WO2009104748A1 - 被露光基板用撥水化剤組成物、レジストパターンの形成方法及び該形成方法により製造した電子デバイス、被露光基板の撥水化処理方法、被露光基板用撥水化剤セット及びそれを用いた被露光基板の撥水化処理方法 - Google Patents
被露光基板用撥水化剤組成物、レジストパターンの形成方法及び該形成方法により製造した電子デバイス、被露光基板の撥水化処理方法、被露光基板用撥水化剤セット及びそれを用いた被露光基板の撥水化処理方法 Download PDFInfo
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- WO2009104748A1 WO2009104748A1 PCT/JP2009/053057 JP2009053057W WO2009104748A1 WO 2009104748 A1 WO2009104748 A1 WO 2009104748A1 JP 2009053057 W JP2009053057 W JP 2009053057W WO 2009104748 A1 WO2009104748 A1 WO 2009104748A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
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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
- G03F7/16—Coating processes; Apparatus therefor
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
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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
- G03F7/09—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
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
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- 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
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- 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
Definitions
- the present invention relates to a water repellent composition for a substrate to be exposed, a method for forming a resist pattern, an electronic device produced by the method, a water repellent treatment method for a substrate to be exposed, a water repellent set for a substrate to be exposed, and The present invention relates to a water repellent treatment method for an exposed substrate using the same.
- the projection optical system of an exposure apparatus and the exposed substrate development of an immersion exposure method in which exposure is performed by filling an immersion liquid with a wafer (including a wafer). Pure water is generally employed as the immersion liquid.
- the immersion liquid used in the exposure processing flows from the peripheral portion of the surface to be processed of the substrate to be exposed to the back surface and contaminates the back surface of the substrate to be exposed.
- HMDS hexamethyldisilazane
- Patent Document 1 a method using a silylating agent having an alkyl group or an alkenyl group substituted with fluorine
- Patent Document 2 a method of performing HMDS treatment on a region within a specific range on the back surface of a semiconductor substrate
- Patent Document 1 has a problem that a chemical solution such as a resist applied to the surface of the substrate is repelled on the surface and cannot be applied, and the method of Patent Document 2 has a problem that the water repellency is insufficient.
- an organic film such as a resist film is formed on a substrate on which a film to be processed is formed.
- the film to be processed and the organic film immediately above the film are processed. Insufficient adhesion to the film, peeling of the film from the wafer edge occurs, and foreign matter peeled off due to convection of the immersion liquid during immersion exposure is mixed into the immersion liquid, causing a pattern defect. is there.
- the resist pattern is likely to collapse.
- the collapse of the resist pattern means that as the resist pattern is miniaturized, the aspect ratio (that is, the film thickness H / line width d) increases, the contact area between the substrate and the resist pattern decreases, and the resist pattern becomes smaller. It means that it is easy to collapse. JP 2007-019465 A JP 2007-194503 A
- the present invention suppresses contamination of the back surface of the substrate to be exposed due to the immersion liquid and improves adhesion between the film to be processed and the organic film immediately above the film, thereby suppressing film peeling and excellent workability.
- Exposed substrate water repellent composition, resist pattern formation method and electronic device produced by the formation method, exposed substrate water repellent treatment method, exposed substrate water repellent set, and the same An object of the present invention is to provide a water repellent treatment method for a substrate to be exposed.
- the water repellent composition for a substrate to be exposed includes at least an organosilicon compound represented by the following general formula (1) and a solvent.
- R 1 is a monovalent organic group having 14 to 30 carbon atoms
- R 2 , R 3 and R 4 are each independently a monovalent organic group having 1 to 10 carbon atoms or a hydrolyzable group
- R 2 , At least one of R 3 and R 4 is a hydrolyzable group.
- the resist pattern forming method of the present invention is a resist pattern forming method by immersion exposure in which exposure is performed with a liquid interposed between a projection optical system of an exposure apparatus and a substrate to be exposed.
- the substrate treated with the water repellent composition for an exposed substrate containing the organosilicon compound represented by (1) and a solvent is exposed.
- R 1 is a monovalent organic group having 14 to 30 carbon atoms
- R 2 , R 3 and R 4 are each independently a monovalent organic group having 1 to 10 carbon atoms or a hydrolyzable group
- R 2 , At least one of R 3 and R 4 is a hydrolyzable group.
- the electronic device of the present invention is manufactured by the resist pattern forming method described above.
- the water repellent treatment method for a substrate to be exposed according to the present invention is characterized by using a water repellent composition containing at least an organosilicon compound represented by the following general formula (1) and a solvent.
- R 1 is a monovalent organic group having 14 to 30 carbon atoms
- R 2 , R 3 and R 4 are each independently a monovalent organic group having 1 to 10 carbon atoms or a hydrolyzable group
- R 2 , At least one of R 3 and R 4 is a hydrolyzable group.
- the organosilicon compound represented by the general formula (1) is hydrolyzed to generate silanol groups, which react with hydroxyl groups on the surface of the wafer and / or the film to be processed to form chemical bonds.
- high water repellency can be imparted to the wafer and / or the film to be processed.
- the water repellency of the wafer can be improved as compared with the conventional HMDS process.
- the contamination of the back surface of the substrate to be exposed by the immersion liquid in the immersion exposure method can be effectively suppressed.
- the adhesion between a film to be processed formed under a fine processing resist film for forming a resist pattern and the resist film immediately above the film can be improved, peeling of the film from the wafer edge can be suppressed.
- the adhesion between the resist pattern and the substrate is also strengthened, so that the resist pattern can be prevented from collapsing, and a high-quality electronic device free from pattern defects can be provided.
- the composition of the present invention is a solution, the processing operation for the substrate is simple, and the water repellent treatment can be selectively performed by locally spraying the composition.
- the improvement in adhesion in the present invention means improvement in adhesion between the surface of a film to be processed and the like formed under the fine processing resist film and the resist film immediately above the surface.
- FIG. It is a schematic cross section which shows one aspect
- FIG. It is a schematic diagram which shows the adhesive evaluation method in this invention.
- (a) shows a process flow,
- (b) is a schematic cross section which shows an example of the structure of a to-be-exposed board
- (a) shows a process flow
- (b) is a schematic cross section which shows an example of the structure of a to-be-exposed board
- (a) shows a process flow
- (b) is a schematic cross section which shows an example of the structure of a to-be-exposed board
- (b) is a schematic cross section which shows an example of the structure of a to-be-exposed board
- (b) is a schematic cross section which shows an example of the structure of a to-be-exposed board
- (a) shows a process flow
- (b) is a schematic cross section which shows an example of the structure of a to-be-exposed board
- it is a graph which shows the relationship between the mixing ratio of the organosilicon compound of General formula (1), and a contact angle at the time of using a short chain type organosilicon compound in addition to the organosilicon compound of General formula (1). is there.
- the water repellent composition for an exposed substrate of the present invention contains at least an organosilicon compound represented by the following general formula (1) and a solvent.
- the organosilicon compound represented by the general formula (1) preferably has no fluorine atom. This is because if it has fluorine atoms, defects are likely to occur in the application of the resist to the substrate to be processed after the water repellent treatment.
- R 1 , R 2 , R 3 , and R 4 being an organic group means that the terminal atom bonded to the silicon atom of the organic group is a carbon atom.
- a hydrolyzable group is a group or atom that reacts with water to form a hydroxyl group bonded to a silicon atom.
- a group (such as an alkoxy group) excluding a hydrogen atom of a hydroxyl group of a hydroxy compound (an alkoxy group, etc.), an acyl group, an amino group, an amino group
- An alkyl group, a chlorine atom, etc. are said.
- Preferred is an alkoxy group, and the organosilicon compound will be described below by taking an alkoxy group as an example.
- at least one of R 2, R 3, R 4 is a hydrolyzable group, preferably R 2, R 3, two or three of R 4 is a hydrolyzable group, R 2, R 3 and R 4 are particularly preferably hydrolyzable groups.
- R 1 is a monovalent organic group having 14 to 30 carbon atoms.
- the monovalent organic group is an organic group that does not contain a functional group that reduces water repellency, and preferably has no fluorine atom.
- a chain alkyl group is preferable. However, it may have an etheric oxygen atom between carbon atoms.
- the chain alkyl group may have a branch or may be a straight chain having no branch, but a straight chain is preferred. This is because the water repellency is more excellent. This is presumed to be because the straight chain forms a better water-repellent surface.
- the alkyl group is preferably an alkyl group represented by C n H 2n + 1 .
- n represents an integer of 1 or more.
- the number of carbon atoms in R 1 is preferably 14-30, more preferably 16-24. This is because within this range, the coating properties on the wafer are excellent.
- R 2 , R 3 and R 4 are organic groups
- the organic group is a monovalent organic group having 1 to 10 carbon atoms or a hydrolyzable group.
- At least one of R 2 , R 3 and R 4 is preferably an organic group, and examples of the organic group include aryl groups such as an alkyl group and a phenyl group. More preferred organic groups are alkyl groups having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.
- alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group, and a methyl group, an ethyl group, and a propyl group are preferable.
- a preferred hydrolyzable group for obtaining high water repellency is a group obtained by removing a hydrogen atom of a hydroxyl group of a hydroxy compound, and examples thereof include an alkoxy group, an alkoxy-substituted alkoxy group, and an aryloxy group.
- the carbon number is preferably 10 or less. More preferred hydrolyzable groups are alkoxy groups or alkoxy-substituted alkoxy groups, and their carbon number is preferably 5 or less, more preferably 3 or less.
- the hydrolyzable group undergoes hydrolysis to become a silanol group (hydroxyl group bonded to a silicon atom), and the silanol group reacts with a hydroxyl group (—OH) on the surface of the substrate to be processed, resulting in a siloxy bond (Si—O—Si).
- a silanol group hydroxyl group bonded to a silicon atom
- —OH hydroxyl group
- Si—O—Si siloxy bond
- Examples of the group excluding the hydrogen atom of the hydroxyl group of the hydroxy compound include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, an alkoxy-substituted alkoxy group such as a 2-methoxyethoxy group, a phenoxy group, and a naphthoxy group.
- An aryloxy group can be illustrated. Among them, an alkoxy group having 5 or less carbon atoms is preferable, and a methoxy group, an ethoxy group, and a propoxy group are particularly preferable.
- organosilicon compound examples include C 16 H 33 Si (OMe) 3 , C 18 H 37 Si (OMe) 3 , C 20 H 41 Si (OMe) 3 , C 24 H 49 Si (OMe) 3 , C 18 H 37 Si (OEt) 3 , C 18 H 37 Si (OPr) 3 , C 18 H 37 Si (OPh) 3 , C 18 H 37 Si (OMe) (OEt) 2 , C 18 H 37 Si (Me) (OMe) 2 etc. can be mentioned.
- organosilicon compounds may be used alone or in combination of two or more.
- the composition of the present invention may contain a short-chain organosilicon compound in addition to the organosilicon compound of the general formula (1).
- a surface having very high water repellency may repel a coating solution such as a resist composition. In such a case, the coatability is lowered and the adhesion is lowered.
- water repellency can be ensured by using a short chain type organosilicon compound together without lowering the adhesion.
- the short-chain organosilicon compound is an organosilicon compound in which R 1 is a monovalent organic group having 1 to 13 carbon atoms in the general formula (1).
- the carbon number of R 1 in the short chain organosilicon compound is particularly preferably 6-12.
- R 2 , R 3 and R 4 are the same as in the case of the specific organosilicon compound, and each independently represents a monovalent organic group having 1 to 10 carbon atoms or a hydrolyzable group, and R 2 , R 3 , at least one of R 4 is a hydrolyzable group.
- the hydrolyzable group is preferably an alkoxy group.
- R 2, R 3, preferably two or three of R 4 is a hydrolyzable group, and particularly preferably all the R 2, R 3, R 4 is a hydrolyzable group.
- the short-chain organic silicon compound C 12 H 25 Si (OMe) 3 or C 10 H 21 Si (OMe) 3 is preferable.
- the ratio is not particularly limited, but the molar ratio (the organosilicon compound of the general formula (1) / short chain) Type organosilicon compound), preferably 1/99 to 20/80, particularly preferably 1/99 to 10/90.
- the ratio of the short-chain type organosilicon compound exceeds 99 by molar ratio, it becomes difficult to ensure sufficient water repellency, and when the ratio of the short-chain type organosilicon compound is less than 80 by molar ratio, the adhesion is reduced. It is because it falls.
- the solvent used in the composition of the present invention preferably has a boiling point of 70 to 200 ° C. at 1 atmosphere. More preferably, the boiling point is 100 to 150 ° C. This is because the composition can be easily applied.
- ether solvents, ether alcohol solvents, ether ester solvents, alcohol solvents, ester solvents, ketone solvents, and amide solvents are preferable. More preferred are ether solvents, ether alcohol solvents, ether ester solvents, alcohol solvents, and ester solvents. This is because these solvents give chemically stable compositions. Furthermore, these solvents are highly soluble in an organosilicon compound and an acid, which will be described later, and are difficult to gel and are easy to apply. These solvents may be used alone or in combination of two or more.
- ether solvents examples include 1,4-dioxane, bis (2-ethylhexyl) ether, diisoamyl ether, ethylene glycol dimethyl ether, and propylene glycol dimethyl ether.
- ether alcohol solvent examples include ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether and the like.
- ether ester solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, 2-ethoxyethyl acetate, carbitol acetate, methyl 3-methoxypropionate and 3-ethoxypropionic acid. Examples thereof include ethyl and methyl ⁇ -methoxyisobutyrate.
- alcohol solvents examples include ethanol, 2-propanol, 1-butanol, 1-hexanol, 2-methyl-1-propanol, 4-methyl-2-pentanol, 2-octanol, and diacetone alcohol. .
- ester solvents include ethyl acetate, isoamyl acetate, ethyl butyrate, propyl butyrate, methyl lactate, ethyl lactate, and ⁇ -butyrolactone.
- ketone solvent examples include methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, N-methylpyrrolidone and the like.
- amide solvents include N, N-dimethylformamide and N, N-dimethylacetamide.
- the composition of the present invention may further comprise at least one auxiliary selected from the group consisting of acids and salts thereof, bases and salts thereof, and onium compounds. Since this auxiliary agent participates in the hydrolysis reaction of the organosilicon compound and the dehydration condensation reaction with the wafer surface, the water repellency and adhesion of the composition can be controlled by controlling the type and concentration.
- auxiliary agent it is preferable to use an acid, a salt thereof, a mixture thereof, or an onium compound, particularly an acid, a salt thereof, or a mixture thereof. This is because it is possible to impart further chemical stability and water repellency to the composition.
- a compound having an onium structure among salts and the like is distinguished as an onium compound.
- the acid may be a free acid or a salt thereof. In the case of a salt, an onium salt or an ammonium salt described later is preferable in order to reduce contamination in the semiconductor manufacturing process.
- the acid may be a mineral acid or an organic acid. Examples of the mineral acid include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and the like. Examples of the organic acid include carboxylic acid, sulfonic acid having an organic group, and phosphoric acid having an organic group. It is preferable to use an organic acid effective in reducing contamination in the semiconductor manufacturing process.
- carboxylic acid is particularly preferable. This is because carboxylic acid is excellent in the balance between the stability of the composition and the water repellency after coating.
- the carboxylic acid is preferably a carboxylic acid having 1 to 10 carbon atoms from the viewpoint of solubility of the acid in the composition and chemical stability of the composition.
- monocarboxylic acid or dicarboxylic acid is preferable, and monocarboxylic acid is more preferable from the viewpoint of chemical stability of the composition.
- the carboxylic acid has 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms.
- carboxylic acid examples include those having no substituent, those substituted with a halogen atom, and those substituted with a functional group such as a hydroxyl group.
- it is a monocarboxylic acid having no substituent represented by the general formula C m H 2m + 1 COOH (m is an integer of 1 to 10, and the alkyl chain may have a branch).
- the acid examples include acetic acid, propanoic acid, heptanoic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, lactic acid, trifluoroacetic acid, malonic acid, maleic acid and the like. These acids may be used alone or in combination of two or more.
- the base may be a free base or a salt thereof.
- a salt an onium salt described later is preferable in order to reduce contamination in the semiconductor manufacturing process.
- an organic base is more preferable, and an organic amine is more preferable.
- Specific examples of organic amines include primary amines such as methylamine, ethylamine and aniline, secondary amines such as dimethylamine and diethylamine, and tertiary amines such as triethylamine, triethanolamine and pyridine.
- An onium compound is a compound containing an element having a lone electron pair such as nitrogen and formed by coordination bonding of a cationic reagent or the like to the lone electron pair.
- the onium compound is preferably an ammonium compound or a phosphonium compound, more preferably an ammonium compound, from the viewpoint of the stability of the semiconductor manufacturing process.
- the onium compound may be onium hydroxide or onium salt.
- the onium salt a salt of the above-mentioned acid is preferable, and a carboxylate is particularly preferable.
- Examples of the onium hydroxide include tetramethylammonium hydroxide.
- Examples of only the cation portion of the onium salt suitable for use in the present invention include tetraalkylammonium ions such as tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, tetramethylphosphonium ion, tetraethylphosphonium ion, tetrabutyl Mention may be made of tetraalkylphosphonium ions such as phosphonium ions.
- ammonium salts suitable for use in the present invention include ammonium formate, ammonium acetate, ammonium trifluoroacetate, ammonium sulfate, and ammonium trifluoromethanesulfonate.
- Ammonium trifluoromethanesulfonate is particularly preferred because of the high chemical stability of the composition.
- the organosilicon compound of the general formula (1) has a low concentration, for example, 0.01 which is lower than 0.1% by mass, without reducing the water repellency and adhesion of the composition. It can be used at a concentration of about mass%.
- the composition of the present invention contains at least the above-mentioned organosilicon compound and the above-mentioned solvent, and further contains the above-mentioned auxiliary agent as necessary.
- the water content in the composition is 10 to 30,000 p of the total composition. A range of pm is preferable. If necessary, a solvent having a water content of 50 ppm or less by distillation or dehydration can be used.
- the ratio of the organosilicon compound in the composition is 0.01 to 6% by mass, preferably 0.1 to 5% by mass, more preferably 0.5 to 0.5%, based on 100% by mass of the entire composition. 3% by mass. This is because if it is within this range, gelation is difficult and water-repellent properties are excellent.
- the proportion of the auxiliary agent in the composition is preferably 0.0001 to 0.5% by mass, more preferably 0.001 to 0.2% by mass, when the entire composition is 100% by mass.
- the auxiliary agent is a free acid or a free base, it is preferably 0.01 to 0.5% by mass, more preferably 0.01 to 0.2% by mass.
- the auxiliary agent is an onium compound, the amount is preferably 0.0001 to 0.05% by mass, more preferably 0.003 to 0.01% by mass.
- an ammonium salt is used as an auxiliary agent, the amount is preferably 0.0001 to 0.05% by mass, more preferably 0.001 to 0.01% by mass.
- the ratio of the organosilicon compound to the auxiliary agent is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 1 part by mass of the organosilicon compound. This is because if it is within this range, gelation is difficult and water-repellent properties are excellent.
- the auxiliary is a free acid or a free base
- the auxiliary is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 1 part by mass of the organosilicon compound.
- the auxiliary is an onium compound
- the auxiliary is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 1 part by mass with respect to 1 part by mass of the organosilicon compound.
- the organosilicon compound and the auxiliary agent can be mixed in advance (one-pack type) or mixed immediately before wafer processing (two-pack type) to ensure storage stability. Therefore, it is preferable to mix immediately before the wafer processing.
- the organosilicon compound represented by the general formula (1) and the auxiliary agent can be prepared separately, but at least the organosilicon compound represented by the general formula (1) and the solvent.
- the liquid A and the liquid mixture when performing the water repellent treatment of the exposed substrate using the water repellent agent set for the exposed substrate, so as to have a predetermined mixing ratio immediately before use, that is, immediately before the wafer processing. It is preferable to mix and use the B liquid.
- the time range from mixing to use is preferably within 24 hours, more preferably from 0 minute to 1.5 hours, and even more preferably from 10 minutes to 1 hour.
- water can be added to the composition of the present invention as necessary in order to promote the hydrolysis reaction of the organosilicon compound.
- the composition of this invention can contain additives other than said adjuvant in the range which does not impair the effect of this invention.
- a surfactant, a leveling agent, a silane coupling agent, and the like can be given.
- the silane coupling agent in the organosilicon compound represented by the formula (1), a silane coupling agent having the same structure except that R 1 is a functional group-containing organic group, or in the formula (1), an organosilicon
- R 1 of the compound is a monovalent organic group having 1 to 13 carbon atoms.
- examples of the functional group-containing organic group include an amino group, a ureido group, an epoxy group, a sulfide group, a vinyl group, an acryloyloxy group, a methacryloyloxy group, and a mercapto group.
- the monovalent organic group having 1 to 13 carbon atoms has the same meaning as the organic group described for R 1 except for the number of carbon atoms.
- R 2 to R 4 have the same meaning as in general formula (1).
- surfactant examples include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.
- a silicone type surfactant, a polyalkylene oxide type surfactant, a fluorine-containing surfactant, etc. can be mentioned.
- leveling agents examples include acrylic leveling agents, vinyl leveling agents, silicone leveling agents, and fluorine leveling agents.
- the silane coupling agent is added to further improve the adhesion, and can be appropriately selected according to the purpose.
- functional groups of the silane coupling agent include amino groups, ureido groups, epoxy groups, sulfide groups, vinyl groups, acryloyloxy groups, methacryloyloxy groups, and mercapto groups.
- this silane coupling agent can be used for any of the above-described one-component type and two-component type, it is preferably used in a two-component type. In that case, it can be added in advance to the solution containing the organosilicon compound, or can be added when mixing the solution containing the organosilicon compound and the solution containing the auxiliary agent.
- the resist pattern forming method of the present invention is a resist pattern forming method by immersion exposure in which a liquid is interposed between a projection optical system of an exposure apparatus and a substrate, and is represented by at least the general formula (1). And a step of exposing a substrate to be exposed treated with the water repellent composition containing an organosilicon compound and a solvent.
- the photosensitive resist layer can be formed as a single layer or a multilayer resist layer. When forming a multilayer resist layer, it can be composed of at least three layers of a lower organic film layer, a silicon-containing intermediate layer, and a photosensitive resist layer.
- a substrate to be processed refers to a substrate having a wafer as a main body before forming a photosensitive resist layer and treated with the water repellent composition.
- a photosensitive resist layer is formed on the top surface of the substrate.
- the top surface of the substrate consists of the surface of the film to be processed and the silicon-containing intermediate layer as described above, and the side surface and the bottom surface consist of the surface of the wafer.
- the film to be processed formed under the fine processing resist film to form the resist pattern includes polysilicon, silicon oxide film, silicon nitride film, CVD-formed amorphous carbon film, or the like.
- a film on which an antireflection film whose lower layer is an inorganic layer is formed and an inorganic film such as a silicon-containing intermediate layer in a multilayer resist layer are included.
- water repellent / adhesion improving treatment is performed on a film to be processed made of an inorganic film.
- the water repellency / adhesion improving treatment (hereinafter referred to as water repellency treatment) is performed by applying the composition of the present invention to the side surface of the substrate, the peripheral portion of the top surface of the substrate, and / or the peripheral portion of the bottom surface of the substrate. It can carry out by apply
- the contact angle of the wafer with water can be 75 ° or more, more preferably 90 ° or more.
- by performing the water repellency treatment on the entire top surface it is possible to further improve the adhesion between the film to be processed and the resist film for microfabrication just above it.
- FIG. 1 shows an example in which the entire top surface of the substrate is water repellent.
- the coating apparatus includes a coating cup 21 that houses a substrate having the film 2 to be processed on the upper surface of the wafer 1, and a spin chuck that is rotatably supported at the center of the coating cup 21 and places the substrate.
- a chemical solution such as a water repellent supplied from the supply pipe 26 is discharged from the front end of the surface nozzle 25 that can move in the horizontal direction and the vertical direction to the film 2 to be processed on the substrate. Then, excess chemical liquid overflowing from the substrate is discharged from a waste liquid port provided on the bottom surface of the application cup 21.
- the composition of the present invention is paddled and a liquid film is formed, so that the entire top surface of the substrate is subjected to water repellent treatment.
- the rotation speed of the substrate is basically stationary (0 rpm), and the liquid can be stirred by giving a swing of 50 rpm at intervals of several seconds.
- the side surface of the substrate can also be subjected to water repellent treatment.
- the portion to be patterned of the resist film for microfabrication to be applied in a later step will be water repellent, so that the coating performance, development performance, and multilayer process dry development performance will be improved.
- it is limited to only the side surface of the substrate excluding the portion to be patterned, the peripheral edge portion of the top surface, and the peripheral edge portion of the bottom surface (hereinafter collectively referred to as “peripheral portion”).
- peripheral portion can be subjected to water repellency treatment.
- a method of locally processing the substrate outer peripheral portion by moving the surface nozzle 25 to the substrate outer peripheral portion can be used.
- the width of the water-repellent treatment region at the peripheral edge can be adjusted to about 0.3 mm to 3.0 mm from the substrate edge by controlling the position of the nozzle with high accuracy using a step motor.
- the peripheral edge of the bottom surface of the substrate can also be subjected to water repellency treatment by spraying the composition of the present invention from the back surface by using the back nozzle shown in FIG.
- the region that requires the water repellent treatment is a portion that generates a force for lifting water by capillary force, and is the outermost surface of the portion where the surface of the substrate edge is not horizontal. The greatest influence is on the side surface portion (bevel portion) of the substrate that is close to the outer peripheral frame of the stage, but it is desirable that the non-horizontal portion of the coating film on the inside is also water repellent. Therefore, the central portion of the substrate does not need to be water repellent, and a predetermined region on the outer peripheral portion of the substrate may be water repellent.
- FIG. 1 shows an example using a front nozzle
- FIG. 2 shows an example using a front nozzle and a back nozzle
- the bevel portion can be made water repellent using only the back nozzle. That is, the bottom surface of the substrate, the top surface of the peripheral portion, and the bevel portion are controlled by controlling the position of the back surface nozzle in FIG. Can be made water repellent.
- the water repellent since it is possible to make the water repellent locally only on the top and side surfaces of the bevel part, it is possible to suppress the coating property deterioration due to the repellency of the coating liquid itself such as a resist due to the expansion of the water repellent treatment surface. Is possible. Further, the risk of contamination can be reduced because the wetted area between the water repellent surface and the immersion liquid can be minimized.
- the water repellent treatment surface is used when a coating solution such as a resist is formed after the water repellent treatment.
- the liquid repelling can be used to simultaneously form a film on a non-water-repellent surface and perform edge cutting along the water-repellent surface (hereinafter referred to as self-alignment edge cutting). This eliminates the need for a separate edge cutting process using a thinner that dissolves a coating film such as a resist.
- the wafer is rarely shifted by several ⁇ m from the center of the wafer and the spin coating process is performed (referred to as eccentricity).
- the edge can be accurately cut along the water repellent surface by self-alignment edge cutting. If eccentricity occurs during normal edge cut processing, the water repellent portion and the edge cut portion may be misaligned, and the non-water repellent surface may be exposed on the substrate surface. A large number of resist pattern defects can be induced.
- the presence or absence of liquid repellency due to the water repellent treatment tends to occur when the water repellency after the water repellent treatment is high, but changes depending on the combination of the water repellent used and the solvent constituting the coating liquid such as resist. To do.
- the contact angle is 90 degrees or more. Tend to occur.
- the cut width of the self-alignment edge cut varies depending on the number of rotations of the coating liquid such as a resist.
- the width of the water repellent surface is X ⁇ m
- the width is (X ⁇ 10) ⁇ m to (X ⁇ 500) ⁇ m. It will be about.
- 10 to 500 ⁇ m a coating film is formed immediately above the water repellent treated surface, but the adhesion of this part is maintained by using the composition and the treatment method of the present invention.
- FIG. 3A is a plan view of the immersion type exposure apparatus.
- An immersion shower head 32 scans the substrate to be exposed 31 placed on the stage 30 in the direction of the arrow.
- the immersion shower head 32 is equipped with a lens 35, and pure water enters from the water inlet 34 and is discharged from the water inlet 33.
- FIG. 3B is a partially enlarged view of the immersion shower head 32 when the peripheral edge of the substrate 31 to be exposed is exposed.
- the two chips marked with ⁇ can be used as operating chips, but the four chips marked with x with a water film protruding outside the wafer are discarded as chip shots.
- Reference numeral 36 denotes a gap between the substrate 31 to be exposed and the outer peripheral frame of the stage 30, and the immersion liquid spilled from here contaminates the back surface of the substrate to be exposed and the exposure apparatus.
- the minimum value of the water-repellent region can be determined by the nozzle positioning accuracy (about 0.2 mm to 0.3 mm). .
- the maximum value can be set to such a value that the effective chips (circles) in the edge exposure shot are not reduced, as can be seen in the partially enlarged view of the exposed substrate edge in FIG.
- the edge removal width of the resist may reach up to about 3.0 mm. In that case, even if water repellent treatment is performed up to 3.0 mm, the product yield is not affected. Therefore, the maximum removal width when the nozzle is used can be used as a value that does not reduce the number of effective chips.
- the hot plate heat The heat treatment can be performed at a temperature of 60 ° C. to 180 ° C. for about 1 minute.
- the invention is illustrated in detail by the following examples.
- the organosilicon compound, acid and solvent shown in Table 1 were mixed at the ratio shown in Table 1.
- concentration is a density
- the column labeled as the amount of water added in the table is the proportion of water added (unit: mass%) when a predetermined amount of water is added to form a composition.
- the mixing ratio in the column of the organosilicon compound indicates a molar ratio.
- the moisture content in the table is the moisture content (unit:%) measured by mixing the solvent and the acid at the same ratio as the composition in the table, and is the so-called brought-in moisture content.
- a Karl Fischer moisture meter MKC-500 manufactured by Kyoto Electronics Industry Co., Ltd. was used. About 0.3 mL (separately weighed) of a sample in which a solvent and an acid were mixed was measured by a coulometric titration method.
- PGME propylene glycol monomethyl ether
- PGMEA propylene glycol monomethyl ether acetate
- IPA 2-propanol HMDS: hexamethyldisilazane
- TMAH tetramethylammonium hydroxide
- TMAA tetramethylammonium acetate
- TFAA trifluoroacetic acid
- AA ammonium acetate
- AF formic acid
- Ammonium ATS ammonium trifluoromethanesulfonate
- TMAH an aqueous solution having a content of 2.38% by mass was used, and the concentration of the aqueous solution was described as the concentration.
- the number after the solvent abbreviation is the mixing ratio (mass ratio). After mixing, the mixture was filtered using a PTFE filter having a nominal value of 0.5 ⁇ m to prepare compositions 1 to 43 and comparative compositions 2 to 7.
- Processing method is as follows. About 0.25 mL of the composition was used for a silicon wafer cut into 4 cm square. Spin coating was performed at 300 rpm for 30 seconds and 3000 rpm for 60 seconds. This was baked for 60 seconds using a 150 ° C. hot plate. The substrate which processed the surface by the above operation was obtained.
- HMDS treatment of Comparative 1 used a substrate obtained by treating a silicon wafer by leaving it at 90 ° C. for 40 seconds in an HMDS atmosphere.
- a contact angle of 75 degrees or more could be obtained. Further, it is preferable that the sliding angle is small and the receding contact angle is large.
- the silicon wafer is fixed to the SUS pin using an adhesive, and after curing all day and night, after spraying pure water onto the bonded portion and leaving it to stand for 60 seconds, the SUS pin is pulled on the vertical line and then the silicon wafer. And topcoat adhesion were measured. The measurement results are shown in Table 7, and it was confirmed that the adhesion strength of the composition 11 was about 8 times that of HMDS (Comparative 1).
- compositions 32 and 37 were spin-coated on the surface of a silicon wafer cut into 4 cm square.
- the set temperature of the hot plate was changed and baked for 60 seconds each.
- the contact angle, falling angle, and backward falling angle were measured in the same manner as in Experimental Examples 1 to 33.
- compositions 32 and 36 to 39 were spin-coated on the surface of a silicon wafer cut into 4 cm square.
- the baking conditions were 110 ° C. and 60 seconds.
- the contact angle, falling angle, and backward falling angle were measured in the same manner as in Experimental Examples 1 to 33.
- concentration of the organosilicon compound is reduced, it is considered that a structure like a monomolecular film suitable for expressing water repellency is formed on the surface.
- compositions 32 and 40 to 43 were spin-coated on the surface of a silicon wafer cut into 4 cm square.
- the baking conditions were 110 ° C. and 60 seconds.
- the contact angle was measured in the same manner as in Experimental Examples 1 to 33.
- Example 1 A semiconductor device was manufactured according to the process flow shown in FIG. FIG. 5B shows an example of the structure of the outer peripheral portion of the substrate to be exposed after the water repellent treatment, and shows a state during immersion exposure.
- a film 2 to be processed was formed on the wafer 1, and then the composition 11 was sprayed by a front nozzle in the top direction and a back nozzle in the bottom direction during rotation at 300 to 2000 rpm by the method shown in FIG. Thereby, the water-repellent treatment layer 3 was formed on the peripheral edge of the top surface of the substrate, the side surface of the substrate, and the peripheral edge of the bottom surface of the substrate.
- the wafer was conveyed from the spinner cup and it heated at 150 degreeC on the hot plate for 60 seconds.
- the adsorption amount of the composition 11 was controlled, and the water repellency and adhesion strength could be adjusted.
- a methacrylate-based ArF chemically amplified positive resist (film thickness: 100 nm to 200 nm) was spin-coated, followed by baking at 105 ° C. for 60 seconds to form a photosensitive resist layer 4.
- baking was performed at 110 ° C. for 60 seconds to form the topcoat layer 5.
- Example 2 In this example, a semiconductor device was manufactured according to the process flow shown in FIG.
- FIG. 6B shows an example of the structure of the outer peripheral portion of the substrate to be exposed after the water repellent treatment, and shows a state during immersion exposure.
- a water repellency treatment was performed in the same manner as in Example 1 except that the surface nozzle was moved and the composition 11 was sprayed onto the entire top surface of the substrate.
- the water-repellent treatment layer 3 was formed on the entire top surface of the substrate, the side surface of the substrate, and the peripheral edge of the bottom surface of the substrate.
- a photosensitive resist layer 4 was formed in the same manner as in Example 1. Next, after spin-coating the topcoat coating solution, baking was performed at 110 ° C. for 60 seconds to form the topcoat layer 5.
- the immersion liquid 11 was not spilled between the stage 10 and the exposed substrate as shown in FIG. No detachment from the exposed substrate edge due to convection of 11 or the like was observed. Thereafter, development processing was performed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to complete pattern formation.
- the film to be processed was plasma dry etched. The film to be processed was performed on polysilicon in the transistor formation process. In any case, after the etching was completed, the resist and the lower organic film layer were removed by O 2 plasma ashing and wet treatment with sulfuric acid and hydrogen peroxide.
- the previously formed water repellent layer was peeled off.
- a silicon oxide film in the contact process was formed, and this example was repeated using the surface as an irradiated surface to complete pattern formation in the contact process.
- the metal process and via process were repeated to complete the semiconductor device.
- the water repellent treatment is performed on the entire top surface of the substrate, the adhesion between the film to be processed and the photosensitive resist layer can be further improved, thereby further reducing the collapse of the resist pattern. Can be suppressed.
- Example 3 In this example, a semiconductor device was manufactured according to the process flow shown in FIG.
- FIG. 7B shows an example of the structure of the outer peripheral portion of the substrate to be exposed after the water repellent treatment, and shows a state during immersion exposure.
- a film 2 to be processed is formed on the wafer 1, and then a lower organic film coating solution is applied to a thickness of about 150 nm to 300 nm, followed by heat curing at 200 ° C. to 250 ° C. for about 1 minute to 1.5 minutes.
- the solvent was sufficiently volatilized and the polymer was cross-linked by the reaction of the thermal reaction active site to form the lower organic film layer 6.
- a silesquioxane-based polymer derivative such as inorganic SOG or organic SOG is spin-coated with a film thickness of about 80 nm, and a dehydration condensation reaction is performed by heat treatment at 200 to 250 ° C. for about 1 to 1.5 minutes.
- the silicon-containing intermediate layer 7 was formed by crosslinking by reacting reactive active sites such as epoxy functional groups.
- the water repellency treatment was performed in the same manner as in Example 1 except that the rotation speed was set to 1000 rpm in the method shown in FIG. Thereby, the water-repellent treatment layer 3 was formed on the peripheral edge of the top surface of the substrate, the side surface of the substrate, and the peripheral edge of the bottom surface of the substrate.
- a photosensitive resist layer 4 was formed in the same manner as in Example 1. Next, after spin-coating the topcoat coating solution, baking was performed at 110 ° C. for 60 seconds to form the topcoat layer 5.
- Example 4 a semiconductor device was manufactured according to the process flow shown in FIG.
- FIG. 8B shows an example of the structure of the outer peripheral portion of the substrate to be exposed after the water repellent treatment, and shows a state during immersion exposure.
- the lower organic film layer 6 and the silicon-containing intermediate layer 7 were formed by the same method as in Example 3.
- water repellency treatment was performed in the same manner as in Example 2.
- the water-repellent treatment layer 3 was formed on the entire top surface of the substrate, the side surface of the substrate, and the peripheral edge of the bottom surface of the substrate.
- a photosensitive resist layer 4 was formed in the same manner as in Example 1. Next, after spin-coating the topcoat coating solution, baking was performed at 110 ° C. for 60 seconds to form the topcoat layer 5.
- the previously formed water repellent layer was peeled off.
- a silicon oxide film in the contact process was formed, and this example was repeated using the surface as an irradiated surface to complete pattern formation in the contact process.
- the metal process and via process were repeated to complete the semiconductor device.
- the water repellent treatment is performed on the entire top surface of the substrate, the adhesion between the film to be processed and the photosensitive resist layer can be further improved, thereby further reducing the collapse of the resist pattern. Can be suppressed.
- Example 5 FIG. Using the composition 11 of Table 1, a semiconductor device was manufactured according to the process flow shown in FIG. FIG. 9B shows an example of the structure of the outer peripheral portion of the substrate to be exposed after the water repellent treatment, and shows a state during immersion exposure.
- a film 2 to be processed is formed on the wafer 1, and then a lower organic film layer 6 and a silicon-containing intermediate layer 7 are formed by the same method as in Example 3.
- a methacrylate-based ArF chemically amplified positive resist (thickness 100 nm) ( ⁇ 200 nm) was applied by spin coating.
- the composition 11 was sprayed from the top nozzle in the top direction and from the back nozzle in the bottom direction.
- the step of forming the water repellent treatment layer 3 on the top peripheral edge of the substrate, the side surface of the substrate, and the bottom peripheral edge of the substrate was simultaneously performed while performing edge cutting of the resist.
- a baking process resist post-bake
- the jetting time of the composition 11 from the nozzle and the rotation speed of the substrate the adsorption amount of the composition 11 was controlled, and the water repellency and adhesion strength could be adjusted.
- top coat coating solution was applied by spin coating, followed by baking at 110 ° C. for 60 seconds to form a top coat layer 5.
- the resist edge is cut using the water repellent composition, but the resist can be cut using a general thinner.
- the water repellent treatment layer 3 can be formed by the method shown in FIG.
- the water-repellent treatment layer was formed before the resist post-baking, but this treatment layer formation may be before or after the resist post-baking, and the reaction with the substrate at the resist post-baking or at room temperature.
- additional heat treatment can be performed within a range that does not adversely affect the resist.
- a wafer can be conveyed from a spinner cup and heated on a hot plate at 150 ° C. for 60 seconds.
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Abstract
Description
本発明の被露光基板用撥水化剤組成物は、少なくとも下記一般式(1)で示される有機ケイ素化合物と溶剤とを含むものである。
上記一般式(1)で示される有機ケイ素化合物は、フッ素原子を有しないものが好ましい。フッ素原子を有していると、撥水処理した後の被加工基板へのレジストの塗工において欠陥が発生しやすくなるからである。
R1、R2、R3、R4が有機基であるとは、有機基のケイ素原子と結合する末端原子が炭素原子であることをいう。加水分解性基とは、水と反応してケイ素原子に結合した水酸基を生じる基や原子をいい、ヒドロキシ化合物の水酸基の水素原子を除いた基(アルコキシ基など)、アシル基、アミノ基、アミノアルキル基、塩素原子などをいう。好ましくはアルコキシ基であり、以下アルコキシ基を例として有機ケイ素化合物を説明する。また、R2、R3、R4の少なくとも1つは加水分解性基であり、R2、R3、R4の2つまたは3つが加水分解性基であることが好ましく、R2、R3、R4のすべてが加水分解性基であることが特に好ましい。
本発明の組成物に用いる溶剤としては、1気圧での沸点が70~200℃であることが好ましい。さらに好ましくは沸点が100~150℃である。組成物の塗工がし易いからである。溶剤には、エーテル系溶剤、エーテルアルコール系溶剤、エーテルエステル系溶剤、アルコール系溶剤、エステル系溶剤、ケトン系溶剤及びアミド系溶剤が好ましい。より好ましくは、エーテル系溶剤、エーテルアルコール系溶剤、エーテルエステル系溶剤、アルコール系溶剤、エステル系溶剤である。これらの溶剤は化学的に安定な組成物を与えるからである。さらに、これらの溶剤は有機ケイ素化合物と後述の助剤である酸に対する溶解性が大きく、かつゲル化しにくく、また塗工がし易い。なお、これら溶剤は1種のみを用いても2種以上を併用してもよい。
本発明の組成物は、さらに、酸及びその塩、塩基及びその塩、そしてオニウム化合物からなる群から選択された少なくとも1種の助剤を含むことができる。この助剤は有機ケイ素化合物の加水分解反応やウェハ表面との脱水縮合反応に関与するため、その種類や濃度を制御することにより、組成物の撥水能や密着能を制御することができる。助剤には、酸、その塩、それらの混合物、またはオニウム化合物、特に酸、その塩、またはそれらの混合物を用いることが好ましい。組成物に対し一層の化学的安定性と撥水能を付与することができるからである。なお、本発明においては、塩などのうちオニウムの構造を有する化合物はオニウム化合物として区別する。
pmの範囲とすることが好ましい。また、必要に応じて、蒸留処理や脱水処理により水分量を50ppm以下とした溶剤を用いることもできる。
本発明のレジストパターン形成方法は、露光装置の投影光学系と基板との間に液体を介在させて露光を行う液浸露光によるレジストパターン形成方法であって、少なくとも上記一般式(1)で示される有機ケイ素化合物と溶剤とを含む前記撥水化剤組成物で処理した被露光基板を露光する工程を含むものである。例えば、ウェハ上に被加工膜を製膜する工程と、本発明の組成物を用いて撥水化・密着性向上処理を行う工程と、微細加工用の感光性レジスト層を塗布する工程と、感光性レジスト層を保護するためのトップコート層を塗布する工程と、液浸露光を行う工程と、感光性レジストの現像を行う工程と、膜エッチングを行う工程と、残膜を除去する工程とで構成することができる。また、感光性レジスト層は単層又は多層レジスト層として形成することができる。多層レジスト層を形成する場合、少なくとも、下層有機膜層、シリコン含有中間層、そして感光性レジスト層の3層で構成することができる。また、多層レジスト層を形成する場合、下層有機層とシリコン含有中間層を形成した後、撥水化・密着性向上処理を行う工程を行うことが好ましい。本発明において被加工基板(単に基板ともいう)とは、ウェハを本体とする、感光性レジスト層を形成する前のものであって、前記撥水化剤組成物で処理されるものをいう。感光性レジスト層はこの基板の天面に形成される。通常、基板天面は上記のように被加工膜、シリコン含有中間層などの表面からなり、側面や底面はウェハの表面からなる。
撥水化・密着性向上処理(以下、撥水化処理と言う。)は、本発明の組成物を、基板の側面と、基板の天面の周縁部及び/又は基板の底面の周縁部とに塗布することにより行うことができる。あるいは、基板の側面と、基板の天面全面と、基板の底面の周縁部とに塗布することにより行うことができる。本発明の組成物を用いた撥水化処理により、ウェハの水との接触角は75度以上、より好ましくは90度以上を得ることができる。なお、天面全面に撥水化処理を行うことにより、被加工膜とその直上の微細加工用レジスト膜との密着性をさらに向上させることができる。
(組成物の調製)
表1に示す有機ケイ素化合物、酸および溶剤を表1に示した割合で混合した。濃度は組成物全体を100質量%とした場合の濃度(単位:質量%)である。有機ケイ素化合物と酸以外は溶剤である。ただし表中で水添加量と表示した欄は、水を所定量添加して組成物とした際の添加した水の割合(単位:質量%)である。また有機ケイ素化合物の欄の混合割合はモル比を示す。
PGME:プロピレングリコールモノメチルエーテル
PGMEA:プロピレングリコールモノメチルエーテルアセテート
IPA:2-プロパノール
HMDS:ヘキサメチルジシラザン
TMAH:テトラメチルアンモニウムヒドロキシド
TMAA:テトラメチルアンモニウム酢酸塩
TFAA:トリフルオロ酢酸
AA:酢酸アンモニウム
AF:ギ酸アンモニウム
ATS:トリフルオロメタンスルホン酸アンモニウム
但し、TMAHについては含有量が2.38質量%の水溶液を用い、水溶液の濃度を濃度として記載した。また溶剤の略号の後ろの数字は混合比(質量比)である。混合後、公称0.5μmのPTFE製フィルターを用いてろ過を行い、組成物1~43、比較組成物2~7を調製した。
組成物1~9、19~35、比較組成物1~7を用いて撥水性の評価を行った。評価としては接触角(単位:度)、転落角(単位:度)、後退接触角(単位:度)を測定した。測定には協和界面科学社製接触角計DM-700を使用した。また、使用した水滴の体積は、接触角は2μLであり、転落角および後退角は50μLである。
酸添加量が貯蔵安定性に与える影響を確認した。組成物10~14、26~27、32~33について、目視および接触角により評価した。調製直後の液は無色透明であった。その後室温にて、9日間保管し安定性を確認した。安定性が悪くなるとゲル化が起こり液は白濁した。白濁した液は表中に白濁と記載した。また目視で異常のないものは接触角を測定した。表中の数字は接触角である。接触角の測定は実験例1~33の場合と同様である。組成物32、33については、21日後においても白濁は認められず、接触角の変化もほとんど見られなかった。
有機ケイ素化合物の濃度の影響を確認した。組成物15~18を用いた。接触角、転落角、後退転落角については実験例1~33の場合と同様にして測定した。
組成物を調製してから塗布するまでの経過時間が撥水性に与える影響を確認した。組成物11について、所定時間経過後に塗布したサンプルの接触角により評価した。表中の数字は接触角である。接触角の測定は実験例1~33の場合と同様にして行った。
実験例1~33の場合と同様にして、組成物11、比較組成物2を用いて、4cm角に切断したシリコンウェハの表面を処理した撥水処理ウェハを得た。ついで同撥水処理ウェハ上に、反射防止膜(BARC)として日産化学製の2ndミニマム有機ARCのARC29、ArFに感光性を持つ化学増幅レジスト、液浸用トップコート、をそれぞれスピンコートし、さらに150℃のホットプレートを用いて60秒間ベークした。以上の操作により表面処理基板上の塗布性を目視で確認した。表中における塗布性の評価は、塗布のできない箇所(欠陥)の有無及び程度で評価した。すなわち、Aは欠陥が見られず良好な塗布性を示したことを、Bは表面処理基板の一部に塗布欠陥が認められたことを、Cは表面処理基板のほぼ全面に欠陥が発生し均一な塗布ができなかったことを表す。
実験例1~33の場合と同様にして、組成物11及びHMDSを用いて、4cm角に切断したシリコンウェハの表面を処理した撥水処理ウェハを得た。ついで同撥水処理ウェハ上に、液浸用トップコートをスピンコートし、110℃のホットプレートを用いて60秒間ベークした。前記処理したシリコンウェハのトップコート表面に、直径3mmのステンレス鋼(SUS304)製ピンを、シアノアクリレート系接着剤(商品名:アロンアルファ、東亞合成製)を用いて接着し、一昼夜硬化反応を進行させた。その後、図4に示すように、シリコンウェハをSUSピンに接着剤を用いて固定し、一昼夜硬化後、純水を接着部分に吹き付けて60秒放置した後、SUSピンを鉛直線上に引っ張りシリコンウェハとトップコートの密着性を測定した。測定結果を表7に示すが、組成物11の密着強度はHMDS(比較1)に比べて約8倍の強度を有していることを確認した。
実験例1~33の場合と同様にして、4cm角に切断したシリコンウェハの表面に、組成物32及び37をスピンコートした。ホットプレートの設定温度を変え、それぞれ60秒間ベークした。接触角、転落角、後退転落角については実験例1~33の場合と同様にして測定した。
実験例1~33の場合と同様にして、4cm角に切断したシリコンウェハの表面に、組成物32、36~39をスピンコートした。ベーク条件は110℃で60秒とした。接触角、転落角、後退転落角については実験例1~33の場合と同様にして測定した。有機ケイ素化合物の濃度を薄くした場合には、表面に撥水性を発現するのに適当な単分子膜のような構造が形成されていると考えられる。また濃度を上げた場合には、積層されるが、加熱により有機ケイ素化合物どうしの縮合によりオリゴマー化が進行する、もしくは、積層された余剰な有機ケイ素化合物が揮発し、撥水基が表面に現れることにより、適当な撥水性が発現していると考えられる。
実験例1~33の場合と同様にして、4cm角に切断したシリコンウェハの表面に、組成物32、40~43をスピンコートした。ベーク条件は110℃で60秒とした。接触角については実験例1~33の場合と同様にして測定した。
表1の組成物11を用い、図5(a)に示すプロセスフローに従い半導体デバイスを製造した。図5(b)は、撥水化処理後の被露光基板外周部の構造の一例であって液浸露光時の状態を示す。
本実施例は、表1の組成物11を用い、図6(a)に示すプロセスフローに従い半導体デバイスを製造した。図6(b)は、撥水化処理後の被露光基板外周部の構造の一例であって液浸露光時の状態を示す。
本実施例は、表1の組成物11を用い、図7(a)に示すプロセスフローに従い半導体デバイスを製造した。図7(b)は、撥水化処理後の被露光基板外周部の構造の一例であって液浸露光時の状態を示す。
本実施例は、表1の組成物11を用い、図8(a)に示すプロセスフローに従い半導体デバイスを製造した。図8(b)は、撥水化処理後の被露光基板外周部の構造の一例であって液浸露光時の状態を示す。
表1の組成物11を用い、図9(a)に示すプロセスフローに従い半導体デバイスを製造した。図9(b)は、撥水化処理後の被露光基板外周部の構造の一例であって液浸露光時の状態を示す。
Claims (14)
- 少なくとも下記一般式(1)で示される有機ケイ素化合物と溶剤とを含む被露光基板用撥水化剤組成物。
- さらに、酸及びその塩、塩基及びその塩、そしてオニウム化合物からなる群から選択された少なくとも1種の助剤を含む請求項1に記載の被露光基板用撥水化剤組成物。
- 前記酸が、炭素数1~10のカルボン酸である請求項2に記載の被露光基板用撥水化剤組成物。
- 前記溶剤の沸点が、70~200℃である請求項1記載の被露光基板用撥水化剤組成物。
- 組成物中の前記有機ケイ素化合物の割合が0.01~6質量%である請求項1記載の被露光基板用撥水化剤組成物。
- 前記の組成物により基板の側面と、基板の天面の周縁部及び/又は基板の底面の周縁部とを処理する請求項6に記載のレジストパターンの形成方法。
- 前記の組成物により、基板の側面と、基板の天面全面と、基板の底面の周縁部とを処理する請求項6に記載のレジストパターンの形成方法。
- 請求項6から8のいずれか一つに記載のレジストパターンの形成方法により製造した電子デバイス。
- 請求項11記載の被露光基板用撥水化剤セットを用い、使用直前にA液とB液とを混合する被露光基板の撥水化処理方法。
- 組成物中の前記有機ケイ素化合物の割合が0.1~5質量%である請求項1記載の被露光基板用撥水化剤組成物。
- 上記助剤が、トリフルオロメタンスルホン酸アンモニウムを含む請求項2に記載の被露光基板用撥水化剤組成物。
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US12/867,670 US8178983B2 (en) | 2008-02-22 | 2009-02-20 | Water repellant composition for substrate to be exposed, method for forming resist pattern, electronic device produced by the formation method, treatment method for imparting water repellency to substrate to be exposed, water repellant set for substrate to be exposed, and treatment method for imparting water repellency to substrate to be exposed using the same |
EP09713242A EP2246876A4 (en) | 2008-02-22 | 2009-02-20 | WATER REPELLENT COMPOSITION FOR ONE TOO EXPONIERENDES SUBSTRATE, METHOD FOR PRODUCING A RESIST STRUCTURE, ON THE BASIS OF THE PRODUCTION PROCESS PRODUCED ELECTRONIC DEVICE, METHOD FOR AWARDING OF WATER REPELLENT EFFECT FOR ONE TOO EXPONIERENDES SUBSTRATE, HYDROPHOBIC SET FOR TOO EXPONIERENDES SUBSTRATE AND METHOD FOR AWARDING OF WATER REPELLENT EFFECT THAT FOR A SUBSTRATE TO BE EXPOSED |
JP2009554402A JP4897056B2 (ja) | 2008-02-22 | 2009-02-20 | 被露光基板用撥水化剤組成物、レジストパターンの形成方法及び該形成方法を用いた電子デバイスの製造方法、被露光基板の撥水化処理方法、被露光基板用撥水化剤セット及びそれを用いた被露光基板の撥水化処理方法 |
CN200980114703.4A CN102027570B (zh) | 2008-02-22 | 2009-02-20 | 被曝光基板用防水剂组合物以及抗蚀图形的形成方法 |
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JP2020013932A (ja) * | 2018-07-19 | 2020-01-23 | 東京エレクトロン株式会社 | 基板処理装置および基板処理方法 |
JP7137986B2 (ja) | 2018-07-19 | 2022-09-15 | 東京エレクトロン株式会社 | 基板処理装置および基板処理方法 |
US20220020582A1 (en) * | 2018-11-22 | 2022-01-20 | Central Glass Company, Limited | Bevel portion treatment agent composition and method of manufacturing wafer |
US11817310B2 (en) * | 2018-11-22 | 2023-11-14 | Central Glass Company, Limited | Bevel portion treatment agent composition and method of manufacturing wafer |
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KR20100121523A (ko) | 2010-11-17 |
CN102027570A (zh) | 2011-04-20 |
JPWO2009104748A1 (ja) | 2011-06-23 |
CN102027570B (zh) | 2013-04-24 |
JP4897056B2 (ja) | 2012-03-14 |
EP2246876A4 (en) | 2012-07-04 |
TW200944943A (en) | 2009-11-01 |
US20110221077A1 (en) | 2011-09-15 |
US8178983B2 (en) | 2012-05-15 |
EP2246876A1 (en) | 2010-11-03 |
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