylpyrrolidone.
上記ウレア化合物として具体的には、例えば、尿素、メチルウレア、1,1−ジメチルウレア、1,3−ジメチルウレア、1,1,3,3−テトラメチルウレア、1,3−ジフェニルウレア、トリ−n−ブチルチオウレア等を挙げることができる。 Specific examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri- Examples thereof include n-butylthiourea.
上記含窒素複素環式化合物として具体的には、例えば、イミダゾール、ベンズイミダゾール、4−メチルイミダゾール、4−メチル−2−フェニルイミダゾール、2−フェニルベンズイミダゾール等のイミダゾール類;ピリジン、2−メチルピリジン、4−メチルピリジン、2−エチルピリジン、4−エチルピリジン、2−フェニルピリジン、4−フェニルピリジン、2−メチル−4−フェニルピリジン、ニコチン、ニコチン酸、ニコチン酸アミド、キノリン、8−オキシキノリン、アクリジン等のピリジン類;および、ピラジン、ピラゾール、ピリダジン、キノザリン、プリン、ピロリジン、ピペリジン、モルホリン、4−メチルモルホリン、ピペラジン、1,4−ジメチルピペラジン、1,4−ジアザビシクロ[2.2.2]オクタン等を挙げることができる。 Specific examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, 2-phenylbenzimidazole; pyridine, 2-methylpyridine. 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline And pyridines such as acridine; and pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2. ] Octane etc. It can be mentioned.
また、上記露光により分解する塩基性化合物としては、例えば、下記一般式(11−1):
上記一般式(11−1)および(11−2)中、R71、R72、R73、R74およびR75は相互に独立に水素原子、炭素数1〜6のアルキル基、炭素数1〜6のアルコキシル基、ヒドロキシル基またはハロゲン原子を示す。Z−はHO−、R−COO−(但し、Rは炭素数1〜6のアルキル基、炭素数1〜6のアリール基若しくは炭素数1〜6のアルカリール基を示す。)または下記一般式(11−3):In the general formulas (11-1) and (11-2), R 71 , R 72 , R 73 , R 74 and R 75 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom. -6 alkoxyl groups, hydroxyl groups or halogen atoms. Z - is HO -, R-COO - ( . Here, R represents an alkyl group, an aryl group or alkaryl group having 1 to 6 carbon atoms having 1 to 6 carbon atoms having 1 to 6 carbon atoms) or the following general formula (11-3):
上記露光により分解する塩基性化合物として具体的には、例えば、トリフェニルスルホニウムハイドロオキサイド、トリフェニルスルホニウムアセテート、トリフェニルスルホニウムサリチレート、ジフェニル−4−ヒドロキシフェニルスルホニウムハイドロオキサイド、ジフェニル−4−ヒドロキシフェニルスルホニウムアセテート、ジフェニル−4−ヒドロキシフェニルスルホニウムサリチレート、ビス(4−t−ブチルフェニル)ヨードニウムハイドロオキサイド、ビス(4−t−ブチルフェニル)ヨードニウムアセテート、ビス(4−t−ブチルフェニル)ヨードニウムハイドロオキサイド、ビス(4−t−ブチルフェニル)ヨードニウムアセテート、ビス(4−t−ブチルフェニル)ヨードニウムサリチレート、4−t−ブチルフェニル−4−ヒドロキシフェニルヨードニウムハイドロオキサイド、4−t−ブチルフェニル−4−ヒドロキシフェニルヨードニウムアセテート、4−t−ブチルフェニル−4−ヒドロキシフェニルヨードニウムサリチレート等が挙げられる。 Specific examples of the basic compound that decomposes upon exposure include triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium hydroxide, and diphenyl-4-hydroxyphenyl. Sulfonium acetate, diphenyl-4-hydroxyphenylsulfonium salicylate, bis (4-t-butylphenyl) iodonium hydroxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium hydro Oxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium salicylate, 4-t-butylphenyl 4- hydroxyphenyl iodonium hydroxide, 4-t-butylphenyl-4-hydroxyphenyl iodonium acetate, include 4-t-butylphenyl-4-hydroxyphenyl iodonium salicylate and the like.
酸拡散制御剤(E)の配合量は、固形成分全重量の0.001〜50重量%が好ましく、0.001〜10重量%がより好ましく、0.001〜5重量%がさらに好ましく、0.001〜3重量%が特に好ましい。上記範囲内であると、解像度の低下、パターン形状、寸法忠実度等の劣化を防止することができる。さらに、電子線照射から放射線照射後加熱までの引き置き時間が長くなっても、パターン上層部の形状が劣化することがない。また、配合量が10重量%以下であると、感度、未露光部の現像性等の低下を防ぐことができる。またこの様な酸拡散制御剤を使用することにより、感放射線性組成物の貯蔵安定性が向上し、また解像度が向上するとともに、放射線照射前の引き置き時間、放射線照射後の引き置き時間の変動によるレジストパターンの線幅変化を抑えることができ、プロセス安定性に極めて優れたものとなる。 The blending amount of the acid diffusion controller (E) is preferably 0.001 to 50% by weight, more preferably 0.001 to 10% by weight, still more preferably 0.001 to 5% by weight, based on the total weight of the solid component. 0.001 to 3% by weight is particularly preferred. Within the above range, it is possible to prevent degradation in resolution, pattern shape, dimensional fidelity, and the like. Furthermore, even if the holding time from electron beam irradiation to heating after radiation irradiation becomes longer, the shape of the pattern upper layer portion does not deteriorate. Further, when the blending amount is 10% by weight or less, it is possible to prevent a decrease in sensitivity, developability of an unexposed portion, and the like. Further, by using such an acid diffusion control agent, the storage stability of the radiation-sensitive composition is improved, the resolution is improved, and the holding time before irradiation and the holding time after irradiation are reduced. Changes in the line width of the resist pattern due to fluctuations can be suppressed, and the process stability is extremely excellent.
本発明のポジ型感放射線性組成物には、本発明の目的を阻害しない範囲で、必要に応じて、その他の成分(F)として、溶解促進剤、溶解制御剤、増感剤、界面活性剤、および有機カルボン酸またはリンのオキソ酸もしくはその誘導体等の各種添加剤を1種または2種以上添加することができる。 The positive radiation-sensitive composition of the present invention has, as necessary, other components (F) as a solubility promoter, a dissolution control agent, a sensitizer, and a surface activity as long as the object of the present invention is not impaired. One kind or two or more kinds of additives such as an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof can be added.
[1]溶解促進剤
低分子量溶解促進剤は、レジスト基材のアルカリ等の現像液に対する溶解性が低すぎる場合に、その溶解性を高めて、現像時の環状化合物の溶解速度を適度に増大させる作用を有する成分であり、本発明の効果を損なわない範囲で使用することができる。前記溶解促進剤としては、例えば、低分子量のフェノール性化合物を挙げることができ、例えば、ビスフェノール類、トリス(ヒドロキシフェニル)メタン等を挙げることができる。これらの溶解促進剤は、単独でまたは2種以上を混合して使用することができる。溶解促進剤の配合量は、使用するレジスト基材の種類に応じて適宜調節されるが、レジスト基材(化合物(A)及び化合物(B)、以下、レジスト基材(R)という。)100重量部当たり、0〜100重量部が好ましく、好ましくは0〜30重量部であり、より好ましくは0〜10重量部、更に好ましくは0〜2重量部である。[1] Dissolution Accelerator A low molecular weight dissolution accelerator increases the solubility of a cyclic compound during development when the solubility of a resist base material in an alkali or other developer is too low, and moderately increases the dissolution rate of a cyclic compound during development. It is a component which has the effect | action to make it use in the range which does not impair the effect of this invention. Examples of the dissolution accelerator include low molecular weight phenolic compounds such as bisphenols and tris (hydroxyphenyl) methane. These dissolution promoters can be used alone or in admixture of two or more. The blending amount of the dissolution accelerator is appropriately adjusted depending on the type of resist base material to be used, but resist base material (compound (A) and compound (B), hereinafter referred to as resist base material (R)) 100. It is preferably 0 to 100 parts by weight per part by weight, preferably 0 to 30 parts by weight, more preferably 0 to 10 parts by weight, still more preferably 0 to 2 parts by weight.
[2]溶解制御剤
溶解制御剤は、レジスト基材がアルカリ等の現像液に対する溶解性が高すぎる場合に、その溶解性を制御して現像時の溶解速度を適度に減少させる作用を有する成分である。このような溶解制御剤としては、レジスト被膜の焼成、放射線照射、現像等の工程において化学変化しないものが好ましい。溶解制御剤としては、例えば、ナフタレン、フェナントレン、アントラセン、アセナフテン等の芳香族炭化水素類;アセトフェノン、ベンゾフェノン、フェニルナフチルケトン等のケトン類;メチルフェニルスルホン、ジフェニルスルホン、ジナフチルスルホン等のスルホン類等を挙げることができる。これらの溶解制御剤は、単独でまたは2種以上を使用することができる。
溶解制御剤の配合量は、使用するレジスト基材(R)の種類に応じて適宜調節されるが、レジスト基材(R)100重量部当たり、0〜100重量部が好ましく、好ましくは0〜30重量部であり、より好ましくは0〜10重量部、更に好ましくは0〜2重量部である。[2] Solubility control agent A solubilization control agent is a component having an action of controlling the solubility of the resist base material when the resist base material is too high in alkali or the like to moderately reduce the dissolution rate during development. It is. As such a dissolution control agent, those that do not chemically change in steps such as baking of resist film, irradiation with radiation, and development are preferable. Examples of the dissolution control agent include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. Can be mentioned. These dissolution control agents can be used alone or in combination of two or more.
The blending amount of the dissolution control agent is appropriately adjusted according to the type of the resist base material (R) to be used. 30 parts by weight, more preferably 0 to 10 parts by weight, still more preferably 0 to 2 parts by weight.
[3]増感剤
増感剤は、照射された放射線のエネルギーを吸収して、そのエネルギーを酸発生剤(C)に伝達し、それにより酸の生成量を増加する作用を有し、レジストの見掛けの感度を向上させる成分である。このような増感剤としては、例えば、ベンゾフェノン類、ビアセチル類、ピレン類、フェノチアジン類、フルオレン類等を挙げることができるが、特に限定はされない。
これらの増感剤は、単独でまたは2種以上を使用することができる。増感剤の配合量は、使用するレジスト基材(R)の種類に応じて適宜調節されるが、レジスト基材(R)100重量部当たり、0〜100重量部が好ましく、好ましくは0〜30重量部であり、より好ましくは0〜10重量部、更に好ましくは0〜2重量部である。[3] Sensitizer The sensitizer absorbs the energy of the irradiated radiation and transmits the energy to the acid generator (C), thereby increasing the amount of acid generated. It is a component that improves the apparent sensitivity. Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes.
These sensitizers can be used alone or in combination of two or more. Although the compounding quantity of a sensitizer is suitably adjusted according to the kind of resist base material (R) to be used, 0-100 weight part is preferable per 100 weight part of resist base material (R), Preferably it is 0 30 parts by weight, more preferably 0 to 10 parts by weight, still more preferably 0 to 2 parts by weight.
[4]界面活性剤
界面活性剤は、本発明のポジ型感放射線性組成物の塗布性やストリエーション、レジストの現像性等を改良する作用を有する成分である。このような界面活性剤は、アニオン系、カチオン系、ノニオン系あるいは両性のいずれでもよい。好ましい界面活性剤はノニオン系界面活性剤である。ノニオン系界面活性剤は、感放射線性組成物の製造に用いる溶媒との親和性がよく、より効果がある。ノニオン系界面活性剤の例としては、ポリオキシエチレン高級アルキルエーテル類、ポリオキシエチレン高級アルキルフェニルエーテル類、ポリエチレングリコールの高級脂肪酸ジエステル類等が挙げられるが、特に限定はされない。市販品としては、以下商品名で、エフトップ(ジェムコ社製)、メガファック(大日本インキ化学工業社製)、フロラード(住友スリーエム社製)、アサヒガード、サーフロン(以上、旭硝子社製)、ペポール(東邦化学工業社製)、KP(信越化学工業社製)、ポリフロー(共栄社油脂化学工業社製)等を挙げることができる。
界面活性剤の配合量は、使用するレジスト基材(R)の種類に応じて適宜調節されるが、レジスト基材(R)100重量部当たり、0〜100重量部が好ましく、好ましくは0〜30重量部であり、より好ましくは0〜10重量部、更に好ましくは0〜2重量部である。[4] Surfactant The surfactant is a component having an action of improving the coating property and striation of the positive radiation-sensitive composition of the present invention, the developability of the resist, and the like. Such a surfactant may be anionic, cationic, nonionic or amphoteric. A preferred surfactant is a nonionic surfactant. Nonionic surfactants have better affinity with the solvent used in the production of the radiation-sensitive composition and are more effective. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers and higher fatty acid diesters of polyethylene glycol, but are not particularly limited. Commercially available products include the following product names: F-top (manufactured by Gemco), Mega-Fac (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Examples include Pepol (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), and the like.
The compounding amount of the surfactant is appropriately adjusted according to the type of the resist base material (R) to be used, but is preferably 0 to 100 parts by weight, preferably 0 to 100 parts by weight per 100 parts by weight of the resist base material (R). 30 parts by weight, more preferably 0 to 10 parts by weight, still more preferably 0 to 2 parts by weight.
[5]有機カルボン酸またはリンのオキソ酸もしくはその誘導体
感度劣化防止またはレジストパターン形状、引き置き安定性等の向上の目的で、さらに任意の成分として、有機カルボン酸またはリンのオキソ酸もしくはその誘導体を含有させることができる。なお、酸拡散制御剤と併用することも出来るし、単独で用いても良い。有機カルボン酸としては、例えば、マロン酸、クエン酸、リンゴ酸、コハク酸、安息香酸、サリチル酸などが好適である。リンのオキソ酸もしくはその誘導体としては、リン酸、リン酸ジ−n−ブチルエステル、リン酸ジフェニルエステルなどのリン酸またはそれらのエステルなどの誘導体、ホスホン酸、ホスホン酸ジメチルエステル、ホスホン酸ジ−n−ブチルエステル、フェニルホスホン酸、ホスホン酸ジフェニルエステル、ホスホン酸ジベンジルエステルなどのホスホン酸またはそれらのエステルなどの誘導体、ホスフィン酸、フェニルホスフィン酸などのホスフィン酸およびそれらのエステルなどの誘導体が挙げられ、これらの中で特にホスホン酸が好ましい。
有機カルボン酸またはリンのオキソ酸もしくはその誘導体は、単独でまたは2種以上を使用することができる。有機カルボン酸またはリンのオキソ酸もしくはその誘導体の配合量は、使用するレジスト基材(R)の種類に応じて適宜調節されるが、レジスト基材(R)100重量部当たり、0〜100重量部が好ましく、好ましくは0〜30重量部であり、より好ましくは0〜10重量部、更に好ましくは0〜2重量部である。[5] Organic carboxylic acid or phosphorous oxo acid or derivative thereof For the purpose of preventing sensitivity deterioration or improving resist pattern shape, retention stability, etc., organic carboxylic acid or phosphorous oxo acid or derivative thereof as an optional component Can be contained. In addition, it can be used in combination with an acid diffusion controller, or may be used alone. As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable. Phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid such as diphenyl ester phosphoric acid or derivatives thereof such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di- Derivatives such as n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester, etc., phosphonic acid or their esters, phosphinic acid, phosphinic acid such as phenylphosphinic acid, and derivatives thereof Of these, phosphonic acid is particularly preferred.
The organic carboxylic acid or phosphorus oxo acid or derivative thereof may be used alone or in combination of two or more. The amount of the organic carboxylic acid or phosphorus oxo acid or derivative thereof is appropriately adjusted according to the type of the resist base (R) to be used, but is 0 to 100 weights per 100 parts by weight of the resist base (R). Parts, preferably 0 to 30 parts by weight, more preferably 0 to 10 parts by weight, still more preferably 0 to 2 parts by weight.
[6]上記溶解制御剤、増感剤、界面活性剤、および有機カルボン酸またはリンのオキソ酸もしくはその誘導体以外のその他の添加剤
更に、本発明の感放射線性組成物には、本発明の目的を阻害しない範囲で、必要に応じて、上記溶解制御剤、増感剤、および界面活性剤以外の添加剤を1種または2種以上配合することができる。そのような添加剤としては、例えば、染料、顔料、および接着助剤等が挙げられる。例えば、染料または顔料を配合すると、露光部の潜像を可視化させて、露光時のハレーションの影響を緩和できるので好ましい。また、接着助剤を配合すると、基板との接着性を改善することができるので好ましい。更に、他の添加剤としては、ハレーション防止剤、保存安定剤、消泡剤、形状改良剤等、具体的には4−ヒドロキシ−4’−メチルカルコン等を挙げることができる。[6] The above-mentioned dissolution control agent, sensitizer, surfactant, and other additives other than organic carboxylic acid or phosphorus oxo acid or derivatives thereof. One or more additives other than the above-mentioned dissolution control agent, sensitizer, and surfactant can be blended as necessary within a range not inhibiting the purpose. Examples of such additives include dyes, pigments, and adhesion aids. For example, it is preferable to add a dye or a pigment because the latent image in the exposed area can be visualized and the influence of halation during exposure can be reduced. In addition, it is preferable to add an adhesion assistant because the adhesion to the substrate can be improved. Furthermore, examples of other additives include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improving agent, and the like, specifically 4-hydroxy-4′-methylchalcone.
本発明のポジ型感放射線性組成物の配合(化合物(A)/化合物(B)/酸発生剤(C)/酸拡散制御剤(E)/その他の成分(F))は、固形物基準の重量%で、好ましくは
10〜49.989/50〜89.989/0.001〜39.99/0.01〜39.999/0〜39.989、
より好ましくは
10〜49.989/50〜89.989/0.001〜39.99/0.01〜39.999/0〜15、
さらに好ましくは
12〜35/60〜70/10〜25/0.01〜3/0〜1
特に好ましくは
12.5〜17.5/60〜70/10〜25/0.01〜3/0である。上記配合にすると、感度、解像度、アルカリ現像性等の性能に優れる。The composition of the positive radiation sensitive composition of the present invention (compound (A) / compound (B) / acid generator (C) / acid diffusion controller (E) / other components (F)) is based on solid matter. %, Preferably 10 to 49.989 / 50 to 89.989 / 0.001 to 39.99 / 0.01 to 39.999 / 0 to 39.989,
More preferably, 10 to 49.989 / 50 to 89.989 / 0.001 to 39.99 / 0.01 to 39.999 / 0 to 15,
More preferably, 12 to 35/60 to 70/10 to 25 / 0.01 to 3/0 to 1
Especially preferably, it is 12.5-17.5 / 60-70 / 10-25 / 0.01-3 / 0. When the above composition is used, the performance such as sensitivity, resolution and alkali developability is excellent.
本発明のポジ型感放射線性組成物は、通常は、使用時に各成分を溶媒に溶解して均一溶液とし、その後、必要に応じて、例えば孔径0.2μm程度のフィルター等でろ過することにより調製される。 The positive radiation sensitive composition of the present invention is usually obtained by dissolving each component in a solvent at the time of use to obtain a uniform solution, and then filtering with a filter having a pore size of about 0.2 μm, for example, if necessary. Prepared.
本発明のポジ型感放射線性組成物の調製に使用される前記溶媒としては、例えば、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ−n−プロピルエーテルアセテート、エチレングリコールモノ−n−ブチルエーテルアセテート等のエチレングリコールモノアルキルエーテルアセテート類;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などのエチレングリコールモノアルキルエーテル類;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モノエチルエーテルアセテート、プロピレングリコールモノ−n−プロピルエーテルアセテート、プロピレングリコールモノ−n−ブチルエーテルアセテート等のプロピレングリコールモノアルキルエーテルアセテート類;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エチルエーテルなどのプロピレングリコールモノアルキルエーテル類;乳酸メチル、乳酸エチル、乳酸n−プロピル、乳酸n−ブチル、乳酸n−アミル等の乳酸エステル類;酢酸メチル、酢酸エチル、酢酸n−プロピル、酢酸n−ブチル、酢酸n−アミル、酢酸n−ヘキシル、プロピオン酸メチル、プロピオン酸エチル等の脂肪族カルボン酸エステル類;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メチル、3−エトキシプロピオン酸エチル、3−メトキシ−2−メチルプロピオン酸メチル、3−メトキシブチルアセテート、3−メチル−3−メトキシブチルアセテート、3−メトキシ−3−メチルプロピオン酸ブチル、3−メトキシ−3−メチル酪酸ブチル、アセト酢酸メチル、ピルビン酸メチル、ピルビン酸エチル等の他のエステル類;トルエン、キシレン等の芳香族炭化水素類;2−ヘプタノン、3−ヘプタノン、4−ヘプタノン、シクロペンタノン、シクロヘキサノン等のケトン類;N,N−ジメチルホルムアミド、N−メチルアセトアミド、N,N−ジメチルアセトアミド、N−メチルピロリドン等のアミド類;γ−ラクトン等のラクトン類等を挙げることができるが、特に限定はされない。これらの溶媒は、単独でまたは2種以上を使用することができる。 Examples of the solvent used in the preparation of the positive radiation-sensitive composition of the present invention include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono- ethylene glycol monoalkyl ether acetates such as n-butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono- n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate Propylene glycol monoalkyl ether acetates such as; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-amyl lactate, etc. Lactate esters; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate; Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxy Other esters such as butyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate and ethyl pyruvate; aromatic carbonization such as toluene and xylene Hydrogen; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone, cyclohexanone; N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. Amides; lactones such as γ-lactone can be exemplified, but are not particularly limited. These solvents can be used alone or in combination of two or more.
本発明のポジ型感放射線組成物は、本発明の目的を阻害しない範囲で、アルカリ水溶液に可溶である樹脂を含むことができる。アルカリ水溶液に可溶である樹脂としては、ノボラック樹脂、ポリビニルフェノール類、ポリアクリル酸、ポリビニルアルコール、スチレン−無水マレイン酸樹脂、およびアクリル酸、ビニルアルコール、またはビニルフェノールを単量体単位として含む重合体、あるいはこれらの誘導体などが挙げられる。アルカリ水溶液に可溶である樹脂の配合量は、使用する環状化合物の種類に応じて適宜調節されるが、上記環状化合物100重量部当たり、0〜30重量部が好ましく、より好ましくは0〜10重量部、さらに好ましくは0〜5重量部、特に好ましくは0重量部である。 The positive radiation sensitive composition of the present invention can contain a resin that is soluble in an alkaline aqueous solution as long as the object of the present invention is not impaired. Resins that are soluble in an alkaline aqueous solution include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and heavy polymers containing acrylic acid, vinyl alcohol, or vinyl phenol as monomer units. A combination, or a derivative thereof may be used. The blending amount of the resin soluble in the alkaline aqueous solution is appropriately adjusted according to the kind of the cyclic compound to be used, but is preferably 0 to 30 parts by weight, more preferably 0 to 10 parts per 100 parts by weight of the cyclic compound. Parts by weight, more preferably 0 to 5 parts by weight, particularly preferably 0 parts by weight.
[レジストパターンの形成方法]
本発明は、上記本発明のポジ型感放射線性組成物を用いて、基板上にレジスト膜を形成する工程、該レジスト膜を露光する工程、および該レジスト膜を現像してレジストパターンを形成する工程を含むレジストパターン形成方法に関する。本発明により得られるレジストパターンは多層レジストプロセスにおける上層レジストとして形成することもできる。
レジストパターンを形成するには、従来公知の基板上に前記本発明の感放射線性組成物を、回転塗布、流延塗布、ロール塗布等の塗布手段によって塗布することによりレジスト膜を形成する。従来公知の基板とは、特に限定されず、例えば、電子部品用の基板や、これに所定の配線パターンが形成されたもの等を例示することができる。より具体的には、シリコンウェハー、銅、クロム、鉄、アルミニウム等の金属製の基板や、ガラス基板等が挙げられる。配線パターンの材料としては、例えば銅、アルミニウム、ニッケル、金等が挙げられる。また必要に応じて、前述基板上に無機系および/または有機系の膜が設けられたものであってもよい。無機系の膜としては、無機反射防止膜(無機BARC)が挙げられる。有機系の膜としては、有機反射防止膜(有機BARC)が挙げられる。ヘキサメチレンジシラザン等による表面処理を行ってもよい。
次いで、必要に応じ、塗布した基板を加熱する。加熱条件は、感放射線性組成物の配合組成等により変わるが、20〜250℃が好ましく、より好ましくは20〜150℃である。加熱することによって、レジストの基板に対する密着性が向上する場合があり好ましい。次いで、可視光線、紫外線、エキシマレーザー、電子線、極端紫外線(EUV)、X線、およびイオンビームからなる群から選ばれるいずれかの放射線により、レジスト膜を所望のパターンに露光する。露光条件等は、感放射線性組成物の配合組成等に応じて適宜選定される。本発明においては、露光における高精度の微細パターンを安定して形成するために、放射線照射後に加熱するのが好ましい。加熱条件は、感放射線性組成物の配合組成等により変わるが、20〜250℃が好ましく、より好ましくは20〜150℃である。[Method of forming resist pattern]
The present invention uses the positive radiation sensitive composition of the present invention to form a resist film on a substrate, to expose the resist film, and to develop the resist film to form a resist pattern. The present invention relates to a resist pattern forming method including a process. The resist pattern obtained by the present invention can also be formed as an upper layer resist in a multilayer resist process.
In order to form a resist pattern, a resist film is formed by applying the radiation-sensitive composition of the present invention on a conventionally known substrate by coating means such as spin coating, cast coating, roll coating or the like. The conventionally known substrate is not particularly limited, and examples thereof include a substrate for electronic parts and a substrate on which a predetermined wiring pattern is formed. More specifically, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. Examples of the wiring pattern material include copper, aluminum, nickel, and gold. If necessary, an inorganic and / or organic film may be provided on the substrate. An inorganic antireflection film (inorganic BARC) is an example of the inorganic film. Examples of the organic film include an organic antireflection film (organic BARC). Surface treatment with hexamethylene disilazane or the like may be performed.
Next, the coated substrate is heated as necessary. Although heating conditions change with the compounding composition etc. of a radiation sensitive composition, 20-250 degreeC is preferable, More preferably, it is 20-150 degreeC. Heating may improve the adhesion of the resist to the substrate, which is preferable. Next, the resist film is exposed to a desired pattern with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. The exposure conditions and the like are appropriately selected according to the composition of the radiation sensitive composition. In the present invention, in order to stably form a high-precision fine pattern in exposure, heating is preferably performed after irradiation with radiation. Although heating conditions change with the compounding composition etc. of a radiation sensitive composition, 20-250 degreeC is preferable, More preferably, it is 20-150 degreeC.
次いで、露光されたレジスト膜をアルカリ現像液で現像することにより、所定のレジストパターンを形成する。前記アルカリ現像液としては、例えば、モノ−、ジ−あるいはトリアルキルアミン類、モノ−、ジ−あるいはトリアルカノールアミン類、複素環式アミン類、テトラメチルアンモニウムヒドロキシド(TMAH)、コリン等のアルカリ性化合物の1種以上を、好ましくは1〜10質量%、より好ましくは1〜5質量%の濃度となるように溶解したアルカリ性水溶液が使用される。上記アルカリ性水溶液の濃度が10質量%以下とすると、露光部が現像液に溶解することを抑制することが出来るので好ましい。
また、前記アルカリ現像液には、メタノール、エタノール、イソプロピルアルコールなどのアルコール類や前記界面活性剤を適量添加することもできる。これらのうちイソプロピルアルコールを10〜30質量%添加することが特に好ましい。これにより、レジストに対する現像液の濡れ性を高めることが出来るので好ましい。なお、このようなアルカリ性水溶液からなる現像液を用いた場合は、一般に、現像後、水で洗浄する。Next, the exposed resist film is developed with an alkaline developer to form a predetermined resist pattern. Examples of the alkaline developer include alkaline such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), choline and the like. An alkaline aqueous solution in which one or more compounds are dissolved so as to have a concentration of preferably 1 to 10% by mass, more preferably 1 to 5% by mass is used. When the concentration of the alkaline aqueous solution is 10% by mass or less, it is preferable because the exposed portion can be prevented from being dissolved in the developer.
In addition, an appropriate amount of alcohols such as methanol, ethanol, isopropyl alcohol, and the surfactant can be added to the alkaline developer. Of these, it is particularly preferable to add 10 to 30% by mass of isopropyl alcohol. This is preferable since the wettability of the developer with respect to the resist can be improved. In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans with water after image development.
レジストパターンを形成した後、エッチングすることによりパターン配線基板が得られる。エッチングの方法はプラズマガスを使用するドライエッチングおよびアルカリ溶液、塩化第二銅溶液、塩化第二鉄溶液等によるウェットエッチングなど公知の方法で行うことが出来る。
レジストパターンを形成した後、めっきを行うことも出来る。上記めっき法としては、例えば、銅めっき、はんだめっき、ニッケルめっき、金めっきなどがある。
エッチング後の残存レジストパターンは有機溶剤や現像に用いたアルカリ水溶液より強アルカリ性の水溶液で剥離することが出来る。上記有機溶剤として、PGMEA(プロピレングリコールモノメチルエーテルアセテート),PGME(プロピレングリコールモノメチルエーテル),EL(乳酸エチル)等が挙げられ、強アルカリ水溶液としては、例えば1〜20質量%の水酸化ナトリウム水溶液や1〜20質量%の水酸化カリウム水溶液が挙げられる。上記剥離方法としては、例えば、浸漬方法、スプレイ方式等が挙げられる。またレジストパターンが形成された配線基板は、多層配線基板でも良く、小径スルーホールを有していても良い。
本発明で得られる配線基板は、レジストパターン形成後、金属を真空中で蒸着し、その後レジストパターンを溶液で溶かす方法、すなわちリフトオフ法により形成することもできる。After forming the resist pattern, the pattern wiring board is obtained by etching. The etching can be performed by a known method such as dry etching using plasma gas and wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like.
Plating can be performed after forming the resist pattern. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.
The residual resist pattern after etching can be peeled off with an organic solvent or a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate) and the like. As the strong alkaline aqueous solution, for example, 1 to 20% by mass of sodium hydroxide aqueous solution or 1-20 mass% potassium hydroxide aqueous solution is mentioned. Examples of the peeling method include a dipping method and a spray method. In addition, the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.
The wiring board obtained by the present invention can also be formed by a method of depositing a metal in vacuum after forming a resist pattern and then dissolving the resist pattern with a solution, that is, a lift-off method.
以下、実施例を挙げて、本発明の実施の形態をさらに具体的に説明する。但し、本発明は、これらの実施例に限定はされない。以下の合成例において、化合物の構造は1H−NMR測定で確認した。Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following synthesis examples, the structure of the compound was confirmed by 1 H-NMR measurement.
<合成例> 化合物(B)の合成
・合成例1
CR−1Bの合成
十分乾燥し、窒素置換した滴下漏斗、ジム・ロート氏冷却管、温度計、攪拌翼を設置した四つ口フラスコ(1000ml)に、窒素気流下で、関東化学社製レゾルシノール(22g、0.2mol)と、4−イソプロピルベンズアルデヒド(29.6g,0.2mol)と、脱水エタノール(200ml)を投入し、エタノール溶液を調整した。この溶液を攪拌しながらマントルヒーターで85℃まで加熱した。次いで濃塩酸(35%)75mlを、滴下漏斗により30分かけて滴下した後、引き続き85℃で3時間攪拌した。反応終了後、放冷し、室温に到達させた後、氷浴で冷却した。1時間静置後、淡黄色の目的粗結晶が生成し、これを濾別した。粗結晶をメタノール500mlで2回洗浄し、濾別、真空乾燥させることにより、目的生成物(以下、CR−1Bと示す)(45.6g、収率95%)を得た。
この化合物の構造は、LC−MSで分析した結果、f)目的物の分子量960を示した。また重ジメチルスルホキシド溶媒中での1H−NMRのケミカルシフト値(δppm,TMS基準)は1.1〜1.2(m,24H)、2.6〜2.7(m,4H)、5.5(s,4H)、6.0〜6.8(m,24H)、8.4,8.5(d,8H)であった。
また、g)アルカリ現像液(TMAH2.38wt%)に可溶であり、h)分子内にフェノール性水酸基を有し、e)Mw/Mn=1.00であった。<Synthesis Example> Synthesis and Synthesis Example 1 of Compound (B)
Synthesis of CR-1B Sufficiently dried, nitrogen-substituted dropping funnel, Jim Roth condenser, thermometer, four-necked flask (1000 ml) equipped with a stirring blade, under a nitrogen stream, resorcinol (manufactured by Kanto Chemical Co., Inc.) 22 g, 0.2 mol), 4-isopropylbenzaldehyde (29.6 g, 0.2 mol) and dehydrated ethanol (200 ml) were added to prepare an ethanol solution. This solution was heated to 85 ° C. with a mantle heater while stirring. Next, 75 ml of concentrated hydrochloric acid (35%) was added dropwise over 30 minutes using a dropping funnel, and then stirred at 85 ° C. for 3 hours. After the completion of the reaction, the mixture was allowed to cool and allowed to reach room temperature, and then cooled in an ice bath. After standing for 1 hour, pale yellow target crude crystals were produced, which were filtered off. The crude crystals were washed twice with 500 ml of methanol, filtered and dried in vacuo to obtain the desired product (hereinafter referred to as CR-1B) (45.6 g, yield 95%).
As a result of analyzing the structure of this compound by LC-MS, f) the molecular weight of the target product was 960. Moreover, the chemical shift value (δppm, TMS standard) of 1 H-NMR in a heavy dimethyl sulfoxide solvent is 1.1 to 1.2 (m, 24H), 2.6 to 2.7 (m, 4H), 5 0.5 (s, 4H), 6.0-6.8 (m, 24H), 8.4, 8.5 (d, 8H).
Further, g) soluble in an alkali developer (TMAH 2.38 wt%), h) a phenolic hydroxyl group in the molecule, and e) Mw / Mn = 1.00.
CR−2Bの合成
CR−1Bの合成例における4−イソプロピルベンズアルデヒドを4−シクロヘキシルアルデヒドに代えた以外はCR−1と同様に合成した。その結果、CR−2B(50g、収率91%)を得た。
この化合物の構造は、LC−MSで分析した結果、f)目的物の分子量1121を示した。また重クロロホルム溶媒中での1H−NMRのケミカルシフト値(δppm,TMS基準)は0.8〜1.9(m,44H)、5.5,5.6(d,4H)、6.0〜6.8(m,24H)、8.4,8.5(m,8H)であった。
また、g)アルカリ現像液(TMAH2.38wt%)に可溶であり、h)分子内にフェノール性水酸基を有し、e)Mw/Mn=1.00であった。 Synthesis of CR-2B Synthesis was performed in the same manner as CR-1 except that 4-isopropylbenzaldehyde in the synthesis example of CR-1B was replaced with 4-cyclohexylaldehyde. As a result, CR-2B (50 g, yield 91%) was obtained.
As a result of analyzing the structure of this compound by LC-MS, f) the molecular weight of the target product was 1121. The chemical shift value (δ ppm, TMS standard) of 1 H-NMR in deuterated chloroform solvent is 0.8 to 1.9 (m, 44H), 5.5, 5.6 (d, 4H), 6. It was 0-6.8 (m, 24H), 8.4, 8.5 (m, 8H).
Further, g) soluble in an alkali developer (TMAH 2.38 wt%), h) a phenolic hydroxyl group in the molecule, and e) Mw / Mn = 1.00.
CR−1A−EE100の合成
十分乾燥し、窒素置換した滴下漏斗、ジム・ロート氏冷却管、温度計、攪拌翼を設置した四つ口フラスコ(1000ml)に、窒素気流下で、CR−1B 9.6g(10mmol)と、p−トルエンスルホン酸ピリジニウム2.5g、400ml アセトンからなる溶液に、エチルビニルエーテル 5.8g(80mmol)を滴下した。反応液を24時間室温で撹拌した。反応終了後、溶媒を除去し、得られた固体を、ヘキサン/酢酸エチル=1/3の混合溶媒を用い、カラムクロマトで精製した。フェノール性水酸基の水素原子の100mol%がエトキシエチル基で置換されたCR−1A−EE100 12.2gを得た。
この化合物の構造は、LC−MSで分析した結果、a)目的物の分子量1537を示した。得られた生成物の重ジメチルスルホキシド溶媒中での1H−NMRのケミカルシフト値(δppm,TMS基準)は0.9〜1.0(m,24H)、1.1〜1.2(m,24H)、1.3〜1.4(m,24H)、2.6〜2.7(m,4H)、3.3〜3.4(m,16H)、5.1(m,8H)、5.5(s,4H)、6.0〜6.8(m,24H)であった。
また、b)アルカリ現像液(TMAH2.38wt%)に不溶であり、c)酸の作用により、アルカリ現像液(TMAH2.38wt%)に可溶となり、d)分子内に酸解離性反応基であるエトキシエチル基を有し、e)Mw/Mn=1.00であった。 Synthesis of CR-1A-EE100 A well-dried, nitrogen-substituted dropping funnel, Jim Roth condenser, thermometer, and four-necked flask (1000 ml) equipped with a stirring blade were placed under a nitrogen stream under CR-1B 9 5.8 g (80 mmol) of ethyl vinyl ether was added dropwise to a solution consisting of .6 g (10 mmol), 2.5 g of pyridinium p-toluenesulfonate, and 400 ml of acetone. The reaction was stirred at room temperature for 24 hours. After completion of the reaction, the solvent was removed, and the resulting solid was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 1/3. CR-1A-EE100 12.2g by which 100 mol% of the hydrogen atoms of the phenolic hydroxyl group was substituted with an ethoxyethyl group was obtained.
As a result of analyzing the structure of this compound by LC-MS, a) the molecular weight of the target compound was 1537. The chemical shift value (δppm, TMS standard) of 1 H-NMR in the heavy dimethyl sulfoxide solvent of the obtained product is 0.9 to 1.0 (m, 24H), 1.1 to 1.2 (m , 24H), 1.3-1.4 (m, 24H), 2.6-2.7 (m, 4H), 3.3-3.4 (m, 16H), 5.1 (m, 8H) ), 5.5 (s, 4H), 6.0 to 6.8 (m, 24H).
And b) insoluble in an alkali developer (TMAH 2.38 wt%), c) soluble in an alkali developer (TMAH 2.38 wt%) by the action of an acid, and d) an acid-dissociable reactive group in the molecule. It had a certain ethoxyethyl group, and e) Mw / Mn = 1.00.
CR−1A−CE100の合成
十分乾燥し、窒素置換した滴下漏斗、ジム・ロート氏冷却管、温度計、攪拌翼を設置した四つ口フラスコ(1000ml)に、窒素気流下で、合成例1で合成したCR−1B 9.6g(10mmol)と、p−トルエンスルホン酸ピリジニウム2.5g、400ml 1,3−ジオキソランからなる溶液に、シクロヘキシルビニルエーテル 10.0g(80mmol)を滴下した。反応液を24時間室温で撹拌した。反応終了後、溶媒を除去し、得られた固体を、ヘキサン/酢酸エチル=1/3の混合溶媒を用い、カラムクロマトで精製した。フェノール性水酸基の水素原子の100mol%がシクロヘキシロキシエチル基で置換されたCR−1A−CE100 12.2gを得た。
この化合物の構造は、LC−MSで分析した結果、a)目的物の分子量1969を示した。得られた生成物の重ジメチルスルホキシド溶媒中での1H−NMRのケミカルシフト値(δppm,TMS基準)は1.0〜3.5(m,148H)、5.5(s,4H)、6.0〜6.8(m,24H)であった。
また、b)アルカリ現像液(TMAH2.38wt%)に不溶であり、c)酸の作用により、アルカリ現像液(TMAH2.38wt%)に可溶となり、d)分子内に酸解離性反応基であるシクロヘキシロキシエチル基を有し、e)Mw/Mn=1.00であった。 Synthesis of CR-1A-CE100 In a four-necked flask (1000 ml) equipped with a well-dried, nitrogen-substituted dropping funnel, Jim Roth condenser, thermometer, and stirring blade in a nitrogen stream under Synthesis Example 1 To a solution consisting of 9.6 g (10 mmol) of the synthesized CR-1B and 2.5 g of pyridinium p-toluenesulfonate and 400 ml of 1,3-dioxolane, 10.0 g (80 mmol) of cyclohexyl vinyl ether was added dropwise. The reaction was stirred at room temperature for 24 hours. After completion of the reaction, the solvent was removed, and the resulting solid was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 1/3. CR-1A-CE100 12.2g by which 100 mol% of the hydrogen atoms of the phenolic hydroxyl group were substituted with a cyclohexyloxyethyl group was obtained.
As a result of analyzing the structure of this compound by LC-MS, a) the molecular weight of the target compound was 1969. The chemical shift value (δppm, TMS standard) of 1 H-NMR in the heavy dimethyl sulfoxide solvent of the obtained product is 1.0 to 3.5 (m, 148H), 5.5 (s, 4H), It was 6.0 to 6.8 (m, 24H).
And b) insoluble in an alkali developer (TMAH 2.38 wt%), c) soluble in an alkali developer (TMAH 2.38 wt%) by the action of an acid, and d) an acid-dissociable reactive group in the molecule. It had a certain cyclohexyloxyethyl group, and e) Mw / Mn = 1.00.
CR−2A−EE100の合成
十分乾燥し、窒素置換した滴下漏斗、ジム・ロート氏冷却管、温度計、攪拌翼を設置した四つ口フラスコ(1000ml)に、窒素気流下で、合成例2Aで合成したCR−1B 11.2g(10mmol)と、p−トルエンスルホン酸ピリジニウム2.5g、400ml アセトンからなる溶液に、エチルビニルエーテル 5.8g(80mmol)を滴下した。反応液を24時間室温で撹拌した。反応終了後、溶媒を除去し、得られた固体を、ヘキサン/酢酸エチル=1/3の混合溶媒を用い、カラムクロマトで精製した。フェノール性水酸基の水素原子の100mol%がエトキシエチル基で置換されたCR−2A−EE100 12.5gを得た。
この化合物の構造は、LC−MSで分析した結果、a)目的物の分子量1697を示した。得られた生成物の重ジメチルスルホキシド溶媒中での1H−NMRのケミカルシフト値(δppm,TMS基準)は0.8〜1.9(m,92H)、3.5(m,16H)、5.5,5.6(d,12H)、6.0〜6.8(m,24H)であった。
また、b)アルカリ現像液(TMAH2.38wt%)に不溶であり、c)酸の作用により、アルカリ現像液(TMAH2.38wt%)に可溶となり、d)分子内に酸解離性反応基であるエトキシエチル基を有し、e)Mw/Mn=1.00であった。 Synthesis of CR-2A-EE100 In a four-necked flask (1000 ml) equipped with a well-dried, nitrogen -fitted dropping funnel, Jim Roth condenser, thermometer, and stirring blade in a nitrogen stream, in Synthesis Example 2A To a solution consisting of 11.2 g (10 mmol) of the synthesized CR-1B, 2.5 g of pyridinium p-toluenesulfonate, and 400 ml of acetone, 5.8 g (80 mmol) of ethyl vinyl ether was added dropwise. The reaction was stirred at room temperature for 24 hours. After completion of the reaction, the solvent was removed, and the resulting solid was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 1/3. 12.5 g of CR-2A-EE100 in which 100 mol% of the hydrogen atoms of the phenolic hydroxyl group were substituted with an ethoxyethyl group was obtained.
The structure of this compound was analyzed by LC-MS. As a result, a) the molecular weight of the target product was 1697. The chemical shift value (δppm, TMS standard) of 1 H-NMR in the heavy dimethyl sulfoxide solvent of the obtained product is 0.8 to 1.9 (m, 92H), 3.5 (m, 16H), 5.5, 5.6 (d, 12H), 6.0-6.8 (m, 24H).
And b) insoluble in an alkali developer (TMAH 2.38 wt%), c) soluble in an alkali developer (TMAH 2.38 wt%) by the action of an acid, and d) an acid-dissociable reactive group in the molecule. It had a certain ethoxyethyl group, and e) Mw / Mn = 1.00.
CR−2A−CE100の合成
十分乾燥し、窒素置換した滴下漏斗、ジム・ロート氏冷却管、温度計、攪拌翼を設置した四つ口フラスコ(1000ml)に、窒素気流下で、合成例2で合成したCR−2B 11.2g(10mmol)と、p−トルエンスルホン酸ピリジニウム2.5g、400ml 1,3−ジオキソランからなる溶液に、シクロヘキシルビニルエーテル 10.0g(80mmol)を滴下した。反応液を24時間室温で撹拌した。反応終了後、溶媒を除去し、得られた固体を、ヘキサン/酢酸エチル=1/3の混合溶媒を用い、カラムクロマトで精製した。フェノール性水酸基の水素原子の100mol%がシクロヘキシロキシエチル基で置換されたCR−2A−CE100 13.2gを得た。
この化合物の構造は、LC−MSで分析した結果、a)目的物の分子量2129を示した。得られた生成物の重ジメチルスルホキシド溶媒中での1H−NMRのケミカルシフト値(δppm,TMS基準)は0.8〜1.9(m,148H)、3.5(m,8H)、5.5,5.6(d,12H)、6.0〜6.8(m,24H)であった。
また、b)アルカリ現像液(TMAH2.38wt%)に不溶であり、c)酸の作用により、アルカリ現像液(TMAH2.38wt%)に可溶となり、d)分子内に酸解離性反応基であるシクロヘキシロキシエチル基を有し、e)Mw/Mn=1.00であった。 Synthesis of CR-2A-CE100 In a four-necked flask (1000 ml) equipped with a well-dried, nitrogen-substituted dropping funnel, Jim Roth condenser, thermometer, and stirring blade in a nitrogen stream under Synthesis Example 2 To a solution consisting of 11.2 g (10 mmol) of the synthesized CR-2B and 2.5 g of pyridinium p-toluenesulfonate and 400 ml of 1,3-dioxolane, 10.0 g (80 mmol) of cyclohexyl vinyl ether was added dropwise. The reaction was stirred at room temperature for 24 hours. After completion of the reaction, the solvent was removed, and the resulting solid was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 1/3. CR-2A-CE100 13.2g by which 100 mol% of the hydrogen atoms of the phenolic hydroxyl group was substituted with a cyclohexyloxyethyl group was obtained.
As a result of analyzing the structure of this compound by LC-MS, a) the molecular weight of the target compound was 2129. The chemical shift value (δppm, TMS standard) of 1 H-NMR in the heavy dimethyl sulfoxide solvent of the obtained product is 0.8 to 1.9 (m, 148H), 3.5 (m, 8H), 5.5, 5.6 (d, 12H), 6.0-6.8 (m, 24H).
And b) insoluble in an alkali developer (TMAH 2.38 wt%), c) soluble in an alkali developer (TMAH 2.38 wt%) by the action of an acid, and d) an acid-dissociable reactive group in the molecule. It had a certain cyclohexyloxyethyl group, and e) Mw / Mn = 1.00.
CR−1A−EE50の合成
CR−1A−EE100の合成例におけるエチルビニルエーテルの仕込み量を半分に代えた以外はCR−1A−EE100と同様に合成し、フェノール性水酸基の水素原子の50mol%がエトキシエチル基で置換されたCR−1A−EE50(混合物)を得た。
なお、得られた化合物は、b)アルカリ現像液(TMAH2.38wt%)に不溶であり、c)酸の作用により、アルカリ現像液(TMAH2.38wt%)に可溶となり、d)分子内に酸解離性反応基であるエトキシエチル基を有している。 Synthesis of CR-1A-EE50 Synthesis was performed in the same manner as CR-1A-EE100 except that the amount of ethyl vinyl ether in the synthesis example of CR-1A-EE100 was changed to half, and 50 mol% of the hydrogen atoms of the phenolic hydroxyl group were ethoxylated. CR-1A-EE50 (mixture) substituted with an ethyl group was obtained.
The obtained compound is b) insoluble in an alkali developer (TMAH 2.38 wt%), c) becomes soluble in an alkali developer (TMAH 2.38 wt%) by the action of an acid, and d) within the molecule. It has an ethoxyethyl group which is an acid dissociable reactive group.
CR−1A−CE50の合成
CR−1A−CE100の合成例におけるエチルビニルエーテルの仕込み量を半分に代えた以外はCR−1A−CE100と同様に合成し、フェノール性水酸基の水素原子の50mol%がエトキシエチル基で置換されたCR−1A−CE50(混合物)を得た。
なお、得られた化合物は、b)アルカリ現像液(TMAH2.38wt%)に不溶であり、c)酸の作用により、アルカリ現像液(TMAH2.38wt%)に可溶となり、d)分子内に酸解離性反応基であるシクロヘキシロキシエチル基を有している。 Synthesis of CR-1A-CE50 Synthesis was performed in the same manner as CR-1A-CE100 except that the amount of ethyl vinyl ether in the synthesis example of CR-1A-CE100 was changed to half, and 50 mol% of the hydrogen atoms of the phenolic hydroxyl group were ethoxylated. CR-1A-CE50 (mixture) substituted with an ethyl group was obtained.
The obtained compound is b) insoluble in an alkali developer (TMAH 2.38 wt%), c) becomes soluble in an alkali developer (TMAH 2.38 wt%) by the action of an acid, and d) within the molecule. It has a cyclohexyloxyethyl group which is an acid dissociable reactive group.
CR−2A−EE50の合成
CR−2A−EE100の合成例におけるエチルビニルエーテルの仕込み量を半分に代えた以外はCR−2A−EE100と同様に合成し、フェノール性水酸基の水素原子の50mol%がシクロヘキシロキシエチル基で置換されたCR−2A−EE50(混合物)を得た。
なお、得られた化合物は、b)アルカリ現像液(TMAH2.38wt%)に不溶であり、c)酸の作用により、アルカリ現像液(TMAH2.38wt%)に可溶となり、d)分子内に酸解離性反応基であるエトキシエチル基を有している。 Synthesis of CR-2A-EE50 Synthesis was performed in the same manner as CR-2A-EE100, except that the amount of ethyl vinyl ether in the synthesis example of CR-2A-EE100 was changed to half, and 50 mol% of the hydrogen atoms of the phenolic hydroxyl group was cyclohexane. CR-2A-EE50 (mixture) substituted with a siloxyethyl group was obtained.
The obtained compound is b) insoluble in an alkali developer (TMAH 2.38 wt%), c) becomes soluble in an alkali developer (TMAH 2.38 wt%) by the action of an acid, and d) within the molecule. It has an ethoxyethyl group which is an acid dissociable reactive group.
CR−2A−CE50の合成
CR−2A−CE100の合成例におけるエチルビニルエーテルの仕込み量を半分に代えた以外はCR−2A−CE100と同様に合成し、フェノール性水酸基の水素原子の50mol%がシクロヘキシロキシエチル基で置換されたCR−2A−CE50(混合物)を得た。
なお、得られた化合物は、b)アルカリ現像液(TMAH2.38wt%)に不溶であり、c)酸の作用により、アルカリ現像液(TMAH2.38wt%)に可溶となり、d)分子内に酸解離性反応基であるシクロヘキシロキシエチル基を有している。 Synthesis of CR-2A-CE50 Synthesis was performed in the same manner as CR-2A-CE100 except that the amount of ethyl vinyl ether used in the synthesis example of CR-2A-CE100 was changed to half, and 50 mol% of the hydrogen atoms of the phenolic hydroxyl group was cyclohexane. CR-2A-CE50 (mixture) substituted with a siloxyethyl group was obtained.
The obtained compound is b) insoluble in an alkali developer (TMAH 2.38 wt%), c) becomes soluble in an alkali developer (TMAH 2.38 wt%) by the action of an acid, and d) within the molecule. It has a cyclohexyloxyethyl group which is an acid dissociable reactive group.
(実施例1〜4および比較例1〜8)
パターニング試験
第1表記載の成分を調合し、均一溶液としたのち、孔径0.1μmのテフロン(登録商標)製メンブランフィルターで濾過して、感放射線性組成物を調製し、各々について以下の評価を行った。結果を第3表に示す。
(1)感度の評価
レジストを清浄なシリコンウェハー上に回転塗布した後、オーブン中で露光前ベーク(PB)して、厚さ60nmのレジスト膜を形成した。該レジスト膜を電子線描画装置(ELS−7500,(株)エリオニクス社製)を用いて、100nm間隔の1:1のラインアンドスペース設定の電子線を照射した。照射後に、それぞれ所定の温度で、90秒間加熱し、2.38重量%TMAH水溶液に60秒間現像を行った。その後、水で30秒間洗浄し、乾燥して、ポジ型のレジストパターンを形成した。得られたラインアンドスペースを走査型電子顕微鏡((株)日立ハイテクノロジー製S−4800)により観察した。またその際のドーズ量(μC/cm2)を感度とした。
A:ドーズ量≦50μC/cm2 (優秀な感度)
B:50μC/cm2<ドーズ量≦120μC/cm2 (良好な感度)
C:120μC/cm2<ドーズ量 (感度不良)(Examples 1-4 and Comparative Examples 1-8)
Patterning test The ingredients listed in Table 1 were mixed to form a uniform solution, and then filtered through a Teflon (registered trademark) membrane filter having a pore size of 0.1 μm to prepare a radiation-sensitive composition. Went. The results are shown in Table 3.
(1) Evaluation of sensitivity After a resist was spin-coated on a clean silicon wafer, pre-exposure baking (PB) was performed in an oven to form a resist film having a thickness of 60 nm. The resist film was irradiated with an electron beam with a line and space setting of 1: 1 at 100 nm intervals using an electron beam drawing apparatus (ELS-7500, manufactured by Elionix Co., Ltd.). After irradiation, each was heated at a predetermined temperature for 90 seconds and developed in a 2.38 wt% TMAH aqueous solution for 60 seconds. Thereafter, it was washed with water for 30 seconds and dried to form a positive resist pattern. The obtained line and space was observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technology Corporation). The dose amount (μC / cm 2 ) at that time was defined as sensitivity.
A: Dose amount ≦ 50 μC / cm 2 (excellent sensitivity)
B: 50 μC / cm 2 <dose amount ≦ 120 μC / cm 2 (good sensitivity)
C: 120 μC / cm 2 <dose amount (sensitivity failure)
(2)ラインエッジラフネス(LER)の評価
100nm間隔の1:1のラインアンドスペースの長さ方向(0.75μm)の任意の300点において、日立半導体用SEM ターミナルPC V5オフライン測長ソフトウェア((株)日立サイエンスシステムズ製)を用いて、エッジと基準線との距離を測定した。測定結果から標準偏差(3σ)を算出した。
A:LER(3σ)≦3.5nm (良好なLER)
C:3.5nm<LER(3σ) (良好でないLER)(2) Evaluation of Line Edge Roughness (LER) Hitachi Semiconductor's SEM Terminal PC V5 offline length measurement software at (300 points in the length direction (0.75 μm) of 1: 1 line and space at 100 nm intervals (( Using Hitachi Science Systems Co., Ltd.), the distance between the edge and the reference line was measured. The standard deviation (3σ) was calculated from the measurement result.
A: LER (3σ) ≦ 3.5 nm (good LER)
C: 3.5 nm <LER (3σ) (not good LER)
パターニング試験の結果から、本発明の特定の化合物(A)および化合物(B)を用いた感放射線性組成物は、比較例の混合物からなる化合物(A)を用いた感放射線性組成物よりも感度およびLERが良好であることが認められた。 From the results of the patterning test, the radiation-sensitive composition using the specific compound (A) and the compound (B) of the present invention is more than the radiation-sensitive composition using the compound (A) composed of the mixture of the comparative example. Sensitivity and LER were found to be good.
また本発明の特定の化合物(A)および化合物(B)はそれぞれ純度100%のものの製造が容易、かつそれぞれを混合するのみで調合でき、品質管理が容易である。一方、比較例の混合物からなる化合物(A)は混合物であり、製造毎にその組成にばらつきが生じ、品質管理が困難であった。 In addition, the specific compound (A) and compound (B) of the present invention can be easily manufactured with a purity of 100%, and can be prepared simply by mixing them, so that quality control is easy. On the other hand, the compound (A) composed of the mixture of the comparative example was a mixture, and the composition thereof varied from production to production, making quality control difficult.
(C)酸発生剤
P−1:トリフェニルベンゼンスルホニウム トリフルオロメタンスルホネート(みどり化学(株))
(E)酸拡散制御剤
Q−1 トリオクチルアミン(東京化成工業(株))
溶媒
S−1 プロピレングリコールモノメチルエーテル(東京化成工業(株))(C) Acid generator P-1: Triphenylbenzenesulfonium trifluoromethanesulfonate (Midori Chemical Co., Ltd.)
(E) Acid diffusion controller Q-1 Trioctylamine (Tokyo Chemical Industry Co., Ltd.)
Solvent S-1 Propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.)
(比較例9)
実施例4において化合物(A)のCR−2A−CE100の代わりに高分子であるポリヒドロキシスチレン(PHS)(Mw=8,000;アルドリッチ製)に常法によりシクロヘキシルオキシエチル基を100mol%導入したPHS−CE100を用いた以外は、同様にパターニング試験を行なった。その結果、LERはCと判定された。(Comparative Example 9)
In Example 4, 100 mol% of a cyclohexyloxyethyl group was introduced into polyhydroxystyrene (PHS) (Mw = 8,000; manufactured by Aldrich), which is a polymer, instead of CR-2A-CE100 of compound (A) by a conventional method. A patterning test was performed in the same manner except that PHS-CE100 was used. As a result, LER was determined to be C.
(比較例10)
実施例4において化合物(B)のCR−2Bの代わりに高分子であるポリヒドロキシスチレン(PHS)(Mw=8,000;アルドリッチ製)を用いた以外は、同様にパターニング試験を行なった。その結果、LERはCと判定された。(Comparative Example 10)
A patterning test was conducted in the same manner as in Example 4 except that polyhydroxystyrene (PHS) (Mw = 8,000; manufactured by Aldrich), which is a polymer, was used instead of CR-2B of the compound (B). As a result, LER was determined to be C.
(比較例11)
実施例4において化合物(A)のCR−2A−CE100の代わりにPHS−CE100を用い、化合物(B)のCR−2Bの代わりに高分子であるポリヒドロキシスチレン(PHS)(Mw=8,000;アルドリッチ製)を用いた以外は、同様にパターニング試験を行なった。その結果、120μC/cm2以下のドーズ量ではパターンが得られなかった。(Comparative Example 11)
In Example 4, PHS-CE100 was used instead of CR-2A-CE100 of compound (A), and polyhydroxystyrene (PHS) (Mw = 8,000), which is a polymer, was used instead of CR-2B of compound (B). A patterning test was conducted in the same manner except that Aldrich was used. As a result, a pattern was not obtained with a dose of 120 μC / cm 2 or less.
また、比較例9〜11のいずれも、スピンコートにより得られた膜に、相溶解性不良によると考えられるむらが認められた。
さらには、高分子であるポリヒドロキシスチレンまたは酸解離性官能基を導入したポリヒドロキシスチレンは、それぞれ分子量分布を有しており、品質管理の観点からも好ましくないことが示唆された。In each of Comparative Examples 9 to 11, unevenness considered to be due to poor phase solubility was observed in the film obtained by spin coating.
Furthermore, it was suggested that polyhydroxystyrene which is a polymer or polyhydroxystyrene having an acid-dissociable functional group introduced has a molecular weight distribution, which is not preferable from the viewpoint of quality control.
本発明は、酸増幅型低分子量ポジ型感放射線性組成物、および該組成物を用いるレジストパターン形成方法に好適に使用される。 The present invention is suitably used for an acid amplification type low molecular weight positive radiation sensitive composition and a resist pattern forming method using the composition.
Claims (2)
a)分子量:400〜3000
b)アルカリ現像液(テトラメチルアンモニウムヒドロキシド(TMAH)2.38wt%)に不溶
c)酸の作用により、アルカリ現像液(TMAH2.38wt%)に可溶となる
d)分子内に少なくとも1つの酸解離性官能基の導入されたフェノール性水酸基またはカルボキシル基を有する
e)1.00≦Mw/Mn≦1.05 (Mn:数平均分子量、Mw:重量平均分子量)
f)分子量:350〜2500
g)アルカリ現像液(TMAH2.38wt%)に可溶
h)分子内に少なくとも1つのフェノール性水酸基またはカルボキシル基を有する
i)1.00≦Mw/Mn≦1.05
(式(5A−1)において、R 2 は炭素数2〜20の置換メチル基、炭素数3〜20の1−置換エチル基、炭素数4〜20の1−置換−n−プロピル基、炭素数3〜20の1−分岐アルキル基、炭素数1〜20のシリル基、炭素数2〜20のアシル基、炭素数2〜20の1−置換アルコキシアルキル基、炭素数2〜20の環状エーテル基、炭素数2〜20のアルコキシカルボニル基およびアルコキシカルボニルアルキル基からなる群から選択される酸解離性官能基である。)
a) Molecular weight: 400 to 3000
b) Insoluble in alkali developer (tetramethylammonium hydroxide (TMAH) 2.38 wt%) c) Soluble in alkali developer (TMAH 2.38 wt%) by the action of acid d) At least one in the molecule E) 1.00 ≦ Mw / Mn ≦ 1.05 (Mn: number average molecular weight, Mw: weight average molecular weight)
f) Molecular weight: 350-2500
g) Soluble in alkali developer (TMAH 2.38 wt%) h) At least one phenolic hydroxyl group or carboxyl group in the molecule i) 1.00 ≦ Mw / Mn ≦ 1.05
(In the formula (5A-1), R 2 represents a substituted methyl group having 2 to 20 carbon atoms, a 1-substituted ethyl group having 3 to 20 carbon atoms, a 1-substituted n-propyl group having 4 to 20 carbon atoms, carbon 1-branched alkyl group having 3 to 20 carbon atoms, silyl group having 1 to 20 carbon atoms, acyl group having 2 to 20 carbon atoms, 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, cyclic ether having 2 to 20 carbon atoms An acid dissociable functional group selected from the group consisting of a group, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an alkoxycarbonylalkyl group.)
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JP2009221195A (en) * | 2008-02-22 | 2009-10-01 | Sumitomo Chemical Co Ltd | Ester compound, and method of preparing the same |
JP2009244804A (en) * | 2008-03-31 | 2009-10-22 | Fujifilm Corp | Positive resist composition and pattern forming method using the same |
JP2010159253A (en) * | 2008-12-11 | 2010-07-22 | Sumitomo Chemical Co Ltd | Compound and photoresist composition |
JP2011028270A (en) * | 2009-07-23 | 2011-02-10 | Internatl Business Mach Corp <Ibm> | Calixarene, blended molecular glass, photoresists and processes of use |
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WO2011070718A1 (en) | 2011-06-16 |
TW201131300A (en) | 2011-09-16 |
JPWO2011070718A1 (en) | 2013-04-22 |
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