CZ291299A3 - Sulfonyloximes for photoresists exhibiting high sensitivity and thickness, intended for exposition in mercury i-line region - Google Patents

Abstract

The light-activatable composition, the essence of which is based on that it contains at least one compound that can be and / or at least one a compound whose solubility changes with acid; as a photoinitiator at least one compound generating acid, especially sulfonic acid, when exposed to light wavelengths ranging from 240 to 390 nm and molar extinction coefficient ε less than 365 nm. These compositions are especially suitable for producing negative and positive photoresists, printing plates, recording material or color filters.

Description

Sulfonyloximes for photoresists with high sensitivity and thickness for mercury i-line exposure

Technical field

The invention relates to compositions containing latent acidic compounds, the use of these compounds as a photosensitive acid generator, in particular in chemically enhanced photoresists, in printing plates, color filters or image-recording materials that are inducible in an alkaline environment, their use as dissolution inhibitors in correspondingly positive a photoresist, as well as a method of producing images using such resists, printing plates or image-recording materials.

As used herein, a chemically enhanced photoresist is a resist composition whose photosensitive component, when irradiated, generates only the amount of acid required to catalyze the chemical reaction of at least one acid-sensitive component of the resist, resulting in the initial development of finite differences solubility of irradiated and non-irradiated regions of the photoresist.

BACKGROUND OF THE INVENTION

Industrial coating formulations, based on a large number of photosensitive oximsulfonates and conventional acid-curable resins, are described in US 4540598. These formulations are first cured by actinic light, in particular using radiation in the region of 250-400 nanometers. The oximinesulfonates generate an acid so that thermal curing can take place during which the material also becomes insoluble in conventional solvents, even

Said patent exposure of the associated or even at very low document temperatures does not mention any corresponding resist film problems, as well as the pictorial properties of numerous formulations falling within the generic range of information provided by the present invention.

soluble in converted to V in combination with

Oximinesulfonates, which are poorly alkaline-water developers, can be soluble forms of the free acid by irradiation; therefore, suitable film-forming resins can be used as dissolution inhibitors to produce positive resists.

Also known from EP 0241423 are conventional positive photoresists based on oximesulfonates and alkali soluble binders, such as typically cresol novolaks or copolymers of hydroxymethacrylate and acrylic acid. According to said document, radiation with a wavelength of 200 to 600 nm can be used to expose the resists. However, the disadvantage of these photoresists is that their resolution and sensitivity are never altogether satisfactory. This is particularly the case when exposure to radiation is carried out in the region of the mercury i-line, which has a wavelength of 365 nanometers, which is often used for image exposure of resist films, since mercury medium- and high-pressure lamps are relatively cheap sources of radiation of these wavelengths with sufficiently good intensity.

Accordingly, there is a need for reactive non-ionic latent acid generators that are thermally and chemically stable and which, after being activated by light, in particular radiation having an i-line wavelength (365 nm), could be used as catalysts for various acid-catalyzed reactions, such as polycondensation reactions, acid-catalyzed depolymerization reactions, acid-catalyzed electrophilic substitution reactions or acid catalyzed deprotection reactions. In particular, there is a need for acid generators that can be activated by light and by which systems having a greater thickness can be exposed in a manner that achieves high sensitivity and good shape and form of resist profiles. Such a large photoresist thickness is, for example, advantageous in ion implantation procedures, in which an ever increasing ion dose requires the use of thicker photoresist layers capable of withstanding such intense ion bombardment. There are other application areas where strong resist layers are required for simple geometric reasons, such as the production of magnetic heads for hard disk drives for storage media. An additional desirable property is the high thermal stability to achieve high ion processing resistance during the ion implantation procedures typically used in the manufacture of semiconductor devices.

US 5627011 discloses the use of oximesulfonate compounds in photoresises having high resolution and high sensitivity and intended to be exposed to radiation in the mercury i-line region. Disclosed herein are oximsulfonate compounds that can generate aromatic sulfonic acids.

EP 780729 and WO 98/10335 disclose chemically cross-linked resist compositions containing oximinesulfonate compounds having sulfonic acid alkyl groups instead of aromatic groups.

JP 9-292704 discloses that a further improvement of the resists is achieved when oximinesulfonate compounds with short alkyl groups are used

(containing 1 to 4 carbon atoms) of sulfonic acids having a molar extinction coefficient ε of less than 100 in the mercury i-line region (365 nm).

SUMMARY OF THE INVENTION

The invention provides photoresist compositions having excellent resist profiles and having excellent sensitivity, even at resist layer thicknesses well in excess of a typical resist layer thickness of 1 to 2 microns. These properties are particularly observed when the resist compositions are exposed to radiation in the region of the mercury i-line, which has a wavelength of about 365 nanometers.

Surprisingly, it has been found that excellent profiles and, at the same time, good sensitivity are achieved with chemically enhanced photoresist compositions which are inducible in aqueous-alkaline media and have a resist thickness greater than 2 micrometers using photoacid generators having a molar extinction coefficient ε less than 10 This applies to both negative and positive photoresists containing an acid-sensitive component that reacts by an acid-catalyzed chemical reaction mechanism that alters the solubility of said compositions in aqueous-alkaline developers.

Accordingly, the invention relates to compositions which can be light activated and which contain

(a) at least one compound which may be crosslinked by acid treatment; and / or

(b) at least one compound which alters its solubility by acid; and

(c) as a photoinitiator, at least one acid-generating compound when exposed to light at 240 to 36 ° C. ·················

390 nm and having a molar extinction coefficient ε less than 10 in the i-line region of mercury (365 nm).

In particular, compound (c) is a sulfonic acid generating compound.

Preference is given to compositions having a thickness greater than 2 micrometers after application to the substrate.

The invention further relates to a composition as described above which, as component c), comprises a structural unit of the formula (I).

_/ C = NO-SO ₂ - _{(|) i} and in which the compounds are characterized by a molar extinction coefficient ε less than 10 at 365 nm.

Preferred compositions are those which comprise as component c) a compound of formula (Ia)

in which

R _lZ R _2, R _3, R ₄ and R ₅ represent independently of one another are hydrogen or unsubstituted or halosubstituted alkyl radical containing from 1 to 12 carbon atoms or R _lZ R _2, R _3, R ₄ and R ₅ are halogen,

R ₆ represents an unsubstituted or halogen substituted alkyl group having 1 to 18 carbon atoms, a phenylalkyl group in which the alkyl moiety contains 1 to 3 carbon atoms, a camphoryl group, a phenyl group, a naphthyl group, anthracyl group or a phenanthryl group, the anthracyl and phenanthryl group is unsubstituted or substituted one or more times with substituents selected from the group consisting of halogen, haloalkyl of up to 4 carbon atoms, CN, NO ₂ , alkyl of 1 to 16 carbon atoms, phenyl, OR ₁₀ , COOR _{A 9} , -O (CO) -alkyl group in which the alkyl radical contains 1 to 4 carbon stomes, an SO ₂ OR ₉ group and an NR ₇ R _{8 group} ,

R ₇ and R ₈ are each independently hydrogen or C 1 -C 12 alkyl which is unsubstituted or substituted by substituents selected from the group consisting of OH, C 1 -C 4 alkoxy, alkylsulfonyl in which: an alkyl radical containing 1 to 12 carbon atoms, a phenylsulfonyl group, a (4-methylphenyl) sulfonyl group and an alkanoyl group having 1 to 6 carbon atoms, or R ₇ and R ₈ represent an alkyl group having up to 12 carbon atoms interrupted by an -O member - and which is unsubstituted or substituted by substituents selected from OH, C1-C4alkoxy, alkylsulfonyl in which the alkyl radical contains 1 to 12 carbon atoms, phenylsulfonyl, (4-methylphenyl) sulfonyl and an alkanoyl group containing 1 to 6 carbons or R @ ₇ and R @ ₈ are phenyl, alkanoyl having 2 to 6 carbon atoms, benzoyl, alkylsulfonyl in which the alkyl is 9999, 9999, 9999, 9999, 9999 and 999, respectively.

9 * 9 · 9 99 99 9 * 9 9 * 9 * 9 * 9999 9 9

9 *** 9 99 9 * 99 99 The radical contains 1 to 6 carbon atoms, phenylsulphonyl, (4-methylphenyl) sulphonyl, naphthylsulphonyl, anthracylsulphonyl or phenanthrylsulphonyl, or R ₇ and R ₈ together with the nitrogen atom. to which they are attached form a 5-, 6- or 7-membered ring which may be interrupted by -O- or -NR member _n -

R ₉ is C 1 -C 12 alkyl which is unsubstituted or substituted by OH and / or C 1 -C 4 alkoxy, or R ₉ is C 2 -C 12 alkyl which is interrupted by - O- and which is unsubstituted or substituted by OH and / or by alkoxy having 1 to 4 carbon atoms,

R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which is unsubstituted or substituted by substituents selected from the group consisting of phenyl, OH, alkoxy of 1 to 12 carbon atoms, alkylsulfonyl group in which the alkyl radical contains 1 up to 12 carbon atoms, a phenylsulfonyl group, a (4-methylphenyl) sulfonyl group and an alkanoyl group having 2 to 6 carbon atoms, or R ₁₀ is an alkyl group having 2 to 12 carbon atoms which is interrupted by -O- and which is unsubstituted; or substituted with substituents selected from the group consisting of phenyl, OH, C 1 -C 12 alkoxy, C 1 -C 12 alkylsulfonyl, C 1 -C 12 alkyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and alkanoyl containing 2 to 6 or R ₁₀ represents a phenyl group,

9 4 4 4 9 4

449 9 9 44 4 4 9 9

4 4 4 4 4

499 49 99 44 44

R _n is hydrogen, unsubstituted or OH-substituted alkyl group having 1 to 12 carbon atoms or an alkyl group containing 2-12 carbon atoms which is interrupted by -0- member, wherein the compounds of formula Ia are characterized by a molar extinction coefficient ε of less than 10 at 365 nm.

It is also possible within the scope of the invention to use mixtures of the isomeric forms (cis-trans isomers, E / Z isomers or syn / anti isomers) of the oximsulfonates of the formula Ia.

C 1 -C 18 alkyl is a straight or branched alkyl group containing, for example, 1 to 16, 1 to 14, 1 to 12, 1 to 8, 1 to 6 or 1 to 4 carbon atoms. Examples of such an alkyl group are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl,

2,4,4-trimethylphenylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl and octadecyl.

C 1 -C 16 alkyl, C 1 -C 12 alkyl and C 1 -C 4 alkyl have the same meanings as given above for the above C 1 -C 18 alkyl group up to the corresponding upper limit of the number of carbon atoms.

Halogen is fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine, preferably fluorine and chlorine.

The halogen substituted alkyl group containing from 1 to 18 carbon atoms or the halogen substituted alkyl group containing from 1 to 12 carbon atoms are φ · · · · φ · · · · φ · φ · φ substitu substitu substitu substitu enty enty enty enty enty enty enty enty substitu enty enty substitu substitu substitu substitu enty enty enty substitu substitu substitu substitu enty enty enty enty substituents. a carbon atom of an alkyl group, a fluoromethyl group, a bromomethyl group, the above-mentioned alkyl groups which are substituted by one or more identical or different halogen atoms. Thus, for example, the alkyl group is substituted with 1 to 3 or 1 or 2 halogen halogen atoms, either on the same or on different atoms. Examples of such groups are chloromethyl, trifluoromethyl,

1-chloroethyl, 2-chloroethyl and the like.

C 1 -C 4 haloalkyl corresponds to C 1 -C 4 alkyl which is substituted by halogen. For these groups, the same explanations as described above apply up to the corresponding upper limit of the number of carbon atoms.

An alkyl group having 2 to 12 carbon atoms and interrupted by an -O- moiety is a straight or branched alkyl group which is, for example, 1 to 6 times interrupted, 1 to 3 times interrupted or interrupted once or twice by an -O- member. These oxygen members are not located immediately in the alkyl chain. For example, the following structural units provide such breaks:

-CH ₂ -O-CH ₂ -,

-ch ₂ ch ₂ -o-ch ₂ ch ₂ -,

- [CH ₂ CH ₂ O] -, where y is 1 to 6,

- [CH ₂ CH ₂ O] _z -CH ₂ -, wherein z represents the number 1 to 5,

- (CH ₂ CH ₂ O) ₅ ch ₂ ch ₂ -,

-CH ₂ -CH (CH ₃ ) -O-CH ₂ -CH (CH ₃ ) - or

-CH ₂ CH (CH ₃₎ -O-CH ₂ -CH ₂ CH ₂ -.

The alkoxy group having 1 to 12 carbon atoms is a straight or branched alkoxy group having in particular 1 to 8, 1 to 6 and 1 to 4 carbon atoms. Such alkoxy groups are, for example, methoxy, ethoxy, propoxy, etc. 9 9 9 9 9 9 9 9 9 99 9 99 99 99 9 99 99 99 99 99 99 99 99 99 99 99 , isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy, tert-butyloxy, pentyloxy, hexyloxy, heptyloxy,

2,4,4-trimethylpentyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy, decyloxy or dodecyloxy, in particular methoxy, ethoxy, propoxy, isopropoxy, n a butyloxy group, a sec-butyloxy group, an iso-butyloxy group or a tert-butyloxy group, preferably a methoxy group.

Alkylsulfonyl groups in which the alkyl radical contains 1 to 12 carbon atoms means an alkyl-O-SO ₂ -group in which the alkyl radical contains 1 to 12 carbon atoms, wherein the alkyl groups have already been defined above.

C 1 -C 6 alkanoyl is a straight or branched alkanoyl group, for example C 1 -C 4 alkanoyl. Examples of such groups are formyl, acetyl, propionyl, butanoyl, isobutanoyl, pentanoyl or hexanoyl, preferably acetyl.

Phenylalkyl in which the alkyl radical contains 1 to 3 carbon atoms is, for example, benzyl, phenylethyl, α-methylbenzyl or α, α-dimethylbenzyl, especially benzyl.

The substituted phenyl, naphthyl, anthracyl and phenanthryl groups are one to four times substituted, for example one, two or three times substituted, especially one or two substituted groups. The substituents on the phenyl ring are

ta · • · ♦♦ • ·· · • · • · • · • · • · • ta ··· • · • · • • • ta ·· • · dad • · ··

located in positions 2; 2.4 ;, 2.6; 3; 3.5; 4 or 5, particularly at the 2-position; 3, 4 or 6 phenyl ring.

In case _R7 and _Rg together with the nitrogen atom to which they are attached, a 5-, 6- or 7-membered ring which may be interrupted by a member saturated or unsaturated aziridine, pyrrole,

-O- or -NR.

these are rings such as a pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, piperidine or morpholine ring.

The terms and / or or / and used in the specification and claims mean that not only one of said alternatives (substituents) may be present, but also several of said alternatives (substituents) together, in particular a mixture of different alternatives (substituents).

The term at least defines one or more subjects.

The molar extinction coefficient ε of the acid generating compounds suitable for the compositions of the invention is less than 10 at 365 nm (i-line of mercury). This coefficient ε is part of the Lambert-Beer equation, which is well known to those skilled in the art. This coefficient is determined from the ultraviolet spectra of the respective compounds, which are measured in conventional organic solvents such as acetonitrile or tetrahydrofuran (THF). Since there is a slight shift in the extinction coefficient ε values depending on the solvent used to measure the ultraviolet spectrum, all extinction coefficient values given in the context of the invention relate to a solvent which is tetrahydrofuran.

In general, any compound which generates an acid after irradiation and which has a molar extinction coefficient ε less than 10 is suitable for the compositions of the invention or claimed photoresists. For example, Lewis acids generating compounds and compounds generating compounds are suitable.

ΦΦΦ φ φ · φ φ φ φ · · φ φ φ φ φ

ΦΦΦΦΦ φφ φφ φφ φφ generating phosphonic acid, PF ₆ BFY, SbF _s and the like acids. Examples of such compounds are sulfonium and iodonium salts, as well as derivatives of nitrobenzylsulfonates and bis-sulfonyldiazomethane. Preferably, sulfonic acid generating compounds such as oximinesulfonate compounds are used in the claimed compositions.

Bronsted carboxylic acids, acids such as sulfonic acid compounds,

In particular, the oximsulfonate compounds which are suitable as acid generators for the compositions according to the invention are those compounds of the formula Ia having a molar extinction coefficient ε less than 10 and in which the formula Ia

R 1, R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen, C 1 -C 8 alkyl, halogen or C 1 -C 4 haloalkyl,

R ₆ represents an alkyl group having 1 to 18 carbon atoms, a phenylalkyl group in which the alkyl moiety contains 1 to 3 carbon atoms, a camphoryl group, a haloalkyl group containing 1 to 10 carbon atoms, a phenyl group, a naphthyl group, anthracyl group or a phenanthryl group; wherein the phenyl, naphthyl, anthracyl and phenanthryl groups are unsubstituted or substituted by one or more substituents selected from the group consisting of haloalkyl of 1 to 4 carbon atoms, CN, NO ₂ , alkyl of 1 to 16 carbon atoms, phenyl and a group OR ₁₀ and R ₁₀ is as defined above.

Said compositions according to the invention preferably comprise compounds of formula Ia having a molar extinction coefficient ε less than 10 and in which formula Ia ftftftft ftftftft ftftft ftftft ···· ftft ftft ftft ftft

Ri, R _2, R _3, R ₄ and R _s independently of one another are hydrogen, alkyl having 1 to 4 carbon atoms, halogen, or halogenoalkyl having 1 to 4 carbon atoms provided that at least two groups of Ri, R ₂ , R ₃ , R ₄ and R ₅ are hydrogen, and

R ₆ represents an alkyl group having 1 to 12 carbon atoms, a phenylalkyl group in which the alkyl moiety contains 1 to 3 carbon atoms, a camphoryl group, a haloalkyl group having 1 to 4 carbon atoms or a phenyl group wherein the phenyl group is unsubstituted or substituted by one or a plurality of substituents selected from the group consisting of halogen, haloalkyl of 1 to 4 carbon atoms, NO ₂ , alkyl of 1 to 8 carbon atoms, phenyl and OR ₁₀ , and

R ₁₀ represents an alkyl group having 1 to 12 carbon atoms.

Examples of latent sulfonic acids of formula (Ia) are methanesulfonates, butanesulfonates, benzenesulfonates, 4-methylphenylsulfonates, 4-methoxybenzenesulfonates and

10-camphorsulfonates of α-hydroxyimino-4-methylbenzylcyanide α-hydroxyimino-4-butylbenzylcyanide, α-hydroxyimino-3-methylbenzylcyanide, α-hydroxyimino-2-methylbenzylcyanide, α-hydroxyimino-2,4-dimethylbenzylcyanide, α-hydroxyimino-3, 4-dimethylbenzylcyanide, α-hydroxyimino-3,4-dibutylbenzylcyanide, α-hydroxyimino-2,4,6-trimethylbenzylcyanide, α-hydroxyimino-2-chlorobenzylcyanide, α-hydroxyimino-2,4-dichlorobenzylcyanide, α-hydroxyimino-4- chlorobenzyl cyanide, α-hydroxyimino-4-fluorobenzyl cyanide.

The oximinesulfonates of formula (I) or (Ia) are prepared by methods described in the literature, e.g.

0 0 0 0 0 0 0 0 0 0

0 0 0 0 0 0 0 0 0 0

000 0000 0 0 00000 00 00 00 00 of the free oximes of formula 2 and the sulfonic acid halides of formula 3 in the presence of a base such as triethylamine or by reaction of the oxime salt with sulfonic acid chloride.

For example, these methods have been published in EP 48615.

NC _from C = N-OH + CI-SO ₂ -R ₆ R (2) (3)

NC

C = NOSR _fi of II ⁶ o

(la) where

R is a group

R R _2, R _3, R _4, R _s and R ₆ are defined above, and

meanings.

The reaction is conveniently carried out in an inert organic solvent in the presence of a tertiary amine.

The sodium salts of said oximes are obtained, for example, by reacting the corresponding oxime with sodium alkoxide in dimethylformamide (DMF).

The oximinesulfonates are obtained in the form of syn (E, cis) or anti (Z, trans) or also as mixtures of both. Either one of said forms or any mixture of said forms may be used within the scope of the invention.

If it is desired to have one of these forms, then this single form is obtained by conventional procedures known to those skilled in the art, such as crystallization, distillation or chromatography.

• • 4 • 4 9 9 4 * • 9 • · * 9 • 9 • 444 • • ·· 9 9 • • • »· * · · · • • • · 9 9 99 • 4 · • 9 •

The oximes of formula (2) required for the reaction are prepared by procedures analogous to known methods, for example by reacting compounds containing reactive methylene groups, such as benzyl cyanide derivatives or phenylacetic acid derivatives, with an alkyl nitrite such as methyl nitrite or isoamyl nitrite, and sodium alkoxide such as sodium methoxide. Such reactions are described, inter alia, in The Systematic Identification of Organic Compounds, John Wiley & Sons, New York, 1980, p. 181, Die Makromolekulare Chemie, 1967, 108, 170, or in Organic Synthesis, 1979, 59, 95.

Oximes can also be obtained, for example, by reacting the corresponding carbonyl compound or thiocarbonyl compound with hydroxylamine.

Another preparative method is nitrosation of hydroxyaromatic compounds.

The preparation of the sulfonic acid halide of formula 3 is known per se and is described, for example, in standard chemical textbooks.

It is a further object of the present invention to provide photoresists containing acid-generating compounds having an molar extinction coefficient ε less than 10 at 365 nm. Accordingly, the present invention provides a chemically enhanced photoresist which is sensitive to radiation in the range of 340 to 390 nm and which comprises a photosensitive acid generator having a molar extinction coefficient ε of less than 10 at 365 nm.

It is another object of the invention to provide photoresists containing compounds of formula I or Ia. Accordingly, the present invention provides a chemically enhanced photoresist which is sensitive to radiation in the region of 340 to 390 nm and which comprises a photosensitive acid generator of the formula I as defined above, characterized in that it has

• 99 • 9 4 9 99 * 9 • 9 r IN 9 « 4 9 9 9 • 449 9 t 44 4 4 4 9 9 9 4 • 9 «9 9 • 99 * • 9 « 4 9 9 4 4 4

a molar extinction coefficient ε of less than 10 nm, as well as a chemically enhanced photoresist which is sensitive to radiation in the range of 340 to 390 nm and which contains a photosensitive acid generator of the formula Ia as defined above, having a molar extinction coefficient ε lower than 10 nm.

These chemically enhanced photoresists preferably have a thickness greater than 2 microns. Also, the composition of the invention is preferably applied at a thickness greater than 2 microns before irradiation.

These resists include chemically enhanced, alkaline-inducible, negative photoresists having a resist thickness greater than 2 micrometers and sensitive to radiation in the range of 340 to 390 nm, based on a photosensitive acid generator having a molar extinction coefficient ε less than 10 at 365 nm.

In particular, said resists include chemically enhanced, alkaline-inducible, negative photoresists having a resist thickness greater than 2 microns and sensitive to radiation in the range of 340 to 390 nm, based on the oximinesulfonates defined as photosensitive generator as defined above. acid.

Another embodiment of the invention relates to chemically enhanced, alkaline-inducible, positive photoresists having a resist thickness greater than 2 micrometers and sensitive to radiation in the range of 340 to 390 nm, based on the oximesulfonates forming the photosensitive as defined above. acid generator.

Both embodiments of the photoresist of the invention are able to readily distinguish structural units having dimensions in the submicron region, wherein the radiation used is radiation in the region of 340 to 390 nm. The structure of the resist left after developing on the substrate has a very good steepness of the side walls. Despite the extremely low optical absorption, said resists have excellent sensitivity to the radiation. In particular, this feature is unexpected since the selected oximinesulfonate acid generators absorb radiation of these wavelengths only to an extremely low range. Moreover, an additional advantage of particularly negative resistors is that they have improved heat resistance, which is a particularly desirable property in the case of ion implantation processes.

crosslinked by dissolution

The invention also relates to the use of compounds of formula I or Ia having a molar extinction coefficient ε less than 10 as photosensitive acid generators in compositions containing compounds which may be acidic and / or as inhibitors for compounds, their solubility varies by acid, everywhere where irradiation is performed, such as image irradiation, and a method of generating acids, wherein the photosensitive acid generator of formula I or Ia having a molar extinction coefficient ε less than 10 is irradiated with light having a wavelength in the range 340 to 390 nm.

In light-curable compositions, oximesulfonic acid esters act as latent cure catalysts: when irradiated with light, they generate an acid that catalyzes the cross-linking reaction. In addition, the acid generated by irradiation can, for example, catalyze the removal of suitable acid-sensitive protecting groups from the polymer structure or cleave polymers containing acid-sensitive groups in the polymer backbone. Further application possibilities are, for example, color-changing systems based on the pH change or solubility of, for example, an acid-sensitive protecting group pigment. Compositions using pH sensitive dyes or latent pigments in combination with oximinesulfonates can be used as light indicators or simply as single use dosimeters. Such dosimeters are particularly useful when the detected light is light invisible to the human eye, such as ultraviolet or infrared light.

The oximinesulfonates of the invention can also be used to mold polymers that undergo an acid-induced transition to a state in which they have the desired properties utilized in photolithography. For example, oximinesulfonates can be used to structure conjugated emission polymers as described by MLRenak, C. Bazan and D. Roitman in Advanced Materials, 1997, 9, 392. Such structured emission polymers can be used in manufacturing microscopic patterned light-emitting diodes (LEDs) that can be used to produce displays and storage media. Similarly, polyimide precursors (e.g., polyimide precursors with acid-labile protecting groups, their solubility varies during development) may be irradiated to form patterned polyimide layers that may serve as protective coatings, insulating layers and barrier layers in the manufacture of microchips and plates with printed circuit boards.

It is known in the literature that conjugated polymers, such as polyanilines, can be converted from semiconductor to conductive by proton doping. The oximinesulfonates of the invention may also be used as acid generators for the visual irradiation of said conjugated polymers in order to ensure that said conversion occurs selectively only on the irradiated areas.

Oximinesulfonic acid esters are poorly soluble in the aqueous-alkaline developer and can be rendered soluble in such a developer by light-induced conversion to the free acid, with the result that they are used as dissolution inhibitors in combination with suitable film-forming resins.

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Resins which can be cross-linked by acid catalysis are, for example, mixtures of polyfunctional alcohols or acrylic or polyester resins containing hydroxy groups or partially hydrolyzed polyvinyl acetals or polyvinyl alcohols with polyfunctional acetal derivatives. Under certain circumstances, for example, acid catalyzed self-condensation of acetal-functionalized resins is also possible.

In addition, oximesulfonates are used, for example, as hardeners which can be light activated for resins containing siloxane groups. For example, these resins may either undergo self-condensation by acid catalyzed hydrolysis or may be cross-linked with a second component of the composition, such as a polyfunctional alcohol, an acrylic or polyester resin containing hydroxy groups, partially hydrolyzed polyvinyl acetal or polyvinyl alcohol. This type of polycondensation of polysiloxanes is described, for example, in J.J. Lebrun, H. Pode, Comprehensive Polymer Science, vol. 5, p. 593, Pergamon Press, Oxford, 1989.

It will be appreciated that the above-described acid-initiated reactions described above in the context of the invention need not necessarily be carried out only with acid generators consisting of oximinesulfonates, but can also be performed using other acid generating compounds having a molar extinction coefficient ε less than 10. Examples of such compounds are given above.

As noted above, the difference in solubility between irradiated and non-irradiated areas due to the acid catalyzed reaction of the resist material during or after irradiation of the resist may be of two types, depending on which other components are present in the formulation or resist. . If the compositions of the invention contain components that increase the solubility of the composition in the developer, then the resist is positive. Conversely, if these

The solubility of the composition, the resin goes by the appropriate components to reduce the negative.

In particular, acid-sensitive components that produce a negative resist are compounds which, when catalyzed by an acid (e.g., acid formed during irradiation of a compound of formula I or a compound of formula Ia), are capable of undergoing an auto-crosslinking reaction, i. a reaction in which cross-linking occurs only within the compound itself, or a cross-linking reaction with one or more other components of the composition. Compounds of this type are known, for example, as acid-curable resins and are, for example, acrylic resins, polyester resins, alkyd resins, melamine resins, urea resins, epoxy and phenolic resins, or mixtures thereof. Highly resins in this case are amino resins, phenolic resins and epoxy resins. Acid-curable resins of this type are generally known and described, for example, in Ullmann's Encyclopadie der technischen Chemie, 4th Ed., Vol.15 (1978), pp.613-628. These resins are generally present at a concentration of 2 to 40% by weight, preferably at a concentration of 5 to 30% resist by weight, based on the resist composition, based on the total dry solids content, negative.

Particularly preferred acid-curable resins are non-etherified or etherified melamine, urea, guanidine or biuret resins, preferably methylated melamine resins or butylated melamine resins corresponding to glycouril and urone. In this context, the term resin usually refers to technical mixtures which usually contain oligomers as well as pure and very pure compounds. Within the scope of the invention, the most preferred acid-curable resins are N-methoxymethylmelamine (Formula 7) and tetramethoxymethylglucoril (Formula 8),

Ν, Ν'-dimethoxymethyluron (Formula 9).

· · · · · · · Β · β · β · jakož · jakož · jakož · jakož · jakož · i · i · jakož ·

N - (CH ₂ OCH ₃ ),

X ch ₃ and ₂ ch ₂ and ₃ (7);

XIN> ° (8);

(CH ₃ OCH ₂ ) ₂ -NN- (CH ₂ OCH ₃ ) ₂

I Ν ¹ i

CH ₃ OCH ₂ CH ₂ OCH ₃

CH ₃ OCH _2X , CH ₃ OCH ₃

Ν N ^{2 3} (g).

Generally, the concentration of the compound, specifically the compound of formula I generating the acid or Ia of the negative resist, is generally 0.1 to 30% by weight, preferably

0.1 to 20 compositions.

%, in particular from 1 to 15% by weight.

The total concentration content is in the dry matter given

If desired, the negative compositions may additionally comprise a film-forming polymeric binder. The binder is preferably an alkali-soluble phenolic resin. Particularly suitable for this purpose are, for example, novolaks derived from an aldehyde, in particular acetaldehyde or furfuralaldehyde, but specifically from formaldehyde, and a phenol, for example an unsubstituted phenol, a mono- or dichloro-substituted phenol such as p-chlorophenol, a mono- or disubstituted phenol containing 1 to 9 carbon atoms such as o-, m- or p-cresol, various xylenols, p-tert-butylphenol, p-nonylphenol, p-phenylphenol, resorcinol, bis (4-hydroxyphenyl) methane or 2,2- bis (4-hydroxyphenyl) propane. Also suitable are homo- and

copolymers based on ethylenically unsaturated phenols, for example homopolymers of vinyl- and 1-propenyl-substituted phenols, such as p-vinylphenol or p- (1-propenyl) phenol, or copolymers of these phenols with one or more ethylenically unsaturated compounds, such as styrenes. The amount of binder is generally 30 to 95% by weight or preferably 40 to 80% by weight.

In a specific embodiment, the invention includes a negative photoresist having a resist thickness of greater than 2 microns which is alkaline-inducible and intended for functional irradiation at a wavelength between 340 and 390 nanometers and comprising the oximesulfonate of formula Ia described above in alkali-soluble phenolic a resin as a binder and a component which, when catalyzed by an acid, undergoes an auto-crosslinking reaction and / or a crosslinking reaction with the binder.

Particularly preferred negative photoresists contain 1 to 15% by weight of oximsulfonate as acid generating agent, 40 to 99% by weight of phenolic resin as binder, for example some of the above resins, and 0.5 to 30% by weight of melamine resin as crosslinker wherein all percentages are based on the dry matter content of the composition. When novolak or especially polyvinylphenol is used as a binder, the negative resist has particularly advantageous properties.

It is preferred to use a negative resist containing N-methoxymethylmelamine or tetramethoxymethylglucoril and N, N'-dimethoxymethyluron having a high purity or technical quality as an amino resin.

Oximinesulfonates are also used as acid generators that can be photochemically activated for acid catalyzed crosslinking, for example, of poly (glycidyl) methacrylates in negative resist systems. Such cross-linking reactions are described, inter alia, by Chae et al. in Pollimo 1993, 17 (3), 292.

The positive character of the photoresist in the novel photoresist compositions of the invention also provides monomeric compounds which are insoluble in alkali but cleavable in the presence of acid or capable of intramolecular rearrangement in such a way as to obtain reaction products that are soluble in conventional alkaline developers, and / or causes the otherwise alkali-insoluble and acid-resistant additional binder to become soluble in the developer. Substances of this type are hereinafter referred to as dissolution inhibitors.

The invention therefore includes, in a further specific embodiment, alkaline-inducible positive photoresists intended for working irradiation at a wavelength of 340 to 390 nm, said resists comprising a compound of formula I or Ia having a molar extinction coefficient ε less than 10 and at least one compound. which substantially prevents dissolution of the composition in the alkaline developer, but which can be resolved in the presence of acid in such a way that the obtained reaction products are soluble in the alkaline developer, and / or cause an acid-resistant additional binder that would otherwise be virtually insoluble in the alkaline developer will become soluble in this developer.

As dissolution inhibitors, monomeric or polymeric organic compounds having functional groups that are themselves soluble in an alkaline medium can be used, for example aromatic hydroxyl groups, carboxyl groups, secondary amino groups and keto groups and aldehyde groups. These monomeric or polymeric organic compounds were chemically modified by treatment with a suitable compound so that they become insoluble in aqueous alkali prior to their use as dissolution inhibitors, the protecting groups formed in said reaction being capable of cleavage by acid catalysis, so that 9 9 9 9 9 9

9 · 9 9 * * * · * φ * 99 99 The functional groups are then restored to their original form.

Suitable protecting groups for the protection of hydroxyl groups, carboxyl groups or secondary amine groups are, for example, dihydrofuran or 3,4-dihydropyran and its derivatives, benzyl halides, alkyl halides, haloacetic acids, haloacetates, chlorocarbonates, alkylsulfonyl halides, aromatic sulfonyl halides, dialkyldicarbonates or trialkylsilyl halides. Said protecting groups are introduced by conventional reactions known to those skilled in the art. Conventional conversion to ketals and acetals is suitable for protecting the keto group and the aldehyde group. Such chemically enhanced positive resist systems are described, inter alia, in: E. Reichmanis, F.M.Houlihan, 0. Nalamasu, T.X. Neenan, Chem. 1991, 3, 349 or in: C. G. Willson, Introduction to Microlithography, 2nd Ed., And in L.S. Thompson, C.G. Willson, M.J. Bowden, publ. Soc., Washington DC, 1994, p.139.

Particularly preferred are compounds bearing blocked aromatic hydroxyl groups, which compounds may be monomers or polymers. The aromatic monomers preferably contain one or more than one aromatic ring containing 6 to 14 ring carbon atoms, preferably 6 ring carbon atoms. The aromatic nucleus, in addition to containing blocked hydroxyl groups, can of course also contain other substituents, preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen. Particularly preferred monomeric dissolution inhibitors are of the biphenyl type, for example compounds of the general formula

Y

OF '/ \

Y • 99 9 9 9 9 9 9 9 • 9 · · · 9 9 9 9 99

999 99 99

Wherein each Y represents an acid-sensitive group such as an ether, carbonate, silyl, tetrahydropyranyl or tetrahydrofuranyl group (see, for example, EP 475903), and Z represents either a direct single bond or any one of the following groups: -S-, -O-, -SO-, -SO ₂ -, -CO-, -C (R _a ) (R b) "wherein R _a represents a hydrogen atom, a methyl group or an aryl group and R ₅ represents a hydrogen atom or a methyl group. Particularly suitable bivalent groups are -CH ₂ -, -C (CH ₃ ) ₂ - and C (CH ₃ ) (Ph) -. Preferred polymeric dissolution inhibitors are derived from conventional phenolic resins, usually polyvinylphenols, whose hydroxyl groups are blocked in a manner consistent with the above description. Dissolution inhibitors carrying protective groups of this type are known in the art. Inhibitors bearing carbonate groups are described, inter alia, by Dennis R. McKean, Scott A. McDonald, Nicholas J. Clecak, and C Grant Willson in Novolac based deep-UV-resists, SPIE, Vol. 920, Advances in Resist Technology and Processing V (1988), pp. 60-63, or by Masamitsu Shirai and Masahiro Tsunooka in the Photochemistry of Imino Sulfonate Compounds and their Application to Chemically Amplified Resists, Journal of Photopolyner Science and Technology, vol.3 (3), 1990, pp. 301-304. Dissolution inhibitors carrying protective groups may be prepared by standard known procedures, for example, those described by JM Frechet, E. Eichler, H.Ito and CG Willson, Polymer 24 (1983), p. trialkylsilyloxy or tert-butyloxy groups are disclosed in EP 0329610; inhibitors bearing tetrahydrofuranyl and tetrahydropyranyl type protecting groups are described, inter alia, by N. Hayashi, SMAHesp, T. Ueno, M. Toriumi, T. Iwayanagi and S. Nonogaki in Polym.Mat.Sci.Eng. 61 (1989), 417-421. Aromatic compounds bearing substituted tetrahydropyranyl groups are described in more detail in EP patent document. Said protecting groups may be obtained in a manner known per se by addition

3,4-dihydropyrans or 3,4-dihydrofurans under acidic conditions.

In the positive resist of said types, the film-forming polymeric dissolution inhibitor may either be the only binder in the photoresist or may be used in admixture with an acid-inert binder and optionally a monomeric dissolution inhibitor.

Examples of acid-inert binders are novolaks, in particular novolaks based on o-, m- or p-cresol and formaldehyde, as well as poles (p-hydroxystyrene), poles (p-hydroxy-alpha-methylstyrene) and copolymers of p-hydroxystyrene, p- hydroxy-alpha-methylstyrene and acetoxystyrene.

Examples of polymeric dissolution inhibitors are novolaks, in particular novolaks based on o-, m- or p-cresol and formaldehyde, poles (p-hydroxystyrene), poles (p-hydroxy-alpha-methylstyrene), copolymers of p-hydroxystyrene or p-hydroxy- alpha-methylstyrene and acetoxystyrene or acrylic and / or methacrylic acid as well as (meth) acrylic esters, which are reacted in a known manner with dihydrofuran,

3,4-dihydropyran, benzyl halides, alkyl halides, haloacetic acid, haloacetates, chlorocarbonates, alkylsulfonyl halides, aromatic sulfonyl halides, dialkyl dicarbonates or trialkyl halides. Also suitable are polymers of p- (2-tetrahydropyranyl) oxystyrene or p- (tert-butyloxycarbonyl) oxystyrene with (meth) acrylic acid, (meth) acrylates and / or p-acetoxystyrene and polymers of p-hydroxystyrene and / or p- (2). (tetrahydropyranyl) oxystyrene with 3-hydroxybenzyl (meth) acrylates, which may optionally be protected by reaction with one of the above compounds.

* ·· • ·· • # · ta ··· # # ·· · · ·········

Particularly suitable polymers are polymers which are transparent in the wavelength range from 180 to 1000 nm and which carry groups which after acid-catalyzed deprotection bring at least a change in solubility, as well as hydrophobic and hydrophilic groups which increase the solubility of the acid generator and ensure the aqueous-alkaline environment. Examples of such polymers are acrylates and methacrylates prepared by co- or ter-polymerization from the corresponding monomers. These monomers can also carry organosilicon groups, for example to increase resistance, especially in the case of dry etching processes. Examples of the corresponding monomers are: methyl (meth) acrylate, (meth) acrylic acid, tert-butyl (meth) acrylate, trimethylsilylmethyl (meth) acrylate,

3-oxocyclohexyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, adamantyl (meth) acrylate, cyclohexyl (meth) acrylate, and norbornil (meth) acrylate.

The invention also relates to a chemically enhanced positive resist containing, as a photosensitive acid generator, a compound of formula I or Ia having a molar extinction coefficient ε less than 10, as well as a photoresist containing polymers that are transparent up to 180 nm.

A specific embodiment of the positive resist according to the invention comprises 75 to 99.5% by weight of a film-forming polymer which contains protecting groups which can be removed by acid catalysis and 0.5 to 25% by weight of an oximsulfonate of the formula I or Ia having a molar extinction coefficient ε below 10, wherein the percentages given are based on the total dry weight of the composition. In this context, compositions containing 80 to 99% by weight of said polymer and 1 to 20% by weight of oximsulfonate are preferred.

Another embodiment of the present invention is a positive resist containing 40 to 90 wt% of an acid-inert film-forming polymer as binder, 5 to 40 wt% of monomeric or polymeric compounds having protective compounds and 0.5 to 25% by weight of the oximsulfonate of formula (I) or (Ia) described above, the percentages given being based on the dry matter content of the composition. Preference is given to compositions comprising 50 to 85% by weight of an acid-inert binder, 10 to 30% by weight of a monomeric or polymeric dissolution inhibitor and 1 to 15% by weight of oximinesulfonates.

Oximinesulfonates can also be used as solubilizing agents that can be light activated.

In this case, compounds that substantially contain no components that polymerize with oximinesulfonate when heated or irradiated with an actinic radiation are added to the film-forming material. However, oximesulfonates reduce the dissolution rate of the film-forming material in a suitable developing environment. This inhibitory phenomenon can be abolished by irradiating the mixture with actinic radiation so that a positive image can be produced. Such an application is described, for example, in EP 241423.

Another specific embodiment of the invention is a positive resist comprising a compound of formula I or Ia having a molar extinction coefficient ε less than 10 and a binder that is virtually insoluble in an alkaline developer and that becomes developer soluble in the presence of photolysis products of a compound of formula I or Ia . In this case, the amount of said oximinesulfonate compound of formula I or Ia is generally 5 to 50% by weight, based on the dry matter content of the composition.

The use of the oximsulfonates of the invention in chemically enhanced systems that operate by deprotection of the polymer generally produces a positive resist. Positive resists are preferable to negative resists in many applications, especially because of their better resolution. However, there is also an interest in producing a negative image using a positive resist mechanism in order to combine the advantages of the high resistivity of the positive resist with the properties of the negative resist. This can be achieved by introducing a so-called image reversal stage, as described, for example, in EP 361906. For this purpose, the image-irradiated resist material is treated, for example, with a gaseous base prior to the development stage, thereby neutralizing the acid which has been image-irradiated. Subsequently, the entire surface of the photoresist is irradiated, after which the resist is heat-treated and the negative image is finally produced in the usual manner.

In addition to the aforementioned compounds, it is also possible to add compounds to both the negative and positive resist compositions containing oximsulfonates that accelerate or intensify acid formation. Such acid-enhancing enhancers are described, inter alia, by K.Arimitsu et al., J.Photopolym. Sci Technol. 1995, 8, p.43, K.Kudo et al., J Photopolym.Sci Technol.1995, 8, p.45 or K. Ichimura et al. Chem.Lett.1995, p.551.

In addition to the ingredients already mentioned, the negative and positive photoresist compositions may additionally contain one or more additives which are commonly used in photoresis in amounts known to those skilled in the art. Examples of such additives are flow control agents, wetting agents, adhesives, thixotropic agents, dyes, pigments, fillers, solubilizers, and the like. However, substances which additionally sensitize compositions to be irradiated in the region of the mercury i-line should not be added, as this could result in a reduced resistivity.

For some purposes, resin mixtures having monomeric or oligomeric components containing polymerizable unsaturated groups are used. Such surface coatings may also be cured using the compounds of formula I or Ia described above. In addition to component c) it is also

99 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 999 99 1 · 1) radical polymerization initiators or 2) photoinitiators. The first bars initiate the polymerization of the unsaturated groups by heat treatment, while the second ones irradiate with ultraviolet light.

Examples of additional photoinitiators for use in the compositions of the invention are radical photoinitiators, benzophenone groups such as dialkoxyacetophenone, alpha-aminoacetophenone, usually acetophenone derivative photoinitiators, alpha-hydroxycycloalkylphenyl ketone, alpha-hydroxyacetophenone or the like.

4-aroyl-1,3-dioxolane, benzoalkylethers and benzil ketals, phenylglyoxalic acid esters and derivatives thereof, dimeric phenylglyoxalic acid esters, peresters such as benzophenotetracarboxylic acid esters as described, for example, in the monoacylphosphine oxides patent, bisacylphosphine oxides, or illustrative examples are particularly illustrative :

1- (4-dodecylbenzoyl) -1-hydroxy-1-methylethane

1- (4-Isopropylbenzoyl) -1-hydroxy-1-methylethane

1-Benzoyl-1-hydroxy-1-methylethane

1- [4- (2-hydroxyethoxy) benzoyl] -1-hydroxy-1-methylethane, 1- [4- (acryolyolyoxyethoxy) benzoyl] -1-hydroxy-1-methylethane, diphenylketone, phenyl-1-hydroxycyclohexylketene, (4-morpholinobenzoyl) ) -1-Benzyl-1-dimethylaminopropane

1- (3,4-dimethoxyphenyl) -2-benzyl-2-dimethylaminobutan-1-one, (4-methylthiobenzoyl) -1-methyl-1-morpholinoethane, benzyldimethylketal, bis (cyclopentadienyl) bis (2,6-difluoro) -3-pyrrylphenyl) titanium, trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dipentoxyphenylphosphine oxide or bis (2, 4,6-trimethylbenzoyl) phenylphosphine oxide.

EP 126541, titanocenes. additional

99 • 9 9

9 9 9

9 9 • 9 99

99

9 9 9

9 «

4 «99

9

99 99 99

Other suitable additional detectors are described, for example, in U.S. Pat. No. 4,950,581 (column 20, line 35 to column 21, line 35. Further examples are trihalomethyltriazine derivatives or hexaarylbisimidazolyl compounds.

Other examples of additional photoinitiators are also cationic photoinitiators, typically peroxide compounds such as benzoyl peroxide (other suitable peroxides are described in US 4950581, column 19, lines 17-25), aromatic sulfonium salts or iodonium salts such as those described, inter alia, in U.S. Pat. No. 4,950,581, column 18, line 60 to column 19, line 10, or cyclopentadienylarene-ferrous complex salts, typically (η ⁶ -isopropylbenzole) (β-cyclopentadienyl) iron-II-hexafluorophosphate.

For the application of said solvent. Examples of suitable methylethylacetone, ethyl acetate, ethylpyruvate, 2-heptanone, the compositions also include solvents such as acetone,

3-methoxymethylpropionate, diethylglycol dimethyl ether, cyclohexanone,

2-ethoxyethanol, cyclopentanone, ethylmethylketone, in particular 1-methoxy-2-propyl acetate propylene glycol methyl etheracer. The solvent is also added as a mixture, for example, of the two solvents. The choice of solvent a will depend, for example, on the nature of the composition and the application method.

The γ-butyrolactone, 2-ethoxyethyl acetate or may be more concentrated to the chosen one

The application solution is uniformly applied to the substrate by known coating techniques, for example centrifuging by icing, dipping, using a knife coating machine, aperture coating, using a brush coating machine, spraying and applying using a counter roller roller coating machine. The photosensitive layer may also be

9 99 9 · 99 99 99 • 9 • 9 9 9 9 9 • 9 • 99 » • 9 99 9 9 9 9 9 9 · 99 99 • 9 99 9 9 99 99 9 9 9 9

applied to a temporary flexible substrate and then transferred to the final substrate (laminating).

The amount applied (thickness of the coating) and the nature of the substrate (bearing the coating) depend on the type of application desired. The coating thickness range may essentially comprise values from about 0.1 micrometer to more than 100 micrometers, although coating thickness values greater than 2 micrometers are particularly preferred in the present invention. Particularly preferred are coating thicknesses of 2 to 100 microns, for example 2.5 to 60 microns or 2.5 to 20 microns.

Possible fields of application of the composition of the invention are as follows: use as electronics photoresists, such as etching resists, electroplating resistors and solder resists, integrated circuit manufacturing or thin film transistor resistors (resist TFT), printing plate manufacturing such as offset printing plates or stencils for screen printing, for use in etching shaped products or for stereolithography techniques, for use in color filters or image recording materials, as well as for all types of lithographic imaging processes, preferably for use as micro-resists in the production of integrated circuits. The coating substrates and processing conditions vary with the type of application and are conventional in the art.

When the compositions of the invention are used as microresists for integrated and industrial scale integrated circuits, which is a preferred application, then the layer thickness of the composition is usually 2 to 30 microns, preferably 2 to 10 microns. The preferred use of the compositions of the invention is within process steps where a relatively large resist thickness results in some advantages or is desirable to achieve the desired functionality of the resulting product. An example of such an application is resistors for the ionic již mentioned above

44

4, in which the thicknesses of the coatings are in the range from 2 to 10, preferably from 2 to 7 micrometers.

The compositions according to the invention are also particularly suitable as coating compositions for coating substrates of all types, in particular wood, textile, paper, ceramics, glass, plastics such as polyesters, polyethylene terephthalate, polyolefins or cellulose acetate, in particular in the form of foil , and in particular for coating metals such as nickel, iron, zinc, magnesium, cobalt or, in particular, copper and aluminum, as well as silicon, oxides or nitrides of silicon, to which the image is to be applied by means of image irradiation. The term image exposure is explained below.

After application of the composition to the substrate, the solvent is generally removed by heating to provide a photoresist layer on the substrate. However, the temperature at which the applied composition is dried on the substrate must be lower than the temperature at which some of the resist components may have been thermally cured. Care should be taken in this respect, especially in the case of negative photoresists. In general, the drying temperature of the applied composition on the substrate is in the range of 80 to 140 ° C.

The resist is then visualized. This predetermined pattern using actinic radiation includes both photomasks containing a predetermined pattern, such as a slide, as well as radiation using a laser beam that moves across the surface of a coated substrate, such as under computer control, to obtain a resist. picture.

Suitable radiation sources are those that emit wavelength radiation corresponding to the working wavelength of the resist, for example radiation with a wavelength between 340 and 390 nanometers. Point sources as well as flat-panel projectors (a set of reflector lamps) are suitable for this purpose. Examples of such sources are: carbon arc lamps, xenon arc lamps, medium-pressure, high-pressure and low-pressure mercury lamps, optionally doped metal halides (metal halide lamps), micro-excited metal vapor lamps, fluorescent lamps, superactinic fluorescent lamps, fluorescent lamps, argon fiber lamps , electronic flash lamps, photographic wide-angle reflectors, electron and X-ray beams generated by synchrotrons, or laser plasma. Particularly suitable sources are mercury vapor lamps, in particular medium-pressure and high-pressure mercury vapor lamps, from which the emission lines and other wavelengths are optionally filtered off. This is particularly true of shortwave radiation. For example, the distance between the lamp and the photoresist substrate to be irradiated may vary from 2 cm to 150 cm depending on the type of intended use and the type and / or intensity of radiation emitted by the lamp. A suitable laser source is, for example, an argon-ion laser that emits radiation at wavelengths of 364 and 388 nanometers. When irradiating with this type of radiation, it is not absolutely necessary to use a photomask in contact with the photopolymer coating; the controlled laser beam is able to write exactly on the surface of the coating. For this purpose, it is particularly suitable to use the high sensitivity of the material according to the invention, which allows a high writing speed at relatively low intensities. After irradiation, the oximsulfonate in the composition decomposes in the irradiated areas of the coating surface to form sulfonic acids. When using light emitting lamps in the wavelength range exceeding the wavelength range 340 to 390 nm, then the desired working wavelength range is stripped of the overlapping wavelength regions by using suitable filters. Interference filters are usually used.

After irradiation and optional heat treatment, the non-irradiated image areas (in the case of positive resists) or the irradiated image areas (in the case of negative resists) of the composition are removed in a manner known per se using a developer.

In general, it is necessary to include a certain waiting period before the development stage, and thus to give the acid-sensitive components of the resist composition sufficient time to react with the generated acid. In order to accelerate this reaction and thereby achieve a sufficient difference in solubility between the irradiated and non-irradiated resist regions in the developer, the coating is preferably heated before developing. This heating may also be performed or already begun during the irradiation. A temperature of 60 to 160 ° C is preferably used for this purpose. The heating time depends on the heating method and the optimal heating time can be readily determined by one skilled in the art by carrying out several routine experiments. Generally, this time varies from a few seconds to a few minutes. For example, in the case of using a hot plate, a time of 10 to 300 seconds is suitable, while in the case of using a conventional oven a heating time of 1 to 30 minutes is preferably used.

The coating is then developed to remove parts of the coating that are more soluble after irradiation in the developer. The development can optionally be accelerated by gently moving the substrate coated in the developer or by gently brushing the brush over the developer coating or by using spraying. Water-alkaline developers which are common in resist technology can be used to develop the coating. Such developers include, for example, sodium hydroxide or potassium hydroxide, sodium carbonate or potassium carbonate, sodium bicarbonate or potassium bicarbonate, and sodium or potassium silicate or metasilicate, but preferably the developer comprises a metal-free base such as ammonia or amines such as ethylamine, n- propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamines, for example dimethylethanolamine, triethanolamine, quaternary ammonium hydroxides, for example tetramethylammonium hydroxide or tetraethylammonium hydroxide. The developing solutions generally have a concentration of up to 0.5 N, but are usually diluted appropriately prior to use. For example, solutions having a normality of about 0.1 are particularly suitable. The choice of developer depends on the nature of the photoresist, particularly the nature of the binder used or the resulting photolysis products. The aqueous developer solutions may optionally also contain relatively small amounts of wetting agents and / or organic solvents. Typical organic solvents that can be added to the developing liquids are, for example, cyclohexanone, 2-ethoxyethanol, toluene, acetone, isopropanol, as well as mixtures of two or more of these solvents. Typical water-organic developing systems are based on a combination of Butylcellosolve and water.

Accordingly, the invention also relates to a method for producing an image, comprising: a) coating a substrate with the composition described above; b) irradiating the coating on the substrate with radiation having a wavelength of 340 to 390 nanometers in a desired pattern; d) removing less soluble areas of the coating by a water-alkaline developer.

The invention also relates to the use of the compositions described above for the production of printing plates, color filters, resist and image recording materials or holographic image recording materials, as well as the use of compounds of formula I or Ia having a molar extinction coefficient of less than 10. a photosensitive acid-sensitive acid generator with a wavelength less than 390 nm for the production of printing plates, color filters, resist and image recording materials or holographic image recording materials.

In addition to the color change, it is also possible that during the acid-catalyzed deprotection of the soluble pigment molecules, pigment crystals are deposited; it can be used in the production of color filters.

The compounds of formula I or Ia are normally added to compositions that can be activated

light, in an amount of 0.1 to 30% by weight, for example in an amount of 0.5 to 20% by weight, preferably in an amount of 1 to 10% by weight.

The present invention also provides a negative photoresist which comprises, as an acid-generating compound (Ia), α- (methanesulfoniumoxyimino) -3,4-dimethylphenylacetonitrile, α- (methanesulfoniumoxyimino) -4-methylphenylacetonitrile, or α- (4-toluenesulfoniumoxyimino) Phenylacetonitrile.

In the following, the invention will be further elucidated by means of examples of specific embodiments thereof, which are provided by way of illustration only and are not intended to limit the scope of the invention as defined by the claims.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Prepare a negative resist composition by mixing parts by weight of polyvinylphenol resin (Maruzen Chemical Co.Ltd.), Parts by weight of hexamethoxymethylmelamine, Cymel303 (American Cyanamide), and

150 parts by weight of propylene glycol methyl ether acetate.

Separately, 5 parts by weight of an acid-generating agent consisting of α-methanesulfoniumoxyimino) -3,4-dimethylphenylacetonitrile (having ε equal to 4.1 in a tetrahydrofuran solution at 365 nm) is dissolved in 10 parts by weight of N, N-dimethylacetamide.

The above solutions are combined to form a resist solution.

The silicon wafer is uniformly coated with said resist solution by centrifugal coating, and then the wafer is dried for 90 seconds at 110 ° C to give a dried photoresist layer having a thickness of 5 microns. The resist layer was then exposed through a mask (Canon PLA501) using a light transmitting interference filter with a wavelength of mercury i-line (365 nm) and heated to 110 ° C for 90 minutes after exposure. The formulation was then developed in a 2.38% (w / w) aqueous solution of tetramethylammonium hydroxide for 60 seconds, then washed with water and air dried.

The sensitivity to the 2pm car body weight, expressed as the exposure dose at which the resist layer on the exposed areas can be completely formed at a 1: 1 ratio, was 210 mJ / cm ² (energy).

In addition, a resist layer patterned with an autopilot pattern with a 2 µm line width and obtained in a manner consistent with the above method was examined by a scanning electron microscope to determine the cross-sectional profile of the line pattern. It has been found that the cross-section has a rectangular shape which is perpendicular to the substrate. Next, the relative line width obtained using a varying exposure dose between 0.8 and 1.2 times the exposure dose initially used versus the relative energy used was plotted. The slope obtained straight is equal to 0.28. The lower this Directive, the better the exposure flexibility of the test system.

Example 2

A resist formulation was prepared as in the example

1. In the present case, however, the acid generating agent, instead of α- (methanesulfoniumoxyimino) -3,4-dimethylphenylacetonitrile, consists of 5 parts by weight of α- (methanesulfoniumoxyimino) -4-methylphenylacetonitrile (having ε equal to 0.35 in tetrahydrofuran solution at 365 nm). Using the same conditions as in Example 1, a sensitivity of 300 mJ / cm ² was achieved. The cross-sectional profile of the resist layer of the 2μτη line was examined by a scanning electron microscope, found to be rectangular in shape and positioned perpendicular to the substrate. The slope of the above-described dependence was determined in the same manner as in Example 1 and in this case was 0.31.

Example 3

A resist formulation was prepared as in Example 1. However, in the present case, the acid generating agent instead of α- (methanesulfoniumoxyimino) -3,4-dimethylphenylacetonitrile is 5 parts by weight of α- (4-toluenesulfoniumoxyimino) -phenylacetonitrile (having ε 0.28 in tetrahydrofuran solution at 365 nm). Using the same conditions as in Example 1, a photosensitivity of 500 mJ / cm ² was achieved. The cross-sectional profile of the 2 µm resist layer was examined by a scanning electron microscope, found to be rectangular in shape and positioned perpendicular to the substrate. The slope of the above-described dependence was determined in the same manner as in Example 1 and in this case was 0.42.

Comparative example

A resist solution was prepared in essentially the same manner as in Example 1 except that the acid generating agent used in Example 1 was replaced here with 5 parts by weight of α- (methanesulfonium oxyimino) -2-thiophenylacetonitrile having ε 58 v tetrahydrofuran solution at 365 nm. In this case, a photosensitivity of 60 mJ / cm ² and a slope of 0.72 are determined.

Claims (16)

PATENT CLAIMS py cv ·: .. 9 9 9 9 9 9 9 9 9 9 9 9 9 99 99 99 A light-activatable composition comprising (a) at least one compound which may be crosslinked by acid treatment; and / or (b) at least one compound whose solubility is altered by the action of an acid; and (c) as a photoinitiator, at least one acid-generating compound when exposed to light at 240 to 390 nm and having a molar extinction coefficient ε less than 10 at 365 nm. Composition according to claim 1, characterized in that it comprises as component (c) a compound comprising a structural unit of the formula (I). / C = NO-SO ₂ - (I), and having a molar extinction coefficient ε less than 10 at 365. Composition according to Claim 1, characterized in that it comprises, as component c), a compound of the general formula Ia in which: Ri, R _2, R _3, R ₄ and R ₅ represent independently of one another are hydrogen or unsubstituted or halosubstituted alkyl radical containing from 1 to 12 carbon atoms or R _IR R _2, R _3, R ₄ and R ₅ are halogen, R ₆ represents an unsubstituted or halogen substituted alkyl group having 1 to 18 carbon atoms, a phenylalkyl group in which the alkyl moiety contains 1 to 3 carbon atoms, a camphoryl group, a phenyl group, a naphthyl group, anthracyl group or a phenanthryl group, the anthracyl and phenanthryl group is unsubstituted or substituted one or more times with substituents selected from the group consisting of halogen, haloalkyl containing C 1 -C 4, CN, NO ₂ , C 1 -C 16 alkyl, phenyl, OR ₁₀ , COOR ₉ , -O (CO) -alkyl, wherein the alkyl moiety contains 1 to 4 carbon atoms stomas, SO ₂ OR ₉ and NR ₇ R _g , R ₇ and R _g represent, independently of one another are hydrogen or alkyl having 1 to 12 carbon atoms, which is unsubstituted or substituted with substituents selected from the group consisting of OH, an alkoxy radical containing 1 to 4 carbon atoms, an alkylsulfonyl group in which an alkyl radical having 1 to 12 carbon atoms, a phenylsulfonyl group, a (4-methylphenyl) sulfonyl group and an alkanoyl group having 1 to 6 carbon atoms, or R ₇ and R ₈ represent an alkyl group containing 2 to 12 carbon atoms which is interrupted by -O- and which is unsubstituted or substituted by substituents selected from the group consisting of OH, alkoxy having 1 to 4 carbon atoms, alkylsulfonyl group in which the alkyl radical is 4; 4 4 4 4 4 It contains 1 to 12 carbon atoms, a phenylsulfonyl group, a (4-methylphenyl) sulfonyl group, and an alkanoyl group containing 1 to 6 carbon atoms. or R ₇ and R ₈ are phenyl, C 2 -C 6 alkanoyl, benzoyl, alkylsulfonyl in which the alkyl moiety contains 1 to 6 carbon atoms, phenylsulfonyl, (4-methylphenyl) sulfonyl, naphthylsulfonyl , anthracylsulfonylovou group or phenanthrylsulfonyl, or _R7 and _Rg together represent with the nitrogen atom to which they are attached form a 5-, 6- or 7-membered ring which may be interrupted by -0- or -NR member _n - R _g is an alkyl group having 1 to 12 carbon atoms which is unsubstituted or substituted by OH and / or an alkoxy group having 1 to 4 carbon atoms, or R ₉ is an alkyl group having 2 to 12 carbon atoms which is interrupted by a member - O- and which is unsubstituted or substituted by OH and / or by alkoxy having 1 to 4 carbon atoms, R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which is unsubstituted or substituted by substituents selected from the group consisting of phenyl, OH, alkoxy of 1 to 12 carbon atoms, alkylsulfonyl group in which the alkyl radical contains 1 up to 12 carbon atoms, phenylsulfonyl, (4-methylphenyl) sulfonyl and 2 to 6 carbon alkanoyl; or R ₁₀ is an alkyl of 2 to 12 carbon atoms interrupted by -O- and unsubstituted or substituted with substituents selected from the group consisting of phenyl, OH, alkoxy • · · • ··· • · · · • · · • ♦ · · • · * · • · Φ • · · · 9 • ··· ·· ·· ·· 9 9 • · C 1 -C 12 alkylsulfonyl, wherein the alkyl moiety contains 1 to 12 carbon atoms, phenylsulfonyl, (4-methylphenyl) sulfonyl, and C 2 -C 6 alkanoyl, or R ₁₀ is phenyl, R _n is hydrogen, unsubstituted or OH-substituted alkyl group having 1 to 12 carbon atoms or an alkyl group containing 2-12 carbon atoms which is interrupted by -0- member having a molar extinction coefficient ε of less than 10 at 365 nm. A chemically enhanced photoresist, characterized in that it is sensitive to radiation with a wavelength in the range of 340 to 390 nm and comprises a photosensitive acid generator of the formula I according to claim 2 having a molar extinction coefficient ε less than 10 at 365 nm. A chemically enhanced photoresist according to claim 4, characterized in that it is sensitive to radiation with a wavelength in the range of 340 to 390 nm and comprises a photosensitive acid generator of the formula Ia according to claim 3 having a molar extinction coefficient ε less than 10 at 365 nm. 6. The chemically enhanced photoresist of claim 4 or 5 having a thickness of greater than 2 microns. 7. A chemically amplified negative photoresist, characterized in that it contains a compound of the formula Ia having a molar extinction coefficient ε of less than 10, is alkali-inducible, has a thickness greater than 2 micrometers and is sensitive to radiation of wavelengths ranging from 340 to 390 nm. 8. A negative photoresist having a thickness of more than 2 micrometers, which is inducible in an alkaline environment for working radiation of a wavelength in the range of 340 to 390 nm, and comprises an oximesulfonate of the formula Ia according to claim 3, an alkali-soluble phenolic resin such as a binder and a component which, when catalyzed by an acid, undergoes an auto-crosslinking reaction and / or a crosslinking reaction with a binder. 9. A chemically enhanced positive photoresist, characterized in that it contains a compound of formula Ia having a molar extinction coefficient ε less than 10, is alkaline-inducible, has a thickness greater than 2 micrometers and is sensitive to radiation of the wavelength range 340 to 390 nm. A positive photoresist comprising a compound of formula Ia according to claim 2 and a binder which is virtually insoluble in an alkaline developer and which becomes soluble in the developer in the presence of photolysis products of the compound of formula Ia. Use of the composition according to claim 1 for the production of negative chemically enhanced photoresists, positive photoresists, printing plates, color filters or image recording materials. 12. A method for producing negative chemically enhanced photoresists, positive photoresists, printing plates, color filters, or image recording materials. 9 9 99 94 • 9 9 999 999 The composition of claim 1 is irradiated with light having a wavelength of 340 to 390 nm. A method of producing an image, characterized in that a) the substrate is coated with the composition of claim 1, b) the obtained coating is irradiated with radiation having a wavelength of 340 to 390 nanometers in a desired pattern, then c) heated to 60 to 160 ° C and d) the more soluble areas of the coating are removed by aqueous-alkaline developer. I or Ia having than 10 as 14. Use of a compound of the formula The molar extinction coefficient ε of a lower photosensitive acid generator in containing compounds which may be acidic and / or as a dissolution inhibitor for compounds, their solubility varies by acidic. compositions 15. A process for generating sulfonic acids, characterized in that the photosensitive acid generator of the formula I or Ia having a molar extinction coefficient ε less than 10 is irradiated with light having a wavelength in the range 340 to 390 nm. A negative photoresist according to claim 8, characterized in that the acid-generating compound of the formula Ia is α- (methanesulfoniumoxyimino) -3,4-dimethylphenylacetonitrile, α- (methanesulfoniumoxyimino) -4-methylphenylacetonitrile or α- (4-toluenesulfoniumoxyimino) phenylacetonitrile .