JP2002287339A - Active component and photosensitive resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having high sensitivity and capable of forming a high resolution pattern. SOLUTION: The photosensitive resin composition is obtained by combining an active metal alkoxide of the formula (X)m-n -M<m> -[(U1 )p -(U2 -Z)t ]n or its polycondensation product and an active component selected from particles of the formula P-[(Y)s - (U<1> )p -(U2 -Z)t }]k with a photosensitive agent. In the formulae, X is H, halogen, alkoxy or alkoxycarbonyl; M is a metal atom whose valence (m) is >=2; U1 is a first linking unit; U2 is a second linking unit; Z is a group which produces a solubility difference owing to irradiation with light; P is a fine particulate carrier; Y is a coupling residue; (n) is an integer of >=1; m>n; (p) is 0 or 1; (t) is 1 or 2; (k) is an integer of >=1; and (s) is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active ingredient useful for forming a fine pattern such as a semiconductor integrated circuit by using a light ray such as an ultraviolet ray or a far ultraviolet ray (including an excimer laser). The present invention relates to a photosensitive resin composition (resist composition) and a pattern forming method using the same.

[0002]

2. Description of the Related Art In the field of semiconductor resist, ultra-L
With the development of SI, more advanced fine processing technology is required. Instead of the conventional high-pressure mercury lamp g-line (wavelength 436 mm) and i-line (wavelength 365 mm), a light source of shorter wavelength, for example, KrF excimer Laser (wavelength 248n
m), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm) and the like are used.

However, conventional resist materials using g-rays or i-rays, for example, novolak resin / diazonaphthoquinone type positive resists, use a KrF excimer laser or an ArF excimer laser due to light absorption of the novolak resin. Also, the sensitivity and the resolving power are greatly reduced.

[0004] Further, as the degree of integration of semiconductor integrated circuits increases, the resolution of resists (formation of submicron or quarter micron or less patterns) and the improvement of etching resistance in dry development processes are required.

For example, as an attempt to improve the resolution by using a conventional dry development process, a method of filling inorganic fine particles into a photosensitive resin is known. In order to achieve both, silica sol or the like is used as the inorganic fine particles. For example, JP-A-5-158235 discloses a resist composition in which silica sol is added to a resist composed of a cresol novolak resin and a naphthoquinonediazidesulfonic acid ester to improve dry etching resistance, and has a two-layer structure. For use as an upper layer resist. JP-A-11-19
No. 4491 proposes a photosensitive resin composition comprising a photosensitive organic oligomer or polymer, a hydrolysis-polymerizable organometallic compound or a condensate thereof, and a functional group-containing inorganic filler (such as silica sol). ing. JP-A-11-327125 discloses a photosensitive resin composition composed of a photosensitive resin and inorganic fine particles (such as silica sol) or inorganic fine particles having a functional group.
I. Sondi and E. Matijevic, Resist Technology and Pr
ocessing XVII, Francis M. Houlihan, Editor, Procee
The first 627 to 637 pages of dings of SPIE Vol.3999 (2000), composed of p- hydroxystyrene -t- butyl acrylate copolymer containing SiO ₂ nanoparticles (sol) film is disclosed, SiO ₂ nano It is described that the particles are highly soluble in bases and act as dissolution promoters, and that resists containing such SiO ₂ nanoparticles exhibit resolution comparable to controls without SiO ₂ . This document also discloses a resist system using transparent SiO ₂ nanoparticles, which is 157.
It is also described that it is useful for wavelengths such as nm.

On the other hand, along with the improvement in miniaturization, particularly recently,
The edge roughness of the resist pattern is a problem. In particular, edge roughness is remarkable in a resist used in a thin film such as a surface resist.

In the above-described resist to which silica sol is added, the size of the silica sol particles is small and the resist is transparent to exposure light, so that a thick film can be formed. Further, since the size of the silica sol particles is small, a thin film can be formed, and the resolution can be improved to some extent. However, since the silica sol itself has high hydrophilicity, dissolution also occurs in the dissolution inhibiting portion (for example, in the case of a positive type, the unexposed portion), and the difference in dissolution rate between the exposed portion and the unexposed portion cannot be so large, The sharpness and edge roughness of the resolution and pattern profile cannot be significantly improved.

Moreover, commercially available silica sols are often produced by the sodium silicate method, and sodium may inevitably remain in the product.

[0009] Japanese Patent Application Laid-Open No. 2000-56463 discloses that an organooxysilane is added to an alcohol solution of a resist material containing an alkali-soluble resin in the presence of moisture.
It is disclosed that a silica-alkali soluble resin hybrid material is obtained by a sol-gel reaction. In this method, a sol-gel reaction is performed in the resist,
The silica component can be uniformly dispersed at the molecular level without precipitating in the resist material. However, according to this method, the solubility difference between the exposed portion and the unexposed portion in the developing solution cannot be increased, and it is difficult to significantly improve the resist performance such as resolution.

As a resist composition, a light-amplification type (chemically-amplification type) resist composition in which a base resin which is desorbed by the action of an acid and becomes alkali-soluble and a photoacid generator is combined is also known. However, even with such a composition, the solubility difference between the exposed part and the unexposed part cannot be increased.

[0011]

Accordingly, an object of the present invention is to provide an active ingredient (including active particles) useful for forming a high-sensitivity, high-resolution pattern, and a photosensitive resin composition containing this active ingredient. And a method for forming a pattern using the photosensitive resin composition.

Another object of the present invention is to provide a photosensitive resin composition and a pattern forming method capable of improving pattern edge roughness while maintaining etching resistance to oxygen plasma.

It is still another object of the present invention to provide a photosensitive resin composition and a pattern forming method which have high sensitivity to light having a shorter wavelength and can greatly improve resolution.

Another object of the present invention is to provide an active ingredient (including active particles) useful for forming a high-sensitivity, high-resolution pattern, in which contamination with impurities is suppressed, and an active ingredient useful for obtaining this active ingredient. An object of the present invention is to provide an active metal alkoxide, a photosensitive resin composition containing the active component, and a pattern forming method using the photosensitive resin composition.

Still another object of the present invention is to provide a photosensitive resin composition and a pattern forming method capable of causing a difference in solubility in a developing solution between an exposed portion and an unexposed portion.

[0016]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, at least an active ingredient having a functional group for introducing a functional group for causing a difference in solubility due to light irradiation has been introduced. Fine particles (active particles) capable of hydrophilizing by removing a hydrophobic leaving group by irradiation, a specific metal alkoxide (active metal alkoxide) or a polycondensate thereof (active particles formed by polycondensation), and the like; When used in combination with a resin composition, a difference in solubility with respect to a developer is caused in an exposed portion and an unexposed portion, and a high-resolution pattern can be formed with high sensitivity. It has been found that when used in combination with the composition, contamination with impurities is reduced and a high-resolution pattern can be formed with higher sensitivity, and the present invention has been completed.

That is, the active ingredient of the present invention is an active ingredient to be used in combination with a photosensitive agent constituting the photosensitive resin composition, and has the following formula (1) (X) _mn -M ^m -[(U ₁ ) _p- (U ₂ -Z) _t ] _n (1) (wherein, X represents a hydrogen atom, a halogen atom, an alkoxy group or an alkoxycarbonyl group, and M represents a metal atom having a valence m of 2 or more. , U ₁ represents a first connection unit, U ₂ represents a second connection unit, Z represents a group that causes a difference in solubility due to light irradiation, n represents an integer of 1 or more, and m represents an integer.
> N, p is 0 or 1, t is an integer of 1 or more (for example, 1 or 2), or an active metal alkoxide or a polycondensate thereof, and the following formula (2) P-[( Y) _s -{(U ₁ ) _p- (U ₂ -Z) _t }] _k (2) (wherein P represents a fine particle carrier, Y represents a coupling residue, and k is an integer of 1 or more) And s is 0 or 1. U ₁ , U ₂ , Z, p and t are the same as those described above).
Note that the first connecting unit U ₁ and the second connecting unit U ₂
May be collectively referred to as a connection unit U. The particles (active particles) represented by the formula (2) may be a reaction product of the active metal alkoxide represented by the formula (1) or a polycondensate thereof and the fine particle carrier P.

The active ingredient may be in the form of particles or oligomers, wherein the group Z is (a) a photocrosslinkable group or a photocurable group, and (b) is removable due to light irradiation. It may be a hydrophilic group protected by a protecting group. The group Z
Is a hydrophilic group protected by a protecting group that can be removed in association with a photosensitizer by light irradiation, and the protecting group can be removed by the action of an acid or the like. Said group Z may be capable of generating a hydroxyl group or a carboxyl group by elimination of a hydrophobic protecting group, such a group Z being, for example, a group -HP-Pro (where HP is a hydrophilic group Indicates that
Pro represents a protecting group that imparts hydrophobicity to the hydrophilic group HP and is released by light irradiation to generate the hydrophilic group HP).

The protecting group is, for example, (i) an alkoxy group
Alkyl, acyl, alkoxycarbonyl, oxa
Selected from cycloalkyl groups and bridged cycloaliphatic groups
Protecting groups for hydroxyl groups, (ii) alkyl groups,
A caruba selected from a rubamoyl group and a bridged cyclic alicyclic group
It may be a protecting group for a boxyl group. More specific
Has a protecting group represented by (1) C_1-6Alkyl-carbonyl
Group, C_1-6Alkoxy-C _1-6Alkyl group, C_1-6Arco
Selected from xy-carbonyl and oxacycloalkyl groups
A protecting group for the selected hydroxyl group, (2) C_1-6
Alkyl group, carbamoyl group, C_1-6Alkyl-carba
Moyl group, C_6-10Aryl-carbamoyl group and bi or
To carboxyl group selected from tricycloalkyl group
It may be a protecting group for.

The metal atom M may be aluminum, titanium, zirconium, silicon or the like.
Silicon.

The linking units U ₁ and U ₂ include various linking groups, for example, at least one selected from a chain hydrocarbon, a hydrocarbon ring, a chain hydrocarbon having a hetero atom, and a heterocycle. Can be composed of units. For example, the connection units U ₁ and U ₂ can be represented by the following equations, respectively.

-(R ¹ ) _q- (B) _r -,-(R ² ) _u- (Ar) _v- (wherein R ¹ and R ² are the same or different and each represents an alkylene group or an alkenylene group. B represents an ester bond, a thioester bond, an amide bond, a urea bond, a urethane bond, a thiourethane bond, an imino group, a sulfur atom or a nitrogen atom, and Ar represents a substituent (for example, a halogen atom,
An alkylene group, etc.). q, r, u and v each represent 0 or 1, and q + r + u + v ≧ 1.) The compound represented by the formula (1) is a hydrophobic protecting group in which Z can be removed by irradiation with light. Wherein the metal atom M is selected from the group consisting of aluminum, titanium, zirconium and silicon, and contains a linking unit (U ₁ ) _p- (U _2-
Z) _t may be a compound represented by the following formula.

[(R ¹ ) _q- (B) _r ] _p -[｛(R ² ) _u −
(Ar) _v ｝ -Z] _t (wherein, R ¹ , R ² , B, Ar, p, q, r, t, u and v are the same as described above). condensates may be a polycondensate of the active metal alkoxide alone represented by the formula (1), and the active metal alkoxide of the formula (1), the following equation (5) (X) _mn-1 M ^m (R ⁵ ) _n-1 (5) (wherein, R ⁵ represents a hydrogen atom or an alkyl group.
M, m and n may be a polycondensate (co-condensate) with the metal alkoxide represented by the same formula.

The ratio (weight ratio) between the active metal alkoxide (1) and the metal alkoxide (5) may be, for example, component (1) / component (5) = about 10/90 to 90/10. . The polycondensate may be particles, for example, particles having an average particle diameter of about 1 to 100 nm.

Particles (active particles) represented by the above formula (2)
The average particle diameter of the fine particle carrier is 1 to 100 nm
Degree. Fine particle carriers include organic fine particle carriers and
It may be an inorganic fine particle carrier (for example, silica sol).
No. The coupling agent is a metal atom of the above formula (1)
It corresponds to the compound having M. Such active particles
(2) is the average particle diameter via the silane coupling agent Y
Connecting unit U coupled to inorganic fine particles P of 1 to 50 nm
And a hydrophilic group bonded to the linking unit,
And a protecting group that protects the functional group. Also, for light irradiation
The group Z that causes a further difference in solubility is protected with the hydrophilic group.
And can be composed of The connection unit is an aromatic C_6-12
Hydrocarbon ring, monocyclic alicyclic hydrocarbon ring, bridged cyclic alicyclic
At least one selected from hydrocarbon rings and aliphatic hydrocarbon chains.
And the hydrophilic group is usually a hydroxyl group.
It is a sil group or a carboxyl group. The protecting group is
(1) C _1-4Alkyl-carbonyl group, C_1-4Alkoxy
-C_1-4Alkyl group, C_1-4An alkoxy-carbonyl group,
And a 5- or 6-membered oxacycloalkyl group
A protecting group for a hydroxyl group, or (2) C_1-4Al
Kill group, carbamoyl group, C_1-4Alkyl-carbamoy
Group, C_6-10Aryl-carbamoyl and bi or tri
For carboxyl groups selected from cycloalkyl groups
Protecting group. Of the silane coupling agent
The ratio is 0.1 to 20 with respect to 100 parts by weight of the fine particle carrier.
It may be about 0 parts by weight.

The present invention also includes a photosensitive resin composition containing the active ingredient, for example, a photosensitive resin composition comprising a base resin, a sensitizer and the active ingredient. This photosensitive resin composition may be a positive type in which the exposed portion can be developed with water or alkali. For example, even if the base resin is composed of a monomer or a copolymer of a monomer capable of generating a hydrophilic group by the action of an acid, and the photosensitive agent is a photosensitive resin composition composed of a photoacid generator. Good. A pattern can be formed by applying such a photosensitive resin composition to a substrate, exposing it to light, heating it, and then developing it.

The present invention also includes an active metal alkoxide represented by the following formula (1).

(X) _mn -M ^m -[(U ₁ ) _p- (U ₂ -Z) _t ] _n (1) (wherein X represents a hydrogen atom, a halogen atom, an alkoxy group or an alkoxycarbonyl group) , M represents a metal atom having a valence m of 2 or more, U ₁ represents a first connecting unit, U ₂ represents a second connecting unit, and Z represents a group that causes a difference in solubility due to light irradiation. N is an integer of 1 or more, and m
> N, p represents 0 or 1, and t represents 1 or 2.) The present invention also includes an oligomer or active particles composed of at least a polycondensate of the active metal alkoxide.

[0029]

DETAILED DESCRIPTION OF THE INVENTION The active ingredient of the present invention is used in combination with a photosensitive agent of a photosensitive resin composition and has at least a unit for causing a difference in solubility due to light irradiation. Such an active ingredient is composed of at least one selected from an active metal alkoxide represented by the above formula (1) or a polycondensate thereof, and particles represented by the above formula (2).

[Active metal alkoxide or polycondensate thereof (1)] (Active metal alkoxide (1a)) In the formula (1), halogen atoms represented by X include fluorine, chlorine, bromine and iodine atoms. Examples of the alkoxy group include, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, s-butoxy, t-butoxy, pentyloxy,
Examples thereof include linear or branched C _1-10 alkoxy groups (preferably C _1-6 alkoxy groups, more preferably C _1-4 alkoxy groups) such as hexyloxy, heptyloxy, octyloxy and decyloxy groups. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, s-butoxycarbonyl,
t-butoxycarbonyl, hexyloxycarbonyl,
Straight chain or branched chain C _1-10 alkoxy such as octyloxy carbonyl group - carbonyl group (preferably C _1-6 alkoxy - carbonyl group, more preferably a C _1-4 alkoxy - carbonyl group) can be exemplified.

The alkoxy group and the alkoxycarbonyl group include a halogen atom, a hydrocarbon group optionally having an unsaturated bond (such as an alkyl group, an alkenyl group, a cycloalkyl group and an aryl group), a heterocyclic group, and an acyl group. And the like.

The m-valent metal atom represented by M is a divalent or higher (eg, divalent to tetravalent) metal capable of forming a metal alkoxide, for example, an alkaline earth metal (magnesium, calcium, etc.), a transition metal , Rare earth metal, or periodic table 3 ~
Group 5 and 13-15 metals. In particular, periodic table 3
Group 4 metals (such as yttrium), Group 4 metals (such as titanium and zirconium), Group 13 metals (such as aluminum) and Group 14 metals (such as silicon). Preferred metals include titanium, zirconium, aluminum, and silicon, with silicon being particularly preferred.

As the group Z, a group that causes a difference in solubility due to light irradiation, such as (a) a photocrosslinkable group or a photocurable group, or (b) a hydrophilic group protected by a protective group. Is mentioned.

The (a) photocrosslinkable group or photocurable group includes an azide group, a cinnamoyl group, a cinnamylidene group,
Examples thereof include a polymerizable group ((meth) acryloyl group, allyl group, vinyl group, and the like). Particularly, a polymerizable group and a crosslinkable group are preferable.

As the hydrophilic group in the hydrophilic group protected by the protecting group (b), in addition to an amino group, an N-substituted amino group (N, N-diC _1-4 alkylamino group, etc.), Water or alkali-soluble groups (groups capable of imparting solubility by the action of water or alkali) such as hydroxyl groups, carboxyl groups, and their corresponding sulfur-containing derivative groups (including mercapto groups, thiocarboxyl groups, and dithiocarboxyl groups) And the like, and particularly preferred are a hydroxyl group (including a phenolic hydroxyl group) and a carboxyl group.

In the above formula (1), n represents an integer of 1 or more (for example, 1 to 3, especially 1 or 2). Where m
> N, and mn = 1 to 3, preferably 2 or 3.

First and second connecting units U₁And U
_TwoIs not particularly limited, various organic chains, for example, chain carbon
Hydrocarbons, hydrocarbon rings, and chain hydrocarbons containing heteroatoms
Units such as elementary and heterocyclic rings alone or in combination of two or more
These organic chains are linked by a linking group.
It may be. As the chain hydrocarbon, an alkylene chain
Such as aliphatic hydrocarbon chains (ethylene, propylene, tri
Linear or branched C such as methylene and hexamethylene chains
_1-10Alkylene chain; vinylene chain, propenylene chain, iso
Linear or branched chain such as propenylene chain and butenylene chain
C_2-10Alkenylene chain, etc.).
The chain hydrocarbon having at least one nitrogen source
Alkylene chain (C)_2-10Alkylene chain
Thio ether chain [thio C_2-10Alkylene ether
Chain, dithio C_2-10Polythio such as alkylene ether chains
C_2-10Alkylene ether chains], ether chains (Oki
C_2-10Alkylene ether chain, dioxy C_2-10Archi
Polyoxy C such as len ether chain _2-10Alkylene
And the like. Benzene is used as the hydrocarbon ring.
Aromatic C such as zen_6-12Hydrocarbon ring; cycloalkane
Ring, for example, C such as cyclohexane_5-10Cycloalka
Ring (monocyclic alicyclic hydrocarbon ring); bridged cyclic hydrocarbon ring
(Bi or tricyclo such as norbornane and adamantane
Alkane ring; C such as cyclohexene_5-10Cycloalkene
Ring; bi- or tricycloalkene ring such as norbornene
Etc.) can be exemplified. Also, multiple hydrocarbon rings are required.
Rings connected by a hydrocarbon chain as required (biphenyl; diph
Bis (C_6-14Aryl) C_1-4Al
Ring corresponding to a can, etc.). For example, chain
Hydrocarbon group (linear or branched C_2-4Alkylene group
Is a linear or branched C_2-4Alkenylene group) and charcoal
Hydrogenated ring groups (arylene groups, cycloalkylene groups,
Is a tricycloalkylene group)
There may be. As a heterocyclic ring, an oxygen atom, a nitrogen atom and
At least one heteroatom selected from sulfur and sulfur atoms
Heterocycle containing a child, especially 5- or 6-membered heterocycle, etc.
Wear. Further, the above-mentioned chain or cyclic hydrocarbon group or heterocyclic group
Are alkyl groups (C_1-5Alkyl group), halogen
And it may have a substituent such as a nitrogen atom.

In the above formula (1), the coefficient p for the first connecting unit U ₁ is 0 or 1, and the coefficient t for the second connecting unit U ₂ is an integer of 1 or more (particularly 1 or 2). .

The connecting unit U ₁ may be a unit represented by the following formula (3a), and the connecting unit U ₂ may be a unit represented by the following formula (3b).

-(R ¹ ) _q- (B) _r- (3a)-(R ² ) _u- (Ar) _v- (3b) (wherein R ¹ , R ² and Ar are the same or different. , A divalent hydrocarbon group, and B represents a divalent bond such as an ester bond, a thioester bond, an amide bond, a urea bond, a urethane bond, a thiourethane bond, an imino group; a divalent bond such as an oxygen atom or a sulfur atom. Or a trivalent atom such as a nitrogen atom. Q, r, u and v each represent 0 or 1, and q + r + u + v ≧ 1.) When B is a nitrogen atom and r = 1, t is 1 or 2, and when B is an atom or group other than a nitrogen atom and r = 1,
Usually, t is 1.

Examples of the divalent hydrocarbon group represented by R ¹ , R ² and Ar include a divalent group (alkylene group such as ethylene, propylene, trimethylene group, etc., vinylene, , An alkenylene group such as an isopropenylene group), and a divalent group (cycloalkylene group, arylene group (phenylene, naphthalene group, etc.), bi- or tricycloalkylene group, biphenylene group corresponding to the above-described hydrocarbon ring And groups corresponding to bisarylalkanes). Preferred R ¹ and R ² are
A linear hydrocarbon group, for example, a linear or branched C _2-8 alkylene group (particularly, a C _2-4 alkylene group, etc.) or a linear or branched C _2-8 alkenylene group (particularly, C _{2- 4} alkenylene group).

Preferred Ar is a hydrocarbon ring group, for example,
Phenylene, an arylene group such as a naphthalene group, a biphenylene group such as a biphenyl group, a bi- or tricycloalkylene group, a group corresponding to a _{bisarylalkane} , and the like, particularly a C _6-12 arylene group (C _6-10 arylene group) or It is a C _5-8 cycloalkylene group. The group Ar is a halogen atom (such as a fluorine, chlorine, or bromine atom), an alkyl group (such as a C _1-4 alkyl group), an alkoxy group (such as a C _1-4 alkoxy group), or an acyl group (such as a C _1-4 alkyl-carbonyl). And the like may have a substituent.

In the above equation, the coefficients q, r, u and v
Is 0 or 1, respectively, and q + r + u + v ≧ 1, and usually q + r = 0 to 2, and u + v = 1 to 2.

The unit (U ₁ ) _p including the connection unit
− (U ₂ −Z) _t is represented, for example, by the following equation (3).

[(R ¹ ) _q- (B) _r ] _p -[｛(R ² ) _u- (Ar) _v ｝ -Z] _t (3) (where R ¹ , R ² , B, Ar , p, q, r, t , u and v can be exemplified the same groups as above as the ^{same) R 1, R 2, R} 1, R 2
Is usually an alkylene group (especially a C _2-4 alkylene group) or an alkenylene group (especially a C _2-4 alkenylene group). B is an ester bond, an amide bond, a urea bond, a urethane bond, an imino group, a sulfur atom or a nitrogen atom;
r is usually a hydrocarbon ring group (for example, a C _6-10 arylene group or a C _5-8 cycloalkylene group), particularly a benzene ring or a cyclohexane ring.

[0046] Such metal alkoxides (1) are units (X) _mn a compound having a M ^m, is reacted with a compound having a group Z, the coupling unit U between the metal M and the group Z
_May be obtained by forming a unit (X) _mn
A compound having -M ^m (particularly (X) _mn -M ^m- (R ¹ ) _q ) and a unit U ₂ -Z (particularly {(R ² ) _u- (Ar) _v }
And may be obtained by a reaction with a compound having -Z). Therefore, the linking unit U ₁ is often a linking group formed by such a reaction, and the linking unit U ₂ is often derived from a compound having the unit U ₂ . Various reactions can be used for the reaction of each component, and examples thereof include a reaction by a combination of the following reactive groups.

(I) hydroxyl group (or mercapto group)
Or an ester bond (or thioester bond) formation reaction between a lower alkyloxy group and a carboxyl group or a reactive derivative group thereof (an acid anhydride group, an acid halide group, etc.), or a hydroxyl group (or a mercapto group) and an isocyanate group (Ii) Ester bond (or thioester bond) formation reaction between carboxyl group or its reactive derivative group and hydroxyl group (or mercapto group) or its lower alkyloxy group, carboxyl group Bond formation reaction between a carboxyl group and an amino group, or ring opening reaction between a carboxyl group and an oxazoline ring (iii) an amino group and a carboxyl group or a reactive derivative group thereof (acid An amide bond (or imino bond) with an anhydride group, etc. Reaction between amino group and epoxy group (imino bond formation reaction etc.) or amino group and isocyanate group urea bond formation reaction (iv) hydroxyl group, mercapto group, amino group or hydrogen atom (eg silyl group SiH etc.) (V) Hech reaction between a halogen atom and a vinyl group (eg, a coupling reaction between an alkene and a halogen-substituted aromatic compound using a palladium catalyst in the presence of a base) Taking the case of a silicon atom as an example, as a compound having the unit (X) _mn M, for example, tri-C _1-4 alkoxysilane such as trimethoxysilane, triethoxysilane, tripropoxysilane; methyldimethoxysilane; phenyl dimethoxy silane; C _1-4 alkyl di C _1-4 alkoxysilane such as methyl diethoxy silane C _6-10 such as phenyl diethoxy silane
Examples include silane compounds having a functional group such as an isocyanate group, an epoxy group, an amino group, a mercapto group, a hydroxyl group, a carboxyl group, and an unsaturated bond (particularly, a silane coupling agent) in addition to aryldi C _1-4 alkoxysilane. it can.

The silane coupling agent includes a compound represented by the following formula (4).

(R ⁶ ) _u Si (D) _4-w (4) (wherein, R ⁶ represents an organic group having a reactive group, and D represents
A hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or OR ⁷ is shown. R ⁷ has 1 to 1 carbon atoms
4 represents an alkyl group, and w is an integer of 0 to 2.) As the organic group represented by R ⁶ , an alkyl group having a reactive group (isocyanate alkyl group, carboxyalkyl group, epoxyalkyl group, aminoalkyl Group, mercaptoalkyl group, hydroxyalkyl group; vinyl group, allyl group, alkyl group having a polymerizable group such as (meth) acryloyl group, etc.) or aryl group having a reactive group (isocyanatoaryl group, carboxyaryl group,
Aminoaryl group, hydroxyaryl group; vinyl group,
An aryl group having a polymerizable group such as an allyl group and a (meth) acryloyl group). The alkyl group represented by R ^7, for example, methyl, ethyl, butyl, etc. t- butyl group can be exemplified.

Examples of the isocyanate group-containing silane coupling agent include 1-isocyanatomethyl-1,1,1-trimethoxysilane and 1- (1- or 2-isocyanatoethyl) -1,1,1-trimethoxysilane. Silane, 1-isocyanatomethyl-1,1,1-triethoxysilane, 1-
(1- or 2-isocyanatoethyl) -1,1,1-triethoxysilane, 1-isocyanatomethyl-1-methyl-1,1-dimethoxysilane, 1-chloro-1-isocyanatomethyl-1, 1-dimethoxysilane, 1- (3
-Aminopropyl) -1-isocyanatoethyl-1,1
-Dimethoxysilane, 1- (3-aminopropyl) -1
-Isocyanatoethyl-1,1-diethoxysilane, 1
Isocyanatoalkylalkoxysilanes such as -isocyanatomethyl-1-phenyl-1,1-dimethoxysilane, 1-isocyanatopropyl-1-phenyl-1,1-dipropoxysilane (for example, isocyanato C _1-6 alkyl C _1-4 alkoxysilane) and the like.

The epoxy group-containing silane coupling agent includes 1- (1,2-epoxypropyl) -1,1,1
-Trimethoxysilane, 1-glycidyl-1,1,1-
Epoxyalkylalkoxysilanes such as trimethoxysilane (for example, epoxy group-containing C _3-8 alkyl-C _1-4
Glycides such as 1- (3-glycidoxypropyl) -1,1,1-trimethoxysilane and 1- (3-glycidoxypropyl) -1-methyl-1,1-dimethoxysilane Xyalkylalkoxysilane (for example, glycidoxy C _1-6 alkyl C _1-4 alkoxysilane) and the like.

As the amino group-containing silane coupling agent, an amino group-containing silane coupling agent corresponding to the above-mentioned isocyanate group-containing silane coupling agent, in particular, 1
-(3-N- (2'-aminoethyl) aminopropyl)
-1-methyl-1,1-dimethoxysilane, 1- (3-
N- (2'-aminoethyl) aminopropyl) -1,
Aminoalkylalkoxysilanes such as 1,1-trimethoxysilane and 1- (3-aminopropyl) -1,1,1-trimethoxysilane (amino C _1-6 alkyl-C _1-4
Alkoxysilane, etc.).

The mercapto group-containing silane coupling agent includes a mercapto group-containing silane coupling agent corresponding to the isocyanate group-containing silane coupling agent.
In particular, 1- (3-mercaptopropyl) -1,1,1-
Trimethoxysilane, 1- (3-mercaptopropyl)
Examples thereof include alkoxysilane having a mercaptoalkyl group such as -1,1,1-triethoxysilane (for example, mercapto C _1-6 alkyl C _1-4 alkoxy silane).

Also, a hydroxyl group-containing silane coupling agent and a carboxyl group-containing silane coupling agent corresponding to the isocyanate group-containing silane coupling agent can be used.

Examples of the silane coupling agent having an unsaturated bond include a silane coupling agent having a polymerizable group such as a vinyl group, an allyl group, and a (meth) acryloyl group. Examples of the vinyl group-containing coupling agent include 1-vinyl-1,1-dimethyl-1-ethoxysilane, 1-vinyl-1-methyl-1,1-diethoxysilane, 1-vinyl-1,1,1 -Trimethoxysilane, 1
-Vinyl-1,1,1-triisopropenoxysilane,
1-vinyl-1,1-dimethyl-1-chlorosilane, 1
-Vinyl-1-methyl-1,1-dichlorosilane, 1-
Vinyl-1-ethyl-1,1-dichlorosilane, 1-vinyl-1,1,1-trichlorosilane, 1-vinyl-1
-Methyl-1,1-bis (methylethylketoximine)
Silane, 1-vinyl-1-methyl-1,1-bis (trimethylsiloxy) silane, 1-vinyl-1-methyl-
1,1-diacetoxysilane, 1-vinyl-1,1,1
-Triphenoxysilane, 1-vinyl-1,1,1-tris (t-butylperoxy) silane and the like. An allyl group-containing silane coupling agent corresponding to the vinyl group-containing silane coupling agent;
Acryloyl group (or (meth) acryloyloxy group)
Included silane coupling agents can also be used. As the silane coupling agent, a commercially available silane coupling agent can be used.

The group Z or the unit U ₂ -Z (particularly R ² -Ar
Examples of the compound having a photocrosslinkable (or photocurable) group or a hydrophilic group corresponding to the compound having -Z) include, in addition to the photocrosslinkable group or the hydrophilic group, a reactive group [for example, a hydroxyl group. Groups having an active hydrogen atom, such as carboxyl group, amino group; isocyanate group and vinyl group ((meth)
Acryloyl group)] and compounds having a reactive atom (eg, a halogen atom).

As the compound having a hydroxyl group,
Aliphatic polyhydroxy compounds (ethylene glycol,
Limethylene glycol, propylene glycol, tetra
Linear or branched C such as methylene glycol_2-10Al
Kylene glycol; di to polyethylene glycol, di
Or polyoxy C such as polypropylene glycol_{2- Four}
Alkylene glycol, etc.), aromatic polyhydroxylation
Compound [eg, hydroquinone, resorcin, catechol
, Phloroglucin, oxyhydroquinone, pyrogallow
, Alkyl gallate (C of gallic acid)_1-4Al
Phenols such as kill esters); xylylene
Hydroxy such as recall and oxybenzyl alcohol
Aralkyl alcohols (eg, hydroxy C_6-10A
Reel-C _1-4Alkyl alcohol); hydroxyben
Zofenones; naphthalene diol, naphthalene thiol
Such as hydroxynaphthalenes; biphenol, biphenol
Sphenols (bisphenol A, bisphenol
F, bisphenol AD, etc.)], alicyclic polyhydride
Roxy compound [monocyclic alicyclic diol (cyclohexane
C such as diol_5-8Cycloalkanediol; cyclo
C such as hexenediol_5-8Cycloalkenedio
, Cyclohexanedimethanol, etc.), cross-linked alicyclic ring
Aliphatic diols (norbornanediol, adamantanediol
Or tricycloalkanediol)
Etc.], a heterocyclic polyhydroxy compound [dihydroxypi
5- to 8-membered unsaturated heterocycle such as orchid and dihydroxyfuran
Formula polyhydroxy compounds (eg, 5 or 6 membered unsaturated
Cyclic di- or trihydroxy compound); dihydroxytet
Lahydrofuran, dihydroxytetrahydropyran, etc.
5-8 membered saturated heterocyclic polyhydroxy compound (for example,
5- or 6-membered saturated heterocyclic di- or trihydroxy compound,
Especially dihydroxyoxacycloalkane), etc.
Roxyl group and halogen atom (bromine atom, iodine atom
[Eg, halogenated alcohols
(Halogenated C_1-10Alkyl alcohol, etc.), halogen
Phenols (bromophenol, iodophenol
Halo C such as le_6-10Aryl alcohol), halogen
Cycloalkanols such as iodohexanol
Logenated C_5-6Cycloalkanol, etc.)
Compound having a loxyl group and a carboxyl group [hydro
Xycarboxylic acids such as hydroxyaliphatic C_2-12Cal
Bonic acid (oxycaproic acid, etc.), hydroxy aromatic C
_6-10Carboxylic acids (salicylic acid, dihydroxybenzoic acid,
Gallic acid, hydroxynaphthoic acid, etc.), hydroxy C
_5-6Cycloalkane-carboxylic acid (hydroxycyclo
Xancarboxylic acid, etc.)
Compounds having an amino group [ethanolamine, propanol
Amino C such as ruamine_2-10Alkyl alcohol, Ami
Nophenols (aminophenol, aminocreso
Amino, such as aminosalicylic acid_6-10Aryl al
Cole), amino C_5-6Cycloalkanol, etc.]
Compounds having a droxyl group and an epoxy group (glycidyl
Glycidyl C such as ruphenol_6-10Aryl alcohol
), Hydroxyl group, vinyl group, (meth)
Compounds having a liroyl group or an allyl group (vinyl
Vinyl C such as knol_6-10Aryl alcohol, hydro
Kishi C_2-6Alkyl (meth) acrylate, allyl alcohol
Call, etc.).

As the compound having a carboxyl group,
Polycarboxylic acid [C_1-12Alkane-dicarboxylic acid (azi
Pinic acid, pimelic acid, sebacic acid, azelaic acid
), Aromatic dicarboxylic acids (benzenedicarboxylic acid,
Phthalenedicarboxylic acid, etc.), C _5-6Cycloalkane-
Dicarboxylic acids (such as cyclohexanedicarboxylic acid)
A compound having a carboxyl group and an amino group [A
Mino C_2-10Alkyl-carboxylic acid, amino C_6-10Ally
Le-carboxylic acid (such as aminobenzoic acid), amino C_{Five- 6}
Cycloalkyl-carboxylic acid (aminocyclohexaneca)
Carboxylic acid and halogen atom)
(Halogenated aliphatic C)_2-10Carvone
Acid, halogenated C_6-10Aryl-carboxylic acids (chloro ammonium
Benzoic acid, iodobenzoic acid, etc.), halogenated C_5-6Shiku
Loalkylcarboxylic acid (chlorocyclohexanecarboxylic acid
Acid, iodocyclohexanecarboxylic acid, etc.)
Compounds having a ruboxyl group and an epoxy group (glycidyl
Glycidyl group-containing C such as benzoic acid_6-10Aryl-ka
Rubonic acid), carboxyl group, vinyl group, (meth)
Compound having a acryloyl group or an allyl group [(meth)
Acrylic acid; vinyl group-containing C such as vinyl benzoic acid_6-10
Aryl-carboxylic acids; itaconic acid, maleic acid, fuma
Unsaturated polycarboxylic acids such as luic acid or its monoalkyl
Esters and the like].

Examples of the compound having an amino group include aliphatic diamines (ethylene diamine, propylene diamine,
1,4-diaminobutane, hexamethylenediamine,
C _2-10 such as 2,5-dimethylhexamethylenediamine
C _6-10 such as alkanediamine, aromatic diamine (metaphenylenediamine, diaminodiphenylmethane, etc.)
Arylenediamine; xylylenediamine, etc. (C _1-4
Alkyl -C _6-10 arylene -C _1-4 alkyl) diamine), alicyclic diamines (menthenediamine, isophoronediamine, etc. diamino C _5-6 cycloalkane such as diaminodicyclohexylmethane) diamine such as mentioned .

As the compound having a halogen atom, di-
Halo C_2-10Alkanes (such as diiodohexane), C_6-10
Aromatic dihalides (such as diiodobenzene), diha
B _5-6Cycloalkane (diiodocyclohexane
Etc.). As a compound having a vinyl group
Is C such as divinylbenzene_6-10Aromatic divinyl compound
Things. Compound having isocyanate group
As fats such as hexamethylene diisocyanate
Aromatic diisocyanate; tolylene diisocyanate, xy
Aromatic diisocyanate such as lylene diisocyanate
G; alicyclic diisocyanates such as isophorone diisocyanate
Anate can also be used.

When such a compound is used, it is easy to control the affinity with the base resin and the solubility in the developer. In these compounds, the hydrophilic group HP (hydroxyl group, carboxyl group, etc.) has the unit (X) _mn
Prior to reaction with a compound having M ^m , the protecting group Pro
May be protected in advance by the unit (X) _m-
After reacting with a compound having a _n M _m, it may be protected with a protecting group Pro. That is, the group Z that produces the solubility difference is
A group -HP-Pro [wherein HP represents a hydrophilic group, Pr
o represents a protective group which is eliminated due to light irradiation and generates the hydrophilic group (particularly, a protective group which imparts hydrophobicity to the hydrophilic group). The protecting group can be formed by a conventional method, for example, an acetalization reaction, an esterification method, an active esterification method, a mixed acid anhydride method, an azide method, a method using a coupling reagent (dicyclohexylcarbodiimide (DCC) method, DCC-additive). , Etc.).

As the protective group Pro for the hydrophilic group HP,
A protecting group for a droxyl group, for example, an alkoxyalkyl group
(For example, 1-methoxyethyl group, 1-ethoxypropyl
C or a 1-methoxy-isopropyl group_1-6Al
Koxy-C_1-6An alkyl group, preferably C_1-4Alkoxy
-C_1-4Acetal protecting groups such as alkyl groups);
Kill carbonyl groups (acetyl, propionyl, isopro
Pionyl, butyryl, t-butylcarbonyl group, isobaric
C such as relyl group_1-6Alkyl-carbonyl group, preferred
Kuha C_1-4Alkyl-carbonyl group), cycloalkyl
Carbonyl group (C such as cyclohexylcarbonyl group
_5-8A cycloalkyl-carbonyl group, preferably C_5-6Shi
Chloroalkyl-carbonyl group), arylcarbonyl group
(C such as benzoyl group_6-10Aryl-carbonyl group
Acyl groups such as methoxycarbonyl, ethoxyca
Rubonyl, t-butoxycarbonyl (t-BOC) group
Which C_1-6An alkoxy-carbonyl group (e.g., C_1-4A
Benzyloxycarbonyl); benzyloxycarbonyl
Aralkyloxycarbonyl groups such as C
_6-10Aryl-C_1-4Alkyloxy-carbonyl
C) such as cyclohexyl group_5-8Cycloalkyl group
(For example, C_5-6Cycloalkyl group); 2,4-dinit
Aryl groups such as rophenyl group (for example, nitro group substitution
Phenyl group); benzyl group, 2,6-dichlorobenzyl
Group, 2-nitrobenzyl group, triphenylmethyl group, etc.
Aralkyl group (for example, optionally substituted C
_6-10Aryl-C _1-4Acetal group)
(Dimethoxy, diethoxy, 1-methoxy-1-butoki)
Di-C_1-6Alkoxy group); tetrahydrofura
Oxacycloa such as nil group and tetrahydropyranyl group
Alkyl group (for example, a 5- to 8-membered oxacycloalkyl
Group); norbornyl group, adamantyl group, hydrogenated naphthyl
Groups such as cross-linked alicyclic hydrocarbon groups (for example,
And the like).

Further, as the protecting group for the carboxyl group,
For example, a C _1-6 alkyl group (eg, a C _1-4 alkyl group) such as a methyl, ethyl, or t-butyl group; carbamoyl group (preferably a C _1-4 alkyl - - carbamoyl) methylcarbamoyl, C _1-6 alkyl, such as ethylcarbamoyl group; group C _6-10 arylcarbamoyl group such as phenylcarbamoyl group); norbornyl group, an adamantyl group A cross-linked cyclic alicyclic hydrocarbon group such as a hydrogenated naphthyl group (for example, a bi-tetracycloalkyl group, etc.); a di-C _1-4 alkylphosphinothioyl group such as a dimethylphosphinothioyl group;
And di-C _6-10 arylphosphinothioyl groups such as diphenylphosphinothioyl groups.

In particular, the protecting group Pro is preferably a hydrophobic protecting group that imparts hydrophobicity to the hydrophilic group HP. For example, as a protecting group for a hydroxyl group, an acyl group (particularly a C _1-4 alkyl-carbonyl group such as a t-butylcarbonyl group), an alkoxycarbonyl group (a C-alkyl group such as a t-BOC group) may be used.
_1-4 alkoxycarbonyl group), 5- or 6-membered oxacycloalkyl group (tetrahydropyranyl group, etc.), bi- or tricycloalkyl group (norbornyl group, adamantyl group, etc.), C _1-4 alkoxy-C _1-4 alkyl And the like. Examples of the carboxyl-protecting group include an alkyl group (C _1-4 alkyl group such as t-butyl group), a carbamoyl group which may have a substituent; Cyclic alicyclic hydrocarbon group (for example, bi-tetracycloalkyl group, etc.)
Is preferred.

In each of the above reactions, a conventional catalyst or solvent may be used if necessary. Examples of the catalyst include an acid (an inorganic acid such as hydrochloric acid and sulfuric acid; an organic acid such as p-toluenesulfonic acid), a base (an organic amine such as a tertiary amine), and a conventional acetal, depending on the type of the reaction. Catalysts (e.g., hydrogen chloride, manganese dioxide, sulfuric acid) and addition reaction catalysts (e.g., transition metal catalysts such as a palladium catalyst) can be used. Examples of the solvent include water, alcohols, glycols, cellosolves, ketones, esters, ethers, amides, hydrocarbons, halogenated hydrocarbons,
Organic solvents such as carbitols and glycol ether esters (such as cellosolve acetate and propylene glycol monomethyl ether acetate) can be used. In the case of using a component having an isocyanate group, for example, under the condition that the activity of the isocyanate group can be maintained (in the absence of water or in the presence of water that does not substantially adversely affect the activity of the isocyanate group, In particular, it is preferable to carry out the reaction in a non-hydrous system.

In the formula (1), preferred combinations of groups include the following combinations: X: C _1-4 alkoxy group, halogen atom (particularly C _1-2 alkoxy group) Z: Due to light irradiation A hydroxyl group or a carboxyl group protected by a hydrophobic protecting group which can be removed, M: a metal atom selected from the group consisting of aluminum, titanium, zirconium and silicon; (U ₁ ) _p- (U ₂ -Z) _t : a unit represented by the above formula (3), n = 1 or 2 p = 0 or 1 (q + r = 0 to 2) t = 1 or 2 (u + v = 1 to 2).

(Polycondensate of Active Metal Alkoxide or Active Particle (1b)) The active ingredient (especially active particle) of the present invention may be composed of the polycondensate of the active metal alkoxide.
Such active ingredients may be active particles in particulate form, oligomers in liquid or solid form. The active ingredient is obtained by polycondensing the active metal alkoxide with the conventional active metal alkoxide by a conventional sol-gel method to form a polymer or sol.

More specifically, it can be produced by dissolving a metal alkoxide component containing at least an active metal alkoxide in an organic solvent, adding water, and then stirring in the presence of a polymerization catalyst. Examples of the organic solvent include hydrophilic or water-soluble solvents, for example, alcohols (eg, methanol, ethanol, isopropanol), ketones (eg, acetone), esters (ethyl acetate; lactic acid esters such as ethyl lactate); propylene glycol methyl ether acetate (Poly) oxyalkylene glycol alkyl ether acetates (eg, PGMEA), and cellosolves (eg, methyl cellosolve, ethyl cellosolve, butyl cellosolve) can be used. These solvents may be the same as the solvent of the resist solution (ethyl lactate, PGMEA, etc.).

The ratio of water is about 0.1 to 10 mmol, preferably about 0.2 to 5 mmol, and more preferably about 0.5 to 2 mmol, per 1 mol of the metal atom of the metal alkoxide component.

As the polymerization catalyst, acids (inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like; organic acids such as acetic acid and the like) or bases (inorganic base such as ammonia and organic base such as amines and the like) can be used. . The ratio of the catalyst is 0.001 to 0.
It is about 1 mmol, preferably about 0.005 to 0.05 mmol.

The polymerization temperature is from 0 to 40 ° C. (for example, from 10 to 40 ° C.).
35 ° C.), preferably room temperature (about 15 to 30 ° C.). The polymerization pressure is not particularly limited, and may be normal pressure, increased pressure or reduced pressure, but is usually normal pressure.
The polymerization time is not particularly limited and can be selected from a wide range of 5 minutes to 1 day, preferably about 10 minutes to 12 hours, and preferably about 30 minutes to 10 hours.

The metal alkoxide component may contain a metal alkoxide represented by the following formula (5) in addition to the active metal alkoxide. That is, the active metal alkoxide may be co-condensed with the metal alkoxide (5).

(X) _mn-1 M ^m (R ⁵ ) _n-1 (5) wherein R ⁵ represents a hydrogen atom or an alkyl group.
In the formula (5), examples of the alkyl group represented by R ⁵ include the same alkyl groups as described above, and a methyl group or an ethyl group is particularly preferable. X is usually a halogen atom or an alkoxy group.

In the case of co-condensing with the metal alkoxide (5), the ratio (weight ratio) of the active metal alkoxide (1) to the metal alkoxide (5) is as follows: component (1) / component (5)
= 5/90 to 90/10 (for example, 10/90 to 90 /
10) can be selected from the range of about 10), usually 5 / 90-80
/ 20 (5 / 95-60 / 40), preferably 10/9
0/50/50, more preferably 20 / 80-40 /
It is about 60.

The average particle size of the particulate active ingredient (active particles) can be adjusted by the degree of polymerization and the like in accordance with the degree of fineness of the pattern.
Average particle size 1 to 500 nm (for example, 1 to 100
nm), and more preferably from about 1 to 50 nm. The average particle size of the preferred active particles is usually 2 to 3
0 nm, preferably 3 to 25 nm (for example, 5 to 25 n
m). In particular, when the average particle diameter of the active particles is reduced, the photosensitive layer can be made thinner, so that the resolution can be improved and the edge roughness can be reduced. Further, when the average particle diameter of the active particles is smaller than the exposure wavelength, since it is substantially transparent to the exposure wavelength, it can be exposed to the deep portion of the photosensitive layer even if the film is thickened, and the sensitivity and resolution can be improved, A high-resolution pattern can be formed with high sensitivity even to a light source having a shorter wavelength.

[Active Particle (2) Having Fine Particle Carrier] The particles represented by the formula (2) are bonded directly or indirectly to the fine particle carrier and have a difference in solubility due to light irradiation. (Particularly, a unit that can be hydrophilized by elimination of a protective group due to light irradiation). In the above-mentioned unit, the protecting group is usually detachable in association with the photosensitive agent by light irradiation.

In the formula (2), examples of the connecting unit represented by U ₁ and U ₂ and the group represented by Z include the connecting unit, the group Z and the coefficient exemplified in the above-mentioned formula (1). , Coefficients p and t are the same as described above.

The active particles are particles in which s and p in the above formula (2) are such that s = p = 0 (for example, particles in which a hydrophilic group of a fine particle carrier such as organic fine particles is protected by a protective group). And particles in which at least one of s and p is 1. In the formula (2), k is a value that depends on the concentration of the reactive group (for example, a hydrophilic group) of the carrier or the amount of the group Z introduced by the coupling agent. In addition, the coupling agent is usually represented by the formula (1)
Corresponds to a compound having a metal atom M.

More specifically, a case where the group Z is a hydrophilic group HP protected by a protecting group Pro will be described. For example, in the case of the carrier P having a reactive group, (a) when the reactive group is a hydrophilic group, the hydrophilic group may be protected with a protecting group (s = p = 0), and (b) ) When the reactive group is not a hydrophilic group, the linking unit U ₁ and / or U ₂
And the hydrophilic group HP may be introduced with the protecting group Pro (s = 0, p = 1 and / or t = 1). When the carrier P is a fine particle such as an inorganic fine particle, a reactive group is introduced using a coupling agent,
(C) When the reactive group is a hydrophilic group HP, the hydrophilic group HP may be protected with a protecting group Pro (s =
1, t = 0), ( d) if the introduced reactive groups are not hydrophilic group through a coupling unit U ₁ by introducing a hydrophilic group HP, the protecting group Pro this hydrophilic group HP (S = 1, p = 1, t = 1). In the present specification, sometimes referred to as unit -U ₂ -HP- and hydrophilic units.

Various reactions can be used for each of the components, ie, the fine particle carrier P, the coupling agent Y, and the connecting units U ₁ and U _{2. Contains the} unit (X) _mn
M ^m and (X) _mn M ^m - a compound having the (R ¹⁾ _q, group Z
Or a unit U ₂ -Z or ｛(R ² ) _u −
A method that can be used for the reaction with a compound having (Ar) _v ｝ -Z, for example, the (i) ester bond (or thioester bond) formation reaction, or the urethane bond (or thiourethane bond) formation reaction, (ii) An ester bond (or thioester bond) forming reaction, an amide bond forming reaction, or a ring opening reaction, (iii) an amide bond (or imino bond) forming reaction, a reaction between an amino group and an epoxy group (such as an imino bond forming reaction), or Urea bond formation reaction, (iv) addition reaction and (v)
A coupling reaction such as a Hech reaction can be exemplified.

Hereinafter, a case where a hydrophilic group is introduced into inorganic fine particles via a coupling agent and a connecting unit will be described as an example. For example, a coupling unit U having two hydroxyl groups (such as a dihydroxy compound such as resorcin) and a coupling agent Y having an isocyanate group
(Silane coupling agent) to form a compound in which the coupling agent is bonded to one hydroxyl group of the unit and has a free hydroxyl group and a coupling group (alkoxy group or halogen atom), Each component may be bound by protecting the free hydroxyl group with a protecting group such as a t-BOC group and then reacting the inorganic fine particle carrier (such as silica sol) with a coupling group (alkoxy group or halogen atom). . Further, for example, the hydroxyl group of a compound having a halogen atom (such as an iodine atom or a bromine atom) and a hydroxyl group (such as a halogen-containing aromatic hydroxy compound such as 4-iodophenol) is protected in advance by a protecting group such as a t-BOC group. And
Next, a coupling reaction with a vinyl group-containing silane coupling agent (such as methacryloxypropyltrimethoxysilane) may be performed by a Hech reaction, and the silane coupling agent may be bonded to the inorganic fine particle carrier at an alkoxy group or a halogen atom site of the silane coupling agent. The order of the reaction of each component is not particularly limited. For example, the carrier and the coupling agent may be reacted in advance, and may be reacted with other components. When a component having an isocyanate group is used, for example, under the condition that the activity of the isocyanate group can be maintained (in the absence of water, or in the presence of water that does not substantially adversely affect the activity of the isocyanate group, In particular, it is preferable to carry out the reaction in a non-hydrous system.

In each reaction step, a conventional catalyst or solvent may be used if necessary. Examples of the solvent include water, alcohols, glycols, cellosolves, ketones, esters, ethers, amides, hydrocarbons, halogenated hydrocarbons, carbitols, glycol ether esters (cellosolve acetate, Organic solvents such as propylene glycol monomethyl ether acetate) can be used.

Hereinafter, an active particle in which the group Z is a hydrophilic group HP protected by a protective group Pro will be described as an example of a representative active ingredient represented by the formula (2).

Examples of the hydrophilic group HP include an amino group, an N-substituted amino group (such as an N, N-diC _1-4 alkylamino group)
In addition to the above, examples thereof include water or alkali-soluble groups such as a hydroxyl group, a carboxyl group, and a sulfur-containing derivative group thereof (a mercapto group, a thiocarboxyl group, a dithiocarboxyl group, etc.). And carboxyl groups.

As the fine particle carrier P, organic fine particles [thermoplastic resin which may be cross-linked (cross-linked polystyrene, styrene- (meth) acrylic acid copolymer, styrene-maleic anhydride copolymer, etc. Styrene-based resin; cross-linked (meth) acrylic resin such as cross-linked polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer); silicone resin;
Crosslinkable or cured thermosetting resins such as polyamide resins, crosslinked melamine resins, crosslinked guanamine resins, etc.] can also be used. The fine particle carrier P has a hydroxyl group,
It may have a hydrophilic group such as a carboxyl group, and the concentration of these hydrophilic groups can be adjusted by the amount of the monomer having a hydrophilic group. In order to improve properties such as heat resistance and dry etching resistance, it is advantageous to use inorganic fine particles.

Examples of the inorganic fine particle carrier include simple metals (gold, silver, copper, platinum, aluminum, etc.), inorganic oxides (silica (silica sol such as colloidal silica, aerosil, glass, etc.), alumina, titania, zirconia, Zinc oxide, copper oxide, lead oxide, yttrium oxide, tin oxide, indium oxide, magnesium oxide, etc., inorganic carbonates (calcium carbonate, magnesium carbonate, etc.), inorganic sulfates (barium sulfate, calcium sulfate, etc.), phosphates (Calcium phosphate, magnesium phosphate, etc.) can be used. The inorganic fine particle carrier also includes sols and gels prepared by a sol-gel method or the like. These inorganic fine particle carriers can be used alone or in combination of two or more.

When the fine particle carrier is used, the developing efficiency with the developing solution can be increased, probably because the developer penetrates between the fine particles.

The shape of the fine particle carrier is not limited to a spherical shape, but may be an elliptical shape, a flat shape, a rod shape, or a fibrous shape.

The average particle diameter of the fine particle carrier is, for example, about 1 to 1000 nm, preferably 5 to 500 n, according to the degree of miniaturization of the pattern.
m (for example, 1 to 100 nm), more preferably 1 to 5
0 nm (for example, 5 to 50 nm) can be selected. In particular, when a fine particle carrier having a small average particle diameter is used, the thickness of the photosensitive layer can be reduced, so that the resolution can be improved and the edge roughness can be reduced. Further, when a fine particle carrier having an average particle diameter smaller than the exposure wavelength (for example, silica sol, etc.) is used, since it is substantially transparent to the exposure wavelength, even if the film is thickened, it can be exposed to the deep part of the photosensitive layer. The resolution can be improved, and a high-resolution pattern can be formed with high sensitivity even to a light source having a shorter wavelength. In addition, such a silica sol is commercially available as an organosol (organosilica sol), and for example, can be obtained from Nissan Chemical Industries, Ltd. as "Snowtex Colloidal Silica".

As the coupling agent corresponding to the coupling agent residue Y, for example, as the metal M, an alkaline earth metal, a transition metal, a rare earth metal, or a periodic table 3 to 5
And an organic metal compound containing a Group 13 to 15 metal element, in particular, an element from Groups 4, 13, and 14 of the periodic table, for example, aluminum, titanium, zirconium, and silicon. Among the organometallic compounds, a titanium coupling agent and a silane coupling agent (particularly, a silane coupling agent) are preferable.

The silane coupling agent includes a coupling agent represented by the above formula (4). The reactive group D for the fine particle carrier of the coupling agent (4) is
Usually, halogen atom (bromine, chlorine atom, etc.), OR
⁷ (R ⁷ is C _1-4 alkyl group indicates a) alkoxy group represented by (a methoxy group, C _1-4 alkoxy group such as ethoxy group, particularly C _1-2, etc. alkoxy group) hydrolysis condensable such Group.

Examples of the silane coupling agent include the same coupling agents as described above [eg, isocyanate group-containing silane coupling agent, epoxy group-containing silane coupling agent, amino group-containing silane coupling agent, mercapto group-containing silane coupling agent. Agent, hydroxyl group-containing silane coupling agent and carboxyl group-containing silane coupling agent corresponding to the isocyanate group-containing silane coupling agent, vinyl group-containing coupling agent, allyl group-containing silane coupling agent, (meth) acryloyl group-containing Silane coupling agent, etc.].

Examples of the organic metal compound containing aluminum, titanium, or zirconium as the metal M include an organic metal compound corresponding to the silane coupling agent.

The ratio of the coupling agent to the inorganic fine particle carrier is, for example, 0.1 to 100 parts by weight of the inorganic fine particle carrier.
1 to 200 parts by weight, preferably 0.5 to 150 parts by weight,
More preferably, it can be selected from the range of about 1 to 100 parts by weight.

The linking unit U may be a unit similar to the above [for example, a chain hydrocarbon (eg, a linear or branched C _1-10 alkylene chain such as a C _2-6 alkylene chain), a hydrocarbon ring (a benzene ring). Such as aromatic C _6-12 hydrocarbon ring (for example,
Aromatic C _6-10 hydrocarbon ring), C _5-10 cycloalkane ring,
A C _5-10 cycloalkene ring, a bridged cyclic hydrocarbon ring (such as a bi- or tricycloalkane ring), a plurality of hydrocarbon chains and / or
Or a ring in which a hydrocarbon ring is linked (C _6-14 aryl-C
_4alkyl -C _6-14 aryl, etc.), etc.), heterocyclic (oxygen atom, and heterocyclic containing at least one hetero atom selected from nitrogen atom and sulfur atom) include units] and the like.

The linking unit U may have a substituent as long as the properties of the active ingredient are not impaired. In addition,
When it has a substituent (such as an alkyl group, a cycloalkyl group, or an aryl group), the affinity and compatibility with the base resin are improved, and the active ingredient can be uniformly dispersed in the photosensitive resin composition. It seems that the solubility difference between the exposed part and the unexposed part can be relatively increased.

Compounds having an active hydrogen atom such as a hydroxyl group, a carboxyl group or an amino group, for example, the compound corresponding to the hydrophilizing unit (—U ₂ —HP—), for example, the compound [exemplary in the case where a plurality of hydroxyl groups Compound, a compound having a plurality of carboxyl groups, a compound having a hydroxyl group and a carboxyl group, a compound having a hydroxyl group and an amino group, a compound having a carboxyl group and an amino group, etc.]. The compound may have a reactive halogen atom, such as the compound having a halogen atom exemplified above. Further, the compound may be a compound having an isocyanate group described above.

When such a compound is used, it is easy to control the affinity with the base resin and the solubility in the developer. In these compounds, the hydrophilic group HP (hydroxyl group, carboxyl group, etc.) may be protected in advance by the protective group Pro as described above, and after the introduction of the hydrophilic group HP, the protective group HP It may be protected by Pro. Examples of the protecting group Pro for the hydrophilic group HP include the protecting groups described above.

In particular, a hydrophobic protecting group for imparting hydrophobicity to a hydrophilic group is preferable. For example, as a protecting group for a hydroxyl group, an acyl group (particularly an alkylcarbonyl group such as a t-butylcarbonyl group), an alkoxycarbonyl group (a C _1-6 alkoxycarbonyl group such as a t-BOC group), an acetal group (for example, Di-C _1-6 alkoxy group), 5- or 6-membered oxacycloalkyl group (such as tetrahydropyranyl group), bi- or tricycloalkyl group (such as norbornyl group and adamantyl group), C _1-4 alkoxy-C _1-4 Alkyl groups and the like are preferred. As a protecting group for a carboxyl group, an alkyl group (C-such as t-butyl group) may be used.
_1-4 alkyl groups), a carbamoyl group which may have a substituent, a bi- or tricycloalkyl group (such as a norbornyl group and an adamantyl group) are preferable.

As described above, also in the particles represented by the formula (2), the group Z that produces a difference in solubility is usually a group -HP-
Pro [wherein HP represents a hydrophilic group, and Pro is a protective group that is released due to light irradiation and generates the hydrophilic group HP (particularly, imparts hydrophobicity to the hydrophilic group HP. A protecting group).

In the particles represented by the formula (2), the following combinations can be exemplified as preferred combinations of groups.

P: inorganic fine particles, Y: silane coupling residue, (U ₁ ) _p- (U ₂ -Z) _t : unit represented by the above formula (3), Z: group -HP-Pro (formula In the formula, HP represents a hydrophilic group (particularly, a hydroxyl group or a carboxyl group), and Pro imparts hydrophobicity to the hydrophilic group HP, and desorbs due to irradiation with light to form the hydrophilic group HP. S: 1 p: 0 or 1 t: an integer of 1 or more (particularly 1 or 2).

Particularly preferred particles are a linking unit bonded to inorganic fine particles having an average particle diameter of 1 to 50 nm via a silane coupling agent, a hydrophilic group bonded to the linking unit, and a protective group for protecting the hydrophilic group. And is composed of
The group Z that causes a difference in solubility by light irradiation is composed of the hydrophilic group and the protecting group. Further, the connection unit is usually at least one selected from an aromatic C _6-12 hydrocarbon ring, a monocyclic alicyclic hydrocarbon ring, a bridged cyclic alicyclic hydrocarbon ring and an aliphatic hydrocarbon chain. It consists of
The hydrophilic group is a hydroxyl group or a carboxyl group. Further, the protective group is generally, (i) C _1-4 alkyl - carbonyl group, C _1-4 alkoxy -C _{1 -4} alkyl group,
(Ii) a protecting group for a hydroxyl group selected from a C _1-4 alkoxy-carbonyl group, a 5- or 6-membered oxacycloalkyl group and a bi- or tricycloalkyl group, or
It is a protecting group for a carboxyl group selected from a _1-4 alkyl group, a carbamoyl group, a C _1-4 alkyl-carbamoyl group, a C _6-10 aryl-carbamoyl group and a bi- or tricycloalkyl group.

The particles represented by the formula (2) may be particles obtained by binding the active metal alkoxide to the above-described fine particle carrier. That is, a coupling reaction between the fine particle carrier and the active metal alkoxide represented by the formula (1) was performed using the group X (alkoxy group, halogen atom, etc.) of the active metal alkoxide represented by the formula (1). It may be a particulate active ingredient.

[Active ingredient] The active ingredient (or photoactive ingredient) of the present invention is useful for use in combination with a photosensitive resin composition. The active ingredient, that is, the formula (1)
The active metal alkoxide represented by or a polycondensate thereof (oligomer or active particles) and the active particles represented by the formula (2) can be used alone or in combination of two or more.

When the active ingredient (1) is used in combination with the photosensitizer of the photosensitive resin composition, a difference in solubility is caused by light irradiation due to the group Z of the active metal alkoxide introduced into the active ingredient. Can be. For example, (a) group Z
Is a photosensitive group such as a crosslinkable group, a photoacid generator and a crosslinking agent, when applied to a negative resist in combination with a photosensitizer such as a photopolymerization initiator, crosslinking or polymerization occurs in the exposed portion, the exposed portion Can be suppressed, and a solubility difference is caused between an exposed portion and an unexposed portion.

Further, in the active components (1) and (2), the protecting group can be eliminated by irradiation with light, particularly in association with a photosensitive agent constituting the photosensitive resin composition by irradiation with light.
(B) When the group Z is a hydrophilic group protected by a protecting group which can be removed by light irradiation, the protecting group is protected from light irradiation by using in combination with a photosensitive agent such as a photoacid generator. (Particularly in connection with the photosensitizer by light irradiation), thereby producing a hydrophilic group such as a hydroxyl group or a carboxyl group. Therefore, particularly when applied to a positive resist, a hydrophilic group such as a hydroxyl group or a carboxyl group is generated in an exposed portion to promote dissolution by a developer, and a protecting group (particularly a hydrophobic protecting group) is formed in an unexposed portion. )
, The affinity with the base resin can be increased to suppress dissolution, and the difference in dissolution rate between the exposed part and the unexposed part can be increased. In particular, by using a hydrophobic group as the protective group, even if the particles P of the formula (2) are inorganic fine particle carriers having high hydrophilicity such as silica sol, the solubility in the unexposed portion can be significantly suppressed. At the same time, swelling of the resist due to development can be suppressed, and the resolution can be improved. The elimination of the protecting group often occurs in connection with the photosensitizer, particularly, by the catalytic action of an acid. As such an acid, it is advantageous to use an acid generated upon irradiation with light (particularly an acid generated from a photoacid generator constituting the photosensitive resin composition).

[Photosensitive Resin Composition] The photosensitive resin composition (or resist composition) of the present invention may be composed of a photosensitive agent and the above-mentioned active ingredient. And a photosensitive agent and the active ingredient. The photosensitive resin composition may be developable with an organic solvent (such as alcohols), but is generally preferably developable with water or an alkali. In particular, a positive photosensitive resin composition that can be developed with water or an aqueous alkaline solution is preferable.

As the base resin, a polar group-containing polymer, for example, a hydroxyl group-containing polymer [polyvinyl acetal, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, a hydroxyl group-containing cellulose derivative (such as hydroxyethyl cellulose), a polyvinylphenol-based resin, Novolak resin (phenol novolak resin) or the like], homo- or copolymer containing carboxyl group-containing polymer [polymerizable unsaturated carboxylic acid ((meth) acrylic acid, maleic anhydride, itaconic acid, etc.), carboxyl group-containing cellulose derivative ( Carboxymethylcellulose or a salt thereof, etc.), an ester group-containing polymer [vinyl carboxylate (such as vinyl acetate),
Monomers or copolymers of monomers such as (meth) acrylates (eg, methyl methacrylate) (polyvinyl acetate, ethylene-vinyl acetate copolymer, (meth) acrylic resins, etc.), polyesters, cellulose esters Etc.], a polymer having an ether group [polyalkylene oxide, polyoxyalkylene glycol, polyvinyl ether resin, silicon resin, cellulose ethers and the like], a carbonate group-containing polymer, a polymer having an amide group or a substituted amide group [polyvinyl pyrrolidone, Polyurethane polymer, polyurea, nylon or polyamide polymer (polyamide using lactam component, dicarboxylic acid component or diamine component (nylon 66, nylon 6, modified nylon, starburst dendrimer (DA
Tomalia. Et. Al., Polymer Journal, 17, 117 (1985))
Poly (meth) acrylamide-based polymer; polyamino acid; polymer having a burette bond; polymer having an allohanate bond; proteins such as gelatin; etc.); (Epoxy resin, glycidyl (meth) acrylate homo- or copolymer, etc.), halogen-containing polymer (polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinylidene chloride polymer, chlorinated polypropylene, etc.), polymerization Oligomer or polymer (eg, an oligomer or polymer having a polymerizable group such as a (meth) acryloyl group, an allyl group, a vinyl group, or a cinnamoyl group). These base resins may be used alone or in combination of two or more.

In order to increase the sensitivity to exposure light having a short wavelength, a resin having high transparency to the exposure wavelength (a non-aromatic resin such as an alicyclic resin) is used as the base resin. Is also good. When a non-aromatic photosensitive resin (composition) is used, a shorter wavelength exposure source can be used,
Finer patterns can be formed.

Usually, the polymerizable oligomer or resin constituting the negative resist includes epoxy (meth) acrylate, polyester (meth) acrylate, unsaturated polyester resin, polyurethane (meth) acrylate, polymerizable polyvinyl alcohol polymer ( For example, a reaction product of polyvinyl alcohol and N-methylolacrylamide, etc.) can be exemplified. Non-polymerizable resins constituting the negative resist include polyvinylphenol resins (homopolymers of vinylphenol, copolymers of vinylphenol and other copolymerizable monomers), polyamide polymers, silicone resins Type polymer and the like.
Examples of the copolymerizable monomer include acrylic monomers (C (meth) acrylic acid, methyl methacrylate and the like).
Examples thereof include hydroxy _C2-4 alkyl (meth) acrylates such as _1-4 alkyl (meth) acrylate and hydroxyethyl methacrylate, glycidyl (meth) acrylate, and the like, and styrene monomers such as styrene.

In a negative resist, if necessary,
Polymerizable monomer or oligomer having a photopolymerizable group ((meth) acryloyl group, acrylamide group, vinyl group, etc.) ((meth) acrylic acid or a derivative thereof ((meth) acrylate, (meth) acrylamide, etc.), acetic acid Monofunctional photopolymerizable compounds such as vinyl, styrene and N-vinylpyrrolidone; and polyfunctional photopolymerizable compounds such as polyol (meth) acrylate (such as ethylene glycol di (meth) acrylate). Is also good.

As the photosensitive agent in the negative resist,
Conventional photosensitizers or photosensitizers, for example, azide compounds (such as aromatic azide compounds, especially aromatic diazide compounds),
Photoacid generators (sulfonic acid esters, Lewis acid salts, etc.) and crosslinking agents (melamine derivatives such as methylolmelamine, alkoxymethylmelamine, etc.), pyrylium salts, thiapyrylium salts, photodimerization sensitizers, photopolymerization initiators [ketones (Acetophenone, propiophenone, anthraquinone, thioxanthone, benzophenone or derivatives thereof), benzoin ether or derivatives thereof, acylphosphine oxide, etc.], and a dissolution inhibitor.

Preferred negative resists include a combination of a resin having a phenolic hydroxyl group (such as a novolak resin or a polyvinylphenol resin) with a photoacid generator and a crosslinking agent.

Typical base resins constituting the positive resist include novolak resins (phenol novolak resins, etc.) and hydrophilic groups (hydroxyl groups and / or carboxyl groups, etc.) protected by removable protective groups. Resin [for example, a polyvinylphenol-based resin in which a phenolic hydroxyl group is protected by a removable protecting group (homopolymer of vinylphenol or a copolymer with the above-described copolymerizable monomer), hydroxyl Group and / or carboxyl group-containing (meth) acrylic resin (for example, (meth)
Acrylate homo- or copolymer, or a copolymer of (meth) acrylate and the above-mentioned copolymerizable monomer), a hydroxyl group- and / or carboxyl group-containing cyclic olefin-based resin, etc.].

The preferred base resin is a homo- or copolymer of a monomer which forms a hydrophilic group (alkali-soluble group or a group imparting alkali-solubility) by the catalytic action of an acid (particularly an acid generated from an acid generator). For example, homopolymers or copolymers of vinyl monomers such as polyvinylphenol resins;
A vinyl or (meth) acrylic monomer having a monocyclic alicyclic hydrocarbon group, a vinyl or (meth) acrylic monomer having a crosslinked cyclic hydrocarbon group such as a norbornyl group or an adamantyl group, alone or Copolymers; homo- or copolymers of cyclic olefins (C _5-8 cyclic monoolefins such as cyclopentene, bridged cyclic or terpene-based C _7-12 cyclic olefins such as norbornene and bornene, cyclopentadiene, dicyclo Examples thereof include a homopolymer of a cyclic diene such as pentadiene, or a copolymer with a copolymerizable monomer (a monomer exemplified above other than maleic anhydride). In these polymers, a hydrophilic group such as a hydroxyl group or a carboxyl group is usually partially or entirely protected by a protecting group. The ratio of the protecting group to the hydrophilic group of the base resin may be about 10 to 100 mol%, preferably about 20 to 100 mol%, and more preferably about 30 to 100 mol%.

The resin that forms a hydrophilic group by the deprotection is obtained by polymerizing a monomer in which the hydrophilic group has been protected in advance by a protecting group (such as the protecting group exemplified in the section of the active alkoxide). Alternatively, it may be obtained by polymerizing a monomer having a hydrophilic group, and protecting the hydrophilic group of the obtained resin with the protective group.

Among the monomers having a hydrophilic group, hydr
As the monomer having a loxyl group, one or more
Polymerizable monomer having a loxyl group, for example, cyclic olefin
(Hydroxycyclohexene, hydroxynorbol
Monocyclic or bridged cyclic olefins such as
Phenolic monomers (hydroxystyrene, hydroxy
Hydroxyvinyl (meth)
Acrylate (hydroxyethyl (meth) acrylate
G, hydroxypropyl (meth) acrylate, 2-h
Hydroxy such as droxybutyl (meth) acrylate
C_2-4(Meth) acrylate, etc.); vinyl hydroxy
Vinyl monomer having a monocyclic alicyclic group such as cyclohexane
Monomer, hydroxycyclohexyl (meth) acrylate
Such as hydroxycycloalkyl (meth) acrylate
(Hydroxycyclo C_5-8Alkyl (meth) aclay
H), hydroxyoxacycloalkyl (meth) a
(Meth) acrylates having a monocyclic alicyclic group such as acrylate
Relate; hydroxynorbornyl (meth) acrylate
G, hydroxyadamantyl (meth) acrylate, etc.
(Meth) acrylates having a crosslinked cyclic alicyclic group
Droxybi or Bird C _7-20Cycloalkyl (meth) ac
C) such as hydroxycyclopentene
_5-8Cyclic monoolefins, hydroxynorbornene,
Bridged cyclic or terpene C such as hydroxybornene
_7-12Cyclic olefins, hydroxycyclopentadie
, Cyclic diene such as hydroxydicyclopentadiene
And the like. Having these hydroxyl groups
Monomers can be used alone or in combination of two or more.

Examples of the monomer having a carboxyl group include:
Polymerizable monomers having one or more carboxyl groups or acid anhydride groups, for example, (meth) acrylic acid, maleic acid, fumaric acid, maleic anhydride, itaconic acid, vinylbenzoic acid, carboxycycloalkyl (meth) (Meth) acrylates having a monocyclic alicyclic group such as acrylates (such as carboxycyclo C _5-8 alkyl (meth) acrylate); cross-linked rings such as carboxynorbornyl (meth) acrylate and carboxyadamantyl (meth) acrylate (Meth) acrylates having a formula alicyclic group (carboxybi or tri-C _7-20 cycloalkyl (meth) acrylate; C _5-8 cyclic monoolefins such as carboxycyclopentene; bridging rings such as carboxynorbornene and carboxybornene formula or terpene C _7-12 cyclic olefins, carboxy Black dicyclopentadiene, and cyclic dienes such as carboxymethyl dicyclopentadiene), and the like. Monomers having a carboxyl group can be used alone or in combination of two or more.

These monomers having a hydrophilic group can be used by combining monomers having different hydrophilic groups, for example, a monomer having a hydroxyl group and a monomer having a carboxyl group. Is also good. Further, a monomer having a hydrophilic group may be used in combination with a copolymerizable monomer.

Examples of the copolymerizable monomer include alkyl (meth) acrylate; glycidyl (meth) acrylate;
Styrene monomers such as styrene; cycloalkyl (meth) acrylate, oxacycloalkyl (meth) acrylate having a monocyclic alicyclic group (meth) acrylate; norbornyl (meth) acrylate, adamantyl (meth) acrylate and the like (Meth) acrylates having a crosslinked cyclic alicyclic group and the like can be mentioned. These copolymerizable monomers can be used alone or in combination of two or more. In the copolymer with the copolymerizable monomer, the ratio of the monomer having a hydrophilic group is 1 to the total amount of the monomer.
It is about 0 to 100% by weight, preferably about 25 to 80% by weight, and more preferably about 30 to 70% by weight.

In the resin that forms a hydrophilic group by the deprotection, the protective group for the hydrophilic group may be a protective group exemplified in the section of the active metal alkoxide, for example, an alkoxyalkyl group, an alkoxycarbonyl group, a cycloalkyl group. And a protecting group for a hydroxyl group such as an oxacycloalkyl group and a bridged cyclic alicyclic group; and a protecting group for a carboxyl group such as an alkyl group.

Typical resins include, for example, resins in which a hydroxyl group is protected by a protective group such as an alkoxyalkyl group, an alkoxycarbonyl group (such as a t-BOC group), or an acetal group (eg, vinylphenols, hydroxycycloalkyl Homo- or copolymers of hydroxyl group-containing alicyclic (meth) acrylates such as (meth) acrylate, hydroxynorbornyl (meth) acrylate and hydroxyadamantyl (meth) acrylate, and cyclic olefins such as hydroxynorbornene and hydroxydicyclopentadiene A hydroxyl group protected by an alicyclic group such as a cycloalkyl group (including a bi- or tricycloalkyl group such as an oxacycloalkyl group, a norbornyl group, and an adamantyl group); (Meta) acri (Meth) acrylic resin in which a carboxyl group is protected by a protective group such as an alkyl group (t-butyl group) ((meth) acrylic) Homo- or copolymers of unsaturated carboxylic acids such as acids and maleic anhydrides or their anhydrides, and carboxyl group-containing alicyclic (meth) acrylates such as carboxynorbornyl (meth) acrylate and carboxyadamantyl (meth) acrylate Or a cyclic olefin such as carboxynorbornene, carboxydicyclopentadiene, or the like).

Preferred positive resists include a phenol novolak resin and a photosensitizer (quinonediazides (diazobensoquinone derivatives, diazonaphthoquinone derivatives, etc.)).
), And a combination of a resin that generates a hydrophilic group by deprotection (particularly, deprotection by the catalytic action of an acid generated from an acid generator) and a photosensitive agent (photoacid generator).

Further, the base resin has various functional groups such as a hydroxyl group, an alkoxy group, a carboxyl group, an acid anhydride group, an alkoxycarbonyl group, an acyl group, an amino group and the like in addition to the hydrophilic group. It may be.

In the positive resist, a conventional photosensitizer or photosensitizer such as diazonium salts (diazonium salts, tetrazonium salts, polyazonium salts), quinonediazides (diazobenzoquinone derivatives, diazonaphthoquinone derivatives, etc.) can be used. ), Photoacid generator,
A dissolution inhibitor or the like can be selected.

Examples of the photoacid generator include the following compounds. For reference, the product name manufactured by Midori Kagaku Co., Ltd. is described in parentheses. Sulfonium salt derivatives [sulfonic acid esters, for example, arylalkanesulfonates such as 1,2,3-tri (methylsulfonyloxy) benzene (especially C _6-10 aryl C _1-2 alkanesulfonates); 2,6-dinitrobenzyltoluene Arylbenzene phosphonates such as sulfonate and benzoin tosylate (particularly C _6-10 aryl toluene phosphonate _optionally having a benzoyl group); aralkylbenzene sulfonates such as 2-benzoyl-2-hydroxy-2-phenylethyltoluene sulfonate (Especially C _6-10 aryl-C _1-4 alkyltoluenesulfonate optionally having a benzoyl group); disulfones such as diphenyldisulfone; Lewis acid salt (triphenylsulfonium hexafluorophosphate (TP
S-102), triphenylsulfonium hexafluoroantimony (TPS-103), 4- (phenylthio) phenyldiphenylsulfonium hexafluoroantimony (DTS-103), 4-methoxyphenyldiphenylsulfonium hexafluoroantimony (MDS-103), tri Phenylsulfonium methanesulfonyl, triphenylsulfonium trifluoromethanesulfonyl (TPS-105), triphenylsulfonium nonafluorobutanesulfonyl (TPS-105)
109), etc.], phosphonium salt derivatives, diarylhalonium salt derivatives [diaryliodonium salts (diphenyliodonium hexafluorophosphate, 4,4′-di (t-butyl) Phenyl) iodonium hexafluorophosphate (BB
I-102), 4,4'-di (t-butylphenyl) iodonium hexafluoroantimonate (BBI-
103), 4,4′-di (t-butylphenyl) iodonium tetrafluoroborate (BBI-101),
4,4′-di (t-butylphenyl) iodonium trifluoromethanesulfonate (BBI-105),
4,4'-di (t-butylphenyl) iodonium camphorsulfonate (BBI-106), diphenyliodonium trifluoromethanesulfonate (DPI-
105), 4-methoxyphenylphenyliodonium trifluoromethanesulfonate (DPI-105)
And diazonium salt derivatives (such as Lewis acid salts such as p-nitrophenyldiazonium hexafluorophosphate), diazomethane derivatives, triazine derivatives [1-methoxy-4- (3,5-
Di (trichloromethyl) triazinyl) benzene (TA
Z-104), 1-methoxy-4- (3,5-di (trichloromethyl) triazinyl) naphthalene (TAZ-1
06), haloalkyltriazinylaryl, 1-
Methoxy-4- [2- (3,5-ditrichloromethyltriazinyl) ethenyl] benzene (TAZ-110),
1,2-dimethoxy-4- [2- (3,5-ditrichloromethyltriazinyl) ethenyl] benzene (TAZ-
113), 1-methoxy-2- [2- (3,5-ditrichloromethyltriazinyl) ethenyl] benzene (TA
Z-118), etc.], imidylsulfonate derivatives [succinimidyl camphorsulfonate (SI-10)
6), succinimidyl phenylsulfonate (SI
-100), succinimidyl toluyl sulfonate (SI-101), succinimidyl trifluoromethyl sulfonate (SI-105), phthalimidyl
Trifluorosulfonate (PI-105), naphthalimidyl camphorsulfonate (NAI-106),
Naphthalimidyl methanesulfonate (NAI-10
0), naphthalimidyl trifluoromethanesulfonate (NAI-105), naphthalimidyl toluylsulfonate (NAI-101), norborneneimidyl trifluoromethanesulfonate (NDI-10)
5) etc.]. Further, sulfone derivatives [for example, trade names “DAM-101”, “DAM-10”
-S such as "2", "DAM-105" and "DAM-201"
Compound having O ₂ —C (＝ N) -unit; “DSM-3
A compound having a —CH ₂ —SO ₂ — unit, such as “01”;
= N-O-SO _2, such as "PAI-101" - such as a compound having a unit] Also included. In particular, Lewis acid salts (Lewis acid salts such as phosphonium salts) are preferred.

In the negative and positive resists, the amount of the photosensitive agent used is, for example, 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the base resin. It can be selected from the range of about parts by weight (particularly 1 to 10 parts by weight).

The photosensitive resin (composition) can be selected according to the exposure wavelength. For example, when a KrF excimer laser (248 nm) is used as an exposure source, a vinyl resin (having a hydroxyl group protected by a leaving group). And acryl-based polymers (such as (meth) acrylic homo- or copolymers in which the carboxyl group is protected with a leaving group) and photosensitizers (such as acid generators and dissolution inhibitors). Can be used.

ArF excimer laser (193 nm)
When is used as an exposure source, for example, a (meth) acrylic resin (where the carboxyl group is protected by a protecting group (leaving group) such as a t-butyl group or an alicyclic hydrocarbon group (such as an adamantyl group)) is used. (Meth) acrylic homo- or copolymers containing aliphatic groups) or resins (homo- or copolymers) containing alicyclic hydrocarbons such as norbornene in the main chain, photosensitizers (acid generators), A chemically amplified positive photosensitive resin composition containing an inhibitor or the like can be used.

Also, an F ₂ excimer laser (157 n
When m) is used as an exposure source, a polymer having a carbon-fluorine bond or a silicon-oxygen bond, or a homo- or copolymer of a phenolic monomer, a photosensitizer (acid generator), a dissolution inhibitor, etc. Chemical-amplification-type positive photosensitive resin compositions can be used.

In the photosensitive resin composition of the present invention, the proportion of the active ingredient can be selected from a range that does not impair the film-forming property, sensitivity, pattern resolution, etc., for example, from a wide range of about 0.01 to 1000 parts by weight. Usually, in terms of solid content, based on 100 parts by weight of the base resin, 5 to 1000 parts by weight, preferably 10 to 500 parts by weight, more preferably 10 to 500 parts by weight.
It is about 300 parts by weight, especially about 10 to 100 parts by weight.

If necessary, the photosensitive resin composition may contain a stabilizer such as an antioxidant, a plasticizer, a surfactant, a dissolution promoter,
Various additives such as coloring agents such as dyes and pigments may be added. Further, the photosensitive resin composition may contain a solvent (eg, the solvent exemplified in the section of the active metal alkoxide) in order to improve workability such as applicability.

The photosensitive resin composition of the present invention can be prepared by a conventional method, for example, a photosensitive resin [a photosensitive resin composition composed of a base resin (polymer or oligomer) and a photosensitive agent].
And an active ingredient. The photosensitive resin composition generally contains a solvent [solvent (eg, a hydrophilic or water-soluble solvent) exemplified in the section of the active alkoxide, for example, lactate such as ethyl lactate; ethylene glycol alkyl ether acetate, propylene glycol methyl ether acetate; (Eg, PGMEA); alkylene glycol alkyl ether acetate; (poly) oxyalkylene glycol alkyl ether acetate).

[Photosensitive Layer] A photosensitive layer can be formed by applying (coating or coating) the photosensitive resin composition to a substrate. The substrate can be appropriately selected from metals (aluminum), glass, ceramics (alumina, copper-doped alumina, tungsten silicate, etc.), plastics, etc., depending on the characteristics and use of the pattern, and is a semiconductor substrate such as a silicon wafer. Is also good.

The substrate may be subjected to a surface treatment in advance in order to improve the adhesion to the photosensitive layer depending on the application. The surface treatment includes, for example, a surface treatment with the silane coupling agent (such as a hydrolyzable polymerizable silane coupling agent having a polymerizable group), an anchor coat agent or a base material (polyvinyl acetal, an acrylic resin, or a vinyl acetate-based agent). Resin, epoxy resin, urethane resin, etc.), or a coating treatment with a mixture of these base materials and inorganic fine particles.

After applying the photosensitive resin composition to the substrate, the solvent may be evaporated by drying. The solvent may be removed by soft baking (pre-baking) using a heating means such as a hot plate, for example.

The photosensitive layer made of the photosensitive resin composition of the present invention is preferably formed on at least the surface of the resist layer because it can improve plasma resistance (oxygen plasma resistance), heat resistance, dry etching resistance and the like. The structure of the photosensitive layer can be selected according to a pattern forming process, a circuit structure, and the like, and may be a single layer structure or a multilayer structure (or a laminated or composite structure). For example, a photosensitive layer having a single-layer structure can be used for a single-layer process of forming a pattern by forming a single-layer photosensitive layer on a substrate, and is particularly suitable for forming a pattern by dry etching. Since the photosensitive layer having a multilayer structure (or a composite structure) can greatly improve oxygen plasma resistance, it is advantageous to increase the resolution even when the exposure wavelength is near the resolution limit of lithography. For example, a photosensitive layer having a two-layer structure
A base resist layer (not necessarily photosensitive) is formed on a substrate, a photosensitive layer is formed on the base resist layer, exposed, patterned by development, and subjected to plasma treatment (such as oxygen plasma). It can be used for a two-layer process in which a resist layer is etched to form a pattern. A three-layered photosensitive layer is formed by sequentially forming a base layer, an intermediate layer, and a photosensitive layer on a substrate, exposing the resist, and patterning by developing. It can be used for a multilayer process for etching an intermediate layer and an underlayer. The underlayer and the intermediate layer may be made of a composition composed of a photosensitive resin (a photosensitive resin composition composed of a base resin and a photosensitive agent) and inorganic fine particles, or a photosensitive resin containing no inorganic fine particles (base resin). And a photosensitive resin composition comprising a photosensitive agent).

The thickness of the photosensitive layer is not particularly limited.
It can be selected from a range of about 0.01 to 10 μm, preferably about 0.05 to 5 μm, preferably about 0.08 to 2 μm, and is usually 0.09 to 1 μm (for example, 0.1 to 0.7 μm).
It is about.

The photosensitive layer can be formed by a conventional coating method,
For example, it can be performed by a spin coating method, a dipping method, a casting method, or the like. If necessary, the photosensitive layer can be formed by drying and removing the solvent.

[Pattern Forming Method] A pattern (particularly a fine pattern) can be formed by using a conventional lithography technique combining exposure, development, etching and the like.

For example, a pattern can be formed by applying the photosensitive resin composition to a substrate to form a photosensitive layer, exposing, and developing. In particular, when a chemically amplified photosensitive resin is used, it is preferable to perform a heat treatment (post-exposure bake (post-exposure bake, PEB)) after the exposure in order to efficiently diffuse the acid generated by the exposure. After patterning by development, etching may be performed by plasma processing (eg, oxygen plasma).

The exposure of the photosensitive layer can be carried out by a conventional method, for example, by irradiating a light beam with a pattern through a predetermined mask or exposing the light beam. As the light beam, various light beams (for example, a wavelength of 50 to 50) are used depending on the photosensitive characteristics of the photosensitive resin composition, the fineness of the pattern, the type of the base resin, and the like.
Light of 450 nm, especially about 100 to 450 nm), for example, light of a halogen lamp, high pressure mercury lamp, UV lamp, etc .; excimer laser (for example, XeCl (308)
nm), KrF (248 nm), KrCl (222n
m), ArF (193 nm), ArCl (172n)
m), F2 (157 nm), electron beam (g-line (43
6 nm), i-rays (365 nm) and the like, X-rays, EB rays and the like, and may be a single wavelength or a composite wavelength. In particular, KrF (248 nm), A
Excimer lasers such as rF (193 nm) and F ₂ (157 nm) can be advantageously used. Also, by using a resist composed of a non-aromatic base resin,
It is transparent to short-wavelength light and can improve sensitivity. For example, a KrF excimer laser (248
nm) as an exposure source, a chemically amplified photosensitive resin composition, for example, a resin that forms a hydrophilic group by deprotection [polyvinyl phenol resin or a carboxyl resin in which a hydroxyl group is protected by a protecting group] A (meth) acrylic resin whose group is protected with a protecting group) and a photosensitive agent (acid generator), or a resin that forms a hydrophilic group by the deprotection. A negative photosensitive resin composition composed of an acid generator and a crosslinking agent can be used.

The exposure energy can be selected according to the photosensitive properties (solubility, etc.) of the photosensitive resin composition, and the exposure time is generally 0.005 seconds to 10 minutes, preferably 0.1 to 10 minutes.
It can be selected from the range of about 01 second to 1 minute.

After the exposure, heat treatment may be performed if necessary. In particular, in the chemically amplified photosensitive composition, the heat treatment (P
EB) is advantageous. Heating (pre-bake and PE
The temperature of B) is 50 to 150 ° C, preferably 60 to 15 ° C.
The heating temperature is 0 ° C, more preferably about 70 to 150 ° C, and the heating time is about 30 seconds to 5 minutes, preferably about 1 to 2 minutes.

After pattern exposure, a high-resolution pattern can be formed by developing with a conventional method. Various developers (water, aqueous alkaline solution, etc.) can be used for development depending on the type of the photosensitive resin composition. A preferred developer is water or an alkaline developer, and if necessary, a small amount of an organic solvent (eg, alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone; ethers such as dioxane and tetrahydrofuran; cellosolves). , A hydrophilic or water-soluble solvent such as cellosolve acetate) or a surfactant. The developing method is not particularly limited, and for example, a paddle (meniscus) method, a dip method, a spray method, and the like can be adopted.

The coating film (photosensitive layer) is heated or cured at an appropriate temperature in an appropriate step from the application of the photosensitive resin composition to the development, not limited to the prebaking and PEB. Is also good. For example, after development
Heat treatment may be performed if necessary.

In the present invention, the active component is introduced into a photosensitive resin (a photosensitive resin composition composed of a base resin and a photosensitive agent) by introducing a group that causes a difference in solubility due to light irradiation into the active component. To form a photosensitive layer in combination with
A solubility difference can be caused between an exposed portion and an unexposed portion. In particular, when the group causing the difference in solubility is a hydrophilic group protected by a protective group, the formed photosensitive layer is protected (particularly, hydrophobicized) and the surface is rendered hydrophobic, so that the positive type is particularly preferred. In the above, the hydrophobic state can be maintained in the unexposed area, and the protective group is deprotected in the exposed area, and the dissolution is promoted. Therefore, the difference in the dissolution rate between the unexposed portion and the exposed portion can be increased. Further, the edge roughness can be improved, and a sharp pattern can be obtained in the plane shape and / or the cross-sectional shape of the edge.

The cause of the edge roughness is as follows.
Although various hypotheses have been proposed, the non-uniformity of the resist composition at the pattern edge portion, the association between a hydrophobic polymer (a polymer before deprotection in the case of a positive chemically amplified resist) and a hydrophilic polymer ( Aggregation) and uneven dispersion of the photoacid generator in the resist are said to be one of the causes.

The present invention can be applied to various uses such as circuit forming materials (resist for semiconductor production, printed wiring boards, etc.),
It can be used for image forming materials (printing plate materials, relief images, etc.). In particular, since high sensitivity and resolution can be obtained, it can be advantageously used for a resist for semiconductor production.

[0151]

According to the present invention, the active component is introduced into a photosensitive resin (a photosensitive resin composition comprising a base resin and a photosensitive agent) by introducing a group that causes a difference in solubility due to light irradiation into the active component. ), The difference in solubility between exposed and unexposed portions can be increased, and a high-sensitivity, high-resolution pattern can be formed. In particular, when the active component is composed of a specific active metal alkoxide or a polycondensate thereof, contamination of impurities can be effectively suppressed. Furthermore, the photosensitive resin composition of the present invention can improve the edge roughness of a pattern while maintaining etching resistance to oxygen plasma, and has high sensitivity even to a light source having a shorter wavelength, and has a high pattern sensitivity. Resolution can be greatly improved.

[0152]

The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples.

Examples 1 and 2 and Comparative Example 1 1. Preparation of Photosensitive Resin Composition (1) Preparation of Photosensitive Resin 37 mol% of the hydroxyl groups was t-BOC (tert-
1 part by weight of a polyvinylphenol resin having a weight average molecular weight of 8,500 substituted with a butoxycarbonyloxy) group,
A positive photoresist was prepared by adding 0.02 parts by weight of a photoacid generator represented by the following formula (A) and mixing 6 parts by weight of propylene glycol monomethyl ether acetate as a solvent.

[0154]

Embedded image

(2) Active ingredient (silica sol) (i) Synthesis of 1- (t-butoxycarbonyloxy) -4-iodobenzene In 1250 mL of acetone, p-iodophenol 12 was added.
5.0 g (568 mmol) and 69 mg (5.7 mmol) of N, N-dimethylaminopyridine were dissolved, and 124 g (568 mmol) of di-t-butyl carbonate was added dropwise at 40 ° C. while stirring the resulting solution. . After completion of the dropwise addition, the mixture was stirred overnight and reacted. After completion of the reaction, the obtained solution was poured into 5 L of ice water. The resulting precipitate is collected by suction filtration, dried, and recrystallized from methanol to give 1- (t-butoxycarbonyloxy) -4.
-113 g of iodobenzene were obtained.

(Ii) 1- [2-{(3-trimethoxysilyl) propyloxycarbonyl} vinyl] -4- (t
Synthesis of 1- (t-butoxycarbonyloxy) -4-iodobenzene 55.0 synthesized in step (i) above in a mixture of 1 L of triethylamine and 200 mL of acetonitrile.
g and acrylic acid 3-trimethoxysilylpropyl ester (42.5 g) were dissolved, and argon was bubbled through the liquid phase to replace the inside of the reaction system with argon. 770.0 mg of palladium acetate as a catalyst was added to the reaction system, and the mixture was refluxed overnight (Hech reaction). After completion of the reaction, the solvent was removed, and the product was extracted from the obtained residue with hexane. By removing hexane from the extract, the target compound 3
-(Trimethoxysilyl) propyl p- (t-butoxycarbonyloxy) cinnamate, ie, 1- [2-
{(3-trimethoxysilyl) propyloxycarbonyl} vinyl] -4- (t-butoxycarbonyloxy)
47.5 g of benzene were obtained.

The reaction scheme including the above steps is shown below.

[0158]

Embedded image

The ¹ H-NMR and IR spectra of the obtained compound are shown in FIGS. 1 and 2, respectively.

¹ H-NMR (CDCl ₃ ) ppm: 0.7
_{(T, 2H, CH 2)} , 1.6 (s, 9H, t-B
u), 1.8 (q, 2H, CH ₂ ), 3.6 (s, 9
H, OCH ₃ ), 4.2 (t, 2H, CH ₂ ), 6.4
(D, 1H, C = CH), 7.2 (d, 2H, C
₆ H ₄ ), 7.5 (d, 2H, C ₆ H ₄ ), 7.6 (d, 1
H, C = CH).

Further, in FIG.
In the vicinity of cm ⁻¹ , C ＝ O of an ester group and a carbonate group
Absorption due to stretching vibration was observed. From these results, it is clear that the target compound has been obtained.

(Iii) Synthesis of Silica Sol In a 300 mL reactor, 70 g of propylene glycol monomethyl ether acetate (PGMEA) and 54 g of 20% by weight ammonia water were charged and stirred at 30 ° C. for 20 minutes. To this solution, 1-synthesized in the step (ii) was added.
22.1 g of [2-{(3-trimethoxysilyl) propyloxycarbonyl} vinyl] -4- (t-butoxycarbonyloxy) benzene, tetraethoxysilane
34 g and 2.0 g of triethoxymethylsilane were added dropwise over 1 hour, and the mixture was further stirred at 30 ° C. for 6 hours. Thereafter, the reaction solution was filtered through a membrane filter having an average hole diameter of 0.1 μm, and the filtrate was washed with pure water to remove ammonia, and further dewatered under reduced pressure to remove water. Next, the content of propylene glycol monomethyl ether acetate (PGMEA) was adjusted by addition or removal under reduced pressure to prepare a propylene glycol monomethyl ether acetate (PGMEA) solution of silica sol having a silica sol content of 30% by weight.

(3) Preparation of photosensitive resin composition The ratio of the photosensitive resin obtained in the above step (1) and the active ingredient (silica sol) obtained in the step (2) shown in Table 1 (solid content excluding solvent) ) To prepare a photosensitive resin composition. In addition, the example which does not add an active ingredient (silica sol) was made into the comparative example 1.

[0164] 2. Pattern formation and evaluation of characteristics (sensitivity, resolution, oxygen plasma resistance) (1) Pattern formation After treating a washed silicon wafer with hexamethyldisilazane, the photosensitive resin composition is dried using a spin coater to form a film. Apply so that the thickness is 0.4 μm,
Heated on a hot plate at 100 ° C. for 1 minute. Next, a reduced projection exposure machine (FPA manufactured by Canon Inc.) having an exposure wavelength of 248 nm (KrF excimer laser)
(-3000EX5, NA = 0.63) using a test mask having a line-and-space pattern with a different line width, and exposing the exposure stepwise.
The wafer was heated on a hot plate at 100 ° C. for 1 minute, and then paddle-developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 1 minute to obtain a positive pattern.

(2) Evaluation of Characteristics Each characteristic of the positive pattern was evaluated as follows.

(I) Sensitivity: The exposure amount was such that the line: space = 1: 1 with a line width of 0.25 μm conformed to the mask dimensions (the smaller the value, the higher the sensitivity).

(Ii) Resolution: Displayed with the minimum size at which the lines are separated by the exposure amount at which the line: space = 1: 1 line width: 0.25 μm matches the mask size (the smaller the value, the higher the resolution).

(Iii) Oxygen plasma resistance: The wafer after development is subjected to a plasma etching apparatus (SUPER manufactured by Tokyo Vacuum Co., Ltd.).
Using a COAT N400 type), etching was performed under the following conditions.

Power supply method: Cathode couple Electrode size: 80 mmφ Processing gas: Oxygen pressure: 8.645 Pa rf Applied voltage: 85 W rf Power density: 1.69 W / cm ² Processing time: 5 minutes The film thickness after etching was measured. The thickness of the film lost by the etching was divided by the etching time, and expressed as an oxygen plasma rate (O ₂ -RIE rate, nm / sec).
The smaller this value is, the higher the oxygen plasma resistance is. Table 1 shows the results.

[0170]

[Table 1]

Examples 3 and 4 and Comparative Example 2 1. Preparation of Photosensitive Resin Composition (1) Preparation of Photosensitive Resin 2-Methyladamantyl methacrylate and γ-butyrolactone methacrylate were dissolved in methyl isobutyl ketone at a charge ratio (molar ratio) of 1/1, and azobisisobutyrate was dissolved. 80 ° C. using lonitrile (AIBN) as an initiator
For 10 hours to obtain a resin having a weight average molecular weight of 14,500. As a reprecipitation solvent, n-
Hexane was used. To 1 part by weight of the obtained resin, 0.02 part by weight of a photoacid generator represented by the following formula (B) was added,
A positive photoresist was prepared by mixing 7 parts by weight of propylene glycol monomethyl ether acetate as a solvent.

[0172]

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(2) Active ingredient (silica sol) (i) Synthesis of tert-butyl 3- [3- (trimethoxysilyl) propylthio] propionate 3- (trimethoxysilyl) -1-propanethiol 5
8.8 g (0.3 mol) and 38.4 g (0.3 mol) of tert-butyl acrylate were dissolved in 300 mL of dehydrated ethyl acetate, and this solution was bubbled with argon gas to replace the inside of the reaction system with argon. 2.94 g of dicumyl peroxide (manufactured by NOF CORPORATION, Perbutyl PV) as a radical initiator was added to the reaction solution, and the mixture was added to the mixture.
Heated to reflux for an hour. After the completion of the reaction, the solvent is removed to obtain tert-butyl 3- [3- (trimethoxysilyl) propylthio] propionate 9 which is the target compound.
6.0 g (0.294 mol) were obtained.

The above reaction scheme is shown below.

[0175]

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The ¹ H-NMR and IR spectra of the obtained compound are shown in FIGS. 3 and 4, respectively.

¹ H-NMR: 0.7, 1.6-1.8 and 2.4-2.8 ppm: methylene (CH ₂ ) 1.4 ppm: t-butyl (CH ₃ ) ₃ C 3.6 ppm: Methoxy (OCH ₃ ) _{3 Further} , in FIG. 4, absorption characteristic of a carbonyl group was observed around 1730 to 1740 cm ⁻¹ . From these results, it is clear that the target compound has been obtained.

(Ii) Synthesis of Silica Sol A 300 mL reactor was charged with 70 g of propylene glycol monomethyl ether acetate (PGMEA) and 54 g of 20% by weight aqueous ammonia, and stirred at 30 ° C. for 20 minutes. This solution was added to the tert-synthesized in step (i).
42.0 g of butyl 3- [3- (trimethoxysilyl) propylthio] propionate, 3.1 g of tetraethoxysilane and 2.7 g of triethoxymethylsilane were added dropwise over 1 hour, and the mixture was further stirred at 30 ° C. for 6 hours. Thereafter, the reaction solution was filtered through a membrane filter having an average hole diameter of 0.1 μm, and the filtrate was washed with pure water to remove ammonia, and further dewatered under reduced pressure to remove water. Next, the content of propylene glycol monomethyl ether acetate (PGMEA) was adjusted by addition or removal under reduced pressure to prepare a propylene glycol monomethyl ether acetate (PGMEA) solution of silica sol having a silica sol content of 30% by weight.

(3) Preparation of photosensitive resin composition The ratio of the photosensitive resin obtained in the above step (1) and the active ingredient (silica sol) obtained in the step (2) shown in Table 2 (solid content excluding solvent) ) To prepare a photosensitive resin composition. An example in which the active component (silica sol) was not added was used as a comparative example.

2. Pattern formation and evaluation of characteristics (sensitivity, resolution, oxygen plasma resistance) (1) Pattern formation After treating a washed silicon wafer with hexamethyldisilazane, the photosensitive resin composition is dried using a spin coater to form a film. Apply so that the thickness is 0.3 μm,
The mixture was heated on a hot plate at 130 ° C. for 1 minute. Next, using a reduction projection exposure machine (NA = 0.63) having an exposure wavelength of 193 nm (ArF excimer laser), the exposure amount is adjusted stepwise through a test mask having a line and space pattern having different line widths. The exposure was changed. This wafer is placed on a hot plate at 130 ° C for 1 hour.
After heating for 2 minutes, a positive pattern was obtained by paddle development with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 1 minute.

(2) Evaluation of Characteristics Each characteristic of the positive pattern was evaluated as follows.

(I) Sensitivity: The exposure amount was such that the line: space = 1: 1 with a line width of 0.20 μm conformed to the mask dimensions (the smaller the value, the higher the sensitivity).

(Ii) Resolution: The display was made with the minimum size at which the lines were separated at an exposure amount where the line: space = 1: 1 with a line width of 0.20 μm was equal to the mask size (the smaller the value, the higher the resolution).

(Iii) Oxygen plasma resistance: Evaluated in the same manner as in Example 1.

Table 2 shows the results.

[0186]

[Table 2]

Examples 5 to 8 and Comparative Example 3 1. Preparation of photosensitive resin composition (1) Preparation of photosensitive resin In 200 mL of toluene, 30 g of methacrylic acid-tert-butyl ester and 0.2 g of azobisisobutyronitrile were dissolved. The inside of the reaction vessel was replaced with argon, and the reaction solution was heated and stirred at 60 ° C. for 12 hours to carry out polymerization.
After the polymerization, pour the reaction solution into a large amount of methanol,
The resin was coagulated and the coagulated resin was washed several times with methanol. The resin was dried overnight at room temperature and under reduced pressure to obtain polytert-butyl methacrylate having a weight average molecular weight of 35,000 in a yield of 33%.

To 1 part by weight of the polytert-butyl methacrylate was added 0.02% of the photoacid generator (B) used in Example 3.
The mixture was mixed with 6 parts by weight of propylene glycol monomethyl ether acetate as a solvent to prepare a positive photoresist.

(2) Active Ingredient (Silica Sol) (i) Synthesis of Silica Sol A 300 mL reactor was charged with 70 g of propylene glycol monomethyl ether acetate (PGMEA) and 54 g of 20% by weight aqueous ammonia, and stirred at 30 ° C. for 20 minutes. 26.3 g of tert-butyl 3- [3- (triethoxysilyl) propylthio] propionate synthesized in steps (2) and (ii) of Example 3, 7.8 g of tetraethoxysilane and triethoxymethylsilane 6 were added to this solution. 0.7g
Was added dropwise over 1 hour, and the mixture was further stirred at 30 ° C. for 6 hours. Thereafter, the reaction solution was filtered through a membrane filter having an average hole diameter of 0.1 μm, and the filtrate was washed with pure water to remove ammonia, and further dewatered under reduced pressure to remove water. Next, the content of propylene glycol monomethyl ether acetate (PGMEA) was adjusted by addition or removal under reduced pressure to prepare a propylene glycol monomethyl ether acetate (PGMEA) solution of silica sol having a silica sol content of 30% by weight.

(3) Preparation of Photosensitive Resin Composition The ratio of the photosensitive resin of step (1) and the active ingredient (silica sol) obtained in step (2) shown in Table 3 (solid content excluding solvent) ) To prepare a photosensitive resin composition. In addition, the example which does not add an active ingredient (silica sol) was made into the comparative example 3.

[0191] 2. Pattern formation and evaluation of characteristics (sensitivity, resolution, oxygen plasma resistance) (1) Pattern formation After treating a washed silicon wafer with hexamethyldisilazane, the photosensitive resin composition is dried using a spin coater to form a film. It was applied to a thickness of 0.12 μm and heated on a hot plate at 130 ° C. for 1 minute. Next, an exposure machine having an exposure wavelength of 157 nm (F ₂ excimer laser) (VUV manufactured by Lithotech Japan KK)
(ES-1200), and exposure was performed while changing the exposure amount stepwise. This wafer was heated on a hot plate at 130 ° C. for 1 minute, and then paddle-developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 1 minute to obtain a positive pattern.

(2) Evaluation of Characteristics Each characteristic of the positive pattern was evaluated as follows.

(I) Sensitivity: Expressed as the minimum exposure amount at which the resist was completely dissolved (the smaller the value, the higher the sensitivity).

(Ii) Resolution: The logarithm of the dissolution rate (nm / sec) with respect to the logarithm of the exposure is plotted, the inclination angle θ of the linear part is obtained, and tanθ is defined as a γ value, which is used as an index of resolution (generally, The higher the γ value, the higher the resolution).

(Iii) Oxygen plasma resistance: Evaluated in the same manner as in Example 1.

The results are shown in Table 3.

[0197]

[Table 3]

Examples 9 to 12 and Comparative Example 4 1. Preparation of Photosensitive Resin Composition (1) Photosensitive resin (i) 35 mol% of the hydroxyl groups was t-BOC (ter
To a 1 part by weight of a polyvinylphenol resin having a weight average molecular weight of 8,000 substituted with a (t-butoxycarbonyloxy) group, 0.02 parts by weight of a photoacid generator represented by the following formula (A) is added, and By mixing with 6 parts by weight of propylene glycol monomethyl ether acetate,
A positive photoresist was prepared.

[0199]

Embedded image

(2) Active ingredient (i) (ii) 1- (t-butoxycarbonyloxy) -4-
Iodobenzene and 1- [2-{(3-trimethoxysilyl) propyloxycarbonyl} vinyl] -4- (t
Synthesis of -Butoxycarbonyloxy) benzene In the same manner as in steps (i) and (ii) of Example 1, 1-
(T-Butoxycarbonyloxy) -4-iodobenzene and 1- [2-{(3-trimethoxysilyl) propyloxycarbonyl} vinyl] -4- (t-butoxycarbonyloxy) benzene were synthesized.

(Iii) Modification of silica sol 1- [2-{(3-trimethoxysilyl) propyloxycarbonyl} vinyl]-obtained in step (ii)
4- (t-butoxycarbonyloxy) benzene 0.4
5 g and colloidal silica (NPC-ST, manufactured by Nissan Chemical Industries, Ltd., silica sol content 30% by weight);
The mixture was mixed with 0.23 g of 0.05 mol / L hydrochloric acid and stirred at room temperature for 16 hours to modify the silica sol. In this example,
3- (trimethoxysilyl) propyl p- (t-butoxycarbonyloxy) cinnamate / silica sol (weight ratio) = 1/10, expressed as a modification amount of 10% (modified silica sol A).

In the silica sol modification step, 1- [2-{(3-trimethoxysilyl) propyloxycarbonyl} vinyl] -4- (t-butoxycarbonyloxy) benzene / colloidal silica NPC-S
T (solid content) / hydrochloric acid (concentration 0.05 mol / L)
The same operation as described above was carried out except that the composition was used at a ratio (weight ratio) of 1.5 / 10 / 0.75 and 3/10 / 1.5, and
Modified silica sols were prepared in which the amount of modification with-(trimethoxysilyl) propyl p- (t-butoxycarbonyloxy) cinnamate was 15% (modified silica sol B) and 30% (modified silica sol C), respectively.

(3) Preparation of photosensitive resin composition The photosensitive resin of the above step (1) and the modified silica sol obtained in the step (2) were mixed at a ratio shown in Table 4 (a ratio of a solid content excluding the solvent). (Indicated)) to prepare a photosensitive resin composition. An example in which the modified silica sol was not added was Comparative Example 4.

2. Pattern formation and evaluation of characteristics [sensitivity, resolution, heat resistance, and oxygen plasma resistance] (1) Pattern formation The above-mentioned photosensitive resin composition was dried on a cleaned silicon wafer using a spin coater to a thickness of 0.40 μm. And heated on a hot plate at 100 ° C. for 1 minute. Next, a reduction projection exposure machine having an exposure wavelength of 248 nm (FPA-3000E, manufactured by Canon Inc.)
X5, NA = 0.63), and exposure was performed by changing the exposure amount stepwise through a test mask having line and space patterns having different line widths. The wafer was heated on a hot plate at 100 ° C. for 1 minute, and then paddle-developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 1 minute to obtain a positive pattern.

(2) Evaluation of Characteristics Each characteristic of the positive pattern was evaluated as follows.

(I) Sensitivity: The sensitivity was evaluated in the same manner as in Example 1.

(Ii) Resolution: Evaluation was performed in the same manner as in Example 1.

(Iii) Heat resistance: The wafer after development was held on a hot plate having a different temperature for 5 minutes, and the temperature at which the pattern having a width of 500 μm began to be deformed was used as an index of heat resistance.

(Iv) Oxygen plasma resistance: Evaluated in the same manner as in Example 1.

Table 4 shows the results.

[0211]

[Table 4]

Example 13 and Comparative Examples 5 to 6 Preparation of photosensitive resin composition (1) Preparation of photosensitive resin (i) 30 g of t-butyl methacrylate and 0.2 g of azobisisobutyronitrile were added to a reaction vessel and dissolved in 200 mL of toluene. The inside of the reaction vessel was purged with argon, stirred at 60 ° C. while heating, and polymerized for 12 hours. After completion of the polymerization, the obtained reaction mixture was poured into a large amount of methanol to coagulate the resin. The coagulated resin was washed several times with methanol, and dried under reduced pressure at room temperature overnight to obtain poly-t-butyl methacrylate having a weight average molecular weight of 35,000 (yield: 33%).

To 1 part by weight of the obtained poly-t-butyl methacrylate resin, 0.1% of a photoacid generator represented by the following formula (B) was added.
By adding 02 parts by weight and mixing with 6 parts by weight of propylene glycol monomethyl ether acetate as a solvent, a positive photoresist was prepared.

[0214]

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(2) Active ingredient (i) Synthesis of t-butyl 3- [3- (triethoxysilyl) propiothio] propionate In the same manner as in step (i) of Example 3, t-butyl 3-
[3- (Triethoxysilyl) propiothio] propionate was synthesized.

(Ii) Modification of silica sol t-butyl 3- [3- (triethoxysilyl) propiothio] propionate synthesized in step (i)
45 g, 15 g of colloidal silica (NPC-ST, manufactured by Nissan Chemical Industries, Ltd., silica sol content 30% by weight),
The mixture was mixed with 0.23 g of 0.05 mol / L hydrochloric acid and stirred at room temperature for 16 hours to modify the silica sol. In this example,
The modification amount was 10% (modified silica sol D).

(3) Preparation of Photosensitive Resin Composition The ratio of the photosensitive resin of step (1) and the modified silica sol D obtained in step (2) shown in Table 5 (solid content excluding solvent) ) To prepare a photosensitive resin composition. Instead of the modified silica sol D, an unmodified silica sol [Colloidal silica, NP manufactured by Nissan Chemical Industries, Ltd.
C-ST, silica sol content of 30% by weight] as Comparative Example 5, and Comparative Example 6 with no modified silica sol added.
And

[0219] 2. Pattern formation and evaluation of characteristics [sensitivity, resolution, heat resistance and oxygen plasma resistance] (1) Pattern formation The above-mentioned photosensitive resin composition was dried on a washed silicon wafer using a spin coater to a thickness of 0.30 μm. And heated on a hot plate at 130 ° C. for 1 minute. Next, using a reduction projection exposure machine (NA = 0.60) having an exposure wavelength of 193 nm, exposure was performed by changing the exposure amount stepwise through a test mask having a line-and-space pattern having a different line width. . The wafer was heated on a hot plate at 130 ° C. for 1 minute, and then paddle-developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 1 minute to obtain a positive pattern.

(2) Evaluation of Characteristics Each characteristic of the positive pattern was evaluated as follows.

(I) Sensitivity, (ii) Resolution, and (iii) Oxygen Plasma Resistance: Evaluation was performed in the same manner as in Example 3.

Table 5 shows the results.

[0222]

[Table 5]

Examples 14 to 16 and Comparative Examples 7 to 8 Preparation of Photosensitive Resin Composition The photosensitive resin (1) used in Example 9 or the photosensitive resin (2) used in Example 13 and the modified silica sol are shown in the ratio (solid content excluding solvent) shown in Table 3. (Represented by a ratio) to prepare a photosensitive resin composition.

In Example 15, in the silica sol modification step of Example 9, 1- [2-{(3-trimethoxysilyl) propyloxycarbonyl} vinyl] -4 was used.
-(T-butoxycarbonyloxy) benzene / colloidal silica NPC-ST (solid content) / hydrochloric acid (concentration 0.5
mol / L), a modified silica sol (modified silica sol E) having a modification amount of 100% obtained by modifying the silica sol in the same manner as in Example 9 except that a ratio (weight ratio) of 10/10/5 was used. .

[0225] 2. Pattern formation and evaluation of properties [sensitivity, resolution, heat resistance and oxygen plasma resistance] (1) Pattern formation The above-mentioned photosensitive resin composition was dried on a washed silicon wafer using a spin coater to a thickness of 0.12 μm. And heated on a hot plate at a temperature shown in Table 3 for 1 minute. Next, exposure was performed by changing the exposure amount stepwise using an irradiation apparatus (VUVES-4500, manufactured by Lithotec Japan KK) using an F ₂ excimer laser (exposure wavelength: 157 nm) as an exposure source. This wafer was heated on a hot plate at a temperature shown in Table 3 for 1 minute (baked after exposure), and then paddle-developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 1 minute to obtain a positive pattern.

(2) Evaluation of Characteristics Regarding the positive pattern, (i) the sensitivity was indicated by the exposure amount at which the film thickness of the exposed portion became 0 (the smaller the value, the higher the sensitivity), and (ii) the resolution was A sensitivity curve is created by plotting the remaining film thickness of the exposed portion with respect to the logarithm of the exposure amount, and the slope (γ value) of the straight line portion at the point where the film thickness becomes 0 is obtained and used as an index of resolution (the value is large). The higher the resolution). (Iii) Oxygen plasma resistance: evaluated in the same manner as in Example 1.

The results are shown in Table 6.

[0228]

[Table 6]

Examples 17 to 20 and Comparative Examples 9 to 11 Preparation of photosensitive resin composition (1) Photosensitive resin 1 part by weight of a polyvinylphenol resin having a weight average molecular weight of 8,500 in which 45 mol% of hydroxyl groups is substituted with ethoxyethyl groups is represented by the formula (A). A positive photoresist was prepared by adding 0.03 parts by weight of a photoacid generator and mixing 6 parts by weight of propylene glycol monomethyl ether acetate as a solvent.

(2) Active ingredient (i) Synthesis of 1- (t-butoxycarbonyloxy) -4-bromobenzene 25.0 g (144.5 mmol) of p-bromophenol
l), 17.7 mg of N, N-dimethylaminopyridine
(0.14 mmol) in 200 ml of acetone dissolved in 31.5 g of di-t-butyl carbonate (144.
5 mmol) was added dropwise at 40 ° C. After completion of the dropwise addition, the mixture was stirred overnight. After completion of the reaction, the reaction solution was poured into 1 L of ice water. The resulting precipitate was filtered off with suction, dried and recrystallized from methanol to obtain 22.6 g of 1- (t-butoxycarbonyloxy) -4-bromobenzene.

(Ii) Synthesis of 1- (2-trimethoxysilylvinyl) -4- (t-butoxycarbonyloxy) benzene 1- (t-butoxycarbonyloxy) -4-bromobenzene synthesized in the above (i) 15.0 g (54.9 mm
ol), 9.76 g of vinyltrimethoxysilane (65.
9 mmol) was dissolved in 20 ml of triethylamine and 40 ml of acetonitrile, and the inside of the system was purged with argon by bubbling argon through the liquid phase. 246.5 mg (1.1 mmol) of palladium acetate as a catalyst was added to the system, and the mixture was refluxed overnight. After the completion of the reaction, the solvent was removed, and the residue was extracted with hexane. The hexane was removed from the extract to obtain 9.5 g of 1- (2-trimethoxysilylvinyl) -4- (t-butoxycarbonyloxy) benzene as a target compound.

The above reaction scheme is shown below.

[0233]

Embedded image

The ¹ H-NMR of the obtained compound is shown in FIG.

¹ H-NMR (CDCl ₃ ) ppm: 1.6
(S, 9H, t-Bu), 3.6 (s, 9H, OC
_{H 3), 6.1 (d,} 1H, C = CH), 7.2 (d,
_{2H, C 6 H 4),} 7.3 (d, 1H, C = CH), 7.
_{5 (d, 2H, C 6} H 4) (iii) synthesized 1- (2-trimethoxysilyl vinyl) a modified step of silica sol (ii)-4-(t-butoxycarbonyl-oxy)
Benzene / colloidal silica (NPC-ST, manufactured by Nissan Chemical Industries, Ltd., silica sol content 30% by weight) /0.05
mol / L hydrochloric acid in weight ratio (excluding solvent in colloidal silica) 5/10 / 2.5 (modification amount 50%), 10/10
/ 10/5 (100% modification amount)
The silica sol was modified by stirring at room temperature for 6 hours (modified silica sol F and modified silica sol G, respectively). (3) Preparation of photosensitive resin composition The photosensitive resin of step (1) and step (2) Was mixed with the modified silica sol obtained in (1) in the ratio shown in Table 7 (indicated by the ratio of solid content excluding the solvent) to prepare a photosensitive resin composition. Examples in which unmodified silica sol was used instead of the modified silica sol were Comparative Examples 9 and 10, and an example in which the modified silica sol was not added was Comparative Example 11.

[0236] 2. Pattern formation and evaluation of characteristics (sensitivity, resolution, and oxygen plasma resistance) The evaluation was performed in the same manner as in Example 9.

[0237]

[Table 7]

Examples 21 to 23 and Comparative Example 12 Preparation of Photosensitive Resin Composition (1) Photosensitive Resin 1 part by weight of a polyvinylphenol resin having a weight average molecular weight of 9,300 in which 40 mol% of hydroxyl groups are substituted with ethoxyethyl groups is represented by the formula (A). Was added, and 6 parts by weight of propylene glycol monomethyl ether acetate as a solvent was mixed to prepare a positive photoresist.

(2) Active ingredient (i) Synthesis of 1-benzyloxy-4-t-butoxycarbonyloxybenzene 25.0 g (124.9) of 4-benzyloxyphenol
mmol), N, N-dimethylaminopyridine 15.3
mg (0.12 mmol) was dissolved in 200 ml of acetone, and 27.2 g of di-tert-butyl carbonate was added to this solution.
(124.9 mmol) was added dropwise at 40 ° C. After completion of the dropwise addition, the mixture was stirred overnight. After completion of the reaction, the reaction solution was poured into 1 L of ice water. The precipitate formed is suction filtered and dried,
By recrystallizing with methanol, 22.8 of 1-benzyloxy-4-t-butoxycarbonyloxybenzene was obtained.
g was obtained.

(Ii) Synthesis of 4-t-butoxycarbonyloxyphenol 1-benzyloxy-4- synthesized in the above step (i)
20.0 g of t-butoxycarbonyloxybenzene (6
(6.6 mmol), 150 ml of ethanol and 0.5 g of 10% -palladium carbon powder are added, and the mixture is reacted with 1492.2 ml (66.6 mmol) of hydrogen at room temperature with stirring. The reaction solution was filtered to remove the palladium carbon powder, and the filtrate was concentrated and redissolved in toluene. After removing the insoluble matter by filtration, the solution was allowed to stand and recrystallized.
4-t-Butoxycarbonyloxyphenol was obtained.

(Iii) Reaction of 4-t-butoxycarbonyloxyphenol with a silane coupling agent n sufficiently dehydrated to 8.4 g (40.0 mmol) of 4-t-butoxycarbonyloxyphenol synthesized in step (ii) -Hexane (20 ml) was added, and 3-isocyanatopropyltriethoxysilane (9.9 g, 40.0 mmol) was added.
l) was added, and the mixture was stirred and reacted at room temperature for 16 hours.

The reaction solution was filtered, and the filtrate was redissolved in 200 ml of hexane / toluene = 1/1 (weight ratio), filtered, and the product was recrystallized from the filtrate.

The above reaction scheme is shown below.

[0244]

Embedded image

FIG. 6 shows the ¹ H-NMR of the obtained product.

¹ H-NMR (CDCl ₃ ) ppm: 0.7
(T, 2H, CH ₂ ), 1.2 (t, 9H, OCH ₂ CH
₃ ), 1.6 (s, 9H, t-Bu), 1.7 (t, 2
_{H, CH 2), 3.3 (} t, 2H, CH 2), 3.9
_{(Q, 6H, CH 2)} , 5.4 (t, 1H, NH),
7.2 (d, 4H, C ₆ H ₄ ) (iv) Modification of silica sol Compound synthesized in step (iii) / colloidal silica (NPC-ST, manufactured by Nissan Chemical Industries, Ltd., silica sol content 30% by weight) / 0.05 mol / L hydrochloric acid was added in a weight ratio of 5/10/2.
5 (50% modification), 10/10/5 (100 modification)
%) And stirred at room temperature for 16 hours to modify the silica sol (respectively referred to as modified silica sol H and modified silica sol I).

(3) Preparation of photosensitive resin composition The photosensitive resin of the above step (1) and the modified silica sol obtained in the step (2) were mixed at a ratio shown in Table 8 (a ratio of a solid content excluding a solvent). (Indicated)) to prepare a photosensitive resin composition. An example in which the modified silica sol was not added was Comparative Example 12.

[0248] 2. Pattern formation and evaluation of characteristics (sensitivity, resolution, and oxygen plasma resistance) The evaluation was performed in the same manner as in Example 9.

[0249]

[Table 8]

Example 24 (i) Synthesis of 1- (1-ethoxy) ethoxy-4-bromobenzene In 100 ml of dehydrated ethyl acetate, 11.0 g (50 mmol) of p-bromophenol, 1.0 mol / L hydrochloric acid / 4.8 ml of an ether solution was added and set at 40 ° C.
To this mixture was added 10.8 g of ethyl vinyl ether (150
mmol) was added dropwise and stirred overnight. After the completion of the reaction, the resultant was washed with an aqueous solution of sodium hydrogen carbonate and then washed with water to remove the solvent.
Purification by silica gel column chromatography (eluent: hexane) gave 10.7 g of 1- (1-ethoxy) ethoxy-4-bromobenzene (36.5 mmol).
1) was obtained.

NMR (CDCl ₃ ) ppm: 1.2
(T, 3H, terminal _{CH 3), 1.49 (t,} 3H, branched _{CH 3), 3.47~3.6 (m,} 1H, OCH),
3.7-3.85 (m, 1H, OCH), 5.34
(Q, 1H, branched OCH), 6.9 (d, 2H, C
_{6 H 4), 7.38 (d} , 2H, C 6 H 4) (ii) 4- [2 - {(3- trimethoxysilyl) propyl oxycarbonyl} vinyl] -1 - {(1-ethoxy)
Synthesis of ethoxydibenzene In step (2) (ii) of Example 1, instead of 1- (t-butoxycarbonyloxy) -4-iodobenzene,
The title compound was obtained in the same manner as in the Heck reaction in step (2) (ii) of Example 1, except that 1- (1-ethoxy) ethoxy-4-bromobenzene synthesized in step (i) was used.

NMR (CDCl_Three) Ppm: 0.7
(T, 2H, CH_Two), 1.2 (t, 3H, terminal C
H_Three), 1.49 (t, 3H, branch CH_Three), 1.8
(T, 2H, CH_Two), 3.55 to 3.65 (m, 9
H, OCH_Three), 3.47 to 3.6 (m, 1H, OC
H), 3.7-3.85 (m, 1H, OCH), 4.2
(T, 2H, CH _Two), 5.34 (q, 1H, branched OC)
H), 6.4 (d, 1H, C = CH), 7.6 (d, 1
H, C = CH), 6.9 (d, 2H, C₆H_Four), 7.3
8 (d, 2H, C₆H_FourExample 25 (i) 1- (1-ethoxy) ethoxy-4-bromobenze
The title compound was prepared in the same manner as in Step (i) of Example 24.
Obtained.

(Ii) Synthesis of 4- [2- (trimethoxysilyl) vinyl] -1- (1-ethoxy) ethoxybenzene 1- (t-butoxycarbonyloxy) -4-iodobenzene and 3-triacrylic acid 1- (1-ethoxy) ethoxy-4- instead of methoxysilylpropyl ester
Except that bromobenzene and trimethoxyvinylsilane were used, the title compound was obtained in the same manner as in the Heck reaction in step (2) (ii) of Example 1.

NMR (CDCl ₃ ) ppm: 1.2
(T, 3H, terminal _{CH 3), 1.49 (t,} 3H, branched _{CH 3), 3.47~3.6 (m,} 1H, OCH),
_{3.6 (m, 9H, OCH 3} ), 3.7~3.85
(M, 1H, OCH), 5.34 (q, 1H, branched OC
H), 6.1 (d, 1H, C = CH), 7.18 (d,
_{2H, C 6 H 4),} 7.25 (d, 1H, C = CH),
_{7.5 (d, 2H, C 6} H 4) Example 26 (i) 1-Synthesis of benzyloxy-3-acetoxy benzene Resolution Lucille monoacetate 30.4g (200mmo
l) was dissolved in 300 ml of dimethyl sulfoxide, and an aqueous sodium hydroxide solution (NaOH / H
₂ O: was 8 g / 30 ml) was added to stirred until homogeneous. Next, 26.5 g of benzyl chloride (210 m
mol) was added and reacted at room temperature for 24 hours. The reaction mixture was poured into 1 L of ice water, the obtained solid was filtered and dried, and then recrystallized with ethanol to give 44.3 g of 1-benzyloxy-3-acetoxybenzene (183 m 2).
mol).

(Ii) Synthesis of 3-benzyloxyphenol 20 g (82 mmol) of 1-benzyloxy-3-acetoxybenzene obtained in step (i) was added to 16.3 g (24%) of potassium hydroxide in 300 ml of 10% aqueous ethanol.
The resulting product was hydrolyzed and neutralized to obtain 14.8 g (74 mmol) of 3-benzyloxyphenol.

(Iii) 1- (1-ethoxy) ethoxy-3
Synthesis of -benzyloxybenzene The title compound was obtained in the same manner as in Step (i) of Example 24 except that 3-benzyloxyphenol was used instead of p-iodophenol.

(Iv) Synthesis of 3- (1-ethoxy) ethoxyphenol In step (2) (ii) of Example 21, the above step (iii) was used instead of 1-benzyloxy-4-t-butoxycarbonyloxybenzene. )) To give the title compound in the same manner as in step (2) (ii) of Example 21 except for using 1- (1-ethoxy) ethoxy-3-benzyloxybenzene.

(V) 1- (1-ethoxy) ethoxy-3-
Synthesis of [(3-triethoxysilyl) propylaminocarbonyloxy] benzene The procedure was as described above, except that 3- (1-ethoxy) ethoxyphenol obtained in the above step (iv) was used in place of 4-t-butoxycarbonyloxyphenol. Example 21 Steps
(2) The title compound was obtained in the same manner as in (iii).

The above reaction scheme is shown below.

[0260]

Embedded image

Example 27 (i) Synthesis of 1-benzyloxy-3-t-butoxycarbonyloxybenzene In step (2) (i) of Example 21, 3-benzyloxy was used instead of 4-benzyloxyphenol. Except that phenol was used, the title compound was obtained in the same manner as in Step (2) (i) of Example 21.

(Ii) Synthesis of 3-t-butoxycarbonyloxyphenol In step (2) (ii) of Example 21, the above-mentioned step (i) was used in place of 1-benzyloxy-4-t-butoxycarbonyloxybenzene. )), Except that 1-benzyloxy-3-t-butoxycarbonyloxybenzene obtained in Example 21 was used, in the same manner as in Step (2) (ii) of Example 21.
The title compound was obtained.

(Iii) Reaction of 3-t-butoxycarbonyloxyphenol with a silane coupling agent In step (2) (iii) of Example 21, step (i) was carried out in place of 4-t-butoxycarbonyloxyphenol.
1- [3- (Trimethoxysilyl) propylaminocarbonyloxy] -3 was obtained in the same manner as in step (2) (iii) of Example 21 except that 3-t-butoxycarbonyloxyphenol obtained in i) was used. -[T-Butoxycarbonyloxy] benzene was obtained.

The reaction scheme is shown below.

[0265]

Embedded image

Example 28: 2- (triethoxysilyl)
Synthesis of -1- (t-butoxycarbonyl) ethane t-acrylic acid in 100 ml of dry tetrahydrofuran
25.8 g (20 mmol) of butyl and 32.8 g (20 mmol) of triethoxysilane were added and the atmosphere was replaced with argon. 10 mg of chloroplatinic acid was added to the mixture, and the mixture was heated under reflux for 24 hours. After completion of the reaction, the solvent was removed to obtain 58.5 g of the title compound.

Example 29: Synthesis of N- [2- (t-butoxycarbonyl) ethyl] -3- (triethoxysilyl) propylamine 3-aminopropyltriethoxysilane 22.1 g (1
(00 mmol) was dissolved in dehydrated ethanol, and 12.8 g (100 mmol) of t-butyl acrylate was added, followed by stirring at room temperature for 24 hours. After completion of the reaction, the solvent was removed to obtain 32.5 g of the title compound.

NMR (CDCl ₃ ) ppm: 0.6
_{(T, 2H, CH 2)} , 1.19 (t, 9H, CH 3),
1.41 (s, 9H, t-Bu), 1.49-1.67
_{(M, 2H, CH 2)} , 2.4 (t, 2H, CH 2),
2.59 (t, 2H, CH ₂ ), 2.8 (t, 2H, C
H _2), shows 3.79 (q, 6H, a OCH ₂₎ Reaction Scheme below.

[0269]

Embedded image

Example 30: Synthesis of N, N'-di- (t-butoxycarbonyl) ethyl-3- (triethoxysilyl) propylamine 25.6 g (200 m) of t-butyl acrylate
Example 29, except that the mixture was heated and refluxed for 24 hours.
As above, the title compound was obtained.

NMR (CDCl ₃ ) ppm: 0.5
_{(T, 2H, CH 2)} , 1.19 (t, 9H, CH 3),
1.39 (s, 18H, t-Bu), 1.41-1.6
_{(M, 2H, CH 2)} , 2.3 (t, 6H, CH 2),
_{2.7 (t, 4H, CH 2} ), 3.75 (q, 6H, O
CH ₂ ) The reaction formula is shown below.

[0272]

Embedded image

The pattern characteristics were evaluated in the same manner as in Example 2, except that the compounds (active ingredients) obtained in Examples 24 to 30 were used instead of the active ingredients used in Example 2. The same result as in Example 2 was obtained.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR spectrum of the compound obtained in steps (2) and (ii) of Example 1.

FIG. 2 is an IR spectrum of the compound obtained in steps (2) and (ii) of Example 1.

FIG. 3 is a ¹ H-NMR spectrum of the compound obtained in step (2) (i) of Example 3.

FIG. 4 is an IR spectrum of the compound obtained in step (2) (i) of Example 3.

FIG. 5 is a ¹ H-NMR spectrum of the compound obtained in steps (2) and (ii) of Example 17.

FIG. 6 is a ¹ H-NMR spectrum of the compound obtained in steps (2) and (iii) of Example 21.

Continued on the front page (72) Inventor Junko Katayama 17 Kyoto Research Park, Shimogyo-ku, Kyoto City Kyoto Research Park Co., Ltd. (72) Inventor Satsuki Kitajima 17 Nakadoji Minamicho, Shimogyo-ku, Kyoto Kyoto Research Park Kansai Co., Ltd. F-term in the new technology laboratory (reference) 2H025 AA01 AA02 AB16 AC04 AC08 AD01 AD03 BE00 BG00 CB29 CB52 CC20 FA03 FA12 FA17

Claims (27)

[Claims] 1. An active ingredient for use in combination with a photosensitive agent constituting a photosensitive resin composition, which is represented by the following formula (1): (X) _mn -M ^m -[(U ₁ ) _p- (U ₂ -Z) _t ] _n (1) (wherein, X represents a hydrogen atom, a halogen atom, an alkoxy group or an alkoxycarbonyl group, M represents a metal atom having a valence of 2 or more, and U ₁ represents a _first atom A linking unit, U ₂ represents a second linking unit, Z represents a group that causes a difference in solubility due to light irradiation, n represents an integer of 1 or more, and m represents an integer.
> N, p is 0 or 1, and t is an integer of 1 or more)
And a polycondensate thereof, and the following formula (2): P-[(Y) _s -{(U ₁ ) _p- (U ₂ -Z) _t }] _k (2) , P represents a fine particle carrier, Y represents a coupling residue, k is an integer of 1 or more, and s is 0 or 1. U ₁ , U ₂ , Z, p and t are the same as described above. An active ingredient composed of at least one selected from particles represented by 2. The active ingredient according to claim 1, which is in the form of particles or oligomers. 3. The group Z is (a) a photocrosslinkable group or a photocurable group, or (b) a hydrophilic group protected by a protective group which can be removed by irradiation with light. The active ingredient as described. 4. The active ingredient according to claim 1, wherein the group Z is a hydrophilic group protected by a protecting group which can be removed in association with a photosensitizer by irradiation with light. 5. The active ingredient according to claim 3, wherein the protecting group is removable by an acid. 6. The active ingredient according to claim 1, wherein the group Z is capable of forming a hydroxyl group or a carboxyl group by elimination of a hydrophobic protecting group. 7. The protecting group is (i) an alkoxyalkyl group,
A protecting group for a hydroxyl group selected from an acyl group, an alkoxycarbonyl group, an oxacycloalkyl group and a bridged cyclic alicyclic group, or (ii) an alkyl group, a carbamoyl group and a bridged cyclic alicyclic group The active ingredient according to claim 3, which is a protecting group for a carboxyl group. 8. The protecting group is (1) a C _1-6 alkyl-carbonyl group, a C _1-6 alkoxy-C _1-6 alkyl group, a C _1-6
A protecting group for a hydroxyl group selected from an alkoxy-carbonyl group and an oxacycloalkyl group, or (2) a C _1-6 alkyl group, a carbamoyl group, a C _1-6 alkyl-carbamoyl group, a C _6-10 aryl-carbamoyl group 4. The active ingredient according to claim 3, which is a protecting group for a carboxyl group selected from a bi- or tricycloalkyl group. 9. The method according to claim 9, wherein the metal atom M is aluminum, titanium,
The active ingredient according to claim 1, which is one kind selected from the group consisting of zirconium and silicon. 10. The active ingredient according to claim 1, wherein the metal atom M is silicon. 11. The connecting units U ₁ and U ₂ each comprise a chain hydrocarbon, a hydrocarbon ring, a chain hydrocarbon having a hetero atom,
The active ingredient according to claim 1, wherein the active ingredient is a unit containing at least one member selected from the group consisting of a heterocyclic ring and a heterocyclic ring. 12. The connecting unit U ₁ and U _2, respectively, the following formula _{^{- (R 1) q - (}} B) r -, - (R 2) u - (Ar) v - ( wherein, R ¹ and R ² is the same or different and represents an alkylene group or an alkenylene group; B represents an ester bond, a thioester bond, an amide bond, a urea bond, a urethane bond, a thiourethane bond, an imino group, a sulfur atom or a nitrogen atom; Ar represents an arylene group or a cycloalkylene group, q, r, u and v each represent 0 or 1, and q + r + u + v ≧ 1). 13. In the formula (1), Z represents a hydroxyl group or a carboxyl group protected by a hydrophobic protecting group which can be eliminated by light irradiation, and the metal atom M is selected from aluminum, titanium, zirconium and A unit selected from the group consisting of silicon and containing a linking unit (U ₁ ) _p − (U ₂
-Z) The active ingredient according to claim 1, wherein _t is represented by the following formula. [(R ¹ ) _q- (B) _r ] _p -[{(R ² ) _u- (Ar) _v }
-Z] _t (wherein R ¹ , R ² , B, Ar, p, q, r, t, u and v are the same as above) 14. The active ingredient according to claim 1, wherein the polycondensate is a polycondensate of an active metal alkoxide represented by the formula (1) and a metal alkoxide represented by the following formula (5). (X) _mn-1 M ^m (R ⁵ ) _n-1 (5) (wherein, R ⁵ represents a hydrogen atom or an alkyl group.
M, m and n are the same as described above) 15. The ratio (weight ratio) between the active metal alkoxide (1) and the metal alkoxide (5) is as follows:
15. Component (5) = 10/90 to 90/10.
The active ingredient as described. 16. The polycondensate has an average particle size of 1 to 100 nm.
The active ingredient according to claim 1, which is a particle of the following. 17. The fine particle carrier has an average particle diameter of 1 to 100.
2. The active ingredient according to claim 1, which is in nm. 18. The active ingredient according to claim 1, wherein the fine particle carrier is an inorganic fine particle carrier. 19. The active ingredient according to claim 1, wherein the fine particle carrier is a silica sol. 20. A connecting unit U bonded to inorganic fine particles P having an average particle diameter of 1 to 50 nm via a silane coupling agent Y, a hydrophilic group bonded to the connecting unit, and protection for protecting the hydrophilic group. And a group Z that causes a difference in solubility upon irradiation with light, is composed of the hydrophilic group and a protective group, and the linking unit is an aromatic C _6-12 hydrocarbon ring or a monocyclic alicyclic group. It is composed of at least one selected from a hydrocarbon ring, a bridged cyclic alicyclic hydrocarbon ring and an aliphatic hydrocarbon chain, wherein the hydrophilic group is a hydroxyl group or a carboxyl group, and the protective group is (1) A) a protecting group for a hydroxyl group selected from a C _1-4 alkyl-carbonyl group, a C _1-4 alkoxy-C _1-4 alkyl group, a C _1-4 alkoxy-carbonyl group and a 5- or 6-membered oxacycloalkyl group; Or ( 2) A protecting group for a carboxyl group selected from a C _1-4 alkyl group, a carbamoyl group, a C _1-4 alkyl-carbamoyl group, a C _6-10 aryl-carbamoyl group and a bi- or tricycloalkyl group. The active ingredient as described. 21. The active ingredient according to claim 20, wherein the proportion of the silane coupling agent is 0.1 to 200 parts by weight based on 100 parts by weight of the fine particle carrier. 22. A photosensitive resin composition comprising a base resin, a photosensitive agent, and the active ingredient according to claim 1. 23. The photosensitive resin composition according to claim 22, wherein the exposed portion is a positive type which can be developed with water or alkali. 24. A base resin comprising a homo- or copolymer of a monomer capable of forming a hydrophilic group by the action of an acid,
The photosensitive resin composition according to claim 22, wherein the photosensitive agent comprises a photoacid generator. 25. A method for forming a pattern by applying the photosensitive resin composition according to claim 22 to a substrate, exposing the substrate to light, subjecting the substrate to a heat treatment, and further developing the substrate. 26. The following formula (1) (X) _mn -M ^m -[(U ₁ ) _p- (U ₂ -Z) _t ] _n (1) (where X is a hydrogen atom, a halogen atom, an alkoxy Represents a group or an alkoxycarbonyl group, M represents a metal atom having a valence m of 2 or more, U ₁ represents a first connecting unit, U ₂ represents a second connecting unit, and Z represents a light irradiation. Represents a group that causes a difference in solubility, wherein n is an integer of 1 or more;
> N, p represents 0 or 1, and t represents 1 or 2). 27. An oligomer or active particle comprising at least a polycondensate of the active metal alkoxide according to claim 26.