JP6332113B2 - Shrink material and pattern forming method - Google Patents

Description

  The present invention relates to a shrink material capable of effectively reducing the size of a resist pattern, and a pattern forming method using the shrink material.

  In recent years, with the higher integration and higher speed of LSIs, there is a demand for finer pattern rules. In light exposure currently used as a general-purpose technology, the intrinsic resolution limit derived from the wavelength of the light source In order to overcome this problem, microfabrication in which double patterning is combined with ArF excimer laser immersion lithography is performed. LELE (Litho-Etch-Litho-Etch) is a double patterning method in which the pattern exposed by etching is transferred to the hard mask of the substrate, and the second exposure is performed at a position shifted by half the pitch to process the hard mask. Law. This method has a problem of causing a positional deviation between two exposures. On the other hand, the SADP (Self-Aligned Double Patterning) method, in which a resist pattern is transferred to a hard mask and a film is formed on both side walls of the hard mask, thereby doubling the pattern, requires only one exposure so that the position is shifted. Problem can be reduced. In order to simplify the process, a SADP method has also been proposed in which a silicon oxide film is formed not on the side wall of the hard mask but on the side wall of the resist pattern after development, thereby doubling the pattern. The pitch of the line pattern can be halved by the SADP method, and the pitch can be reduced to ¼ by repeating SADP twice.

  Along with the reduction of the line pattern, it is also necessary to reduce the hole pattern. Without the reduction of the hole pattern, the reduction of the entire chip is incomplete. As a hole pattern shrinking method, the RELACS method described in Patent Document 1 can be cited. In this method, the dimension of the hole pattern is reduced by applying a water-soluble material containing a crosslinking agent onto the resist pattern after development and crosslinking the resist surface by baking to increase the thickness of the resist pattern. Patent Document 2 reports a polymer material having an amino group and a shrink material containing a polyamine as a material that is thickened by adhering to a carboxyl group on the resist surface while performing a neutralization reaction. Furthermore, a method of shrinking a hole pattern using a block copolymer self-alignment technique (DSA) has also been proposed (Non-patent Document 1).

  In shrinking by the RELACS method, when an acid-catalyzed cross-linking agent in a resist is used, there is a problem that the size of holes after shrinking becomes non-uniform due to non-uniform acid diffusion. In shrink due to neutralization adhesion of amino polymer, the pattern thickness is increased by directly reflecting the unevenness of the resist surface, so that the resist pattern dimensional variation after development and the dimensional variation after shrink are the same. In shrinking by DSA using a block copolymer, there is an advantage that the shrink amount is large and the dimensional variation after shrinking is small. However, if DSA is applied to holes with different dimensions, the shape of the block copolymer may be shrunk when the hole dimensions cause inconsistencies in the arrangement of the block copolymer, or multiple hole patterns may be formed when DSA is applied to the trench pattern. It has been pointed out the problem.

  Therefore, there is a demand for the development of a shrink material that can shrink the hole pattern without changing the shape and can improve the dimensional variation and edge roughness (LWR) of the resist pattern after development.

Japanese Patent Laid-Open No. 10-73927 JP 2008-275995 A JP 2007-293294 A

Proc. SPIE, Vol. 8323, p83230W-1 (2012)

  As described above, the method of applying a crosslinking type or neutralization reaction type RELACS agent on the resist pattern cannot reduce the dimensional variation of the resist pattern, although the shape is not deformed. Further, Patent Document 3 proposes an alkaline aqueous solution type shrink material for a positive tone resist pattern formed by alkali development. However, with respect to pattern shrink of a narrow pitch hole pattern, a sufficient shrink amount and good dimensions are proposed. Variations cannot be obtained.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a shrink material capable of shrinking a hole pattern while improving dimensional variations, and a pattern forming method using the shrink material.

  In order to achieve the above object, the present inventors have studied a shrink material that can efficiently reduce a resist pattern after development, and a pattern forming method using the shrink material. As a result, a predetermined polymer is formed on a negative tone resist pattern formed by exposure and organic solvent development on a resist film based on a polymer compound having a carboxyl group substituted with an acid labile group and an acid generator. A shrink material containing a compound and a solvent containing a solvent that does not erase the resist pattern after development is applied, further baked, and the excess material is peeled off with an organic solvent, so that the hole and / or slit portion of the resist pattern is removed. The inventors have found that the dimensions can be reduced with good control, and have completed the present invention.

（式中、Ａは、単結合、又は鎖の中間にエーテル性酸素原子を含んでもよい炭素数１〜１０のアルキレン基を表す。Ｒ¹は、水素原子、フッ素原子、メチル基又はトリフルオロメチル基を表す。Ｒ²は、それぞれ独立に、水素原子、ハロゲン原子、ハロゲン置換されていてもよい炭素数２〜８の直鎖状、分岐状若しくは環状のアシルオキシ基、ハロゲン置換されていてもよい炭素数１〜６の直鎖状、分岐状若しくは環状のアルキル基、又はハロゲン置換されていてもよい炭素数１〜６の直鎖状、分岐状若しくは環状のアルコキシ基を表す。Ｌは、水素原子、鎖の中間にエーテル性酸素原子、カルボニル基若しくはカルボニルオキシ基を含んでもよい炭素数１〜１０の直鎖状、分岐状若しくは環状の１価脂肪族炭化水素基、又は置換基を有してもよい１価芳香環含有基を表す。Ｚは、これが結合する炭素原子と共に形成される炭素数５〜１５の脂環基を表す。Ｒ^x及びＲ^yは、それぞれ独立に、水素原子、ヒドロキシ基若しくはアルコキシ基で置換されていてもよい炭素数１〜１５の直鎖状、分岐状若しくは環状のアルキル基であるが、Ｒ^x及びＲ^yの少なくとも一方は、炭素数５〜１５の環状のアルキル基である。ｆは１〜３の整数を表し、ｓは０〜２の整数を表し、ａは（５＋２ｓ−ｆ）である。ｍは０又は１を表す。）
［２］前記高分子化合物が、更に、下記式（２）で表される繰り返し単位を含む［１］のシュリンク材料。

（式中、Ｂは、単結合、又は鎖の中間にエーテル性酸素原子を含んでもよい炭素数１〜１０のアルキレン基を表す。Ｒ¹は前記と同じ。Ｒ³は、それぞれ独立に、水素原子、ハロゲン原子、ハロゲン置換されていてもよい炭素数２〜８の直鎖状、分岐状若しくは環状のアシルオキシ基、ハロゲン置換されていてもよい炭素数１〜６の直鎖状、分岐状若しくは環状のアルキル基、又はハロゲン置換されていてもよい炭素数１〜６の直鎖状、分岐状若しくは環状のアルコキシ基を表す。ｇは０〜３の整数を表し、ｔは０〜２の整数を表し、ｂは（５＋２ｔ−ｇ）である。ｎは０又は１を表す。）
［３］前記高分子化合物が、更に、下記式（４）及び（５）で表される繰り返し単位から選ばれる少なくとも１つを含む［１］又は［２］のシュリンク材料。

（式中、Ｒ⁵及びＲ⁶は、それぞれ独立に、水素原子、ハロゲン原子、ハロゲン置換されていてもよい炭素数２〜８の直鎖状、分岐状若しくは環状のアシルオキシ基、ハロゲン置換されていてもよい炭素数１〜６の直鎖状、分岐状若しくは環状のアルキル基、又はハロゲン置換されていてもよい炭素数１〜６の直鎖状、分岐状若しくは環状のアルコキシ基を表す。ｉ及びｊは、それぞれ独立に０〜２の整数である。ｄは（６−ｉ）である。ｅは（４−ｊ）である。）
［４］前記高分子化合物が、更に、下記式（Ａ）〜（Ｅ）で表される繰り返し単位から選ばれる少なくとも１つを含む［１］〜［３］のいずれかのシュリンク材料。

（式中、Ｒ¹は、前記と同じ。Ｘ^Aは、酸不安定基を表す。Ｘ^B及びＸ^Cは、それぞれ独立に、単結合、又は炭素数１〜４の直鎖状若しくは分岐状の２価炭化水素基を表す。Ｘ^Dは、炭素数１〜１６の直鎖状、分岐状又は環状の２〜５価の脂肪族炭化水素基を表し、該炭化水素基を構成する−ＣＨ₂−が−Ｏ−又は−Ｃ(＝Ｏ)−に置換されていてもよい。Ｘ^Eは、酸不安定基を表す。Ｙ^Aは、ラクトン、スルトン又はカーボネート構造を有する置換基を示す。Ｚ^Aは、水素原子、又は炭素数１〜３０のフルオロアルキル基又は炭素数１〜１５のフルオロアルコール含有置換基を示す。ｋ^1Aは、１〜３の整数を示す。ｋ^1Bは、１〜４の整数を表す。）
［５］前記高分子化合物が、更に、下記式（Ｆ）で表される繰り返し単位を含む［１］〜［４］のいずれかのシュリンク材料。

（式中、Ｒ¹⁰¹は、水素原子又はメチル基である。Ｘは、単結合、−Ｃ(＝Ｏ)−、−Ｃ(＝Ｏ)−Ｏ−又は−Ｃ(＝Ｏ)−ＮＨ−である。Ｒ¹⁰²は、単結合、又は炭素数１〜１０の直鎖状、分岐状若しくは環状のアルキレン基であり、エーテル基、エステル基、カルボニル基、−Ｎ＝又は−Ｓ−を有していてもよく、又はフェニレン基若しくはナフチレン基である。Ｒ¹⁰³及びＲ¹⁰⁴は、それぞれ独立に、水素原子、炭素数１〜４の直鎖状又は分岐状のアルキル基又は酸不安定基であり、Ｒ¹⁰³とＲ¹⁰⁴とが結合してこれらが結合する窒素原子と共に環を形成してもよく、環の中にエーテル結合を有していてもよく、Ｒ¹⁰³及びＲ¹⁰⁴のどちらか一方がＲ¹⁰²と結合してこれらが結合する窒素原子と共に環を形成してもよい。ｋ^1Cは１又は２である。）
［６］更に、下記式（９）で表される塩を含む［１］〜［５］のいずれかのシュリンク材料。

（式中、Ｒ¹¹は、炭素数１〜２０の直鎖状、分岐状若しくは環状のアルキル基、炭素数２〜２０の直鎖状、分岐状若しくは環状のアルケニル基、又は炭素数６〜２０の１価芳香環含有基を表し、これらの基の炭素原子に結合する水素原子の一部又は全部が、フッ素原子、ラクトン環含有基、ラクタム環含有基又はヒドロキシ基で置換されていてもよく、これらの基の炭素−炭素結合間に、エーテル基、エステル基又はカルボニル基が介在していてもよい。Ｍ⁺は、スルホニウムカチオン、ヨードニウムカチオン又はアンモニウムカチオンを表す。）
［７］更に、下記式（１０）で表される塩を含む［１］〜［６］のいずれかのシュリンク材料。

（式中、Ｒ¹²は、酸素原子を含んでもよい炭素数１〜３５の直鎖状、分岐状又は環状の１価炭化水素基を表し、この基の炭素原子に結合する水素原子の一部又は全部がフッ素原子で置換されていてもよいが、スルホン酸のα位の炭素原子に結合する水素原子はフッ素原子で置換されない。Ｍ⁺は、スルホニウムカチオン、ヨードニウムカチオン又はアンモニウムカチオンを表す。）
［８］更に、第１級、第２級及び第３級の脂肪族アミン類、混成アミン類、芳香族アミン類、複素環アミン類、カルボキシル基を有する含窒素化合物、スルホニル基を有する含窒素化合物、ヒドロキシ基を有する含窒素化合物、ヒドロキシフェニル基を有する含窒素化合物、アルコール性含窒素化合物、アミド誘導体、イミド誘導体並びにカーバメート類から選ばれる少なくとも１種の塩基性化合物を含む［１］〜［７］のいずれかのシュリンク材料。
［９］前記現像後のレジストパターンを消失させない溶剤が、炭素数７〜１６のエステル系溶剤、炭素数８〜１６のケトン系溶剤又は炭素数４〜１０のアルコール系溶剤である［１］〜［８］のいずれかのシュリンク材料。
［１０］前記炭素数７〜１６のエステル系溶剤が、酢酸ペンチル、酢酸イソペンチル、酢酸２−メチルブチル、酢酸ヘキシル、酢酸２−エチルヘキシル、酢酸シクロヘキシル、酢酸メチルシクロヘキシル、ギ酸ヘキシル、吉草酸エチル、吉草酸プロピル、吉草酸イソプロピル、吉草酸ブチル、吉草酸イソブチル、吉草酸ｔ−ブチル、吉草酸ペンチル、吉草酸イソペンチル、イソ吉草酸エチル、イソ吉草酸プロピル、イソ吉草酸イソプロピル、イソ吉草酸ブチル、イソ吉草酸イソブチル、イソ吉草酸ｔ−ブチル、イソ吉草酸イソペンチル、２−メチル吉草酸エチル、２−メチル吉草酸ブチル、ピバル酸エチル、ピバル酸プロピル、ピバル酸イソプロピル、ピバル酸ブチル、ピバル酸ｔ−ブチル、ペンテン酸エチル、ペンテン酸プロピル、ペンテン酸イソプロピル、ペンテン酸ブチル、ペンテン酸ｔ−ブチル、クロトン酸プロピル、クロトン酸イソプロピル、クロトン酸ブチル、クロトン酸ｔ−ブチル、プロピオン酸ブチル、プロピオン酸イソブチル、プロピオン酸ｔ−ブチル、プロピオン酸ベンジル、ヘキサン酸エチル、ヘキサン酸アリル、酪酸プロピル、酪酸ブチル、酪酸イソブチル、酪酸３−メチルブチル、酪酸ｔ−ブチル、２−メチル酪酸エチル、２−メチル酪酸イソプロピル、安息香酸メチル、安息香酸エチル、安息香酸プロピル、安息香酸ブチル、酢酸フェニル、酢酸ベンジル、フェニル酢酸メチル、ギ酸ベンジル、ギ酸フェニルエチル、３−フェニルプロピオン酸メチル、フェニル酢酸エチル及び酢酸２−フェニルエチルから選ばれる１種以上の溶剤であり、前記炭素数８〜１６のケトン系溶剤が、２−オクタノン、３−オクタノン、４−オクタノン、２−ノナノン、３−ノナノン、４−ノナノン、５−ノナノン、ジイソブチルケトン、エチルシクロヘキサノン、エチルアセトフェノン、エチル−ｎ−ブチルケトン、ジ−ｎ−ブチルケトン及びジイソブチルケトンから選ばれる１種以上の溶剤であり、前記炭素数４〜１０のアルコール系溶剤が、１−ブタノール、２−ブタノール、イソブチルアルコール、ｔ−ブチルアルコール、１−ペンタノール、２−ペンタノール、３−ペンタノール、ｔ−ペンチルアルコール、ネオペンチルアルコール、２−メチル−１−ブタノール、３−メチル−１−ブタノール、３−メチル−３−ペンタノール、シクロペンタノール、１−ヘキサノール、２−ヘキサノール、３−ヘキサノール、２,３−ジメチル−２−ブタノール、３,３−ジメチル−１−ブタノール、３,３−ジメチル−２−ブタノール、２,２−ジエチル−１−ブタノール、２−メチル−１−ペンタノール、２−メチル−２−ペンタノール、２−メチル−３−ペンタノール、３−メチル−１−ペンタノール、３−メチル−２−ペンタノール、３−メチル−３−ペンタノール、４−メチル−１−ペンタノール、４−メチル−２−ペンタノール、４−メチル−３−ペンタノール、シクロヘキサノール及び１−オクタノールから選ばれる１種以上の溶剤である［９］のシュリンク材料。
［１１］前記溶剤が、前記現像後のレジストパターンを消失させない溶剤に加えて、更に２−オクタノン、２−ノナノン、２−ヘプタノン、３−ヘプタノン、４−ヘプタノン、２−ヘキサノン、３−ヘキサノン、ジイソブチルケトン、メチルシクロヘキサノン、アセトフェノン、メチルアセトフェノン、酢酸プロピル、酢酸ブチル、酢酸イソブチル、酢酸ペンチル、酢酸ブテニル、酢酸イソペンチル、ギ酸プロピル、ギ酸ブチル、ギ酸イソブチル、ギ酸ペンチル、ギ酸イソペンチル、吉草酸メチル、ペンテン酸メチル、クロトン酸メチル、クロトン酸エチル、プロピオン酸メチル、プロピオン酸エチル、３−エトキシプロピオン酸エチル、乳酸メチル、乳酸エチル、乳酸プロピル、乳酸ブチル、乳酸イソブチル、乳酸ペンチル、乳酸イソペンチル、２−ヒドロキシイソ酪酸メチル、２−ヒドロキシイソ酪酸エチル、安息香酸メチル、安息香酸エチル、酢酸フェニル、酢酸ベンジル、フェニル酢酸メチル、ギ酸ベンジル、ギ酸フェニルエチル、３−フェニルプロピオン酸メチル、プロピオン酸ベンジル、フェニル酢酸エチル及び酢酸２−フェニルエチルから選ばれる１種以上の溶剤を含む［１］〜［１０］のいずれかのシュリンク材料。
［１２］カルボキシル基が酸不安定基で置換された繰り返し単位を含むベース樹脂と、酸発生剤と、有機溶剤とを含むレジスト材料を基板上に塗布し、加熱処理をする工程；
高エネルギー線で前記レジスト膜を露光し、加熱処理をする工程；
現像液として有機溶剤を用いてネガティブレジストパターンを形成する工程；
［１］〜［１１］のいずれかのシュリンク材料を塗布し、加熱処理をする工程；及び
余分なシュリンク材料を有機溶剤で除去する工程
を含むことを特徴とするパターン形成方法。
［１３］前記ベース樹脂が、下記式（１１）で表される、カルボキシル基が酸不安定基で置換された繰り返し単位ａを含むものである［１２］のパターン形成方法。

（式中、Ｒ²¹は、水素原子又はメチル基を表す。Ｒ²²は酸不安定基を表す。Ｚは、単結合又は−Ｃ(＝Ｏ)−Ｏ−Ｒ²³−を表し、Ｒ²³は、炭素数１〜１０の直鎖状、分岐状若しくは環状のアルキレン基、又はナフチレン基を表し、前記アルキレン基においては、炭素−炭素結合間に、エーテル結合又はエステル結合が介在していてもよい。）
［１４］前記現像液として用いる有機溶剤が、２−オクタノン、２−ノナノン、２−ヘプタノン、３−ヘプタノン、４−ヘプタノン、２−ヘキサノン、３−ヘキサノン、ジイソブチルケトン、メチルシクロヘキサノン、アセトフェノン、メチルアセトフェノン、酢酸プロピル、酢酸ブチル、酢酸イソブチル、酢酸ペンチル、酢酸ブテニル、酢酸イソペンチル、ギ酸プロピル、ギ酸ブチル、ギ酸イソブチル、ギ酸ペンチル、ギ酸イソペンチル、吉草酸メチル、ペンテン酸メチル、クロトン酸メチル、クロトン酸エチル、プロピオン酸メチル、プロピオン酸エチル、３−エトキシプロピオン酸エチル、乳酸メチル、乳酸エチル、乳酸プロピル、乳酸ブチル、乳酸イソブチル、乳酸ペンチル、乳酸イソペンチル、２−ヒドロキシイソ酪酸メチル、２−ヒドロキシイソ酪酸エチル、安息香酸メチル、安息香酸エチル、酢酸フェニル、酢酸ベンジル、フェニル酢酸メチル、ギ酸ベンジル、ギ酸フェニルエチル、３−フェニルプロピオン酸メチル、プロピオン酸ベンジル、フェニル酢酸エチル及び酢酸２−フェニルエチルから選ばれる少なくとも１種である［１２］又は［１３］のパターン形成方法。
［１５］前記シュリンク材料を除去する工程において用いる有機溶剤が、酢酸プロピル、酢酸ブチル、酢酸イソブチル、酢酸ブテニル、酢酸ペンチル、酢酸イソペンチル、酢酸２−メチルブチル、酢酸ヘキシル、酢酸２−エチルヘキシル、酢酸シクロヘキシル、酢酸メチルシクロヘキシル、ギ酸プロピル、ギ酸ブチル、ギ酸イソブチル、ギ酸ペンチル、ギ酸イソペンチル、ギ酸ヘキシル、吉草酸メチル、吉草酸エチル、吉草酸プロピル、吉草酸イソプロピル、吉草酸ブチル、吉草酸イソブチル、吉草酸ｔ−ブチル、吉草酸ペンチル、吉草酸イソペンチル、イソ吉草酸エチル、イソ吉草酸プロピル、イソ吉草酸イソプロピル、イソ吉草酸ブチル、イソ吉草酸イソブチル、イソ吉草酸ｔ−ブチル、イソ吉草酸イソペンチル、２−メチル吉草酸エチル、２−メチル吉草酸ブチル、クロトン酸メチル、クロトン酸エチル、クロトン酸プロピル、クロトン酸イソプロピル、クロトン酸ブチル、クロトン酸ｔ−ブチル、プロピオン酸メチル、プロピオン酸エチル、ペンテン酸メチル、ペンテン酸エチル、ペンテン酸プロピル、ペンテン酸イソプロピル、ペンテン酸ブチル、ペンテン酸ｔ−ブチル、乳酸メチル、乳酸エチル、乳酸プロピル、乳酸ブチル、乳酸イソブチル、乳酸ペンチル、乳酸イソペンチル、２−ヒドロキシイソ酪酸メチル、２−ヒドロキシイソ酪酸エチル、ピバル酸エチル、ピバル酸プロピル、ピバル酸イソプロピル、ピバル酸ブチル、ピバル酸ｔ−ブチル、プロピオン酸ブチル、プロピオン酸イソブチル、プロピオン酸ｔ−ブチル、プロピオン酸ベンジル、３−エトキシプロピオン酸エチル、ヘキサン酸エチル、ヘキサン酸アリル、酪酸プロピル、酪酸ブチル、酪酸イソブチル、酪酸３−メチルブチル、酪酸ｔ−ブチル、２−メチル酪酸エチル、２−メチル酪酸イソプロピル、安息香酸メチル、安息香酸エチル、安息香酸プロピル、安息香酸ブチル、酢酸フェニル、酢酸ベンジル、フェニル酢酸メチル、ギ酸ベンジル、ギ酸フェニルエチル、３−フェニルプロピオン酸メチル、フェニル酢酸エチル、酢酸２−フェニルエチル、２−ヘプタノン、３−ヘプタノン、４−ヘプタノン、２−ヘキサノン、３−ヘキサノン、２−オクタノン、３−オクタノン、４−オクタノン、２−ノナノン、３−ノナノン、４−ノナノン、５−ノナノン、メチルシクロヘキサノン、エチルシクロヘキサノン、アセトフェノン、メチルアセトフェノン、エチルアセトフェノン、エチル−ｎ−ブチルケトン、ジ−ｎ−ブチルケトン、ジイソブチルケトン、１−ブタノール、２−ブタノール、イソブチルアルコール、ｔ−ブチルアルコール、１−ペンタノール、２−ペンタノール、３−ペンタノール、ｔ−ペンチルアルコール、ネオペンチルアルコール、２−メチル−１−ブタノール、３−メチル−１−ブタノール、３−メチル−３−ペンタノール、シクロペンタノール、１−ヘキサノール、２−ヘキサノール、３−ヘキサノール、２,３−ジメチル−２−ブタノール、３,３−ジメチル−１−ブタノール、３,３−ジメチル−２−ブタノール、２,２−ジエチル−１−ブタノール、２−メチル−１−ペンタノール、２−メチル−２−ペンタノール、２−メチル−３−ペンタノール、３−メチル−１−ペンタノール、３−メチル−２−ペンタノール、３−メチル−３−ペンタノール、４−メチル−１−ペンタノール、４−メチル−２−ペンタノール、４−メチル−３−ペンタノール、シクロヘキサノール及び１−オクタノールから選ばれる少なくとも１種である［１２］〜［１４］のいずれかのパターン形成方法。
［１６］高エネルギー線が、波長３６４ｎｍのｉ線、波長２４８ｎｍのＫｒＦエキシマレーザー、波長１９３ｎｍのＡｒＦエキシマレーザー、波長１３.５ｎｍの極端紫外線、又は電子線である［１２］〜［１５］のいずれかのパターン形成方法。 Accordingly, the present invention provides the following shrink material and a pattern forming method using the shrink material.
[1] A polymer compound containing at least one unit selected from repeating units represented by the following formulas (1a) and (1b), and a solvent containing a solvent that does not erase the resist pattern after development. And shrink material.

(In the formula, A represents a single bond or an alkylene group having 1 to 10 carbon atoms which may contain an etheric oxygen atom in the middle of the chain. R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or trifluoromethyl. R ² each independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic acyloxy group having 2 to 8 carbon atoms which may be halogen-substituted, or halogen-substituted. A straight-chain, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a straight-chain, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be halogen-substituted, L represents hydrogen Having an etheric oxygen atom, a carbonyl group or a carbonyloxy group in the middle of the atom or chain, a linear, branched or cyclic monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a substituent Even Represents a good monovalent aromatic ring-containing group, Z represents an alicyclic group having 5 to 15 carbon atoms formed together with the carbon atom to which R is bonded, and R ^x and R ^y each independently represent a hydrogen atom, a hydroxy group Or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms which may be substituted with an alkoxy group, and at least one of R ^x and R ^y is a cyclic alkyl group having 5 to 15 carbon atoms. F represents an integer of 1 to 3, s represents an integer of 0 to 2, a represents (5 + 2s−f), and m represents 0 or 1.)
[2] The shrink material according to [1], wherein the polymer compound further includes a repeating unit represented by the following formula (2).

(In the formula, B represents a single bond or an alkylene group having 1 to 10 carbon atoms that may contain an etheric oxygen atom in the middle of the chain. R ¹ is the same as above. R ³ is independently hydrogen. Atom, halogen atom, C2-C8 linear, branched or cyclic acyloxy group which may be halogen-substituted, C1-C6 linear, branched or cyclic which may be halogen-substituted A cyclic alkyl group, or a C1-C6 linear, branched or cyclic alkoxy group which may be halogen-substituted, g represents an integer of 0 to 3, and t represents an integer of 0 to 2 And b is (5 + 2t-g). N represents 0 or 1.)
[ 3 ] The shrink material according to [1] or [ 2], wherein the polymer compound further includes at least one selected from repeating units represented by the following formulas (4) and (5).

Wherein R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic acyloxy group having 2 to 8 carbon atoms that may be halogen-substituted, or halogen-substituted. Represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be halogen-substituted. And j are each independently an integer of 0 to 2. d is (6-i), and e is (4-j).)
[ 4 ] The shrink material according to any one of [1] to [ 3 ], wherein the polymer compound further includes at least one selected from repeating units represented by the following formulas (A) to (E).

(In the formula, R ¹ is the same as described above. X ^A represents an acid labile group. X ^B and X ^C are each independently a single bond or a linear or branched group having 1 to 4 carbon atoms. X ^D represents a linear, branched or cyclic 2- to 5-valent aliphatic hydrocarbon group having 1 to 16 carbon atoms, and —CH constituting the hydrocarbon group ₂ — may be substituted with —O— or —C (═O) —, X ^E represents an acid labile group, and Y ^A represents a substituent having a lactone, sultone or carbonate structure. Z ^A represents a hydrogen atom, a fluoroalkyl group having 1 to 30 carbon atoms, or a fluoroalcohol-containing substituent having 1 to 15 carbon atoms, k ^1A represents an integer of 1 to 3. k ^1B represents 1 to 1 Represents an integer of 4.)
[ 5 ] The shrink material according to any one of [1] to [ 4 ], wherein the polymer compound further includes a repeating unit represented by the following formula (F).

(In the formula, R ¹⁰¹ represents a hydrogen atom or a methyl group. X represents a single bond, —C (═O) —, —C (═O) —O— or —C (═O) —NH—). R ¹⁰² is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and has an ether group, an ester group, a carbonyl group, —N═ or —S—. R ¹⁰³ and R ¹⁰⁴ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an acid labile group, and a phenylene group or a naphthylene group. R ¹⁰³ and R ¹⁰⁴ may be bonded to form a ring together with the nitrogen atom to which they are bonded, and the ring may have an ether bond, and either R ¹⁰³ or R ¹⁰⁴ is R ¹⁰² and combined with good .k ^1C to form a ring together with the nitrogen atom to which they are attached is 1 or 2.)
[ 6 ] The shrink material according to any one of [1] to [ 5 ], further comprising a salt represented by the following formula (9).

(In the formula, R ¹¹ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, or 6 to 20 carbon atoms. A part or all of hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a fluorine atom, a lactone ring-containing group, a lactam ring-containing group or a hydroxy group. An ether group, an ester group or a carbonyl group may be interposed between the carbon-carbon bonds of these groups, and M ⁺ represents a sulfonium cation, an iodonium cation or an ammonium cation.)
[ 7 ] The shrink material according to any one of [1] to [ 6 ], further including a salt represented by the following formula (10).

(In the formula, R ¹² represents a straight, branched or cyclic monovalent hydrocarbon group having 1 to 35 carbon atoms which may contain an oxygen atom, and a part of hydrogen atoms bonded to the carbon atom of this group. Alternatively, all of them may be substituted with fluorine atoms, but the hydrogen atom bonded to the carbon atom at the α-position of the sulfonic acid is not substituted with a fluorine atom, and M ⁺ represents a sulfonium cation, an iodonium cation or an ammonium cation.)
[ 8 ] Further, primary, secondary and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group [1] to [1] including at least one basic compound selected from a compound, a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative and carbamates 7 ] The shrink material in any one of.
[ 9 ] The solvent that does not erase the resist pattern after development is an ester solvent having 7 to 16 carbon atoms, a ketone solvent having 8 to 16 carbon atoms, or an alcohol solvent having 4 to 10 carbon atoms. The shrink material according to any one of [ 8 ].
[1 0] ester solvent of the 7-16 carbon atoms, pentyl acetate, isopentyl acetate, acetic acid 2-methylbutyl, hexyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methyl acetate cyclohexyl, hexyl formate, ethyl valerate, Gil Propyl herbate, isopropyl valerate, butyl valerate, isobutyl valerate, t-butyl valerate, pentyl valerate, isopentyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, iso Isobutyl valerate, t-butyl isovalerate, isopentyl isovalerate, ethyl 2-methylvalerate, butyl 2-methylvalerate, ethyl pivalate, propyl pivalate, isopropyl pivalate, butyl pivalate, t-pivalate Butyl, ethyl pentenoate, propyl pentenoate, pen Isopropyl acetate, butyl pentenoate, t-butyl pentenoate, propyl crotonate, isopropyl crotonate, butyl crotonate, t-butyl crotonate, butyl propionate, isobutyl propionate, t-butyl propionate, benzyl propionate, Ethyl hexanoate, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, t-butyl butyrate, ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate One or more solvents selected from butyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, ethyl phenylacetate and 2-phenylethyl acetate, Carbon number 8 to 16 ketone solvents are 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, diisobutylketone, ethylcyclohexanone, ethylacetophenone, ethyl-n- It is at least one solvent selected from butyl ketone, di-n-butyl ketone and diisobutyl ketone, and the alcohol solvent having 4 to 10 carbon atoms is 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1 -Pentanol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopent Tanol, 1-hexanol, 2-hexanol, 3-hex Diol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2,2-diethyl-1-butanol, 2-methyl-1-pentanol 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl- The shrink material according to [ 9 ], which is one or more solvents selected from 1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, and 1-octanol.
[1 1 ] In addition to the solvent that does not erase the developed resist pattern, the solvent further comprises 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, and 3-hexanone. , Diisobutyl ketone, methylcyclohexanone, acetophenone, methyl acetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, pentene Methyl acid, Methyl crotonate, Ethyl crotonate, Methyl propionate, Ethyl propionate, Ethyl 3-ethoxypropionate, Methyl lactate, Ethyl lactate, Propyl lactate, Butyl lactate, Isobutyl lactate, Pentyl lactate, Isope lactate Chill, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, propionic acid The shrink material according to any one of [1] to [1 0 ], which contains at least one solvent selected from benzyl, phenylethyl acetate, and 2-phenylethyl acetate.
[1 2 ] A step of applying a heat treatment to a base resin containing a repeating unit in which a carboxyl group is substituted with an acid labile group, an acid generator, and an organic solvent.
Exposing the resist film with a high energy beam and performing a heat treatment;
Forming a negative resist pattern using an organic solvent as a developer;
A pattern forming method comprising: a step of applying the shrink material according to any one of [1] to [1 1 ] and performing a heat treatment; and a step of removing excess shrink material with an organic solvent.
[1 3 ] The pattern forming method according to [1 2 ], wherein the base resin includes a repeating unit a represented by the following formula (11), wherein a carboxyl group is substituted with an acid labile group.

(In the formula, R ²¹ represents a hydrogen atom or a methyl group. R ²² represents an acid labile group. Z represents a single bond or —C (═O) —O—R ²³ —, and R ²³ represents Represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, or a naphthylene group, and in the alkylene group, an ether bond or an ester bond may be interposed between carbon-carbon bonds. .)
[1 4 ] The organic solvent used as the developer is 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methyl Acetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonic acid, ethyl crotonic acid , Methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, -Ethyl hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenyl acetate, benzyl formate, phenyl ethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate and 2-phenyl acetate The pattern forming method of [1 2 ] or [1 3 ], which is at least one selected from ethyl.
[ 15 ] The organic solvent used in the step of removing the shrink material is propyl acetate, butyl acetate, isobutyl acetate, butenyl acetate, pentyl acetate, isopentyl acetate, 2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate. Methyl cyclohexyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, hexyl formate, methyl valerate, ethyl valerate, propyl valerate, isopropyl valerate, butyl valerate, isobutyl valerate, t -Butyl, pentyl valerate, isopentyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, t-butyl isovalerate, isopentyl isovalerate, 2- Methyl valerate Butyl 2-methylvalerate, methyl crotonate, ethyl crotonate, propyl crotonate, isopropyl crotonate, butyl crotonate, t-butyl crotonate, methyl propionate, ethyl propionate, methyl pentenoate, ethyl pentenoate , Propyl pentenoate, isopropyl pentenoate, butyl pentenoate, t-butyl pentenoate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, 2-hydroxy Ethyl isobutyrate, ethyl pivalate, propyl pivalate, isopropyl pivalate, butyl pivalate, t-butyl pivalate, butyl propionate, isobutyl propionate, t-butyl propionate, benzyl propionate, 3-ethoxypropiate Ethyl onate, ethyl hexanoate, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, t-butyl butyrate, ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate, methyl benzoate, ethyl benzoate , Propyl benzoate, butyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, ethyl phenylacetate, 2-phenylethyl acetate, 2-heptanone, 3-heptanone 4-heptanone, 2-hexanone, 3-hexanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, methylcyclohexanone, ethylcyclohexanone, acetophenone, methylacetophene Non, ethyl acetophenone, ethyl n-butyl ketone, di-n-butyl ketone, diisobutyl ketone, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol T-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2,2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl 1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, The pattern formation method according to any one of [1 2 ] to [1 4 ], which is at least one selected from cyclohexanol and 1-octanol.
[1 6 ] The high-energy rays are i-rays with a wavelength of 364 nm, KrF excimer lasers with a wavelength of 248 nm, ArF excimer lasers with a wavelength of 193 nm, extreme ultraviolet rays with a wavelength of 13.5 nm, or electron beams [1 2 ] to [1 5 ] The pattern formation method in any one of.

  When the shrink material of the present invention is used, a negative tone pattern hole obtained by organic solvent development on a resist film having a polymer compound having a carboxyl group substituted with an acid labile group and an acid generator and / or The dimension of the slit portion can be reduced with good control.

It is a schematic diagram explaining the pattern formation method (shrink method) of this invention. (A) is a cross-sectional view of a state where a resist film is formed on a substrate via a hard mask, (B) is a cross-sectional view of a state where the resist film is exposed, and (C) is after post-exposure baking (PEB) (D) is a cross-sectional view of a state in which a shrink material is applied, and (E) is a state in which the resist space pattern is reduced by baking and removing excess shrink material. Cross-sectional view (F) is a cross-sectional view in a state where the substrate is dry-etched using the shrinked space pattern as a mask.

[Shrink material]
The polymer compound contained in the shrink material of the present invention (hereinafter also referred to as polymer compound for shrink material) contains at least one unit selected from repeating units represented by the following formulas (1a) and (1b). It is a waste.

  In formulas (1a) and (1b), A represents a single bond or an alkylene group having 1 to 10 carbon atoms which may contain an etheric oxygen atom in the middle of the chain. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a cyclopentylene group, a cyclohexylene group, and those structural isomers having a branched or ring structure. The body is mentioned. Among these, A is preferably a single bond, a methylene group, an ethylene group, a propylene group, a trimethylene group or the like. When A contains an etheric oxygen atom, when m in the formula (1) is 1, it enters any position except between the α-position carbon and the β-position carbon with respect to the ester oxygen. May be. In addition, when m is 0, the atom bonded to the main chain is an etheric oxygen atom, and is located at any position except between the α-position carbon and the β-position carbon with respect to the etheric oxygen atom. Two etheric oxygen atoms may enter.

In formula (1), R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ² each independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic acyloxy group having 2 to 8 carbon atoms which may be halogen-substituted, or 1 to 1 carbon atoms which may be halogen-substituted. 6 linear, branched or cyclic alkyl groups, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be halogen-substituted.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, a pivaloyloxy group, a cyclohexylcarbonyloxy group, and the like.

  Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, and heptyl group. Octyl group, nonyl group, decanyl group, undecyl group, dodecyl group, norbornyl group, adamantyl group and the like.

  Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclopentyloxy group, cyclohexyloxy group, Examples include 1-methyl-1-cyclopentyloxy group, 1-ethyl-1-cyclopentyloxy group, 1-methyl-1-cyclohexyloxy group, 1-ethyl-1-cyclohexyloxy group, and the like.

  In formula (1), L is a hydrogen atom, a linear, branched or cyclic monovalent aliphatic having 1 to 10 carbon atoms which may contain an etheric oxygen atom, a carbonyl group or a carbonyloxy group in the middle of the chain. It is a monovalent aromatic ring-containing group which may have a hydrocarbon group or a substituent.

  Examples of the monovalent aliphatic hydrocarbon group include linear, branched or cyclic alkyl groups, alkenyl groups, and alkynyl groups. As an alkyl group, a C1-C10 thing is mentioned among what was mentioned above. As the alkenyl group, vinyl group, allyl group, propenyl group, cyclopropenyl group, butenyl group, cyclobutenyl group, cyclopentenyl group, pentenyl group, hexenyl group, cyclohexenyl group, heptenyl group, cycloheptenyl group, methylcyclohexenyl group Octenyl group, dimethylcyclohexenyl group, cyclooctenyl group and the like. Examples of the alkynyl group include ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group and the like.

  Examples of the monovalent aromatic ring-containing group include a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a pyrenyl group, a biphenylyl group, an acenaphthenyl group, and a fluorenyl group.

  L is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a methylcarbonyl group, a phenyl group, or the like.

Z represents a C5-C15 alicyclic group formed with the carbon atom to which it is bonded. Examples of such alicyclic groups include, but are not limited to, the following groups.

In the formula (1b), R ^x and R ^y are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms which may be substituted with a hydroxy group or an alkoxy group. However, at least one of R ^x and R ^y is a cyclic alkyl group having 5 to 15 carbon atoms.

R ^x and R ^y are preferably a methyl group, an ethyl group, a propyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a norbornyl group, and the like, and further a hydroxy group or The thing by which the alkoxy group was substituted is mentioned.

  In formulas (1a) and (1b), f represents an integer of 1 to 3, s represents an integer of 0 to 2, and a is (5 + 2s−f). m represents 0 or 1;

（式中、Ｒ¹、Ｒ^x、Ｒ^y、Ｌ及びｆは前記と同じ。） Among the repeating units represented by the formulas (1a) and (1b), those represented by the following formulas (1a ′) and (1b ′) are particularly preferable.

(In the formula, R ¹ , R ^x , R ^y , L and f are the same as above.)

  Although the preferable example of the repeating unit represented by Formula (1a) and (1b) is shown below, it is not limited to these. In the following examples, Me represents a methyl group, and Ac represents an acetyl group.

In order to obtain a sufficient amount of attachment to the resist pattern and substrate adhesion, the polymer compound for shrink material can be used to remove acid labile groups contained in the repeating unit represented by formula (1a) or (1b). It includes a repeating unit represented by the following formula (2) and / or (3), which is a unit allowing an appropriate thermal vibration of a polymer, which can advantageously proceed with the insolubilization reaction to the shrink material peeling solution. Although it is preferable, it is particularly preferable to include a repeating unit represented by the following formula (2).

  In the formula (2), B represents a single bond or an alkylene group having 1 to 10 carbon atoms which may contain an etheric oxygen atom in the middle of the chain. Specific examples of the alkylene group are the same as those described in the description of A above.

In formula (2), R ¹ is the same as described above. R ³ each independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic acyloxy group having 2 to 8 carbon atoms that may be halogen-substituted, or 1 to 1 carbon atoms that may be halogen-substituted. 6 linear, branched or cyclic alkyl groups, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be halogen-substituted. Specific examples of the acyloxy group, alkyl group, and alkoxy group include the same as those described in the description of R ² .

  In formula (2), g represents an integer of 0 to 3, t represents an integer of 0 to 2, and b is (5 + 2t−g). n represents 0 or 1.

  In formula (2), g represents the number of hydroxy groups bonded to the aromatic ring. In order to obtain a sufficient amount of shrinkage by ensuring high activity against the insolubilization reaction in the developer accompanying the elimination of the acid labile group contained in the repeating unit represented by the formula (1a) or (1b) Is preferably 1 or more in g. Furthermore, it is preferable that 50 mol% or more of g is 1 or more in the repeating unit represented by Formula (2). In addition, g having 0 can be used for adjusting the dissolution rate and adjusting the tolerance of thermal vibration of the polymer, but may not be included depending on the design.

  Of the repeating units represented by the formula (2), when g is 1 or more, n is 0 and B is a single bond, that is, an aromatic ring is directly bonded to the main chain of the polymer compound, that is, a linker When there is no such unit, such a unit is a unit derived from a monomer in which a 1-position substituted or unsubstituted vinyl group is bonded to an aromatic ring substituted with a hydroxy group represented by a hydroxystyrene unit. Examples of such a unit include those derived from 3-hydroxystyrene, 4-hydroxystyrene, 5-hydroxy-2-vinylnaphthalene, 6-hydroxy-2-vinylnaphthalene, and more preferably Examples thereof include those derived from 3-hydroxystyrene or 4-hydroxystyrene represented by the formula (2 ′).

（式中、Ｒ¹は前記と同じ。ｋは１〜３の整数である。）

(In the formula, R ¹ is the same as described above. K is an integer of 1 to 3.)

  In addition, when n is 1, that is, when having an ester skeleton as a linker, the repeating unit represented by the formula (2) is a vinyl monomer unit substituted with a carbonyl group represented by (meth) acrylic acid ester It is.

  Of the repeating units represented by the formula (2) including a linker (—CO—O—B—) derived from a (meth) acrylic acid ester, preferable examples in which g is 1 or more are shown below. It is not limited.

  Among the repeating units represented by the formula (2), those in which g is 0 are substituted with halogen atoms, acyloxy groups, alkyl groups, alkoxy groups or the like on styrene, vinyl naphthalene, vinyl anthracene and their aromatic rings. Things. Moreover, as a thing containing g (0) and the linker (-CO-O-B-) derived from (meth) acrylic acid ester, a hydroxy group is remove | excluded from the preferable example in case g mentioned above is 1 or more. And those in which a hydrogen atom of a hydroxy group is substituted with an acyl group or an alkyl group.

  In Formula (3), C represents a C1-C10 alkylene group which may contain an etheric oxygen atom in the middle of a single bond or a chain | strand. Specific examples of the alkylene group are the same as those described in the description of A above.

In formula (3), R ¹ is the same as described above. R ⁴ each independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic acyloxy group having 2 to 8 carbon atoms that may be halogen-substituted, or 1 to 1 carbon atoms that may be halogen-substituted. 6 linear, branched or cyclic alkyl groups, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be halogen-substituted. Specific examples of the acyloxy group, alkyl group, and alkoxy group include the same as those described in the description of R ² .

  In the formula (3), D is a single bond or a linear, branched or cyclic (v + 1) having 1 to 10 carbon atoms which may contain an etheric oxygen atom, a carbonyl group or a carbonyloxy group in the middle of the chain. Represents a valent hydrocarbon group, and part or all of the hydrogen atoms bonded to the carbon atoms of this group may be substituted with fluorine atoms. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and specific examples include a group obtained by removing v hydrogen atoms from the monovalent aliphatic hydrocarbon group exemplified as L.

In formula (3), Rf ¹ and Rf ² each independently represents an alkyl group having 1 to 6 carbon atoms having at least one fluorine atom. Rf ¹ may be bonded to D to form a ring together with the carbon atom to which they are bonded. Examples of the alkyl group having at least one fluorine atom include monofluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2,2-pentafluoroethyl. Group, pentafluoroethyl group, 2,2,2-trifluoro-1-trifluoromethyl-ethyl group, perfluoroisopropyl group, heptafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2, 2,3,3,3-pentafluoropropyl group, 3,3,3-trifluoro-2-trifluoromethyl-propyl group, nonafluorobutyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H -Nonafluoropentyl group, perfluoropentyl group, 1H, 1H-4-trifluoromethylperfluoropentyl group, perfluorohexyl group, 4 Pentafluoroethyl perfluoro cyclohexyl, IH, IH, 2H, 2H-perfluorohexyl group, a perfluoro cyclohexyl group.

  In formula (3), h represents an integer of 1 to 3, u represents an integer of 0 to 2, and c represents (5 + 2u−h).

  In formula (3), r is 0 or 1. When r is 1, an aromatic ring is inserted between the polymer main chain and a hydroxy group bonded to carbon in which the adjacent carbon is substituted with a fluorine atom-containing group. At this time, the substitution number v of D is 1 or 2. Here, when D is not a single bond, D has one or two hydroxy groups bonded to carbon in which the adjacent carbon is substituted with a fluorine atom-containing group (that is, v is 1 or 2).

  When r is 0, h is 1 and C is a single bond, but D is not a single bond. At this time, D is bonded to the polymer main chain via a carbonyloxy group. In this case as well, D has one or two hydroxy groups bonded to carbon in which the adjacent carbon is substituted with a fluorine atom-containing group.

  Preferable examples of the repeating unit represented by the formula (3) include, but are not limited to, those represented by the following formula.

  The repeating unit represented by formula (2) or (3) may be used singly or in combination of two or more.

The polymer compound for shrink material may further contain at least one selected from repeating units represented by the following formulas (4) and (5) as a main structural unit of the polymer. In this case, by adding a ring structure to the main chain in addition to the etching resistance of the aromatic ring, it is possible to impart dry etching resistance to the shrinked resist pattern.

In the formula, R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic acyloxy group having 2 to 8 carbon atoms which may be halogen-substituted, or halogen-substituted. Or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be halogen-substituted. Specific examples of the acyloxy group, alkyl group, and alkoxy group include the same as those described in the description of R ² .

  In the formula, i and j are each independently an integer of 0 to 2. d is (6-i). e is (4-j).

  The repeating unit represented by formula (4) or (5) may be used singly or in combination of two or more.

When i and j are 1 or more in order to increase the etching resistance of the polymer compound from the relationship with other repeating units constituting the polymer compound for shrink material, the following derivatives are easily available, The effect of can be preferably achieved.

The polymer compound for shrink material may further contain at least one selected from repeating units represented by the following formulas (A) to (E). These units can be used supplementarily as a unit that provides adhesion of the polymer compound for shrink material to the resist pattern, or for the purpose of adjusting the solubility of the polymer compound for shrink material itself in a solvent.

In the formula, R ¹ is the same as described above. X ^A represents an acid labile group. X ^B and X ^C each independently represent a single bond or a linear or branched divalent hydrocarbon group having 1 to 4 carbon atoms. X ^D represents a linear, branched or cyclic divalent to pentavalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, and —CH ₂ — constituting the hydrocarbon group is —O— or —C. (= O)-may be substituted. X ^E represents an acid labile group. Y ^A represents a substituent having a lactone, sultone or carbonate structure. Z ^A represents a hydrogen atom, a fluoroalkyl group having 1 to 30 carbon atoms, or a fluoroalcohol-containing substituent having 1 to 15 carbon atoms. k ^1A represents an integer of 1 to 3. k ^1B represents an integer of 1 to 4.

The repeating unit represented by the formula (A) is a unit that decomposes by the action of an acid to generate a carboxylic acid. By this unit, the solubility of the polymer compound for shrink material in an organic solvent developer can be adjusted. The acid labile group X ^A can be variously used, and specifically, a group represented by any one of the following formulas (L1) to (L4), having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms. Examples include tertiary alkyl groups, trialkylsilyl groups having 1 to 6 carbon atoms, and oxoalkyl groups having 4 to 20 carbon atoms.

In the formula, R ^L01 and R ^L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. R ^L03 represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. For example, linear, branched or cyclic alkyl And a group in which a part of these hydrogen atoms are substituted with a hydroxy group, an alkoxy group, an oxo group, an amino group, an alkylamino group, or the like, or an ether oxygen atom intervening. R ^L04 is a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, a trialkylsilyl group in which each alkyl group is an alkyl group having 1 to 6 carbon atoms, or an oxo group having 4 to 20 carbon atoms. An alkyl group or a group represented by the formula (L1) is represented. R ^L05 represents an ^optionally substituted linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. R ^L06 represents an ^optionally substituted linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. R ^{L07 to} R ^L16 each independently represent a hydrogen atom or an ^optionally substituted monovalent hydrocarbon group having 1 to 15 carbon atoms. x is an integer of 0-6. y is 0 or 1, z is an integer of 0 to 3, and 2y + z = 2 or 3. The broken line represents a bond.

In formula (L1), ^examples of the alkyl group represented by R ^L01 and R ^L02 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a s-butyl group, a t-butyl group, a cyclopentyl group, Examples include cyclohexyl group, 2-ethylhexyl group, n-octyl group, adamantyl group and the like.

Examples of the monovalent hydrocarbon group represented by R ^L03 include the same groups as those described above as the alkyl group represented by R ^L01 and R ^L02 . ^Examples of the substituted alkyl group represented by R ^L03 include the groups shown below.

R ^L01 and R ^L02 , R ^L01 and R ^L03 , or R ^L02 and R ^L03 may be bonded to each other to form a ring together with the carbon atom or oxygen atom to which they are bonded. In the formula, R ^L01 , R ^L02 and R ^L03 involved in ring formation each represent a linear or branched alkylene group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms.

In the formula (L2), specific examples of the tertiary alkyl group represented by R ^L04 include a t-butyl group, a t-pentyl group, a 1,1-diethylpropyl group, a 2-cyclopentylpropan-2-yl group, 2-cyclohexylpropan-2-yl group, 2- (bicyclo [2.2.1] heptan-2-yl) propan-2-yl group, 2- (adamantan-1-yl) propan-2-yl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl-2- Examples thereof include an adamantyl group and a 2-ethyl-2-adamantyl group. Specific examples of the trialkylsilyl group represented by R ^L04 include a trimethylsilyl group, a triethylsilyl group, a dimethyl-t-butylsilyl group, and the like. Specific examples of the oxoalkyl group represented by R ^L04 include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, and a 5-methyl-2-oxooxolan-5-yl group. Can be mentioned.

Specific examples of the alkyl group represented by R ^L05 in the formula (L3) include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, and t-pentyl. A linear, branched or cyclic alkyl group such as a group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, bicyclo [2.2.1] heptyl group, and a part of these hydrogen atoms A hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an oxo group, an amino group, an alkylamino group, a cyano group, a mercapto group, an alkylthio group, a sulfo group, etc., or a part of these methylene groups is oxygen The thing substituted by the atom or the sulfur atom etc. are mentioned. Specific examples of the aryl group represented by R ^L05 include a phenyl group, a methylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a pyrenyl group.

Specific examples of the alkyl group and aryl group represented by R ^L06 in the formula (L4) include the same examples as those described as represented by R ^L05 .

Specific examples of the monovalent hydrocarbon group having 1 to 15 carbon atoms represented by R ^{L07 to} R ^L16 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t- Butyl group, t-pentyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclopentylbutyl group A linear, branched or cyclic alkyl group such as a cyclohexylmethyl group, a cyclohexylethyl group, and a cyclohexylbutyl group, and some of these hydrogen atoms are a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an oxo group, an amino group, Groups substituted by alkyl groups, alkylamino groups, cyano groups, mercapto groups, alkylthio groups, sulfo groups, etc. It is.

R ^{L07 to} R ^L16 may be bonded to each other to form a ring together with the carbon atom to which they are bonded (for example, R ^L07 and R ^L08 , R ^L07 and R ^L09 , R ^L08 and R ^L10 , R ^L09 and R ^L10 , R ^L11 and R ^L12 , R ^L13 and R ^L14, etc.), in which case the group involved in ring formation represents a divalent hydrocarbon group such as an alkylene group having 1 to 15 carbon atoms. Specific examples of the divalent hydrocarbon group include those obtained by removing one hydrogen atom from those mentioned as the monovalent hydrocarbon group. R ^{L07 to} R ^L16 may be bonded to each other adjacent to each other to form a double bond (for example, R ^L07 and R ^L09 , R ^L09 and R ^L15 , R ^L13 and R ^L15 etc.).

Among the acid labile groups represented by the formula (L1), examples of the linear or branched group include, but are not limited to, the following groups. The broken line represents a bond.

  Among the acid labile groups represented by the formula (L1), examples of the cyclic group include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, and 2-methyltetrahydropyran. And 2-yl group.

  Examples of the acid labile group represented by the formula (L2) include t-butoxycarbonyl group, t-butoxycarbonylmethyl group, t-amyloxycarbonyl group, t-amyloxycarbonylmethyl group, and 1,1-diethylpropyloxy. Carbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2-cyclo Examples include pentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

  Examples of the acid labile group represented by the formula (L3) include 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-n-propylcyclopentyl group, 1-isopropylcyclopentyl group, 1-n-butylcyclopentyl group, 1 -S-butylcyclopentyl group, 1-cyclohexylcyclopentyl group, 1- (4-methoxy-n-butyl) cyclopentyl group, 1- (bicyclo [2.2.1] heptan-2-yl) cyclopentyl group, 1- ( 7-oxabicyclo [2.2.1] heptan-2-yl) cyclopentyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 3-methyl-1-cyclopenten-3-yl group, 3-ethyl-1 -Cyclopenten-3-yl group, 3-methyl-1-cyclohexen-3-yl group, 3-ethyl-1-cyclohexen-3-yl Etc. The.

（式中、Ｒ^L41は、それぞれ独立に、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基等の１価炭化水素基を表す。破線は結合手を表し、その方向は結合方向を表す。） As the acid labile group represented by the formula (L4), groups represented by the following formulas (L4-1) to (L4-4) are particularly preferable.

(In the formula, R ^L41 each independently represents a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. The broken line represents a bond, and its direction is a bond. Represents the direction.)

  In the formulas (L4-1) to (L4-4), specific examples of the monovalent hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t- Examples thereof include a butyl group, a t-pentyl group, an n-pentyl group, an n-hexyl group, a cyclopentyl group, and a cyclohexyl group.

In the groups represented by the formulas (L4-1) to (L4-4), stereoisomers (enantiomers or diastereomers) may exist, but these are represented by the formulas (L4-1) to (L4-4). All the stereoisomers are represented as representatives. When the acid labile group X ^A is a group represented by the formula (L4), a plurality of stereoisomers may be contained.

（式中、Ｒ^L41は、前記と同じ。） For example, the formula (L4-3) represents one or a mixture of two selected from the groups represented by the following formulas (L4-3-1) and (L4-3-2). .

(In the formula, R ^L41 is the same as described above.)

（式中、Ｒ^L41は、前記と同じ。） The formula (L4-4) represents one or a mixture of two or more selected from groups represented by the following formulas (L4-4-1) to (L4-4-4). To do.

(In the formula, R ^L41 is the same as described above.)

  Formulas (L4-1) to (L4-4), (L4-3-1), (L4-3-2), and formulas (L4-4-1) to (L4-4-4) Enantiomers and mixtures of enantiomers are also shown representatively.

  In addition, the coupling | bonding of Formula (L4-1)-(L4-4), (L4-3-1), (L4-3-2), and Formula (L4-4-1)-(L4-4-4) High reactivity in the acid-catalyzed elimination reaction is realized when the direction is on the exo side with respect to the bicyclo [2.2.1] heptane ring, respectively (see JP 2000-336121 A). In the production of a monomer having a tertiary exo-alkyl group having a bicyclo [2.2.1] heptane skeleton as a substituent, it is represented by the following formulas (L4-1-endo) to (L4-4-endo). In some cases, the exo ratio is preferably 50% or more, and the exo ratio is 80% or more in order to achieve good reactivity. Is more preferable.

（式中、Ｒ^L41は、前記と同じ。）

(In the formula, R ^L41 is the same as described above.)

Examples of the acid labile group represented by formula (L4) include, but are not limited to, the groups shown below. In addition, a broken line represents a joining hand and the direction represents a joining direction.

Further, as a tertiary alkyl group having 4 to 20 carbon atoms represented by X ^A , a trialkylsilyl group in which each alkyl group is an alkyl group having 1 to 6 carbon atoms, and an oxoalkyl group having 4 to 20 carbon atoms, ^Are the same as those described in the description of R ^L04 .

Examples of the repeating unit represented by the formula (A) include, but are not limited to, those shown below. In the following formulae, R ¹ is the same as described above.

Examples of the repeating unit represented by the formula (B) include, but are not limited to, those shown below. In the following formulae, R ¹ is the same as described above.

Examples of the repeating unit represented by the formula (C) include, but are not limited to, those shown below. In the following formulae, R ¹ is the same as described above.

Examples of the repeating unit represented by the formula (D) include, but are not limited to, those shown below. In the following formulae, R ¹ is the same as described above.

The polymer containing the repeating unit represented by the formula (E) is decomposed by the action of an acid to produce a hydroxy group, thereby changing the solubility in various solvents. In the formula (E), the acid labile group X ^E can be variously used. As in the case of the acid labile group X ^A , groups represented by the formulas (L1) to (L4) and a carbon number of 4 to 20 tertiary alkyl groups, trialkylsilyl groups in which each alkyl group is an alkyl group having 1 to 6 carbon atoms, oxoalkyl groups having 4 to 20 carbon atoms, and the like.

Examples of the repeating unit represented by the formula (E) include, but are not limited to, those shown below. In the following formulae, R ¹ is the same as described above.

  Among the repeating units represented by the formulas (A) to (E), the units represented by the formulas (A) to (C) are particularly preferable because solvent solubility and adhesion can be easily adjusted.

The polymer compound for shrink material may further contain a repeating unit represented by the following formula (F). This unit can cause a neutralization reaction with a carboxyl group present on the surface of the resist pattern film to which the shrink agent is applied. As a result, the polymer compound adheres to the resist film surface, so that the amount of attachment can be increased.

In the formula, R ¹⁰¹ is a hydrogen atom or a methyl group. X is a single bond, —C (═O) —, —C (═O) —O— or —C (═O) —NH—. ^R102 is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and may have an ether group, an ester group, a carbonyl group, -N = or -S-. Or a phenylene group or a naphthylene group. R ¹⁰³ and R ¹⁰⁴ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an acid labile group, and R ¹⁰³ and R ¹⁰⁴ are bonded to form a bond. May form a ring together with the nitrogen atom to be bonded, and may have an ether bond in the ring, and either R ¹⁰³ or R ¹⁰⁴ is bonded to R ¹⁰² and the ring is bonded to the nitrogen atom to which these are bonded May be formed. k ^1C is 1 or 2.

Examples of the monomer for obtaining the repeating unit represented by the formula (F) include those represented by the following formula (Fa). In the formula, R ^{101 to} R ¹⁰⁴ , X, and k ^1C are the same as described above.

Examples of the monomer represented by the formula (Fa) include, but are not limited to, those shown below. In the following formulae, R ^{101 to} R ¹⁰⁴ are the same as described above.

  The polymer compound for shrink material can be used by mixing two or more kinds of polymer compounds, but if not mixed, after determining the repeating unit having the respective functions, The composition ratio is designed to give a preferable shrink amount and dimensional uniformity when a shrink material is used.

  The polymer compound for shrink material can be obtained by a known method by combining monomers giving each repeating unit by combining protection and deprotection reactions as necessary. The copolymerization reaction is not particularly limited, but radical polymerization is preferred.

  In the polymer compound for shrink material, the content of the repeating unit represented by the formula (1a) and / or (1b) is preferably 5 mol% or more, more preferably 10 mol% or more in all repeating units.

  The content of the repeating unit represented by the formula (2) is preferably 0 to 90 mol% in all repeating units, but in order to obtain a sufficient amount of attachment to the resist pattern and substrate adhesion, 5 to 85 mol%. Is preferable, and 10 to 80 mol% is more preferable.

  The content of the repeating unit represented by the formula (3) is preferably 0 to 90 mol% in all repeating units. However, in order to obtain a sufficient amount of attachment to the resist pattern and substrate adhesion, 5 to 85 mol%. Is preferable, and 10 to 80 mol% is more preferable.

  The content of the repeating unit represented by the formula (4) or (5) is preferably 0 to 30 mol% in all repeating units, but in order to obtain an effect of improving etching resistance, 5 to 30 mol%. Is preferable, and 5 to 20 mol% is more preferable.

  The content of the repeating units represented by the formulas (A) to (E) is preferably 0 to 30 mol% in all the repeating units, but in order to obtain the effect of adjusting the adhesion and solubility, 1 to 30 is preferable. Mol% is preferable, and 5 to 20 mol% is more preferable.

  The content of the repeating unit represented by the formula (F) is preferably 0 to 30 mol% in all repeating units, but in order to obtain an effect of increasing the amount of attachment, 1 to 30 mol% is preferable, and 1 -20 mol% is more preferable.

  In the polymer compound for shrink material, a unit selected from the repeating unit represented by the formula (1a) and / or (1b) and the repeating unit represented by the formulas (2), (4) and (5) Preferably accounts for 60 mol% or more of all repeating units constituting the polymer compound. This ensures the properties of the shrink material of the present invention. It is more preferable that the repeating units represented by the formula (1a) and / or (1b), (2), (4) and (5) occupy 70 mol% or more of all repeating units, and 85 mol% or more. It is more preferable to occupy.

  Moreover, the high molecular compound for shrink material whose all structural units are selected from the repeating unit represented by Formula (1a) and / or (1b), (2), (4) and (5) was used. In this case, it is excellent in both high etching resistance and resolution. Units other than the repeating units represented by formula (1a) and / or (1b), (2), (4) and (5) include (meth) acrylic acid protected with a commonly used acid labile group An ester unit or a (meth) acrylic acid ester unit having an adhesive group such as a lactone structure can be used. Although these other repeating units may finely adjust the characteristics of the resist film, these units may not be included.

  The weight average molecular weight (Mw) of the polymer compound for shrink material is preferably 1,000 to 500,000, more preferably 2,000 to 100,000, and still more preferably 2,000 to 20,000. If Mw is too small, the acid diffusion distance may increase and the amount of shrinkage may become too large to control. If Mw is too large, the solubility in the peeling solvent may be reduced, and scum may be generated in the space portion after the peeling process, which may cause a skirting phenomenon. In the present invention, Mw is a measured value in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

  Further, in the polymer compound for shrink material, when the molecular weight distribution (Mw / Mn, Mn is the number average molecular weight) is wide, there is a low molecular weight or high molecular weight polymer. It may be seen or the shape of the pattern may deteriorate. Therefore, since the influence of such molecular weight and molecular weight distribution tends to increase as the pattern rule becomes finer, in order to obtain a shrink material suitably used for fine pattern dimensions, the multi-component copolymer used is used. The molecular weight distribution is preferably 1.0 to 2.0, particularly 1.0 to 1.5 and narrow dispersion.

  Moreover, as the polymer compound for shrink material, a blend of two or more polymers having different composition ratios, molecular weight distributions and molecular weights can be used.

  The shrink material of this invention contains the solvent which does not lose | disappear the resist pattern after image development. Examples of such solvents include ether solvents having 6 to 12 carbon atoms, hydrocarbon solvents having 6 to 12 carbon atoms, ester solvents having 7 to 16 carbon atoms, ketone solvents having 8 to 16 carbon atoms, and carbon numbers. 4-10 alcohol solvents, water, etc. are mentioned. However, as long as the solvent that does not erase the resist pattern after development is contained in an amount of 50% by mass or more of the total solvent, a solvent that eliminates the resist pattern after development may be contained.

  Many water-based shrink materials have been proposed so far, but water is difficult to apply quickly to large diameter wafers due to its high surface tension. In particular, in a fine hole pattern formed by negative development, when an aqueous solvent having a high surface tension is used when embedding the shrink material by spin coating, there is a problem that the shrink material is not embedded to the bottom of the hole. is there. Here, by applying a shrink material dissolved in an organic solvent having a surface tension lower than that of water, the filling property to the bottom of the hole is improved. As an organic solvent used for the shrink material, it is necessary to dissolve the polymer compound of the shrink material.

  For this reason, as a solvent used for the shrink material of the present invention, an ester solvent having 7 to 16 carbon atoms, a ketone solvent having 8 to 16 carbon atoms, and a carbon number of 4 having a high dissolving power for the polymer compound for shrink material. 10 to 10 alcohol solvents are preferred.

  Examples of the ester solvent having 7 to 16 carbon atoms include pentyl acetate, isopentyl acetate, 2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, hexyl formate, ethyl valerate, propyl valerate, Isopropyl valerate, butyl valerate, isobutyl valerate, t-butyl valerate, pentyl valerate, isopentyl valerate, ethyl isovalerate, isopropyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate , T-butyl isovalerate, isopentyl isovalerate, ethyl 2-methylvalerate, butyl 2-methylvalerate, ethyl pivalate, propyl pivalate, isopropyl pivalate, butyl pivalate, t-butyl pivalate, pentene Ethyl acetate, propyl pentenoate, pentene Isopropyl, butyl pentenoate, t-butyl pentenoate, propyl crotonate, isopropyl crotonate, butyl crotonate, t-butyl crotonate, butyl propionate, isobutyl propionate, t-butyl propionate, benzyl propionate, hexanoic acid Ethyl, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, t-butyl butyrate, ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, benzoate Examples include butyl acid, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, ethyl phenylacetate, 2-phenylethyl acetate, and the like.

  Examples of the ketone solvent having 8 to 16 carbon atoms include 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, diisobutylketone, ethylcyclohexanone, ethylacetophenone, Examples include ethyl-n-butyl ketone, di-n-butyl ketone, and diisobutyl ketone.

  Examples of the alcohol solvent having 4 to 10 carbon atoms include 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neo Pentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl- 2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2,2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pen Butanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3 -Methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, 1-octanol and the like.

  These solvents may be used alone or in combination of two or more.

  In order to prevent mixing of the shrink material and the resist pattern, in addition to the solvent, an ether solvent having 8 to 12 carbon atoms, an alkane having 6 to 12 carbon atoms, an alkene or alkyne, an aromatic solvent, or the like is added. You can also.

  Specific examples of the ether solvent having 8 to 12 carbon atoms include di-n-butyl ether, diisobutyl ether, di-s-butyl ether, di-n-pentyl ether, diisopentyl ether, di-s-pentyl ether, Examples include di-t-pentyl ether and di-n-hexyl ether. Examples of the alkane having 6 to 12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, and cyclononane. It is done. Examples of the alkene having 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, and cyclooctene. Examples of the alkyne having 6 to 12 carbon atoms include hexyne, heptin, octyne and the like. Examples of the aromatic solvent include toluene, xylene, ethylbenzene, isopropylbenzene, t-butylbenzene, mesitylene, anisole and the like. These solvents may be used alone or in combination of two or more.

  The shrink material of the present invention includes 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone and diisobutyl, in addition to a solvent that does not erase the resist pattern after development. Ketone, methylcyclohexanone, acetophenone, methyl acetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate , Methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isope lactate Chill, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, propionic acid One or more solvents selected from benzyl, ethyl phenylacetate and 2-phenylethyl acetate (hereinafter referred to as other solvents) may also be included. When other solvents are included, the blending amount is preferably less than 50% by mass in the total solvent.

  The blending amount of the solvent is preferably 100 to 100,000 parts by mass, more preferably 200 to 50,000 parts by mass with respect to 100 parts by mass of the polymer compound for shrink material.

  The shrink material of the present invention may contain a salt, a basic compound, a surfactant and the like as necessary. Examples of salts that can be added include known sulfonium salts, iodonium salts, ammonium salts, and the like as additives for resist materials. As basic compounds that can be added, known primary, secondary or tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, carboxyl groups as additives for resist materials are added. A nitrogen-containing compound having a sulfonyl group, a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and carbamates. By adding the salt or the basic compound, diffusion of excessive acid from the resist film can be suppressed, and the shrink amount can be controlled. As the surfactant, a known additive as a resist material can be added.

（式中、Ｒ¹¹は、炭素数１〜２０の直鎖状、分岐状若しくは環状のアルキル基、炭素数２〜２０の直鎖状、分岐状若しくは環状のアルケニル基、又は炭素数６〜２０の１価芳香環含有基を表し、これらの基の炭素原子に結合する水素原子の一部又は全部が、フッ素原子、ラクトン環含有基、ラクタム環含有基又はヒドロキシ基で置換されていてもよく、これらの基の炭素−炭素結合間に、エーテル基、エステル基又はカルボニル基が介在していてもよい。Ｍ⁺は、スルホニウムカチオン、ヨードニウムカチオン又はアンモニウムカチオンを表す。） Specifically, the salt is preferably a carboxylate represented by the following formula (9).

(In the formula, R ¹¹ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, or 6 to 20 carbon atoms. A part or all of hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a fluorine atom, a lactone ring-containing group, a lactam ring-containing group or a hydroxy group. An ether group, an ester group or a carbonyl group may be interposed between the carbon-carbon bonds of these groups, and M ⁺ represents a sulfonium cation, an iodonium cation or an ammonium cation.)

  Specific examples of the alkyl group, alkenyl group and monovalent aromatic ring-containing group include the same groups as described above.

（式中、Ｒ¹⁰¹〜Ｒ¹⁰⁹は、それぞれ独立に、炭素数１〜１２の直鎖状、分岐状若しくは環状のアルキル基若しくはオキソアルキル基、炭素数２〜１２の直鎖状、分岐状若しくは環状のアルケニル基若しくはオキソアルケニル基、炭素数６〜２０の１価芳香環含有基、又は炭素数７〜１２のアラルキル基若しくはアリールオキソアルキル基を表し、これらの基の水素原子の一部又は全部が、ハロゲン原子、アルキル基、アルコキシ基等によって置換されていてもよい。また、Ｒ¹⁰¹とＲ¹⁰²と又はＲ¹⁰⁶とＲ¹⁰⁷とは、互いに結合してこれらが結合する硫黄原子又は窒素原子とともに環を形成してもよく、環を形成する場合には、これらが結合して形成される基は、炭素数１〜１０のアルキレン基又はアリーレン基であり、環の中にエーテル基、エステル基、スルトン基又はアミノ基を有していてもよい。） As the sulfonium cation, iodonium cation and ammonium cation, those represented by the following formulas (P1) to (P3) are preferable. By adding a carboxylate having such a cation, acid diffusion can be effectively controlled.

(Wherein R ^{101 to} R ¹⁰⁹ are each independently a linear, branched or cyclic alkyl or oxoalkyl group having 1 to 12 carbon atoms, a linear or branched chain having 2 to 12 carbon atoms, or Represents a cyclic alkenyl group or an oxoalkenyl group, a monovalent aromatic ring-containing group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms, and part or all of the hydrogen atoms of these groups May be substituted by a halogen atom, an alkyl group, an alkoxy group, etc. Also, R ¹⁰¹ and R ¹⁰² or R ¹⁰⁶ and R ¹⁰⁷ are bonded to each other together with a sulfur atom or a nitrogen atom to which they are bonded. A ring may be formed, and in the case of forming a ring, the group formed by combining these is an alkylene group or an arylene group having 1 to 10 carbon atoms, and an ether group, (It may have a tellurium group, a sultone group or an amino group.)

  Specific examples of the alkyl group, alkenyl group and monovalent aromatic ring-containing group include the same groups as described above. Examples of the oxoalkyl group and oxoalkenyl group include those in which an oxo group is bonded to the carbon atom of the aforementioned alkyl group and alkenyl group. Examples of the aralkyl group include a benzyl group, a 1-phenylethyl group, and a 2-phenylethyl group. Examples of the aryloxoalkyl group include 2-aryl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like. An oxoethyl group etc. are mentioned.

As the anion of the carboxylate, the anion of carboxylic acid described in Japanese Patent No. 3991462, and those shown below are preferable, but are not limited thereto.

As the cation of the carboxylate, those shown below are preferable, but are not limited thereto.

（式中、Ｍ⁺は前記と同じ。Ｒ¹²は、酸素原子を含んでもよい炭素数１〜３５の直鎖状、分岐状又は環状の１価炭化水素基を表す。また、炭素原子に結合する水素原子の一部又は全部がフッ素原子で置換されていてもよいが、スルホン酸のα位の炭素原子に結合する水素原子はフッ素原子で置換されない。） Moreover, you may add the sulfonate represented by following formula (10) as said salt.

(In the formula, M ⁺ is the same as above. R ¹² represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 35 carbon atoms which may contain an oxygen atom. Some or all of the hydrogen atoms may be substituted with fluorine atoms, but the hydrogen atoms bonded to the α-position carbon atom of the sulfonic acid are not substituted with fluorine atoms.)

（式中、Ｍ⁺は前記と同じ。Ｒ¹¹⁰及びＲ¹¹¹は、それぞれ独立に、水素原子又はトリフルオロメチル基を表す。ｌは１〜３の整数である。） As the sulfonate represented by the formula (10), those represented by the following formula (10 ′) are preferable.

(In the formula, M ⁺ is the same as above. R ¹¹⁰ and R ¹¹¹ each independently represents a hydrogen atom or a trifluoromethyl group. L is an integer of 1 to 3.)

  0-50 mass parts is preferable with respect to 100 mass parts of high molecular compounds for shrink materials, and, as for the compounding quantity of the said salt, 0.1-20 mass parts is more preferable.

  Examples of the basic compound include primary, secondary, and tertiary amine compounds described in paragraphs [0146] to [0164] of JP-A-2008-111103, particularly a hydroxy group, an ether group, Examples thereof include an amine compound having an ester group, a lactone ring, a cyano group, and a sulfonic acid ester group, and a compound having a carbamate group described in Japanese Patent No. 3790649.

  Of these, tertiary amine compounds, particularly amine compounds having a hydroxy group, an ether group, an ester group, a lactone ring, and a compound having a carbamate group are preferred.

  0-30 mass parts is preferable with respect to 100 mass parts of high molecular compounds for shrink materials, and, as for the compounding quantity of a basic compound, 0.1-20 mass parts is more preferable.

  As the surfactant, those described in paragraphs [0165] to [0166] of JP-A-2008-111103 can be used. 0-10 mass parts is preferable with respect to 100 mass parts of high molecular compounds for shrink materials, and, as for the compounding quantity of surfactant, 0.1-5 mass parts is more preferable.

[Resist material]
The resist material used in the pattern forming method of the present invention includes a base resin, a compound that generates an acid in response to high energy rays (an acid generator) and an organic solvent, and, if necessary, a basic compound, a dissolution controller, A surfactant, acetylene alcohols and other components may be included.

（式中、Ｒ²¹は、水素原子又はメチル基を表す。Ｒ²²は酸不安定基を表す。Ｚは、単結合又は−Ｃ(＝Ｏ)−Ｏ−Ｒ²³−を表し、Ｒ²³は、炭素数１〜１０の直鎖状、分岐状若しくは環状のアルキレン基、又はナフチレン基を表し、前記アルキレン基においては、炭素−炭素結合間に、エーテル結合又はエステル結合が介在していてもよい。） The base resin preferably includes a repeating unit a represented by the following formula (11) in which a carboxyl group is substituted with an acid labile group.

(In the formula, R ²¹ represents a hydrogen atom or a methyl group. R ²² represents an acid labile group. Z represents a single bond or —C (═O) —O—R ²³ —, and R ²³ represents Represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, or a naphthylene group, and in the alkylene group, an ether bond or an ester bond may be interposed between carbon-carbon bonds. .)

  Examples of the alkylene group are the same as those described above. Examples of the acid labile group include groups described in paragraphs [0039] to [0044] of JP-A-2014-088557.

  The base resin has a repeating unit b containing an adhesive group selected from a hydroxy group, a lactone ring, an ether group, an ester group, a carbonyl group and a cyano group in order to improve the adhesion to the substrate and prevent pattern collapse. May be included. The base resin further includes a repeating unit c derived from indene, acenaphthylene, chromones, coumarins or norbornadiene described in paragraph [0085] of JP 2012-37867 A, and paragraph [0088]. As an acid generator described in paragraphs [0089] to [0091] of the same publication, and may contain a repeating unit d derived from styrenes, vinylnaphthalenes, vinylanthracenes, vinylpyrenes or methyleneindanes. It may contain a repeating unit e derived from an onium salt having a polymerizable olefin that functions.

  In the base resin, the content of the repeating unit a is more than 0 mol% in all repeating units, preferably 100 mol% or less, preferably 1 mol% or more and less than 100 mol%, and more preferably 20 to 90 mol%. The content of the repeating unit b is preferably 0 mol% or more and less than 100 mol%, and more preferably 10 to 80 mol% in all repeating units. In particular, the total of repeating units a and b is preferably 30 to 100 mol%. When repeating units c to e are included, the content of repeating unit c is preferably 0 to 40 mol%, the content of repeating unit d is preferably 0 to 20 mol%, and the content of repeating unit e is 0 to 30 mol% is preferable, and the total of these is preferably 0 to 70 mol%.

  The Mw of the base resin is preferably 1,000 to 500,000, more preferably 2,000 to 100,000, and still more preferably 2,000 to 20,000. If Mw is too small, the diffusion distance of the acid generated from the acid generator becomes too long, and the resolution may decrease. If Mw is too large, the solubility in the developer becomes too small, and the resolution may be lowered.

  Furthermore, in the base resin, when the molecular weight distribution (Mw / Mn) is wide, low molecular weight or high molecular weight polymers exist, so that foreign matter is seen on the pattern after exposure or the shape of the pattern deteriorates. There is a risk of Therefore, since the influence of such molecular weight and molecular weight distribution tends to increase as the pattern rule becomes finer, the molecular weight distribution of the base resin is 1 in order to obtain a resist material suitably used for fine pattern dimensions. It is preferably a narrow dispersion of 0.0 to 2.0, particularly 1.0 to 1.5.

  As the base resin, a blend of two or more polymers having different composition ratios, molecular weight distributions, and molecular weights can be used.

  In particular, the resist material may contain an acid generator for functioning as a chemically amplified positive resist material. For example, the resist material may contain a compound that generates an acid in response to actinic rays or radiation (photoacid generator). . In this case, 0.5-30 mass parts is preferable with respect to 100 mass parts of base resin, and, as for the compounding quantity of a photo-acid generator, 1-20 mass parts is more preferable. Any photoacid generator may be used as long as it is a compound that generates an acid upon irradiation with high energy rays. Suitable photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, oxime-O-sulfonate type acid generators, and the like. These may be used singly or in combination of two or more. Examples of the acid generated from the acid generator include sulfonic acid, imide acid, and methide acid. Of these, sulfonic acids in which the α-position is fluorinated are most commonly used. However, when the acid labile group contained in the base resin is an acetal group that is easily deprotected, the α-position is not necessarily fluorinated. There is no need. When the base resin contains an acid generator repeating unit, an additive type acid generator is not always essential.

  Examples of the organic solvent include ketones such as cyclohexanone and methyl-2-n-pentyl ketone; 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol Alcohols such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , Ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxypropion Ethyl acetate t-butyl, t- butyl propionate, and propylene glycol monobutyl t-butyl ether acetate; .gamma.-butyrolactone lactones such as such, and a mixed solvent thereof and the like. When an acetal acid labile group is used, a high-boiling alcohol solvent such as diethylene glycol, propylene glycol, glycerin, 1,4-butanediol, 1,3-butanediol is used to accelerate the deprotection reaction of the acetal group. Butanediol and the like can also be added.

  The blending amount of the organic solvent is preferably 100 to 10,000 parts by mass, more preferably 300 to 8,000 parts by mass with respect to 100 parts by mass of the base resin.

  Examples of the basic compound include primary, secondary, and tertiary amine compounds described in paragraphs [0146] to [0164] of JP-A-2008-111103, particularly hydroxy groups, ether groups, and esters. And an amine compound having a group, a lactone ring, a cyano group, and a sulfonic acid ester group, or a compound having a carbamate group described in Japanese Patent No. 3790649.

  Further, a sulfonic acid which is not fluorinated at the α-position described in JP 2008-158339 A, a sulfonium salt, an iodonium salt, and an ammonium salt of a carboxylic acid described in Japanese Patent No. 3991462 and Japanese Patent No. 426803. Etc. can also be used together as a quencher. These quenchers can also be added to the shrink material.

  When the acid labile group is an acetal group that is particularly sensitive to an acid, the acid for removing the protecting group is not necessarily a sulfonic acid, imide acid, methido acid or the like fluorinated at the α-position. In some cases, the deprotection reaction may proceed even with a sulfonic acid in which the α-position is not fluorinated. Since the onium salt of sulfonic acid cannot be used as the quencher at this time, in such a case, it is preferable to use the onium salt of imido acid alone.

  0.0001-30 mass parts is preferable with respect to 100 mass parts of base resins, and, as for the compounding quantity of a basic compound, 0.001-20 mass parts is more preferable.

  The surfactant is described in paragraphs [0165] to [0166] of JP-A-2008-111103, and the dissolution controller is described in paragraphs [0155] to [0178] of JP-A-2008-122932. As the acetylene alcohols, those described in paragraphs [0179] to [0182] of JP-A-2008-122932 can be used.

  The blending amounts of the surfactant, the dissolution control agent and the acetylene alcohols can be appropriately selected according to the blending purpose.

  A polymer compound (water repellency improver) for improving the water repellency of the resist surface after spin coating can also be added to the resist material. The water repellency improver can be used in immersion lithography that does not use a top coat. The water repellency improver preferably has a 1,1,1,3,3,3-hexafluoro-2-propanol residue having a specific structure. JP-A-2007-297590, JP-A-2008-111103 It is illustrated in the gazette etc. The water repellency improver needs to be dissolved in an organic solvent developer. The above-mentioned water repellency improver having a specific 1,1,1,3,3,3-hexafluoro-2-propanol residue has good solubility in a developer. As a water-repellent additive, a polymer compound copolymerized with amino groups or amine salts as a repeating unit has a high effect of preventing the evaporation of an acid in PEB and preventing a defective opening of a hole pattern after development. 0.1-20 mass parts is preferable with respect to 100 mass parts of base resin of a resist material, and, as for the compounding quantity of a water repellency improving agent, 0.5-10 mass parts is more preferable.

[Pattern formation method]
The pattern forming method of the present invention comprises:
Applying the above-described resist material onto a substrate and performing a heat treatment;
Exposing the resist film with a high energy beam and performing a heat treatment;
Forming a negative resist pattern using an organic solvent as a developer;
A step of applying the shrink material of the present invention and heat-treating; and a step of removing excess shrink material with an organic solvent.

  A specific example of the pattern forming method of the present invention is shown in FIG. First, a resist film 30 made of a chemically amplified positive resist material is formed on the processing film 20 on the substrate 10 through a hard mask layer as necessary (A). Next, the resist film 30 is exposed by a conventional method (B), PEB, developed, and a resist pattern 30a is formed (C). A shrink material 40 is applied on the obtained resist pattern 30a (D). Next, baking is performed, and acid is diffused from the resist pattern 30a to the shrink material 40 by the heat. As a result, a deprotection reaction is caused in the polymer compound of the shrink material, and the resist pattern 30a is thickened by removing the excess shrink material 40 by solvent peeling, thereby narrowing the width of the resist pattern space ( E). The film to be processed is processed by dry etching using the shrinked pattern as a mask (F).

In this case, a silicon substrate is generally used as the substrate. The film to be _{processed, SiO 2, SiN, SiON,} SiOC, p-Si, α-Si, TiN, WSi, BPSG, SOG, Cr, CrO, CrON, MoSi, low dielectric films and etching stop film or the like can be mentioned It is done. As the hard _{mask, SiO 2, SiN, SiON,} p-Si or the like is used. Instead of the hard mask, an underlayer film made of a carbon film and a silicon-containing intermediate film may be laid, and an organic antireflection film may be laid between the hard mask and the resist film.

  In the pattern forming method of the present invention, a resist film made of a positive resist material is formed directly on the film to be processed or via the intermediate intervening layer. The thickness of the resist film is preferably 10 to 1,000 nm. 20-500 nm is more preferable. The resist film is heat-treated (prebaked) before exposure, and the processing temperature and time are preferably 50 to 180 ° C. and 10 to 300 seconds, more preferably 60 to 150 ° C. and 15 to 200 seconds.

  The exposure is performed using a high energy beam or electron beam having a wavelength of 400 nm or less. Examples of the high energy ray include i-line having a wavelength of 364 nm, KrF excimer laser having a wavelength of 248 nm, ArF excimer laser having a wavelength of 193 nm, and extreme ultraviolet light having a wavelength of 13.5 nm. Among them, exposure at 193 nm with an ArF excimer laser is most preferably used. The exposure may be a dry atmosphere in the air or a nitrogen stream, or may be immersion exposure in water. In ArF immersion lithography, a highly transparent liquid having a refractive index of 1 or more such as pure water or alkane is used as an immersion solvent. In immersion lithography, pure water or other liquid is inserted between a pre-baked resist film and a projection lens. As a result, it is possible to design a lens having an NA of 1.0 or more, and a finer pattern can be formed. Immersion lithography is an important technique for extending the life of ArF lithography. In the case of immersion exposure, pure water rinsing (post-soak) after exposure to remove the water droplet residue remaining on the resist film may be performed, and elution from the resist film is prevented, and the surface lubricity of the film is prevented. In order to increase the thickness, a protective film may be formed on the resist film after pre-baking. As a resist protective film used for immersion lithography, for example, a polymer compound having a 1,1,1,3,3,3-hexafluoro-2-propanol residue that is insoluble in water and dissolved in an alkaline developer is used. The base is preferably formed from a material dissolved in an alcohol solvent having 4 to 10 carbon atoms, an ether solvent having 8 to 12 carbon atoms, and a mixed solvent thereof. After the resist film is formed, pure water rinsing (post-soak) may be performed to extract the acid generator or the like from the film surface or to wash out particles, or to remove water remaining on the film after exposure. (Post-soak) may be performed.

Exposure amount in exposure is preferably about 1 to 200 mJ / cm ^2, about 10 to 100 mJ / cm ² is more preferable. Next, PEB is preferably performed at 50 to 150 ° C. for 30 seconds to 5 minutes, more preferably at 60 to 120 ° C. for 30 seconds to 3 minutes on a hot plate.

  Using an organic solvent as a developer, development is performed for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, by a conventional method such as a dip method, a puddle method, or a spray method. A negative resist pattern is formed on the substrate. Organic solvents used in the developer include 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methyl acetophenone, propyl acetate , Butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate , Ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, 2-hydroxy Ethyl isobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, 2-phenylethyl acetate, etc. Is preferred. These solvents may be used alone or in combination of two or more.

  Rinsing can be performed at the end of development. As the rinsing liquid, a solvent which is mixed with the developer and does not dissolve the resist film is preferable. As such a solvent, an alcohol solvent having 3 to 10 carbon atoms, an ether solvent having 8 to 12 carbon atoms, an alkane, alkene and alkyne having 6 to 12 carbon atoms, an aromatic solvent, or the like is preferably used.

  Specific examples of the alcohol solvent having 3 to 10 carbon atoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, and 2-pen. Tanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2 -Hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1 -Pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, -Methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3- Examples include pentanol, cyclohexanol, and 1-octanol. Examples of the alkane having 6 to 12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, and cyclononane. It is done. Examples of the alkene having 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, and cyclooctene. Examples of the alkyne having 6 to 12 carbon atoms include hexyne, heptin, octyne and the like. Examples of the ether solvent having 8 to 12 carbon atoms include di-n-butyl ether, diisobutyl ether, di-s-butyl ether, di-n-pentyl ether, diisopentyl ether, di-s-pentyl ether, di-t- Examples include pentyl ether and di-n-hexyl ether. Examples of the aromatic solvent include toluene, xylene, ethylbenzene, isopropylbenzene, t-butylbenzene, mesitylene and the like. These solvents may be used alone or in combination of two or more.

  After applying the rinse solution, drying is performed by spin drying and baking. Rinsing is not always necessary, and drying can be performed by spin drying after development, and rinsing can be omitted.

  After development, the shrink material of the present invention is applied on the obtained resist pattern. After application, baking is performed at 40 to 180 ° C. for 5 to 300 seconds. Not only does the solvent evaporate by baking, but also changes in polarity due to the diffusion of acid from the resist film to the shrink material, the acid desorption reaction, and the olefin and cross-linked structure generated in the shrink material film, which makes it insoluble in organic solvent developers. . The thickness of the shrink material film is preferably 1 to 150 nm, and more preferably 30 to 80 nm.

  Peeling of the shrink material is preferably performed with an organic solvent. Examples of such organic solvents include propyl acetate, butyl acetate, isobutyl acetate, butenyl acetate, pentyl acetate, isopentyl acetate, 2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, propyl formate, formic acid Butyl, isobutyl formate, pentyl formate, isopentyl formate, hexyl formate, methyl valerate, ethyl valerate, propyl valerate, isopropyl valerate, butyl valerate, isobutyl valerate, t-butyl valerate, pentyl valerate, valeric acid Isopentyl, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, t-butyl isovalerate, isopentyl isovalerate, ethyl 2-methylvalerate, 2-methylvaleric Butyl herbate, crotonic acid Chill, ethyl crotonate, propyl crotonate, isopropyl crotonate, butyl crotonate, t-butyl crotonate, methyl propionate, ethyl propionate, methyl pentenoate, ethyl pentenoate, propyl pentenoate, isopropyl pentenoate, pentenoic acid Butyl, t-butyl pentenoate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl pivalate, propyl pivalate Isopropyl pivalate, butyl pivalate, t-butyl pivalate, butyl propionate, isobutyl propionate, t-butyl propionate, benzyl propionate, ethyl 3-ethoxypropionate, ethyl hexanoate, hexa Allyl acid, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, t-butyl butyrate, ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, Phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, ethyl phenylacetate, 2-phenylethyl acetate, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, methylcyclohexanone, ethylcyclohexanone, acetophenone, methylacetophenone, ethylacetophenone, ethyl-n -Butyl ketone, di-n-butyl ketone, diisobutyl ketone, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl Alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2 -Butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2,2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pen Examples include butanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, 1-octanol and the like.

  Moreover, the organic solvent used for peeling of shrink material may be the same as the organic solvent used as a developing solution. As a result, the development of the organic solvent and the peeling of the shrink material can be performed with the same solvent, and there is an advantage that only one nozzle is required.

  By the pattern forming method using the shrink material of the present invention, the size of the hole and / or slit portion of the negative tone pattern obtained by development can be reduced with good control.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example. In addition, Mw is a polystyrene conversion measured value by GPC.

[1] Synthesis of Polymer [Synthesis Example 1] Synthesis of Polymer 1 Under a nitrogen atmosphere, in a 200 mL dropping cylinder, 37.43 g of 4-acetoxystyrene, 5.85 g of acenaphthylene, 4- (1-hydroxy-1-cyclopropyl) 21.72 g of styrene, 7.08 g of dimethyl-2,2′-azobis- (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., trade name V601), and 60 g of methyl ethyl ketone as a solvent were added, and the solution was dissolved. Prepared. Further, 48 g of methyl ethyl ketone was added to another 500 mL polymerization flask under a nitrogen atmosphere, and the above solution was added dropwise over 4 hours in a state heated to 80 ° C. After completion of dropping, stirring was continued for 18 hours while maintaining the polymerization temperature at 80 ° C., and then cooled to room temperature. The obtained polymerization solution was added dropwise to 1,000 g of hexane, and the precipitated copolymer was separated by filtration. The copolymer separated by filtration was washed twice with 200 g of hexane. The obtained copolymer was dissolved in a mixed solvent of 126 g of tetrahydrofuran and 42 g of methanol in a 1 L flask under a nitrogen atmosphere, 16.9 g of ethanolamine was added, and the mixture was stirred at 60 ° C. for 3 hours. The reaction solution was concentrated under reduced pressure, the resulting concentrate was dissolved in a mixed solvent of 300 g of ethyl acetate and 80 g of water, the resulting solution was transferred to a separatory funnel, 8.5 g of acetic acid was added, and a liquid separation operation was performed. Went. The lower layer was removed, and 80 g of water and 11.3 g of pyridine were added to the obtained organic layer to carry out a liquid separation operation. The lower layer was removed, and 80 g of water was further added to the obtained organic layer, followed by washing with water. The washing was performed 5 times in total. The separated organic layer was concentrated and then dissolved in 140 g of acetone, and the obtained acetone solution was added dropwise to 2500 g of water. The resulting crystallized precipitate was filtered, washed with water, and suction filtered for 2 hours. The filter separated product obtained again was dissolved in 150 g of acetone, and the obtained acetone solution was added dropwise to 2,800 g of water. The resulting crystallized precipitate was filtered, washed with water, and dried to obtain 45.0 g of a white polymer. When the obtained polymer was measured by ¹³ C-NMR, ¹ H-NMR and GPC, the following analysis results were obtained.
Hydroxystyrene: Acenaphthylene: 4- (1-Hydroxy-1-cyclopropyl) styrene = 60.0: 10.0: 300.0
Mw = 4,000
Mw / Mn = 1.66

[Synthesis Examples 2 to 22 and Comparative Synthesis Examples 1 to 3] Synthesis of Polymers 2 to 22 and Comparative Polymers 1 to 3 Except for changing the type and blending ratio of each monomer, the same procedure as in Synthesis Example 1 was performed. Resins shown in Table 1 were produced. In Table 1 below, the introduction ratio indicates a molar ratio.

  In Table 1, the structure of each unit is shown in Tables 2-5.

[Synthesis Examples 23 and 24] Synthesis of Resist Polymer 1 and Water-Repellent Polymer 1 Each monomer is combined and subjected to a copolymerization reaction in a tetrahydrofuran solvent, crystallized in methanol, and further washed with hexane, then isolated and dried. As a result, a resist copolymer 1 and a water-repellent polymer 1 of random copolymers having the following compositions were obtained. When the obtained polymer was measured by ¹ H-NMR and GPC, the following analysis results were obtained.

撥水性ポリマー１
Ｍｗ＝７,８００
Ｍｗ／Ｍｎ＝１.５５

Resist polymer 1
Mw = 7,500
Mw / Mn = 1.61

Water repellent polymer 1
Mw = 7,800
Mw / Mn = 1.55

[2] Preparation of shrink material [Examples 1-42, Comparative Examples 1-6]
According to the compositions shown in Tables 6 and 7 below, Polymers 1-22, Comparative Polymers 1-3, acid generator, onium salt, basic compound, and solvent are mixed, and a 0.2 μm Teflon (registered trademark) filter is used. Filter to prepare a shrink material. In Tables 6 and 7, sulfonium salts 1 to 15, iodonium salt 1, ammonium salt 1, amine quencher 1 and amine quencher 2 are as follows.

[3] Preparation of resist material According to the composition shown in Table 8 below, each component was mixed, and 3M surfactant FC-4430 was added to 100 ppm, and the resulting solution was 0.2 μm. A resist material was prepared by filtering through a size filter. In Table 8, PGMEA is propylene glycol monomethyl ether acetate. In Table 8, PAG1 is as follows.

[4] ArF exposure patterning evaluation For a trilayer process in which a spin-on carbon film ODL-101 made by Shin-Etsu Chemical Co., Ltd. is 180 nm on a silicon wafer and a silicon-containing spin-on hard mask SHB-A940 is formed on the silicon wafer to a thickness of 40 nm. The resist material was spin-coated on the substrate and baked at 100 ° C. for 60 seconds using a hot plate to obtain a resist film having a thickness of 90 nm. While changing the exposure using an ArF excimer laser immersion scanner (Nikon NSR-610C, NA 1.30, σ 0.90 / 0.70, annular illumination, 6% halftone phase shift mask) After exposure, PEB was carried out at 90 ° C. for 60 seconds, followed by paddle development with n-butyl acetate for 30 seconds to form a hole pattern with a pitch of 150 nm and 50 nm. The shrink material shown in Tables 6 and 7 is applied on the resist pattern, baked at the temperature shown in Tables 9 and 10 for 60 seconds, and paddle-developed with 4-methyl-2-pentanol for 10 seconds. The material was peeled off. The dimensional variation of holes with a pitch of 150 nm after development and after shrink treatment was measured with a length measurement SEM (CG-4000 manufactured by Hitachi, Ltd.). The results are shown in Tables 9 and 10.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and this embodiment has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present embodiment. It is included in the technical scope of the invention.

DESCRIPTION OF SYMBOLS 10 Substrate 20 Processed film 30 Resist film 30a Resist pattern 40 Shrink material

Claims (16)

The shrink containing the high molecular compound containing the at least 1 unit chosen from the repeating unit represented by following formula (1a) and (1b), and the solvent containing the solvent which does not lose | disappear the resist pattern after image development. material.

(In the formula, A represents a single bond or an alkylene group having 1 to 10 carbon atoms which may contain an etheric oxygen atom in the middle of the chain. R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or trifluoromethyl. R ² each independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic acyloxy group having 2 to 8 carbon atoms which may be halogen-substituted, or halogen-substituted. A straight-chain, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a straight-chain, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be halogen-substituted, L represents hydrogen Having an etheric oxygen atom, a carbonyl group or a carbonyloxy group in the middle of the atom or chain, a linear, branched or cyclic monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a substituent Even Represents a good monovalent aromatic ring-containing group, Z represents an alicyclic group having 5 to 15 carbon atoms formed together with the carbon atom to which R is bonded, and R ^x and R ^y each independently represent a hydrogen atom, a hydroxy group Or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms which may be substituted with an alkoxy group, and at least one of R ^x and R ^y is a cyclic alkyl group having 5 to 15 carbon atoms. F represents an integer of 1 to 3, s represents an integer of 0 to 2, a represents (5 + 2s−f), and m represents 0 or 1.) The shrink material of Claim 1 in which the said high molecular compound further contains the repeating unit represented by following formula (2).

(In the formula, B represents a single bond or an alkylene group having 1 to 10 carbon atoms that may contain an etheric oxygen atom in the middle of the chain. R ¹ is the same as above. R ³ is independently hydrogen. Atom, halogen atom, C2-C8 linear, branched or cyclic acyloxy group which may be halogen-substituted, C1-C6 linear, branched or cyclic which may be halogen-substituted A cyclic alkyl group, or a C1-C6 linear, branched or cyclic alkoxy group which may be halogen-substituted, g represents an integer of 0 to 3, and t represents an integer of 0 to 2 And b is (5 + 2t-g). N represents 0 or 1.) The shrink material according to claim 1 or 2 , wherein the polymer compound further contains at least one selected from repeating units represented by the following formulas (4) and (5).

Wherein R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, a linear, branched or cyclic acyloxy group having 2 to 8 carbon atoms that may be halogen-substituted, or halogen-substituted. Represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be halogen-substituted. And j are each independently an integer of 0 to 2. d is (6-i), and e is (4-j).) The shrink material according to any one of claims 1 to 3 , wherein the polymer compound further includes at least one selected from repeating units represented by the following formulas (A) to (E).

(In the formula, R ¹ is the same as described above. X ^A represents an acid labile group. X ^B and X ^C are each independently a single bond or a linear or branched group having 1 to 4 carbon atoms. X ^D represents a linear, branched or cyclic 2- to 5-valent aliphatic hydrocarbon group having 1 to 16 carbon atoms, and —CH constituting the hydrocarbon group ₂ — may be substituted with —O— or —C (═O) —, X ^E represents an acid labile group, and Y ^A represents a substituent having a lactone, sultone or carbonate structure. Z ^A represents a hydrogen atom, a fluoroalkyl group having 1 to 30 carbon atoms, or a fluoroalcohol-containing substituent having 1 to 15 carbon atoms, k ^1A represents an integer of 1 to 3. k ^1B represents 1 to 1 Represents an integer of 4.) The shrink material according to any one of claims 1 to 4 , wherein the polymer compound further includes a repeating unit represented by the following formula (F).

(In the formula, R ¹⁰¹ represents a hydrogen atom or a methyl group. X represents a single bond, —C (═O) —, —C (═O) —O— or —C (═O) —NH—). R ¹⁰² is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and has an ether group, an ester group, a carbonyl group, —N═ or —S—. R ¹⁰³ and R ¹⁰⁴ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an acid labile group, and a phenylene group or a naphthylene group. R ¹⁰³ and R ¹⁰⁴ may be bonded to form a ring together with the nitrogen atom to which they are bonded, and the ring may have an ether bond, and either R ¹⁰³ or R ¹⁰⁴ is R ¹⁰² and combined with good .k ^1C to form a ring together with the nitrogen atom to which they are attached is 1 or 2.) Furthermore, the shrink material of any one of Claims 1-5 containing the salt represented by following formula (9).

(In the formula, R ¹¹ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, or 6 to 20 carbon atoms. A part or all of hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a fluorine atom, a lactone ring-containing group, a lactam ring-containing group or a hydroxy group. An ether group, an ester group or a carbonyl group may be interposed between the carbon-carbon bonds of these groups, and M ⁺ represents a sulfonium cation, an iodonium cation or an ammonium cation.) Furthermore, the shrink material of any one of Claims 1-6 containing the salt represented by following formula (10).

(In the formula, R ¹² represents a straight, branched or cyclic monovalent hydrocarbon group having 1 to 35 carbon atoms which may contain an oxygen atom, and a part of hydrogen atoms bonded to the carbon atom of this group. Alternatively, all of them may be substituted with fluorine atoms, but the hydrogen atom bonded to the carbon atom at the α-position of the sulfonic acid is not substituted with a fluorine atom, and M ⁺ represents a sulfonium cation, an iodonium cation or an ammonium cation.) Further, primary, secondary and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, hydroxy nitrogen-containing compound having a group, nitrogen-containing compounds having hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, claim 1-7 comprising at least one basic compound selected from imide derivatives, and carbamates The shrink material according to 1. Solvent wherein not abolished the resist pattern after development, ester solvent 7-16 carbon atoms, more of claims 1-8 is an alcohol-based solvent a ketone solvent or 4 to 10 carbon atoms of 8 to 16 carbon atoms The shrink material of Claim 1. The ester solvent having 7 to 16 carbon atoms is pentyl acetate, isopentyl acetate, 2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, hexyl formate, ethyl valerate, propyl valerate, Isopropyl herbate, butyl valerate, isobutyl valerate, t-butyl valerate, pentyl valerate, isopentyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, T-butyl isovalerate, isopentyl isovalerate, ethyl 2-methylvalerate, butyl 2-methylvalerate, ethyl pivalate, propyl pivalate, isopropyl pivalate, butyl pivalate, t-butyl pivalate, pentenoic acid Ethyl, propyl pentenoate, pentenoic acid iso Lopyl, butyl pentenoate, t-butyl pentenoate, propyl crotonic acid, isopropyl crotonic acid, butyl crotonic acid, t-butyl crotonic acid, butyl propionate, isobutyl propionate, t-butyl propionate, benzyl propionate, hexanoic acid Ethyl, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, t-butyl butyrate, ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, benzoate One or more solvents selected from butyl acid, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, ethyl phenylacetate and 2-phenylethyl acetate, and the carbon number 8-16 The ketone solvent is 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, diisobutylketone, ethylcyclohexanone, ethylacetophenone, ethyl-n-butylketone, di- One or more solvents selected from n-butyl ketone and diisobutyl ketone, wherein the alcohol solvent having 4 to 10 carbon atoms is 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1- Hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2,2-diethyl-1-butanol, 2-methyl-1-pentanol, 2 -Methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1- The shrink material according to claim 9, which is one or more solvents selected from pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol and 1-octanol. In addition to the solvent that does not erase the resist pattern after development, the solvent further includes 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, Methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, croton Methyl acetate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, 2 Methyl hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzylpropionate, phenylacetic acid The shrink material according to any one of claims 1 to 10 , comprising at least one solvent selected from ethyl and 2-phenylethyl acetate. Applying a base resin containing a repeating unit in which a carboxyl group is substituted with an acid labile group, an acid generator and an organic solvent onto a substrate, followed by heat treatment;
Exposing the resist film with a high energy beam and performing a heat treatment;
Forming a negative resist pattern using an organic solvent as a developer;
The pattern formation method characterized by including the process of apply | coating the shrink material of any one of Claims 1-11, and heat-processing; and the process of removing excess shrink material with an organic solvent. Wherein the base resin is represented by the following formula (11) The pattern forming method according to claim 1 wherein the carboxyl group are those comprising recurring units (a) substituted with an acid labile group.

(In the formula, R ²¹ represents a hydrogen atom or a methyl group. R ²² represents an acid labile group. Z represents a single bond or —C (═O) —O—R ²³ —, and R ²³ represents Represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, or a naphthylene group, and in the alkylene group, an ether bond or an ester bond may be interposed between carbon-carbon bonds. .) The organic solvent used as the developer is 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methyl acetophenone, propyl acetate , Butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate , Ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, 2-hydro From ethyl isoisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate and 2-phenylethyl acetate at least one of claims 1 2 or 1 3 the pattern forming method according chosen. The organic solvent used in the step of removing the shrink material is propyl acetate, butyl acetate, isobutyl acetate, butenyl acetate, pentyl acetate, isopentyl acetate, 2-methylbutyl acetate, hexyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate. Propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, hexyl formate, methyl valerate, ethyl valerate, propyl valerate, isopropyl valerate, butyl valerate, isobutyl valerate, t-butyl valerate, valeric acid Pentyl herbate, isopentyl valerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, t-butyl isovalerate, isopentyl isovalerate, ethyl 2-methylvalerate , 2- Butyl tilvalate, methyl crotonate, ethyl crotonate, propyl crotonate, isopropyl crotonate, butyl crotonate, t-butyl crotonate, methyl propionate, ethyl propionate, methyl pentenoate, ethyl pentenoate, propyl pentenoate , Isopropyl pentenoate, butyl pentenoate, t-butyl pentenoate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, Ethyl pivalate, propyl pivalate, isopropyl pivalate, butyl pivalate, t-butyl pivalate, butyl propionate, isobutyl propionate, t-butyl propionate, benzyl propionate, 3-ethoxypropionate , Ethyl hexanoate, allyl hexanoate, propyl butyrate, butyl butyrate, isobutyl butyrate, 3-methylbutyl butyrate, t-butyl butyrate, ethyl 2-methylbutyrate, isopropyl 2-methylbutyrate, methyl benzoate, ethyl benzoate, benzoic acid Propyl acid, butyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, ethyl phenylacetate, 2-phenylethyl acetate, 2-heptanone, 3-heptanone, 4 -Heptanone, 2-hexanone, 3-hexanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, methylcyclohexanone, ethylcyclohexanone, acetophenone, methylacetophenone, D Tylacetophenone, ethyl-n-butyl ketone, di-n-butyl ketone, diisobutyl ketone, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, t -Pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2 , 3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2,2-diethyl-1-butanol, 2-methyl-1-pentanol, 2- Methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pen Butanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol and at least one kind of claim 1 2-1 4 pattern forming method according to any one of selected from 1-octanol. High-energy rays, i-rays of wavelength 364 nm, KrF excimer laser having a wavelength of 248 nm, ArF excimer laser with a wavelength of 193 nm, extreme ultraviolet, or any one of claims 1 2 to 1 5 is an electron beam with a wavelength of 13.5nm The pattern formation method as described.

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