Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • 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
• • 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
  • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
• • 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
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
  • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
  • H01L21/3105—After-treatment
  • H01L21/311—Etching the insulating layers by chemical or physical means
  • H01L21/31127—Etching organic layers
  • H01L21/31133—Etching organic layers by chemical means
  • H01L21/31138—Etching organic layers by chemical means by dry-etching
• • 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
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
  • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
  • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
  • H01L21/321—After treatment
  • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
  • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
  • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
  • H01L21/32136—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas
  • H01L21/32137—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas of silicon-containing layers
• • 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
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
  • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
  • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
  • H01L21/321—After treatment
  • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
  • H01L21/32139—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer using masks
• • 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
  • H01L21/0276—Photolithographic processes using an anti-reflective coating

Definitions

• the present invention relates to a pattern forming method, and particularly relates to a method for forming an antireflection film made of an organic material on an etching target film on a semiconductor substrate.
• the present invention relates to a method of forming a pattern made of a film to be etched by performing etching.
• an organic antireflection film for absorbing an energy beam is provided under the photosensitive material film, and the energy beam that has passed through the photosensitive material film is absorbed by the antireflection film. After the energy beam has passed through the photosensitive material film A method for preventing a situation in which light is reflected in a non-uniform direction has been proposed.
• an antireflection film 3 made of an organic material and absorbing an energy beam is formed on an etching target film 2 deposited on a semiconductor substrate 1. Further, a photosensitive material film is formed on 3. Next, after irradiating the photosensitive material film with an energy beam through a mask, the irradiated or unirradiated portion of the photosensitive material film is removed with a developing solution, and the photosensitive material film is formed of an unirradiated portion or an irradiated portion. A patterned photosensitive material film 4 is formed.
• the energy beam passing through the photosensitive material film 4 is absorbed by the anti-reflection film 3, so that even if the semiconductor substrate 1 or the film to be etched 2 has a stepped shape, it is not uniform. Since there is no reflection and the unirradiated portion of the energy beam is not exposed, the etched film pattern 2A with high dimensional accuracy is formed.
• a chemically amplified resist material is often used as the photosensitive material film.
• a chemically amplified resist material is used as the photosensitive material film, and a chemically amplified resist material is used.
• the protective material was provided on the anti-reflection film, it was found that a reaction product 5 was formed on the interface between the anti-reflection film 3 and the photosensitive material film 4, as shown in Fig. 3 (a). .
• This reaction product 5 When the photosensitive material film 4 and the anti-reflection film 3 are processed under the conventional developing conditions or etching conditions, they remain on the etching film 2 without being removed.
• the reaction product 5 remaining on the film 2 to be etched serves as an etching mask, and as shown in FIG. 3 (b).
• a residue 6 consisting of the film 2 to be etched is formed in a region (space region) to be etched away, or the pattern sidewall 2a of the film 2 to be etched is required to have a vertical shape. Or other problems.
• the residue 6 is uniformly generated without being affected by the pattern aperture ratio of the photosensitive material film 4, that is, regardless of the density of the pattern. Therefore, the residue 6 is also generated in the space between the patterns in the region where the patterns are dense.
• dry etching is performed under conditions that can remove the reaction product. It is conceivable to remove the reaction product together.However, the method of removing the reaction product 5 together with the antireflection film 3 by dry etching the antireflection film 3 is as follows. It is not an effective means for forming a pattern. That is, in order to remove the reaction product 5, stronger etching conditions are required than when the anti-reflection film 3 is removed, and if an etching condition that can remove the reaction product is selected, the anti-reflection film 3 is removed.
• the patterned photosensitive material film 4 having similar etching characteristics is also etched at the same time, so that a resist pattern with good dimensional accuracy does not remain. For this reason, the patterned photosensitive material film 4 does not function as a mask.
• dry etching is performed on the antireflection film 3 by using etching conditions such that the patterned photosensitive material film 4 is not removed as much as possible by dry etching. When etching is performed, a large amount of the reaction product 5 and the antireflection coating 3 remain on the film to be etched 2.
• the film is peeled off from the side wall of the anti-reflection film 3.
• the deposited material tends to adhere to the film 2 to be etched, and the deposited material serves as a mask to form a residue 6 made of the film to be etched.
• FIG. 4 is an enlarged view of a region indicated by a dashed line in FIG. 3 (b).
• a gate electrode 7 made of a polysilicon film which is a film to be etched is formed on a semiconductor substrate 1, and a region between the gate electrodes 7 in the semiconductor substrate 1, that is, a source Residue 6 consisting of a polysilicon film exists in the drain region.
• a side wall 8 made of an insulating material such as Si 3 N 4 , TE ⁇ S or HT ⁇ is formed on the side surface of the gate electrode 7, and the side wall 8 is formed to reduce the resistance of the integrated circuit element.
• the surfaces of the gate electrode 7 and the source / drain region are silicided by TiSi 2 or the like, and are covered with a silicide layer 9.
• the side surface shape of the gate electrode 7 is not uniform, the gate electrode 7 is exposed from the side wall 8, and the silicide layer 9 is also formed in a region of the gate electrode 7 exposed from the side wall 8.
• a silicide layer 9 is also formed on the surface of the polysilicon residue 6. Therefore, the gate electrode 7 is electrically connected to the source / drain region via the silicide layer 9 on the surface of the gate electrode 7 or the silicide layer 9 on the surface of the residue 6, and the gate electrode 7 is connected to the source / drain region.
• An abnormal leakage current flows between the drain region One.
• the film to be etched 2 is made of a conductive material such as, for example, polysilicon
• the wiring patterns formed on the same conductive layer are connected via the conductive residue 6.
• a conductive layer formed on the semiconductor substrate 1 and a wiring pattern formed on the conductive layer via an inter-layer insulating film via an electrically conductive residue 6 Due to the electrical connection, a leak current flows between the wiring patterns or between the conductive layer and the wiring pattern, which causes a problem that the characteristics of the semiconductor integrated circuit device are deteriorated or the yield is reduced. appear.
• chemically amplified resist compositions include (a) an organic substance having a substituent which can be released by an acid and (b) a compound which generates an acid upon irradiation with a radiation (b) comprising an onium salt compound.
• a chemically amplified resist material containing an acid generator is known.
• the onium salt compound has a strong effect of inhibiting the dissolution of the resist film, thereby reducing the solubility of the unexposed portion of the photosensitive material in the developing solution, and generating a relatively strong acid upon exposure.
• An object of the present invention is to provide a method for forming a pattern free of the above-mentioned drawbacks.
• a first object of the present invention is to provide a method for forming a film between a film to be etched and a photosensitive material film. Despite the presence of an anti-reflection film made of an organic material, the reaction product is prevented from being generated at the interface between the anti-reflection film and the photosensitive material film, thereby forming the film to be etched.
• An object of the present invention is to provide a pattern formation method in which the number of residues is reduced.
• a second object of the present invention is to form a high-resolution resist image with good dimensional accuracy without formation of a standing wave or T-top, thereby forming a high-quality etching film pattern. To provide a way.
• a third object of the present invention is to provide an anti-reflection film without affecting a patterned photosensitive material film even when a reaction product is generated at the interface between the anti-reflection film and the photosensitive material film.
• An object of the present invention is to provide a pattern forming method in which a reaction product is removed together with an anti-reflection film during etching, whereby the number of residues formed of the film to be etched is reduced. Disclosure of the invention
• both the anti-reflection film and the photosensitive material film are made of organic materials
• light such as ultraviolet rays, far ultraviolet rays, or an energy beam composed of an electron beam or X-rays
• Radicals are generated inside the anti-reflection film and the photosensitive material film, respectively, and the radicals react with each other at the interface between the anti-reflection film and the photosensitive material film, thereby generating an aromatic reaction product.
• the photosensitive material film contains an oxidized salt-based acid generator
• aromatization occurs at the interface between the antireflection film and the photosensitive material film. It was found that more reactive products were produced.
• the pattern forming method according to the first invention comprises a first step of forming an antireflection film made of an organic material and absorbing an energy beam on a film to be etched formed on a semiconductor substrate; A second step of forming a photosensitive material film on the prevention film, and after irradiating the photosensitive material film with an energy beam, selectively removing an irradiated portion or an unirradiated portion of the photosensitive material film, A third step of forming a patterned photosensitive material film, and dry etching of the etching target film using the patterned photosensitive material film as a mask to form a pattern of the etching target film
• the photosensitive material film comprises at least one of (a) an organic substance having a substituent which can be released by an acid and (b) an onium salt compound.
• the fourth step is that the sulfur-based etching is performed using the photosensitive material film patterned on the antireflection film as a mask. After the anti-reflection film is patterned by dry etching with a gas, the film to be etched is dry-etched using the patterned photosensitive material film and the anti-reflection film as a mask to be etched. It includes a step of forming a pattern made of a film.
• a semiconductor substrate 10 made of silicon is placed on a semiconductor substrate 10 via, for example, a silicon oxide film serving as an etching stopper.
• a film to be etched 11 made of, for example, a polysilicon film
• an organic material is formed on the film 11 to be etched, and energy such as light such as ultraviolet rays and far ultraviolet rays, electron beam or X-ray is formed.
• An antireflection film 12 for absorbing a beam is applied and formed.
• a chemically amplified resist material is applied on the anti-reflection film 12 to form a photosensitive material film 13, and then a light, an electron beam, or an X-ray is formed through a mask 14.
• Irradiate energy beam 15 After dissolving and removing the irradiated portion 13a of the photosensitive material film 13 by development, dry etching is performed on the antireflection film 12 using the patterned photosensitive material film 13b as a mask.
• the pattern is transferred to the anti-reflection film 11 by transferring the pattern to the anti-reflection film 12 and performing dry etching on the film 11 to be etched using the patterned photosensitive material film as a mask.
• the photosensitive material As the photosensitive material, a so-called negative type, in which the energy beam irradiated portion is dissolved and removed by development, instead of a so-called positive type, the energy beam non-irradiated portion is dissolved and removed by development, A photosensitive material can also be used. After the etching of the anti-reflective film, the patterned photosensitive material film and the anti-reflective film on the semiconductor substrate 10 are removed, as shown in FIG. Thus, the pattern of the film to be etched is obtained on the semiconductor substrate 10. In FIG.
• the surface of the gate electrode 16 made of a polysilicon film as the film 11 to be etched and the surface of the source / drain region between the gate electrodes 16 on the semiconductor substrate 10 are T It is silicided by iSi2 or the like and covered by silicide layer 18. Further, a side wall 17 made of an insulating material such as Si 3 N 4 , TEOS or HTO is formed on a side surface of the gate electrode 16. There is no residue on the source and drain regions, and the gate electrode 16 is not exposed from the side wall 17 because the side surface shape of the gate electrode 16 is uniform. No silicide layer 18 is formed on the side surface of 16.
• the gate electrode 16 and the source / drain region are not electrically connected to each other via the silicide layer on the surface of the gate electrode 16 or the silicide layer on the surface of the residue. Since an abnormal leak current does not flow between the device and the region, deterioration of device characteristics can be prevented.
• the photosensitive material film comprises ( a ) at least one kind of an organic substance having a substituent which can be released by an acid and (b) an ionic salt compound, and a sulfone compound and a sulfonate compound.
• It is composed of a chemically amplified resist material containing a compound that generates an acid when irradiated with at least one kind of radiation selected from compounds. It contains a dissolution inhibitor, a basic compound, and other conventionally known additives.
• a solvent is used to make these resist materials a uniform solution.
• the components of these resist materials will be specifically described.
• the organic substance containing a substituent which can be released by an acid includes fuynol Alkali-soluble polymers having a functional group that has an affinity for an alkaline developer such as a hydroxyl group, a carboxyl group, etc., have a substituent that is released in the presence of an acid.
• fuynol Alkali-soluble polymers having a functional group that has an affinity for an alkaline developer such as a hydroxyl group, a carboxyl group, etc. have a substituent that is released in the presence of an acid.
• soluble polymer constituting the acid-decomposable group-containing resin include a vinyl polymer having a repeating unit represented by the following formula 1 or 2, and a phenol resin represented by a novolak resin. And the like.
• Examples of the polymer containing the repeating unit of the following formula 1 include polyhydroxystyrene, polyhydroxy ⁇ - methyl styrene, polyhydroxymethyl styrene, etc. Examples thereof include homo- or copolymers of acrylic acid or methacrylic acid.
• Examples of the acid-decomposable group to be added include a vinyl ether compound and a dialkyl carbonate.
• Specific examples of the vinyl ether compound include a compound represented by the following formula 3, and more specifically, isopropininolemethyl ether, 3,4-dihydro1-2-pyran, butanediol 1 , 4-divinyl enoate, ethylene glycol divinyl ether, or triethylene glycol divinyl ether are preferred.
• Specific examples of dialkyl carbonate include di-tert-butyl carbonate.
• the alkali-soluble polymer and the acid-decomposable group may be used alone or in combination of two or more.
• R 1 represents a hydrogen atom or an alkyl group
• R 2 represents an alkyl group
• m is 0 or an integer of 1-4.
• R 3 represents a hydrogen atom or an alkyl group.
• R 4 , R 5 , and R 6 each independently represent a hydrogen atom or a linear, branched, cyclic, or cyclic alkyl group containing a heteroatom having 1 to 6 carbon atoms;
• R 7 is a linear, branched, cyclic or heterocyclic group having 1 to 10 carbon atoms which may be substituted with a halogen atom, an alkoxy group, an aralkyloxycarbonyl group, or an alkylcarbonylamino group. Represents a cyclic alkyl or aralkyl group containing an atom.
• any compounds known to generate an acid upon irradiation with radiation can be used.
• examples include sulfonium salt compounds such as phenylsulfonium methane, etc., rhododium salt compounds such as diphenyl odonium trifluoromethane sulfonate, phosphonium chloride compounds, diazonium salt compounds, and pyridinium salt compounds.
• sulfonium salt compounds and rhododium salt compounds are preferred, and sulfonium salt compounds are particularly preferred.
• Particularly preferred sulfonium salt compounds and iodonium salt compounds that can be used in the present invention are triphenylsulfonium triflate, triphenylenolesnorethonium propionate, and triphenyl sulfonium tripropionate. It is a fenolinorenodium hexaflate and a diphenylenolidium triflate.
• sulfone compound examples include ketosulfone, ⁇ -sulfonyl sulfone, and their diazo compounds. It also includes disulfone compounds. Specific examples of these sulfone compounds include:
• Methylsulfoninole p-tonolenesulfonylmethane bis (pheninolenoslehoninole) methane, bis (4-methylphenylenolesnolehoninole) methane, bis (3-methylphenylsnolehonyl) ) Methanane, bis (4-ethynolephenylsulfonyl) methane, bis (2,4-dimethinolephenylenolesnorefonyl) methane, bis (4-t-butylphenylsulfonyl) methane, bis (4 -Methoxyphenylsulfonyl) methane, bis (4-fluorophenylsnolephonyl) methane, bis (4-cyclopheninolesulfoninole) methane, bis (4-bromophenylenolesnolefonyl) methane
• Diazomethane biscyclohexinole snorehoninolemethane, bispheninoresnolehoninolemethane, bis (4-methinolephenylsulfonyl) methane, etc.
• snorephonate compound examples include an alkyl sulfonate, a nornolequinolenoslenoate, an esternolenoresolenoate, and imino sulfonate.
• alkyl sulfonate examples include an alkyl sulfonate, a nornolequinolenoslenoate, an esternolenoresolenoate, and imino sulfonate.
• esters such as snorephonate esters such as benzene.
• Pirogarorutori scan main Tansunorehone DOO, to spread one Honoré preparative list Li off rate, benzoin preparative Shiray bets are like c
• the contents of the above-mentioned onium salt compound, sulfone compound and sulfonate compound in the chemically amplified resist material can achieve the object of the present invention. Any amount may be used as long as the amount falls within a certain range.
• 100 to 100 parts by weight of the onium salt compound is used in an amount of 0.5 to 10 parts by weight, sulfonate.
• the compound is used in an amount of 1 to 10 parts by weight, and the sulfonate compound is used in an amount of 1 to 10 parts by weight.
• the mixing ratio of the sodium salt compound to the sulfone compound and the sulfonate compound is 0.1 to 5 parts by weight, more preferably 0 to 5 parts by weight, based on 100 parts by weight of the organic substance having a substituent which can be released by an acid.
• 0.5 to 2 parts by weight and the total amount of the sulfone compound and the sulfonate compound are preferably 0.5 to 10 parts by weight; for example, only one type of the sulfone compound is used. When this is done, the “total amount of both” is the amount of the one compound.
• the content of the onium salt compound when the content of the onium salt compound is less than 0.1 part by weight, the dimensional difference between the isolated pattern and the line width of the dense pattern becomes large, and the isoform compound and the sulfone compound and the Z or sulfonate compound
• the effect of the combined use is not so much observed, and when the amount of the onium salt compound is more than 5 parts by weight, the effect of the combined use is almost impossible, for example, the cross section of the formed pattern exhibits a T-top shape and becomes tapered. Other defects such as scum at the time of development may occur even if the effect of the combination is observed.
• the amounts of the sulfone compound and the sulfonate compound are less than 0.5 part by weight, the effect of suppressing the formation of reaction products at the interface between the antireflection film and the photosensitive material film is sufficiently obtained. May not be expected, and a remarkable standing wave is formed. Efficacy is hardly observed when used in combination with a homogenous chloride, and when it exceeds 10 parts by weight, the line width of isolated patterns and dense patterns Disadvantages, such as a large dimensional difference between the two, or the cross-sectional shape of the pattern is tapered, or a combination of an ionic compound with a sulfone compound and / or a sulfonate compound.
• the mixing ratio (weight) is preferably 1: 0.5 to 1: 1 °.
• the total amount of the acid generator is preferably 1 to 10 parts by weight based on 100 parts by weight of the organic substance having a substituent which can be released by an acid.
• the use of a sulfone compound or a sulfonate compound together with the onium salt compound can suppress the formation of a reaction product at the interface between the antireflection film and the photosensitive material film.
• the development inhibitory effect is strong in the unexposed area, and a pattern image with high solubility in the developer is formed in the exposed area, resulting in high resolution.
• a development pattern can be formed.
• the dissolution inhibitor itself contains an acid-decomposable protecting group, controls the solubility of the acid-decomposable group-containing resin in an alkaline developer, and decomposes in the presence of an acid. It is a substance that has the effect of accelerating the solubility of acid-decomposable group-containing resins that have been decomposed to become soluble in water, such as dibutoxycarbonyl bisphenol A, dibutoxy canolepon bis bisphenol F, 4 Examples thereof include compounds such as 1-butoxycanoleboninolephenyl, t-butyl collate, t-butyl deoxy collate, tertiary butyl diphenol diester, and tri (hydroxyphenyl) methane derivative.
• a typical example is bis (41-t-butoxycarbonylmethyioxy 2,2,5-dimethinolephenyl) methinole-41-t-butoxycanoleboninolemethyloxybenzene.
• Basic compounds any of a radiation-sensitive basic compound that is decomposed by irradiation with radiation and a radiation-insensitive basic compound can be used.
• a basic compound By adding a basic compound, deterioration of pattern characteristics can be suppressed even if processing steps are performed at various delay time intervals when forming a pattern. The addition is preferable because the contrast can be prevented from lowering due to diffusion into the metal.
• the basic compound is preferably added in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the organic substance having a substituent which can be released by an acid.
• a sulfonium compound, a rhododium compound and the like are preferably used as the radiation-sensitive basic compound.
• additives include, for example, surfactants, sensitizers, light absorbers, dyes, pigments, organic carboxylic acids, leveling agents, stabilizers, low molecular weight compounds, plasticizers, and the like.
• any solvent can be used as long as it can dissolve each component in the chemically amplified resist material and form a uniform photosensitive material film.
• ethylene glycol monomethyl ester can be used.
• PMEA monomethinoleate acetate
• Estenoles such as ethanolate, acetate, methylethylketone, cyclopentanone, cyclopentanone, cyclohexanone, or
• any gas which has been conventionally used for removing an organic film can be used. It is an etching gas, a mixed gas of chlorine gas (C 1 2) and oxygen gas ( ⁇ 2) (hereinafter. Referred to as “chlorine Etsuchin Gugasu”), nitrogen gas (N 2) and oxygen gas ( ⁇ mixed gas (hereinafter the 2), “nitrogen-based etching gas” hereinafter.), sulfur dioxide gas (S_ ⁇ 2) a mixed gas of oxygen gas ( ⁇ 2) (hereinafter "sulfur-containing etching gas” are commonly used. The etching characteristics of each of these etching gases will be described below.
• the sulfur-based etching gas causes problems such as etching of the etching film 2 made of polysilicon, dimensional variation and dimensional variation of the etching film pattern. Since there is no problem of becoming large, it is preferable as an etching gas.
• Chlorine-based etching gas has a higher ionic property, that is, sputtering property, than sulfur-based etching gas, so that deposits generated by the etching gas in the dry etching process for the antireflection film 12 are reflected. It has a low degree of adhesion to the top surface of the anti-reflection film 12 after being peeled off after being attached to the side wall of the anti-reflection film 12, and also has a function of etching away reaction products generated at the interface between the anti-reflection film and the photosensitive material film. Therefore, the number of residues composed of the film to be etched generated by using the deposits or reaction products as a mask is small.
• the photosensitive material film 13 b patterned with respect to the antireflection film 12 is used.
• the number of residues was measured in the same manner as in Example 1. As a result, it was about 50,000 Z wafers, which was smaller than that in Example 1.
• the chlorine-based etching gas also etched the film-to-be-etched 11 made of polysilicon, following the dry etching of the antireflection film 12.
• the nitrogen-based etching gas also has a stronger ionic property, that is, a sputtering property, than the sulfur-based etching gas, the deposition of the anti-reflection film to be etched in the dry etching process for the anti-reflection film 12 is performed. Since the degree of adhesion of the substance to the side wall of the anti-reflection film is low and the reaction product generated at the interface between the anti-reflection film and the photosensitive material film is largely removed by etching, the deposit or the reaction product is removed. The number of residues generated as a mask is small.
• the photosensitive material film 13 b patterned with respect to the antireflection film 12 is masked.
• the number of residues was measured in the same manner as in Example 1. As a result, it was about 50,000 / wafer, which was smaller than that in Example 1.
• polysilicon which was observed in the case of chlorine-based etching gas was used. The phenomenon that the film 11 to be etched made of was etched did not appear.
• the patterned photosensitive material film 13 b is also greatly shaved, so that the dimensional variation and dimensional variation of the patterned antireflection film increase.
• the pattern width is 0.2 mm with a sulfur-based etching gas.
• the pattern width of an isolated pattern is 0.18 ⁇ m, and the pattern width is 0.20 m in the area of line width: space width of 1: 1.
• the dimensional fluctuations in the sparse and dense areas of the pattern were large as well as large.
• the nitrogen-based etching gas can reduce the number of residues as compared with the sulfur-based etching gas, but has a large dimensional variation and dimensional variation of the pattern formed of the film 11 to be etched. There is a problem that the yield decreases.
• the photosensitive material contains a sulfone compound or a sulfonate compound, as described above, the formation of an aromatic reaction product at the interface between the antireflection film 12 and the photosensitive material film 13 is prevented. Therefore, when a pattern composed of the film 11 to be etched is formed, the number of residues composed of the film to be etched formed on the semiconductor substrate 10 can be reduced.
• the patterned photosensitive material film 13b containing a sulfone compound or a sulfonate compound is used as a mask and dry etching is performed on the film 11 to be etched using a sulfur-based etching gas.
• a sulfur-based etching gas it is possible to reduce the dimensional variation and the dimensional variation of the pattern of the film to be etched, and further, the film to be etched formed on the semiconductor substrate 10. The number of residues can be reduced.
• FIG. 1 is a cross-sectional view showing an exposed state of a semiconductor substrate provided with a photosensitive material film according to the present invention.
• FIG. 2 is an enlarged sectional view illustrating the effect of the pattern forming method according to the first embodiment of the present invention.
• FIG. 3 is a cross-sectional view showing a problem in a conventional pattern forming method.
• FIG. 4 is a sectional view of a patterned etching film formed by a conventional pattern forming method.
• an etching film 11 made of polysilicon is deposited on a 200 mm semiconductor substrate 10 made of silicon via a silicon oxide film as an etching stopper, a polysulfone copolymer is deposited.
• An organic material dissolved in a liquid hexanone as a solvent was applied on the etching target film 11 to form an antireflection film 12 having a thickness of 150 nm.
• a photosensitive material film having a thickness of 0.690 ⁇ m was formed.
• This photosensitive material film is selectively exposed through a mask by using a 28.4.4 nm KrF excimer laser beam, and exposed to a direct hot plate at 110 ° C for 90 seconds. PEB) and then paddle with an alkaline developer (2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH)) for 60 seconds to obtain a positive-type line 'and' base pattern. .
• TMAH tetramethylammonium hydroxide
• the anti-reflection film 12 is etched using a mixed gas of sulfur dioxide gas (S 0 2 ) and oxygen gas (0 2 ) using the patterned photosensitive material film 13 b as a mask. Dry etching was performed using a gas to form a patterned antireflection film.
• the patterned photosensitive material film 13b and the antireflection film are used as masks for the etching film 11 made of polysilicon, and hydrogen bromide gas (HBr) and oxygen gas (O2 Dry etching was performed using an etching gas composed of a mixed gas with 2 ) to form a pattern composed of the film 11 to be etched.
• a wiring pattern having a design rule of 0.25 ⁇ m was formed by changing the density, and the pattern occupancy was about 5%.
• the number of residues having a size of about 50 nm or more was measured, it was about 600 pieces / wafer.
• An anti-reflection film similar to that of Example 1 is formed on a film to be etched made of polysilicon deposited on a semiconductor substrate, and a bis-cyclohexylsulfonyldiazomethane is formed on the anti-reflection film.
• the same photosensitive material film as in Example 1 was formed except that no film was contained, and a pattern consisting of the film to be etched was formed under the same conditions as in Example 1, the number of residues was about 100,000. It was a Z wafer.
• Example 1 As can be seen from the comparison between Example 1 and Comparative Example 1, according to Example 1, the number of residues could be reduced by about 40%. As a result, it is possible to reduce the occurrence of leakage current between the wiring patterns or between the conductive layer and the wiring pattern in the semiconductor integrated circuit device by about 40%.
• Example 2 Of an etching film consisting of polysilicon deposited on a semiconductor substrate The same photosensitive material film as in Example 1 was formed without forming an anti-reflection film, and a pattern consisting of the film to be etched was formed under the same conditions as in Example 1. The number was 500 / wafer.
• Comparative Example 1 the organic materials for forming the anti-reflection film were DUV-18, CD9, and CD11 (all manufactured by Bruce-Science) and AR2 (manufactured by Shipley). Even when the same evaluation test as in Example 1 was performed using materials such as SWK-EX2 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) and KrF-2A (manufactured by Clariant), the number of residues was not It was much more than two. From this, it can be seen that when an antireflection film is interposed between the film to be etched and the photosensitive material film, the number of residues is inevitably increased as compared with the case where no antireflection film is interposed. .
• An etching pattern was formed in the same manner as in Example 1 except that biscyclohexylsulfonyldiazomethane was used instead of biscyclohexylsulfonyldiazomethane.
• the number of residues was about 8400 / wafer, and the number of residues could be reduced by about 16% as compared with Comparative Example 1.
• An etching pattern was formed in the same manner as in Example 1 except that bis (3-methylphenylsulfonyl) methane was used in place of bishexylsulfonyl2′-noresazomethane.
• the number of residues was about 600 / wafer, and the number of residues could be reduced by about 40% as compared with Comparative Example 1.
• An etching pattern was formed in the same manner as in Example 1 except that bis (3-methylphenylsulfonyl) diazomethane 1.O g was used instead of bishexylsulfonyldiazomethane.
• the number of residues is about 460 Z wafers, and the number of residues should be reduced by about 64% compared to Comparative Example 1. Was completed.
• Example 6 An etching pattern was formed in the same manner as in Example 1 except that 1.0 g of a compound represented by the following formula was used in place of bishexylsulfonyldiazomethane. The number of residues was about 600 wafers, and the number of residues could be reduced by about 40% as compared with Comparative Example 1.
• Example 6
• An etching pattern was formed in the same manner as in Example 1 except that 1.0 g of pyrogallotrenoletrismethanesulfonate was used in place of bishexolenolesolefinoresinazomethane.
• the number of residues was about 450.000 Z wafers, and the number of residues could be reduced by about 55% as compared with Comparative Example 1.
• the dry etching step in the present invention is not limited to the method of dry etching only the antireflection film described above.
• the method of performing the same dry etching on the antireflection film 12 and the film 11 to be etched has a great advantage that the process can be shortened.
• This method is also one of the useful methods of the pattern forming method of the present invention. It is.
• the photosensitive material film contains a sulfone compound and Z or a sulfonate compound
• an array generated from these compounds is generated.
• the radical-based acid suppresses the radical reaction at the interface between the antireflection film and the photosensitive material film, thereby preventing the formation of an aromatic reaction product at the interface between the antireflection film and the photosensitive material film. Therefore, when dry etching is performed on the film to be etched using the patterned photosensitive material film and antireflection film as a mask to form a pattern consisting of the film to be etched, the pattern formed on the semiconductor substrate is formed. Thus, the number of residues formed of the film to be etched can be reduced.
• the pattern forming method of the present invention when the film to be etched is a conductive film, in the semiconductor integrated circuit device, the wiring patterns formed on the same conductive layer form conductive residues. Electrically between the wiring patterns, or between the wiring patterns or between the conductive layer and the conductive layer, by electrically connecting the conductive layer formed on the semiconductor substrate to the wiring pattern via a conductive residue. It is possible to reliably prevent a situation in which a leak current flows between the pattern and the semiconductor integrated circuit device, thereby deteriorating the characteristics of the device.
• the photosensitive material contains an acid salt generator and a sulfonate compound and / or a sulfonate compound as an acid generator, it has high resolution, standing waves, formation of T-tops, and isolated patterns. Dense A high-resolution resist pattern having no difference in pattern line width can be formed, and a high-resolution etching pattern having a designed line width can be formed.
• the fourth step is a step of performing dry etching with a sulfur-based etching gas using the photosensitive material film patterned on the antireflection film as a mask to form the antireflection film.
• the dimensional variation and dimensional variation of the pattern formed by the film to be etched can be reduced, and the pattern formed on the semiconductor substrate can be reduced.
• the number of residues composed of the film to be etched can be reduced.
• the pattern forming method of the present invention is useful as a fine pattern forming method for manufacturing a semiconductor integrated circuit device and the like.

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