JPH04162040A - Positive type photo-resist composition - Google Patents

Abstract

PURPOSE: To obtain a positive photoresist composition capable of being applied on an electrical conductive surface by electrode position by incorporating a mixture of a film forming polymer-containing acid curable resin system, an acid or an acid generating material and a base generating compound by light to form a cross-linked incorporated material. CONSTITUTION: The photoresist composition contains at least on kind of the film forming polymer-containing acid curable resin system, the acid or the acid generating material (preferably an acid generating agent by heating) for cross-linking the acid curable resin system and the base generating compound by light. And the photoresist composition contains 5-80wt.% cross-linking agent, 0.4-20wt.% base generating compound by light, 0.04-5wt.% acid or acid generating compound and optionally further contains 0-10wt.% photosensitizing agent. Where, the base generating compound by light is a carbamate, a benzoyl carbamate, o-carbamoyl hydroxyl amine, o-carbomoyl oxim, an aromatic sulfoamide, an α-lactone, N-(2-arylethenyl) amide or an azide.

Description

[Detailed Description of the Invention] The present invention provides a positive image crosslinked on the surface of a substrate.
The present invention is directed to improved acid-curable photoresist compositions useful for forming crosslinked images, such as for use in the manufacture of integrated circuits and printed wiring circuit boards. More specifically, the present invention provides photobase generators.
Positive-acting photoresist compositions that use acid-curing techniques in conjunction with a tar
ngphotoresist composition
). in the acid present in the non-imagewise exposed areas of the photoresist film in combination with the ability of the acid to crosslink the photoresist in the areas of the film that do not contain photochemically generated base by heating the photoresist film. By selecting a Japanese photobase generator, a positive image (positive image) crosslinked on the substrate surface.
can be formed.

Light Plate ■ Background The present invention is directed to photoresist compositions containing acid-curable resins and methods of using them, as well as conventional positive-working photoresist compositions, as described in European Patent Application No. 85303807. No. 3, Publication No. 016424
It is related to those described before the present invention, such as No. 8.

Positive-acting photoresists are typically film-forming compositions containing a film-forming polymer and a photosensitive compound dissolved in a suitable solvent.

The photoresist composition is applied to a substrate surface, such as an integrated circuit or computer chip.
silicon wafers in the production of
evafer) as a film. A photomask is placed between the substrate surface having the photoresist film and the exposing radiation source. A photomask functions like a stencil, having portions that are transparent to the exposing radiation used and portions that are opaque to the exposing radiation. Photomasks are designed and fabricated to replicate the electronic circuit pattern desired to be transferred onto a substrate. The exposing radiation used typically includes actinic radiation in the ultraviolet or shorter wavelength spectrum, such as X-rays and electron beams.
radiation of a single wavelength or a narrow range of wavelengths, referred to as radiation. The photoresist film is exposed to selected exposing radiation through a photomask at a predetermined dose and time. Through appropriate locations of the photomask in relation to the photoresist film, only those portions of the photoresist juxtaposed to the transparent portions of the photomask are exposed to actinic radiation. Exposure radiation absorbed by the photoactive compounds in the photoresist film causes a chemical reaction in the exposed portions of the film. In the case of positive photoresists, this chemical reaction is
The exposed portions of the photoresist film are made to be more soluble in a selected type of solution, known as a developer, than the unexposed portions of the film. The difference in solubility between the exposed and unexposed portions of the photoresist film in such a developer causes the exposed portions to be selectively removed during development, thereby leaving the unexposed portions of the photoresist film on the substrate. let This is accomplished by subsequent deposition of conductive metals, insulators, or dopants on portions of the substrate not protected by the remaining photoresist portions.
pattern for patterning) or etching of the substrate (e.g.
tching). These residual photoresist portions are removed from the substrate by removing the photoresist using a selected removal solvent after deposition of the conductive metal circuitry.

In the aforementioned method, the photoresist has a solubility that is as wide as possible between the exposed and unexposed areas of the film, and the unexposed areas are compatible with the next chemical and conditions used in the next step. It is desirable to have the ability to be as resistant as possible.

In the case of negative-working photoresist compositions, the unexposed portions of the photoresist film on the substrate are selectively removed during the development step, while the exposed portions of the photoresist remain. Therefore, if it is desired to create a circuit pattern on the same substrate as described above using a positive-working photoresist composition using a negative-working photoresist composition, then - photosensitive compound, method. and it is necessary to change the type of photomask. In the case of a photomask,
Portions of the positive photomask that are transparent to the exposing radiation must be opaque to the exposing radiation, and those portions of the positive photomask that are opaque to the exposing radiation must be transparent to the exposing radiation. Portions of the photomask need to be transparent to exposing radiation.

Similarly, the photosensitive compounds used in the photoresist composition are selected such that the exposed portions of the photoresist film are less soluble in the selected developer than the unexposed portions of the photoresist film. There is a need.

Although recent advances in the use of acid-curing chemicals in high-resolution photoresists have now stimulated significant interest in negative-tone photoresists, the majority of high-resolution commercially available photoresists are still positive-tone. Based on chemical agents. Acid curing chemicals in negative photoresists offer the benefit of creating high resolution crosslinked polymer images on the substrate. These cross-linked images not only provide improved chemical and thermal resistance during subsequent processing of the substrate, but also due to increased solubility differences between exposed and unexposed photoresist film portions. This allows for wide processing latitude for the development process.

The acid-curing chemical agent uses a combination of an acid-curing resin system and an acid that catalyzes crosslinking of the acid-curing resin system into the photoresist when the photoresist film is heated.

Photoresist compositions that utilize Sumiragi Tatsugi strained polymer resin systems and photosensitizers are known in the art.

U.S. Pat. No. 3,201,239 describes a combination of a thermoplastic phenol-formaldehyde resin and a naphthoquinonediazide or naphthoquinonediazide sulfonic acid ester photosensitizer as a positive coating agent.

U.S. Pat. No. 3,692,560 describes the use of acid curable resins such as urea resins and melamine resins and photoacidogenic halogen-substituted benzophenones. These photoacid generators, when exposed to ultraviolet light, produce strongly acidic hydrogen decogenide, which catalyzes the formation of negative organic solvent developable images.

US Pat. No. 3,697,274 describes a method for making printing plates using a negative resist system containing an acid-curable resin and an organohalogen compound. This method requires imagewise exposure, heating of the film, and removal of unexposed areas using an organic solvent developer.

U.S. Pat. No. 3,402,044 discloses a photosensitive coating for printing plates containing an aqueous base developable naphthoquinonediazide sulfonic acid enhancer and an alkali-soluble phenol or gresol formaldehyde novola resin. agent is listed. This positive resist system is
It is thermoplastic and does not undergo further polymerization upon baking. The generated image is approximately 100°C to approximately 15°C.
It is thermally unstable at temperatures in the 0°C range.

U.S. Pat. No. 3,666,473 is directed to an aqueous base developable thermoplastic positive resist that utilizes a mixture of novola resin and resol resin with conventional photosensitizers. Mixtures of these resins with different solubility in aqueous base solutions improve photospeed (
It has been taught to increase the photospeed.

U.S. Pat. No. 3,759,711 uses a phenol-formaldehyde novolak or resole resin with a photosensitive polymeric compound in which a quinonediazide group is linked to the polymer backbone through a nitrogen atom. , photosensitive coatings developable with aqueous base solutions for graphicarts are described. This patent specifically warms the resin as opposed to heating it and cures the resin in a non-imagewise manner.

U.S. Pat. No. 3,890.152 discloses a dual resist that utilizes a positive 0-quinoline diazide photosensitizer and a negative diazonium salt in combination with various resins.
dual acting resist) is described. Positive images are developed using an aqueous base solution and negative images are developed using an aqueous acid solution. It is taught that re-exposing the positive after development hardens the image.

U.S. Pat. No. 4,007,047 is also directed to a dual-type resist in which the resist is exposed to form a positive image soluble in an aqueous base solution, and then the film is exposed to light containing hydrogen ions. Treatment with a solution reduces the solubility of the exposed areas in an aqueous base solution. The entire resist can then be re-exposed to form a negative image developable with an aqueous base solution. This resist is made from an alkali-soluble phenol formaldehyde resin and a naphthoquinonediazide sulfonic acid ester sensitizer. This patent also describes a method for forming a negative starting with a positive containing a thermoplastic phenol-formaldehyde novolac resin and a naphthoquinone sensitizer. Exposure and development produces a positive image, but at the same time, in a modified manner, the resist is heated in an acidic solution to provide exposed areas that are insoluble in the aqueous base solution. The entire resist is then re-exposed and developed to a negative image with an aqueous base solution.

U.S. Pat. No. 4,115,128 describes a positive resist containing an 0-naphthoquinonediazide sensitizer, an alkali-soluble phenolic resin, and 1 to 5% by weight of a cyclic organic acid anhydride. This cyclic organic acid anhydride is taught to increase the photospeed of the resist.

U.S. Pat. No. 4.1.96,003 discloses a dual photosensitive copying layer containing O-quinonediazide, a thermoplastic phenol-formaldehyde resin or a thermoplastic bresol-formaldehyde resin, and a secondary or tertiary amine. oriented towards.

Heat treatment of the exposed resist is taught to promote insolubilization of the exposed areas to aqueous base solutions. No. 4,196,003 describes tertiary cyclic amines such as hexamethylenetetramine as suitable tertiary amines. In addition to rendering the exposed resist insoluble in aqueous base upon heating, this tertiary cyclic amine was found to crosslink the resin.

Further, US Pat. No. 4,356,254 is directed to a dual resist in which a basic dye having carbonium ions acts to insolubilize exposed areas of the resist.

Also, U.S. Pat. No. 4,356,255 describes a Schul-type resist using a quinone diazide sensitizer and a quinone or aromatic ketone.

As seen in other prior art dual systems, the exposed areas become insoluble in aqueous base solutions.

British Patent No. 1,494,640 is directed to a dual-type resist based on a similar mechanism with compounds containing hydroxy groups, such as hydroxy group-containing novolacs, bisphenol A1 pyrogallol, and triethanolamine.

Other documents describing thermostable positive resists based on completely different resin systems and chemical mechanisms from the present invention include U.S. Pat. No. 4,404.357 and No. 4,424.315 are included.

European Patent Application No. 85303807.3, Publication No. 0164248 describes photoresist compositions containing an acid-curing resin system and a photoacid generator. By manipulating the processing sequence, the photoresist composition can be made to be either crosslinked positive or negative.

European Patent Application No. 87300220.8, Publication No. 0232973 describes EPA 85303807.8 for creating three-dimensionally crosslinked microplastic structures.
The use of negative-working photopolymer compositions such as those described in No. 3 is described.

European patent application no. Negative photoresist compositions are described that utilize photoacid generators selected for use in forming submicron and submicron crosslinked images.

Also related to the present invention is US Pat. No. 4,592,816. This patent describes negative-working photopolymer compositions that can be electrophoretically electrodeposited onto conductive surfaces. The photopolymer composition comprises an aqueous or emulsified solution of at least one film-forming polymer free of ethylenically unsaturation and containing a charged carrier group, a photoinitiator, and an unsaturated crosslinking monomer. Made from cloudy liquid. Polymers containing such carrier groups useful in the invention include acrylic polymers, epoxy polymers, polyurethanes, polyesters, and polyamides. Positively charged carrier groups on polymers for electrophoretic electrodeposition include protonated quaternary ammonium groups, sulfonium groups, and sulfoxonium groups.
) are included. Negative carrier groups for electrophoretically electrodepositing include carboxylic acid groups. The photopolymer composition contains a photoinitiator that polymerizes unsaturated groups in the crosslinkable monomer when the photoresist film is exposed to actinic radiation. Suitable photoinitiators are described in U.S. Pat.
No. 92,816, No. 1 ON, line 40 to column 11, line 20.

British Tokukitsuki No. 1,330,100 describes a positive photoresist containing an epoxy, an amine curing agent, and a halogenated polycarboxylic acid anhydride. Imagewise exposure produces acid in the exposed portions of the film, which acid is neutralized by the amine curing agent. Heating the film selectively crosslinks the unexposed areas. The exposed areas are removed by development using a halogenated hydrocarbon solvent.

Other suitable publications relating to the acid-curing technology include: ゛ ° 傛 肱 りょう う Ｇｕｍｅ ４ｍ訳■, 5PIE-Vol, 773. E
ledron-Beam, X-Ray, and I
on-BeamlJjhographies Vl,
5-6 March 1987.5anta C1ar
a, California, E, Tai, B,
Fay, C.M.

5tein and W, Feely.

, 5PIE-Vol, 631, Advance
es in Re5ist Technology a
ndProcessing lit 10-11 Ma
rch 1986.5anta C1ara, Ca1
ifornia, W, E, Feely, Roh
mandHaasCo.

Septem H+r, 1986 Vol, 26.
No, 16. W, E, Feely, J, C,1
mhof, and C,M, 5jetn.

Rohm Haas Company.

1 9 self
3-1-1, J, Vac, 5cien
ce of Technology, s, +, Y
, Liu, Hewle, Packard Co., M.
, P. deGranpre & W. E. Feely, J.O.
hmandHaasCo,, 1988Vo1.6°N0
11, 379-83°'-W, E, Feely, Rohm and
Haas Company.

-i', J, Ele
ciro-Chemical Society, M.
M, 0Toole, Hewle+t Packar
d Co,; M, P, deGrandp+e &
W, E, Feely.

Rohm and Haas Co, 1988. V
ol, 135 No. (4) X-Ray, and
Ion-Beam Technology: Subm
icrome+er Lithography V
ll.

, pp 160-166.11987), D, J.
senblaHandJ, N., Zemel, Un
iv, ozPenna; W, ε, Feely
, Rohm and Haas Co 5pie -
Vol, 923 Electron-Beam, X-
Ray, and ton-Beam Technology
ogy: SubmicromalerLijhogr
aphies Vll,.

4-, May 3- June 2.1989. H, Y, Shu, J
, Seeger & E., Poon, Hewle
tt Packard Co; R, Jolsen;
K, A, Graziano & S, E An
darson, Rohm and Haas Co.
, EIPB-33rd International S
Symposium on Electron, Ion
and Photon Beams and Photon Beams It is an object of the present invention to provide a positive photoresist composition that forms a crosslinked image.

It is also an object of the present invention to provide positive-working photoresist compositions that can be applied to electrically conductive surfaces by electrodeposition.

The present invention provides positive-working photoresist compositions that form crosslinked images and methods for using the photoresist compositions. The photoresist composition comprises an acid-curable resin system containing at least one film-forming polymer, an acid or acid-generating material (preferably a thermal acid generator) for crosslinking the acid-curable resin system, and It is a mixture containing a photobase generating compound.

This photoresist m-acid is applied to a substrate surface to produce a photoresist film. Portions of the photoresist film are then imagewise exposed to actinic radiation.

As used herein, the term [image
Exposure means exposing a portion of the photoresist film to actinic radiation through a photomask so as to create an image in the exposed photoresist film portion that substantially corresponds to the desired final image pattern to be transferred onto the substrate. This refers to the process of selectively exposing to light. The actinic radiation used in the imagewise exposure process generates base in the exposed portions of the photoresist film from a photobase generator in the photoresist film. Therefore, the acids present in the imagewise exposed portions of the film are neutralized by the photochemically generated bases. The unexposed areas of the photoresist film (these areas of the film contain the acid but not the photochemically generated base) are exposed to unneutralized acid and acid by heating the film. Crosslinks by reaction with curable resin System J. The imagewise exposed portions of the photoresist film are then removed by the action of a developer, thereby leaving a crosslinked positive on the substrate.

In an alternative embodiment of the invention, a photoresist composition can be applied to a conductive substrate surface by electrodeposition.

The photoresist composition of the present invention is a mixture containing an acid curable resin system containing at least one film-forming polymer, an acid or an acid-generating compound, and a photobase generator. .

The film-forming acid curable resin system comprises at least one
a film-forming polymer; and at least one compound that crosslinks the film-forming polymer in the presence of acid and heat.

Alternatively, the film-forming polymer or polymer mixture may contain acid-catalyzed pendant crosslinking functionality.
ant acid catalyzable cross
One or more polymers having a slinking functional property can be included. In such cases, there is no need to use a separate crosslinker compound. Typically, the film-forming polymer or polymer mixture can be any polymer or polymer mixture that is free of self-crosslinking functionality and that forms a film at ambient temperature. However, the condition is that at least one kind of polymer in the polymer or polymer mixture contains a plurality of hydroxy groups, carboxyl groups, amide groups, or imide groups. Suitable film-forming polymers include film-forming polymers containing reactive hydrogen-containing groups, such as novolak resins, polyvinylphenols, polyglutarimides, polyacrylic acid or polymethacrylic acid copolymers, alkali-soluble polyacrylamides. and polymethacrylamide copolymers, copolymers containing 2-hydroxyethyl acrylate and methacrylate, and polyvinyl alcohols such as those made from partially hydrolyzed polyvinyl acetate, alkali-soluble styrene-allylic alcohol copolymers. , and mixtures thereof.

Preferred film-forming polymers include acrylic polymers,
Epoxy polymers, polyurethanes, polyesters, and polyamides, more preferably (meth)acrylate copolymers containing either or both pendant hydroxyl or carboxyl groups in the electrodeposition embodiment of the present invention. It is a combination. Preferred monomers useful for making film-forming polymers include:
Included are acrylic and methacrylic acids, lower alkyl (C+-CJ esters of (meth)acrylic acid, and droxy-substituted (meth)acrylates such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.

Other vinyl monomers containing pendant carrier groups can be polymerized with acrylic or methacrylic monomers to provide pendant carrier groups on the polymer backbone for electrodeposition of photoresist compositions. can be entered.

These vinyl comonomers include, for example, styrene and substituted styrenes, vinyl halides such as vinyl chloride, vinyl esters such as vinyl acetate, and vinyl ethers such as methyl vinyl ether, and may be used alone or in combination.

The polymer or polymer mixture should preferably have a glass transition temperature (Tg) low enough so that the photoresist composition forms a film at ambient temperature. Typically, the Tg of the polymer or polymer mixture is about 25° C. or less, but the polymer or polymer mixture is mixed with a solvent, plasticizer or coalescing agent and the resulting photoresist) If the &H composition is allowed to form a film at ambient temperature, it may be above 25°C.

Polymers and polymer mixtures have a molecular weight of about 3,000 to about 200
．． It should have a weight average molecular weight in the range of 0.000. Polymers having weight average molecular weights of about 100,000 or less are preferred. When applying the photoresist composition electrophoretically onto a conductive substrate surface, the weight average molecular weight of the polymer preferably ranges from about 5,000 to about ioo, ooo, more preferably about 10. 000 to about 80.0
The range is 00.

If the acid-curable resin system contains a polymer with crosslinkable functionality, such polymer may be labeled as
echet, S.

Matuszczak, B., Beck, and C.G.
, Willson, 1989° Vol, 60.147-
Polymers with pendant epoxy groups, vinyl polymers made by copolymerization of N-(alkoxymethyl)acrylamide or methacrylamide, and copolymers of vinylphenol and (acetoxymethyl)styrene, as described in No. 50 Consolidation is included.

If the film-forming polymer does not contain acid-catalyzed self-crosslinking functionality, the acid-curable resin system reacts with the film-forming polymer or polymer mixture in the presence of an acid catalyst and heat. That is, at least one crosslinking compound is required.

This compound will hereinafter be referred to as a crosslinker or crosslinker mixture (cro
sslinker or crosslinkers)
”. Suitable crosslinking agents for use in the photoresists of the present invention include aminoplasts and phenolplasts. Suitable aminoplast resins include, for example, urea-formaldehyde resins, melamine-formaldehyde resins, benzoguanamine-formaldehyde resins,
Included are glycoluril-formaldehyde resins, and mixtures thereof. Polymeric aminoplasts can be prepared by reaction of acrylamide or methacrylamide or methacrylamide copolymers with formaldehyde in an alcohol-containing solution or, alternatively, with other suitable monomers of N-(alkoxymethyl)acrylamide or methacrylamide. It can be produced by copolymerization with Examples of some suitable aminoplasts include American Cyanamid
Melamine resins manufactured by Cymel Company, such as Cymel” 300.301.303, 350.370
, 380.1116 and 1130; benzoguanamine resins such as Cymel 1123 and 1125;
Glycolyl resins, such as Cymel 1170; and urea-based resins, such as BeetleR
60, 65 and 80 are included. A large number of similar aminoplasts are currently available from a variety of suppliers. These resins can then be purified by distillation to remove trace impurities. A preferred and purified aminoplast is hexamethylmethoxymelamine, which is described in US Patent Application No. 376,713. Note that the description in this patent application specification is incorporated into the present specification.

The photoresist composition must contain an effective amount of acid to catalyze the acid curing crosslinking reaction in the portion of the photoresist film. The inventors have discovered that any strong acid, such as sulfuric acid, or weak acid, such as lactic acid, or at least one neutral compound that produces an effective amount of acid when needed, can be used in the photoresist composition.

If the photoresist composition is applied by electrodeposition,
Strong acids are preferred. Since acids can cause crosslinking to a small extent at ambient temperatures, we have developed a method for improving photoresist production by using a neutral compound that produces an effective amount of acid in the photoresist film when desired. It has been found that extending shelf life is desirable. Acids are made from such neutral compounds by the action of heat or radiation.

The compound that generates an acid upon heating is a neutral compound that generates an acid when the photoresist film is heated. A photoacid-generating compound is a neutral compound that generates an acid when the photoresist film is exposed to the selected radiation. When a photoresist composition uses a photoacid generator, the photoacid generator is such that the wavelength of the exposing radiation used to generate the acid is such that the photobase generator in the photoresist composition has a substantial amount of base. The quantity must be chosen so that they are not produced at the same time. The sensitivity of photoacid generators, photobase generators, or both to certain wavelengths of exposing radiation uses conventional photosensitizers selected for their sensitivity to specific wavelengths of radiation. It can be expanded by doing.

The inventor has found that it is preferable to choose strong acids such as sulfonic acids. However, when a strong acid is used directly in a photoresist composition containing a polymer emulsion, the acid may
Does not associate with polymer emulsions. For this reason, the inventors have used strong acids containing hydrophobic moieties, such as dodecylbenzenesulfonic acid (DDBSA), directly in electrodepositable photoresist compositions containing polymer emulsions. We have found this to be particularly effective.

Thermal acid generators are compounds that are not acids, but which convert to acids upon heating of the photoresist film. Suitable thermal acid generators useful in the present invention include ammonium salts of acids when the corresponding amine is volatile. Ammonium salts of acids can be made by neutralizing the acid with ammonia or amines. The amine is a primary, secondary, or tertiary amine. The amine must be volatile. This is because the amine must be evaporated from the photoresist film by heating it to the temperature required to crosslink the photoresist film. When amines or ammonia evaporate from photoresist films upon heating, they leave behind acids in the film.

This acid is then present in the photoresist film and, if it is not neutralized by a corresponding amount of base, is used to catalyze the acid-curing crosslinking reaction by heating. Suitable thermal acid generators include hendiintosylate, 2-nitrobenzyl tosylate, and alkyl esters of organic sulfonic acids. When hendiintosylate is heated, toluenesulfonic acid is produced by a substitution reaction. Alkyl sulfonates, which produce sulfonic acids upon removal by heating, are also suitable thermal acid generators.

If a photoacid generator is used in a photoresist composition,
The photoacid generator must be selected so that it generates acid at the exposure wavelength at which the photobase generator does not produce a substantial amount of base. When using such photoacid generators, the photoresist film requires two exposure steps.

The one is an imagewise exposure chosen to generate bases in selected portions of the photoresist film;
and a second floodexposure at another wavelength that generates acid on the entire photoresist film.
ure). The acid generated within the photoresist film is neutralized by the base generated by the photobase generator in the exposed film areas during the image-forming exposure step, thus modifying the selected image features of the photoresist film. It is not possible to catalyze the crosslinking reaction in the exposed areas. On the other hand, the acid generated in the photoresist film that is not exposed during the imagewise exposure process is not neutralized by the photochemically generated base, and the acid in those parts of the photoresist film is removed by heating the photoresist film. Catalyzes the curable crosslinking reaction.

Photoacid generators suitable for the photosensitive coating compositions of the present invention include:
It is a neutral compound or a mixture of these compounds which is converted to an acid, preferably a strong acid, such as a sulfonic acid, upon exposure of the photoresist film. Several photoacid generators have been found useful in the practice of this invention, such as benzointosylate and halogenated organic compounds such as tris(2,3-dibromopropyl)isocyanurate. Photoacid generators that are esters of naphthoquinonediazide sulfonic acid can also be used. Suitable naphthoquinone diazides and polymers of this type suitable for the present invention are described in the following U.S. patents: U.S. Pat.
No. 3,046.118, No. 3.046.12
No. 1, No. 3,148,983, No. 3.201, 2
No. 39, No. 3,635,709, No. 3,640,
No. 992, No. 3,666.473, No. 3.759
, No. 711, No. 3,785,825, and No. 4,308.368.

All these naphthoquinone diazides and polymers are
Photoresist Material and 7
．． W.

J, DeForest, McGraw Hill;
(1975).
J.

Wiley and 5ons (1965), pag
The indenecarboxylic acid is generated by a Wolff rearrangement reaction, which is described in detail in [Es 343-35].

The inventor optionally incorporates a photosensitizer into the photoresist composition, and the wavelength of the exposing radiation (these wavelengths are determined by the photobase generator or the photoacid generator or both). (to the wavelengths of the exposing radiation) that either or both of the photogenerating compounds are not sensitive to these wavelengths or are not sensitive to these wavelengths as desired due to the particular process used. In contrast, we have discovered that the sensitivity of photoresist films can be expanded. Examples of preferred sensitizers that can be used to extend the sensitivity of photoresists to 365 nm exposure radiation include 2-chlorothioxanthone, 9-methylanthracene, benzanthrone, perylene, hensyl, 2-isopropyl. Included are thioxanthone, and phenothiazine. Other suitable photosensitizers include the following compounds: probiophenone, xanthone, L3,5-triacetylbenzene, 1,3-diphenyl-2-propane,
Benzaldehyde, triphenylmethylphenylketone, 1,2-dihenzoylbenzene, 4,4'-dichlorobenzophenone, 4-cyanobenzophenone, biphenyl, thioxanthone, anthraquinone, phenanthrene, ethyl glyoxylate, 2,6-naphthalenedisulfone Acid disodium salt, 2-naphthaldehyde, 1-naphthaldehyde, 5.12-naphthoacetoquinone, biacetyl, acetylpropionyl, fluorenone, 1,2,
5.6-dihenzuanthracene, 1,2,3.4-dihenzuanthracene, acetophenone, 4-methoxyacetophenone, anthracene, 9,10-dicyanoanthracene, 2,6,9.10-tetracyano Anthracene, 1,4-dicyanohenzene, methyl 4-cyanobenzoate, methyl benzoate, benzophenone, chloranil, chrysene, fluorene, naphthalene, 1-cyanonaphthalene, 114-dicyanonaphthalene, 2-methoxynaphthalene, phenanthrene, pyrene , trans-stilbene, triphenylene, 2-chlorothioxanthone, 9-methylanthracene, penduanthrone-berylene, benzyl, 2-isopropylthioxanthone, phenothiazine photobase generators such as 2-nitrobenzyl carbamate, 300 r+m), but essentially insensitive to 365 nm radiation.

The selection of a photobase generator for use in the photoresist compositions of the invention is an important aspect of the invention. Photobase generators are neutral compounds that generate bases upon exposure to selected radiation.

Suitable photobase generators that can be used are those that generate amine bases upon exposure to light, such as the benzyl carbamate Ar-C-
0-C-NR'R" Formula (1) [wherein R = H or an alkyl group (as described below) R.2-Alkyl group or an aryl group (as described below) R', R'-alkyl group, substituted alkyl group, aryl group or substituted aryl group, Ar-aryl group] Next 11 [Reference Carver R3-0-C-NR'RZ Formula (2) [In the formula, R' = H or an alkyl group (as described below); R2-alkyl group or aryl group (as described below); R3-alkyl group, substituted alkyl group, aryl group or substituent aryl group] [wherein R '=H or alkyl group (as described below) R2-alkyl group or aryl group (as described below) Ar=aryl group or substituted aryl group] Waxami 2 dishes R2H-0-C-NR'R" Formula (4) [wherein R4, R' = H or an alkyl group (as described below) R2-Alkyl group or an aryl group (as described below) R3, R' = H, alkyl group, substituted alkyl group, aryl group, substituent aryl group or acyl group]
N-0-(, -NRIR" formula (5) [wherein R' = H or an alkyl group (as described below) R2-alkyl group or aryl group (as described below) R", R' = H, alkyl group, substituted alkyl group, aryl group or substituted aryl group] Sulfonamide Ar-S-NR
'R' of formula (6) [where R' = H or an alkyl group (as described below) R2 = an alkyl group or an aryl group (as described below) Ar- an aryl group or a substituted aryl group ]1[ [wherein R2-alkyl group, aryl group (as described below) R3=alkyl group, substituted alkyl group, aryl group or substituted aryl group] R3C-N-CH=CH-Ar Formula (8 ) (wherein, R3-alkyl group, substituted alkyl group, aryl group or substituted aryl group R4-alkyl group, substituted alkyl group Ar-aryl group) Medium, A
In all the above structural formulas, R' is , H is an alkyl group or substituted alkyl.

R2 is an alkyl group, a substituted alkyl group, an aromatic group, or a substituted aromatic group.

The photobase generator should not contain amine substituents with a pKa greater than about 3. Furthermore, the combined population of R' and R2 must be sufficient to prevent substantial loss of the photochemically generated amine by evaporation during the heating step.

The polymeric materials incorporated into the aforementioned compounds are also useful as photogenerators. Polyurethane is an example of such a polymer.

Preferred photobase generators are 2-nitrobenzyl carbamates of formula (1), where the aromatic group is a 2-nitrobenzyl group, formula (3), where R'=H1R"=C
,-C,. alkyl group, and Ar-phenyl)
benzoin carbamate of formula (4) (wherein R
” = C6-CIO alkyl group, and R3 and R4 are phthalyl groups).

When separate crosslinking agents are used, the concentrations of each of the photoresist components as weight percentages are shown in Table 1, based on the weight of the film-forming polymer or polymer mixture.

Crosslinking agent 5-80 5-40 5-20 Photobase generator 0.4-20 1-10 2-8 Acid or acid generator 0.04-5 0.05-30.1-2 Photosensitizer O ~10 0-8 0-5 Film-forming polymer or polymer mixture, crosslinker, photobase generator, acid or acid generator, and optional photosensitizer, as a solution or as an emulsion , compounded in a liquid. The concentration of film-forming polymer or polymer mixture in this liquid typically ranges from about 5 to about 50% solids by weight.

Liquids that can be used to formulate photoresist compositions typically include non-reactive solvents such as glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Propasol B and p (Propasol B a
nd P), etc.; cellosolve esters, such as methyl cellosolve acetate, ethyl cellosolve acetate, and acetates of propazole B and P; aromatic hydrocarbons, such as toluene, xylene, etc.; ketones, such as methyl ethyl ketone, cyclopentanone, cyclohexanone etc., esters such as ethyl acetate, butyl acetate, isobutyl isobutyrate, butyrolactone, etc., amides such as dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), dimethylformamide (DM
F), etc.; chlorinated hydrocarbons such as ethylene dichloride, chlorobenzene, ortho-dichlorobenzene, etc.; nitrobenzene: dimethyl sulfoxide; and mixtures thereof.

Mixtures of these solvents containing small amounts of other suitable compounds are also useful solvent systems.

In an alternative embodiment of the invention, the photoresist composition can be deposited as a photoresist by electrophoretically electrodepositing it onto the surface of an electrically conductive substrate. In this embodiment, it is preferred to formulate the photoresist composition as an aqueous emulsion. In this electrodeposition mode,
It is essential that the film-forming polymer contain pendant carrier groups. These carrier group moieties must be negatively charged for electrodeposition of photoresist films from photoresist compositions. Suitable charged carrier groups for inclusion in the film-forming polymer include carboxylic acids that react with volatile bases such as volatile ammonia or volatile amines to convert them to negatively charged carboxylate salts. During electrodeposition, the charged carrier groups neutralized by the added base are reprotonated. When using a sulfonic acid as an acid catalyst, the acid is neutralized with a base to form a salt, e.g. Functions as a thermal acid generator for the reaction.

The film-forming polymers can be modified by incorporating pendant carrier groups as described in my previous US Pat. No. 4,592,81.6.

This patent is incorporated herein by reference.

However, the at least one polymer must contain at least 50 to about 350 milliequivalents of carrier groups per 100 g of polymer or polymer mixture for photoresist compositions that are water-dispersible and electrodepositable. No.

If it is desired to use an aqueous solution to process (process) a deposited photoresist film, typically only a portion of the total number of carrier groups in the polymer or polymer mixture will be charged. It is necessary that the In this connection, it is generally not necessary that all carrier groups of the polymer or polymer mixture be charged. Typically, preferably no more than about 80% of the carrier groups are charged, provided that a minimum concentration of charged carrier groups of at least about 50 milliequivalents is present for electrodeposition. is necessary.

The photoresist composition of the present invention can be processed in the same manner as negative acid-curable photoresists. After the photoresist composition is deposited as a homogeneous photoresist film on a substrate by conventional spin coating or by electrodeposition, portions of the film are imagewise exposed to actinic radiation through a positive mask. .

The exposed portions of the film contain photochemically generated base and insufficient acid to catalyze the crosslinking reaction. The acid is then generated in the photoresist film by exposing the film to light in the case of a photoacid generator, or by heating the film in the case of a thermal acid generator. generate.

When a thermal acid generator is used in the photoresist composition, the entire photo is brought to a temperature high enough to generate acid in the photoresist film and catalyze the crosslinking reaction of the unexposed portions of the film. Heat the resist film. The acid generated in the imagewise exposed areas of the photoresist film is neutralized by the photogenerated base in those areas. Therefore, when the photoresist film is heated, no significant crosslinking occurs in the imagewise exposed portions of the photoresist film. The exposed, uncrosslinked portions are then removed from the substrate by the action of a developer, leaving a crosslinked positive on the substrate surface.

When a photoacid generator is used in the photoresist composition, the entire photoresist film is exposed to actinic radiation that generates acid in the photoresist film.

As with thermal acid generators, the portions of the photoresist film that are imagewise exposed or exposed to different exposing radiation wavelengths contain photochemically generated bases. This base neutralizes the photochemically generated acid. Therefore, by heating this film,
Only those portions of the photoresist that were not imagewise exposed to photobase-generating radiation are cross-linked, leaving the imagewise exposed portions to be selectively removed by the developer, thereby leaving the imagewise exposed portions behind after development. A crosslinked positive image remains on the substrate surface.

Also, when a photoacid generator and a photobase generator are used, the order of the exposure steps can be reversed to form a crosslinked positive image. In this sequence, the photoresist film was flood exposed to generate acid within the photoresist film, and then the photoresist film was selectively imagewise exposed to photobase-generating radiation. The entire photoresist film was then heated to crosslink those portions of the photoresist film that did not contain photochemically generated base. Because in this order the acid is generated before the base is generated, this order is less preferred because crosslinking begins to occur indiscriminately in those portions of the photoresist film that contain acid.

The following examples illustrate manufacturing and processing methods using photoresists of the present invention. These examples are illustrative only and are not intended, nor should they be construed, as limiting the scope of the invention. Permutations and other modifications to the invention will become apparent to those skilled in the art from this description. Unless otherwise specified, all percentages are by weight.

Example 1 A banquet to Rikindome Equipped with a mechanical stirrer, a reflux condenser, a thermometer, and a nitrogen sparge, and an oil bubbler for releasing gas.
3i! sealed using bubbler) , 4, a round bottom flask was flushed with nitrogen for 15 minutes.
sh) した. Next, 50.0 g of 2-hydroxyethyl methacrylate, 64.0 g of methyl methacrylate, and 86.0 g of butyl methacrylate. Charged were Og, 2.0 g of peroctanoic monobutyl free radical initiator, and 200 g of 1-methoxy-2-propatol solvent.

The reaction mixture was sparged with nitrogen for 15 minutes. The flask was then heated using a heating mantle on a Jack-o-Matic O adjusted to pull the mantle > 0.5 °C when the temperature of the reaction mixture reached 105 °C. °C for 15 minutes. Due to the exothermic polymerization reaction, the temperature of the reaction mixture rose to boiling! (117 °C). The reaction mixture was gradually cooled to 105 °C and then kept at that temperature. One hour after the exotherm occurred, 0.20 g of monobutyl peroctanoic acid was added and the reaction temperature was maintained at 105"C for 30 minutes.

At the end of this time, another 0.20 g of monobutyl octanoic acid was added. After another 30 minutes at 105°C, the reaction mixture was cooled to 60°C and then poured from the reaction flask. The composition is 51% solids and all monomers are 25% by weight 2-hydroxyethyl methacrylate (IEMA), 32% by weight
It was shown that the polymer had been converted into a polymer having a composition of methyl methacrylate (MMA) and 43% by weight of methyl methacrylate (BMA).

Example 2 2I was equipped with a mechanical stirrer, a reflux condenser, a thermometer, and a nitrogen sparge, and was sealed with an oil bubbler to allow gas to escape! , 4 t-butyl peroctoate in a round bottom flask 5. Og together with a 10 wt% initiator solution dissolved in 45.0 g of propylene glycol monomethyl ether (PM) and an additional 455 g of PM.
together with methacrylic acid (MAA) 75, Dg, 2-hydroxyethyl methacrylate 125.0g, methacrylate 1
, 1) chill 60. 0g, and 10% by weight of a monomer mixture of 240°Og butyl methacrylate.

The reaction mixture was sparged with nitrogen for 15 minutes. The flask was then fitted with a Jack-o-Mati tube, which was adjusted to pull the mantle when the reaction mixture reached 105°C.
Heated at 7 using a heating mantle over cO. The reaction mixture was heated to 105 °C with stirring for the remainder of the reaction.
maintained.

After 15 minutes, the remainder of the monomer mixture and initiator solution was
Metered into the reaction flask over time. t-butyl peroctoate 1.20 minutes after adding the monomer mixture and initiator solution. Og was added to the reaction mixture. 20
After 1-butyl peroctoate 1. Additional Og was added. After 30 minutes, the reaction mixture was cooled to about 80°C and then poured from the flask. The solids content of the reaction product is 5
3% and essentially all monomers are 15% by weight methacrylic acid, 25% by weight 2-hydroxyethyl methacrylate, 12% by weight methyl methacrylate, and 48% by weight.
It was shown that the polymer was converted into a polymer having the composition of butyl methacrylate.

Example 3 Purge with nitrogen for 5 minutes In a 50 ml dry pear-shaped flask equipped with a lid, condenser, thermometer, and septum, 2.5 g of cyclohexyl isocyanate h.
, 3.1 g of 2-nitrobenzyl alcohol.

and 10% toluene were added. The reactor was kept blanketed with nitrogen and stirred with a magnetic stir bar. The temperature of the reaction mixture was increased to 110°C over 1 hour. The progress of the reaction was followed by thin layer chromatography (TLC) eluting with ethyl acetate/hexane (30/70 volume ratio).
EM As5ociaties Silica Gel 6OFF
254.0.25 inch thick).

The reaction was held at approximately 110-120°C for an additional period of time. TLC showed some 2-nitrohensyl alcohol remaining. Therefore, 0.50 g of cyclohexyl isocyanate was added.

One hour after this addition, 1. Otd was added to the reaction flask and the contents were then immediately poured into a beaker and cooled to room temperature over approximately 30 minutes.

White crystals formed as a reaction mixture and were cooled.

The beaker was then cooled in a water bath for approximately 15 minutes and filtered under reduced pressure. The crystals were heated indoors at about 100°C under reduced pressure.
for 1 hour and then weighed. This reaction results in 2
-Nitrohensylcyclohekidyl-rubame) 5.3
g was obtained.

Example 4 Positive photoresist "n-Positive photoresist composition was mixed with soluble polymer A (Sol
tion PolymerA) 4.0 g, distilled Cyme 1300 melamine crosslinker 0.43 g,
1 inch of dodecylbenzenesulfonic acid, 10 inch of 2-nitrohensylcyclohexyl carbamate (Example 3), and 1.2-dimethoxyethane solvent (DME) 1.
Made from 0 g.

This photoresist composition was made as follows. C
ymel 300, dodecylbenzenesulfonic acid, and 2-nitrobenzylcyclohexylcarbamate
Dissolved in MH. This was mixed with meltable polymer A.

This photoresist composition was applied to an o, ooi inch
A drawdown rod with 7 gaps
Silicon wafer (silico bar)
n wafer). The film was allowed to dry for 30 minutes. The film thickness was approximately 10μ.

A photomask was made by placing a line of opaque adhesive on a quartz plate. This photomask was then placed on the film and exposed to 254 nm light (1,5 d/am2) for 5 minutes. Then, the photoresist film is
Bake for 30 seconds at 100°C on a hot plate (ba
heating by ccking). The photoresist was developed with acetone at room temperature for about 1 minute with light brushing. An image was created that was the positive of the photomask. Little, if any, unexposed film thickness was lost.

A second film of photoresist was made as described above and the sensitivity of the photoresist film to 365 nm light compared to 254 nn+ light was measured. A portion of the photoresist film was exposed to a beam of 365nI11 (
2.0 mW/cm2) for 5 minutes.

Other parts of the photoresist film were left unexposed. The photoresist film was heated by baking on a hot plate at 100°C for 30 seconds. The film was developed with acetone for about 1 minute at room temperature with light brushing, removing only the portion of the film that had been exposed to 254 nm light. Films exposed to 365 nm light were not removed.

The results showed that the film had little or no sensitivity to 365 nm light.

Example 5 A photoresist composition was prepared using 3 g of soluble polymer A4, 1 distilled C.
ymel 300 O-410-4l nitrobenzyl cyclohexyl chloride t-20 mg.

It was made from 1 inch of dodecylbenzenesulfonic acid, 11 inches of phenothiazine sensitizer, and 1.1 g of 1,2-dimethoxyethane. 2-Nitrohensyl cyclohexyl carbamate, dodecylbenzenesulfonic acid, and phenothiazine were dissolved in DME.

The polymer solution and Cymel crosslinker were then added.

The photoresist composition was spin coated on a 3 inch silicon wafer at 4000 rpm and dried in a fume hood for 1 hour at room temperature to produce a 11 micron thick film. The photoresist film was exposed to 365 nm light (2, 5 mW/cm2) for 5 minutes through a copper foil mask with 5III11 lines and spacing.

This photoresist was then heated to 100"C on a hot plate.
The mixture was heated by baking for 15 seconds.

Developed with acetone at ambient temperature to produce positives of good quality.

Example 6 Ammonium dodecylbenzene sulfonate (ADDBS)
) paste with 1.0 g of dodecylbenzenesulfonic acid
was prepared by neutralizing with 0.30 d of concentrated ammonium hydroxide.

The photoresist composition was mixed with 84.2 g of dissolved polymer and 0.44 g of distilled Cymel 300 (7).
JLi ammonium benzenesulfonate paste 2■
, 2-nitrohenzylcyclohexylcarbamate 50
(2) and 1.0 mg of 1,2-dimethoxyethane. Cymel, ADDBS paste, and 2-diF lohenzyl cyclohexyl carbamate were dissolved in DMH and then mixed with polymer solution B.

4 photoresist films on silicon wafers
000 rpm and dried for 1 hour at room temperature.

A mask was made from copper foil with 5IDII1 wide lines and spacing. This mask is placed on the film and the film is exposed to UV vA at 254 nm (1,5 mW/c
m2) for 5 minutes and then heated by baking on a hot plate for 15 seconds at OO'C. Turn on this photoresist film 1.
Developed for 10 seconds using an aqueous NaOH solution to produce a positive of good quality.

Example 7 Photoresist This example illustrates the use of a photoacid generator as an acid source for a positive photoresist.

The photoresist was prepared from a double coalescing solution (M
Diglyme (bis 2-methoxyethyl ether) solution was prepared by the procedure of Example 2 from 100 g of AA, 50 g of HEMA, and HEMA (49% solids).
2.0 g, 0.10 g of Cymel 300,
Penduincyclohexyl carbamate 0.072g,
A photoresist solution containing 0.015 g of tris(2,3-dibromopropyl) isocyanurate, 8 g of phenol-thiazine, and 3.0 g of diglyme was deposited on a silicon wafer.
Spin coating at 000rprrrl and apply at 80rpm on hot plate.
Beta at °C for 60 seconds to remove residual solvent. The thickness of the film was 1.2μ. This film is passed through a mask and exposed to far ultraviolet light (Hybrid Technol).
ogies Group, Inc., 5eries
80 exposureuni, 37 mJ/sqcm at approximately 254 r++n). It was then flood exposed to near ultraviolet light (Blak-Ray XX15. 150 mJ/sqcm at approximately 365 nm) and baked for 105 seconds at 130''C on a hot plate.

The photoresist was developed using 0.05 N NaOH aqueous solution for 70 seconds to produce a good quality positive.

Example 8 A polymerized solution of a photoresist photoresist emulsion prepared from [HEMA 75 g, 125 g, MMA 25 g.

Butyl acrylate (BA) 275 g (52,8
% solids) by the procedure of Example 2, as a DME solution] 5. Q g , 3.0 g of Cymel 1130, 0.20 g of 2-nitrohensylcyclohexyl hydroxide), 0.20 g of 2-isopropylthioxanthone (photosensitizer), 0.20 g of Ero Cl blue dye (Ero Bl
ue Dye) 0.08 g.

DME2.0g, dodecylbenzenesulfonic acid (D
1.0 g of a 10% aqueous solution of DBSA), 0.24 g of a concentrated aqueous ammonium hydroxide solution, and 77.3 g of deionized water.

2-Nitrohensylcyclohexylcarbamate, 2-
Isopropylthioxanthone, Cyme11130, and dye were dissolved in DME. Then the polymer and D
The DBSA solution was added to the DME solution and mixed. Then,
Ammonium hydroxide was added to this mixture. Deionized water was slowly added to this with stirring to form a photoresist emulsion. From this photoresist emulsion, 0
．． 040 inch Metsuki through hole (plated)
A photoresist film was electrodeposited onto a 1.5 x 4 Xi/16 inch double-sided circuit board material with through holes. The circuit board was immersed in the photoresist emulsion to a depth of 1.75 inches. Electrodeposition was carried out at 100 volts to produce a 9μ thick film.

The through holes were coated with photoresist. The coated circuit board was dried for 1 hour at room temperature. Foil strip (
aluminum) was placed on each side of the sample covering the through-holes. Each side of the sample was exposed to a 365 nm light beam (1,4
mW/cm2) for 3.75 minutes, baked at 120° C. for 6.5 minutes in a forced air oven, and developed with 0.02 N aqueous NaOH for 1 minute at room temperature. It produced a good quality resist positive image and the through-hole resist was intact.

Example 9 A paste of ammonium P-toluenesulfonate, which gives the impression of irradiation by a beam beam, was prepared by adding 1.0 g of P-toluenesulfonic acid to a concentrated aqueous ammonium hydroxide solution.
．． It was made by neutralizing with 40 g. The photoresist composition is made of poly(vinylphenol) (Maru
zen M) 2.1 g, distilled Cymel 30
0.20 g of hendiine cyclohexyl carbamate, 0.15 g of ammonium p-toluenesulfonate paste, and 6.0 g of diglyme. A photoresist film is placed on a silicon wafer with a thickness of 400 nm.
Spin on in the Orpm and bake on a hot plate for 60 seconds at 80°C.

Residual solvent was removed.

7 pads of 0.25 square inches
electron Visions Corp, Elec
The samples were exposed to e-beam radiation (10 kV) with a ton Cure 30SC e-beam exposure system. The exposure energy is 2.4.2.0.1.6.1, respectively.
．． 2.0.8.0,4, and 0.2 microcoulombs/
It was c+n 2. Heat the wafer on a hot plate for 120 minutes.
Beta for 60 seconds at 0,1. ON Na
Developed using an OH aqueous solution for 15 seconds at room temperature. 1
゜2 microcoulombs/cI! Pads that received 12 or more were completely removed by development. The unexposed film remained intact with a moderate reduction in thickness.

Claims (24)

[Claims] (1) A positive-working photoresist composition that produces a crosslinked image, containing a mixture of an acid curable resin system containing a film-forming polymer, an acid or acid-generating material, and a photobase-generating compound. (2) The composition of claim (1), wherein the film-forming polymer-containing acid-curable resin system contains a crosslinker compound. (3) about 5 to about 80% by weight crosslinking agent, about 0.4 to about 20% by weight;
% photobase generator, about 0.04% to about 5% acid or acid-generating compound, and optionally further contains 0% to about 10% photosensitizer. , and the said %
3. The composition of claim 2, wherein: is based on the weight of the polymer in the acid curable resin system. (4) The photobase-generating compound is carbamates, benzoin carbamates, O-carbamoylhydroxylamines, O-carbamoyloximes, aromatic sulfonamides, alpha-lactones, N-(2-arylethenyl) The composition of claim (1), which is selected from the group consisting of amides and azides. (5) Claim (
1) Composition. (6) Claim (5), wherein the strong acid contains a hydrophobic moiety.
Composition of. (7) The composition of claim (6), wherein the strong acid containing the hydrophobic moiety is dodecylbenzenesulfonic acid. (8) The composition of claim (1), wherein the acid generating compound is a thermal acid generator. (9) The composition of claim (8), wherein the thermal acid generator is an ammonium salt of a strong acid generated from a volatile amine. (10) The thermal acid generator is benzointosylate,
2-Nitrobenzyl tosylate, and alkyl esters of organic sulfonic acids.
9) Composition. (11) The composition of claim (1), wherein the acid-generating compound is a photoacid-generating compound. (12) The composition of claim (11), wherein the photoacid-generating compound is a neutral compound that generates a strong acid upon exposure to actinic radiation. (13) The composition of claim (12), wherein the photoacidogenic compound is selected from the group consisting of benzointosylate and tris(2,3-dibromopropyl)isocyanurate. 14. The composition of claim 2, wherein the crosslinking agent is selected from the group consisting of urea-formaldehyde resins, melamine-formaldehyde resins, benzoguanamine-formaldehyde resins, glycolyl-formaldehyde resins, and mixtures thereof. (15) The film-forming acid curable resin system is about 3
The composition of claim 1, comprising at least one film-forming polymer having a weight average molecular weight in the range of ,000 to about 200,000. (16) The film-forming polymer consists of novolaks, polyvinylphenol, polyglutarimides, poly(meth)acrylic acid, poly(meth)acrylamide, polyvinyl alcohols, styrenic polymers, and mixtures thereof. The composition of claim (15) selected from the group. (17) The composition of claim (1), wherein the film-forming polymer and photobase-generating compound of the acid-curable resin system are polyurethanes. (18) The composition of claim (15), wherein the film-forming polymer contains pendant carrier groups. (19) depositing a photoresist film containing a film-forming polymer-containing acid-curable resin system, an acid, and a photobase-generating compound onto a substrate surface; imagewise exposing to a source of actinic radiation, and said imagewise radiation being selected to generate base from said photobase generating compound in said exposed portions of said film, and heating said film to A method of forming a crosslinked positive image on a substrate surface comprising crosslinking said areas free of photogenerated base and removing said exposed areas using a suitable developer. (20) depositing a photoresist film containing a film-forming acid-curable resin system, an acid-generating compound, and a photobase-generating compound onto a substrate surface, and depositing one or more portions of the film on the substrate surface; imagewise exposure to a source of actinic radiation, and said imagewise radiation is selected to generate base from said photobase-generating compound in said exposed portions of said film; and said acid-generating compound in said photoresist film. A method of forming a crosslinked positive image on a substrate surface comprising generating an acid from a compound and removing said exposed areas using a suitable developer. (21) The acid-generating compound is a photoacid-generating compound, and the acid-generating step includes a second exposure step, and the photoresist film is heated so that the second exposure step does not interfere with the crosslinking step. 21. The method of claim 20, wherein the exposure is to a different radiation from that used in the imagewise exposing step. (22) the acid-generating compound is a photoacid-generating compound, the acid-generating step includes a first exposure step, the imagewise exposure step is a second exposure step, and the photoresist film is 21. The method of claim 20, wherein the first exposure step is exposed to radiation different from the radiation used in the next imagewise exposure step so as not to interfere with the crosslinking step. (23) depositing a photoresist film containing a film-forming acid-curable resin system, a thermally acid-generating compound, and a photobase-generating compound onto a substrate surface; is imagewise exposed to a source of actinic radiation, and the imagewise radiation is selected to generate base from the photobase-generating compound in the exposed portions of the film, and heating the film to produce the generating said acid in a photoresist film and crosslinking said light-generated base-free areas, and removing said exposed areas using a suitable developer. A method of forming a crosslinked positive image. (24) The method of any one of claims (20), (21), (22), or (23), wherein the photoresist film is deposited on the substrate by electrodeposition.