WO1991004512A1 - Resines de liaison selectionnees d'un copolymere novolaque en masse et leurs utilisation dans des compositions sensibles aux rayonnements - Google Patents

Resines de liaison selectionnees d'un copolymere novolaque en masse et leurs utilisation dans des compositions sensibles aux rayonnements Download PDF

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WO1991004512A1
WO1991004512A1 PCT/US1990/004307 US9004307W WO9104512A1 WO 1991004512 A1 WO1991004512 A1 WO 1991004512A1 US 9004307 W US9004307 W US 9004307W WO 9104512 A1 WO9104512 A1 WO 9104512A1
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Prior art keywords
radiation
group
halogen
ortho
sensitive composition
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PCT/US1990/004307
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English (en)
Inventor
Alfred J. Jeffries
Kenji Honda
Andrew J. Blakeney
Sobhy Tadros
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Ocg Microelectronic Materials, Inc.
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Publication of WO1991004512A1 publication Critical patent/WO1991004512A1/fr

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    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins

Definitions

  • the present invention relates to selected block copolymer novolak resins containing at least one unit which is a condensation reaction product of the selected reactive ortho, ortho-bonded phenolic oligomers and selected phenolic moieties. Furthermore, the present invention relates to radiation-sensitive compositions useful as positive-working photoresist compositions, particularly, those containing these phenolic resins and o-quinonediazide photosensitizers. Still further, the present invention also relates to substrates coated with these radiation-sensitive compositions as well as the process of coating, imaging and developing these radiation-sensitive mixtures on these substrates.
  • Photoresist compositions are used in microlithographic processes for making miniaturized electronic components such as in the fabrication of integrated circuits and printed wiring board circuitry.
  • a thin coating or film of a photoresist composition is first applied to a substrate material, such as silicon wafers used for making integrated circuits or aluminum or copper plates of printed wiring boards.
  • the coated substrate is then baked to evaporate any solvent in the photoresist composition and to fix the coating onto the substrate.
  • the baked coated surface of the substrate is next subjected to an image-wise exposure of radiation. This radiation exposure causes a chemical transformation in the exposed areas of the coated surface.
  • Visible light, ultraviolet (UV) light, electron beam and x-ray radiant energy are radiation types commonly used today in microlithographic processes.
  • the coated substrate is treated with a developer solution to dissolve and remove either the radiation-exposed or the unexposed areas of the coated surface of the substrate.
  • a developer solution to dissolve and remove either the radiation-exposed or the unexposed areas of the coated surface of the substrate.
  • photoresist compositions negative-working and positive-working.
  • negative- working photoresist compositions are exposed image-wise to radiation, the areas of the resist composition exposed to the radiation become less soluble to a developer solution (e.g. a cross-linking reaction occurs) while the unexposed areas of the photoresist coating remain relatively soluble to a developing solution.
  • treatment of an exposed negative-working resist with a developer solution causes removal of the non-exposed areas of the resist coating and the creation of a negative image in the photoresist coating, and thereby uncovering a desired portion of the underlying substrate surface on which the photoresist composition was deposited.
  • positive-working photoresist compositions are exposed image-wise to radiation, those areas of the resist composition exposed t the radiation become more soluble to the developer solutio (e.g. a rearrangement reaction occurs) while those areas no exposed remain relatively insoluble to the developer solution.
  • treatment of an exposed positive-working resist with the developer solution causes removal of the exposed areas of the resist coating and the creation of a positive image in the photoresist coating. Again, a desire portion of the underlying substrate surface is uncovered.
  • the now partiall unprotected substrate may be treated with a substrate-etchant solution or plasma gases and the like.
  • This etchant solution or plasma gases etch the portion of the substrate where the photoresist coating was removed during development.
  • the areas of the substrate where the photoresist coating still remains are protected and, thus, an etched pattern is created in the substrate material whic corresponds to the photomask used for the image-wise exposure of the radiation.
  • the remaining areas of the photoresist coating may be removed during a stripping operation, leaving a clean etched substrate surface.
  • Positive-working photoresist compositions are currently favored over negative-working resists because the former generally have better resolution capabilities and pattern transfer characteristics.
  • Photoresist resolution is defined as the smallest feature which the resist composition can transfer from the photomask to the substrate with a high degree of image edge acuity after exposure and development. In many manufacturing applications today, resist resolution on the order of one micron or less are necessary.
  • the developed photoresist wall profiles be near vertical relative to the substrate. Such demarcations between developed and undeveloped areas of the resist coating translate into accurate pattern transfer of the mask image onto the substrate. Increased resolution has been noted in positive photoresist systems whose novolaks possess a high degree of ortho, ortho bonding.
  • ortho, ortho bonding is used to refer to the location and positions of attachment of the methylene bridge between cresol nuclei. Thus, the bridge which connects two phenolic nuclei which is ortho to both phenolic hydroxyl groups is regarded as ortho, ortho.
  • ortho, ortho bonding increases the interactions between the novolak and the photoactive compound in positive photoresists compared to positive photoresists containing novolaks which lack a high degree of ortho, ortho bonding in their micro- structure.
  • the exact character of these interactions is speculative, e.g., hydrogen bonding, van der Waals forces, etc., there is a correlation between increased resolution and contrast observed in these positive resists whose novolaks contain a high degree of ortho, ortho bonding compared to positive resists whose novolaks lack this high degree of ortho, ortho bonding.
  • the present invention is directed to a block copolymer novolak binder resin comprising at least one uni of the reaction product of an alkali-soluble phenolic moie (Compound A) with a reactive ortho-ortho bonded phenolic oligomer (Compound B) which has the formula (I):
  • x is from 2 to 7; wherein R is selected from hydrogen, a lower alkyl group o lower alkoxy group having 1-4 carbon atoms and a halogen group; and Y, is either a hydroxyl group, an alkoxy group, or a halogen group and Y 2 is hydrogen, lower alkyl or lower alkoxy having 1-4 carbon atoms, halogen, a hydroxyl group, a -CH-OH group, -CH-- halogen group, or -CH_-alkoxy group.
  • the present invention is directed to a radiation-sensitive composition useful as a positive photoresist comprising an admixture of o-quinonediazide compound and binder resin comprising at least one unit of the condensation product described above; the amount of sai o-quinonediazide compound or compounds being about 5% to about 40% by weight and the amount of said binder resin being about 60% to 95% by weight, based on the total solid content of said radiation-sensitive composition.
  • the present invention encompasses said coated substrates (both before and after imaging) as novel articles of manufacture.
  • the present invention also encompasses the process of coating substrates with these radiation-sensitive compositions and then imaging and developing these coated substrates.
  • the alkali soluble phenolic moiety (Compound A) is any alkalia soluble phenolic moiety which has at least two phenolic nuclei and at least two unsubstituted positions ortho and para to the hydroxyls in the moiety.
  • Preferred alkali soluble phenolic moieties are polyvinyl phenol, and polymers or oligomers made from the acid catalyzed condensation reaction of formaldehyde with phenol, substituted phenols, or mixtures thereof.
  • Preferred substituted phenols include m-cresol, o-cresol, 3,4-xylenol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2-chlorophenol, 3-chlorophenol , 2-chloro-3-methylphenol, 2-chloro-5-methyl ⁇ henol, 3-chloro-5-methylphenol,
  • Compounds A are oligomers and polymers prepared from m-cresol, o-cresol, or phenol condensed with an aldehyde source.
  • Compounds A are commercially available or may be prepared by the acid and heat catalyzed condensation of formaldehyde or formadehyde equivalent with phenol, substituted phenols, or mixtures thereof.
  • Suitable acid catalysts include oxalic acid maleic acid, hydrochloric acid, sulfonic acids, and other acid catalysts known to those skilled in the art of novolak synthesis.
  • the formaldehyde to phenolic ratio (f/p ratio) used in the preparation of Compounds A is about 0.8 or lower.
  • Compounds B may be any phenolic block which is connected by ortho, ortho bonds and substituted as defined above.
  • Preferred R groups include methyl, ethyl, methoxy, ethoxy, chlorine, and bromine. Most preferred are methyl and methoxy.
  • Preferred x is 2-6. Most preferred x is 2-4 Preferred Y-. is hydroxyl or chloro or bromo groups.
  • Preferred Y_ is hydrogen, CH_OH, CH-Cl, CH_Br, methyl, methoxy, chloro, and bromo.
  • Compounds B may be prepared by mono- or bishydroxymethylation or mono or bischloromethylation of th corresponding block segment.
  • Bishydroxymethylation is conveniently carried out by reaction with excess formaldehyde or equivalent with heat under basic conditions.
  • Suitable base catalysts include the hydroxides of sodium, potassium, and tetramethyl ammonium.
  • An additional water miscible solvent e.g., methanol or ethanol
  • Mono or bischloromethylation of phenolics may be carried out using chloromethyl methyl ether and a zinc chloride. Alternatively, the mono or bischloromethyl compound may be prepared from the chlorination of the corresponding methanol.
  • the precursors, Compounds A and B are placed in a reaction vessel which also contains an acid catalyst and solvent.
  • the mixture is then heated to a temperature in the range from about 60°C to about 120°C, more preferably from about 80-110°C, for the condensation polymerization or grafting process to occur.
  • the reaction time will depend on the specific reactants and catalyst used. Reaction times from 3-24 hours are generally suitable.
  • the reaction volatiles and solvent are then removed by distillation to yield the desired product.
  • Typical catalysts include oxalic acid, maleic acid, hydrochloric acid, sulfonic acids, and other acid catalysts known to those skilled in the art of novolak synthesis.
  • Preferred catalysts include oxalic and maleic acid.
  • the most preferred catalyst is oxalic acid.
  • the acid catalyst concentration may range from about 0.1% to about 1%.
  • Solvents which may be employed are those of medium polarity which are not extremely acid and/or water sensitive. Suitable solvents include ethereal solvents such as THF and dioxane, alcoholic solvents such as ethanol, butanol, and l-methoxy-2-propanol, or other solvents such as toluene and xylene. Preferred solvents are the alcoholic or ethereal solvents with boiling points between 80 and 220°C.
  • the above-discussed resins of the present invention may be mixed with photoactive compounds to make radiation-sensitive mixtures which are useful as positive acting photoresists.
  • the preferred class of photoactive compounds is o-quinonediazide compounds particularly esters derived from polyhydric phenols, alkyl-polyhydroxyphenones, aryl-polyhydroxyphenones, and the like which can contain up to six or more sites for esterification.
  • the most preferred o-quinonediazide esters are derived from o-naphthoquinone-(l,2)-diazide-4-sulfonic acid and o-naphthoquinone-(l,2) diazide-5-sulfonic acid.
  • resorcinol l,2-naphthoquinonediazide-4-sulfonic acid esters pyrogallol l,2-naphthoquinonediazide-5-sulfonic acid esters, 1,2-quinonediazidesulfonic acid esters of (poly)hydroxyphenyl alkyl ketones or (poly)hydroxyphenyl aryl ketones such as 2,4-dihydroxyphenyl propyl ketone l,2-benzoquinonediazide-4-sulfonic acid esters, 2,4,dihydroxyphenyl hexyl ketone 1,2-naphthoquinone- diazide-4-sulfonic acid esters, 2,4-dihydroxy- benzophenone 1,2-naphthoquinonediazide-5-sulfonic acid esters, 2,3,4-trihydroxyphenyl hexyl ketone, l,2-na ⁇ hthoquinonediazide-4-
  • 1,2-quinonediazidesulfonic acid esters of bis[(poly)- hydroxyphenyl]alkanes such as bis( ⁇ -hydroxyphenyl)- methane l,2-naphthoquinonediazide-4-sulfonic acid esters, bis(2,4-dihydroxyphenyl)methane 1,2-naphthoquinone- diazide-5-sulfonic acid esters, bis(2,3,4-trihydroxy ⁇ phenyl)methane l,2-naphthoquinonediazide-5-sulfonic acid esters, 2,2-bis(p_-hydroxyphenyl)propane 1,2-naphthoquinone- diazide-4-sulfonic acid esters, 2,2-bis(2,4-dihydroxy- phenyl)propane l,2-naphthoquinone-diazide-5-sulfonic acid esters and 2,2-bis(2,3,4-tri-hydroxy
  • 1,2-quinonediazide compounds exemplified above
  • these materials may be used in combinations of two or more.
  • mixtures of substances formed when less than all esterification sites present on a particular polyhydric phenol, alkyl- polyhydroxyphenone, aryl-polyhydroxyphenone and the like have combined with o-quinonediazides may be effectively utilized in positive acting photoresists.
  • 1,2-quinonediazide compounds may be used alone or in combination of two or more.
  • 1,2-naphthoquinone- 5-diazide compounds are 2,3,4-trihydroxybenzophenone l,2-naphthoquinonediazide-5-sulfonic acid esters, and 2,3,4,4'-tetrahydroxybenzophenone 1,2-naphthoquinone- diazide-5-sulfonic acid esters.
  • the proportion of the sensitizer compound in the radiation-sensitive mixture may preferably range from about 5 to about 40%, more preferably from about 10 to about 25% by weight of the non-volatile (e.g. non-solvent) content of the radiation-sensitive mixture.
  • the proportion of total binder resin of this present invention in the radiation-sensitive mixture may preferably range from about 60 to about 95%, more preferably, from about 75 to 90% of the non-volatile (e.g. excluding solvents) content of the radiation-sensitive mixture.
  • These radiation-sensitive mixtures may also contain conventional photoresist composition ingredients such as other resins, solvents, actinic and contrast dyes, anti-striation agents, plasticizers, speed enhancers, and the like. These additional ingredients may be added to the binder resin and sensitizer solution before the solution is coated onto the substrate.
  • binder resins may also be added beside the resins of the present invention mentioned above. Examples include phenolic-formaldehyde resins, cresol-formaldehyde resins, phenol-cresol-formaldehyde resins and polyvinylphenol resins commonly used in the photoresist art. If other binder resins are present, they will replace a portion of the binder resins of the present invention. Thus, the total amount of the binder resin in the radiation-sensitive composition will be from about 60% to about 95% by weight of the total non-volatile solids content of the radiation-sensitive composition.
  • the resins and sensitizers may be dissolved in a solvent or solvents to facilitate their application to the substrate.
  • suitable solvents include methoxyacetoxy propane, ethyl cellosolve acetate, n-butyl acetate, diglyme, ethyl lactate, ethyl 3-ethoxy propionate, propylene glycol alkyl ether acetates, or mixtures thereof and the like.
  • the preferred amount of solvent may be from about 50% to about 500%, or higher, by weight, more preferably, from about 100% to about 400% by weight, based on combined resin and sensitizer weight.
  • Actinic dyes help provide increased resolution on highly reflective surfaces by inhibiting back scattering of light off the substrate.
  • actinic dyes include those that absorb light energy at approximately 400-460 nm [e.g. Fat Brown B (C.I. No. 12010); Fat Brown RR (C.I. No. 11285); 2-hydroxy-l,4- naphthoquinone (C.I. No. 75480) and Quinoline Yellow A (C.I. No. 47000)] and those that absorb light energy at approximately 300-340 nm [e.g. 2,5-diphenyloxazole (PPO-Chem. Abs. Reg. No.
  • the amount of actinic dyes may be up to ten percent weight levels, based on the combined weight of resin and sensitizer.
  • Contrast dyes enhance the visibility of the developed images and facilitate pattern alignment during manufacturing.
  • contrast dye additives that may be used together with the radiation-sensitive mixtures of the present invention include Solvent Red 24 (C.I. No. 26105), Basic Fuchsin (C.I. 42514), Oil Blue N (C.I. No. 61555) and Calco Red A (C.I. No. 26125) up to ten percent weight levels, based on the combined weight of resin and sensitizer.
  • Anti-striation agents level out the photoresist coating or film to a uniform thickness. Anti-striation agents may be used up to five percent weight levels, based on the combined weight of resin and sensitizer.
  • One suitable class of anti-striation agents is non-ionic silicon-modified polymers. Non-ionic surfactants may also be used for this purpose, including, for example, nonylphenoxy poly(ethyleneoxy) ethanol; octylphenoxy (ethyleneoxy) ethanol; and dinonyl phenoxy poly(ethyleneoxy) ethanol.
  • Plasticizers improve the coating and adhesion properties of the photoresist composition and better allow for the application of a thin coating or film of photoresist which is smooth and of uniform thickness onto the substrate.
  • Plasticizers which may be used include, for example, phosphoric acid tri-(B-chloroethyl)-ester; stearic acid; dicamphor; polypropylene; acetal resins; phenoxy resins; and alkyl resins up to ten percent weight levels, based on the combined weight of resin and sensitizer.
  • Speed enhancers tend to increase the solubility of the photoresist coating in both the exposed and unexposed areas, and thus, they are used in applications where speed of development is the overriding consideration even though some degree of contrast may be sacrificed, i.e. in positive resists while the exposed areas of the photoresist coating will be dissolved more quickly by the developer, the speed enhancers will also cause a larger loss of photoresist coating from the unexposed areas.
  • Speed enhancers that may be used include, for example, picric acid, nicotinic acid or nitrocinnamic acid at weight levels of up to 20%, based on the combined weight of resin and sensitizer.
  • the prepared radiation-sensitive resist mixture can be applied to a substrate by any conventional method used in the photoresist art, including dipping, spraying, whirling and spin coating.
  • spin coating for example, the resist mixture can be adjusted as to the percentage of solids content in order to provide a coating of the desired thickness given the type of spinning equipment and spin speed utilized and the amount of time allowed for the spinning process.
  • Suitable substrates include silicon, aluminum or polymeric resins, silicon dioxide, doped silicon dioxide, silicon resins, gallium arsenide, silicon nitride, tantalum, copper, polysilicon, ceramics and aluminum/copper mixtures.
  • the photoresist coatings produced by the above described procedure are particularly suitable for application to thermally grown silicon/silicon dioxide-coated wafers such as are utilized in the production of microprocessors and other miniaturized integrated circuit components.
  • An aluminum/aluminum oxide wafer can be used as well.
  • the substrate may also comprise various polymeric resins especially transparent polymers such as polyesters and poly ⁇ lefins.
  • the coated substrate is baked at approximately 70°C to 125°C until substantially all the solvent has evaporated and only a uniform radiation-sensitive coating remains on the substrate.
  • the coated substrate can then be exposed to radiation, especially ultraviolet radiation, in any desired exposure pattern, produced by use of suitable masks, negatives, stencils, templates, and the like.
  • radiation especially ultraviolet radiation
  • Conventional imaging process or apparatus currently used in processing photoresist-coated substrates may be employed with the present invention.
  • a post-exposure bake at a temperature about 10°C higher than the soft bake temperature is used to enhance image quality and resolution.
  • aqueous alkaline developing solution This solution is preferably agitated, for example, by nitrogen gas agitation.
  • aqueous alkaline developers include aqueous solutions of tetramethyl- ammonium hydroxide, sodium hydroxide, potassium hydroxide, ethanolamine, choline, sodium phosphates, sodium carbonate, sodium etasilicate, and the like.
  • the preferred developers for this invention are aqueous solutions of either alkali metal hydroxides, phosphates or silicates, or mixtures thereof, or tetramethylammonium hydroxide.
  • the substrates are allowed to remain in the developer until all of the resist coating has dissolved from the exposed areas. Normally, development times from about 10 seconds to about 3 minutes are employed.
  • the coated wafers in the developing solution are preferably subjected to a deionized water rinse to fully remove the developer or any remaining undesired portions of the coating and to stop further development.
  • This rinsing operation (which is part of the development process) may be followed by blow drying with filtered air to remove excess water.
  • a post-development heat treatment or bake may then be employed to increase the coating's adhesion and chemical resistance to etching solutions and other substances.
  • the post-development heat treatment can comprise the baking of the coating and substrate below the coating's thermal deformation temperature.
  • the developed substrates may then be treated with a buffered, hydrofluoric acid etching solution or plasma gas etch.
  • the resist compositions of the present invention are believed to be resistant to a wide variety of acid etching solutions or plasma gases and provide effective protection for the resist-coated areas of the substrate.
  • the remaining areas of the photoresist coating may be removed from the etched substrate surface by conventional photoresist stripping operations.
  • a 5 liter three-necked flask was equipped with a mechanical stirring apparatus and a thermometer.
  • the flask was charged with p-cresol (2391.1 g, 22 moles), which had been warmed to 40-45°C, and concentrated HC1 (47.3 g, 0.47 moles).
  • 2,6-Bis(hydroxymethyl)-p-cresol (371.9 g, 2.2 moles) was added portionwise over a 15-20 minute period to the stirred reaction mixture.
  • the temperature was controlled to a maximum temperature range of 50-55°C.
  • the reaction mixture was stirred for an additional 2 hours (40-45°C after cooling from 50-55°C) .
  • the reaction mixture was transferred to a 12 liter flask.
  • the warm reaction was filtered to remove suspended solids.
  • the filtrate was transferred to a 12 liter flask and 5 liters of deionized water added.
  • Glacial acetic acid 120 ml was added with vigorous stirring to lower the pH from about 10.7 to about 4.9.
  • n-Butanol 2.5 liters was added to the stirred, viscous slurry while maintaining the temperature at about 50°C to dissolve the crude product. After stirring for 10 minutes, the phases were allowed to separate and the bottom aqueous phase was discarded.
  • the top phase was mixed with 1 liter of water, and heated to 70°C while stirring to break up an emulsion. The two phases were separated while warm and the top phase (butanol solution) was retained.
  • a one liter three-necked flask was fitted with a mechanical stirring apparatus, thermometer, and reflux condenser.
  • m-cresol 216.3 g, 2 moles
  • 37% formalin solution for amounts and CH_0 moles see Table I.
  • the flask and its contents were immersed in an oil bath at 95°C.
  • Oxalic acid dihydrate, dissolved in hot deionized water (10 mL) was added to the solution in one portion and rinsed in with hot deionized water (5 mL) .
  • the oil bath's temperature was increased to about 120°C and the reaction was allowed to reflux for 16. hours.
  • the condenser was adjusted for downward distillation and the oil bath temperature was increased to 200°C.
  • the flask and its contents were subjected to increasing vacuum. After the maximum vacuum was reached (1-5 millibar), the oil bath temperature was increased to 220°C and distillation was continued for one hour.
  • the reactions were conducted in a 250 mL three-necked flask which had been fitted with a mechanical stirring apparatus, reflux condenser and a thermometer. To the flask were added one of the m-cresol polymers (29.73 g) prepared in Example 3 and l-methoxy-2-propanol (solvent) . The flask and its contents were immersed in a 75°C oil bath and the mixture was stirred until it had completely dissolved.
  • the condenser was adjusted for atmospheric distillation and the bath temperature was increased to about 12 ⁇ C.
  • the bath temperature was increased to 200°C over 30 minutes and atmospheric distillation was completed, about 45 minutes total.
  • the flask and its contents were subjected to a gradually increasing vacuum, and once maximum vacuum is reached (about 1-5 millibar) , the temperature of the oil bath was increased to about 215°C and the distillation was continued for two hours.
  • the reaction mixture was transferred to a 12 liter flask and 3750 ml of deionized water added. The warm reaction mixture was quickly filtered to remove suspended solids. The collected solid was washed with warm water and refiltered. The filtrates were combined and allowed to cool to room temperature. The precipitate was collected by filtration and transferred to a 4 liter beaker. n-Butanol (1 liter) and glacial acetic acid (100 ml) were added and the slurry heated with stirring to 50-60°C to dissolve the crude product. The aqueous bottom layer was separated and discarded. The n-butanol layer was allowed to cool overnight at 0-5°C. The precipitate was collected by filtration and vacuum dried at 40-45°C to yield 94.5 g (32% yield) product. A second crop yielded an additional 45.8 g (20% yield) of product.
  • p-Cresol dimer block copolymers are prepared according to the general procedure described in Example 3 using proportions shown in Table III.
  • a 250 mL three-neck flask is fitted with a mechanical stirring apparatus and a thermometer charged with p-cresol (16.8 g, 0.155 mole) and concentrated HC1 (0.21 g, about 0.0022 m) .
  • 3 ,3 '-[ (2-Hydroxy-5- methyl-1, 3-benzene) dimethyleneJbis[2-hydroxy- 5-benzenemethanol] (2.91 g, 0.0102 mole) (p-cresol trimer bismethylol from Example 2) is added in small portions over about 15 minutes keeping the reaction mixture temperature ⁇ 45°C with a water bath. The solution is then maintained at 40-45°C for two hours.
  • the oil bath temperature is increased to 200°C and a gradually increasing vacuum applied to remove reaction volatiles and excess p-cresol. After reaching maximum vacuum (about 20 millibar), the reaction mixture is heated for an additional hour to ensure removal of the unreacted p-cresol.
  • the p-cresol pentamer bismethylol is prepared according to the procedure used in Example 2 for the p-cresol trimer bismethylol.
  • p-Cresol pentamer block copol mers are prepared according to the procedure used in Example 4 using proportions shown in Table IV.
  • Photoresist formulations were prepared by dissolving in ethyl lactate three parts by weight of some of the alkali-soluble resins made in Example 4 with one part photoactive compound prepared by condensation of 1 mole 2,3,4,4'-tetrahydroxy-benzophenone with 2.75 moles • ⁇ - ⁇ o-napthoquinone-(l,2)-diazide-5-sulfonic acid chloride.
  • Photoresist solutions prepared above were spin-coated onto four inch silicon wafers, which had been primed with hexamethyldisilazane (HMDS) .
  • the coated wafer were soft baked on a hot plate for 50 seconds at 110°C.
  • Uniform coatings, of about 1.2 micron in thickness were obtained by spinning at velocities ranging from 4000 to 60 RPM for 30 seconds, depending upon the solution viscosity. If necessary, the solids content was adjusted to fit this spin speed range.
  • Photoresist coatings were exposed on a Canon G lin step and repeat exposure tool equipped with a 0.43 numerica aperture lens. This exposure tool provided a narrow spectral output at 436 nm.
  • the exposed photoresist coatings were puddle developed using a 2.38 percent weight percent tetramethyl ammonium hydroxide aqueous developer solution in a two second spray and 58 second dwell cycle followed by rinsing and spin drying.
  • Photoresist Performance Evaluations The photoresist formulations were evaluated for photospeed; line and space resolution; scum; and profile.
  • the photoresists are made from the Example 4 novolaks exhibited better profiles than the comparison resists.
  • the Example 4 resists also exhibited similar photospeeds.
  • the line and space resolution of the optimize comparison resist was about 0.65 microns, whereas the resolution of the unoptimized Example 4 resist were about 0.8-1 microns.
  • the comparison resist showed no scum, whereas the resolution of Example 4 resists were limited by some scum. It is believed that resolution and objectionable scum in the Example 4 resist could be improved by adjust ⁇ ments in the formulation (i.e., more or less photoactive compound or use of different photoactive compound) . Changes in the photoresist processing conditions are expected to improve performance characteristics.

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Abstract

Une composition de résine copolymère novolaque en masse comprend au moins une unité du produit de réaction d'un polymère phénolique soluble dans l'alcali et un ortho-oligomère réactif ou un oligomère lié ortho réactif ayant la formule (I) où x varie de 2 à 7; où R est choisi entre de l'hydrogène, un groupe d'alkyle inférieur ou un groupe d'alkoxy inférieur ayant de 1 à 4 atomes de carbone et un groupe halogène; et Y1 est soit un groupe hydroxyle; un groupe alkoxy ou un groupe halogène; et Y2 est de l'hydrogène, de l'alkyle, de l'alkoxy, de l'halogène, de l'hydroxyle, du -CH2OH, du -CH2- halogène, ou du -CH2- groupe alkoxy. Ceci est utile pour les compositions sensibles aux rayonnements et aux produits revêtus d'une couche d'un composé de o-quinone diazide pour lesquels on obtient une image à réserve positive après un traitement par le rayonnement et un développement ultérieur.
PCT/US1990/004307 1989-09-07 1990-08-02 Resines de liaison selectionnees d'un copolymere novolaque en masse et leurs utilisation dans des compositions sensibles aux rayonnements WO1991004512A1 (fr)

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US5413894A (en) * 1993-05-07 1995-05-09 Ocg Microelectronic Materials, Inc. High ortho-ortho bonded novolak binder resins and their use in radiation-sensitive compositions
US8173745B2 (en) 2009-12-16 2012-05-08 Momentive Specialty Chemicals Inc. Compositions useful for preparing composites and composites produced therewith
US8617641B2 (en) 2009-11-12 2013-12-31 Guardian Industries Corp. Coated article comprising colloidal silica inclusive anti-reflective coating, and method of making the same

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US4377631A (en) * 1981-06-22 1983-03-22 Philip A. Hunt Chemical Corporation Positive novolak photoresist compositions
DD211415A1 (de) * 1983-02-16 1984-07-11 Fotochem Werke Berlin Veb Positiv-fotokopierlack mit verbesserten eigenschaften
JPS59184337A (ja) * 1983-04-04 1984-10-19 Hitachi Ltd 感光性耐熱材料
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JPS6097347A (ja) * 1983-11-01 1985-05-31 Hitachi Chem Co Ltd 画像形成性感光性組成物
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EP0273026A2 (fr) * 1986-12-23 1988-06-29 Shipley Company Inc. Solvants pour compositions de photoréserve
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US5413894A (en) * 1993-05-07 1995-05-09 Ocg Microelectronic Materials, Inc. High ortho-ortho bonded novolak binder resins and their use in radiation-sensitive compositions
US5473045A (en) * 1993-05-07 1995-12-05 Ocg Microelectronic Materials, Inc. High ortho-ortho bonded novolak binder resins and their use in radiation-sensitive compositions
US5494785A (en) * 1993-05-07 1996-02-27 Ocg Microelectronic Materials, Inc. High ortho-ortho bonded novolak binder resins and their use in a process for forming positive resist patterns
US8617641B2 (en) 2009-11-12 2013-12-31 Guardian Industries Corp. Coated article comprising colloidal silica inclusive anti-reflective coating, and method of making the same
US8173745B2 (en) 2009-12-16 2012-05-08 Momentive Specialty Chemicals Inc. Compositions useful for preparing composites and composites produced therewith
US8445590B2 (en) 2009-12-16 2013-05-21 Momentive Specialty Chemicals Inc. Compositions useful for preparing composites and composites produced therewith

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