JPWO2016133073A1 - COMPOUND, COMPOSITION CONTAINING THE COMPOUND AND DEVICE MANUFACTURING METHOD USING THE SAME - Google Patents

Abstract

A compound represented by the following general formula (1) having a Hammett substituent constant σ of −0.05 or less. [In the formula (1), Ar1 and Ar2 are each independently a phenylene group optionally having substituent (s), and R1 is a thio optionally having substituent (s)). Any one selected from the group consisting of an alkoxy group, an arylthio group, an alkoxyphenyl group and a thioalkoxyphenyl group, and X is any one selected from the group consisting of a sulfur atom, an oxygen atom and a direct bond; Is either an optionally substituted alkyl group or a phenyl group, Y is independently an oxygen atom or a sulfur atom, and R3 and R4 are independently Each of them is any one selected from the group consisting of a linear, branched or cyclic alkyl group, alkenyl group and alkynyl group which may have a substituent, and R3 and R4 are bonded to each other. 2 in the ceremony Y and the ring structure may also be formed.)

Description

  Some embodiments of the present invention relate to a compound that can be used for forming a resist pattern, a composition containing the compound, and a device manufacturing method using the compound.

  In a highly integrated circuit element typified by a semiconductor device, for example, a DRAM, there is a high demand for higher density, higher integration, and higher speed. Accordingly, in various electronic device manufacturing fields, there is an increasing demand for the establishment of microfabrication technology on the order of half a micron, for example, the development of photolithography technology for forming fine patterns. In order to form a fine pattern in the photolithography technique, it is necessary to improve the resolution. Here, the resolution (R) of the reduction projection exposure apparatus is expressed by the Rayleigh equation R = k · λ / NA (where λ is the wavelength of exposure light, NA is the numerical aperture of the lens, and k is a process factor). Therefore, the resolution can be improved by shortening the wavelength λ of the active energy ray (exposure light) used in forming the resist pattern.

Chemically amplified photoresists have been proposed as photoresists suitable for short wavelengths (Patent Documents 1 to 3). A characteristic of chemically amplified photoresists is that proton acid is generated from the photoacid generator that is a component when exposed to exposure light, and this proton acid undergoes an acid-catalyzed reaction with the resist compound and the like by heat treatment after exposure. is there.
With the miniaturization of semiconductor devices, there is an increasing demand for EUV lithography technology that uses EUV (Extreme Ultra Violet) light having a wavelength of 13.5 nm as exposure light. However, the biggest drawback of EUV lithography is the lack of output of the EUV light source. For this reason, a highly sensitive photoresist is required, but there is a trade-off relationship among sensitivity, resolution, and LWR (Line Width Roughness). Therefore, there is a problem that increasing the sensitivity lowers resolution and increases roughness.

  In order to solve the above problems, how to improve the generation efficiency of protonic acid in a photoresist is an important issue for practical use.

Japanese Patent Laid-Open No. 10-7650 JP 2003-327572 A JP 2008-7410 A

  One object of some embodiments of the present invention is to provide a compound capable of improving the generation efficiency of protonic acid. In addition, another object of some aspects of the present invention is to provide a composition containing the above compound, which is preferably used as a photoresist satisfying high sensitivity, high resolution, and high LWR characteristics, and a device manufacturing method using the composition Is to provide.

As a result of intensive studies to solve the above problems, the present inventors have found that the generation efficiency of protonic acid can be improved by using a specific compound that is acid-dissociated by an acid in a photoresist.
More specifically, in pattern formation using a chemically amplified photoresist containing a photoacid generator, a composition containing a specific compound is used as the chemically amplified photoresist. For example, the composition can be obtained by using EUV light, electron beam (EB), or the like. The compound is acid-dissociated with an acid generated from the photoacid generator by 1 irradiation, and the acid-dissociated compound is further irradiated with UV light or the like to cause electron transfer to the photoacid generator. It has been found that the generation efficiency is improved.

  One embodiment of the present invention is a compound represented by the following general formula (1) having a Hammett substituent constant σ of −0.05 or less.

（上記式（１）中、Ａｒ^１及びＡｒ^２は、独立して各々に、置換基を有していてもよいフェニレン基であり、
Ｒ^１は、置換基を有していてもよいチオアルコキシ基、アリールチオ基、アルコキシフェニル基及びチオアルコキシフェニル基からなる群より選択されるいずれかであり、
Ｘは、硫黄原子、酸素原子及び直接結合からなる群より選択されるいずれかであり、
Ｒ²は、置換基を有していてもよいアルキル基及びフェニル基のいずれかであり、
Ｙは、独立して各々に、酸素原子及び硫黄原子のいずれかであり、
Ｒ^３及びＲ^４は、独立して各々に、置換基を有してもよい、直鎖状、分岐鎖状又は環状のアルキル基、アルケニル基及びアルキニル基からなる群より選択されるいずれかであり、
上記Ｒ^３及びＲ^４は、互いに結合して式中の２つのＹと環構造を形成していてもよい。）

(In the above formula (1), Ar ¹ and Ar ² are each independently a phenylene group optionally having a substituent,
R ¹ is any one selected from the group consisting of an optionally substituted thioalkoxy group, arylthio group, alkoxyphenyl group and thioalkoxyphenyl group;
X is any selected from the group consisting of a sulfur atom, an oxygen atom and a direct bond;
R ² is either an alkyl group which may have a substituent or a phenyl group,
Y is each independently one of an oxygen atom and a sulfur atom,
R ³ and R ⁴ are each independently selected from the group consisting of a linear, branched or cyclic alkyl group, alkenyl group, and alkynyl group, each of which may have a substituent. Yes,
R ³ and R ⁴ may be bonded to each other to form a ring structure with two Ys in the formula. )

  The compound which is one aspect of the present invention is preferably used as a precursor of a photosensitizer for improving the acid generation efficiency of a photoacid generator and forming a photoresist having high sensitivity, high resolution and high LWR characteristics. It is done.

  Hereinafter, the present invention will be described in detail.

<1> Compound A compound according to one embodiment of the present invention has a Hammett substituent constant σ of −0.05 or less, and is represented by the following general formula (1).

In the above formula (1), Ar ¹ and Ar ² are each independently a phenylene group optionally having a substituent,
R ¹ is any one selected from the group consisting of an optionally substituted thioalkoxy group, arylthio group, alkoxyphenyl group and thioalkoxyphenyl group;
X is any selected from the group consisting of a sulfur atom, an oxygen atom and a direct bond;
R ² is either an alkyl group which may have a substituent or a phenyl group,
Y is each independently one of an oxygen atom and a sulfur atom,
R ³ and R ⁴ are each independently selected from the group consisting of a linear, branched or cyclic alkyl group, alkenyl group and alkynyl group which may have a substituent. ,
R ³ and R ⁴ may be bonded to each other to form a ring structure with two Ys in the formula.

In the present invention, the Hammett substituent constant σ is defined in 1935 in order to quantitatively discuss the influence of substituents on the reaction or equilibrium of benzene derivatives. P. It is a value (total of σp value, σm value, and σo value) obtained by an empirical rule proposed by Hammett.
Among the substituent constants determined by Hammett's rule, the values of σp value and σm value are, for example, J. A. It is disclosed in detail in the Dean edition, “Lange's Handbook of Chemistry”, 12th edition, 1979 (McGraw-Hill) and “Area of Chemistry”, 122, 96-103, 1979 (Nankodo).
Further, the σo value discussed regarding the influence of steric hindrance is, for example, Nuclear magnetic resonance studies of ortho-substituted phenols in dimethyl sulfoxide solutions. Electronic effects of orthostitutants J.E. Am. Chem. Soc. , 1969, 91 (2), pp 379-388, M .; Thomas and James G. It is disclosed in detail by Traynham.

The Hammett substituent constant of the above compound is −0.05 or less, and preferably −3.00 or more.
When the Hammett substituent constant σ of the above compound is within the above range, electron donating property is obtained, and the acid generation efficiency of the photoacid generator can be improved as a sensitizer. In order to set the Hammett substituent constant σ to −0.05 or less, according to the Hammett substituent constant disclosed above, an electron donating group or an electron withdrawing substituent is appropriately selected and introduced into Ar ¹ and Ar ^2. In addition, the Hammett substituent constant may be adjusted by introducing an electron donating group at an appropriate position.

Ar ¹ and Ar ² in the above formula (1) are each a phenylene group, and each may have a substituent (hereinafter, the substituents of Ar ¹ and Ar ² are referred to as “first substituent”). Good.
Examples of the first substituent include an electron donating group, and specific examples of the electron donating group include an alkyl group, an alkenyl group, an alkoxy group, and a thioalkoxy group. Examples of the first substituent include a long-chain alkoxy group having a polyethylene glycol chain (— (CO ₂ H ₄ ) _n —). Further, when the first substituent is bonded to the para position of Ar ¹ or Ar ² , an OH group may be included as the first substituent.
In the present invention, the substitution position of such "para" of Ar ¹ or Ar ² are, Ar ¹ or two Y and Ar ¹ in the formula (1) located on the benzene ring of the phenylene group as Ar ² And the position with respect to the group bonded to the quaternary carbon bonded to Ar ² . For not only the first substituent but also other groups, the criterion for the substitution position such as “para-position” is the position with respect to the group bonded to the quaternary carbon.
The alkyl group as the first substituent is not particularly limited, but includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, t-butyl group, cyclohexyl group, adamantyl group, and the like. Examples thereof include linear, branched and cyclic alkyl groups having 1 to 20 carbon atoms. Although there is no restriction | limiting in particular as an alkoxy group as a 1st substituent, C1-C20 alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, are mentioned. Examples of the alkenyl group as the first substituent include those in which part of the carbon-carbon single bond of the alkyl group as the first substituent is an unsaturated bond (double bond). Examples of the thioalkoxy group as the first substituent include thioalkoxy groups having 1 to 20 carbon atoms such as a thiomethoxy group, a thioethoxy group, a thiopropoxy group, and a thiobutoxy group.

A group in which any methylene group of the alkyl group in the first substituent is substituted with a —C (═O) — group or a —O—C (═O) — group may be used. However, it is preferable that the —C (═O) — group and the —O—C (═O) — group are not directly bonded to Ar ¹ and Ar ² in the ^first substituent. The first substituent preferably does not have a continuous chain of heteroatoms such as —O—O— and —S—S—.
When the first substituent is an alkoxy group, it is preferably bonded to the ortho position and / or the para position of the phenylene group that is Ar ¹ and Ar ² . At that time, the number of substituents is preferably 3 or less.

R ¹ in the above formula (1) is any selected from the group consisting of a thioalkoxy group, arylthio group, alkoxyphenyl group and thioalkoxyphenyl group which may have a substituent.
Specifically, the thioalkoxy group for R ¹ is preferably a thioalkoxy group having 1 to 20 carbon atoms such as a thiomethoxy group, a thioethoxy group, a thio n-propoxy group, or a thio n-butoxy group. An alkoxy group is more preferable.
Specific examples of the arylthio group for R ¹ include a phenylthio group and a naphthylthio group.

Specific examples of the alkoxyphenyl group represented by R ¹ include a phenyl group to which an alkoxy group having 1 to 20 carbon atoms such as a methoxyphenyl group, an ethoxyphenyl group, a propoxyphenyl group, and a butoxy group phenyl is bonded. There is no particular restriction on the substitution position of alkoxy group bonded to the phenylene group at R ^1, it is the para position is preferred from the viewpoint of increasing the electron donating property.

Specific examples of the thioalkoxyphenyl group represented by R ¹ include a phenyl group to which a thioalkoxy group having 1 to 20 carbon atoms such as a thiomethoxyphenyl group, a thioethoxyphenyl group, a thiopropoxyphenyl group, and a thiobutoxy group phenyl is bonded. It is done. No particular restriction on the substitution position of thioalkoxy group attached to the phenylene group in R ^1, but it is the para position is preferred from the viewpoint of increasing the molar extinction coefficient of the electron-donating and 365 nm.
R ¹ is preferably bonded to the ortho or para position of the phenylene group that is Ar ¹ .

R ² in the above formula (1) is either an alkyl group which may have a substituent or a phenyl group.
Examples of the alkyl group for R ² include a straight chain or branched chain having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a t-butyl group, and a cyclohexyl group. And cyclic alkyl groups.

R ¹ and R ² in the above formula (1) may have a substituent, and as the substituent (hereinafter, the substituents of R ¹ and R ² are referred to as “second substituent”), Although not particularly limited, in addition to the first substituent, an electron withdrawing group, a polymerizable group, and the like can be given. Examples of the electron withdrawing group include a nitro group and a sulfonyl group.
Among these, it is preferable that R ¹ and R ² have at least one polymerizable group as the second substituent because a sensitizing action can be imparted to the polymer. Examples of the polymerizable group include a (meth) acryloyloxy group, an epoxy group, and a vinyl group.
In addition, when the second substituent has either a —C (═O) — group or an —O—C (═O) — group, like the first substituent, —C (═O) — The group and —O—C (═O) — group are preferably not directly bonded to the Ar ¹ and Ar ² . In the second substituent, it is preferable that the hetero substituents such as —O—O— and —S—S— are not continuously connected.

When X in the formula (1) is an oxygen atom or a sulfur atom, it is preferable that the X is an ortho position or a para position of Ar ² . When X is a direct bond, it is preferable that X is an ortho or para position of Ar ² .

The total carbon number of R ^{1 in} the above formula (1) is not particularly limited, and the compound may be a constituent component of the polymer. When R ¹ has a substituent, the total carbon number is 1 to 20. It is preferable. The total carbon number of R ^{2 in} the above formula (1) is not particularly limited, and the compound may be a constituent component of the polymer, but when R ² has a substituent, the total carbon number is 1 to 20. It is preferable.
The above compounds may have been a component of the via R ¹ or R ² polymer, it is preferable that the total number of carbon atoms of R ¹ and R ² except the portion constituting the polymer is 1 to 20.

Y is each independently either an oxygen atom or a sulfur atom.
R ³ and R ⁴ are each independently selected from the group consisting of a linear, branched, or cyclic alkyl group, alkenyl group, alkynyl group, and aralkyl group that may have a substituent. Either. As the alkyl group of R ³ and R ⁴ , a straight chain having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, t-butyl group, cyclohexyl group, Examples include branched and cyclic alkyl groups. R ³ and Examples of the alkenyl group of R ⁴ a part of carbon atoms in the alkyl group of the R ³ and R ⁴ - those carbon single bonds becomes unsaturated bond (double bond) can be mentioned, R ³ and R ⁴ Examples of the alkynyl group include those in which part of the alkyl groups of R ³ and R ⁴ is a triple bond. The aralkyl group of R ³ and R ^4, part of the hydrogen of the above-described alkyl group and R ³ and R ⁴ is a phenyl group include those substituted with an aryl group such as phenyl or naphthyl.
From the viewpoint of synthesis, R ³ and R ⁴ are preferably the same.
In the present invention, when R ³ and R ⁴ are the groups shown above, the compound can be deprotected with an acid to have a carbonyl group.

R ³ and R ⁴ may be bonded to each other to form a ring structure with two Ys in the formula. That is, the compound of one embodiment of the present invention is represented by the following formula (2). In the following formula (2), —R ⁵ —R ⁶ — is preferably — (CH ₂ ) _n —, and n is an integer of 2 or more. Although n is not particularly limited as long as it is 2 or more, it is preferably 8 or less for ease of synthesis. R ⁵ and R ⁶ correspond to those in which R ³ and R ⁴ in the above formula (1) are bonded to each other to form a ring.

R ³ and R ⁴ in the above formula (1) may have a substituent, and the substituent (hereinafter, the substituent of R ³ and R ⁴ is referred to as “third substituent”) Although not particularly limited, in addition to the second substituent, aryl groups such as a phenyl group and a naphthyl group are also exemplified.

The total number of carbon atoms of R ³ and R ^{4 in} the above formula (1) is not particularly limited, and the compound may be a component of the polymer, but when R ³ or R ⁴ has a substituent, It is preferable that it is C1-C20. In the above formula (2), R ⁵ and R ⁶ may have the same third substituent as R ³ and R ⁴ .
Incidentally, when the compound has a structure component through the R ³ or R ⁴ polymer, it is preferable that the total number of carbon atoms of R ³ and R ⁴ except the portion constituting the polymer is 1 to 20.

The compound after acid treatment of the compound, that is, the compound having a carbonyl group that is generated when the compound is deprotected with an acid, has a molar extinction coefficient at 365 nm of 1.0 × 10 ⁵ cm ² / mol or more. Is preferred. A higher molar extinction coefficient at 365 nm is preferable, but a practical value is 1.0 × 10 ¹⁰ cm ² / mol or less. In order to make the molar extinction coefficient within the above range, the compound contains, for example, one or more thioalkoxy groups, arylthio groups, alkoxyphenyl groups, thioalkoxyphenyl groups, or two or more alkoxy groups or aryloxy groups. And so on.
In the present invention, the molar extinction coefficient is at 365 nm measured with a UV-VIS absorption altimeter using chloroform as a solvent.
In addition, the compound of one aspect of the present invention includes -YR ³ and -YR ⁴ , or -YR ³ -R ^{4 in the} whole compound from the viewpoint of ease of synthesis and light absorption characteristics. It is preferable that the number of groups selected from the group consisting of thioalkoxy groups other than -Y-, arylthio groups, alkoxyphenyl groups, thioalkoxyphenyl groups, alkoxy groups and aryloxy groups is 4 or less.

  As a preferable example as a compound represented by the said Formula (1), the following compound can be illustrated, for example. The compounds of some aspects of the invention are not limited thereto.

<2> Compound Synthesis Method A compound synthesis method according to one embodiment of the present invention will be described.
When one embodiment of the present invention has a structure represented by the following formula (3), for example, it can be synthesized by the following method. First, an alkoxybenzoyl chloride or thioalkoxybenzoyl chloride having a -X-R ² group is reacted with a halogenated benzene having an R ¹ group by a Grignard reaction to obtain a benzophenone derivative. Next, the benzophenone derivative and an ortho ester such as trialkyl orthoformate (R ³ , R ⁴ = alkyl group) are reacted at 0 to reflux temperature for 1 to 120 hours, thereby being represented by the following formula (3). Derivatives can be obtained.

  In the case where one embodiment of the present invention has a structure represented by the following formula (4), the derivative represented by the above formula (3) obtained above and ethylene glycol are added in the presence of an acid such as camphorsulfonic acid in the presence of 0 to 0. It can be obtained by reacting at 100 ° C. for 1 to 120 hours.

  When one embodiment of the present invention has a structure represented by the following formula (5), the derivative represented by the above formula (3) obtained above and methanethiol are -78 in the presence of a Lewis acid such as boron trichloride. It can obtain by making it react for 1 to 120 hours at deg.

  In the case where one embodiment of the present invention has a structure represented by the following formula (6), a derivative represented by the above formula (3) obtained above and 2-mercaptoethanol are converted to a Lewis acid such as zirconium chloride (IV). It can obtain by making it react at 0-100 degreeC for 1 to 120 hours in presence.

  In the case where one embodiment of the present invention has a structure represented by the following formula (7), the derivative represented by the above formula (3) obtained above and methanethiol are reduced to 0 in the presence of a Lewis acid such as boron trichloride. It can be obtained by reacting at ~ 100 ° C for 1 to 120 hours.

  In the case where one embodiment of the present invention has a structure represented by the following formula (8), a derivative represented by the above formula (3) obtained above and 1,2-ethanedithiol are converted to a Lewis acid such as boron trichloride. It can obtain by making it react at 0-100 degreeC for 1 to 120 hours in presence.

The compound according to one embodiment of the present invention has a specific structure, so that the acetalization reaction can be efficiently advanced. Ar ¹ and Ar ² may have a ring structure directly or via a divalent group and the quaternary carbon. However, when Ar ¹ and Ar ² have a ring structure directly or via a divalent group and the quaternary carbon, for example, when having a skeleton such as thioxanthone, it is difficult to efficiently advance the acetalization reaction. There is a case. Therefore, it is preferable in the synthesis that Ar ¹ and Ar ² do not have a ring structure directly or via a divalent group and the quaternary carbon.

<3> Composition Containing Compound One aspect of the present invention is a composition containing the above compound, a photoacid generator, and an acid reaction compound that reacts with an acid.
In one embodiment of the compound according to some embodiments of the present invention, in the above composition, the photoacid generator generates an acid by irradiation with active energy rays or the like, and can be deprotected by the acid to become a photosensitizer. .
In the present invention, the photoacid generator generates an acid by the first irradiation of active energy rays or the like, the compound is deprotected by the acid to become a photosensitizer, and the photosensitizer emits light. It is preferable that the photoacid generator can generate an acid again only in the portion where the first irradiation is performed by the action of the photosensitizer by performing the second irradiation of the wavelength to be absorbed. Thereby, while the said acid generates a photosensitizer further, the acid reaction compound which reacts with an acid can be made to react.

Examples of the acid reaction compound include a compound having a protecting group that is deprotected with an acid, a compound having a polymerizable group that is polymerized with an acid, and a crosslinking agent having a crosslinking action with an acid.
There is no restriction | limiting in particular as a photo-acid generator, Ion type photo-acid generators, such as a sulfonium and an iodonium salt; Nonionic type photo-acid generators, such as an imide sulfonate and an oxime sulfonate; Specifically, phenyl dibenzothionium-nonafluorobutane sulfonate, diphenyl iodonium-nonafluorobutane sulfonate, N-nonafluorobutanesulfonyloxy-1,8-naphthalimide and the like are preferable. A photo-acid generator can be used individually by 1 type or in combination of 2 or more types.

  A compound having a protecting group that is deprotected by an acid is, for example, a compound in which the solubility in a developer is changed when a protective group is deprotected by an acid to form a polar group when the composition is used as a resist composition. It is. For example, in the case of aqueous development using an alkaline developer or the like, it is insoluble in an alkaline developer, but the protective group is deprotected in the exposed area by an acid generated from the photoacid generator upon exposure, whereby an alkaline developer. It is a compound that becomes soluble in.

  In the present invention, the developer is not limited to an alkaline developer, and may be a neutral developer or an organic solvent development. Therefore, when an organic solvent developer is used, the compound having a protecting group that is deprotected by an acid is deprotected in the exposed area by the acid generated from the photoacid generator upon exposure, and the organic solvent developer Is a compound whose solubility is reduced.

Examples of the polar group include a hydroxyl group, a carboxyl group, an amino group, and a sulfo group.
Specific examples of the protecting group to be deprotected with an acid include an ester group, an acetal group, a tetrahydropyranyl group, a siloxy group, and a benzyloxy group. As the compound having the protecting group, a compound having a styrene skeleton, a methacrylate or an acrylate skeleton pendant with these protecting groups is preferably used.

  For example, when the composition is used as a resist composition, the compound having a polymerizable group that is polymerized with an acid is a compound whose solubility in a developer is changed by polymerization of the polymerizable group with an acid. For example, in the case of aqueous development, it is soluble in an aqueous developer, but the polymerizable group is polymerized in the exposed area by the acid generated from the photoacid generator upon exposure, and is soluble in the aqueous developer. It is a compound that decreases. Also in this case, an organic solvent developer may be used instead of the aqueous developer.

  Examples of the polymerizable group that is polymerized with an acid include an epoxy group, a vinyloxy group, and an oxetanyl group. As the compound having a polymerizable group, a compound having a styrene skeleton, a methacrylate or an acrylate skeleton having these polymerizable groups is preferably used.

  For example, when the composition is used as a resist composition, the crosslinking agent having a crosslinking action with an acid is a compound that changes the solubility in a developer by crosslinking with an acid. For example, in the case of aqueous development, aqueous development It acts on a compound that is soluble in a liquid and reduces the solubility of the compound in an aqueous developer after crosslinking. Specifically, methylated melamine such as 2,4,6-tris [bis (methoxymethyl) amino] -1,3,5-triazine, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, etc. And methylated urea. At this time, examples of the cross-linking partner compound include compounds having a phenolic hydroxyl group or a carboxyl group.

Specific examples of the composition according to one embodiment of the present invention include the following.
A resist composition comprising a compound having a protecting group that is deprotected by the acid and a photoacid generator; a resist comprising a compound having a polymerizable group that is polymerized by the compound and the acid, and the photoacid generator A composition comprising the above compound, a crosslinking agent having a crosslinking action by an acid, a compound that reacts with the crosslinking agent to change solubility in a developer, and a photoacid generator; .
The compound of one embodiment of the present invention can be preferably used as a sensitizer for positive and negative resist compositions.

10-500 mass parts is preferable with respect to 100 mass parts of photoacid generators, and, as for content of the said compound in the composition of 1 aspect of this invention, it is more preferable that it is 100-200 mass parts.
The content of the photoacid generator in the composition of one embodiment of the present invention is preferably 1 to 50 parts by mass, and 1 to 30 parts by mass with respect to 100 parts by mass of the composition component excluding the photoacid generator. More preferably, it is 1-15 mass parts. By containing the photoacid generator in the composition within the above range, for example, even when the composition is used as a permanent film such as an insulating film such as a display body, the light transmittance can be increased.
In the present invention, the compound and the acid reaction compound may be polymer constituents. That is, when the said compound has a polymeric group, the aspect which comprises the said acid reaction compound and a polymer is mentioned. An embodiment in which the photoacid generator is also a constituent component of the polymer is also mentioned as a preferable configuration. This configuration is preferable from the viewpoint of making the distribution of the compound in the composition uniform.

In the composition of one embodiment of the present invention, the organic solvent, quencher, acidic compound, dissolution inhibitor, stabilizer and dye used in a normal resist composition are further included as optional components in addition to the above components as necessary. May contain other sensitizers in combination.
The composition of one aspect of the present invention is obtained by mixing the components of the above composition, and the mixing method is not particularly limited.

<4> Device Manufacturing Method According to one aspect of the present invention, a resist film forming step in which the composition is applied onto a substrate to form a resist film, and the resist film is irradiated with a first active energy ray in a pattern. A device comprising: a first irradiation step; a second irradiation step of irradiating the pattern film-irradiated resist film with second active energy; and a pattern formation step of developing the resist film to obtain a photoresist pattern. It is a manufacturing method.

As described above, in the present invention, the photoacid generator generates an acid by the first irradiation of active energy rays or the like, the compound is deprotected by the acid to become a photosensitizer, and the photosensitizer is used. It is preferable that the photoacid generator can generate an acid again only in a portion where the first irradiation is performed by the action of the photosensitizer by performing the second irradiation at a wavelength at which the sensitizer absorbs light. Thereby, while the said acid generates a photosensitizer further, the acid reaction compound which reacts with an acid can be made to react.
The first active energy ray used in the first irradiation step may be any light that can activate the photoacid generator contained in the composition to generate an acid, such as KrF excimer laser light, ArF excimer laser light, F ₂ excimer laser light, electron beam, UV, visible light, X-ray, ion beam, g-line, h-line, i-line, EUV, etc. Of these, electron beam, X-ray, EUV and the like are preferable.
The second active energy used in the second irradiation step has a wavelength that is absorbed by the photosensitizer produced by deprotection of R ³ and R ⁴ of the compound represented by the above formula (1). For example, KrF excimer laser light, ArF excimer laser light, F ₂ excimer laser light, UV, visible light, ion beam, g-line, h-line, i-line, etc. may be used.

  Except using the composition containing the said compound, what is necessary is just to follow the manufacturing method of a normal device.

  One embodiment of the present invention is a method for manufacturing a substrate having a pattern before obtaining a singulated chip, including a coating film forming step, a photolithography step, and a pattern forming step using the above composition. Good.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited at all by these Examples. In the following synthesis examples, the molar extinction coefficient after acid treatment of a compound, that is, the molar extinction coefficient at 365 nm of a benzophenone compound derivative obtained by deprotecting the compound was measured with a UV-VIS spectrophotometer (Hitachi Co., Ltd.). It was determined using chloroform as a solvent by U-3300).

<Synthesis of Compound 1a and Compound 1b>
<1-1> Synthesis of 4-methoxy-4′-methylthiobenzophenone 8.0 g of 4-bromothioanisole was dissolved in 32 g of tetrahydrofuran, and 39 ml of 1 mol / L methylmagnesium bromide in THF was added dropwise at 5 ° C. or less. did. After dropping, the mixture was stirred at 5 ° C. or lower for 30 minutes to obtain a THF solution of 4-methylthiophenylmagnesium bromide. To a solution of 7.5 g of 4-methoxybenzoyl chloride in 15 g of THF, a THF solution of 4-methylthiophenylmagnesium bromide was added dropwise at 10 ° C. or lower, and then stirred at 25 ° C. for 1 hour. After stirring, 50 g of a 10% by mass aqueous ammonium chloride solution was added at 20 ° C. or lower and the mixture was further stirred for 10 minutes, and the organic layer was extracted with 80 g of ethyl acetate. After washing with water, ethyl acetate and tetrahydrofuran were distilled off to obtain crude crystals. The crude crystals were recrystallized using 120 g of ethanol to obtain 7.0 g of 4-methoxy-4′-methylthiobenzophenone. The molar extinction coefficient at 365 nm was 4.2 × 10 ⁵ cm ² / mol.

<1-2> Synthesis of (4-methoxy) phenyl- (4′-methylthio) phenyl-dimethoxymethane (Compound 1a) 5.0 g of 4-methoxy-4′-methylthiobenzophenone, 47 mg of sulfuric acid, and 13.5 g of trimethyl orthoformate Were dissolved in 12.5 g of methanol, and this was stirred at reflux temperature for 3 hours. Thereafter, the mixture was cooled to room temperature, and 50 g of a 5% by mass aqueous sodium hydrogen carbonate solution was added thereto, followed by further stirring for 10 minutes, and the precipitated crystals were filtered. The crystals were collected and redissolved in 50 g of ethyl acetate and washed with water. Then, ethyl acetate was distilled off to obtain 4.2 g of (4-methoxy) phenyl- (4′-methylthio) phenyl-dimethoxymethane (Compound 1a).

<1-3> Synthesis of 2- (4-methoxy) phenyl-2- (4′-methylthio) phenyl-1,3-dioxolane (Compound 1b) (4-methoxyphenyl)-(4′-methylthiophenyl)- 4.0 g of dimethoxymethane, 0.10 g of camphorsulfonic acid, and 2.5 g of ethylene glycol were dissolved in 12 g of THF and stirred at 25 ° C. for 72 hours. Thereafter, THF was distilled off and distilled, and the residue was dissolved in 20 g of dichloromethane. To this was added a 5% by mass aqueous sodium hydrogen carbonate solution, and the mixture was stirred and washed with water after liquid separation. Thereafter, dichloromethane was distilled off, and the residue was purified by silica gel column chromatography (ethyl acetate: hexane: triethylamine = 10: 90: 0.01) to give 2- (4-methoxy) phenyl-2- (4 2.5 g of '-methylthio) phenyl-1,3-dioxolane (compound 1b) was obtained. The Hammett substituent constant was -0.28.

<Synthesis of Compound 2>
(Synthesis of 2- (2-methoxyphenyl) -2- (4′-methylthiophenyl) -1,3-dioxolane (Compound 2))
In the same manner as in Example 1 except that 2-methoxybenzoyl chloride is used instead of 4-methoxybenzoyl chloride in <1-1> of Example 1, 2- (2-methoxyphenyl) -2- ( 4'-methylthiophenyl) -1,3-dioxolane was obtained. The Hammett substituent constant was -0.37. The molar extinction coefficient at 365 nm of 2-methoxy-4′-methylthiobenzophenone was 1.0 × 10 ⁵ cm ² / mol or more.

<Synthesis of Compound 3>
(Synthesis of 4- (4-methoxyphenyl) -4′-methoxybenzophenone)
5.4 g of 4-phenylanisole and 4.9 g of aluminum chloride were dissolved in 15 g of dichloromethane. 4-methoxybenzoyl chloride 5.0g was dripped at this at 5 degrees C or less over 30 minutes. Thereafter, after stirring at 5 ° C. for 2 hours, 15 g of water was added so as to be 25 ° C. or less, and further stirred for 10 minutes. The organic layer was washed with water after separation and collection, dichloromethane was distilled off, and the resulting residue was produced by recrystallization using 70 g of ethanol to give 4- (4-methoxyphenyl) -4′- 6.5 g of methoxybenzophenone was obtained. The molar extinction coefficient at 365 nm was 2.5 × 10 ⁵ cm ² / mol.

Synthesis of (2-[(4-methoxyphenyl) -phenyl] -2- (4′-methoxyphenyl) -1,3-dioxolane (Compound 3) 4-methoxy-4 in <1-2> of Example 1 2-[(4-Methoxyphenyl) -phenyl] -2 in the same manner as in Example 1 except that 4- (4-methoxyphenyl) -4'-methoxybenzophenone is used instead of '-methylthiobenzophenone. -(4'-methoxyphenyl) -1,3-dioxolane was obtained, and the Hammett substituent constant was -0.56.

<Synthesis of Compound 4>
(Synthesis of 2- (2 ′, 4′-dimethoxy) phenyl-2- (4-methylthio) phenyl-1,3-dioxolane (Compound 4))
In the same manner as in Example 1 except that 2,4-dimethoxybenzoyl chloride is used in place of 4-methoxybenzoyl chloride in <1-1> of Example 1, 2- (2 ′, 4′-dimethoxy is used. ) Phenyl-2- (4-methylthio) phenyl-1,3-dioxolane was obtained. The Hammett substituent constant was -0.65. The molar extinction coefficient at 365 nm of 2,4-dimethoxy-4′-methylthiobenzophenone was 1.1 × 10 ⁶ cm ² / mol.

<Synthesis of Compound 5>
(Synthesis of 2- (4-methoxyphenyl) -2- (4′-phenylthiophenyl) -1,3-dioxolane (Compound 5))
In the same manner as in Example 1 except that diphenyl sulfide is used instead of 4-phenylanisole in Example 3, 2- (4-methoxyphenyl) -2- (4′-phenylthiophenyl) -1, 3-dioxolane was obtained. The Hammett substituent constant was -0.05 or more. The molar extinction coefficient at 365 nm of 4-methoxy-4′-phenylthiobenzophenone was 6.5 × 10 ⁵ cm ² / mol.

<Synthesis of Compound 6 (Monomer 1)>
(Synthesis of 4- (2-vinyloxy) ethylthiobromobenzene)
4-Bromothiophenol 5.0 g, chloroethyl vinyl ether 5.7 g and potassium carbonate 7.3 g were dissolved in acetone 20 g and stirred at reflux temperature for 3 hours. Then, it cooled to room temperature, 60 g of pure waters were added, and it stirred for 5 minutes. To this, 90 g of toluene was added for extraction, followed by separation and washing with water. Thereafter, toluene was distilled off to obtain 6.4 g of 4- (2-vinyloxy) ethylthiobromobenzene.

(4- (2-vinyloxy) ethylthio-2 ′, 4′-dimethoxybenzophenone)
In the same manner as in Example 1 except that 4- (2-vinyloxy) ethylthiobromobenzene was used instead of 4-bromothioanisole in <1-1> of Example 1, 4- (2-vinyloxy ) Ethylthio-2 ', 4'-dimethoxybenzophenone was obtained.

(Synthesis of 4- (2-hydroxy) ethylthio-2 ′, 4′-dimethoxybenzophenone)
4- (2-vinyloxy) ethylthio-2 ′, 4′-dimethoxybenzophenone (5.0 g), pure water (3.3 g) and pyridinium-p-toluenesulfonic acid (0.44 g) were added to acetone (30 g) at reflux temperature. Stir for 3 hours. After cooling to room temperature, 85 g of pure water was added and the mixture was stirred for 5 minutes and extracted with ethyl acetate. This was separated and washed with water, and then ethyl acetate was distilled off to obtain 4.6 g of 4- (2-hydroxy) ethylthio-2 ′, 4′-dimethoxybenzophenone.

(Synthesis of 4- (2-methacryloxy) ethylthio-2 ′, 4′-dimethoxybenzophenone)
4- (2-Hydroxy) ethylthio-2 ′, 4′-dimethoxybenzophenone and methacrylic anhydride are dissolved in THF, and triethylamine is added dropwise over 30 minutes so that the temperature is 20 ° C. or less. After dripping, after stirring at 25 ° C. for 3 hours, pure water is added and the mixture is further stirred for 10 minutes. This is extracted with ethyl acetate and separated and washed with pure water. Thereafter, the target 4- (2-methacryloxy) ethylthio-2 ′, 4′-dimethoxybenzophenone was obtained by distilling off ethyl acetate. The molar extinction coefficient at 365 nm was 1.1 × 10 ⁶ cm ² / mol.

Synthesis of (2- {4-[(2-methacryloxy) ethylthio] -phenyl} -2- (2 ′, 4′-dimethoxyphenyl) -1,3-dioxolane (monomer 1) <1- 1> except that 4- (2-methacryloxy) ethylthio-2 ′, 4′-dimethoxybenzophenone is used instead of 4-methoxy-2 ′, 4′-dimethylthiobenzophenone. Thus, 2- {4-[(2-methacryloxy) ethylthio] -phenyl} -2- (2 ′, 4′-dimethoxyphenyl) -1,3-dioxolane (monomer 1) was obtained as Compound 6. Hammett The substituent constant was -0.65.

<Preparation of Resin A>
α-methacryloyloxy-γ-butyrolactone 5.0 g, 2-methyladamantane-2-methacrylate 6.0 g, 3-hydroxyadamantane-1-methacrylate 4.3 g, dimethyl-2,2′-azobis (2- 0.51 g of methyl propionate (product name V601, manufactured by Wako Pure Chemical Industries, Ltd. (hereinafter referred to as “V601”)) was dissolved in 26 g of tetrahydrofuran and degassed under reduced pressure. This is dripped over 4 hours in the flask which refluxed THF4g. After dropping, the mixture was stirred for 2 hours and then cooled to 25 ° C. This solution was reprecipitated by dropping it into a mixed solvent consisting of 160 g of hexane and 18 g of tetrahydrofuran. This was filtered, dispersed and washed twice with 37 g of hexane, and vacuum dried after filtration to obtain 8.5 g of the desired copolymer (resin A) as a white powder.

<Preparation of resin B>
0.80 g of the monomer 1, 3.9 g of α-methacryloyloxy-γ-butyrolactone, 2.9 g of 2-methyladamantane-2-methacrylate, 3.0 g of 3-hydroxyadamantane-1-methacrylate, and butyl mercaptan 0.13 g and 0.58 g of V601 were dissolved in 12.5 g of tetrahydrofuran, and degassed under reduced pressure. After deaeration, the solution was added dropwise over 4 hours to a flask in which 4 g of THF was refluxed by flowing nitrogen. After dropping, the mixture was stirred for 2 hours and then cooled to 25 ° C. After cooling, it was reprecipitated by dropping it into a mixed solvent consisting of 107 g of hexane and 11 g of tetrahydrofuran.
This was filtered, dispersed and washed twice with 37 g of hexane, filtered, and vacuum-dried to obtain 6.2 g of the desired copolymer (resin B) as a white powder.

<Preparation of Resin C>
0.80 g of the monomer 1, 3.9 g of α-methacryloyloxy-γ-butyrolactone, 2.9 g of 2-methyladamantane-2-methacrylate, 3.0 g of 3-hydroxyadamantane-1-methacrylate, 0.49 g of phenyldibenzothiophenium 1,1-difluoro-2- (2-methacryloyloxy) -ethanesulfonate, 0.13 g of butyl mercaptan and 0.56 g of V601 were weighed and dissolved in 12.2 g of tetrahydrofuran. Then, vacuum degassing was performed. After deaeration, the solution was added dropwise over 4 hours to a flask in which 4 g of THF was refluxed by flowing nitrogen. After dropping, the mixture was stirred for 2 hours and then cooled to 25 ° C. After cooling, it was reprecipitated by dropping it into a mixed solvent consisting of 107 g of hexane and 11 g of tetrahydrofuran. This was filtered, dispersed and washed twice with 37 g of hexane, vacuum-dried after filtration to obtain 6.6 g of the desired copolymer (resin C) as a white powder.

<Preparation of sample for sensitivity evaluation ("evaluation sample")>
Evaluation samples 1 to 17 were prepared as follows. 7000 mg of cyclohexanone, any resin selected from 500 mg of the above resin A, 507 mg of resin B and 497 mg of resin C, and diphenyliodonium-nonafluorobutanesulfonate (DPI-Nf) or phenyldibenzothionium-nona as a photoacid generator (PAG) 0.043 mmol of fluorobutane sulfonate (PBpS-Nf), compounds 1a, 1b and 2-5 as precursors of photosensitizers and 2,2-diphenyl-1,3-dioxolane (compound 7) as a comparative compound (hammet) (Substituent constant is 0.0043, molar extinction coefficient at 365 nm is 6.3 × 10 ⁴ cm ² / mol), and 0.043 mmol each is added as a quencher, and 0.0043 mmol is added as a quencher. Sample with adjusted sample Showing the details of the in Table 1.

<Sample evaluation>
Each evaluation sample 1-16 was apply | coated on the Si wafer which performed the hexamethyldisilazane (HMDS) process previously, spin-coated, and it heated at 110 degreeC, and obtained the resist film with a film thickness of 100 nm.
Next, the evaluation sample was exposed by changing the exposure amount so that a 1: 1 line and space pattern having a line width half pitch of 100 nm was formed by an EB drawing apparatus of 30 keV. Thereafter, the entire surface of the wafer was irradiated with ultraviolet rays using a UV light having an emission line of 365 nm. Subsequently, it heated on the hotplate at 110 degreeC for 1 minute. In Examples 1 to 13, it is preferable to perform ultraviolet irradiation after heating at 40 to 100 ° C. after exposure with the EB drawing apparatus.
After heating, developing is performed for 1 minute using a developer (product name NMD-3, tetramethylammonium hydroxide 2.38 mass%, manufactured by Tokyo Ohka Kogyo Co., Ltd.), and rinsed with pure water. Got a pattern. This was observed with a microscope, and the exposure amount at which the resist was completely peeled was defined as E size (minimum exposure amount).
For EB exposure, an EBL system JSM-7000F beam draw system (JEOL) of 30 keV was used. For UV exposure, a UV light (product name FL-6BL, manufactured by Hitachi, Ltd.) was used, and the UV dose was calculated by measuring a 365 nm illuminometer (USHIO UIT-150UVD-S365, manufactured by USHIO INC.). The pattern shape was confirmed using a scanning probe microscope SPM9600 (manufactured by Shimadzu Corporation). Table 2 shows the results of evaluating the minimum exposure amount as sensitivity.

As shown in Table 2, Examples 1 to 10 and 14 using resist compositions prepared by mixing the compounds of some embodiments of the present invention as photosensitizer precursors showed the lowest EB by UV irradiation after EB irradiation. The exposure amount became small. Thereby, in the resist composition of Examples 1-10 and 14, it turns out that acid generation | occurrence | production improved and the sensitivity improved.
The effect of UV irradiation tended to increase in sensitivity as the electron donating property and molar extinction coefficient of the compound increased.
As shown in Examples 11 and 12, when the photosensitizer precursor is bound in the polymer, the efficiency of acid generation by UV irradiation is higher than in Examples 1-10 and 14. This is because the photosensitizer generated is uniformly dispersed in the resist, and therefore the reaction probability between the photosensitizer and the photoacid generator is higher than when the photosensitizer precursor is mixed in the resist. It is thought that. As shown in Example 13, when the photosensitizer precursor and PAG were combined in the polymer, the efficiency of acid generation by UV irradiation was higher than in Examples 11 and 12.
The compound 8 added in Comparative Example 3 has a low Hamsent's sensitization efficiency because the Hammett substituent constant is -0.05 or more and the molar extinction coefficient at 365 nm is as very low as 6.3 × 10 ⁴ cm ² / mol. The UV irradiation at 200 mJ / cm ² did not improve the acid generation amount and did not increase the sensitivity.
From the above, it is considered that a highly sensitive photosensitizer precursor can be obtained by adding an electron-donating group to the compound to increase the molar absorption coefficient at 365 nm.

  According to the present invention, it is possible to provide a compound that is preferably used as a precursor of a photosensitizer for improving the acid generation efficiency and obtaining a photoresist having high sensitivity, high resolution, and high LWR characteristics.

Claims (11)

A compound represented by the following general formula (1) having a Hammett substituent constant σ of −0.05 or less.

(In the formula (1), Ar ¹ and Ar ² are each independently a phenylene group which may have a substituent,
R ¹ is any one selected from the group consisting of an optionally substituted thioalkoxy group, arylthio group, alkoxyphenyl group and thioalkoxyphenyl group;
X is any selected from the group consisting of a sulfur atom, an oxygen atom and a direct bond;
R ² is either an alkyl group which may have a substituent or a phenyl group,
Y is each independently one of an oxygen atom and a sulfur atom,
R ³ and R ⁴ are each independently selected from the group consisting of a linear, branched or cyclic alkyl group, alkenyl group, and alkynyl group, each of which may have a substituent. Yes,
R ³ and R ⁴ may be bonded to each other to form a ring structure with two Ys in the formula. ) The compound according to claim 1, wherein a molar extinction coefficient at 365 nm after the compound is treated with an acid is 1.0 × 10 ⁵ cm ² / mol or more. The compound according to claim 1 or 2, wherein Ar ¹ and / or Ar ² has an electron-donating group as a substituent.   The compound according to claim 3, wherein the electron donating group is selected from the group consisting of an alkyl group, an alkenyl group, an alkoxy group, and a thioalkoxy group. The compound according to any one of claims 1 to 4, wherein R ¹ and / or R ² has at least one polymerizable group as the substituent. The Ar ¹ and / or Ar ² has at least one selected from the group consisting of an alkoxy group and a thioalkoxy group as a substituent, and the substituent is the ortho position of the Ar ¹ and / or Ar ² And / or a compound according to any one of claims 1 to 5 bonded to the para position. The compound according to any one of claims 1 to 6, wherein R ¹ is bonded to the ortho-position or para-position of Ar ¹ . The compound according to any one of claims 1 to 7, wherein when X is a sulfur atom or an oxygen atom, X is bonded to the ortho-position or para-position of Ar ² .   The Hammett substituent constant (delta) of the said compound is -3.00 or more, The compound as described in any one of Claims 1-8.   The composition containing the compound as described in any one of Claims 1-9, a photo-acid generator, and the acid reaction compound which reacts with an acid. A resist film forming step of applying the composition according to claim 10 on a substrate to form a resist film;
A first irradiation step of irradiating the resist film with a first active energy ray in a pattern;
A second irradiation step of irradiating the resist film irradiated in the pattern with second active energy;
A pattern forming step of developing the resist film to obtain a photoresist pattern.