JP2007526351A5 - - Google Patents

Description

Photoresist polymers and compositions with acrylic acid or methacrylic acid based polymer resins prepared by a living free radical process

(Background of the Invention)
Processes for patterning semiconductor wafers typically rely on lithographic transfer of the desired image from a thin film of radiation sensitive resist material. This process requires the formation of a “resist”, a sacrificial layer, which is patterned by photolithography. Generally, these resists are referred to as “photoresists”.

  Resist patterning includes exposing the resist to a selected light source through an appropriate mask to record a latent image of the mask, and then developing and removing selected areas of the resist. Several steps are required. For "positive" resists, such areas change so that the exposed areas are selectively removed; whereas for "negative" resists, the unexposed areas are more easily removed.

  This pattern can be transferred to the surface texture on the wafer by etching with reactive gas using the remaining patterned resist as a protective mask layer. Alternatively, if the wafer is “masked” by a resist pattern, it can be processed to form effective electronic devices and circuits by depositing a conductive or semiconductor material or by implanting a dopant. .

  Materials used in single layer photoresists for optical lithography should achieve several objectives. Low optical density at the exposure wavelength and resistance to image transfer processes such as plasma etching are two important objectives achieved by such photoresist materials. The shorter the emission wavelength, the higher the resolution possible. The most common wavelengths currently used in semiconductor lithography are 365 nm, 248 nm, and most recently 193 nm. The demand for thinner line widths and higher resolution has stimulated interest in photoresist materials that can be patterned with light of even shorter wavelengths.

  In the field of fine processing, the processing size has become extremely small in order to increase the degree of integration. Recently, there has been a strong interest in the development of lithography processes that enables stable microfabrication with a line width of 0.5 microns, more preferably with a line width of 0.2 microns or less. .

  In a conventional lithography process, near ultraviolet radiation such as i-line is used. However, it is difficult to form a fine pattern with high accuracy using a conventional method using visible light (wavelength: 700 to 400 nm) or near ultraviolet light (wavelength: 400 to 300 nm). To address this problem, lithographic processes have been developed that use radiation at shorter wavelengths (wavelength: 300 nm or less). With such shorter wavelength radiation, a wider range of depth of focus can be achieved and this radiation is effective in ensuring design rules with a minimum size.

  Similar to X-rays such as synchrotron radiation, charged particle beams such as electron beams, and the like, specific examples of short-wavelength and far-ultraviolet radiation such as KrF excimer laser (wavelength: 248 nm) or ArF excimer laser (wavelength: 193 nm) Can also be used.

  As a resist applicable to excimer laser radiation, a component having an acid dissociable functional group, and an acid generating component (hereinafter referred to as “photo acid generator”) that generates an acid upon irradiation (hereinafter referred to as “exposure”) Numerous resists have been proposed that take advantage of the chemical amplification effect between the two. Such a resist is hereinafter referred to as a chemically amplified resist.

  Japanese Patent Publication 2-27660 discloses a chemically amplified resist containing a polymer having a t-butyl ester group of a carboxylic acid or a t-butyl = carbonate group of a phenol, and a photoacid generator. The t-butyl ester group or t-butyl carbonate group in the polymer is dissociated by the action of an acid generated during exposure. Thereby, the polymer has acidic groups such as carboxyl groups or phenolic hydroxyl groups. As a result, the exposed areas of the resist film are easily dissolved in an alkaline developer.

  In general, conventional KrF chemically amplified resists include a phenolic resin as a base resin. However, the ArF laser beam is strongly absorbed by the aromatic ring, so that a sufficient amount of ArF laser beam does not reach the lower part of the resist film effectively, the irradiation dose on the upper part of the resist film increases, and the lower part is irradiated. The dose is reduced. As a result, the resist pattern after development remains in a trapezoidal shape such as a resist pattern with a thin upper portion and a thick lower portion, so that the phenol resin is not suitable for use in an ArF photoresist. Sufficient resolution is generally not obtained. If the developed resist pattern has a trapezoidal shape, the desired dimensional accuracy cannot be achieved in the next step such as an etching step or an ion implantation step. Furthermore, when the shape of the upper part of the resist pattern is not rectangular, the resist removal rate by dry etching increases, thereby making it difficult to control the etching conditions.

  The shape of the resist pattern can be improved by increasing the radiation transmittance of the resist film. For example, an acrylic (methacrylic) resin such as polymethyl methacrylate is a highly desirable resin from the viewpoint of radiation transmittance. This is because acrylic (methacrylic) resin is highly transparent to deep ultraviolet rays. For example, Japanese Published Patent Publication No. 4-226461 discloses a chemically amplified resist using a methacrylate resin. However, since the aromatic ring is not present, the dry etching resistance of the composition is insufficient, but the performance of the composition in microfabrication is sufficient. This makes it difficult to perform etching with high accuracy. Thus, compositions that have both transparency to radiation and dry etch resistance are not provided in this manner.

  In order to improve the dry etching resistance of chemically amplified resists, a method for introducing an aliphatic ring instead of an aromatic ring into a resin component in a resist polymer has been studied as a means without impairing transparency to radiation. For example, Japanese Patent Publication No. 7-234511 discloses a chemically amplified resist using an acrylic (methacrylic) resin having an aliphatic ring.

  In order to further improve the performance of ArF photoresists, one or more repeating units have been introduced into the above resins. For example, Japanese Patent No. 3042618 discloses a chemically amplified resist using a resin by incorporating a repeating unit having a lactone skeleton. Japanese Patent Publication No. 2002-296783A discloses a chemically amplified resist using a resin by incorporating more repeating units than the above.

  However, the acrylic acid (methacrylic acid) based photoresist resins currently under consideration are prepared by conventional free radical polymerization processes. For example, see also: US Pat. Nos. 6,013,416, 6,087,063, 6,207,342, 6,303,266, and 6,596,458 No., these are incorporated herein by reference. The monomers therein are quite different in both molecular size and polarity for their chemical structure, so copolymerizing them by conventional free radical polymerization has some disadvantages in the molecular properties of the resin: (1) Wideness of polydispersity (2) Monomer drift between polymer chains (3) Difficulties in controlling reproducibility of polymerization.

  There is a need in the art for new polymer materials that are transparent for use in DUVs and that are transparent enough for use in DUVs and that are sufficiently durable to withstand further processing conditions. .

  Furthermore, there is a need for polymer resins that overcome one or more of the above-identified drawbacks of currently available photoresist polymer resins.

(Simple Summary of Invention)
In one aspect, the invention provides an acrylic or methacrylic acid based formula (1)

ここで、Ｒ^１は水素原子またはメチル基を表し、それぞれのＲ^２は独立して、直鎖もしくは分枝鎖で、非置換のもしくは置換された、１〜４の炭素原子を有するアルキル基を表すか、または、架橋されたもしくは非架橋で、非置換のもしくは置換された、４〜２０の炭素原子を有する一価の脂環式炭化水素基を表し、任意の二つのＲ^２基が互いに、その二つのＲ^２基が結合する炭素原子と一緒になって、架橋されたもしくは非架橋で、非置換のもしくは置換された、４〜２０の炭素原子を有する二価の脂環式炭化水素基を形成し得、残りのＲ^２基は直鎖もしくは分枝鎖で、非置換のもしくは置換された、１〜４の炭素原子を有するアルキル基である；を有するモノマー単位を有するポリマーであって、式：

Here, R ¹ represents a hydrogen atom or a methyl group, and each R ² independently represents a linear or branched, unsubstituted or substituted alkyl group having 1 to 4 carbon atoms. or represents, or, in cross-linking have been or unbridged, unsubstituted or substituted, and display the alicyclic monovalent hydrocarbon radical having from 4 to 20 carbon atoms, any two R ² groups Are divalent alicyclic having from 4 to 20 carbon atoms, bridged or unbridged, unsubstituted or substituted, together with the carbon atom to which the two R ² groups are bonded. having a monomer unit having; may form a hydrocarbon group, the remaining R ² groups in straight or branched chain, which is or substituted unsubstituted, alkyl group Ru der having 1 to 4 carbon atoms A polymer having the formula:

ここで、Ｒ^ｘはそのフリーラジカル型として放出されるほど十分に不安定な基であり、Ｔは炭素またはリンであり、Ｚは可逆的なフリーラジカル付加分解反応に関するＣ＝Ｓ二重結合を活性化させる任意の基である；を有する連鎖移動剤（ＣＴＡ）の存在下でのリビングフリーラジカルプロセスによって調製されるポリマーを提供する。

Where R ^x is a sufficiently unstable group to be released as its free radical form, T is carbon or phosphorus, Z is a C = S double bond for a reversible free radical addition decomposition reaction. Provided is a polymer prepared by a living free radical process in the presence of a chain transfer agent (CTA) having any group to be activated.

  In certain embodiments, Z is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and combinations thereof.

  In other embodiments, Z is hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted acyl, optionally. Substituted aroyl, optionally substituted alkoxy, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkylsulfonyl, optionally substituted Selected from the group consisting of optionally substituted alkylphosphonyl, optionally substituted arylsulfinyl and optionally substituted arylphosphonyl.

  The polymer resin of the present invention has the formula (2):

ここで、Ｅは非架橋もしくは架橋された、非置換のもしくは置換された脂環式炭化水素に由来する基を表し、Ｒ^３は水素原子、トリフルオロメチル基またはメチル基である
を有する少なくとも一つの追加的な繰り返し単位をさらに含むことができる。

Here, E represents a non-bridged or bridged group derived from an unsubstituted or substituted alicyclic hydrocarbon, and R ³ is at least one having a hydrogen atom, a trifluoromethyl group or a methyl group. One additional repeat unit may be further included.

In another aspect, the invention relates to a photoresist composition comprising (A) a photoacid generator and (B) an acrylic acid or methacrylic acid based polymer resin:
Where the polymer has the formula:

ここで、Ｒ^ｘ、ＴおよびＺは上記の定義と同じである；を有する連鎖移動剤（ＣＴＡ）の存在下でのリビングフリーラジカルプロセスによって調製される。

Where R ^x , T and Z are as defined above; prepared by a living free radical process in the presence of a chain transfer agent (CTA).

  In certain embodiments, Z is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and combinations thereof.

  In other embodiments, Z is hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted acyl, optionally. Substituted aroyl, optionally substituted alkoxy, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkylsulfonyl, optionally substituted Selected from the group consisting of optionally substituted alkylphosphonyl, optionally substituted arylsulfinyl and optionally substituted arylphosphonyl.

  In a further aspect, the polymer resin of the photoresist composition can comprise repeating units having formula (1) as defined above.

  The polymer resin of the photoresist composition may further comprise at least one additional repeating unit having the formula (2) defined above.

  The polymer resin (eg, of a photoresist composition) generally has a molecular weight between about 2,000 and about 30,000. In addition, the polymer resin generally has a polydispersity of about 1.5 or less. Finally, the polymer resin prepared by the method of the present invention generally contains CTA fragments that can be cleaved by the methods disclosed throughout this specification.

  In general, the polymers of the present invention are random copolymers and can be prepared in a batch process or under semi-continuous polymerization reaction conditions.

In another aspect of the invention, the polymer (e.g., of the photoresist composition) has a polydispersity index of less than about 1.7, and more specifically between about 1.2 and about 1.4. Having a polydispersity index of The molecular weight (M _w ) of the polymers of the present invention ranges between about 2,000 and about 30,000.

  Both acrylic and methacrylic type resins containing esters and mixtures thereof and having sterically large ester groups are encompassed by the present invention and are useful for coating applications such as photoresist materials.

  In certain aspects of the invention, the polymer resin (eg, in a photoresist composition) is insoluble or sparingly soluble in alkali, but becomes soluble in alkali by the action of an acid.

  In another aspect of the invention, the terminal position of the polymeric resin (acrylic acid derivative or methacrylic acid derivative) (eg of a photoresist composition) comprises a thiocarbonylthio moiety. In one embodiment, at the terminal position of the polymer, the formula:

ここで、Ｒ’はＣＮまたはＣＯＯＭｅである；を有する末端基が含まれるような切断条件にこのチオカルボニルチオの部分を従わせることもできる。あるいは、選択される条件に応じて、末端の位置を水素原子、モノマー単位またはＲＡＦＴ基によってキャップすることができる。

Where R ′ is CN or COOMe; the thiocarbonylthio moiety can also be subjected to cleavage conditions to include end groups having: Alternatively, the terminal position can be capped with a hydrogen atom, monomer unit or RAFT group depending on the conditions selected.

  While multiple aspects are disclosed, those skilled in the art will appreciate still other aspects of the present invention by the following detailed description, which illustrates and describes aspects of the invention. As will be appreciated, various obvious aspects of the invention may be modified without departing from the spirit and scope of the invention. Accordingly, the drawings and detailed description are to be construed as illustrative in nature and not as restrictive.

(Detailed explanation)
This application is a co-pending US patent application entitled “Photoresist Polymer Compositions” filed June 25, 2004 by Didier Benoiit et al. And U.S. patent application entitled “Photoresist Polymers” filed June 25, 2004 by Didier Benoit et al. The contents of which are incorporated herein by reference.

High absorption at 193 nm or 157 nm limits the transmission of light into the resist, making complete resist exposure below the resist impossible. Unless the resist is completely exposed, the resist cannot obtain an image accurately. If the resist is made thin enough to guarantee complete exposure, it may not be thick enough to withstand subsequent processing steps such as plasma etching or ion implantation. To compensate for this problem, resist designers often rely on multilayer resists with a sufficiently thin resist deposited on top of a second photoreactive higher resist. While these composite resists are effective, resolution is compromised by cutting or expanding the bottom of the exposed areas during development. The present invention produces a single or multi-layer thin resist that is sufficiently thick to withstand etching and / or other post-exposure processing steps while being thin enough to allow light to sufficiently penetrate the bottom of the resist Materials and methods are provided. After exposure to the radiant energy source, the exposed base soluble polymer can be removed using a conventional aqueous developer.

The ability to form a photolithographic pattern is defined by the Rayleigh equation, where R represents the resolution or line width of the optical system. Rayleigh's equation is:
R = kλ / NA,
Where λ represents the wavelength of exposure, NA is the numerical aperture of the lens, and k is a process factor. It should be understood from the Rayleigh equation that in order to achieve higher resolution or to obtain smaller R, the value of the exposure wavelength λ must be reduced. For example, high pressure mercury lamps are widely known to emit a defined band of radiation (“i-line”) at a wavelength of 365 nm. A mercury lamp has been used as a light source for manufacturing a dynamic random access memory (DRAM) having an integration density of 64 Mbit or less. Similarly, KrF excimer lasers that emit radiant energy at a wavelength of 248 nm are widely used for mass production of 256-bit DRAM devices. This manufacturing process requires processing dimensions of less than 0.25 microns. Shorter wavelengths are required for the manufacture of DRAMs having an integration density exceeding 1 Gbit. Such devices will require processing dimensions of less than 0.2 microns. For this purpose, other excimer lasers are currently being investigated, such as a KrCl laser with a wavelength of 222 nm, an ArF laser with a wavelength of 193 nm, and an F ₂ laser with a wavelength of 157 nm.

  In one aspect, the invention provides an acrylic or methacrylic acid based formula:

ここで、Ｒ^１は水素原子またはメチル基を表し、それぞれのＲ^２は独立して、直鎖もしくは分枝鎖で、非置換のもしくは置換された、１〜４の炭素原子を有するアルキル基を表すか、または、架橋されたもしくは非架橋で、非置換のもしくは置換された、４〜２０の炭素原子を有する一価の脂環式炭化水素基を表し、任意の二つのＲ^２基が互いに、その二つのＲ^２基が結合する炭素原子と一緒になって、架橋されたもしくは非架橋で、非置換のもしくは置換された、４〜２０の炭素原子を有する二価の脂環式炭化水素基を形成し得、残りのＲ^２基は直鎖もしくは分枝鎖で、非置換のもしくは置換された、１〜４の炭素原子を有するアルキル基である；を有するモノマー単位を有するポリマーであって、式：

Here, R ¹ represents a hydrogen atom or a methyl group, and each R ² independently represents a linear or branched, unsubstituted or substituted alkyl group having 1 to 4 carbon atoms. or represents, or, in cross-linking have been or unbridged, unsubstituted or substituted, and display the alicyclic monovalent hydrocarbon radical having from 4 to 20 carbon atoms, any two R ² groups Are divalent alicyclic having from 4 to 20 carbon atoms, bridged or unbridged, unsubstituted or substituted, together with the carbon atom to which the two R ² groups are bonded. having a monomer unit having; may form a hydrocarbon group, the remaining R ² groups in straight or branched chain, which is or substituted unsubstituted, alkyl group Ru der having 1 to 4 carbon atoms A polymer having the formula:

ここで、Ｒ^ｘはそのフリーラジカル型として放出されるほど十分に不安定な基であり、Ｔは炭素またはリンであり、Ｚは可逆的なフリーラジカル付加分解反応に関するＣ＝Ｓ二重結合を活性化させる任意の基である；を有する連鎖移動剤（ＣＴＡ）の存在下でのリビングフリーラジカルプロセスによって調製されるポリマーを提供する。

Where R ^x is a sufficiently unstable group to be released as its free radical form, T is carbon or phosphorus, Z is a C = S double bond for a reversible free radical addition decomposition reaction. Provided is a polymer prepared by a living free radical process in the presence of a chain transfer agent (CTA) having any group to be activated.

  In certain embodiments, Z is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and combinations thereof.

  In other embodiments, Z is hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted acyl, optionally. Substituted aroyl, optionally substituted alkoxy, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkylsulfonyl, optionally substituted Selected from the group consisting of optionally substituted alkylphosphonyl, optionally substituted arylsulfinyl and optionally substituted arylphosphonyl.

  In a further aspect, the polymer resin of the present invention has the formula:

ここで、Ｅは非架橋もしくは架橋された、非置換のもしくは置換された脂環式炭化水素に由来する基を表し、Ｒ^３は水素原子、トリフルオロメチル基またはメチル基である
を有する少なくとも一つの追加的な繰り返し単位をさらに含むことができる。

Here, E represents a non-bridged or bridged group derived from an unsubstituted or substituted alicyclic hydrocarbon, and R ³ is at least one having a hydrogen atom, a trifluoromethyl group or a methyl group. One additional repeat unit may be further included.

  In another aspect, the present invention provides a photoresist composition comprising a photoacid generator and an acrylic acid or methacrylic acid polymer resin, wherein the polymer has the formula:

ここで、Ｒ^ｘ、ＴおよびＺは上記に定義された通りである；を有する連鎖移動剤（ＣＴＡ）の存在下でのリビングフリーラジカルプロセスによって調製される。

Wherein R ^x , T and Z are as defined above; prepared by a living free radical process in the presence of a chain transfer agent (CTA) having:

  In certain embodiments, Z is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and combinations thereof.

  In other embodiments, Z is hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted acyl, optionally. Substituted aroyl, optionally substituted alkoxy, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkylsulfonyl, optionally substituted Selected from the group consisting of optionally substituted alkylphosphonyl, optionally substituted arylsulfinyl and optionally substituted arylphosphonyl.

  In a further aspect, the photoresist composition comprises a photoacid generator and a polymer resin that can include a repeating unit having formula (1) as defined above.

  The polymer resin (eg of the photoresist composition) can further comprise at least one additional repeating unit of formula (2) as defined above.

  The molecular weight of the polymer resin (eg, in a photoresist composition) is generally between about 2,000 and about 30,000. Further, the polymer resin polydispersity is generally about 1.5 or less. Finally, the polymer resin prepared by the method of the present invention generally contains CTA fragments that can be cleaved by the methods disclosed throughout this specification.

  It should be understood that combinations of all monomers (and monomer units derived from the polymers shown herein) are within the scope of the present invention.

  In one aspect, the polymer resin (eg, in a photoresist composition) is insoluble or sparingly soluble in alkali, but becomes soluble in alkali by the action of an acid. As disclosed throughout this specification, a polymer resin having the general formula (1) as described above is prepared by LFRP in the presence of CTA. Hereinafter, this polymer resin is referred to as “polymer resin (A)”.

  As used herein, the term “alkali insoluble or sparingly soluble” means that a resist pattern is formed using a resist film formed from a radiation sensitive resin composition containing a resin (A) (for example, a photoresist composition). When developing a resist film consisting only of the resin (A) (for example of a photoresist composition) under the alkaline development conditions employed when forming, 50% or more of the initial film thickness remains after development. Means the characteristic.

  The polymer resin (A) (eg, of a photoresist composition) can include one or more additional repeating monomer units described throughout the specification. For example, these repeating units include those listed above, such as those having formula (2) as described above.

Specific examples of the group represented by —C (R ² ) ₃ in the repeating unit (1) include a t-butyl group and the following formula:

の基またはそれらの置換された異形体である。上記に特定された−Ｃ（Ｒ^２）_３基が、個々にまたは（例えばフォトレジスト組成物の）ポリマー樹脂（Ａ）の範囲の一つ以上の追加的なモノマーと組み合わせた形のいずれかで存在し得ることを理解すべきである。

Or a substituted variant thereof. The —C (R ² ) ₃ groups identified above are either individually or in combination with one or more additional monomers in the range of the polymer resin (A) (eg of a photoresist composition). It should be understood that it can exist.

  E in Formula (2) is a group derived from a non-bridged or bridged alicyclic hydrocarbon, and more preferably, cyclohexane, norbornane, tricyclodecane, adamantane, or these groups are substituted with a methyl group. A group derived from a compound having one or more hydrogen atoms.

  Preferred examples of the E structure in the formula (2) include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy -N-propyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n-butyl group, 3-hydroxycyclopentyl group, 4- Hydroxycyclohexyl group, 5-hydroxy-2-norbornyl group, 8-hydroxy-3-tricyclodecanyl group, 8-hydroxy-3-tetracyclododecanyl group, 3-hydroxy-1-adamantyl group, 3-oxocyclopentyl Group, 4-oxocyclohexyl group, 5-oxo-2-norbornyl group, 8-oxo-3-tricyclo Canyl group, 8-oxo-3-tetracyclododecanyl group, 4-oxo-1-adamantyl group, cyanomethyl group, 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 3-cyanocyclopentyl group, 4-cyanocyclohexyl group, 5-cyano-2-norbornyl group, 8-cyano-3-tricyclodecanyl group, 8-cyano-3-tetracyclododecanyl group, 3-cyano-1 -Adamantyl group, 2-hydroxy-2,2-di (trifluoromethyl) ethyl group, 3-hydroxy-3,3-di (trifluoromethyl) -n-propyl group, 4-hydroxy-4,4-di (Trifluoromethyl) -n-butyl group, 5- [2-hydroxy-2,2-di (trifluoromethyl) ethyl] -2-norbornyl group, 8- [2-hydroxy group -2,2-di (trifluoromethyl) ethyl] -3-tricyclodecanyl group, 8- [2-hydroxy-2,2-di (trifluoromethyl) ethyl] -3-tetracyclododecanyl group and A 3- [2-hydroxy-2,2-di (trifluoromethyl) ethyl] -1-adamantyl group may be mentioned.

  In one embodiment, the percentage of repeat units (1) in resin (A) (eg, in the photoresist composition) is about 10 to about 80 mol%, more preferably about 20 to about 70 mol%, More specifically, it is about 20 to about 60 mol% of the total content of repeating units. The total percentage of repeat units (2) in resin (A) (eg, in the photoresist composition) is from about 20 to about 80 mol%, more preferably from about 20 to about 60 mol%, and even more specifically, About 30 to about 60 mol% of the total content of repeating units. The content of other repeating units described throughout the specification that can be incorporated into the resin (A) (eg, of a photoresist composition) is generally about 50 mol% or less of the total content of repeating units. More preferably, it is 30 mol% or less.

  Resin (A) (eg of a photoresist composition) can be prepared by LFRP. Polymerization of unsaturated monomers in a suitable solvent in the presence of a chain transfer agent (CTA) and a radical polymerization initiator as described throughout this specification, such as hydroperoxides, dialkyl peroxides, diacyl peroxides or azo compounds. I do.

  The weight average molecular weight (hereinafter referred to as “Mw”) of the resin (A) measured by gel permeation chromatography (GPC) with a reduced polystyrene is generally about 1,000 to about 100,000, More preferably from about 1,000 to about 50,000, even more specifically from about 2,000 to 30,000, and even more specifically from about 4,000 to about 12,000.

  Ratio of Mw to number average molecular weight (hereinafter referred to as “Mn”) of polystyrene-reduced polymer resin (A) (for example, in a photoresist composition) as measured by gel permeation chromatography (GPC) (Mw / Mn) is generally from about 1 to about 1.8, more preferably from about 1 to about 1.5, for example about 1.6.

  It is preferred that the resin (A) (for example of a photoresist composition) contains little impurities such as halogen or metal. As the amount of such impurities decreases, the sensitivity, resolution, processing stability, pattern shape, and the like of the polymer resin when used for coating such as a photoresist are improved. By using chemical purification processes such as reprecipitation, water washing, liquid extraction or a combination of chemical purification processes, and physical purification processes such as ultrafiltration or centrifugation (eg of photoresist compositions) Resin (A) can be purified.

  The present invention, at least in part, combines a photoacid generator with an acrylic acid or methacrylic acid based polymer resin of a photoresist composition that contains a sterically large ester group, a wavelength of less than 248 nm, That is, based on the discovery that a photosensitive composition for use at 193 nm or 157 nm can be formulated. In one aspect, the ester moiety is a monocyclic, bicyclic, tricyclic or tetracyclic non-aromatic ring having 5 or more carbon atoms, as well as combinations thereof, within the ring structure A lactone may further be included. Generating the acid by photolysis within the photoresist composition includes cleavage of ester groups in the polymer resin. This results in the result that the polymeric carboxylic acid can be removed by treatment with a base.

  Suitable sterically large ester groups include those described throughout the specification, for example, cyclopentane, cyclohexane, adamantane and norbornane. For example, by reacting the corresponding hydroxyl adamantane or norbornane with either methacrylic acid or acrylic acid derivatives of acrylic acid, such as acyl chloride or acetic anhydride, for the synthesis of the polymer resins of the invention (for example in photoresist compositions). Useful monomers can be produced.

  Typically, the two or more monomers identified above are polymerized in either a batch process, a continuous or semi-continuous feed process.

Generally, the polymer resin of the present invention has a weight average molecular weight (M _w ) between about 2,000 and about 30,000. In certain aspects of the invention, the molecular weight of the polymer resin is between about 2,000 and about 20,000, between about 3,000 and about 12,000, and even between about 3,000 and about 8,000. Between.

  Another important feature of the novel polymers encompassed by the present invention is their low polydispersity. The terms “polydispersity” and “polydispersity index” (PDI) are recognized in the art and refer to the ratio of the weight average molecular weight to the number average molecular weight. The polymeric resin of the photoresist composition typically has a PDI value of less than about 2, generally less than about 1.7, especially between about 1.2 and about 1.4. In some cases, the PDI value is between about 1.1 and about 1.2 or less.

  Acrylic resins containing acrylic esters, methacrylic resins containing methacrylic esters and mixtures thereof having sterically large ester groups are encompassed by the present invention and are useful in coating applications such as photoresist materials.

  The present invention provides a chemically amplified photosensitive polymer resin. It is suitable to use a polymer resin for a photoresist system using excimer laser lithography such as ArF laser lithography or KrF laser lithography. The polymer resin of the present invention (eg, of a photoresist composition) provides excellent properties such as resolution, features, sensitivity, dry etching resistance, adhesion, etc. when used in a photoresist.

  The monomers can be polymerized according to conventional methods such as bulk polymerization or by semi-continuous polymerization. For example, a polymer resin can be obtained by dissolving a necessary monomer in an organic solvent and then performing a polymerization reaction in the presence of a polymerization initiator such as an azo compound. It may be advantageous to use a chain transfer agent (CTA) during the polymerization process.

  Examples of the organic solvent suitable for the polymerization reaction of the present invention include ketones, ethers, polar aprotic solvents, esters, aromatic solvents, and both linear and cyclic aliphatic hydrocarbons. Typical ketones include methyl ethyl ketone (2-butanone) (MEK), acetone and the like. Typical ethers include alkoxyalkyl ethers such as methoxymethyl ether or ethyl ether, tetrahydrofuran, 1,4-dioxane. Examples of the polar aprotic solvent include dimethylformamide and dimethyl sulfoxide. Suitable esters include alkyl acetates such as ethyl acetate and methyl acetate. Examples of the aromatic solvent include alkylaryl solvents such as toluene and xylene, and halogenated aromatic compounds such as chlorobenzene. Examples of the hydrocarbon type solvent include hexane and cyclohexane.

  As polymerization conditions that can be used, the temperature for polymerization is usually in the range of about 20 ° C. to about 110 ° C., more specifically in the range of about 50 ° C. to about 90 ° C., and even more specific. Specifically, it is in the range of about 60 ° C to about 80 ° C. An advantageous inert atmosphere such as nitrogen or argon can be used to control the atmosphere. The molecular weight of the polymer is controlled by adjusting the ratio of monomer to CTA. In general, the molar ratio of monomer to CTA ranges from about 5: 1 to about 200: 1, more specifically from about 10: 1 to about 100: 1, and most preferably 10: 1 to about 50: 1.

  A free radical source is fed into the polymerization mixture. This source can be generated from naturally occurring free radicals upon heating, or in one aspect from a free radical initiator (radical source generator). In the latter case, the initiator is added to the polymerization mixture at a concentration that results in a sufficiently acceptable polymerization rate (eg, industrially fully converted within a specific time as listed below). Conversely, if the ratio of free radical initiator to CTA is too high, it will favor the formation of unnecessary, meaningless polymers via radical-radical coupling reactions that lead to polymer materials with uncontrollable properties. Let's go. The molar ratio of free radical initiator to CTA for the polymerization is typically in the range of about 0.5: 1 to about 0.02: 1, for example 0.2: 1.

  Within the context of the present invention, the expression “free radical source” can, roughly speaking, lead to the formation of radical species under appropriate operating conditions (thermal activation, irradiation, redox conditions, etc.). Any and all possible compounds or mixture of compounds.

  The time required for the reaction is also listed in the polymerization conditions, which can be from about 0.5 hours to about 72 hours, more preferably in the range of about 1 hour to about 24 hours, and even more preferably from about 2 hours to The range is about 12 hours. Conversion of the monomer to polymer is at least about 50%, more preferably at least about 75%, and even more preferably at least about 90% or more.

The initiator employed in the present invention can be a commercially available free radical initiator. In general, however, an initiator is used which has a short half-life, especially at the polymerization temperature. Such initiators are utilized because the speed of the initiation process can affect the polydispersity index of the resulting polymer. That is, if all chains start substantially simultaneously, the controlled living polymerization kinetics are such that less polydisperse polymer samples are generated. More specifically, suitable free radical initiators include any initiator by heat, redox or by light, specifically alkyl peroxides, substituted alkyl peroxides, aryl peroxides, substituted Aryl peroxide, acyl peroxide, alkyl hydroperoxide, substituted alkyl hydroperoxide, aryl hydroperoxide, substituted aryl hydroperoxide, heteroalkyl peroxide, substituted heteroalkyl peroxide, heteroalkyl hydroperoxide, substituted hetero Alkyl hydroperoxide, heteroaryl peroxide, substituted heteroaryl peroxide, heteroaryl hydroperoxide, substituted heteroaryl hydroperoxide Sid, alkyl peresters, substituted alkyl peresters, aryl peresters, substituted aryl peresters, azo compounds and halide compounds. Specific initiators include cumene hydroperoxide (CHP), t-butyl hydroperoxide (TBHP), t-butyl perbenzoate (TBPB), sodium carbonate peroxide, benzoyl peroxide (BPO), lauroyl peroxide (LPO), 45% methyl ethyl ketone peroxide, potassium persulfate, ammonium persulfate, 2,2-azobis (2,4-dimethylvaleronitrile) (VAZO®-65), 1,1-azobis (cyclohexanecarbonitrile) (VAZO®) Trademark) -40), 2,2-azobis (N, N′-dimethyleneisobutylamidine) dihydrochloride (VAZO®-044), 2,2-azobis (2-amidinopropane) dihydrochloride (VAZO ( Registered trademark) -50) And 2,2-azobis (2-amidopropane) dihydrochloride. Redox pairs such as persulfate / sulfite and Fe (2 ⁺ ) / peroxide are also useful. As is known in the art, depending on the mode of implementation, initiation can also be performed by heat or UV light (eg, modified initiators or RAFT techniques discussed herein or UV light may be used for MIXIX technology). One skilled in the art can select a suitable initiator within the scope of the present invention.

  Chain transfer agents (CTAs) are known in the art and are used to help control free radical polymerization. Eventually, many different types of CTAs can be introduced at the ends of the polymer, as further described below. Suitable examples of CTAs useful in the present invention are described in US Pat. No. 6,512,021, WO 98/01478, WO 99/35177, WO 99/31144, WO 99/05099 and WO 98/58974. Each of which is incorporated herein by reference.

As a further example, US Pat. Nos. 6,395,850, 6,518,364, filed Apr. 3, 2003, “Cleaving and Replacing Thio Control Agents From Polymers Polymers
US patent application Ser. No. 10 / 407,405 (Attorney Docket No. 2000-089CIP3) entitled “made by Living-Type Free Radical Polymerization” and US Patent Application No. 10/104 filed on March 22, 2002. , 740, the entire teachings of which are incorporated herein by reference.

  The use and mechanism of reversibly controlling substances for free radical polymerization is now generally known and newly created as RAFT (Reversible Addition Fragmentation Transfer). See, for example, US Pat. No. 6,153,705, WO 98/01478, WO 99/35177, WO 99/31144 and WO 98/58974. Here each of these is incorporated herein by reference. Recently, new materials have been disclosed that allow the desired monomers to be readily polymerized under industrially acceptable conditions. This includes converting with high efficiency at the lowest of the possible number of reactions and at a lower temperature, eg, US Pat. Nos. 6,380,335, 6,395,850 and See 6,518,364. Here each of these is incorporated herein by reference.

  In general, CTAs useful in the present invention have the general formula:

ここで、Ｒ^ｘはそのフリーラジカル型として放出されるほど十分に不安定な一般的な基であり、Ｔは炭素またはリンであり、Ｚは可逆的なフリーラジカル付加分解反応に関するＣ＝Ｓ二重結合を活性化させる任意の基であって、アミノおよびアルコキシからなる基より選択してもよい；を有する。その他の態様においては、Ｚは、炭素原子（ジチオエステル）、窒素原子（ジチオカルバマート）、イオウ原子（トリチオカルボナート）または酸素原子（ジチオカルボナート）を介してＣ＝Ｓと接触している。Ｚについての具体例は、ＷＯ９８／０１４７８号、ＷＯ９９／３５１７７号、ＷＯ９９／３１１４４号およびＷＯ９８／５８９７４号に見られ、これらのそれぞれは引用によって本明細書に取り込まれる。いくつかの態様においては、Ｚは、ヒドロカルビル、置換されたヒドロカルビル、ヘテロ原子含有ヒドロカルビル、置換されたヘテロ原子含有ヒドロカルビルおよびそれらの組み合わせからなる群より選択される。より具体的には、Ｚは、水素、必要に応じて置換されるアルキル、必要に応じて置換されるアリール、必要に応じて置換されるアルケニル、必要に応じて置換されるアシル、必要に応じて置換されるアロイル、必要に応じて置換されるアルコキシ、必要に応じて置換されるヘテロアリール、必要に応じて置換されるヘテロシクリル、必要に応じて置換されるアルキルスルホニル、必要に応じて置換されるアルキルスルフィニル、必要に応じて置換されるアルキルホスホニル、必要に応じて置換されるアリールスルフィニルおよび必要に応じて置換されるアリールホスホニルからなる群より選択されてもよい。

Where R ^x is a general group that is sufficiently unstable to be released as its free radical form, T is carbon or phosphorus, and Z is C = S 2 for a reversible free radical addition decomposition reaction. Any group that activates the heavy bond, which may be selected from the group consisting of amino and alkoxy. In other embodiments, Z is in contact with C = S via a carbon atom (dithioester), nitrogen atom (dithiocarbamate), sulfur atom (trithiocarbonate) or oxygen atom (dithiocarbonate). Yes. Specific examples for Z can be found in WO 98/01478, WO 99/35177, WO 99/31144 and WO 98/58974, each of which is incorporated herein by reference. In some embodiments, Z is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and combinations thereof. More specifically, Z is hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted acyl, optionally. Substituted aroyl, optionally substituted alkoxy, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkylsulfonyl, optionally substituted May be selected from the group consisting of optionally substituted alkylphosphonyl, optionally substituted arylsulfinyl and optionally substituted arylphosphonyl.

  In particular, suitable CTAs useful in the present invention include those specified in US Pat. No. 6,380,335, the contents of which are incorporated by reference. More specifically, the particular subject CTAs, combined with the monomers utilized throughout this specification, have the general formula:

という特徴を有し、
ここで、ＤはＳ、ＴｅまたはＳｅである。一つの側面においては、Ｄはイオウである。下記の（ＤをＳとして見る）スキームＡ：

It has the characteristics that
Here, D is S, Te, or Se. In one aspect, D is sulfur. Scheme A below (see D as S):

で表現されるように、Ｒ^４は一般的に、付加分解反応時にそのフリーラジカル型（Ｒ^４・）の下で容易に放出される任意の基である。

R ⁴ is generally any group that is readily released under its free radical form (R ^4. ) During the addition-decomposition reaction.

In Scheme A, P. is a free radical, typically a macro radical such as a polymer chain. More specifically, R ⁴ is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl and substituted heteroatom-containing hydrocarbyl and combinations thereof. Even more specifically, R ⁴ is optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted alkoxy, optionally. And optionally substituted heterocyclyl, optionally substituted alkylthio, optionally substituted amino, and optionally substituted polymer chains. Even more specifically, R ⁴ is —CH ₂ Ph, —CH (CH ₃ ) CO ₂ CH ₂ CH ₃ , —CH (CO ₂ CH ₂ CH ₃ ) ₂ , —C (CH ₃ ) ₂ CN, Selected from the group consisting of —CH (Ph) CN, —C (CH ₃ ) ₂ CO ₂ R (alkyl, aryl, etc.) and —C (CH ₃ ) ₂ Ph.

Further, R ⁵ and R ⁶ of CTA are each independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl and substituted heteroatom-containing hydrocarbyl, and combinations thereof. More specifically, R ² and R ³ are each hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted, respectively. Acyl, optionally substituted aroyl, optionally substituted alkoxy, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkylsulfonyl, required May be independently selected from the group consisting of optionally substituted alkylsulfinyl, optionally substituted alkylphosphonyl, optionally substituted arylsulfinyl and optionally substituted arylphosphonyl. . Specific embodiments of R ⁵ and / or R ⁶ include those listed above in addition to perfluorinated aromatic rings such as perfluorophenyl. In addition, when R ⁵ and R ⁶ are optionally substituted alkenyl moieties, optionally, R ⁵ and R ⁶ are taken together to form a double bond alkenyl group separated from the nitrogen atom. A portion may be formed.

Finally, R ⁷ of CTA is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl and substituted heteroatom-containing hydrocarbyl and combinations thereof; optionally, R ⁷ is R ^It may combine with ⁵ and / or R ⁶ to form a ring structure, the ring having from 3 to 50 non-hydrogen atoms. In particular, R ⁷ is hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted acyl, optionally substituted Selected from the group consisting of aryl, amino, thio, optionally substituted aryloxy and optionally substituted alkoxy. Specific R ⁴ groups include methyl and phenyl.

As used herein, the phrase “having a structure” is not intended to be limiting and is used similarly to the widely used term “including”. The term “independently selected from the group consisting of” is used herein to indicate that the listed elements, such as R groups, may be the same or different (eg, formula (1) R ⁵ and R ⁶ in the structure may be all substituted alkyl groups, or R ⁵ may be hydride, R ⁶ may be methyl, etc.).

  “Any” or “as required” means that the event or situation described below may or may not occur and the description is an example of when the event or situation occurs and when it does not occur It means to include an example. For example, the phrase “optionally substituted hydrocarbyl” means that the hydrocarbyl moiety may or may not be substituted, and that the description includes both unsubstituted hydrocarbyl and substituted hydrocarbyl. means.

  The term “alkyl” as used herein typically does not necessarily contain from 1 to about 24 carbon atoms, but means a branched or unbranched saturated hydrocarbon group such as methyl, There are ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. Further, although generally not necessarily, alkyl groups herein contain from 1 to about 12 carbon atoms. The term “lower alkyl” intends an alkyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. “Substituted alkyl” refers to alkyl substituted with one or more substituents, and the terms “heteroatom-containing alkyl” and “heteroalkyl” refer to substitution of at least one carbon atom with a heteroatom. Means alkyl.

  The term “alkenyl” as used herein typically does not necessarily include from 2 to about 24 carbon atoms and at least one double bond, but includes branched or unbranched hydrocarbon groups. Meaning, for example, ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl and the like. Further, although generally not necessarily, an alkenyl group herein contains from 2 to about 12 carbon atoms. The term “lower alkenyl” intends an alkenyl group of 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. “Substituted alkenyl” means alkenyl substituted with one or more substituents, and the terms “heteroatom-containing alkenyl” and “heteroalkenyl” refer to substitution of at least one carbon atom with a heteroatom. Means alkenyl.

  The term “alkynyl” as used herein typically means a branched or unbranched hydrocarbon group, although it need not necessarily contain from 2 to about 24 carbon atoms and at least one triple bond. Examples thereof include ethynyl, n-propynyl, isopropynyl, n-butynyl, isobutynyl, octynyl, decynyl and the like. Further, although generally not necessarily, an alkynyl group herein contains 2 to about 12 carbon atoms. The term “lower alkynyl” intends an alkynyl group of 2 to 6 carbon atoms, preferably 3 or 4 carbon atoms. “Substituted alkynyl” refers to alkynyl substituted with one or more substituents, and the terms “heteroatom-containing alkynyl” and “heteroalkynyl” are those in which at least one carbon atom is replaced with a heteroatom. Means alkynyl.

  The term “alkoxy” as used herein intends an alkyl group attached through one terminal ether linkage; that is, an “alkoxy” group may be represented as —O-alkyl, where Alkyl is as defined above. By “lower alkoxy” group is intended an alkoxy group containing from 1 to 6, more preferably from 1 to 4 carbon atoms. Similarly, the term “aryloxy” is used with aryl as defined below.

  Similarly, the term “alkylthio” as used herein intends an alkyl group attached through a single terminal thioether bond; that is, an “alkylthio” group may be represented as —S-alkyl. Where alkyl is as defined above. By “lower alkylthio” group is intended an alkylthio group containing 1 to 6, more preferably 1 to 4 carbon atoms.

  The term “allenyl” is used herein in the conventional sense to mean a portion of a molecule having the structure —CH═C═CH 2. An “allenyl” group can be unsubstituted or optionally substituted with one or more non-hydrogen substituents.

  Unless otherwise specified, the term “aryl” as used herein refers to an aromatic substituent containing one aromatic ring, or a covalently bonded or methylene moiety or ethylene moiety. By an aromatic substituent comprising a plurality of aromatic rings attached to a common group such as a moiety. This common linking group may be a carbonyl found in benzophenone, an oxygen atom found in diphenyl ether, or a nitrogen atom in diphenylamine. Preferred aryl groups include one aromatic ring or an aromatic ring in which two are fused or bonded, and examples thereof include phenyl, naphthyl, biphenyl, diphenyl ether, diphenylamine, and benzophenone. In certain embodiments, aryl substituents have 1 to about 200 carbon atoms, typically 1 to about 50 carbon atoms, preferably 1 to about 20 carbon atoms. “Substituted aryl” means an aryl moiety substituted with one or more substituents (eg, tolyl, mesityl and perfluorophenyl), and the terms “heteroatom-containing aryl” and “heteroaryl” are , Means aryl in which at least one carbon atom is replaced by a heteroatom.

  The term “aralkyl” refers to an alkyl group with an aryl substituent, the term “aralkylene” refers to an alkylene group with an aryl substituent; the term “alkaryl” refers to an aryl group with an alkyl substituent. And the term “alkalylene” means an arylene group with an alkyl substituent.

  The terms “halo” and “halogen” are used in the conventional sense and refer to a chloro, bromo, fluoro or iodo substituent. The term “haloalkyl”, “haloalkenyl” or “haloalkynyl” (or “halogenated alkyl”, “halogenated alkenyl” or “halogenated alkynyl”) means that at least one of the hydrogen atoms in the group is a halogen atom, respectively. Means an alkyl, alkenyl or alkynyl group substituted with

  The term “heteroatom-containing” as found in a “heteroatom-containing hydrocarbyl group” refers to a molecule in which one or more carbon atoms are replaced by atoms other than carbon, such as nitrogen, oxygen, sulfur, phosphorus or silicon. Or a fragment of a molecule. Similarly, the term “heteroalkyl” means an alkyl substituent containing a heteroatom, the term “heterocyclic” means a cyclic substituent containing a heteroatom, and the term “heteroaryl” is , Means an aryl substituent containing a heteroatom and the like. When the term “heteroatom-containing” appears before the list of possible heteroatom-containing groups, it is intended to add the term to all members of the group. That is, the expression “heteroatom-containing alkyl, alkenyl and alkynyl” should be interpreted as “heteroatom-containing alkyl, heteroatom-containing alkenyl and heteroatom-containing alkynyl”.

  "Hydrocarbyl" means a monovalent hydrocarbyl radical containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, branched or unbranched Of saturated or unsaturated species, specifically alkyl groups, alkenyl groups, aryl groups, and the like. The term “lower hydrocarbyl” intends a hydrocarbyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. “Substituted hydrocarbyl” means a hydrocarbyl substituted with one or more substituents, and the terms “heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” are those in which at least one carbon atom is replaced with a heteroatom. Means hydrocarbyl.

  “Substituted” found in “substituted hydrocarbyl”, “substituted aryl”, “substituted alkyl”, “substituted alkenyl”, etc., as implied in some of the above definitions. Is a hydrocarbyl, hydrocarbylene, alkyl, alkenyl or other moiety wherein at least one hydrogen atom bonded to a carbon atom is substituted with one or more of hydroxyl, alkoxy, thio, phosphino, amino, halo, silyl, etc. It means that it is substituted with a group. When the term “substituted” appears before the list of possible substituents, it is intended to add the term to all members of the group. That is, the expression “substituted alkyl, alkenyl and alkynyl” should be interpreted as “substituted alkyl, substituted alkenyl and substituted alkynyl”. Similarly, “optionally substituted alkyl, alkenyl and alkynyl” is to be interpreted as “optionally substituted alkyl, optionally substituted alkenyl and optionally substituted alkynyl”. Should be.

  The term “silyl” as used herein, means a —SiZ1Z2Z3 radical, wherein each of Z1, Z2 and Z3 is hydride and optionally substituted alkyl, alkenyl, alkynyl, aryl, aralkyl. Independently selected from the group consisting of alkaryl, heterocyclic, alkoxy, aryloxy and amino.

  The term “phosphino” as used herein refers to the group —PZ1Z2, where each of Z1 and Z2 is hydride and optionally substituted alkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl. Independently selected from the group consisting of heterocyclic and amino.

  The term “amino” is used herein to mean the group —NZ1Z2, where each of Z1 and Z2 is hydride and optionally substituted alkyl, alkenyl, alkynyl, aryl, Independently selected from the group consisting of aralkyl, alkaryl and heterocyclic.

  The term “thio” is used herein to mean the group —SZ1, where Z1 is a hydride and optionally substituted alkyl, alkenyl, alkynyl, aryl, aralkyl, alkaryl and heteroaryl. Selected from the group consisting of rings.

  As used herein, all references to elements and groups of the Periodic Table of Elements are for the periodic table edition published by Handbook of Chemistry and Physics, CRC Press, 1995; Here, a new IUPAC system of numbered groups is shown.

In certain embodiments, R ⁷ is combined with either R ⁵ or R ⁶ to form a substituted or unsubstituted pyrazole moiety.

  Examples of typical CTAs include the following.

いくつかの態様においては、得られる（例えばフォトレジスト組成物の）上記のポリマーは、例えば（ＣＴＡからの）チオ基を有する一つ以上の末端を持つことになる。ポリマーを対象とする応用例に依存して、チオ基は望ましくないかもしれない。従って、本発明は、ポリマー樹脂の末端から脱離したＣＴＡを有するポリマー樹脂も提供する。

In some embodiments, the resulting polymer (eg, of a photoresist composition) will have one or more ends having, for example, thio groups (from CTA). Depending on the application intended for the polymer, thio groups may not be desirable. Accordingly, the present invention also provides a polymer resin having CTA detached from the end of the polymer resin.

  In the specific embodiments described throughout this specification, the resulting polymer has a CTA moiety (dithiocarbonyl) at the end, whether the end is the backbone, star arm, comb end, branch end or graft end. Part of CTA). CTA removal can be achieved by several methods described below. Mechanistically, free radical chain transfer reactions are believed to cleave residues such as dithioCTA moieties from polymer ends by the addition of an external radical source.

  In one embodiment, in some cases, the CTA moiety (eg, thiocarbonylthio moiety, thio group) is cleaved from the polymer end to remove at least the sulfur of the CTA from the polymer terminal position (if present). It is convenient to remove the part containing. In one embodiment, this can be accomplished by reducing the radical of the dithiocarbonyl or dithiophosphoryl group by using a free radical initiator and a compound having an unstable hydrogen atom. This method essentially removes unwanted groups from the ends of the polymer chain and replaces them with hydrogen atoms. See, for example, WO 02/090397. Here, the entirety of this is incorporated herein by reference.

In another aspect, “Cleaving and” filed on Apr. 3, 2003.
Reprinting Thio Control Agent Moieties from Polymers made by Living-Type Free Radical Polymerization ”, as described in US Patent Application No. 10 / 407,405 (representative number 2000-089 CIP) Can be used to replace the CTA, whereby the fragment product of the initiator replaces the CTA at the end of the polymer, the entire teachings of which are incorporated herein by reference.

In yet another aspect, “Cleaving and Reprinting Thio Control Agents from Polymers made by Live-Type Free” filed on April 3, 2003.
It is possible to replace CTA by using an initiator in combination with a RAFT agent as described in US patent application Ser. No. 10 / 407,405 (Attorney Docket No. 2000-089 CIP3) entitled “Radical Polymerization”. The entire teachings of which are incorporated herein by reference.

  In yet another aspect, “Removal of the Thiocarbonythio or Thiophosphorythio End Group of Polymers and Furters of the United States No. 25, filed on June 26, 2003” As described in Personnel Number 2003-042), CTA can be replaced by a monomer that cannot be homopolymerized with a radical source introduced, the entire teaching of which is incorporated herein by reference.

Unless wishing to be bound by any particular theory, cleaving the thio group from the polymer is described below in Schemes 1 and 2:
I ₂ → 2I ・
(Scheme 1)
P-S-T (= S) -Z + I. → P. + IS-T (= S) -Z
(Scheme 2)
Considered to proceed according to a set of reactions described in
Where P represents a polymer, T is carbon or phosphorus, S is sulfur, I ₂ is a free radical source, I · is a free radical resulting from decomposition of I ₂ , and Z is the above As defined in Scheme 1 represents the activation of a free radical initiator to generate the radical I .; and Scheme 2 represents the addition decomposition of I. on the dithio-terminated polymer to generate the polymer radical P.

  In some embodiments, the external radical source is a common radical initiator, such as any of the initiators listed above. Regardless of its exact nature, the free radical source carried out in the process according to the invention is utilized under the conditions of a cleavage reaction that allows the generation of free radicals. In one embodiment, by thermal activation, i.e., the temperature of the reaction medium is typically in the range of about room temperature (about 20 ° C) to about 200 ° C, in particular about 40 ° C to about 180 ° C, and more specifically. Specifically, it is achieved by raising the temperature to about 50 ° C to about 120 ° C. In other embodiments, free radicals are generated by activation with light. This includes free radical sources that can be activated by UV light, such as benzoin ethers and benzophenones. High energy radiation, such as gamma rays and electron rays, is known to generate radicals.

  The free radical source utilized can be introduced into the reaction medium in increments. However, it can also be introduced gradually, either in parts or continuously.

  Conditions for the cleavage reaction that can be used include conditions such as temperature, pressure, atmosphere, number of reactions, and ratio of reaction components. Useful temperatures range from about room temperature (about 20 ° C.) to about 200 ° C., specifically about 40 ° C. to about 180 ° C., more specifically about 50 ° C. to about 120 ° C. is there. In some embodiments, an inert atmosphere such as nitrogen or argon can be utilized to control the atmosphere. In other embodiments, an ambient atmosphere is used. Cleavage reaction conditions also include open or closed atmospheres and pressures at ambient conditions. In embodiments where the cleavage reaction is carried out in a closed atmosphere and the temperature is above room temperature, the pressure will increase as a result of any heated solvent. In some embodiments, it is also desirable to control the light. Specifically, this reaction can be carried out with visible light or under UV light.

  The amount of free radical source depends on its effectiveness, the manner in which the source is introduced, and the desired end product. In an amount such that the amount of free radicals that the source can release is between about 1% and about 800% (molar concentration) relative to the total molar amount of groups in the polymer where cleavage is desired. In an amount that is between about 50% and about 400% (molar concentration), and more specifically in an amount that is between about 100% and about 300% (molar concentration). Specifically, the free radical source utilized can be introduced in an amount that is between about 200% and about 300%. In some embodiments, complete removal or as nearly complete as possible is desired, and in these embodiments, an excess amount of free radical source is introduced.

Excess free radical sources aim not only at the loss of free radicals expected to be caused by the cage effect, but also to reveal well-known side reactions in free radical processes such as those described below (eg, Scheme 5) And When available, the efficiency factor f of the free radical source is defined as the ratio of active radicals to total radicals generated during the decomposition of the free radical source and can be used to adjust the concentration of I ₂ .

  As long as the half-life time (defined as the time after half of the free radical source is destroyed) is between about 10 minutes and 20 hours, most known free radical sources can be used.

  Typical initiators that can be used as free radical sources are alkyl peroxides, substituted alkyl peroxides, aryl peroxides, substituted aryl peroxides, acyl peroxides, alkyl hydroperoxides, substituted alkyl hydroperoxides, aryl hydroperoxides Substituted aryl hydroperoxide, heteroalkyl peroxide, substituted heteroalkyl peroxide, heteroalkyl hydroperoxide, substituted heteroalkyl hydroperoxide, heteroaryl peroxide, substituted heteroaryl peroxide, heteroaryl hydroperoxide, substituted Heteroaryl hydroperoxide, alkyl perester, substituted alkyl perester, aryl Peresters, substituted aryl peresters, dialkyl Peruji carbonate, inorganic peroxides, are selected from between hypophosphite nitrate and azo compounds. Specific initiators include lauroyl and benzoyl peroxide (BPO) and AIBN. Some azo compounds include 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2′-. Azobis (2-methylpropionate), 1-[(cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), 2,2′-azobis ( 2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2 ′ -Azobis (N-butyl-2-methylpropionamide), 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, , 2′-Azobis [2- (2-imidazolin-2-yl) propanedisulfate dihydrate, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate Japanese, 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2′-azobis {2-methyl-N- [1 , 1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis [2- ( 2-Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamido) dihydrochloride, 2,2'-azobis [2- (3,4,5, -Tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] and 2,2'-azobis {2-methyl-N- [2- (1-hydroxybutyl)] propionamide}. This includes initiators that can be activated by UV, such as benzoin ethers and benzophenones. High energy can activate other initiators, such as gamma rays and electron beams. The half-life time can be adjusted by setting the reaction temperature within the required range. Initiator decomposition rate via the supplier's documentation file or using literature (eg, “The Chemistry of Free Radical Polymerization, G. Mod, D. H. Salomon, Eds. Pergamon Pub. 1995). The latter is determined by the temperature dependence, especially when the initiator is oxidizing such as peroxides, the addition of a reducing agent also adjusts the decomposition rate and thus radical generation: eg metabisulfite, ascorbine Acids, sulfite-formaldehyde adducts, amines and low oxidation state metals can be used in conjunction with peroxide type initiators to accelerate radical flux.

  The conditions for the cleavage reaction also include the reaction time, which can be from about 0.5 hours to about 72 hours, more preferably in the range of about 1 hour to about 24 hours, and even more preferably about 2 hours. Within the range of time to about 12 hours. For example, cleaving thio groups from a polymer is at least about 50%, more specifically at least about 75%, more specifically at least about 85%, and even more specifically , At least about 95%. Thio group substitution is at least about 50%, more specifically at least about 75%, more specifically at least about 85%, and even more specifically at least about 95%. is there.

  Various RAFT agents and the like can replace various different moieties and thio groups as detailed above. In one embodiment, the thio moiety of CTA can be replaced with a hydrogen atom, as described in WO 02/090397 (delegated to Rhodia Chimie). In another embodiment, the thio group can be replaced with a monomer unit that cannot be homopolymerized. In yet another embodiment, only the free radical source is introduced to cap the polymer ends.

The cleavage reaction mixture can use a reaction medium, typically a solvent. The conditions for the cleavage reaction include stirring or refluxing of the reaction medium. The resulting polymer radical P · can then be capped in one of three ways as shown in Schemes 3, 4 and 5 below:
P ・ + I ・ → PI
(Scheme 3)
P ・ + I ₂ → P−I + I ・
(Scheme 4)
P · + P · → coupling product (Scheme 5).

  Scheme 3 represents the radical coupling of the polymer radicals generated in Scheme 2 and the free radicals generated in Scheme 1, thereby forming the resulting capped polymer PI. Scheme 4 represents a transfer reaction between the polymer radical generated in Scheme 2 and the cleaved polymer as well as a free radical initiator that generates a new source of free radicals. Scheme 5 represents a coupling reaction between two polymer radicals.

  In one embodiment, Schemes 3 and 4 are the desired reactions. Scheme 5 is a side reaction that contributes to increasing the molecular weight of most polymer samples and broadening the molecular weight distribution. It has been found that the cleavage reaction conditions described, for example, cause quantitative cleavage of the dithio compounds with little to no change in molecular weight properties (Mw and polydispersity index).

  In one embodiment, the polymer is treated with a free radical source, such as an initiator, under conditions of a cleavage reaction that favors reactions 3 and 4. These conditions include an amount such that the amount of free radicals that can be released by the source is between about 200% and about 500% (molar concentration) relative to the total molar amount of groups in the polymer where cleavage is desired. In particular, it includes introducing the radical source in an amount of between about 200% and about 300% (molar concentration).

  The resulting polymer has new groups at its ends that make the polymer more desirable for a particular application. For example, the above polymers are more suitable for applications that cannot tolerate the amount of sulfur present in the unmodified polymer, such as household and personal care products where the presence of odor can be a problem. Would be desirable.

  It is advantageous to purify the reaction product with or without CTA end groups, such as by reprecipitation after completion of the polymerization reaction. Typical precipitating agents include low molecular weight alcohols such as isopropyl alcohol, methyl alcohol, ethyl alcohol and butyl alcohol.

  In one aspect, the present invention is a photoresist polymer composition comprising a photoacid generator (hereinafter referred to as “photoacid generator (B)”) that generates an acid when exposed to an energy source.

  The photoacid generator (B) causes dissociation of the acid dissociable group in the resin (A) by the action of an acid generated during exposure. As a result, the exposed areas of the resist film are more easily dissolved in an alkaline developer, thereby forming a positive tone resist pattern.

  As a useful photoacid generator (B) of the present invention, the following formula (5):

で示されるこれらの化合物が挙げられる。

These compounds shown by these are mentioned.

Here, R ¹³ is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxyl group having 1 to 10 carbon atoms, or Represents a linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms, R ¹⁴ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, and p is An integer of 0 to 3, and each R ¹⁵ is a linear or branched alkyl group having 1 to 10 carbon atoms, a phenyl group or a naphthyl group optionally having one or more substituents. Or two R ¹⁵ groups together may form a substituted or unsubstituted divalent group having 2 to 10 carbon atoms, q is an integer from 0 to 2 and Z is, for example C An anion having the structure of - F _2a + 1 SO _3. Here, a is an integer of 1-10.

Specific examples of the linear or branched alkyl group having about 1 to about 10 carbon atoms represented by R ¹³ , R ¹⁴ or R ¹⁵ in the formula (5) include a methyl group, an ethyl group, n- Propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n- Octyl, 2-ethylhexyl, n-nonyl and n-decyl groups are typical.

Specific examples of the linear or branched alkoxyl group having about 1 to about 10 carbon atoms represented by R ¹³ in the formula (5) include a methoxy group, an ethoxy group, an n-propoxy group, i- Propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n- Examples include octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group and n-decyloxy group.

Specific examples of the linear or branched alkoxycarbonyl group having about 2 to about 11 carbon atoms represented by R ¹³ in the formula (5) include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl Group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyl Examples thereof include an oxycarbonyl group, an n-heptyloxycarbonyl group, an n-octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, an n-nonyloxycarbonyl group, and an n-decyloxycarbonyl group.

Specific examples of R ¹³ in the formula (5) include a hydrogen atom, a hydroxyl group, a methoxy group, an ethoxy group, and an n-butoxy group.

As the group of R ¹⁴ in formula (5), a hydrogen atom and a methyl group are particularly noted.

  In certain embodiments, p is either 0 or 1.

Specific examples of the substituted or unsubstituted phenyl group represented by R ¹⁵ in the formula (5) include the following groups:
For example, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3 , 4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group and 4-ethylphenyl group or the like, or one or more having about 1 to about 10 carbon atoms An alkyl-substituted phenyl group which may be substituted with a linear, branched or cyclic alkyl group of: and a phenyl group or a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxyl group, an alkoxyalkyl group, an alkoxycarbonyl group Obtained by substituting an alkyl-substituted phenyl group with one or more groups such as a group and an alkoxycarbonyloxy group Group.

  Specific examples of alkoxyl groups that can function as substituents for phenyl groups or alkyl-substituted phenyl groups include straight, branched, or cyclic alkoxyl groups having from about 1 to about 20 carbon atoms. For example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, cyclopentyloxy group and cyclohexyloxy group It is representative.

  Specific examples of the alkoxyalkyl group include linear, branched or cyclic alkoxyalkyl groups having about 2 to about 21 carbon atoms, such as a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, The 2-methoxyethyl group, 1-ethoxyethyl group and 2-ethoxyethyl group are representative.

  Specific examples of the alkoxycarbonyl group include linear, branched or cyclic alkoxycarbonyl groups having about 2 to about 21 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, cyclopentyloxycarbonyl group and cyclohexyloxycarbonyl group.

  Specific examples of the alkoxycarbonyloxy group include linear, branched or cyclic alkoxycarbonyloxy groups having about 2 to about 21 carbon atoms, such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n -Propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group, cyclopentyloxycarbonyl group, and cyclohexyloxycarbonyl group.

Specific examples of the substituted or unsubstituted naphthyl group represented by R ¹⁵ include a hydrogen atom by a linear, branched or cyclic alkyl group having about 1 to about 10 carbon atoms in the naphthyl group and naphthyl group. Naphthyl group derivatives obtained by substitution of, for example, 1-naphthyl group, 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl- 1-naphthyl group, 5-methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 2,3-dimethyl-1-naphthyl Group, 2,4-dimethyl-1-naphthyl group, 2,5-dimethyl-1-naphthyl group, 2,6-dimethyl-1-naphthyl group, 2,7-dimethyl-1-naphthyl group, 2,8- Dimethyl-1 -Naphthyl group, 3,4-dimethyl-1-naphthyl group, 3,5-dimethyl-1-naphthyl group, 3,6-dimethyl-1-naphthyl group, 3,7-dimethyl-1-naphthyl group, 3, 8-dimethyl-1-naphthyl group, 4,5-dimethyl-1-naphthyl group, 5,8-dimethyl-1-naphthyl group, 4-ethyl-1-naphthyl group, 2-naphthyl group, 1-methyl-2 -One or more hydrogen atoms in the naphthyl group, 3-methyl-2-naphthyl group and 4-methyl-2-naphthyl group, and naphthyl group or alkyl-substituted naphthyl group are substituted with hydroxyl group, carboxyl group, cyano group, nitro group There are groups obtained by further substitution with groups, alkoxyl groups, alkoxyalkyl groups, alkoxycarbonyl groups or alkoxycarbonyloxy groups.

  Specific examples of alkoxyl groups, alkoxyalkyl groups, alkoxycarbonyl groups and alkoxycarbonyloxy groups, which are substituents for naphthyl groups or alkyl-substituted naphthyl groups, have been described for phenyl groups and alkyl-substituted phenyl groups It can be given as a group.

A divalent group having from about 2 to about 10 carbon atoms can be a group formed by two R ¹⁵ groups that together with a sulfur atom in the formula forms a 5- or 6-membered cyclic structure. In particular, it may be a group that forms a 5-membered ring structure (specifically, a tetrahydrothiophene ring structure).

  Specific examples of suitable substituents for the divalent groups specified above are those described as suitable substituents for phenyl groups and alkyl-substituted phenyl groups, such as hydroxyl groups, carboxyl groups, and the like. And cyano group, nitro group, alkoxyl group, alkoxyalkyl group, alkoxycarbonyl group and alkoxycarbonyloxy group are representative.

In particular, R ¹⁵ in formula (5) can be a methyl group, an ethyl group or a phenyl group. Examples of the divalent group having a tetrahydrothiophene ring structure formed from two R ¹⁵ groups include a sulfur atom.

  “Q” in formula (5) can be either 0 or 1.

The C _a F _{2a + 1} group in F _{2a + 1} SO ₃ ^— represented by Z in the formula (5) is a perfluoroalkyl group having “a” number of carbon atoms, which is either a straight chain or a branched chain But you can.

  “A” can be about 4 to about 8.

Specific examples of the generator (5) include the following:
Triphenylsulfonium = trifluoromethanesulfonate, triphenylsulfonium = nonafluoro-n-butanesulfonate, triphenylsulfonium = perfluoro-n-octanesulfonate, 1-naphthyldimethylsulfonium = trifluoromethanesulfonate, 1-naphthyldimethylsulfonium = Nonafluoro-n-butanesulfonate, 1-naphthyldimethylsulfonium = perfluoro-n-octanesulfonate, 1-naphthyldiethylsulfonium = trifluoromethanesulfonate, 1-naphthyldiethylsulfonium = nonafluoro-n-butanesulfonate, 1-naphthyl Diethylsulfonium = perfluoro-n-octanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium = tri Fluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium = nonafluoro-n-butanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium = perfluoro-n-octanesulfonate, 4-hydroxy-1-naphthyldiethylsulfonium = Trifluoromethanesulfonate, 4-hydroxy-1-naphthyldiethylsulfonium = nonafluoro-n-butanesulfonate, 4-hydroxy-1-naphthyldiethylsulfonium = perfluoro-n-octanesulfonate, 4-cyano-1-naphthyldimethyl Sulfonium = trifluoromethanesulfonate, 4-cyano-1-naphthyldimethylsulfonium = nonafluoro-n-butanesulfonate, 4-cyano-1-naphthyldimethylsulfone Um = perfluoro-n-octanesulfonate, 4-cyano-1-naphthyldiethylsulfonium = trifluoromethanesulfonate, 4-cyano-1-naphthyldiethylsulfonium = nonafluoro-n-butanesulfonate, 4-cyano-1-naphthyl Diethylsulfonium = perfluoro-n-octanesulfonate, 4-nitro-1-naphthyldimethylsulfonium = trifluoromethanesulfonate, 4-nitro-1-naphthyldimethylsulfonium = nonafluoro-n-butanesulfonate, 4-nitro-1- Naphthyldimethylsulfonium = perfluoro-n-octanesulfonate, 4-nitro-1-naphthyldiethylsulfonium = trifluoromethanesulfonate, 4-nitro-1-naphthyldiethylsulfonium = Nonafluoro-n-butanesulfonate, 4-nitro-1-naphthyldiethylsulfonium = perfluoro-n-octanesulfonate, 4-methyl-1-naphthyldimethylsulfonium = trifluoromethanesulfonate, 4-methyl-1-naphthyldimethylsulfonium = Nonafluoro-n-butanesulfonate, 4-methyl-1-naphthyldimethylsulfonium = perfluoro-n-octanesulfonate, 4-methyl-1-naphthyldiethylsulfonium = trifluoromethanesulfonate, 4-methyl-1-naphthyldiethyl Sulfonium = nonafluoro-n-butanesulfonate, 4-methyl-1-naphthyldiethylsulfonium = perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl Tetrahydrothiophenium = trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium = nonafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) ) Tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- (4-n-butoxyphenyl) tetrahydrothiophenium = trifluoromethanesulfonate, 1- (4-n-butoxyphenyl) tetrahydrothiophenium = nonafluoro -N-butanesulfonate, 1- (4-n-butoxyphenyl) tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium = trifluoromethyl 1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium = nonafluoro-n-butanesulfonate, 1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium = perfluoro-n-octanesulfone Narate, 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium = trifluoromethanesulfonate, 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium = nonafluoro-n-butanesulfonate, 1 -(4-Methoxynaphthalen-1-yl) tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- (4-ethoxynaphthalen-1-yl) tetrahydrothiophenium = trifluoromethanesulfonate, 1- (4 -Ethoxy Naphthalen-1-yl) tetrahydrothiophenium = nonafluoro-n-butanesulfonate, 1- (4-ethoxynaphthalen-1-yl) tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- (4-n -Butoxynaphthalen-1-yl) tetrahydrothiophenium = trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium = nonafluoro-n-butanesulfonate, 1- (4- n-butoxynaphthalen-1-yl) tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- (4-methoxymethoxynaphthalen-1-yl) tetrahydrothiophenium = trifluoromethanesulfonate, 1- (4- Methoxymethoxynaphthalene 1-yl) tetrahydrothiophenium = nonafluoro -n- butane sulfonate,
1- (4-methoxymethoxynaphthalen-1-yl) tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- (4-ethoxymethoxynaphthalen-1-yl) tetrahydrothiophenium = trifluoromethanesulfonate, 1 -(4-Ethoxymethoxynaphthalen-1-yl) tetrahydrothiophenium = nonafluoro-n-butanesulfonate, 1- (4-ethoxymethoxynaphthalen-1-yl) tetrahydrothiophenium = perfluoro-n-octanesulfonate 1- [4- (1 □ methoxyethoxy) naphthalen-1-yl] -tetrahydrothiophenium = trifluoromethanesulfonate, 1- [4- (1-methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium = Nonafluo -N-butanesulfonate, 1- [4- (1-methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- [4- (2 □ methoxyethoxy) naphthalene- 1-yl] -tetrahydrothiophenium = trifluoromethanesulfonate, 1- [4- (2-methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium = nonafluoro-n-butanesulfonate, 1- [4- (2-methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- (4-methoxycarbonyloxynaphthalen-1-yl) -tetrahydrothiophenium = trifluoromethanesulfonate, 1- (4-methoxycarbonyloxy) Naphthalen-1-yl) -tetrahydrothiophenium = nonafluoro-n− / butanesulfonate, 1- (4-methoxycarbonyloxynaphthalen-1-yl) -tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1 -(4-Ethoxycarbonyloxynaphthalen-1-yl) -tetrahydrothiophenium = trifluoromethanesulfonate, 1- (4-ethoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium = nonafluoro-n-butanesulfonate 1- (4-ethoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- (4-n-propoxycarbonyloxynaphthalen-1-yl) -tetrahydrothiophene Um = trifluoromethanesulfonate, 1 - (4-n- propoxycarbonyloxy-1-yl) - tetrahydrothiophenium = nonafluoro -n- butanesulfonate, 1- (4-n- propoxycarbonyloxy-l -Yl) -tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- (4-i-propoxycarbonyloxynaphthalen-1-yl) -tetrahydrothiophenium = trifluoromethanesulfonate, 1- (4-i -Propoxycarbonyloxynaphthalen-1-yl) -tetrahydrothiophenium = nonafluoro-n-butanesulfonate, 1- (4-i-propoxycarbonyloxynaphthalen-1-yl) -tetrahydrothiophenium = perfluoro-n Octanesulfonate, 1- (4-n-butoxycarbonyloxynaphthalen-1-yl) -tetrahydrothiophenium = trifluoromethanesulfonate, 1- (4-n-butoxycarbonyloxynaphthalen-1-yl) -tetrahydrothio Phenium = nonafluoro-n-butanesulfonate, 1- (4-n-butoxycarbonyloxynaphthalen-1-yl) -tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- (4-t-butoxycarbonyl Oxynaphthalen-1-yl) -tetrahydrothiophenium = trifluoromethanesulfonate, 1- (4-t-butoxycarbonyloxynaphthalen-1-yl) -tetrahydrothiophenium = nonafluoro-n-butanesulfonate, 1- (4-t- Butoxycarbonyloxynaphthalen-1-yl) -tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- (4-benzyloxynaphthalen-1-yl) tetrahydrothiophenium = trifluoromethanesulfonate, 1- (4 -Benzyloxynaphthalen-1-yl) tetrahydrothiophenium = nonafluoro-n-butanesulfonate, 1- (4-benzyloxynaphthalen-1-yl) tetrahydrothiophenium = perfluoro-n-octanesulfonate, (2-Naphthalen-1-yl-2-oxoethyl) tetrahydrothiophenium = trifluoromethanesulfonate, 1- (2-naphthalen-1-yl-2-oxoethyl) tetrahydrothiophenium = nonafluoro-n-butanesulfo And 1- (2-naphthalen-1-yl-2-oxoethyl) tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- [4- (2-tetrahydrofuranyloxy) naphthalen-1-yl]- Tetrahydrothiophenium = trifluoromethanesulfonate, 1- [4- (1-tetrahydrofuranyloxy) naphthalen-1-yl] -tetrahydrothiophenium = nonafluoro-n-butanesulfonate, 1- [4- (2- Tetrahydrofuranyloxy) naphthalen-1-yl] -tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- [4- (2-tetrahydropyranyloxy) naphthalen-1-yl] tetrahydrothiophenium = trifluoromethane Sulfonate, 1- [4- ( -Tetrahydropyranyloxy) naphthalen-1-yl] -tetrahydrothiophenium = nonafluoro-n-butanesulfonate and 1- [4- (2-tetrahydropyranyloxy) naphthalen-1-yl] -tetrahydrothiophenium = Perfluoro-n-octanesulfonate.

  In particular, as the photoacid generator (5), triphenylsulfonium = nonafluoro-n-butanesulfonate, triphenylsulfonium = perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) Tetrahydrothiophenium = nonafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- (4-hydroxynaphthalene-1- Yl) tetrahydrothiophenium = nonafluoro-n-butanesulfonate, 1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalene-) 1-yl) tetrahi Rothiophenium = nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium = perfluoro-n-octanesulfonate, 1- (2-naphthalen-1-yl-2- Oxoethyl) tetrahydrothiophenium = nonafluoro-n-butanesulfonate, 1- (2-naphthalen-1-yl-2-oxoethyl) tetrahydrothiophenium = perfluoro-n-octanesulfonate, and the like.

  Specific examples of acid generators other than the acid generator having formula (5) (hereinafter referred to as “other acid generators”) include onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonate compounds, and the like. Is mentioned.

Specific examples of these other acid generators are shown below:
Onium salt.

  Specific examples of onium salts include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts.

  Specific examples of onium salts include: diphenyliodonium = trifluoromethanesulfonate, diphenyliodonium = nonafluoro-n-butanesulfonate, diphenyliodonium = perfluoro-n-octanesulfonate, bis (4-t -Butylphenyl) iodonium = trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium = nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium = perfluoro-n-octanesulfonate, cyclohexyl 2-oxocyclohexyl-methylsulfonium trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate and 2-o Seo cyclohexyl dimethyl sulfonium = trifluoromethanesulfonate.

Halogen-containing compounds:
Specific examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds.

  Specific examples of halogen-containing compounds include (trichloromethyl) such as phenylbis (trichloromethyl) -s-triazine, 4-methoxyphenylbis (trichloromethyl) -s-triazine and 1-naphthylbis (trichloromethyl) -s-triazine. ) -S-triazine derivatives and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane.

Diazo ketone compounds:
Specific examples of the diazo ketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, and a diazonaphthoquinone compound.

  Specific examples of the diazoketone compound include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1,2-naphtho of 2,3,4,4′-tetrahydroxybenzophenone. Quinonediazido-4-sulfonate or 1,2-naphthoquinonediazide-5-sulfonate, and 1,1, naphthoquinonediazide-4-sulfonate and 1,2-naphthoquinonediazide of 1,1,1-tris (4-hydroxyphenyl) ethane -5-sulfonate.

Sulfone compounds:
Specific examples of the sulfone compound include ketosulfone, sulfonylsulfone, and diazo compounds of these compounds.

  Specific examples of the sulfone compound include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, and the like.

Sulfonate compounds:
Specific examples of the sulfonate compound include alkyl sulfonate, alkylimide sulfonate, haloalkyl sulfonate, aryl sulfonate, and imino sulfonate.

  Specific examples of the sulfone compound include benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, nonafluoro-n-butanesulfonylbicyclo [2.2.1] -hept-5-ene-2,3-dicarboximide, perfluoro-n-octanesulfonylbicyclo [2 2.1] -Hept-5-ene-2,3-dicarboximide, N-hydroxysuccinimide = trifluoromethanesulfonate, N-hydroxysuccinimide = nonafluoro-n-butanesulfonate, N-hydroxysuccinimide = perfluoro- n-oct 1,8-naphthalenedicarboxylic imide = trifluoromethanesulfonate, 1,8-naphthalenedicarboxylic imide = nonafluoro-n-butane sulfonate and 1,8-naphthalenedicarboxylic imide = perfluoro-n-octane sulfonate Can be mentioned.

  Among these acid generators, the following compounds are of particular interest: diphenyliodonium = trifluoromethanesulfonate, diphenyliodonium = nonafluoro-n-butanesulfonate, diphenyliodonium = perfluoro-n-octanesulfonate, bis (4- t-butylphenyl) iodonium = trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium = nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium = perfluoro-n-octanesulfonate, Cyclohexyl-2-oxocyclohexyl-methylsulfonium = trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium = trifluoromethanesulfonate, 2-oxo Chlohexyldimethylsulfonium = trifluoromethanesulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, nonafluoro-n-butanesulfonylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, perfluoro-n-octanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-hydroxysuccinimide = trifluoromethanesulfonate N-hydroxysuccinimide = nonafluoro-n-butanesulfonate, N-hydroxysuccinimide = perfluoro-n-octanesulfonate and 1,8-naphthalenedicarboxylic acidimide = trifluoromethanesulfonate.

  In the photoresist composition, the acid generator (B) can be used either individually or in combination with two or more acid generators.

  In the photoresist composition of the present invention, in order to guarantee the sensitivity and developability of the photoresist, the amount of the acid generator (B) is usually based on 100 parts by weight of the polymer resin (A) or 100 parts by weight. Is about 0.1 to about 20 parts by weight, more preferably about 0.5 to about 10 parts by weight, based on the resin (A1) and resin (A2) mixture. If the amount of acid generator (B) is less than about 0.1 parts by weight, the sensitivity and developability of the resulting resist will be reduced. If the amount of acid generator exceeds 20 parts by weight, it will be difficult to obtain a rectangular resist pattern because the transparency of the photoresist composition to radiation is reduced.

(Additive)
Various types of additives such as an acid diffusion controller, an alicyclic additive having an acid dissociation group, a surfactant, and a sensitizer are added to the photoresist composition of the radiation-sensitive polymer resin of the present invention as necessary. Can be added.

  The acid diffusion control agent controls the diffusion phenomenon in the photoresist film composition of the acid generated from the acid generator (B) during exposure. As a result, undesired chemical reactions are prevented in the unexposed areas.

  The addition of an acid diffusion control agent further improves the storage stability of the resulting radiation sensitive resin photoresist composition and the resolution of the resist. Furthermore, the addition of an acid diffusion controller is useful for suppressing changes in the line width of the resist pattern due to changes in post-exposure delay (PED) between exposure and development. Thereby, a composition having extremely excellent processing stability can be obtained.

  As the acid diffusion control agent, a nitrogen-containing organic compound that does not change the basicity of the compound during exposure or heating for forming a resist pattern is preferable.

Specific examples of such nitrogen-containing organic compounds include the following formula (6):
N (R ¹⁶ ) ₃
Wherein each R ¹⁶ is independently a hydrogen atom, a substituted or unsubstituted, straight, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or substituted or A compound which may be an unsubstituted aralkyl group (hereinafter referred to as “nitrogen-containing compound (a)”), a compound having two nitrogen atoms in the molecule (hereinafter referred to as “nitrogen-containing compound (b)”); Polyamino compounds and polymers having three or more nitrogen atoms in the molecule (hereinafter collectively referred to as “nitrogen-containing compounds (c)”); and amide group-containing compounds, urea compounds and other nitrogen-containing heterocyclic compounds Can be mentioned.

  Specific examples of the nitrogen-containing compound (a) include mono- (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and cyclohexylamine; di-n- Such as butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine and dicyclohexylamine Di (cyclo) alkylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, Tri-n-nonylamine, tri-n-decylamine, Tri (cyclo) alkylamines such as cyclohexyldimethylamine, methyldicyclohexylamine and tricyclohexylamine; and aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline , Aromatic amines such as 4-nitroaniline, diphenylamine, triphenylamine and naphthylamine.

  Specific examples of the nitrogen-containing compound (b) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diamino. Diphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-amino) Phenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methyl ester Le] benzene, bis (2-dimethylaminoethyl) ether and bis (2-diethylaminoethyl) ether.

  Specific examples of the nitrogen-containing compound (c) include polymers of polyethyleneimine, polyallylamine and 2-dimethylaminoethylacrylamide.

  Specific examples of the amide group-containing compound include Nt-butoxycarbonyl-di-n-octylamine, Nt-butoxycarbonyl-di-n-nonylamine, Nt-butoxycarbonyl-di-n-decylamine, Nt-butoxycarbonyl-dicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-1 -Adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4'-diaminodiphenylmethane, N, N'-di-t-butoxycarbonyl Hexamethylenediamine, N, N, N ′, N′-tetra-t-butoxycarbonyl hex Methylenediamine, N, N′-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t- Butoxycarbonyl-1,9-diaminononane, N, N′-di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12-diaminododecane, N, N '-Di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenz Nt-butoxycarbonyl group-containing amino compounds such as imidazole, formamide, N-methylformamide, , N- dimethylformamide, acetamide, N- methylacetamide, N, N- dimethylacetamide, propionamide, benzamide, and a pyrrolidone and N- methylpyrrolidone.

  Specific examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea and tri-n-. Butyl thiourea is mentioned.

  Specific examples of nitrogen-containing heterocyclic compounds include: imidazoles such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole and 2-phenylbenzimidazole; pyridine, 2-methylpyridine, 4-methyl Pyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline And pyridines such as acridine; piperazines such as piperazine and 1- (2-hydroxyethyl) piperazine; pyrazine, pyrazole, pyridazine, quinoxaline, purine, pyrrolidine, piperidine, 3-piperidinone-1,2- Propanediol, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine and 1,4-diazabicyclo [2.2.2] octane.

  Of the nitrogen-containing organic compounds, nitrogen-containing compounds (a), amide group-containing compounds, and nitrogen-containing heterocyclic compounds are particularly interesting.

  Acid diffusion control agents can be used either individually or as a mixture of two or more.

  The alicyclic additive having an acid dissociable group improves dry etching resistance, pattern shape, and adhesion to the substrate.

Specific examples of such alicyclic additives include:
t-butyl-1-adamantane carboxylate, t-butoxycarbonylmethyl-1-adamantane carboxylate, di-t-butyl-1,3-adamantane dicarboxylate, t-butyl-1-adamantane acetate, t-butoxy Adamantane derivatives such as carbonylmethyl-1-adamantane acetate and di-t-butyl-1,3-adamantane diacetate; t-butyldeoxycholate, t-butoxycarbonylmethyldeoxycholate, 2-ethoxyethyldeoxycholate, 2 Deoxycholates such as cyclohexyloxyethyl deoxycholate, 3-oxocyclohexyl deoxycholate, tetrahydropyranyl deoxycholate and mevalonolactone deoxycholate; and t-butyllitho And lithocholates such as t-butoxycarbonylmethyl litholate, 2-ethoxyethyl lithocholate, 2-cyclohexyloxyethyl lithocolat, 3-oxocyclohexyl lithocholate, tetrahydropyranyl lithocholate and mevalonolactone lithocholate It is done.

  The alicyclic additives can be used either individually or as a mixture of two or more.

  In many cases, surfactants improve application range, striation, developability, and the like.

  Suitable specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol diester. Nonionic surfactants such as laurate and polyethylene glycol distearate; and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW No. 75, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), FTOP EF301, EF303, EF352 (manufactured by Tohchem Products), MEGAFAC F171, F173 (manufactured by Dainippon Ink & Chemicals), Fluorad FC430, FC431 (manufactured by Sumitomo 3M), Asahi G7 Examples include commercially available products such as Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, and SC-106 (manufactured by Asahi Glass Co., Ltd.).

  Surfactants can be used either individually or as a mixture of two or more.

  The sensitizer absorbs radiant energy and transfers energy to the acid generator (B). As a result, the amount of acid generated during exposure increases. Thus, the sensitizer improves the apparent sensitivity of the radiation sensitive resin composition.

  Specific examples of the sensitizer include acetophenone, benzophenone, naphthalene, biacetyl, eosin, rose bengal, pyrene, anthracene and phenothiazine.

  Sensitizers can be used either individually or as a mixture of two or more.

  The addition of dyes or pigments helps visualize the latent image in the exposed areas, thus reducing the halation effect during exposure. By using the adhesion improver, the adhesion to the substrate is improved.

  As other additives, the following alkali-soluble resins, low-molecular weight alkali-soluble control agents containing acid-dissociable protecting groups, halation inhibitors, storage stabilizers, antifoaming agents, and the like are included in the scope of the present invention. Conceivable.

(Preparation of composition solution :)
The photoresist composition is dissolved in a solvent such that the total solids content is typically between about 5 and about 50% by weight, preferably between about 10 and about 25% by weight, and the pore diameter is, for example, about By filtering this solution using a 0.2 μm filter, the radiation sensitive photoresist resin composition of the present invention is converted into a composition solution.

  Specific examples of solvents useful for preparing the photoresist composition solution include 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, and 3-methyl-2. Linear or branched ketones such as pentanone, 3,3-dimethyl-2-butanone, 2-heptanone and 2-octanone; cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2 Cyclic ketones such as 1,6-dimethylcyclohexanone and isophorone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene Propylene glycol monoalkyl ether acetates such as ethylene glycol mono-n-butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate and propylene glycol mono-t-butyl ether acetate; methyl 2-hydroxypropionate, ethyl-2-hydroxypropionate, n-propyl-2-hydroxypropionate, i-propyl-2-hydroxypropionate, n-butyl-2-hydroxypropionate, alkyl-2-hydroxypropionates such as i-butyl-2-hydroxypropionate, sec-butyl-2-hydroxypropionate and t-butyl-2-hydroxypropionate; Alkyl-3-alkoxypropionates such as til-3-methoxypropionate, ethyl-3-methoxypropionate, methyl-3-ethoxypropionate and ethyl-3-ethoxypropionate; and n-propyl Alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether , Diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomer Chill ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, toluene, xylene, 2- Hydroxy-2-methylethyl propionate, ethyl ethoxy acetate, ethyl hydroxy acetate, methyl-2-hydroxy-3-methyl butyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl aceto Cetrate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, capron Other solvents such as acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, gamma-butyrolactone, ethylene carbonate and propylene carbonate .

  The solvents can be used either individually or as a mixture of two or more.

  It is particularly suitable to use linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, alkyl-2-hydroxypropionates, alkyl-3-alkoxypropionates, gamma-butyrolactone, etc. It is.

(Formation of resist pattern)
The radiation sensitive photoresist resin composition of the present invention is useful as a chemically amplified resist.

  In the chemically amplified resist, the acid dissociable group in the resin (A) is dissociated by the action of an acid generated from the acid generator (B) upon exposure to energy. As a result, a carboxyl group is generated. As a result, the solubility of the exposed portion of the resist in an alkaline developer is improved, whereby the exposed portion is dissolved and removed by the alkaline developer, resulting in a positive tone resist pattern.

For example, by adding a photoresist composition solution to a substrate such as a silicon wafer or a wafer coated with aluminum using a suitable application method for forming a resist film such as spin coating, mold coating and roll coating. A resist pattern is formed from the radiation-sensitive photoresist resin composition of the present invention. Next, the resist film is pre-baked (hereinafter referred to as “PB”) as necessary and exposed to form a predetermined resist pattern. In order to use radiation for exposure, visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, and the like are appropriately selected according to the type of the acid generator (B). It is particularly preferable to use far ultraviolet rays such as ArF excimer laser (wavelength: 193 nm), KrF excimer laser (wavelength: 248 nm), and F ₂ excimer laser (wavelength: 157 nm).

  In the present invention, post-exposure baking (hereinafter referred to as “PEB”) is preferably performed. PEB allows for rapid dissociation of acid dissociable groups. The heating temperature for PEB is usually between about 30 and about 200 ° C., preferably between about 50 and about 170 ° C., but the heating conditions can be varied depending on the composition of the radiation sensitive resin composition. Can do.

  In order to maximize the possibilities of the radiation-sensitive resin composition of the present invention, an organic or inorganic antireflection film is formed on a substrate as described in, for example, Japanese Patent Publication No. 1994-12452. May be. Further, a protective film may be formed on the resist film as described in Japanese Patent Publication No. 1993-188598 and the like in order to suppress the influence of basic impurities and the like in the surrounding atmosphere. You may use combining these techniques.

  Next, in order to form a predetermined resist pattern, the exposed resist film is developed using an alkaline developer.

  Specific examples of the alkaline developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, and di-n-propyl. Amine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene or 1,5-diazabicyclo -Alkaline aqueous solution prepared by dissolving at least one alkali compound such as [4.3.0] -5-nonene in water.

  The concentration of the alkaline aqueous solution is generally about 10% by weight or less. When the concentration of the alkaline aqueous solution exceeds 10% by weight, the unexposed part may be dissolved in the developer.

  An organic solvent can be added to the aqueous alkaline solution.

  Suitable specific examples of organic solvents useful in the developer include acetone, methyl ethyl ketone, methyl i-butyl ketone, ketones such as cyclopentanone, cyclohexanone, 3-methylcyclopentanone and 2,6-dimethylcyclohexanone; methyl alcohol, Alcohols such as ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol and 1,4-hexanedimethylol; tetrahydrofuran and Ethers such as dioxane; esters such as ethyl acetate, n-butyl acetate and i-amyl acetate; aromatic hydrocarbons such as toluene and xylene; phenol, acetonylacetone and dimethylform Bromide, and the like.

  Organic solvents can be used either individually or as a mixture of two or more.

  The amount of the organic solvent used is preferably 100% by volume or less of the alkaline aqueous solution. When the amount of the organic solvent exceeds 100% by volume, the developability is deteriorated, and thus the exposed portion may remain undeveloped.

  A surfactant can be added to the alkaline aqueous solution.

  In general, after developing with an alkaline aqueous solution, the resist film is washed with water.

  Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention.

Claims (21)

Acrylic acid or methacrylic acid based formula:

Here, R ¹ represents a hydrogen atom or a methyl group, and each R ² independently represents a linear or branched, unsubstituted or substituted alkyl group having 1 to 4 carbon atoms. or represents, or, in cross-linking have been or noncrosslinked, were or substituted unsubstituted, and display the alicyclic monovalent hydrocarbon radical having from 4 to 20 carbon atoms, provided that any two R ² A divalent alicyclic ring having 4 to 20 carbon atoms, which is bridged or unbridged, unsubstituted or substituted, together with the carbon atom to which the two R ² groups are bonded to each other can form formula hydrocarbon group, the remaining R ² groups in straight or branched chain, unsubstituted or substituted, Ru alkyl der having 1 to 4 carbon atoms;
A polymer comprising monomer units comprising the formula:

Where R ^x is a sufficiently unstable group to be released as its free radical form, T is carbon or phosphorus, Z is a C = S double bond for a reversible free radical addition decomposition reaction. Any group to be activated;
A polymer prepared by a living free radical process (LFRP) in the presence of a chain transfer agent (CTA) having The polymer of claim 1, wherein the acrylic or methacrylic acid based polymer resin comprises sterically large ester groups. The sterically large ester group is selected from the group consisting of monocyclic, bicyclic, tricyclic and tetracyclic non-aromatic rings having 5 or more carbon atoms and combinations thereof. The polymer described. 4. A polymer according to claim 3, wherein the sterically large ester group comprises a lactone in its ring structure. The polymer has the formula:

Here, E represents a non-bridged or bridged group derived from an unsubstituted or substituted alicyclic hydrocarbon, and R ³ is at least one having a hydrogen atom, a trifluoromethyl group or a methyl group. The polymer of claim 1 further comprising two additional repeat units. The polymer of claim 1, wherein the Mw of the polymer is between about 2,000 and 30,000. The polymer of claim 1, wherein the polydispersity of the polymer is about 1.5 or less. The polymer of claim 1, wherein Z is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and combinations thereof. Z is hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted acyl, optionally substituted aroyl, Optionally substituted alkoxy, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally 2. The polymer of claim 1 selected from the group consisting of optionally substituted alkyl phosphonyl, optionally substituted aryl sulfinyl and optionally substituted aryl phosphonyl. The polymer of claim 1, wherein the end groups of the polymer having a CTA fragment are treated such that the CTA fragment is cleaved. A photoresist composition comprising a photoacid generator and an acrylic acid or methacrylic acid based polymer resin, wherein the polymer has the formula:

Where R ^x is a sufficiently unstable group to be released as its free radical form, T is carbon or phosphorus, Z is a C = S double bond for a reversible free radical addition decomposition reaction. Any group to be activated;
A photoresist composition prepared by a living free radical process (LFRP) in the presence of a chain transfer agent (CTA) having The photoresist composition of claim 11, wherein the acrylic or methacrylic acid based polymer resin comprises a sterically large ester group. The sterically large ester group is selected from the group consisting of monocyclic, bicyclic, tricyclic and tetracyclic non-aromatic rings having 5 or more carbon atoms and combinations thereof. The photoresist composition as described. The photoresist composition of claim 13 wherein the sterically large ester group comprises a lactone in its ring structure. The polymer resin has the formula:

Here, R ¹ represents a hydrogen atom or a methyl group, and each R ² independently represents a linear or branched, unsubstituted or substituted alkyl group having 1 to 4 carbon atoms. or represents, or, in cross-linking have been or unbridged, unsubstituted or substituted, and display the alicyclic monovalent hydrocarbon radical having from 4 to 20 carbon atoms, provided that at least one R ² group of but a straight chain or branched chain, or an alkyl group having 1 to 4 carbon atoms, or any two R ² groups together, together with the two carbon atoms to which R ² groups are attached , crosslinked with or uncrosslinked, unsubstituted or substituted, can form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms and the remaining R ² groups linear or branched Chain having 1 to 4 carbon atoms, unsubstituted or substituted That alkyl groups der Ru; containing photoresist composition of claim 11. The polymer has the formula:

Here, E represents a non-bridged or bridged group derived from an unsubstituted or substituted alicyclic hydrocarbon, and R ³ is at least one having a hydrogen atom, a trifluoromethyl group or a methyl group. The photoresist composition of claim 15 further comprising one additional repeat unit. The photoresist composition of claim 11, wherein the Mw of the polymer resin is between about 2,000 and 30,000. The photoresist composition of claim 11, wherein the polydispersity of the polymer resin is about 1.5 or less. The photoresist composition of claim 11, wherein Z is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and combinations thereof. Z is hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted acyl, optionally substituted aroyl, Optionally substituted alkoxy, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally 12. The photoresist composition of claim 11 selected from the group consisting of optionally substituted alkyl phosphonyl, optionally substituted aryl sulfinyl and optionally substituted aryl phosphonyl. The photoresist composition of claim 11, wherein the end groups of the polymer having a CTA fragment are treated such that the CTA fragment is cleaved.