KR20020073258A - Photosensitive resin composition for detecting system error of exposure device - Google Patents

Abstract

PURPOSE: A photosensitive composition to form such images that an exposed part can be recognized from a non-exposed part only by exposure to radiation is provided, and a photosensitive resin composition having high sensitivity to which stable visualizing property by exposure necessary and sufficient for the alignment measurement of exposure device is imparted is provided. CONSTITUTION: In a photosensitive resin composition that is used to detect the system error in an exposure device when a mask pattern is transferred to a photosensitive resin composition film by transferring the mask pattern onto the photosensitive resin composition film only by exposure to radiation and detecting the focused state of the transferred pattern image, the photosensitive resin composition for detection of the system error of an exposure device is characterized in that the photosensitive resin composition contains (A) a compound which produces an acid by exposure to radiation and (B) a resin which changes its volume by the reaction with the acid produced by (A).

Description

PHOTOSENSITIVE RESIN COMPOSITION FOR DETECTING SYSTEM ERROR OF EXPOSURE DEVICE}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition used for detecting a system error of an exposure apparatus used in manufacturing semiconductor devices of IC and LSIZ.

Exposure apparatus for semiconductor element manufacturing, such as IC and LSI, requires two basic performances, namely, a resolution performance and a polymerization performance. The former is the ability to form a fine pattern on the photoresist surface applied on the surface of the semiconductor substrate (hereinafter referred to as the "wafer"), and the latter how to accurately pattern the pattern on the photomask with respect to the pattern formed on the wafer surface in the previous step. The ability to transcribe in position.

Currently, the required resolution performance is 130 nm or less, and an exposure apparatus using KrF excimer laser (248 nm), ArF excimer laser (193 nm), and F ₂ excimer laser (157 nm) as light sources for achieving this resolution. An exposure apparatus using an electron beam as an exposure light source and an exposure apparatus using an X-ray as an exposure light source have been studied. In any exposure method, the polymerization precision generally requires a value of 1/3 to 1/5 of the minimum baking line width, and achieving this accuracy generally involves the same or higher difficulty in achieving the resolution performance. have.

Conventionally, as a method of correcting the relative alignment of a pattern on a reticle surface and a pattern on a wafer surface, that is, a system error of alignment, a resist is applied to a reference wafer which is guaranteed a magnification and a SHOT arrangement, and alignment and exposure are performed in a usual procedure. It was common to take out from the apparatus, develop the resist, read the error amount by relying on a mark such as a vernier, and input the calculated value therein into the apparatus as an offset value.

In this method, however, the operation rate of the apparatus is lowered, the labor of the operator is increased, and a lot of time is required for a series of operations, so that there is a problem that the change over time progresses with time after exposure.

As a method for solving such a problem, Japanese Patent Publication No. Hei 6-50716 discloses a magneto-optical material or a photochromic material, but the sensitivity of the photosensitive material is insufficient. Japanese Patent Laid-Open Publication No. Hei 5-158226 and Japanese Patent Laid-Open Publication No. Hei 9-160229 disclose a photosensitive material which changes color by acid, but the visibility, sensitivity, and stability of the formed image only under an exposure of 300 nm or less. This was insufficient.

It is an object of the present invention to provide a photosensitive resin composition having a high sensitivity and imparting stable exposure visibility necessary for alignment measurement of an exposure apparatus.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the relationship between the film thickness and exposure amount used in order to demonstrate a volume variation rate.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the constituent material of the photosensitive resin composition, this inventor discovered that the objective of this invention is achieved by using the compound which generate | occur | produces an acid by exposure of specific resin and a specific radiation, and to this invention, Reached.

That is, the said object is achieved by the following structures.

(1) The photosensitive resin for detecting the system error of the exposure apparatus when the mask pattern is transferred onto the photosensitive resin composition film by transferring the mask pattern onto the photosensitive resin composition film only by the exposure of radiation, and detecting the imaging state on the transfer pattern. As a composition,

A) a compound that generates an acid by exposure to radiation and

B) The photosensitive resin composition for system error detection of the exposure apparatus containing resin which changes in volume by reaction with the acid generated from said A).

(2) A photosensitive resin composition for detecting a system error of the exposure apparatus according to (1), further comprising a dye in which the spectral characteristics of the wavelength region of 400 nm or more change by reaction with an acid generated by exposure.

(3) The photosensitive resin composition for detecting a system error of the exposure apparatus according to (2), wherein the dye is a compound represented by the structure of the following general formula (I).

In formula (I), R <_11> -R <_15> , R <_21> -R <_25> , R <_31> -R <_35> may mutually be same or different, A hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, carboxyl group , Halogen atom, nitro group, hydroxyl group, substituted or unsubstituted carbonyl group of 1 to 6 carbon atoms, substituted or unsubstituted amino group, substituted or unsubstituted aryl group of 6 to 12 carbon atoms, substituted or unsubstituted C6 to 12 carbon atoms An aryloxy group is shown.

In addition, two of R ₁₁ to R ₁₅ may be bonded to each other to form a ring. Two of R ₂₁ to R ₂₅ may be bonded to each other to form a ring. Two of R ₃₁ to R ₃₅ may be bonded to each other to form a ring. When forming a ring, you may form a ring including an oxygen atom, a sulfur atom, and a nitrogen atom.

Provided that one of R ₁₁ , R ₁₅ , R ₂₁ , R ₂₅ , R ₃₁ and R ₃₅ is a C 1-6 alkoxy group, carboxyl group, halogen atom, nitro group, hydroxyl group, substituted or unsubstituted C 1-6 Carbonyl group, substituted or unsubstituted amino group, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms.

Each substituent may be bonded via an amide bond.

(4) The exposure apparatus according to any one of (1) to (3), wherein the resin of B) is an alkali insoluble resin which protects 30 mol% or more of the alkali-soluble group of the alkali-soluble resin with an acetal group. Photosensitive resin composition for system error detection.

(5) The minimum value of the transmittance | permeability with respect to the light of 400 nm-800 nm wavelength region of the photosensitive composition unexposed part of 1000 nm film thickness is 85% or more, and the transmittance | permeability with respect to the light of 400 nm-800 nm wavelength region of the photosensitive resin composition exposure part. The photosensitive resin composition for detecting a system error of the exposure apparatus according to any one of (1) to (4), wherein the minimum value is 75% or less.

Preferred embodiments are described below.

(6) As a compound which generates an acid by exposure of the said radiation, the sulfonium salt represented by the structure of following General formula (II), the iodonium salt represented by the structure of following General formula (III), and the following general formula (IV) A photosensitive resin composition for detecting a system error of the exposure apparatus according to any one of (1) to (5), characterized by containing at least one compound selected from the group of sulfonyldiazomethane represented by the structure of (1) to (5). .

Formula (II), in the formula _{(III), Ra 1 ~Ra 5} , Rb 1 ~Rb 5, Rc 1 ~Rc 5, Re 1 ~Re 5 and Rf ₁ ~Rf ₅ are each independently a hydrogen atom, A straight, branched or cyclic alkyl group of 1 to 6 or a straight, branched or cyclic alkoxy group of 1 to 6 carbon atoms is represented.

X ^- is R ₃ -SO ₃ ^- and display ^- or R ₃ -COO. R ₃ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 20 carbon atoms, and a straight chain having 1 to 20 carbon atoms. , A branched or cyclic perfluorouroalkyl group, or a substituted or unsubstituted perfluorofluoroaryl group having 6 to 20 carbon atoms.

In formula (IV), Rd ₁ and Rd ₂ are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or substituted or substituted with 6 to 20 carbon atoms, or Unsubstituted aralkyl group is shown.

(7) A photosensitive resin composition for detecting a system error of the exposure apparatus according to any one of (1) to (6), further comprising an organic basic compound and / or an organic carboxylic acid.

(8) The photosensitive resin composition for detecting a system error of the exposure apparatus according to (4), wherein the acetal group is an acetal group selected from the group represented by the following structure.

Hereinafter, each component used for this invention is demonstrated in detail.

[1] resins of B)

If the photosensitive resin composition for detecting a system error of the exposure apparatus using light as a light source, the resin used in the present invention has a minimum value of 60% or more at an exposure wavelength at a film thickness of 1000 nm, It is important to contain that the volume increases or decreases in reaction with acid generated by exposure.

As preferable resin which reduces a volume in reaction with the acid which generate | occur | produced in exposure, what contains an acetal structure decomposed | dissolved into acid, and is insoluble in aqueous alkali solution is mentioned. Insoluble in aqueous alkali solution means that the dissolution rate of the resin film in the 2.38% aqueous tetramethylammonium solution is 3000 seconds / µm or less.

The crosslinking of alkali solubilizing groups of the resin in the acetal bond decomposed to an acid is more preferable because of its high molecular weight, solubility in alkali is lowered, and the change in volume is also large. When the exposure light source is an energy ray such as an electron beam or X-ray, the transmittance of the resin is not limited.

In the present invention, the change in volume in the acid generated by the exposure of the radiation means that the volume decreases or increases, but preferably the volume decreases. For example, an acetal group decomposed into an acid is decomposed by an acid generated by exposure to radiation, and a decrease in the volume of the resin after exposure can be used.

As much as possible, the volume change rate is good, and it is required at least 3% or more, preferably 5% or more based on the volume of the resin before exposure.

Volume variation can be estimated by the film thickness of the composition spin-coated on a silicon substrate, for example. The composition of the present invention is spin-coated on a silicon substrate, baked at 90 DEG C / 90 seconds, dried, and the film thickness is measured by a commercially available thickness gauge (this film thickness is referred to as FT _init ).

This film is exposed with a KrF excimer laser, and the film thickness of the exposed portion is measured by a thickness gauge. The graph as shown in FIG. 1 is produced, changing exposure amount, and FT _exp (film thickness at the time of film thickness fluctuation) is calculated | required.

In this case, the volume change rate (%) may be defined as (FT _exp -FT _init ) / FT _init × 100. When the volume shrinks, it becomes negative, and when the volume increases, it becomes positive.

In this invention, once the volume of the said resin changes by reaction with an acid, the volume is hard to fluctuate and stabilizes with subsequent time.

As resin of this invention, it is preferable that it is alkali-insoluble resin which protected 30-50 mol% of alkali-soluble group of alkali-soluble resin with an acetal group.

Examples of the alkali-soluble resin include novolak resins, hydrogenated novolak resins, acetone-pyrogarol resins, polyhydroxystyrenes, alkyl or alkoxy substituted polyhydroxystyrenes, hydroxystyrene-styrene copolymers, and hydroxystyrene- N-substituted maleimide copolymers, some alkylates or acylates of hydroxyl groups of polyhydroxystyrene, styrene-maleic anhydride copolymers, carboxyl group-containing methacrylic resins, carboxyl group-containing acrylic resins and derivatives thereof can be exemplified. It is not limited to.

Preferred alkali-soluble resin among these is polyhydroxy styrene, carboxyl group-containing methacryl-type resin, and carboxyl group-containing acrylic resin. Acetal is particularly preferable as a group or a bond decomposed by reaction with an acid.

Especially preferable resin used for this invention is resin represented by Formula (A) or Formula (B).

In Formulas (A) and (B), BL ₁ and BL ₂ may be the same or different and represent an acetal group represented by the structure of the following general formula (I).

L ₁ represents a group which does not decompose into a hydrogen atom or an acid.

0.1 ≦ a ≦ 0.5, 0.1 ≦ b ≦ 0.5, and 0.0 <c ≦ 0.3.

In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms. W represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. n represents the integer of 1-4.

In said Formula (I), as W, a linear, branched or cyclic C1-C6 alkyl group, and n is 1 or 2 are preferable.

Moreover, as an acetal group represented by the structure of said Formula (I), there exists especially preferably the group represented by the following structure.

L ₁ is not particularly limited as long as it is a group that does not decompose in an acid, but is preferably a hydrogen atom, a straight chain, branched or cyclic alkyl group having 1 to 6 carbon atoms, a straight chain, branched or cyclic alkoxy group having 1 to 6 carbon atoms, or halogen A group selected from the group of an atom, a nitro group, an amino group, or a cyano group. Especially preferably, they are a hydrogen atom, a C1-C6 linear, branched or cyclic alkyl group, and a C1-C6 linear, branched or cyclic alkoxy group.

The protection rate and molecular weight of the resin are greatly influenced by alkali solubility of the resin. In general, the higher the protection rate, the lower the alkali solubility of the resin and the larger the volume change. Therefore, the higher the protection rate is, the more preferable it is to achieve the effect of the present invention. Specifically, 30% or more is preferable.

However, if the protection rate is too high, contamination by decomposition products generated during deprotection is concerned, and as the protection rate, 30% or more and 50% or less are more preferable.

Although the higher the molecular weight of the polymer is, the higher the molecular weight of the polymer is, the lower the alkali solubility. However, when the molecular weight is too high, the rigidity of the polymer is increased, the volume variation after exposure is reduced, and the filterability of the composition is also deteriorated. As for molecular weight, 8000 or more and 600000 or less are preferable.

Outside the appropriate ranges of the protective ratio and the molecular weight, the alkali solubility of the resin is increased and the volume change is not obtained. Therefore, the effect of the present invention cannot be obtained.

The weight average molecular weight and the dispersion degree can be obtained by gel permeation chromatography (polystyrene conversion value).

In the photosensitive resin composition of this invention, 40-99.99 weight% is preferable, and, as for the compounding quantity of the whole composition of all the resin which concerns on this invention in total solid content, More preferably, it is 50-99.97 weight%.

[2] a compound that generates an acid by exposure to radiation (hereinafter referred to as a "photoacid generator")

The photoacid generator used in the present invention is a compound that generates an acid by irradiation of radiation.

Such photoacid generators include photoinitiators of photocationic polymerization, photoinitiators of radical photopolymerization, photochromic agents of pigments, photochromic agents, micro resists, and the like. Preferably, g-rays, h-rays, i-rays, KrF excimer laser light), ArF excimer laser light, electron beams, X-rays, molecular rays or ion beams can be selected and used as appropriate.

In addition, as other photoacid generators used in the present invention, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenium salts, arsonium salts, and organic halogen compounds, for example. Photo-degraded compounds, such as organometallic / organic halides, photoacid generators having o-nitrobenzyl-type protecting groups, iminosulfonates, sulfonic acid, disulfone compounds, diazoketosulphones, diazodisulfone compounds Etc. can be illustrated.

Moreover, the compound which introduce | transduced the group or compound which generate | occur | produces an acid by these light in the polymer main chain or side chain can be used.

However, as the photoacid generator of the present invention, the trihaloalkyl compound, the diazonium salt compound, and the olutoquinone diazide compound are not preferable because of low sensitivity.

As a preferable photo-acid generator, the sulfonium salt represented by the structure of following General formula (II), the iodonium salt represented by the structure of following General formula (III), and the sulfonyl diazomethane represented by the structure of following General formula (IV) It is preferable to use at least 1 sort (s) of the compound chosen from the group of.

Formula (II), in the formula _{(III), Ra 1 ~Ra 5} , Rb 1 ~Rb 5, Rc 1 ~Rc 5, Re 1 ~Re 5 and Rf ₁ ~Rf ₅ are each independently a hydrogen atom, The linear, branched or cyclic alkyl group of 1 to 6, and the linear, branched or cyclic alkoxy group of 1 to 6 carbon atoms are shown.

X ^- is R ₃ -SO ₃ ^- and display ^- or R ₃ -COO.

R ₃ is a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 20 carbon atoms, and a straight chain having 1 to 20 carbon atoms. , A branched or cyclic perfluorouroalkyl group, or a substituted or unsubstituted perfluorofluoroaryl group having 6 to 20 carbon atoms.

In formula (IV), Rd ₁ and Rd ₂ are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or substituted or substituted with 6 to 20 carbon atoms, or Unsubstituted aralkyl group is shown.

Examples of the linear, branched or cyclic alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, i-pentyl group and t- A pentyl group, n-hexyl group, i-hexyl group, t-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group can be illustrated.

As a linear, branched or cyclic alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, n-pentyloxy group, i Examples of -pentyloxy group, t-pentyloxy group, n-hexyloxy group, i-hexyloxy group, t-hexyloxy group, cyclopropyloxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group and the like can do.

As an aryl group, a phenyl group, a naphthyl group, etc. can be mentioned.

Examples of the aralkyl group include a substituted or unsubstituted benzyl group, a substituted or unsubstituted naphthylmethyl group, a substituted or unsubstituted fryl group, and a substituted or unsubstituted thienyl group.

The perfluorofluoroalkyl group may be linear, branched or cyclic, and may be a trifluoromethyl group, a pentafuluroethyl group, an n-peptafluorofluoro group, an i-peptafluoropropyl group, and a t-peptafluoropropyl group. And a perfluorocyclohexyl group.

As a perfluoro aryl group, a pentafluoro phenyl group etc. can be mentioned.

These substituents include a hydroxyl group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a perfuluroalkyl group and the like.

Although the following are mentioned as a specific example of a photo-acid generator, It is not limited to these.

Photo-acid generators can be used individually by 1 type or in combination of 2 or more types. Preferable addition amount is 1-20 weight% with respect to solid content except the solvent of a composition, Preferably it is 1-10 weight%.

[3] pigments whose spectral characteristics change over a wavelength range of 400 nm or more due to reaction with acids generated during exposure

Various dyes, such as basic dye, oil-soluble dye, and acid dye, can be used as a pigment | dye which the spectral characteristic of 400 nm or more wavelength range changes by reaction with the acid which generate | occur | produced by exposure.

In the present invention, once the spectral characteristic of the dye is changed by the reaction with acid, the spectral characteristic is difficult to change due to the subsequent time and is stable.

Spectroscopic characteristics are the physical-property values measured with a commercially available spectrophotometer and a spectroscopic ellipsometer. More specifically, the transmittance, extinction coefficient, extinction coefficient, refractive index, reflectance, and the like are shown.

Preferred pigments include pentamethoxy red, ethyl violet, methyl violet, crystal violet, p-methyl red, p-aminoazobenzene, 4-phenylaxiphenylamine, oil yellow GE, oil green 3G, and the like.

Especially preferable pigment | dye is a compound represented by the following general formula (I).

In formula (I), R <_11> -R <_15> , R <_21> -R <_25> , R <_31> -R <_35> may mutually be same or different, A hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, carboxyl group , Halogen atom, nitro group, hydroxyl group, substituted or unsubstituted carbonyl group of 1 to 6 carbon atoms, substituted or unsubstituted amino group, substituted or unsubstituted aryl group of 6 to 12 carbon atoms, substituted or unsubstituted C6 to 12 carbon atoms An aryloxy group is shown.

In addition, two of R ₁₁ to R ₁₅ may be bonded to each other to form a ring. Two of R ₂₁ to R ₂₅ may be bonded to each other to form a ring. Two of R ₃₁ to R ₃₅ may be bonded to each other to form a ring. When forming a ring, you may form a ring including an oxygen atom, a sulfur atom, and a nitrogen atom.

Provided that one of R ₁₁ , R ₁₅ , R ₂₁ , R ₂₅ , R ₃₁ and R ₃₅ is a C 1-6 alkoxy group, carboxyl group, halogen atom, nitro group, hydroxyl group, substituted or unsubstituted C 1-6 Carbonyl group, substituted or unsubstituted amino group, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms.

Each substituent may be bonded via an amide bond.

The alkyl group may be linear, branched or cyclic, and may be methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, t-pentyl group, n-hexyl group, i-hexyl group, t-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group can be illustrated.

As an alkoxy group, linear, branched, or cyclic may be sufficient, and a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, n-pentyloxy group i-pentyloxy group, t-pentyloxy group, n-hexyloxy group, i-hexyloxy group, t-hexyloxy group, cyclopropyloxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group, etc. Can be illustrated.

Examples of the carbonyl group having 1 to 6 carbon atoms include methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, n-butylcarbonyl group, i-butylcarbonyl group, t-butylcarbonyl group, pentylcarbonyl group, hexylcarbonyl group and the like. .

As an aryl group, a phenyl group, a naphthyl group, etc. can be mentioned.

Examples of the aryloxy group include phenoxy group, naphthyloxy group, and the like.

As a ring formed by combining two of R ₁₁ to R ₁₅ , two of R ₂₁ to R ₂₅ , and two of R ₃₁ to R ₃₅ , a three-membered ring is preferably a seven-membered ring, and includes nitrogen, sulfur, and oxygen atoms. The heterocyclic to be mentioned can be illustrated.

As these substituents, a hydroxyl group, a halogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, etc. can be illustrated.

Moreover, the following are mentioned as a preferable thing among the compound represented by the said General formula (I).

In general, since the pigments often contain several tens of ppm or more of metals such as sodium, potassium, iron, etc., it is preferable to perform a metal reduction treatment and use a metal having a metal content of 1 ppm or less. As the metal reduction treatment method, generally known treatment with an ion exchange resin, recrystallization method, or the like can be used.

The addition amount of a pigment is 1 weight%-20 weight% with respect to solid content, Preferably it is 1 weight%-15 weight%.

[4] basic compounds

Since the pigment | dye used for this invention is sensitive to acid concentration, the image formed by exposure is unstable, but it is possible to stabilize the image formed by adding a basic compound. In addition, since the spectral characteristics may change only by the acidity of the solvent, it is very effective to add a basic compound.

As a basic compound which can be used, although an organic basic compound and ammonium hydroxide salt can be illustrated, an organic basic compound is especially preferable.

Preferable organic basic compounds which can be used in the present invention are compounds which are more basic than phenol. Among them, nitrogen-containing basic compounds are preferable. By adding the organic basic compound, the sensitivity change over time is improved.

As such an organic basic compound, what has a structure shown below is mentioned.

Where R²⁵⁰, R²⁵¹And R²⁵²Are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R²⁵¹And R²⁵²May combine with each other to form a ring.

(Wherein, R ²⁵³ , R ²⁵⁴ , R ^255, and R ²⁵⁶ each independently represent an alkyl group having 1 to 6 carbon atoms.)

Further preferred compounds are nitrogen-containing basic compounds having at least two nitrogen atoms of different chemical environments in one molecule, particularly preferably compounds containing both substituted or unsubstituted amino groups and ring structures containing nitrogen atoms or A compound having an alkylamino group. Preferred embodiments include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine , Substituted or unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine, and the like. Preferred substituents are amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxy group and cyano group.

As a preferred embodiment of the nitrogen-containing basic compound, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylamino Pyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) Piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) -pyrrolidine , Pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4 -Diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyra Lean, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4.3.0] nona-5-ene, 1,8-diazabicyclo [5.4.0] ound Car-7-ene, 1,4-diazabicyclo [2.2.2] octane, 2,4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmol Tertiary morpholine derivatives such as porin, N-benzyl morpholine, cyclohexyl morpholinoethylthiourea (CHMETU), and interference amines described in Japanese Patent Application Laid-Open No. 11-52575 (for example, described in the above publication) But is not limited to these.

As a particularly preferred embodiment, 1,5-diazabicyclo [4.3.0] nona-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [ 2.2.2] tertiary morpholines such as octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines and CHMETU And interference amines such as bis (1,2,2,6,6-pentamethyl-4-piperidyl) sevagate, N, N-dicyclohexylmethylamine, and the like.

Among them, 1,5-diazabicyclo [4.3.0] nona-5-ene, 1,8-diazabicyclo [5.4.0] undeca-7-ene, 1,4-diazabicyclo [2.2.2 ] Octane, 4-dimethylaminopyridine, hexamethylenetetramine, CHMETU, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sevagate, N, N-dicyclohexylmethylamine desirable.

These organic basic compounds are used individually or in combination of 2 or more types. As for the usage-amount of an organic basic compound, 5 weight% or less is preferable normally with respect to the total composition solid content of the photosensitive resin composition.

[5] acidic compounds

It is also possible to add an acidic compound to the photosensitive resin composition of this invention in the range which does not inhibit the image formation by exposure, in order to adjust a sensitivity. Examples of the acidic compound that can be added include organic carboxylic acids and organic technical acids, but organic carboxylic acids are particularly preferred.

As the organic carboxylic acid, any of saturated or unsaturated aliphatic carboxylic acid, alicyclic carboxylic acid, oxycarboxylic acid, alkoxy carboxylic acid, ketocarboxylic acid, aromatic carboxylic acid, and the like can be used. no.

For example, monovalent or polyaliphatic carboxylic acids, 1,1-cyclohexanedicarboxylic acid, 1, such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid and azipine acid Alicyclic carboxylic acids, such as 2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,1-cyclohexyl dibutane, acrylic acid, Unsaturated aliphatic carboxylic acids such as crotonic acid, isocrotonic acid, 3-butenoic acid, methacrylic acid, 4-pentenoic acid, propiolic acid, 2-butynic acid, maleic acid, fumaric acid, acetylenecarboxylic acid, and oxyacetic acid Examples thereof include alkoxycarboxylic acids such as oxycarboxylic acid, methoxy acetic acid and ethoxy acetic acid, ketocarboxylic acids such as pyruvic acid, and aromatic carboxylic acids represented by general formula (V) and general formula (VI). can do.

In formula (V), R <^13> and R <^14> represents a hydrogen atom, a hydroxyl group, a nitro group, a carboxyl group, or a vinyl group each independently, except that R <^13> and R <^14> are all hydrogen atoms.

In formula (VI), n represents 0 or the integer of 1-10.

Especially alicyclic carboxylic acid, unsaturated aliphatic carboxylic acid, and aromatic carboxylic acid are used preferably.

As an aromatic carboxylic acid represented by the said general formula (V), p-hydroxy benzoic acid, o-hydroxy benzoic acid, 2-hydroxy-3- nitro benzoic acid, 3, 5- dinitro benzoic acid, 2- Nitro benzoic acid, 2,4-dihydroxy benzoic acid, 2,5-dihydroxy benzoic acid, 2,6-dihydroxy benzoic acid, 3,4-dihydroxy benzoic acid, 3,5-dihydroxy benzoic acid, 2- Vinyl benzoic acid, 4-vinyl benzoic acid, phthalic acid, telephthalic acid, isophthalic acid and the like, and especially benzoic acid having a substituent on o-, such as o-hydroxy benzoic acid, o-nitro benzoic acid, phthalic acid, etc. are preferable. Do.

In addition, as the aromatic carboxylic acid compound represented by the general formula (VI), although n in the formula may be used singly or in combination of heterogeneous ones, SAX (trade name, Mitsuiido) is commercially available as a phenol compound. Atsuka Chemical Co., Ltd.) is used preferably.

Any organic carboxylic acid can be used individually by 1 type or in combination of 2 or more types. As for the preferable addition amount, 5 weight% or less is preferable with respect to solid content except the solvent of a composition.

[6] fluorine and / or silicone surfactants

The photosensitive resin composition of the present invention preferably contains a fluorine-based and / or silicone-based surfactant.

The photosensitive resin composition of the present invention preferably contains any one or two or more of a fluorine-based surfactant, a silicone-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom.

When the photosensitive resin composition of this invention contains the said acid-decomposable resin and the said surfactant, roughness dependency is improved.

As these surfactant, For example, Unexamined-Japanese-Patent No. 62-36663, 61-226746, 61-226745, 62-170950, 63-34540, JP 7-230165, A 8-62834, 9-54432, 9-9988, U.S. Patent 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511 and 5,824,451 The surfactant described can be enumerated, and the following commercially available surfactant can also be used as it is.

As commercially available surfactants that can be used, for example, Eftop EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florad FC430, FC431 (manufactured by Sumitomoto 3M Co., Ltd.), Megafac F171, F173, F176, F189 and R08 (manufactured by Dainippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, and 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), etc. And fluorine-based surfactants or silicone-based surfactants. Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone type surfactant.

The compounding quantity of surfactant is 0.001 to 2 weight% normally based on solid content in the composition of this invention, Preferably it is 0.01 to 1 weight%. These surfactants may be added alone, or may be added in any combination.

As surfactants which can be used other than the above, specifically, polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and polyoxyethylene Polyoxyethylene alkylallyl ethers such as octyl phenol ether and polyoxyethylene nonyl phenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorb Sorbitan fatty acid esters such as non-molecular monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate Polyoxyethylene sorbitan tree Les oleate, polyoxyethylene, and the like sorbitan tristearate, etc., polyoxyethylene sorbitan fatty acid non-ionic surfactants such as esters.

The compounding quantity of these other surfactant is 2 weight part or less normally per 100 weight part of solid content in the composition of this invention, Preferably it is 1 weight part or less.

[7] solvents

The photosensitive resin composition of this invention is propylene glycol monoalkyl ether acetates, such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, lactic acid alkyl esters, such as methyl lactate and ethyl lactate, and propylene glycol monomethyl as a coating solvent. Propylene glycol monoalkyl ethers such as ether and propylene glycol monoethyl ether, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and the like. Pyruvic acids such as ethylene glycol monoalkyl ether acetates, alkyl alkoxypropionates such as 2-heptanone, γ-butylolactone, methyl methoxy propionate and ethyl ethoxypropionate, methyl pyruvate and ethyl pyruvate Alkyl esters, N-methylpyrroli , Is applied using N, N- dimethylacetamide, dimethylsulfoxide, at least one kind of solvent selected from the seed.

Preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl lactate, and ethyl lactate are mentioned.

Although these solvents are used individually or in mixture, it is particularly preferable to add one or more kinds of solvents having high solubility of materials such as propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates and lactic acid alkyl esters. The proportion of solvent to be added can be changed freely without affecting the solubility and applicability of the material.

In this invention, it is preferable to melt | dissolve 5-40 weight% of solid content of the photosensitive resin composition containing each said component as solid content concentration in the said mixed solvent, More preferably, it is 5-30 weight%.

[8] other additives

The photosensitive resin composition of this invention can contain a dye, a plasticizer, a photosensitizer, an acid-decomposable dissolution inhibiting compound, the compound which accelerates the solubility to a developing solution, etc. as needed.

Such a photosensitive resin composition of the present invention is applied onto a substrate to form a thin film. The film thickness of the island coat is preferably 0.1 to 10 µm, preferably 0.5 to 5 µm.

In this invention, the minimum value of the transmittance | permeability with respect to the light of 400 nm-800 nm wavelength region of the photosensitive resin composition unexposed part of 1000 nm film thickness is 85% or more, and the light of 400 nm-800 nm wavelength region of the photosensitive resin composition exposure part. It is preferable that the minimum value of the transmittance | permeability with respect to 75% or less.

In the present invention, a commercially available inorganic or organic antireflection film can be used if necessary.

As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon, SiON, tungsten Si, polysilicon, or an organic film type made of a light absorber and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, a sputtering apparatus, etc. to form the film. As the organic antireflection film, for example, a condensation product of a diphenylamine derivative described in Japanese Patent Publication No. Hei 7-69611 and a formaldehyde-modified melamine resin, an alkali-soluble resin, a light absorber, or a maleic anhydride disclosed in US Pat. A reactant of a copolymer with a diamine light absorber, containing a resin binder as described in Japanese Patent Application Laid-open No. Hei 6-118631 and a methirolmelamine-based thermal crosslinking agent; An acrylic resin type antireflection film having a group in the same molecule, consisting of methirolmelamine and a benzophenone light absorber described in Japanese Patent Application Laid-open No. Hei 8-87115, low molecular weight in a polyvinyl alcohol resin described in Japanese Patent Application Laid-open No. Hei 8-179509 And a light absorber is added.

As the organic antireflection film, DUV-30 series manufactured by Brewers Science, DUV-40 series, AC-2, AC-3 manufactured by Shippress, etc. may be used.

Appropriate coating method such as spinner, coater, etc. on the substrate (e.g. silicon or silicon / silicon dioxide coating) used for the manufacture of the precision integrated circuit device (on the substrate on which the anti-reflection film is provided, if necessary) After the coating is carried out, a good resist pattern can be obtained by exposing through a predetermined mask, baking and developing.

The exposure light is preferably light having a wavelength of 150 nm to 250 nm. Typical examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-rays, electron beams, and the like.

In addition, in view of the purpose of use, the composition of the present invention makes it essential to form a stable image which can distinguish the exposed portion and the non-exposed portion only by exposure without developing.

Moreover, since the sensitivity is excellent and the obtained image is stabilized, the composition of the present invention can be used for alignment measurement of the exposure apparatus, and the system error can be detected with high accuracy.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

(Example 1 and Comparative Example 1)

30 parts by weight of a resin obtained by substituting 40% of the hydroxyl group of VP-8000 (manufactured by Nippon Soda, polyhydroxystyrene resin) with ethoxyethyl ether, 1.5 parts by weight of triphenylsulfonium triflate, 1 part by weight of pentamethoxy red, and Troy 0.15 weight part of sol S-366 (made by Troy Chemical Co., Ltd.) was dissolved in 120 weight part of 1-methoxy-2-propanol.

This solution was filtrated with a 0.1 micron Teflon filter to prepare Photosensitive Resin Composition A (Example 1). On the other hand, the solution using only the resin VP-8000 was similarly fine filtered to prepare a photosensitive resin composition X (Comparative Example 1).

Each of the photosensitive resin compositions was applied to a silicon wafer with a spin coater, and then heated on a 90 ° C. hot plate for 90 seconds to form a photosensitive resin composition coating film having a film thickness of about 2.5 μm. This was exposed with a KrF excimer laser stepper (NA = 0.63) manufactured by Kennon Corporation.

In the photosensitive resin composition A, the distinction between an exposed part and an unexposed part was visually confirmed at 2 mJ / cm 2 or more, and it was confirmed that it was very highly sensitive.

A digital image was created by integrating an image having a line width of 10 μm pattern at 30 mJ / cm 2 by a CCD camera 50 times to produce a digital image. The line width was measured by 32 points, and 3 times the standard deviation was 3σ _A. Similarly, the line width of the 10 μm pattern formed by exposure was measured 10 times by a laser diffraction measurement method, and three times the standard deviation was 3σ _B.

3σ and _A and _B are both 4㎚ 3σ of the photosensitive resin composition A, and the 3σ _A photosensitive resin composition X 3σ _B was all 15㎚.

In addition, for the evaluation of the stability of the image, 3 sigma _A and 3 sigma _B were re-measured 24 hours after exposure, and 3 sigma _A24 and 3 sigma _B24 , respectively. 3σ _A24 of the photosensitive resin composition A was 6 nm, 3σ _B24 was 3 nm, and both 3σ _A24 and 3σ _B24 of the photosensitive resin composition X were 20 nm.

In addition, the volume variation rate was evaluated as follows.

[Evaluation Method of Volume Variation Rate]

The photosensitive resin composition of the present invention is applied to each silicon wafer by a spin coater, and then heated for 90 seconds on a 90 ° C. hot plate to form a film of the photosensitive resin composition.

Using the KrF excimer laser stepper manufactured by Kennon Co., Ltd., the exposure was changed from 0 mJ / cm 2 to 140 mJ / cm 2 in 2 mJ / cm 2 steps, and the exposure was performed in an area of about 1 cm 2 to measure the film thickness for each exposure amount.

The value was created with the graph shown in FIG. 1, and the value calculated | required by (FT _exp -FT _init ) / FT _init x100 was made into the volume variation rate.

(Examples 2-6, Comparative Examples 2-4)

The photosensitive resin composition shown in Table 1 was prepared, the same evaluation as Example 1 was performed, and the result was shown in Table 2.

Moreover, used resin, a photo-acid generator, a pigment | dye, other additives, and a solvent are shown below.

Poly-1: Resin which substituted 40% of hydroxyl groups of VP-8000 (made by Nippon Soda, polyhydroxy styrene resin) with the ethoxy ethyl ether group

Poly-2: Resin which substituted 35% of hydroxyl groups of VP-8000 (made by Nippon Soda, polyhydroxy styrene resin) with i-butoxyethyl ether group

Poly-3: Resin which substituted 30% of hydroxyl groups of VP-15000 (made by Nippon Soda, polyhydroxy styrene resin) with t-butoxyethyl ether group

Poly-4: Resin which substituted 5% of hydroxyl groups of VP-8000 (made by Nippon Soda, polyhydroxy styrene resin) with an ethoxy ethyl ether group

PMMA: Poly (methyl methacrylate)

PAG-1: Triphenylsulfonium Triplate

PAG-2: Bis (cyclohexylsulfonyl) diazomethane

PAG-3: Diphenyl Iodide Triplate

Dye-1: pentamethoxy red

Dye-2: 1,3,3, -trimethylindolino-6'-nitrobenzopyros pyran (spiropyran)

ADD-1: dicyclohexylmethylamine

ADD-2: Salicylic Acid

S-1: Troisol S-366 (product of Troy Chemical Company)

PGME: 1-methoxy-2-propanol

MEK: methyl ethyl ketone

The result of Table 2 shows that the composition of this invention is excellent in the sensitivity, and excellent in the measurement reproducibility at the time of measuring the pattern formed by exposure by laser diffraction light.

According to the present invention, there is provided a photosensitive resin composition having a high sensitivity and providing stable exposure visibility necessary for alignment measurement of an exposure apparatus, as a photosensitive composition in which an image capable of identifying an exposed portion and a non-exposed portion is formed only by exposure to radiation. Can be.

Claims (5)

As a photosensitive resin composition for detecting the system error of the exposure apparatus when the mask pattern is transferred onto the photosensitive resin composition film by transferring the mask pattern onto the photosensitive resin composition film only by the exposure of radiation and detecting the imaging state on the transfer pattern. , A) a compound that generates an acid by exposure to radiation and B) The photosensitive resin composition for system error detection of the exposure apparatus containing resin which changes in volume by reaction with the acid generated from said A). The photosensitive resin composition for detecting a system error of an exposure apparatus according to claim 1, further comprising a dye in which the spectral characteristics of the wavelength region of 400 nm or more change due to a reaction with an acid generated by exposure. The photosensitive resin composition for detecting a system error of an exposure apparatus according to claim 2, wherein said dye is a compound represented by the structure of the following general formula (I). (In formula (I), R <_11> -R <_15> , R <_21> -R <_25> , R <_31> -R <_35> may mutually be same or different, A hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, Carboxyl group, halogen atom, nitro group, hydroxyl group, substituted or unsubstituted carbonyl group of 1 to 6 carbon atoms, substituted or unsubstituted amino group, substituted or unsubstituted aryl group of 6 to 12 carbon atoms, substituted or unsubstituted C6 to C6 The aryloxy group of 12 is shown. In addition, two of R ₁₁ to R ₁₅ may be bonded to each other to form a ring. Two of R ₂₁ to R ₂₅ may be bonded to each other to form a ring. Two of R ₃₁ to R ₃₅ may be bonded to each other to form a ring. When forming a ring, you may form a ring including an oxygen atom, a sulfur atom, and a nitrogen atom. Provided that one of R ₁₁ , R ₁₅ , R ₂₁ , R ₂₅ , R ₃₁ and R ₃₅ is a C 1-6 alkoxy group, carboxyl group, halogen atom, nitro group, hydroxyl group, substituted or unsubstituted C 1-6 Carbonyl group, substituted or unsubstituted amino group, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms. Each substituent may be bonded via an amide bond.) The system error detection according to any one of claims 1 to 3, wherein the resin of B) is an alkali insoluble resin which protects 30 mol% or more of the alkali-soluble group of the alkali-soluble resin with an acetal group. Photosensitive resin composition for use. The minimum value of the transmittance | permeability with respect to the light of the 400 nm-800 nm wavelength range of the photosensitive composition unexposed part of 1000 nm film thickness is 85% or more, The 400 of the photosensitive resin composition exposed part of any one of Claims 1-4. A photosensitive resin composition for detecting a system error of an exposure apparatus, wherein the minimum value of the transmittance with respect to light in the wavelength range of nm to 800 nm is 75% or less.