JP2010230995A - Photosensitive composition for optical decoloring layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical decoloring layer photosensitive composition which increases the contrast and improve the resolution. <P>SOLUTION: This is a photosensitive composition containing a compound shown by formula (1) and a resin to use for an optical decoloring layer. In formula (1), R<SP>1</SP>and R<SP>2</SP>respectively represent aliphatic hydrocarbon group having a hydrogen atom and 1-12 carbons, and an alkoxy group, acryloyl group, or methacryloyl group having 1-12 carbons. The hydrogen atom contained in the aliphatic hydrocarbon group and alkoxy group may be replaced with a fluorine atom. The aliphatic hydrocarbon group and the alkoxy group may have carbon-carbon double bonds. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photosensitive composition for a photo-decolorable material layer.

As a technique for improving the resolution of a photosensitive resin composition used in a lithography technique or the like in a semiconductor process, a resist pattern forming method using a contrast enhancement lithography technique (CEL) is known (for example, Patent Document 1: Special). (Kaihei 6-310391 and Patent Document 2: JP-A-5-90149).
Specifically, a photoresist layer and a photo-decolorable material layer are sequentially laminated on the substrate, and the first exposure is focused on the center of the photo-decolorable material layer. Decolorization is performed and a second exposure is performed to focus on the center of the photoresist layer and to pattern the resist layer.
However, there has not been much research on what is specifically useful as the photo-decolorable material of the photo-decolorable material layer. It is not specifically described.
In recent years, in photolithography, attention has been paid to double patterning technology such as a double exposure method using a 193 nm wavelength. In particular, development of a photo-decolorable material at a wavelength of 193 nm is required.

  An object of this invention is to provide the photosensitive composition for photodecolorable material layers which can make contrast high and can make resolution performance favorable.

［式（１）中、Ｒ^１及びＲ^２は、互いに独立に、水素原子、炭素数１〜１２の脂肪族炭化水素基、炭素数１〜１２のアルコキシ基、アクリロイル基又はメタクリロイル基を表す。前記脂肪族炭化水素基及びアルコキシ基に含まれる水素原子は、フッ素原子で置換されていてもよく、前記脂肪族炭化水素基及びアルコキシ基は、炭素−炭素二重結合を有していてもよい。］ The photosensitive composition for photodecolorable material layer of the present invention contains a compound represented by formula (1) and a resin.

[In Formula (1), R < ¹ > and R < ² > represents a hydrogen atom, a C1-C12 aliphatic hydrocarbon group, a C1-C12 alkoxy group, an acryloyl group, or a methacryloyl group mutually independently. A hydrogen atom contained in the aliphatic hydrocarbon group and the alkoxy group may be substituted with a fluorine atom, and the aliphatic hydrocarbon group and the alkoxy group may have a carbon-carbon double bond. . ]

In such a photodecolorable material layer photosensitive composition, the resin is:
(B1) a structural unit having an acid labile group in the side chain;
(B2) a structural unit having a hydroxyl group in the side chain;
Preferably, the resin contains at least one structural unit selected from the group consisting of (b3) a structural unit having a lactone structure in the side chain, and (b4) a structural unit having a structure containing fluorine in the side chain. .

［式（Ｉ）中、Ｘは、単結合、炭素数１〜６のアルキレン基、炭素数１〜６のアルキレン−カルボニルオキシ基又は炭素数１〜６のアルキレンオキシ基を表す。
Ｒ^３は、水素原子、ハロゲン原子、炭素数１〜６のアルキル基又は炭素数１〜６のハロゲン化アルキル基を表す。
Ｒ^４は、炭素数３〜２０の脂環式炭化水素基、５〜７員のラクトン環基、５〜７員のラクトン環を含む縮合環基を表し、これらの基に含まれる水素原子は、水酸基、シアノ基、カルボキシル基、炭素数１〜６のアルキル基、炭素数１〜６のフッ素化アルキル基及び炭素数１〜６のヒドロキシアルキル基からなる群から選択される少なくとも１種で置換されていてもよく、これらの基に含まれるメチレン基は、酸素原子及び／又はカルボニル基で置換されていてもよい。］ The structural units (b1) to (b2) are preferably structural units represented by the formula (I).

[In formula (I), X represents a single bond, a C1-C6 alkylene group, a C1-C6 alkylene-carbonyloxy group, or a C1-C6 alkyleneoxy group.
R ³ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogenated alkyl group having 1 to 6 carbon atoms.
R ⁴ represents an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a 5- to 7-membered lactone ring group, and a condensed ring group containing a 5- to 7-membered lactone ring, and the hydrogen atoms contained in these groups are Substituted with at least one selected from the group consisting of a hydroxyl group, a cyano group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and a hydroxyalkyl group having 1 to 6 carbon atoms The methylene group contained in these groups may be substituted with an oxygen atom and / or a carbonyl group. ]

  Furthermore, the structural unit contained in the resin is preferably a structural unit derived from an acrylic monomer having a di (trifluoromethyl) hydroxymethyl group.

［式（Ｉ）中、Ｗは、炭素数６〜１２の脂環式炭化水素基を表し、
Ｒ^ａは、水素原子又はメチル基を表す。
Ｒ^ｂは、ジ（トリフルオロメチル）ヒドロキシメチル基で置換された炭素数１〜６のアルキル基を表す。］ Moreover, it is preferable that the structural unit derived from the acrylic monomer having a di (trifluoromethyl) hydroxymethyl group is a structural unit derived from the compound represented by the formula (b4-1).

[In formula (I), W represents a C6-C12 alicyclic hydrocarbon group,
R ^a represents a hydrogen atom or a methyl group.
R ^b represents a C 1-6 alkyl group substituted with a di (trifluoromethyl) hydroxymethyl group. ]

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive composition for photodecolorable material layers which can increase contrast and can make resolution performance favorable can be provided.

It is a graph which shows the light absorbency with respect to the exposure amount of the photosensitive composition for photodecolorable material layers of this invention.

The photosensitive composition for photodecolorable material layer of the present invention (hereinafter sometimes abbreviated as CEL composition) mainly contains a compound represented by the formula (1) and a resin.
In the present specification, unless otherwise specified, examples of each substituent are applied to any chemical structural formula having the same substituent while appropriately selecting the number of carbon atoms. Those that can be both linear and branched include both.
Moreover, the description of (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

［式（１）中、Ｒ^１及びＲ^２は、互いに独立に、水素原子、炭素数１〜１２の脂肪族炭化水素基、炭素数１〜１２のアルコキシ基、アクリロイル基又はメタクリロイル基を表す。前記脂肪族炭化水素基及びアルコキシ基に含まれる水素原子は、フッ素原子で置換されていてもよく、前記脂肪族炭化水素基及びアルコキシ基は、炭素−炭素二重結合を有していてもよい。］ The compound represented by Formula (1) is as follows.

[In Formula (1), R < ¹ > and R < ² > represents a hydrogen atom, a C1-C12 aliphatic hydrocarbon group, a C1-C12 alkoxy group, an acryloyl group, or a methacryloyl group mutually independently. A hydrogen atom contained in the aliphatic hydrocarbon group and the alkoxy group may be substituted with a fluorine atom, and the aliphatic hydrocarbon group and the alkoxy group may have a carbon-carbon double bond. . ]

等の多環式炭化水素基等が挙げられる。 Here, examples of the aliphatic hydrocarbon group include linear, branched, and cyclic (including monocyclic, polycyclic, condensed ring, and ring assembly) hydrocarbon groups, and groups obtained by combining these.
Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3 -Methylbutyl group, 1-ethylpropyl group, 2-ethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, isopropyl group, sec-butyl group, tert- Alkyl groups such as butyl group, 2-ethylhexyl group, tert-octyl group;
Monocyclic hydrocarbon groups such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group;

And the like, and the like.

  Examples of the alkoxy group include methoxy group, ethoxy group, n-propyloxy group, n-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, and n-nonyloxy group. , N-decyloxy group, n-undecyloxy group, n-dodecyloxy group, isopropoxy group, sec-butoxy group, tert-butoxy group, 2-ethylhexyloxy group and tert-octyloxy group.

  Examples of the group in which a hydrogen atom contained in an aliphatic hydrocarbon group is substituted with a fluorine atom include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, a perfluoro group. Examples include octyl group, perfluorononyl group, perfluorodecyl group, perfluoroundecyl group, and perfluorododecyl group.

  Examples of the group in which the hydrogen atom contained in the alkoxy group is substituted with a fluorine atom include a perfluoromethoxy group, a perfluoroethoxy group, a perfluoropropoxy group, a perfluorobutoxy group, a perfluoropentyloxy group, a perfluorohexyloxy group, a perfluoroheptyloxy group, Examples include a perfluorooctyloxy group, a perfluorononyloxy group, a perfluorodecyloxy group, a perfluoroundecyloxy group, and a perfluorododecyloxy group.

R ¹ and R ² are preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a sec-butyl group and a tert-butyl group, more preferably a methyl group and an ethyl group. More preferably, a methyl group is mentioned.
R ¹ and R ² may be different from each other but are preferably the same.

The resin is (b1) a structural unit having an acid labile group in the side chain;
(B2) a structural unit having a hydroxyl group in the side chain;
(B3) contains at least one structural unit selected from the group consisting of a structural unit having a lactone structure in the side chain, and (b4) a structural unit having a structure containing fluorine in the side chain. That is, these structural units may contain only one type of structural unit, or may contain two or more types of structural units. However, each of these structural units may be a structural unit having any of the characteristics (b1) to (b4), but two structural types (b1) to (b4) are included in one structural unit. Those having the above characteristics may exist.

  As the resin used here, any resin can be used as long as it is usually used for a photoresist. For example, various known resins such as JP-A-2008-233613, JP-A-2006-126818, JP-A-2005-331918 are exemplified.

［式（Ｉ）中、Ｘは、単結合、炭素数１〜６のアルキレン基、炭素数１〜６のアルキレン−カルボニルオキシ基又は炭素数１〜６のアルキレンオキシ基を表す。
Ｒ^３は、水素原子、ハロゲン原子、炭素数１〜６のアルキル又は炭素数１〜６のハロゲン化アルキル基を表す。
Ｒ^４は、炭素数３〜２０の脂環式炭化水素基、５〜７員のラクトン環基、５〜７員のラクトン環を含む縮合環基を表し、これらの基に含まれる水素原子は、水酸基、シアノ基、カルボキシル基、炭素数１〜６のアルキル基、炭素数１〜６のフッ素化アルキル基及び炭素数１〜６のヒドロキシアルキル基からなる群から選択される少なくとも１種で置換されていてもよく、これらの基に含まれるメチレン基は、酸素原子及び／又はカルボニル基で置換されていてもよい。］ Examples of the structural units (b1) to (b4) include those having a structural unit represented by the formula (I).

[In formula (I), X represents a single bond, a C1-C6 alkylene group, a C1-C6 alkylene-carbonyloxy group, or a C1-C6 alkyleneoxy group.
R ³ represents a hydrogen atom, a halogen atom, an alkyl having 1 to 6 carbon atoms, or a halogenated alkyl group having 1 to 6 carbon atoms.
R ⁴ represents an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a 5- to 7-membered lactone ring group, and a condensed ring group containing a 5- to 7-membered lactone ring, and the hydrogen atoms contained in these groups are Substituted with at least one selected from the group consisting of a hydroxyl group, a cyano group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and a hydroxyalkyl group having 1 to 6 carbon atoms The methylene group contained in these groups may be substituted with an oxygen atom and / or a carbonyl group. ]

  Here, as the alkylene group, methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, sec-butylene group, tert-butylene group, n-pentylene group, 1-methylbutylene group, 2 -Methylbutylene group, 3-methylbutylene group, 1-ethylpropylene group, 2-ethylpropylene group, n-hexylene group, 1-methylpentylene group, 2-methylpentylene group, 3-methylpentylene group, 4 -Methylpentylene group, 1-ethylbutylene group, 2-ethylbutylene group, 3-ethylbutylene group, etc. are mentioned.

Examples of the alkylene-carbonyloxy group include a methylenecarbonyloxy group, an ethylenecarbonyloxy group, and a propylenecarbonyloxy group. Of these, a methylenecarbonyloxy group is preferable.
Examples of the alkyleneoxy group include a methyleneoxy group and an ethyleneoxy group.

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

  Examples of the halogenated alkyl group include those in which one or more hydrogen atoms, preferably all hydrogen atoms in the alkyl group described above are substituted with halogen atoms, preferably fluorine atoms. Preferably a trifluoromethyl group and a perfluoroethyl group are mentioned, More preferably, a trifluoromethyl group is mentioned.

などが挙げられる。
５〜７員のラクトン環としては、

等が例示される。結合部位としては、好ましくはカルボニル基の隣接位が挙げられる。 Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include, in addition to the above-described monocyclic hydrocarbon group and polycyclic hydrocarbon group, a cyclononyl group, a cyclodecyl group, a 1-adamantyl group, an isobornyl group,

Etc.
As a 5- to 7-membered lactone ring,

Etc. are exemplified. The binding site is preferably a position adjacent to the carbonyl group.

  As the condensed ring group containing a lactone ring, for example, those containing an alicyclic hydrocarbon group or heterocyclic group having 4 to 10 carbon atoms are preferred.

等が例示される。これらの基の結合位置は、好ましくはヘテロ原子の隣接位置である。 As the heterocyclic group,

Etc. are exemplified. The bonding position of these groups is preferably adjacent to the hetero atom.

等が例示される。 As a condensed ring group containing a lactone ring,

Etc. are exemplified.

  These alicyclic hydrocarbon groups, lactone ring groups, and lactone ring-containing condensed ring groups are all hydroxyl groups, cyano groups, carboxyl groups, alkyl groups having 1 to 6 carbon atoms, and fluorinated alkyls having 1 to 6 carbon atoms. It may be substituted with one or more selected from the group consisting of a group and a hydroxyalkyl group having 1 to 6 carbon atoms. Preferred are those substituted with a substituent containing a hydroxyl group and / or a fluorinated alkyl group, and more preferred are those substituted with both a hydroxyl group and a fluorinated alkyl group.

［式（Ｉ）中、Ｗは、炭素数６〜１２の脂環式炭化水素基を表し、
Ｒ^ａは、水素原子又はメチル基を表す。
Ｒ^ｂは、ジ（トリフルオロメチル）ヒドロキシメチル基で置換された炭素数１〜６のアルキル基を表す。］ In particular, the structural units (b1) to (b4) constituting the resin are all suitably structural units derived from an acrylic monomer, and are derived from an acrylic monomer having a di (trifluoromethyl) hydroxymethyl group. Those containing a structural unit are preferred.
Examples of such a structural unit include a structural unit derived from a compound represented by the formula (b4-1).

[In formula (I), W represents a C6-C12 alicyclic hydrocarbon group,
R ^a represents a hydrogen atom or a methyl group.
R ^b represents a C 1-6 alkyl group substituted with a di (trifluoromethyl) hydroxymethyl group. ]

Specific examples of the compound represented by the formula (b4-1) include the following compounds.

  Examples of the resin described above include those containing structural units derived from the following monomers (1) to (46).

The resin used in the present invention can be produced by a method known in the art. For example, radical polymerization is exemplified.
First, one or more monomers are dissolved in an organic solvent, and then one or more radical polymerization initiators are dissolved. And resin can be manufactured by heat-retaining the obtained reaction solution in predetermined reaction temperature.

As the organic solvent used for the polymerization, a solvent capable of dissolving all of the monomer, the initiator and the obtained polymer is preferable. Examples of such organic solvents include hydrocarbons such as toluene, 1,4-dioxane, tetrahydrofuran, methyl isobutyl ketone, isopropyl alcohol, γ-butyrolactone, propylene glycol monomethyl ether acetate, and ethyl lactate. Alternatively, two or more kinds of solvents may be mixed and used.
The reaction temperature in the method for producing a resin used in the present invention is in the range of 0 to 150 ° C, preferably in the range of 40 to 100 ° C.

  The polymerization initiator used for production of the resin of the present invention is not particularly limited, and known ones can be used. Specific examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2′-azobis (2-methylpropio) Azo) compounds such as 2,2′-azobis (2-hydroxymethylpropionitrile); lauryl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide Diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, tert Organic peroxides such as butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide; inorganic peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide Etc.

  In the CEL composition of the present invention, the resin is contained in the range of about 80 to 99.9% by weight and the compound of the formula (1) in the range of about 0.1 to 20% by weight with respect to the total solid content. Is suitable.

  The photo-decolorable material layer photosensitive composition further contains a small amount of various additives such as a sensitizer, a dissolution inhibitor, other resins, a surfactant, a stabilizer, and a dye as necessary. You can also.

  The CEL composition of the present invention can be usually applied on a photosensitive resin composition used in the art applied on a substrate such as a silicon wafer according to a commonly used method such as spin coating. The solvent used here may be any solvent that dissolves each component, has an appropriate drying rate, and gives a uniform and smooth coating film after the solvent evaporates. Can be used.

  For example, glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate, esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate, acetone, methyl isobutyl ketone, 2-heptanone And ketones such as cyclohexanone and cyclic esters such as γ-butyrolactone. These solvents can be used alone or in combination of two or more.

The photodecolorable material layer coated on the photosensitive resin composition and dried is subjected to an exposure process for patterning the photosensitive resin composition, optionally subjected to a heat treatment, and then subjected to an alkali development. Develop with liquid.
The alkaline developer used here may be various alkaline aqueous solutions used in this field, but generally an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline) is used. Is suitable.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Hereinafter, unless otherwise specified, parts represent parts by weight. The average molecular weight of the obtained resin was calculated by gel permeation chromatography.
The measurement conditions are as follows.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TOSOH TSKGEL Multipore H _XL- M 3 connection + guard column (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Flow rate: 1.0 mm / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μL
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

上記のモノマー５０ｇ及び１，４−ジオキサン１００ｇの混合物に、前記モノマーの合計モル数に対して、アゾビスイソブチロニトリル、１．５ｍｏｌ％とアゾビス（２，４−ジメチルバレロニトリル）４．５ｍｏｌ％とを添加し、得られた混合物を７５℃で５時間加熱した。その後、得られた混合物を、混合物に対して大過剰量の、メタノールと水の容量比４：１の混合溶媒中に注いで、粗製樹脂１を沈殿させ、該粗製樹脂１を濾過して取り出した。得られた粗製樹脂１の全量を、テトラヒドロフラン１００ｇに溶解させて樹脂溶液を調整し、これを先と同組成の大過剰量の混合溶媒に注いで、粗製樹脂２を沈殿させ、該粗製樹脂２を濾過して取り出した。同じ操作をさらに１回繰り返して、精製された樹脂（Ａ１）を、取り出した。
得られた樹脂（Ａ１）の重量平均分子量は約１６，０００であり、その収率９３％はであった。 [Synthesis of Resin A1]

In a mixture of 50 g of the above monomer and 100 g of 1,4-dioxane, azobisisobutyronitrile, 1.5 mol% and azobis (2,4-dimethylvaleronitrile) 4.5 mol, based on the total number of moles of the monomer And the resulting mixture was heated at 75 ° C. for 5 hours. Thereafter, the obtained mixture is poured into a mixed solvent having a volume ratio of 4: 1 of methanol and water in a large excess with respect to the mixture to precipitate the crude resin 1, and the crude resin 1 is filtered out. It was. The total amount of the obtained crude resin 1 is dissolved in 100 g of tetrahydrofuran to prepare a resin solution, which is poured into a large excess amount of a mixed solvent having the same composition as above to precipitate the crude resin 2, and the crude resin 2 Was filtered off. The same operation was repeated once more, and the purified resin (A1) was taken out.
The weight average molecular weight of the obtained resin (A1) was about 16,000, and the yield was 93%.

Example 1
Each component in Table 1 was mixed and dissolved at the stated ratio, and further filtered through a fluororesin filter having a pore size of 0.2 μm to prepare CEL composition 1.

The CEL composition 1 was applied onto a glass substrate using a spin coater, and the solvent in the composition was removed by heating on a hot plate. It was 805 nm when the film thickness of the obtained dry film was measured with the film thickness meter (KT-22; manufactured by Foothill).
The obtained dry film is exposed using an exposure machine (VUVES-4800; manufactured by RISOTEC Japan Co., Ltd.), the integrated exposure amount and the transmittance at 193 nm of the dry film are measured, and this is converted into absorbance. And plotted on a graph.
Conversion to absorbance was performed using the following formula (1).
Absorbance = −1 ÷ film thickness × log (transmittance (%) ÷ 100) Formula (1)
Here, the log used a natural logarithm with e as the base.
The unit of film thickness was nm. The unit of absorbance is 1 / nm.
The result is shown in FIG.

Comparative Example 1
Each component in Table 1 was mixed and dissolved at the stated ratio, and further filtered through a fluororesin filter having a pore size of 0.2 μm to prepare CEL composition 2.
A dry film was formed in the same manner as in Example 1, and the film thickness was measured and found to be 803 nm. In the same manner as in Example 1, the dry film was exposed to light, and the integrated exposure amount and the transmittance at 193 nm of the dry film were measured. This was converted into absorbance and plotted on a graph.
Conversion to absorbance was performed using equation (1).
The result is shown in FIG.

From the results of FIG. 1, it can be seen that when the composition of Example 1 is used, the absorbance decreases as the integrated exposure increases, and it has a function as a photodecolorable material.
On the other hand, in the comparative example, as the integrated exposure amount increases, the absorbance slightly increases and does not have a function as a photodecolorable material.

Example 2
A commercially available ArF chemically amplified photoresist composition is applied onto a silicon substrate using a spin coater, and prebaked on a hot plate to obtain a dry film.
On the obtained dried film, the CEL composition 1 used in Example 1 was applied using a spin coater and heated on a hot plate to remove the solvent in the composition.
Using the exposure machine ArF excimer stepper [FPA5000-AS3; manufactured by Canon Inc., NA = 0.75, 2/3 Annular], focus on the layer of the ArF chemically amplified photoresist composition. In addition, patterning exposure is performed through a predetermined photomask.
Next, post-exposure baking is performed, and development is performed using an alkaline developer. Furthermore, when it rinses using ultrapure water and it dries, the target pattern will be obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive composition for photodecolorable material layers which can increase contrast and can make resolution performance favorable can be provided.

JP-A-6-310391 Japanese Patent Laid-Open No. 5-90149

Claims (5)

A photosensitive composition for a photo-decolorable material layer, comprising a compound represented by formula (1) and a resin.

[In Formula (1), R < ¹ > and R < ² > represents a hydrogen atom, a C1-C12 aliphatic hydrocarbon group, a C1-C12 alkoxy group, an acryloyl group, or a methacryloyl group mutually independently. A hydrogen atom contained in the aliphatic hydrocarbon group and the alkoxy group may be substituted with a fluorine atom, and the aliphatic hydrocarbon group and the alkoxy group may have a carbon-carbon double bond. . ] The resin is
(B1) a structural unit having an acid labile group in the side chain;
(B2) a structural unit having a hydroxyl group in the side chain;
2. A resin containing at least one structural unit selected from the group consisting of (b3) a structural unit having a lactone structure in the side chain, and (b4) a structural unit having a structure containing fluorine in the side chain. A composition according to 1. The composition according to claim 2, wherein the structural units (b1) to (b2) are structural units represented by the formula (I).

[In formula (I), X represents a single bond, a C1-C6 alkylene group, a C1-C6 alkylene-carbonyloxy group, or a C1-C6 alkyleneoxy group.
R ³ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogenated alkyl group having 1 to 6 carbon atoms.
R ⁴ represents an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a 5- to 7-membered lactone ring group, and a condensed ring group containing a 5- to 7-membered lactone ring, and the hydrogen atoms contained in these groups are Substituted with at least one selected from the group consisting of a hydroxyl group, a cyano group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and a hydroxyalkyl group having 1 to 6 carbon atoms The methylene group contained in these groups may be substituted with an oxygen atom and / or a carbonyl group. ]   The composition according to any one of claims 1 to 3, wherein the structural unit contained in the resin is a structural unit derived from an acrylic monomer having a di (trifluoromethyl) hydroxymethyl group. The composition according to claim 4, wherein the structural unit derived from the acrylic monomer having a di (trifluoromethyl) hydroxymethyl group is a structural unit derived from the compound represented by the formula (b4-1).

[In formula (I), W represents a C6-C12 alicyclic hydrocarbon group,
R ^a represents a hydrogen atom or a methyl group.
R ^b represents a C 1-6 alkyl group substituted with a di (trifluoromethyl) hydroxymethyl group. ]

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