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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/42—Stripping or agents therefor
  • G03F7/422—Stripping or agents therefor using liquids only
  • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/38—Treatment before imagewise removal, e.g. prebaking
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/42—Stripping or agents therefor
  • G03F7/422—Stripping or agents therefor using liquids only
  • G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
• • 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

Definitions

• the present invention relates to a photoresist remover composition comprising ammonium fluoride, more particularly to a photoresist remover composition comprising ammonium fluoride for removing photoresists in the manufacturing process of semiconductor components such as large scale integration, very large scale integration, etc. (b) Description of the Related Art
• the lithography process in which conductive layer patterns are formed on a semiconductor substrate plate by etching and removing a conductive layer of an area that is not covered with photoresist patterns is repeated tens of times.
• the photoresist patterns which are used as masks are stripped from the conductive layer by a photoresist remover after the conductive layer patterning process.
• the etching process for forming conductive layer patterns has consisted mainly of a dry etching process, so it has become difficult to remove photoresists in the subsequent process of stripping.
• the etching process is carried out using a gas phase - solid phase reaction between a plasma etching gas and a membrane of material such as a conductive layer.
• Dry etching has recently predominated the mainstream of etching processes due to its ease of control and sharp patterns.
• the dry etching process causes complicated chemical reactions between ions and radicals among plasma etching gases and the photoresist film on the photoresist surface, thus rapidly curing the photoresists and making their removal difficult.
• Photoresist remover compositions in which organic amine compounds and organic solvents are mixed together have been developed as photoresist removers to be used in the conventional stripping process.
• a photoresist remover composition comprising monoethanolamine as an essential constituent among organic amine compounds is most widely used.
• a two component photoresist remover composition comprising a) organic amine compounds such as monoethanolamine, 2-(2- aminoethoxy) ethanol, etc., and b) polar solvents such as N.N'- dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, carbitol acetate, methoxyacetoxypropane, etc.
• organic amine compounds such as monoethanolamine, 2-(2- aminoethoxy) ethanol, etc.
• polar solvents such as N.N'- dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, carbitol acetate, methoxyacetoxypropane, etc.
• a two component photoresist remover composition comprising a) organic amine compounds such as monoethanolamine, monopropanolamine, methylamilethanol, etc., and b) amide solvents such as N-methylacetamide, N.N'-dimethylacetamide, N,N-dimethylformamide, N,N-diethylacetamide, N, N-dipropylacetamide, N, N-dimethylpropionamide, N, N-diethylbutylamide, N-methyl-N-ethylpropionamide, etc.
• organic amine compounds such as monoethanolamine, monopropanolamine, methylamilethanol, etc.
• amide solvents such as N-methylacetamide, N.N'-dimethylacetamide, N,N-dimethylformamide, N,N-diethylacetamide, N, N-dipropylacetamide, N, N-dimethylpropionamide, N, N-diethylbutylamide
• a two component photoresist remover composition comprising a) organic amine compounds such as monoethanolamine, etc., and b) non protonic polar solvents such as 1 ,3-dimethyl-2-imidazolidinone, 1 ,3-dimethyl- tetrahydropyrimidone, etc. (German Patent Laid-open Publication No. 3,828,513); a photoresist remover composition in which a) alkylenepolyamine in which alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, etc.
• sulfonic compounds such as sulfolane, etc.
• glycol monoalkyl ethers such as diethylene glycolmonoethyl ether, diethylene glycolmonobutyl ether, etc. are mixed in a specific ratio
• a photoresist remover composition comprising a) aqueous amines such as monoethanolamine, diethanolamine, etc. and b) 1 ,3- dimethyl-2-imidazolidinone (Japanese Patent Laid-open Publication No.
• a positive resist remover composition comprising a) amines such as monoethanolamine, ethylenediamine, pipe dine, benzylamine, etc., b) polar solvents such as N.N'-dimethylacetamide; N- methylpyrrolidone, dimethyl sulfoxide, etc., and c) surfactants (Japanese Patent Laid-open Publication No.
• a positive resist remover composition in which a) nitrogen contained organic hydroxyl compounds such as monoethanolamine, etc., b) one or more solvents selected from the group consisting of diethylene glycol monoethyl ether, diethylene glycol dialkyl ether, ⁇ -butyrolactone, and 1 ,3-dimethyl-2- imidazolinone, and c) dimethyl sulfoxide are mixed in a specific ratio (Japanese Patent Laid-open Publication No.
• a positive resist remover composition comprising a) organic amine compounds such as monoethanolamine, etc., b) non protonic polar solvents such as diethylene glycol monoalkyl ether, N.N'-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, etc., and c) phosphoric ester based surfactants (Japanese Patent Laid-open Publication No. Heisei 4-124668); a photoresist remover composition comprising a) 1 ,3-dimethyl-2-imidazolinone, b) dimethyl sulfoxide, and c) organic amine compounds such as monoethanolamine, etc.
• Water based photoresist removers have been suggested as compositions for removing the hard baked photoresists.
• a photoresist remover composition comprising a) hydroxylamines , b) alkanolamines, and c) water
• a photoresist remover composition comprising a) hydroxylamines, b) alkanolamines, c) water, and d) anticorrosion agent
• Heisei 6-266119 a photoresist remover composition comprising a) polar solvents such as GBL (y - butyrolactone), N,N-dimethylformamide, N.N'-dimethylacetamide, N- methylpyrrolidone, etc., b) amino alcohols such as 2-methylaminoethanol, etc., and c) water
• a photoresist remover composition comprising a) amino alcohols such as monoethanolamine, etc., b) water, and c) butyl diglycol (Japanese Patent Laid-open Publication No.
• Heisei 8-123043 a photoresist remover composition comprising a) alkanolamines, alkoxyalkylamines, b) glycol monoalkyl ether, c) sugar alcohols, d) quaternary ammonium hydroxide, and e) water
• a photoresist remover composition comprising a) alkanolamines, alkoxyalkylamines, b) glycol monoalkyl ether, c) sugar alcohols, d) quaternary ammonium hydroxide, and e) water
• a photoresist remover composition comprising a) alkanolamines of monoethanolamine or/and 2-(2-aminoethoxy) ethanol, b) hydroxylamine, c) diethyleneglycol monoalkyl ether, d) saccharides (sorbitol), and e) water
• a photoresist remover composition comprising a) alkanolamines of monoethanolamine or/and 2-(2-aminoethoxy) ethanol, b) hydroxylamine, c) diethyleneglycol monoalkyl ether, d) saccharides (sorbitol), and e) water
• Heisei 9-152721 a photoresist remover composition comprising a) hydroxylamines, b) water, c) amines having 7.5 to 13 of acid dissociation integer (pKa), d) water soluble organic solvent, and e) anticorrosion agent (Japanese Patent Laid-open Publication No. Heisei 9-96911 ), etc. have been suggested.
• the so-called popping phenomenon occurs such that the photoresist film surface is destroyed by solvents remained inside photoresists as an internal pressure of photoresists is increased during the ashing process.
• the surface-curing layer scattered by this popping phenomenon becomes a residual image which is difficult to remove by general remover compositions.
• These degenerated photoresists are changed into residual images and particles which also become pollution sources as well as reasons for deteriorating production yields during the very large scale integration manufacturing process.
• the degeneration of photoresists causes defective products to be produced during the stripping process.
• the present invention provides a photoresist remover composition
• a photoresist remover composition comprising 0.1 to 0.3 weight% of ammonium fluoride, 25 to 45 weight% of water, 4 to 15 weight% of an organic phenol based compound having 2 or 3 hydroxyl groups, and 40 to 70 weight% of alkyl amide.
• FIG. 1 is a scanning electron microscope photograph taken on a profile structure of patterns which have been in the dry etching and ashing processes after coating photoresist (6) on a substrate plate in which aluminum alloy metallic film (1 ), titanium nitride film (2), tetraethyl orthosilicate (3), flowable oxide (4), and tetraethyl orthosilicate (5) are laid up in order and form via hole patterns;
• FIG. 2 is a scanning electron microscope photograph showing the results of a photoresist removing capability test which is performed at 65 ° C using a photoresist remover composition of COMPARATIVE EXAMPLE 3 after removing part of the photoresist (6) by performing the ashing process on patterns of FIG. 1 ; and FIG.
• FIG. 3 is a scanning electron microscope photograph showing the results of a photoresist removing capability test which is performed at 65 ° C using a photoresist remover composition of EXAMPLE 1 after removing part of the photoresist (6) by performing the ashing process on patterns of FIG. 1 .
• An ammonium fluoride content is preferably from 0.1 to 0.3 weight% in a photoresist remover composition according to the present invention. That is, it is difficult to fully remove a side wall resist polymer which is degenerated by dry etching in the via hole patterning process and ashing process, etc. when the ammonium fluoride content is less than 0.1 weight%, and there are problems of severe corrosion in a flowable oxide layer film among the films that are laid up on the via hole patterns when the ammonium fluoride content exceeds 0.3 weight%.
• an essential constituent of water is preferably purified water which is filtered through an ion-exchange resin, and more preferably ultra-purified water having specific resistance of more than 18 mega-ohms (M ⁇ ).
• the water content is preferably from 25 to 45 weight%.
• a side wall resist polymer that is degenerated by dry etching in the via hole patterning process and ashing process, etc. removed excessively when the content of water in a photoresist remover composition according to the present invention is less than 25 weight%, but also corrosion of a flowable oxide layer among the laid-up layers occurs.
• water content exceeds 45 weight%, there is a problem of excessive corrosion on a lower area metallic film.
• content of water in a photoresist remover composition is preferably from 25 to 45 weight%.
• the phenol compound having 2 or 3 hydroxyl groups is a compound represented as in the following Chemical Formula 1 : [Chemical Formula 1]
• n is an integer of 2 or 3.
• a phenol compound having the 2 or 3 hydroxyl groups fulfils its function to help ammonium bifluoride (NH HF 2 ), which is produced when the ammonium fluoride and water constituents of a remover composition are heated to be used during the stripping process, effectively penetrate a contact surface between a photoresist layer and a substrate plate.
• NH HF 2 ammonium bifluoride
• the content of the phenol compound having 2 or 3 hydroxyl groups is preferably from 4 to 15 weight%. There is a problem in that a side wall resist polymer is not fully removed when the content of a phenol compound is less than 4 weight% while there is a problem that viscosities of a photoresist remover composition are increased resulting in a deterioration of convenience in use when the content of a phenol compound exceeds 15 weight%.
• the alkyl amide is a compound represented as in the following Chemical Formula 2:
• R ⁇ , R 2 , and R 3 are hydrogen or one or more alkyl groups, and the alkyl group is a straight chained alkyl group having one to two carbons.
• the alkyl amide content is preferably from 40 to 70 weight%.
• the solubility capabilities on a photoresist are deteriorated when the alkyl amide content is 40 weight% or less, while the water content is relatively reduced resulting in flowable oxide layer corrosion when the alkyl amide content exceeds 70 weight%.
• the present invention is described through EXAMPLES further in detail, and the range of the present invention is not restricted to the following EXAMPLES. Additionally, percentages and mixing ratios are based on weight when not mentioned specifically. In EXAMPLES and
• Tetraethyl orthosilicate, flowable oxide, and again tetraethyl orthosilicate were deposited using CVD (chemical vapor deposition) equipment on the surface of an 8 inch silicone wafer in which 800 A of aluminum alloy membrane and 150 A of titanium nitride membrane were deposited respectively from the bottom, in order.
• a commonly used positive photoresist composition DPR-i900 of Dongjin Semichem Co. Ltd., was spin coated such that the final membrane thickness could be 1.2 /.an. Subsequently, the photoresist membrane was pre-baked on a hot plate at a temperature of 1 10 °C for 90 seconds.
• Photoresist patterns formed on the sample were used as a mask such that a lower part of the titanium nitride membrane which was not covered by photoresist patterns was etched using a mixed gas of SF 6 and Cl 2 as a dry etching gas from dry etching equipment M318 of Hitachi Corporation, for 35 seconds. Thereafter, most of the photoresists were removed by ashing equipment using O 2 plasma, thus manufacturing the samples. Photoresist removing test
• Sample A was digested in a photoresist remover composition at a temperature of 65 ° C for 5 minutes, 10 minutes, and 20 minutes respectively. Subsequently, after taking the sample out of the photoresist remover composition, washing with ultra-purified water, and drying with nitrogen gas, photoresist removing capabilities were evaluated according to the following standards, by inspecting with a scanning electron microscope to determine whether or not photoresist polymer remained on the side wall surface in a via hole pattern profile, and the results are represented in the following Table 2.
• O represents when resist polymer residues on the via hole pattern side wall are completely removed.
• ⁇ represents when more than 80 % of resist polymer residues on the via hole pattern side wall are removed.
• Sample B was prepared in the same way as sample A.
• Sample B was digested in a photoresist remover composition at a temperature of 65 °C for 5 minutes, 10 minutes, and 20 minutes respectively. Subsequently, after taking the sample out of the photoresist remover composition, washing with ultra-purified water, and drying with nitrogen gas, degrees of corrosion were evaluated according to the following standards, by inspecting with a scanning electron microscope to determine whether or not undercut phenomenon occurred on the lower area of metallic film in a via hole pattern profile, and the results are represented in the following Table 3.
• O represents when no undercut phenomenon exists on the lower area of metallic film.
• ⁇ represents when partial undercut phenomenon exists on the lower area of metallic film.
• X when severe undercut phenomenon exists on the lower area of metallic film.
• Photoresist remover compositions of EXAMPLES 1 to 5, and COMPARATIVE EXAMPLES 1 to 3 were prescribed respectively by mixing contents of the constituents a) to d) in the ratios represented in the following Table 1.
• the above described (1) photoresist removing test and (2) metallic film corrosion test were performed on the resultant obtained photoresist remover compositions, and the results are represented in the following Tables 2 and 3.
• FIG. 2 and FIG. 3 represent scanning electron microscope (model S-
• FIG. 1 to FIG. 3 show the results of a photoresist removing capability test which is done with a photoresist remover composition temperature being 65 "C, for a sample A.
• 1 is a profile structure of patterns which have been processed in the dry etching and ashing processes after coating photoresist (6) on a substrate plate in which aluminum alloy metallic film (1 ), titanium nitride film (2), tetraethyl orthosilicate (3), flowable oxide (4), and tetraethyl orthosilicate (5) are laid up in order and form via hole patterns. It can be confirmed that a side wall resist polymer exists over the total profile of a via hole in this pattern profile photograph.
• FIG. 2 is a scanning electron microscope photograph showing the results of a photoresist removing capability test which is done at 65 "C using a photoresist remover composition of COMPARATIVE EXAMPLE 3.
• FIG. 3 is a scanning electron microscope photograph showing the results of a photoresist removing capability test which is done at 65 °C using a photoresist remover composition of EXAMPLE 1.
• a photoresist remover composition according to the present invention can easily remove a side wall resist polymer which has degenerated and been cured by dry etching in the via hole patterning process and ashing process within a short time. Furthermore, a photoresist remover composition according to the present invention has merits in that corrosion of the lower part metal wiring, particularly aluminum wiring, can be minimized during the photoresist removing process, and rinsing can be done only with water without organic solvents such as isopropyl alcohol or dimethyl sulfoxide in the subsequent rinsing process.

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• General Physics & Mathematics (AREA)
• Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Computer Hardware Design (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Manufacturing & Machinery (AREA)
• General Chemical & Material Sciences (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Power Engineering (AREA)
• Architecture (AREA)
• Structural Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Chemical & Material Sciences (AREA)
• Detergent Compositions (AREA)

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• 2000
  • 2000-06-19 KR KR1020000033705A patent/KR20010113396A/ko not_active Application Discontinuation
  • 2000-06-26 CN CN 00819669 patent/CN1217236C/zh not_active Expired - Lifetime
  • 2000-06-26 AU AU2000255752A patent/AU2000255752A1/en not_active Abandoned
  • 2000-06-26 WO PCT/KR2000/000663 patent/WO2001098837A1/en active Application Filing
  • 2000-06-26 JP JP2002504538A patent/JP3742624B2/ja not_active Expired - Lifetime
  • 2000-08-03 TW TW89115643A patent/TW594443B/zh not_active IP Right Cessation

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