Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • 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
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
  • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/02—Polyamines
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
  • C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
• • 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
  • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
• • 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
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • 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
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/094—Multilayer resist systems, e.g. planarising layers
• • 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
  • G03F7/16—Coating processes; Apparatus therefor
• • 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
  • G03F7/16—Coating processes; Apparatus therefor
  • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
• • 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
  • G03F7/20—Exposure; Apparatus therefor
• • 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers
• • 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
  • G03F7/405—Treatment with inorganic or organometallic reagents after imagewise removal
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
  • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
  • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
  • H01L21/0274—Photolithographic processes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
  • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
  • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
  • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
  • H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
  • H01L21/76816—Aspects relating to the layout of the pattern or to the size of vias or trenches

Definitions

• the present invention relates to a composition for obtaining a resist pattern having a fine size by forming a resist pattern in a manufacturing process of a semiconductor or the like and further thickening the resist pattern, and a pattern forming method using the composition. is there.
• a resist pattern is exposed using an optical developer technique, for example, a positive resist that becomes highly soluble in an alkaline developer when exposed, and after exposing the resist, using an alkaline developer. The portion is removed to form a positive pattern.
• an optical developer technique for example, a positive resist that becomes highly soluble in an alkaline developer when exposed, and after exposing the resist, using an alkaline developer. The portion is removed to form a positive pattern.
• the part that depends on the exposure light source and the exposure method is large, and expensive and special equipment and peripheral materials that can provide the light source and method are necessary, which is a huge investment Is required.
• a practical method is to cover a resist pattern formed in a range that can be stably obtained by conventional methods with a composition containing a water-soluble resin and additives as necessary, and thicken the resist pattern.
• the hole diameter or the separation width is made finer.
• the following techniques are known as such methods.
• the resist pattern is thickened by removing the non-crosslinked portion with a developer, and the hole diameter or separation width of the resist pattern is refined (see Patent Documents 1 and 2).
• the present invention is a composition capable of suppressing the occurrence of defects on the surface while achieving a large pattern miniaturization effect in the miniaturization of a resist pattern using a chemically amplified positive photoresist. And a pattern forming method using the same.
• composition for forming a fine pattern according to the present invention is used to make a pattern fine by thickening the resist pattern in a method of forming a positive resist pattern using a chemically amplified positive photoresist composition. Because A polymer containing an amino group in the repeating unit; Solvent and acid, It is characterized by comprising.
• a method for forming a positive resist pattern includes: Forming a photoresist layer by applying a chemically amplified photoresist composition on a semiconductor substrate; Exposing the semiconductor substrate coated with the photoresist layer; Developing with a developer after the exposure to form a photoresist pattern; Applying a fine pattern forming composition comprising a polymer containing an amino group in a repeating unit, a solvent, and an acid to the surface of the photoresist pattern; It is characterized by comprising a step of heating a coated photoresist pattern and a step of washing and removing an excessive fine pattern forming composition.
• composition for forming a fine pattern
• the composition for forming a fine pattern according to the present invention comprises a polymer containing an amino group in a repeating unit, a solvent and an acid.
• the polymer used in the present invention contains an amino group.
• the amino group refers to a primary amino group (—NH 2 ), a secondary amino group (—NHR), and a tertiary amino group (—NRR ′).
• These amino groups may be contained in the side chain of the repeating unit, or may be contained in the main chain structure of the polymer.
• examples of the polymer containing a repeating unit having a primary amino group in the side chain include polyvinylamine, polyallylamine, polydiallylamine, and poly (allylamine-co-diallylamine).
• examples of the polymer in which the amino group is contained in the polymer main chain include polyalkyleneimines such as polyethyleneimine and polypropyleneimine.
• a polymer containing an amide bond —NH—C ( ⁇ O) — in the main chain can also be used.
• a polymer having a structure in which a nitrogen atom is bonded to one adjacent atom via a double bond and is bonded to another adjacent atom via a single bond can be used in the composition according to the present invention.
• Such a structure may be included in either the side chain or main chain of the polymer, but is typically included in the side chain as part of a heterocyclic structure.
• the heterocyclic ring having such a structure include an imidazole ring, an oxazole ring, a pyridine ring, and a bipyridine ring.
• the polymer used in the present invention can be appropriately selected from the viewpoints of the type of resist pattern to be applied, the availability of the polymer, and the like from the above.
• polyvinylamine, polyvinylimidazole, polyvinylpyrrolidone and the like are preferably used because advantageous results are obtained in coating properties and pattern reduction amount.
• a copolymer containing a repeating unit that does not contain an amino group as long as the scope of the present invention is not impaired can also be used in the composition for forming a fine pattern according to the present invention.
• a copolymer containing polyacrylic acid, polymethacrylic acid, polyvinyl alcohol and the like as copolymerized units can be mentioned.
• the repeating unit not containing an amino group is preferably 50 mol% or less, more preferably 30 mol% or less, of the polymer unit constituting the polymer.
• the molecular weight of the polymer containing an amino group used in the present invention is not particularly limited, but the weight average molecular weight is generally selected from the range of 5,000 to 200,000, preferably 8,000 to 150,000.
• a weight average molecular weight means the polystyrene conversion average weight molecular weight measured using gel permeation chromatography.
• a typical high-resolution positive photoresist composition contains a combination of an alkali-soluble resin having a terminal group protected with a protecting group and a photoacid generator.
• the photoacid generator releases an acid in the irradiated portion, and the protective group bonded to the alkali-soluble resin by the acid. Is dissociated (hereinafter referred to as deprotection). Since the deprotected alkali-soluble resin is soluble in an alkali developer (eg, tetramethylammonium aqueous solution), it can be removed by development processing.
• an alkali developer eg, tetramethylammonium aqueous solution
• the permeability to the resist tends to be good, but the resist in the vicinity of the partially deprotected surface may be dissolved.
• the desired refining effect cannot be obtained because the photoresist elutes in the rinsing liquid in the rinsing process performed after development near the interface between the photoresist and the composition layer during the refining process. In some cases, the pattern was rough.
• composition in the present invention comprises an acid in order to satisfy the requirements.
• the type of acid that can be used in the present invention is not particularly limited as long as it does not adversely affect the resist pattern, and can be selected from inorganic acids and organic acids.
• organic acids acetic acid, propionic acid, butyric acid, benzoic acid, phthalic acid, glutamic acid, citric acid, fumaric acid, methoxyacetic acid, glucolic acid, glutaric acid and other carboxylic acids
• methanesulfonic acid, ethane Preferred examples include sulfonic acids such as sulfonic acid, 2-aminoethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, pentafluoropropionic acid, and 10-camphorsulfonic acid.
• p-toluenesulfonic acid, trifluoromethanesulfonic acid, and pentafluoropropionic acid are highly soluble in water and have a relatively high boiling point, so they are less likely to volatilize from the coating during heating in the manufacturing process.
• the inorganic acid sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, or the like can be used. Of these, sulfuric acid or nitric acid is preferable because it does not bring in an element that has a strong influence on electrical characteristics and thus has excellent affinity for semiconductor processes.
• the composition according to the present invention comprises a solvent.
• the solvent is not particularly limited as long as it does not dissolve the resist pattern, but water is preferably used.
• the water used is preferably water from which organic impurities, metal ions, and the like have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, and the like, particularly pure water.
• a small amount of an organic solvent may be used as a cosolvent in order to improve wettability and the like.
• Such a solvent examples include alcohols such as methyl alcohol, ethyl alcohol, and propylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl lactate and ethyl acetate.
• the solvent should be selected from those which do not dissolve or modify the resist film to which the composition is applied.
• the fine pattern forming composition according to the present invention contains a polymer acid having a specific structure as described above, and a solvent.
• concentration of the polymer can be arbitrarily selected according to the type and size of the target resist pattern, the target pattern size, and the like.
• concentration of the polymer containing the specific structure is generally 0.1 to 10% by weight, preferably 1.0 to 7.0% by weight, based on the total weight of the composition.
• the acid content of the composition is preferably 0.5 to 50% by weight, and preferably 2.5 to 30% by weight, based on the total weight of the polymer containing amino groups in the composition. preferable.
• the pH of the composition for forming a fine pattern is generally preferably 2 or more and 11 or less, more preferably 3 or more and 10 or less. If the pH is less than 2 or more than 11, dissolution of the photoresist pattern may occur, and the surface of the photoresist resist pattern may be roughened. Therefore, it is preferable to adjust the pH appropriately.
• the fine pattern forming composition according to the present invention may contain other additives as required.
• additives include surfactants, bactericides, antibacterial agents, preservatives, and fungicides.
• a composition contains surfactant from a viewpoint of the applicability
• surfactant from a viewpoint of the applicability
• These additives in principle do not affect the performance of the composition for forming a fine pattern, and are generally 1% or less, preferably 0.1% or less, more preferably based on the total weight of the composition. Is 0.05% or less.
• the effect of application property improvement can also be acquired by apply
• a typical pattern forming method to which the composition for forming a fine pattern of the present invention is applied includes the following method.
• a chemically amplified photoresist layer is formed by applying a chemically amplified photoresist to a surface of a substrate such as a silicon substrate, which has been pretreated as necessary, by a conventionally known coating method such as a spin coating method.
• a conventionally known coating method such as a spin coating method.
• an antireflection film may be formed on the substrate surface. Such an antireflection film can improve the cross-sectional shape and the exposure margin.
• a chemically amplified photoresist generates an acid upon irradiation with light such as ultraviolet rays, and forms a pattern by increasing the solubility of the light irradiated portion in an alkaline developer by a chemical change caused by the catalytic action of this acid.
• An acid-generating compound that generates an acid upon irradiation with light; and an acid-sensitive group-containing resin that decomposes in the presence of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group; an alkali-soluble resin;
• an alkali-soluble resin The thing which consists of a crosslinking agent and an acid generator is mentioned.
• the chemically amplified photoresist layer formed on the substrate is pre-baked, for example, on a hot plate as necessary to remove the solvent in the chemically amplified photoresist, and the photoresist has a thickness of typically about 50 nm to 500 nm. It is made a film.
• the pre-baking temperature varies depending on the solvent used or the chemically amplified photoresist, but is usually 50 to 200 ° C., preferably about 70 to 150 ° C.
• the photoresist film is then used with a known irradiation device such as a high-pressure mercury lamp, a metal halide lamp, an ultra-high pressure mercury lamp, a KrF excimer laser, an ArF excimer laser, a soft X-ray irradiation device, an electron beam drawing device, and through a mask as necessary. Exposure is performed.
• a known irradiation device such as a high-pressure mercury lamp, a metal halide lamp, an ultra-high pressure mercury lamp, a KrF excimer laser, an ArF excimer laser, a soft X-ray irradiation device, an electron beam drawing device, and through a mask as necessary. Exposure is performed.
• the resist is developed using an alkaline developer.
• the developer that can be used can be arbitrarily selected from tetramethylammonium hydroxide aqueous solution, potassium hydroxide aqueous solution and the like. It is preferable that the resist pattern is rinsed (washed) using a rinse solution after the development treatment. At this time, it is preferable to use pure water as the rinse liquid.
• the composition for forming a fine pattern according to the present invention is applied to refine the pattern.
• water or an organic solvent that does not dissolve the resist pattern can be applied to the surface of the resist pattern.
• the applicability of the composition can be improved and the composition can be applied uniformly. That is, coatability can be improved without using an additive for improving coatability such as a surfactant in the composition.
• Such a process is sometimes called a pre-wet process.
• the composition for forming a fine pattern according to the present invention is applied so as to cover the resist pattern, and the resist pattern is thickened by the interaction between the resist pattern and the composition for forming a fine pattern.
• the interaction that occurs here is thought to be that the polymer permeates or adheres to the resist, thereby causing the resist pattern to thicken.
• the fine pattern forming composition according to the present invention permeates or adheres to the inner wall of the groove or hole formed on the surface of the resist pattern, and the pattern becomes thicker. It is possible to effectively reduce the size or the hole opening size to below the limit resolution.
• any method such as a spin coating method conventionally used when applying a photoresist resin composition may be used. it can.
• the resist pattern after the fine pattern forming composition is applied is pre-baked as necessary.
• Pre-baking may be performed by heating at a constant temperature or by heating while raising the temperature stepwise.
• the conditions for the heat treatment after applying the composition for forming a fine pattern are, for example, a temperature of 40 to 200 ° C., preferably 80 to 180 ° C., 10 to 300 seconds, and preferably about 30 to 120 seconds. Such heating promotes penetration and adhesion of the polymer to the resist pattern.
• the resist pattern After applying and heating the composition for forming a fine pattern, the resist pattern is thickened, the line width of the resist pattern is thickened, and the hole pattern has a small hole diameter.
• Such a change in size can be appropriately adjusted according to the temperature and time of the heat treatment, the type of the photoresist resin composition to be used, and the like. Therefore, if these conditions are set depending on how fine the resist pattern is to be made, in other words, how much the line width of the resist pattern is increased and how small the hole diameter of the hole pattern is required. Good.
• the difference before and after the application of the fine pattern forming composition is generally 5 to 30 nm.
• an excessive fine pattern forming composition that did not act on the resist can be removed by rinsing with water or a solvent as necessary.
• water or a solvent used for such rinsing treatment, an excessive composition that has low solubility and does not penetrate or adhere to the fine pattern forming composition that penetrates or adheres to the resist pattern. Is selected so as to have high solubility.
• the solvent used for the composition for forming a fine pattern, particularly pure water is preferably used for the rinsing treatment.
• the resist pattern obtained in this manner is substantially miniaturized because the pattern size of the resist pattern immediately after development is changed by the action of the composition for forming a fine pattern.
• the resist pattern manufactured using the composition for fine pattern formation by this invention is useful for manufacture of the semiconductor element etc. which have a finer pattern in manufacture of a semiconductor element.
• Example A resist pattern forming spin coater (manufactured by Tokyo Electron Limited) was used to apply an antireflection film AZ ArF-1C5D (trade name, manufactured by AZ Electronic Materials Co., Ltd.) to an 8-inch silicon wafer, and at 60.degree. Baking was performed for 2 seconds to obtain an antireflection film having a thickness of 37 nm.
• a photosensitive resin composition AZ AX2110P (trade name, manufactured by AZ Electronic Materials Co., Ltd.) was baked at 110 ° C. for 60 seconds to obtain a film thickness of 120 nm.
• the mask was rotated in a direction orthogonal to the first exposure, and a second exposure was performed.
• development treatment was performed with an aqueous tetramethylammonium hydroxide solution (2.38%) for 30 seconds to obtain a resist pattern having a pitch of 160 nm and a hole size of 80 nm.
• composition A Preparation of a composition for forming a fine pattern
• Polyallylamine having a polystyrene-equivalent weight average molecular weight of 25,000 was prepared as a polymer used for the composition for forming a fine pattern. This polymer was dissolved in pure water to obtain a 2% by weight aqueous solution. Further, polyoxyethylene nonylphenyl ether (the following formula (1)) in an amount of 500 ppm with respect to the aqueous solution was added as a surfactant. This is composition A.
• composition B An allylamine / dimethylallylamine copolymer having a polystyrene-equivalent weight average molecular weight of 30,000 was prepared as a polymer used in the composition for forming a fine pattern. This polymer was dissolved in pure water to obtain a 2% by weight aqueous solution. Further, as the surfactant, acetylene-based diol polyoxyalkylene ether (the following formula (2)) in an amount of 500 ppm with respect to the aqueous solution was added. This is designated Composition B.
• Polyvinylimidazole having a polystyrene-equivalent weight average molecular weight of 70,000 was prepared as a polymer used in the composition for forming a fine pattern. This polymer was dissolved in pure water to obtain a 2% by weight aqueous solution. Furthermore, polyoxyethylene-laurylamine (the following formula (3)) in an amount of 500 ppm with respect to this aqueous solution was added as a surfactant. This is composition C.
• a polyethylene oxide / polyvinylimidazole block copolymer (50 mol%: 50 mol%) having a polystyrene-equivalent weight average molecular weight of 15,000 was prepared as a polymer used in the composition for forming a fine pattern. This polymer was dissolved in pure water to obtain a 2% by weight aqueous solution. Further, polyoxyethylene monostearate (the following formula (4)) in an amount of 300 ppm with respect to this aqueous solution was added as a surfactant. This is composition D.
• Polyvinylpyrrolidone having a polystyrene-equivalent weight average molecular weight of 67,000 was prepared as a polymer used in the composition for forming a fine pattern. This polymer was dissolved in pure water to obtain a 2% by weight aqueous solution. Furthermore, as a surfactant, dimethyl lauryl-amine oxide (the following formula (5)) in an amount of 700 ppm with respect to the aqueous solution was added. This is composition E.
• Samples were prepared by adding various acids to the respective compositions such that the amounts of the acids were 5% by weight, 20% by weight, or 45% by weight with respect to the resin.
• Each composition was applied to a resist pattern prepared in advance using a spin coater (manufactured by Tokyo Electron Limited).
• the thickness of the resist layer was 100 nm.
• the film thickness was determined by measuring at the resist flat portion. After heating at 140 ° C. for 1 minute, excess composition was removed using pure water. After drying, the defect generated on the processed pattern surface was examined using a defect inspection apparatus. Also. The amount of pattern refinement by the refined composition was also evaluated. The obtained results were as shown in Tables 1a to d and 2a to d below.
• the evaluation criteria for defects on the pattern surface were as follows. a: Extremely good b: Defects are observed but there is virtually no problem c: Defect
• PFPS pentafluoropropionic acid
• PTS p-toluenesulfonic acid
• TFMS trifluoromethanesulfonic acid

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