JP2000267286A - Novel polymer and photoresist composition using it - Google Patents

Abstract

(57) [Problem] To provide a novel polymer containing a carboxy group and / or a group serving as a carboxyl precursor, which can be applied without problems even in high-performance practical use,
And the use of such polymers as photoresist compositions. SOLUTION: The polymer of the present invention contains a carboxyl group or a carboxyl precursor group as a side group, and this group is not directly bonded to the main chain of the polymer but is attached to the main chain by one or more groups. Through more atoms than the keto group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polymer,
And a photoresist composition of such a polymer,
In particular, it relates to the use as a resin binder component for a chemically amplified positive resist. The polymer of the present invention comprises a carboxyl and / or a carboxyl precursor group which is not directly bonded to its main chain (this group is a photoacid-labile group capable of producing —COOH and —COOH).
ups).

[0002]

BACKGROUND OF THE INVENTION Photoresists are photosensitive films used to transfer images to a substrate. A photoresist coating layer is formed on a substrate, and the photoresist layer is exposed through a photomask with an active radiation source.
The photomask is activated radiated (active rad).
i.e., opaque areas and other transparent areas. Exposure by actinic radiation is used to transfer the pattern of the photomask to a substrate coated with the photoresist as the photoresist changes from light. Subsequent to exposure, the photoresist is developed to create a relief image, allowing the substrate to be selected.

[0003] The photoresist may be positive or negative. In many negative-acting photoresists, portions of the coating layer exposed to actinic radiation polymerize or crosslink in the reaction between the photoactive compound and the polymerization reagents of the photoresist composition. As a result, the exposed film portion is less likely to be dissolved in the developer than the unexposed portion. In a positive photoresist, the exposed portions are easily dissolved in the developing solution, but the unexposed portions remain relatively hard to be dissolved in the developing solution.

More recently, chemically amplified resists have become increasingly used, especially for submicron imaging and other high performance applications. Such photoresists may be negative or positive, and may be photogenerating (photogenera).
te) It is common to carry out many crosslinking phenomena (in the case of a negative resist) or a protective reaction (in the case of a positive resist) for each unit of the acid which has been subjected. In the case of positive-acting chemically amplified resists, certain cationic photoinitiators are used to cleave the "block" groups, which are the side chains of the photoresist binder, and to bind the photoresist. It has been used to cause cleavage of the groups that make up the backbone of the agent. For example, US Patent 5,
Nos. 075,199; 4,968,581; 4,8
Nos. 83,740; 4,810,613; and 4,491,628 and Canadian Patent Application No. 2,000.
See 1,384. Cleavage of the blocking groups by exposing the coating layer of such a resist results in the formation of polar functional groups, such as carboxyl or imide, which are exposed to the exposed areas of the resist coating layer. Different regions have different solubilities. Proceding of SPI (Proc) by RD Allen et al.
eating of SPIE 2724: 334-3
43 (1996) "; and Trefonas (P. Tre.
fonas) et al., "Proceedings of the Elevens International Conference on Photopolymer.
11th International Confession
rence on Photopolymers (So
c. of Plastic Engineers), 44
-58 (Oct. 6, 1997).

[0005] Although recently available photoresists are suitable for many practical applications, they suffer severe defects, especially in high-performance applications at high resolutions of 0.5 microns or less or 0.25 microns or less. Is also exposed.

[0006]

SUMMARY OF THE INVENTION The present invention provides a high resolution,
It can be applied without problems even in high-performance practical use,
Novel polymers, including carboxy groups and / or precursors of carboxy groups (such as carboxylate), and the use of such polymers as photoresist resin binder components are provided.

[0007]

The polymer of the present invention usually contains at least one repeating unit that is a carboxylic acid and / or a unit that can form a carboxylic acid, which is the main chain of the polymer. Not directly linked to Generally, at least one atom, preferably a carbon or heteroatom, is located between the polymer backbone and the carboxy group or precursor of the carboxy group. Usually, the carbon atom spacer or heteroatom spacer disposed therebetween is saturated or contains at least something other than a keto (C = 0) group.

It has been found that a resist containing the resin of the present invention exhibits excellent characteristics, thereby making it possible to form a resist image with high resolution. Resists that are too soluble show relatively low resolution, especially when printing at micron or sub-micron. In particular, since the carboxyl or carboxyl-forming unit is not directly bonded to the main chain of the polymer, the difference in solubility between the exposed portion and the unexposed portion of the resist coating layer containing the polymer is actually suitable. Was found to have an effect. For example, see the results shown in the examples described below. In particular, the solubility of the exposed portions of the photoresist containing the polymer of the present invention is very favorably enhanced as compared to a comparative resist having an acid component directly attached to the polymer backbone.

In general, the preferred polymers of the present invention are
Providing a carboxyl or carboxyl precursor (eg, a carboxylate or ester group) that is not directly attached to the polymer backbone, including units obtained by polymerization of one or more acrylates. . Suitable acrylate units that can provide, for example, carboxyl precursor groups that are not directly attached to the polymer backbone include acryloxy (C _1-12 alkyl) esters and methacryloxy (C _1-12 alkyl) esters Group to generate light (ph
and those which react with an acid that has been generated to provide a carboxy group. That is, acryloxy (C _1-12 alkyl) COOH and methacryloxy (C _1-12 alkyl) COOH.

[0010] Preferred polymers further include carboxyl or carboxyl precursor groups (which, again, are -CO2 when exposed to a photoacid).
Carboxylate or other groups capable of forming OH) are not directly attached to the polymer backbone, but rather through 1 to about 16 or 20 carbon or heteroatoms with the backbone. Preferably via 1 to about 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbons. Carbon and heteroatoms are placed between the backbone as suitable spacers, but the carboxyl or precursor groups are not directly attached to the backbone of the polymer, but other polyvalent atoms such as Si. It may be used and disposed between the main chain. Still further, the spacer linkage may include one or more unsaturated groups, for example, one or more unsaturated carbon-carbon bonds, such as one to about three carbon-carbon double bonds. May be included, but this may not be preferred. On the other hand, in some cases, it may be unsaturated or even more preferred. For example, succinate groups such as ethyl succinate spacer and other C _1-8 succinate groups (with keto carbons) are suitable spacer groups.

[0011] The polymer of the present invention may contain other units. Examples include an optionally substituted phenyl group (eg, obtained by copolymerization of a styrene compound), cyano (provided by copolymerization of acrylonitrile or methacrylonitrile), an optionally substituted alicyclic (eg, Adamantyl, norbornyl, isobornyl, cyclohexyl) and other units.

The present invention provides a photoresist composition containing the resin obtained according to the present invention. Preferred photoresists in the present invention include chemically amplified resists,
Particularly, there is a positive resist composition. Depending on the configuration of each resist composition, an I-line (365 nm),
Deep UV, especially at 248 nm, below 200 nm such as 193 nm and 157 nm, e-beam, EUV, ion projection lithography
hy; IPL) and a variety of exposure radiations are available, such as very short wavelength exposures such as X-rays and other sub-20 nm imaging.

The present invention also provides a method for forming a relief image. In this method, for example, in a line pattern, side walls perpendicular to each line are always provided, and the line width is about 0.40 μm or smaller, further about 0.25 μm or smaller, and high. A method for forming a resolution relief image is included. The present invention further provides a photoresist and relief image of the present invention,
Articles of manufacture are also provided that include substrates such as microelectronic wafers or liquid crystal displays and other flat panel display substrates. Other aspects of the invention are disclosed below.

[0014]

DETAILED DESCRIPTION OF THE INVENTION As mentioned above, the polymers of the present invention contain a carboxyl or carboxyl precursor group, wherein at least one atom, preferably a hetero or carbon atom, is attached to the backbone of the polymer and the carboxyl. Alternatively, it is contained between a group that is a precursor of carboxyl. "Polymer backbone" herein
By its widely accepted definition is defined a portion of a polymer that is linked to another polymer repeat unit by at least two bonds, and is distinguished from side groups that are connected but not similar. Thus, in the chemical formula (I) shown below, although the alkylene unit (in parentheses of w, x, and y) is a part of the polymer main chain, the side chain W and the phenyl group are the main components. Not included in the chain.

Preferred carboxyl precursor groups generate carboxyls in the presence of photoacids, ie, photoacid-labile groups. Here, the photoacid-labile group is suitably not directly attached to the polymer backbone, for example, via 1 to about 20 carbon atoms between the polymer backbone. More typically, between 1 and approximately 2, 3, 4, 5, 6, 7,
8, 9 or 10 carbon or hetero (N, O,
Or S) via an atom.

As mentioned above, preferred examples of the acid-labile group not directly bonded to the main chain of the polymer include:
Acryloxy _{(C 1-2} alkyl) esters, methacryloxy _{(C 1-12} alkyl) ester, acryloxy _{(C 1-12} heteroalkyl) esters, and methacryloxy _{(C 1-12} heteroalkyl) esters, react with the photogenerated federated Acid There is an acrylate group that provides a carboxy group. That is, acryloxy (C _1-12 alkyl) COOH, methacryloxy (C _1-12 alkyl) COOH, acryloxy (C
_1-12 heteroalkyl) COOH, and methacryloxy (C _1-12 heteroalkyl) COOH. More typically utilized are acryloxy (C _1-8 alkyl) esters, methacryloxy (C _1-8 alkyl) esters, acryloxy (C _1-8 heteroalkyl) esters, and methacryloxy (C _1-8 heteroalkyl) esters. ) Ester. The heteroatoms in the heteroalkyl chain are usually sulfur or oxygen. Nitrogen linkages are also used, at least in some cases, but are less preferred in terms of photoresist practicality, as undesirable combinations with photogenerated acid can occur. “Heteroalkyl” is used according to the accepted definition of an alkyl (including alkylene) chain and includes one or more hetero (N, O, or S) atoms as part of a chain. . Heteroalkyl groups containing one or two heteroatoms are typical.

Particularly preferred acrylate compounds for reacting carboxy groups and carboxylate acid-labile groups which are not directly attached to the main chain in the polymers according to the invention include: t
-Butyl acryloxy acetate (ie CH ₂ ＣＨC
HCOOCH ₂ COO-t-butyl); t-butyl-methacryloxypropyl acetate (i.e. _CH 2 = C _(CH 3)
COOCH ₂ COO-t-butyl); 2- carboxymethyl acrylate (i.e. _{CH 2} = CHCOOCH 2
COOH); 2-carboxymethyl meth Tari rate (i.e. _{CH 2 = C (CH 3)} COOCH 2 COOH);
Acryloxypropionic acid (ie, CH ₂ ＣＨCHCO
OCH ₂ CH ₂ COOH); t- butyl acryloxy propionate (i.e. _{CH 2} = CHCOOCH 2 _CH 2
COO-t-butyl); methylacryloxypropionic acid (ie, CH ₂ C (CH ₃ ) COOCH ₂ CH ₂
COOH); t-butyl (methyl) acryloxypropionate (ie, CH ₂ ＣC (CH ₃ ) COOCH ₂ C
H ₂ COO-t-butyl); acryloxy cis succinate (i.e. _{CH 2} = CHCOOCH 2 _CH 2 OOCCH
₂ CH ₂ COOH); _t- butyl acrylate roxithromycin succinate (i.e. _{CH 2} = CHCOOCH 2 _CH 2 OOC
CH ₂ CH ₂ COO-t- butyl); methyl acryloxy Kista glycinate (i.e. _{CH 2 = C (CH 3)} COO
CH ₂ CH ₂ OOCCH ₂ CH ₂ COOH); and t
- butyl (methyl) acryloxy Kista glycinate (i.e. _{CH 2 = C (CH 3)} COOCH 2 CH 2 OOCCH
₂ CH ₂ COO-t-butyl)

It is also preferred that the carboxylate photoacid-labile group has an ester formed with a quaternary carbon atom other than t-butyl. For example, a photoacid-labile ester group that is not directly attached to the backbone of another suitable polymer may be one of those described by the inventors of Trefnas et al.
U.S. Patent Application Serial No. 09/1998, filed August 28, 998;
No. 143,462. Examples of such an ester include —C (= 0) OC (CH ₃ ) ₂ CH (CH
₃ ) ₂ , —C (= 0) OC (CH ₃ ) ₂ C (C
H _{3) 3,} and _{-C (= 0) OC (CH} 3) 2 CH 2
There is a CH _3.

As noted above, the polymers of the present invention may contain various other units in addition to carboxyl and carboxylate or other precursors of carboxyl. Thus, for example, other desirable groups include phenyl groups optionally substituted with hydroxy or halogen, alkoxy, nitro, or other substituents; alicyclic groups such as norbornyl, adamantyl, cyclohexyl, etc .; There is.

Suitable added units include substituted and unsubstituted allyl and cycloaliphatic radicals. For example, groups having about 6 to 18 aromatic carbons, such as substituted or unsubstituted styrene, naphthylene, acenaphthylene, and other groups provided by condensation, as well as substituted or unsubstituted vinyl. Substituted and unsubstituted vinylalicyclic groups containing from 5 to about 18 carbon atoms, such as norbornyl, vinyladamantyl, or vinylcyclohexane. The cyan side groups are also suitable as a unit to be added. Acyclic substituted and unsubstituted alkyl groups can also be utilized. For example, those having from 1 to about 12 carbon atoms, but are less preferred than allyl or alicyclic groups. Suitable substituents on substituted groups include, for example, C _1-8 alkoxy, especially methoxy, ethoxy and propoxy; cyano; nitro; halogen (F, Cl, B
r or I) alkynyl having 2 to about 10 carbon atoms; alkylthio having 1 to about 10 carbon atoms; and the like.

For use in resists imaged below about 200 nm, it is better for the polymer to be substantially free of aromatic groups, ie, the polymer will be free of phenyl or other aromatic groups for all units of the polymer. About 4 tribal units
Alternatively, the content is preferably 5 mol% or less. More preferably, the polymer has less than about 1 or 2 mole percent of phenyl or other aromatic units, based on all units in the polymer. It is even more preferred that the polymer has no more than 0.5 mole percent of aromatic units, or no aromatic units, based on all units in the polymer.
Such an aromatic unit sufficiently absorbs imaging irradiation of 200 nm or less.

When used to image above about 200 nm, such as 248 nm and 365 nm, the polymers of the present invention benefit the aqueous developability of photoresists containing polymers such as resin binders. It preferably contains a hydroxyphenyl group capable of exhibiting the following. Such units can be obtained by polymerizing an adapted monomer such as, for example, optionally substituted para-hydroxystyrene, para-hydroxy α-methylstyrene, meta-hydroxystyrene, meta-hydroxy α-methylstyrene. Obtained by

Furthermore, when the resist is applied, the polymer of the present invention containing a hydroxyphenyl unit has no or substantially no carboxy group, and a group which is not directly bonded to the main chain of the polymer but is a precursor of carboxyl. It is preferable to include. In such polymers, the difference in solubility between exposed and unexposed portions of the resist coating layer is not significantly affected by the synergistic effect of the hydroxyphenyl and carboxyl units. Yes. The fact that the polymer is substantially free of carboxy groups means that the polymer contains less than about 4 or 5 mole percent carboxy groups, based on total units of the polymer. More preferably, the carboxy groups contained in the polymer are less than about 2, 3, or 4 mole percent relative to all units of the polymer, and the carboxy groups contained in the polymer are less than about 1 or 0. Even more preferably, it is at most 5 mole percent.

As described above, in particular, the I line or 2
At the time of 48 nm imaging, the preferred polymer of the present invention contains a phenol group as shown in the following chemical formula (I).

Wherein w is a photoacid-labile group that is not directly attached to the polymer backbone but is through one or more atoms between the backbone and the polymer.
R ¹ and R ² are the same or different non-hydrogen substituents; R ³ , R ⁴ and R ⁵ are each independently hydrogen or optionally substituted alkyl; m
Is an integer from 0 to 5; n is an integer from 0 to 4; w and y are each greater than 0; the mole fraction or percent of each polymer unit; and x is 0 or greater; It is the mole fraction or percent of the specified phenyl units. )

As mentioned above, the photoacid-labile groups not directly attached to the backbone of a suitable polymer can be acryloxy (alkyl) esters or acryloxy (hetero groups) as in the polymer of formula (II): Alkyl) ester groups.

Wherein Z is an optionally substituted alkyl or optionally substituted heteroalkyl (including alkylene and heteroalkylene) chain, preferably having from 1 to about 16 atoms and preferably from 1 to about 16 more preferably as having an 8 atom, and carbon from one to about three optionally - has carbon unsaturated bond, and in accordance with a preferred embodiment Z is for example -CH 2 _-, - CH ₂ CH ₂ -, - C
H ₂ CH ₂ CH ₂ — or —CH ₂ OOCCH ₂ C
H ₂ —; R is optionally substituted alkyl, preferably having about 4 to about 16 atoms, acyclic groups such as t-butyl and other quaternary carbon groups and adamantyl or It is preferred that alicyclic groups such as norbornyl are branched; and R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , m, n, w, x, and y are the same as defined in the chemical formula (I).

As mentioned above, some of the preferred polymers of the present invention further contain repeating units.
In particular, the repeating unit preferably does not contain an acid (for example, hydroxy, carboxy) group or a reactive (for example, photoacid-labile component) group. More specifically, suitable polymers of the present invention include those represented by the following chemical formula (III).

Embedded image (Wherein w, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , m, and n are each the same as defined in the above chemical formula (I); R ⁶ is R ³ in the chemical formula (I) S is the same as defined for R ⁴ and R ⁵ ; S is a group containing no acid or reactive component, such as cyano, alkyl including alicyclic, heteroalicyclic, etc .; w ′, y ′ , And Z ′ are each greater than 0 and the mole fraction or percent of each polymer unit; and x ′ is greater than 0 or 0 and is the mole fraction or percent of the specified unit.)

As noted above, 193 nm and 157
For imaging below about 200 nm, such as nm, it is preferred that the polymers of the present invention be substantially or completely free of any phenyl or other aromatic groups. Thus, for imaging at short wavelengths, the polymer may be, for example, as defined by formula (III) above, with a mole fraction x'y 'of less than about 2 or 3 percent relative to all units of the polymer. Preferably. More preferably, the sum of x 'and y' is 0 or less than about 1 mole percent based on all units of the polymer.

Polymers of the above formula may contain various mixtures as w and R groups, for example by using various acryloxy (alkyl) esters or acryloxy (heteroalkyl) ester monomers during polymer synthesis. Good.

With respect to hydroxyphenyl of the above formula, it is preferred that the hydroxy group be substituted at the meta or para position of the phenyl ring.

R ¹ and R ^{2 in} the above formula are usually, for example, halogens (especially F, Cl or Br); C _1-8
Alkyl; C _1-8 alkoxy; C _2-8 alkenyl;
C _2-8 alkenyl or alkynyl, allyl such as phenyl; alkanoyl such as C _1-6 alkanoyl such as acyl; and the like. Generally, R ¹ and R ² groups are, for example, hydroxy, carboxy, —COO
It should not be an acid or reactive group that can react with a photoacid, such as an acid labile ester, such as H or other groups.

The R ³ , R ⁴ , R ⁵ , and R ⁶ substituents in the above formula are typically C _1-4 alkyl and hydrogen, and more typically methyl and hydrogen.

The above optionally substituted groups (W, R,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ ) can be substituted at one or more substitutable positions with one or more halogen (especially F, Cl or B).
r); C _1-8 alkyl; C _1-8 alkoxy; C
_2-8 alkenyl, that is, C _2-8 alkenyl or alkynyl, allyl such as phenyl;
Alkanoyl, such as _1-6 alkanoyl; may be substituted with other suitable groups. The component to be replaced is typically substituted at one, two, or three substitutable positions.

In the above formulas, the molar fractions and percentages of the units specified in each case have appropriate values within a relatively wide range. For example, in each formula, w is suitably from 1 to about 90 mole percent, more typically from about 5 to about 80 mole percent, and even more typically from about 10 to about 30 mole percent; x (formula And y are each independently about 5 or 10
From about 50 mole percent is more suitable, more typically about 15 or 20 to 40 mole percent; and in formula (III), z is about 1
From about 70 or 80 mole percent, more typically from about 5 or 10 mole percent to about 30, 40, 50, or 60 mole percent.

In a particularly preferred embodiment of the invention, in the above formula w is from about 5 to about 50 mole percent, more preferably from about 5 or 10 to about 30 mole percent.
Or 35; x (when indicated in the formula) is from about 5 to about 40 mole percent, more preferably from about 10 to about 20 or 25;
From about 90, more preferably about 55 or 60
From about 80.

The chemical formulas (I), (II) and (I)
The groups indicated in II) form the main part of the copolymer. More specifically, in Formulas (I) and (II), w,
A preferred sum of x and y is at least about 60 percent, more preferably at least about 70 percent, and an even more preferred sum of w, x and y is at least about 80, 85, 90 or 95 mole percent. In many instances, it is particularly preferred that the copolymer only contain the indicated acid labile and phenyl groups, and para-hydroxyphenyl units. That is, chemical formulas (I) and (I)
Each of I) results in 100% in w, x, and y. Similarly, the chemical formula (III)
Also, the preferred sum of w, x, y and z is at least about 60 percent, more preferably at least about 70 percent, and even more preferably w,
The sum of x, y and z is at least about 80, 85,
90 or 95 mole percent. Again, in many instances, the copolymer of formula (III) may have an acid labile group and a phenyl unit, and a para-hydroxyphenyl unit, and a non-acid /
It is particularly preferred that they only contain a non-reactive group S. That is, in chemical formula (III), w ', x'y', and z 'are 100%.

A particularly preferred polymer of the present invention has the structure of formula (IV):

Wherein R, R ³ , R ⁴ , R ⁵ , w, x, and y are each as defined above in Formula (II), and R is t-butyl. And other quaternary carbon groups, and alicyclic groups such as adamantyl and norbornyl, and R ³ , R ⁴ , R
Preferably, each ⁵ is independently methyl or hydrogen, and preferably the phenolic hydroxyl group is substituted at the meta or para position. The position of para is more preferable.

Polymers of formulas (IVA) and (IVB) are also suitable. These formulas has the formula (IVA) in the side chain photoacid - (repeating units of mole percent w) Rebiru group is the _{-C (= O) OCH 2 CH} 2 C (= O) OR, in formula IVB - C (= O) OCH ₂ CH ₂ O
It is the same as the above formula (IV) except that (ＯＲO) CCH ₂ CH ₂ C (=) OR. The preferred R, R ³ , R ⁴ , R ⁵ groups and substitution positions in the above formula (IV) are also preferable in the formulas (IVA) and (IVB). Formulas (IV), (IVA) and (IV)
In each of B), the preferred sum of w, x, and y is at least about 60 percent, more preferably at least about 70, 80, or 90 percent, and even more preferably at least about 95, 98, or 100 percent. .

The polymer of the present invention can be produced, for example, by radical polymerization. Alternatively, a plurality of monomers may be reacted at a high temperature, such as about 70 ° C. or higher, in an inert atmosphere (eg, N ₂ or argon) in the presence of a radical initiator as described above. It can be produced by providing various different units. However, the reaction temperature varies depending on the reactivity of the specific reagent used and the boiling point of the reaction solvent (when a solvent is used).
Suitable reaction temperatures for any particular system can be readily determined empirically by those skilled in the art based on the present specification. See Examples 2 and 3 below for exemplary reaction conditions. See also Examples 1 and 7 for the synthesis of monomers useful for making the polymers of the present invention.

The reaction solvent may be used as needed. Suitable solvents include alcohols such as DEB, propane and butanol, and aromatic solvents such as benzene, chlorobenzene, toluene, and xylene.
Dimethyl sulfide and dimethyl formamide are also suitable. The polymerization reaction also proceeds reliably.

Various radical initiators are used to make the copolymers of the present invention. For example, azo-bis-2,
2'-isobutyronitrile (AIBN) and 1,1 '
An azo compound such as azo-bis (cyclohexanecarbonitrile) may be used. Peroxides, peresters, peracids, and persulfates can also be used.

Monomers containing hydroxy (such as para-hydroxystyrene) and other reactive components are optionally condensed in "masked" form to enable polymer synthesis. For example, para-acetoxystyrene is used as the "masked" form of para-hydroxystyrene. Other hydroxy masking or protecting groups may be used. For example, (CH ₃ ) ₃ Si—, (CH ₃ ) _{2
(Butyl) Si -, ((CH 3} ) 3 C) 3 Si-, ( to form the silyl ether with a hydroxy component) Others such as alkylsilyl group _{and, CH 3 CH 2 C (=} O)
And other alkyl esters such as others.
After completion of the reaction, the formed polymer can be removed, for example, with NH ₄ OH or NH ₄ to remove the masking groups under basic conditions.
₄ is heated in the presence of a base such as OAc. See Example 3 below for exemplary conditions.

In general, a suitable weight average molecular weight (weight average molecular weight) of the copolymer of the present invention is used.
(larweight; Mw) is from about 1000 to about 100,000, more preferably from about 2000 to about 30,000. In addition, a suitable molecular weight distribution (mo
rectangular weight distributi
on; Mw / Mn) is about 3 or less, more preferably about 2 or less. The molecular weight (Mw or Mn) of the polymer of the present invention can be appropriately determined by gel permeation chromatography. Suitable molecular weight distributions of the copolymers of the present invention fall in the range of about 1 to 5, more typically about 1 to 3 or 4.

As mentioned above, the polymers of the present invention are highly useful as resin-binding components of photoresist compositions. Photoresists of the invention generally comprise a photoactive composition and a resin-binding composition comprising a polymer of the invention. The photoactive component comprises one or more photoacid generators (ie, PAGs)
And used in sufficient amounts to be exposed to actinic radiation to produce a latent image in the coating of the resist.

One group in a preferred PAG for use in the resists of the present invention comprises an imidosulfonate such as a compound of formula (V):

Embedded image (Where R is camphor, adamantane, alkyl (eg, C _1-12 alkyl) and perfluoro (C _1-12
Alkyl), especially perfluoroalkyl such as perfluoroanions such as perfluoroctansulfonate and perfluorononanesulfonate. A particularly preferred PAG is N-[(perfluoroctansulfonyl)
Oxy] -5-norbornene-2,3-dicarboximide. )

Sulfonate compounds such as sulfonate salts can also be used. Two suitable drugs PAG1 and P
AG2 can be represented by the following chemical formulas (VI) and (VII).

Embedded image

Embedded image

The preparation of such sulfonate compounds is disclosed in European Patent Application No. 96118111.2 (Issue No. 078136).

The above two iodonium compounds complexed with anions other than those already mentioned are also suitable.
In particular, the formula RSO ₃ Suitable anion ^- are those of. Where R is adamantane, alkyl (eg, C
_1-12 alkyl) and perfluoro (C _1-12)
Perfluoroalkyl such as alkyl), especially perfluorocounter anions such as perfluorooctanesulfonate, perfluorononanesulfonate.

[0048] Other known PAGs can also be used in the resists of the present invention. For example, N-sulfonyloxyimides can be used, as described in International Application WO 94/10608. Alternatively, for example, Thackeray (Th
U.S. Pat. No. 5,128,23 to Ackeray et al.
No. 2 and European Patent Application Nos. 0164248 and 0232972, when exposed to actinic radiation, halogen acid (eg HBr)
A non-ionic halogenated PAG, which produces the following, can also be used.

A preferred component material of the resist composition of the present invention is a dye compound. Preferred dies facilitate the resolution of the patterned resist image. This is usually made possible by reducing the effects and effects (eg, notching) of the exposure radiation on the resist image. Suitable dies include substituted and unsubstituted phenothiazines, phenoxazines, anthracenes and anthalobin compounds. A substituted phenothiazine,
Suitable substituents on phenoxazine, anthracene and anthrarobin include, for example, halogen, C _1-12 alkyl, C _1-12 alkoxy, C _2-12 alkenyl, C _1-12 alkanoyl such as acetyl, phenyl and the like. Allyl and others. Copolymers of such compounds can also be used as dies. Examples are anthracene acrylate polymers and copolymers.

Other optional additions which are preferred are added bases, especially tetrabutylammonium hydroxide (TBAH), or lactates of TBAH, which can enhance the resolution of the developed resist relief image. . Additive salts are used in relatively small amounts, for example, about 1 to 20 weight percent based on the photoactive component (PAG).

The photoresist of the present invention also optionally contains other materials. For example, other optional additions include anti-wrinkling agents, plasticizers, rate enhancers, and the like. Such optional addition is contained at a low concentration in the photoresist body. However, the filler and die are relatively high in concentration, for example, about 5 to 30 weight percent based on the total weight of the dried resist.

These components of the present invention can be easily manufactured by those skilled in the art. For example, the photoresist composition of the present invention may be obtained by adding a photoresist constituent material to an appropriate solvent. Solvents include, for example, ethyl lactate, 2-methoxyethyl ether (diglyme), glycol ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether; cellosolve esters such as methyl ethyl ketone;
There is ethoxyethyl propionate. Typically, the solids content of the composition will vary between approximately 5 and 35 weight percent based on the total weight of the photoresist composition. The resin binder and the PAG component must be sufficient to form a film coating layer and a fine latent and relief image. See Example 8 below which shows suitable amounts of resist constituents by way of example.

The compositions of the present invention are used according to generally known processing methods. The liquid coating composition of the present invention is applied to a substrate by spinning, dipping, roller coating or other conventional coating techniques. In spin coating, adjusting the solids content of the coating solution produces a film of the required thickness based on the particular spinning equipment used, viscosity of the solution, spinner speed and spinnable time.

The resist composition of the present invention can be applied to substrates conventionally used in processes involving coating with a photoresist. For example, the resist composition can be applied to silicon or silicon dioxide wafers for microprocessors and other integrated circuit component materials. Aluminum-aluminum oxide, gallium arsenide, ceramic,
Quartz or copper substrates also apply. Substrates used in liquid crystal displays and other flat panel displays, such as glass substrates, substrates coated with indium tin oxide, etc., are also suitable.

After coating on the surface of the photoresist,
Preferably, until the photoresist film has no wrinkles
Heat and dry to remove solvent. Thereafter, an image is formed through a mask as in the conventional manner. Exposure is sufficient to effectively activate the photoactive components of the photoresist system to form a patterned image in the resist overlayer. More specifically, this exposure energy typically ranges from about 1 to 3 depending on the composition of the exposure article and the photoresist.
It changes within the range of 00 mJ / cm ² .

The coating layer of the resist composition of the present invention is preferably photoactivated by an exposure wavelength in the deep UV range. Deep UV range is 350nm
Or less, more preferably in the range of about 300 nm or less, and about 150 to 300
Alternatively, it is typically 450 nm. A particularly preferred exposure wavelength is around 248 nm. Other suitable wavelengths include I-line (365 nm), 193 nm and 157 nm. In addition, ion projection lithography (ion projection lith)
It is also possible to use a source such as extremely short wavelength imaging such as O.G. (IPL), E-beam, EUV, X-ray.

After exposure, it is preferred to bake the film layer of the resist composition at a temperature in the range of about 70 ° C. to about 150 ° C. Thereafter, the film is developed. The exposed resist film is developed in a positive mold using a polar developer. It is preferable to use an aqueous developer such as an inorganic alkali. To give an example of inorganic alkali,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Quaternary ammonium hydroxide solutions such as sodium bicarbonate, sodium silicate, sodium metasilicate, tetraalkyl ammonium hydroxide solutions; ethylamine, n-
Various amine solutions such as propylamine, diethylamine, di-n-propylamine, triethylamine or methyldiethylamine; alcohol amines such as diethanolamine and triethanolamine; cyclic amines such as pyrrole, pyridine and others There is. Development is generally carried out according to technically required measures.

After developing the photoresist coating on the substrate, the developed substrate is selectively treated where the resist is exposed. For example, portions of the substrate where the resist is exposed are chemically etched or plated according to procedures known in the art. In the production of microelectronic substrates, for example in the production of silicon dioxide wafers,
Suitable etchants include gaseous etchants, such as CF ₄ or CF ₄ / CH applied as a plasma stream.
There are etchant which is based on chlorine or fluorine, such as F _3. After such treatment, the resist is removed from the treated substrate using known stripping procedures.

All of the documents referred to herein are attached to the referenced application. The following examples are not intended to limit the present invention but to illustrate it.

Common Comments on the Examples Methacrylic acid (M)
AA), acrylic acid (A)
A), 2- (methylacryloxy) ethyl succinate (2- (methylacryloxy) ethyl)
succinate; MES) and styrene (st
yrene; Sty) is AldrichChemic
purchased from Al. Acetoxystyrene (aceto
xystyrene (AS) was also purchased and used without post-purification purification. Acryloxypropionic acid (ac
ryloxypropionic acid; AOP
A) was purchased from Polyscience and subjected to a purification treatment including two vacuum distillation steps. In the first distillation step, AOPA (40 g) and hydroxytempo (70 m
In g), a short path height device was used. Raw material A
OPA (〜9 g) was boiled at 95 ° C./1 mmHg.
In the second distillation step, raw material AOPA (9 g) and hydroxytempo (40 mg)
Then, use a low active column with a cooling cylinder (jackete
d bigerous column). Pure A
OPA (〜8 g) boiled at 85 ° C./1 mmHg. The polymerization was carried out with 2,2′-azobis (2,4-dimethylpentanenitrile) (Vazo52) or 2,2′-azobisisobutyronitrile.

Examples 1-6: Preparation of the Polymers of the Invention Example 1: para-hydroxyphenyl (hydroxy)
phenyl; HP) / phenyl / t-butyl methacryloxy-acetate (tert-butylmethyl)
Synthesis of cryoxy-acetate (t-BMAOA) polymer. t-butyl acryloxy acetate (monomer)

Embedded image

In a 500 mL round bottom flask, 23.7
8 g, 0.22 mol of acrylic acid, 30.12 g.
0.2 mol of t-butyl bromoacetate, 100 m
L DMF was charged. The resulting white suspension was stirred and heated at 100-110 ° C for 48 hours. After cooling to room temperature, the suspension was filtered to obtain a light brown solution. This was extracted with 3 L of DI water and 200 mL of hexane. The hexane solution was dried over MgSO ₄ and collect. The solvent was removed under reduced pressure.

The synthesis of t-butyl methacryloxy acetate is performed in the same manner as described above, except that acrylic acid is replaced with methacrylic acid. Monomer purity is ¹³ C and ¹ H
Confirmed by NMR.

Part 2: Polymer synthesis

Embedded image

Para-hydroxystyrene (HS) 7 in diethylene glycol
5 g (31%) (HS is 23.25 g, 194 mmo
l), styrene (5.75 g, 55 mmol), and tBMAOA (5.51 g, 26 mmol) were placed in a reaction flask. Further, 5.32 g of HS in DEG (H
S is 1.65 g, 14 mmol) and AIBN (1.
42 g, 9 mmol, 3 mol%) and 120 g of acetonitrile. The reaction was deoxygenated with nitrogen while stirring and refluxed for 14 hours. The resulting solution was precipitated in water, filtered and air dried. The polymer was then suspended in dichloromethane (10x) for 4 hours. The polymer was filtered and dried under reduced pressure at 40 ° C. overnight.

Example 2 Para-hydroxyphenyl (h
hydroxyphenyl; HP) / phenyl / t-butylacryloxy-acetate (tert-butyl)
Synthesis of acryloxy-acetate (t-BAOA) polymer

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Part 1.4 4-Acetoxystyrene (6
1.32 g, 420 mmols), styrene (12.4
8 g, 120 mmols) and t-butylacryloxy-acetate (11.16 g, 60 mmols) were dissolved in 300 mL of isopropyl alcohol. The reaction solution was deoxygenated by stirring for 20 minutes and gently bubbling a stream of nitrogen. It was then placed under a nitrogen blanket. The polymerization solution is then gently refluxed. Subsequently, azo-bis-2,2′-isobutyronitrile (2,2′-azobisisobutyron) dissolved in 40 mL of acetonitrile was used.
itrile; AIBN, 3.94 g, 24 mmol
s, 4 mol%) was added to the mixture that was gently refluxed for 10-15 minutes or more. The polymer was refluxed with stirring for 18 hours.

Part 2. Deacetylation. The refluxing polymer solution was allowed to cool for approximately 3 hours. Then ammonium hydroxide (14.7 g, 420 mmols) was added over 15 minutes. The solution was refluxed for 48 hours.

Part 3. Base removal. In a room temperature polymer solution, conditioned IRN-77 beads (strongly acidic, cation exchange beads; see preparation below) 200
g was added and the mixture was gently stirred for 2 hours.
The polymer solution was filtered and the polymer was separated by precipitation into 3 L of water. The polymer was further filtered, washed well with water and dried. Drying was performed in a vacuum oven at 40 ° C. for 24 hours.

Example 3 Synthesis of poly (styrene-CO-2-carboxymethylmethacrylic acid)

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T-Butyl methacryloxy acetate (0.02 mol), 0.06 mol of styrene, and 32 mL of 1,4-dioxane were placed in a 100 mL round bottom flask. After the reaction solution was deoxygenated with nitrogen, 0.53 mol of Vazo52 was added. The reaction solution was stirred and refluxed for 24 hours. Hydrochloric acid (8m
L) was added to the stirred reaction solution and the resulting mixture was refluxed for 24 hours. This copolymer is 3000
Fractionated by precipitation into mL of water and dried in a vacuum oven at 50 ° C. for 48 hours. 79/21 poly (styrene-CO-2-carboxymethylmethacrylic acid)
% Yield was obtained. Tg = 77 ° C., Mw = 16140A
MU, PD = 3.85, Acid = 0.22eq / mo
1, DR (0.26N) = 1170 A / s.

Example 4: Poly (hydroxystyrene-C
Synthesis of O-2-carboxymethyl methacrylic acid).

Embedded image

T-Butyl methacryloxy acetate (0.01 mol), 0.115 mol of acetoxystyrene, and 52 mL of 1,4-dioxane were added to 12
Placed in a 5 mL round bottom flask. After the reaction solution was deoxygenated with nitrogen, 0.004 mol of Vazo52 was added. The reaction solution was stirred and refluxed for 24 hours.
Hydrochloric acid (10 mL) was added to the stirred reaction solution and the resulting mixture was refluxed for 24 hours. The copolymer was separated by precipitation into 4000 mL of water,
It was dried in a vacuum oven at ℃ for 48 hours. 96/4 poly (hydroxystyrene-CO-2-carboxymethylmethacrylic acid) gave a 62% yield. Tg = 157 ° C.,
DR (0.26N) = 4000 A / S.

Example 5: Poly (hydroxystyrene-C
O-2- (methylacryloxy) ethyl stacinate
Synthesis of

Embedded image

2- (methylacryloxyl) ethyl succinate (0.02 mol), 0.14 mol of acetoxystyrene, and 68 mL of tetrahydrofuran were placed in a 100 mL round bottom flask. After deoxidizing the reaction solution with nitrogen, 0.008 mol of Vazo
52 were added. The reaction solution was stirred and refluxed for 24 hours. The copolymer was fractionated by precipitation into 3000 mL of hexane and dried in a vacuum oven at 40 ° C. for 24 hours.
Let dry for hours.

MES / A dissolved in 20 mL of THF
The S copolymer (5 g) was gently refluxed for 0.5 hour. Next, 0.29 mol of ammonium acetate dissolved in 5 mL of water was added dropwise to the stirring solution. The resulting mixture was refluxed for 24 hours. The MES / AS copolymer was fractionated by precipitation into 500 mL of water. The yield was 70%. IR (H
(S peak) = 1720 cm < ^-1 >.

MES dissolved in 120 mL of THF /
The HS copolymer (3.5 g) was acidified at room temperature. Hydrochloric acid (5 mL) was added dropwise into the stirred solution.
The MES / HS copolymer was fractionated by precipitation into 500 mL of water and dried in a vacuum oven at 80 ° C. for 48 hours. 90/10 poly (hydroxystyrene-CO-
5- (2- (methylacryloxy) ethyl succinate)
A yield of 5% was obtained. Tg = 130 ° C., Mw = 8125
AMU, polydispersity (P
D) = 2.23, Acid = 0.07 eq / mol, dissolution rate (DR)
(0.26N) = 1170A / s.

Example 6: Poly (hydroxystyrene-C
Synthesis of Ot-butyl methacryloxy acetate).

Embedded image

T-Butyl methacryloxy acetate (0.14 mol), 0.25 mol of acetoxystyrene, and 175 mL of tetrahydrofuran
Placed in a 50 mL round bottom flask. After the reaction solution was deoxygenated with nitrogen, 0.01 mol of Vazo52 was added. The reaction solution was stirred and refluxed for 24 hours.
The copolymer was fractionated by precipitation into 3000 mL of hexane and dried in a vacuum oven at 40 ° C. for 24 hours.

BMS / A dissolved in 20 mL of THF
The S copolymer (5.4 g) was gently refluxed for 0.5 hours. Then 0.51 mol dissolved in 28 mL of water
Was added dropwise to the stirred solution. The resulting mixture was refluxed for 24 hours. Two types of solvent layers, an organic layer and an aqueous layer, were formed. The copolymer was fractionated by precipitation of two layers into 500 mL of water and dried in a vacuum oven at 80 ° C. for 48 hours.

62/38 poly (hydroxystyrene-C
(Ot-butyl methacryloxy acetate) gave a 68% yield. Tg = 173 ° C., Mw = 12386AM
U, PD = 1.98, Acid = 0.01eq / mo
1, DR (0.26N) = 8 A / s (baked at 90 ° C.). All acetoxystyrene for BMA peak in IR overlap can not confirm whether the converted hydroxystyrene, but clearly demonstrated hydroxystyrene peak (155 ppm) in C ^{13 NMR} spectrum.

Example 7: Synthesis of monomers used to prepare the polymer of the present invention t-butyl-2- (methacryloylox
(ethyl) Preparation of succinate. In a round bottom flask, 8.51 grams of 2- (methha)
(Cryloyloxyethyl) ethyl succinate was dissolved in 37 mL of methylene chloride and t-butyl trichloroacetimidate dissolved in 147 mL of cyclohexane was added. The mixture was stirred under nitrogen. Then 750 μL of boron trifluoride diethyl etherate was added and the mixture was stirred for approximately 18 hours. The reaction solution was then filtered through silica gel and a glass funnel. After adding 10 g of NaHCO ₃ to the filtrate, 50 mL of 80/20 cyclohexane / CH ₂ was added.
Cl ₂ was poured into the filtrate through silica. Required product, t-butyl-2- (methacryloyloxyethyl)
The succinate was fractionated under a roto-vap and dried in a vacuum oven.

2. t- butyl acryloxypropionic propionate _{(CH 2 = CHC (=)} OCH 2 CH 2 C (=) OC
_{(CH 3))} 3 manufacturing. In a 500 mL three-necked flask with a condenser, t-
Butyl alcohol ethyl acetate (14.8 grm
s; 0.2 moles), acryloxypropionate (39.6 grams; 0.275 moles), and dimethylaminopyridine (0.6 grams). The resulting solution was cooled in an ice bath to 5 ° C. And 1,3-diclohexylcarbodiimide (ethylcyclohexylcarb) in ethyl acetate.
odiimide (DCC) solution (45.4 grams)
s; 0.22 moles) was added slowly over 45 minutes. During that time, the reaction temperature was kept below 10 ° C. After the end of the DCC addition, the reaction mixture was then stirred for 48 hours. The reaction mixture was then filtered through cel; ite and the filtrate was roto-vapor provided the title compound, t-butylacryloxypropionate.

Example 8 Production of Photoresist and Lithographic Processing The polymer of the present invention was blended as a constituent material of a positive photoresist composition, and the value of the lithographic processing was examined.

The polymers of Examples 1, 2 and 6 were formulated into separate resist compositions, defined herein as Resists 1 to 3, respectively. That is, the polymer of Example 1 was blended into the resist 1, the polymer of Example 2 was blended into the resist 2, and the polymer of Example 6 was blended into the resist 3. These polymers are 17
% Solids. The polymer is dried and the PAG (5% by weight based on polymer), base (tetrabutylammonium hydroxide, 0.4% by weight based on polymer), and surfactant (based on total solids) 0.5% by weight) as a solution in ethyl lactate. The PAG is di (4-t-butylphenyl) iodonium (+/-)-10-camphor sulfonate (the synthesis of which is disclosed in Example 2 of European Patent Application No. 78136).

Each of the resists 1, 2, and 3 was processed as follows. 600 on the surface of the resist in advance
A silicon wafer substrate coated with an Angstrom antireflective composition layer. The resist film had a thickness of 7000 Å +/− 25 Å and was baked slowly at 130 ° C. for 60 seconds. Next, this resist layer is applied to GCA XLS 780
Exposure to patterned 248 nm radiation using a 0 stepper (0.53N, 0.74 °). The exposed coating layer was baked after exposure at 130 ° C. for 90 seconds, and developed by a single paddle method for 45 seconds using a 0.26 N aqueous solution of tetramethylammonium hydroxide.
A high-resolution resist relief image including characteristics of 0.25 μm and 0.25 μm or less was obtained.

The foregoing description of the invention is merely illustrative of the invention, and modifications and changes may be made without departing from the spirit and scope of the invention as set forth in the appended claims. It should be understood that.

[0088]

As is apparent from the above description, the present invention contains a group which is a carboxyl and / or a carboxyl precursor (such as carboxylate) which can be applied without problems even in high-performance practical use. New polymers have been provided, and such polymers have been effectively used as photoresist resin binder materials.

 ────────────────────────────────────────────────── ─── Continuation of the front page (71) Applicant 596156668 455 Forest Street, Marlborough, MA 01752 U.S.A. A (72) Inventor Matthew A. King, United States 02134 Massachusetts Boston Apartment # 1 Higgins Street 26 (72) Inventor George G. Berkeley United States 01522 Jefferson Main Street, Massachusetts 1566 (72) Inventor Amy M・ Kwok 6H8 K1C Grosseter Place de Labins, Ontario, Canada 1700 (72) Inventor Zibiao Mao United States 01545 Massachusetts Shrewsbury Green Draive Eve Shrewsbury 56K (72) Inventor Roger EF Sinta United States of America 01503 Woburn, MA, Anna Road 9F Term (Reference) 2H025 AA02 AB16 AB17 AC01 AC03 AD03 BE00 BG00 CB14 CB17 CB41 CB43 FA03 FA12 FA17

Claims (23)

[Claims] 1. A photoresist composition comprising a photoactive component and a polymer, wherein the polymer contains carboxyl or a carboxyl precursor group as a side group, and the group is directly bonded to the main chain of the polymer. A photoresist composition comprising one or more atoms other than a keto group between the main chain and the main chain. 2. The polymer according to claim 1, wherein the polymer is a photoacid-labile group (photot) as the side group which is not directly bonded to its main chain.
The photoresist composition according to claim 1, wherein the photoresist composition comprises an acid-labile group. 3. The polymer according to claim 1, wherein the polymer is a photoacid-labile ester group as the side group not directly bonded to its main chain.
2. The photoresist composition of claim 1, wherein the photoresist composition comprises: 4. The carboxyl or a carboxyl precursor group as a side group is not directly bonded to the main chain of the polymer but has one or more saturated carbon atoms interposed between the main chain and the polymer. The photoresist composition according to claim 1. 5. The photoresist composition according to claim 1, wherein the polymer further contains a phenol group. 6. The photoresist composition of claim 1, wherein said polymer is substantially free of aromatic groups. 7. A photoacid-labile group (photoac) as the side group which is not directly bonded to the main chain of the polymer.
The photoresist composition of claim 2, wherein the (id-labile groups) is an acrylate group. 8. The photoac-labile group (photoac)
id-labilegroups is acryloxy (C _1-12 alkyl) ester, methacryloxy (C
_1-12 alkyl) ester, acryloxy (C
_1-12 heteroalkyl) ester or methacryloxy _{(C 1-12} heteroalkyl) ester group, a photoresist of claim 2. 9. The photoresist composition according to claim 1, wherein the polymer is represented by the following chemical formula (I). Embedded image (Wherein w is a photoacid-labile group that is not directly attached to the polymer backbone but is through one or more atoms between the backbone and the polymer.
s); R ¹ and R ² are the same or different non-hydrogen substituents; R ³ , R ⁴ and R ⁵ are each independently hydrogen or optionally substituted alkyl; m is 0
N is an integer from 0 to 4; w and y are
X is greater than or equal to 0 and the mole fraction or percent of each polymer unit, respectively; and x is 0 or greater and is the mole fraction or percent of the specified phenyl unit. ) 10. The method according to claim 10, wherein W is a photoacid-labile ester (p
photoacid-labile ester gro
10. The photoresist composition of claim 9, comprising an (ups) group. 11. The photoresist composition of claim 9, wherein the sum of w, x, and y is at least substantially 90 percent. 12. The polymer of the following formula (II):
The photoresist composition according to claim 1, wherein Embedded image Wherein Z is optionally substituted alkyl or optionally substituted heteroalkyl; R is optionally substituted alkyl; R ¹ and R ² are each the same or different non-hydrogen substituents; R ³ , R ⁴ and R ⁵ are each independently hydrogen or optionally substituted alkyl; m is
An integer from 0 to 5; n is an integer from 0 to 4; w and y
Is greater than 0 each and the mole fraction or percent of each polymer unit; and x is 0 or greater and is the mole fraction or percent of the specified phenyl unit. ) 13. The photoresist composition of claim 12, wherein the sum of w, x, and y is at least substantially 90 percent. 14. The polymer of the following formula (IV):
The photoresist composition according to claim 1, which is represented by the formula: Embedded image Wherein R is an optionally substituted alkyl having about 4 to about 18 carbon atoms, a branched acyclic or alicyclic group; R ¹ and R ² are each the same or different Non-hydrogen substituents; R ³ , R ⁴ and R ⁵ are each independently hydrogen or optionally substituted alkyl; m and n are each independently 0 to 5; w and y are each greater than 0 , In mole percent of each polymer unit; and x is 0 or greater, which is the mole fraction of each unit.) 15. The photoresist composition of claim 14, wherein the sum of w, x, and y is at least substantially 90 percent. 16. A method of forming an article of manufacture, comprising: a) applying a layer of the photoresist composition of claim 1 on a substrate; and b) exposing with a patterned image, the method comprising the steps of: Developing said photoresist layer to obtain a photoresist relief image. 17. The method of claim 16, wherein said substrate is a microelectronic wafer of a flat panel display substrate. 18. The method according to claim 1, wherein the photoresist layer has a thickness of about 365 n.
17. The method according to claim 16, wherein the exposure is performed with radiation having a wavelength of m, 248 nm, 193 nm or 157 nm. 19. An industrial product comprising a substrate coated with the photoresist of claim 1. 20. An industrial product according to claim 19, wherein said substrate is a microelectronic wafer or a flat panel display substrate. 21. A polymer comprising a carboxyl or a carboxyl precursor group as a side group,
The above-mentioned polymer, wherein the group has one or more atoms other than a keto group interposed between the main chain and the main chain without directly bonding to the main chain of the polymer. 22. The method according to claim 21, wherein the carboxyl group or a group that is a precursor of carboxyl is not directly bonded to the main chain of the polymer but has one or more unsaturated carbon atoms between the main chain and the main chain. The polymer as described. 23. The compound represented by the following chemical formula (I).
The polymer according to 1. Wherein w is a photoacid-labile group that is not directly attached to the polymer backbone but is through one or more atoms between the backbone and the polymer.
R ¹ and R ² are the same or different non-hydrogen substituents; R ³ , R ⁴ and R ⁵ are each independently hydrogen or optionally substituted alkyl; m
Is an integer from 0 to 5; n is an integer from 0 to 4; w and y are each greater than 0; the mole fraction or percent of each polymer unit; and x is 0 or greater; It is the mole fraction or percent of the specified phenyl units. )