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WO1997048677A1 - Generateurs de photoacides non ioniques presentant une efficacite quantique amelioree - Google Patents

Generateurs de photoacides non ioniques presentant une efficacite quantique amelioree Download PDF

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Publication number
WO1997048677A1
WO1997048677A1 PCT/US1997/008344 US9708344W WO9748677A1 WO 1997048677 A1 WO1997048677 A1 WO 1997048677A1 US 9708344 W US9708344 W US 9708344W WO 9748677 A1 WO9748677 A1 WO 9748677A1
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WO
WIPO (PCT)
Prior art keywords
groups
group
grams
compound
dinitro
Prior art date
Application number
PCT/US1997/008344
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English (en)
Inventor
Neil D. Mcmurdie
Charles F. Ii Kahle
Gregory J. Mccollum
James B. O'dwyer
Original Assignee
Ppg Industries, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ppg Industries, Inc. filed Critical Ppg Industries, Inc.
Publication of WO1997048677A1 publication Critical patent/WO1997048677A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/73—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings

Definitions

  • the present invention relates to nonionic photoacid generator compounds useful in photolithographic compositions, and to methods for making said compounds.
  • photoacid generators in combination with acid sensitive polymers comprise photolithographic compositions wherein ultraviolet light exposure results in a difference in solubility between the photoexposed areas and the unexposed areas.
  • Photoacid generator compounds are particularly useful in photoresists requiring sensitivity to deep ultraviolet exposure (220 to 300 nanometers).
  • An object of the present invention is to provide novel photoacid generators having improved quantum efficiency.
  • Known agents for photo generating acid catalysts include sulfonate esters of nitrobenzyl alcohol, e.g.: G. G. Barclay et al., "The Photosensitized Dissociation of 4-Nitrobenzylsulfonate Esters by Phenolic Matrices," Chemistry of Materials 1995, 7(7), pages 1315-1324. Disclosures of mononitrobenzyl tosylates may be found in U.S. Patent Nos. 5,135,838 and 5,200,544. Dinitrobenzyl tosylates are disclosed in "Nitrobenzyl Ester Chemistry for Polymer Processes Involving Chemical Amplification" by F. M. Houlihan et al, Macromolecules, Vol. 21, No.
  • U.S. Patent No. 4,996,136 discloses a molecular structure that theoretically includes substituted dinitrobenzyl tosylates, but provides no enablement for substituted dinitrobenzyl groups.
  • Hayase et al. disclose nitrobenzylsilylethers in J. Electrochem. Soc: Solid-State Science and Technology, Vol. 134, No. 9, September 1987.
  • Similar nitrobenzyl silane structures are disclosed in U.S. Patent No. 5,017,453.
  • Photosensitive methyl methacrylic polymers containing nitrobenzyl groups are disclosed in U.S. Patent No. 4,666,820.
  • nitrobenzyl alcohol structures are theoretically encompassed by generic structures in Japanese Patent Applications 63-146029, 03-131626, 03-141357, and 63- 247749. These applications disclose nitro-containing benzyl alcohol derivatives specifically for use in applications employing short wavelength ultraviolet radiation in the region of 248 nanometers. They are non-enabling as to a synthesis for the particular dinitro structures of the present invention.
  • the nitrobenzyl alcohol synthesis disclosed in the Japanese publications for other species is not suitable for producing the dinitrobenzyl alcohol intermediates of the present invention at practical yield levels.
  • Commonly owned, copending U.S. Patent Application Serial No. 08/274,614 filed July 13, 1994, is directed to synthesis of dinitro-bis(chloromethyl)benzyl compounds that are used as intermediates in the production of the compounds of the present invention.
  • the photoacid generator compounds of the present invention are 2,6-dinitrobenzyl sulfonates substituted at the 4 position of the dinitrobenzyl group with an electron donating aryloxymethyl group.
  • the photoacid generator compounds of the present invention may be represented by the following structure:
  • R is an alkyl group, aryl group, or alkylaryl group, any of which may be substituted or unsubstituted.
  • the aryloxymethyl group substituted at the 4 position of the dinitrobenzyl group increases the quantum efficiency of the photoacid generator. This increase is attainable without significant loss of mermal stability.
  • a wide variety of electron-rich aryloxymethyl groups may be employed in the compounds of the present invention.
  • the R' substitution in the aryloxymethyl group in the structure shown above may include a wide range of groups, including hydrogen, alkyl, aryl, alkyloxy, dialkyloxy, aryloxy, diaryloxy, halo, or dialkylamino groups.
  • the present invention further includes the synthesis of compounds of the above structure employing 2,6-dinitro-l ,4-bis(haloalkyl)benzene as an intermediate.
  • dinitro substitution in the benzyl group increases photosensitivity compared to mononitro substitution in some prior art photoacid generating compounds. Even further enhancement of sensitivity is believed to be yielded by dinitro substitution in the 2,6 positions in particular.
  • the photochemistry relies on the photooxidation of the benzyl group by the nitro groups.
  • each photoreaction causes die formation of a sulfonic acid group which provides acid catalyst for deprotection of acid sensitive polymers during a subsequent bake step. This is useful, for example, in positive-acting photoresist compositions.
  • Characteristic of the present invention is an additional substitution at the 4 position on the dinitrobenzyl group of an electron donating aryloxyalkyl group, which increases the quantum efficiency of me photoacid generating sulfonate compound.
  • R is an alkyl group, aryl group, or alkylaryl group, any of which may be substituted or unsubstituted. Substitutions within R may include nitro groups and sulfonate groups. Particular examples of R include methyl, phenyl, p-toluyl, nitrophenyl, dinitrophenyl, p-methoxyphenyl, and benzenesulfonate groups.
  • the R' substitution in the aryloxymethyl group may include a wide range of groups, including hydrogen, alkyl, aryl, alkyloxy, dialkyloxy, aryloxy, diaryloxy, halo, or dialkylamino groups.
  • R' include methyl, methoxy, phenyl, bromo, and dimethyl amino groups.
  • other aryloxymethyl groups that are electron-rich may be used at the 4-position to attain the benefits of the present invention.
  • the first step in the production of the subject compounds is the synthesis of a bis(haloalkyl) dinitrobenzene compound. A specific method is described in greater detail in Example 1, and employs as the starting material commercially available ⁇ , ⁇ '-dichloro-p-xylene, which is nitrated to yield 2,6-dinitro-l ,4-bis(chloromethyl)benzene (Structure 2).
  • the 4-chloromethyl group can men be substituted with a phenol (R' ⁇ OH) to form a product having Structure 3 (where ⁇ represents a benzene ring) and R' is as defined above.
  • the remaining chloro group in Structure 3 may then be converted to an alcohol such as by a hydrolysis technique.
  • the alcohol group can then be reacted with a substituted or unsubstituted alkyl or aryl sulfonyl halide to form the sulfonate photoacid generator of the present invention represented by Structure 4 where Q is the sulfonate residue of the sulfonyl reactant.
  • the sulfonyl halide may, for example, be toluene sulfonyl chloride, nitrobenzene sulfonyl chloride, or benzene disulfonyl chloride.
  • O ⁇ Jer sulfonyl structures are known (see Barclay et al, supra) and may also be used.
  • R' ⁇ - is: 4-methoxyphenyl, 2-biphenyl, 2,6- dimethoxyphenyl, 2-methylphenyl, 3-biphenyl, or 3-methylphenyl.
  • Examples of compounds of the present invention having Structure 4 have been synmesized with the following combinations of R' ⁇ - and Q:
  • the bis(haloalkyl) dinitrobenzene compound may be dimerized by reaction with a di-functional material such as bisphenol A, yielding Structure 5.
  • Structure 5 can then be converted to an alcohol and reacted with a sulfonyl halide compound to yield Structure 6 (where Q, as above, is the residue of the sulfonyl compound.
  • materials that may be used instead of bisphenol A include 4,4'- dihydroxybiphenyl, 4,4'-dihydroxybenzophenone, resorcinol, and 2,6-dihydroxynaphthalene.
  • Examples 1 through 4 describe the synthesis steps for producing 2,6- dinitro-4-((4'-methoxy)phenoxy-methyl)benzyl tosylate, a preferred embodiment of photoacid generator of the present invention.
  • Concentrated sulfuric acid (density 1.84, 95 milliliters), 13 milliliters of oleum (27- 33%, density 1.94) and 150 milliliters of concentrated nitric acid (at least 90%, density 1.50) were combined in an ice bath cooled 1 liter flask equipped with mechanical stirring, condenser, and thermometer. The acid mixture exothermed slightly upon mixing. After the mixture cooled to below 25°C, ⁇ , ⁇ '-dichloro-p-xylene (35.0 grams, 0.2 mole) was added in small portions over 30 minutes so that the reaction temperature did not exceed 35°C.
  • Example 5 is a description of a synthesis of a resin that may be combined with the photoacid generator compounds of the present invention to enable measurement of acid generation upon exposure to light.
  • this resin was combined with the photoacid generating compound of Example 4 and tested for photoactivity.
  • the initial charge was heated in a reactor with agitation to reflux temperature (110°C). Then Feed 1 was added in a continuous manner over a period of 3 hours. At the completion of Feed 1, the reaction mixture was held at reflux for 30 minutes. Then one half of Feed 3 was added and held for one hour, followed by the addition of the remainder of Feed 3 and a 30 minute hold. The product was then cooled and poured from the vessel.
  • the resultant acrylic polymer had a total solids content of 67.98 percent determined at 110°C. for one hour and a theoretical T g of 28.97 °C.
  • the carrier resin of Example 5 was mixed with me photoacid generator of Example
  • the photoresist composition had 15 percent by weight solids.
  • the composition was drawn down onto six separate copper laminates that had been precleaned. Coating mickness was about 8 microns. All the coated laminates were baked for 5 minutes at 110°C, after which each was weighed. Each laminate was exposed to 365 nanometer U. V. light in a range of exposure dosages from 0 to 836 millijoules per square centimeter as indicated in Table I. After exposure, each laminate was washed in m-pyrol and rinsed with acetone. The laminates were dried for 5 minutes at 110°C, cooled, and the weight loss measured for each.
  • Acid values of the dissolved portions of the coatings were determined by titration of the solvent, from which the amount of acid generated by the photoexposure was calculated. These results are shown in Table I, where the gross acid value includes the acid content of the acrylic resin plus that attributable to the photoacid generator. The percent of theoretical figures represent the percentage of photoacid generators present that cleaved to form acid groups. Acid value is measured in terms of milligrams KOH to neutralize one gram of resin.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des composés générateurs de photoacides. Ces composés sont des 2,6-dinitrobenzyle sulfonates substitués à la position 4 du groupe dinitrobenzyle par un groupe phénoxyméthyle donneur d'électrons. L'invention traite aussi de procédés pour assurer la synthèse des composés photoréactifs à partir du 2,6-dinitro-1,4-bis(haloalkyle)benzène.
PCT/US1997/008344 1996-06-17 1997-05-19 Generateurs de photoacides non ioniques presentant une efficacite quantique amelioree WO1997048677A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US66341896A 1996-06-17 1996-06-17
US08/663,418 1996-06-17

Publications (1)

Publication Number Publication Date
WO1997048677A1 true WO1997048677A1 (fr) 1997-12-24

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ID (1) ID18340A (fr)
WO (1) WO1997048677A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4996136A (en) * 1988-02-25 1991-02-26 At&T Bell Laboratories Radiation sensitive materials and devices made therewith
WO1996002491A1 (fr) * 1994-07-13 1996-02-01 Ppg Industries, Inc. Composes photoreactifs positifs synthetises a base de groupes 2,6-dinitrobenzyle

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4996136A (en) * 1988-02-25 1991-02-26 At&T Bell Laboratories Radiation sensitive materials and devices made therewith
WO1996002491A1 (fr) * 1994-07-13 1996-02-01 Ppg Industries, Inc. Composes photoreactifs positifs synthetises a base de groupes 2,6-dinitrobenzyle

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ID18340A (id) 1998-04-02

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