WO2010016350A1 - 残渣剥離液組成物およびそれを用いた半導体素子の洗浄方法 - Google Patents
残渣剥離液組成物およびそれを用いた半導体素子の洗浄方法 Download PDFInfo
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- WO2010016350A1 WO2010016350A1 PCT/JP2009/062335 JP2009062335W WO2010016350A1 WO 2010016350 A1 WO2010016350 A1 WO 2010016350A1 JP 2009062335 W JP2009062335 W JP 2009062335W WO 2010016350 A1 WO2010016350 A1 WO 2010016350A1
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/34—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5013—Organic solvents containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
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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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
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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
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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
- H01L21/04—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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Definitions
- the present invention relates to a residue remover composition used in the wiring process of semiconductor elements such as IC and LSI and liquid crystal panel elements, and a method for removing resist residues and residues derived from wiring materials using the composition. is there. More specifically, in the manufacturing process of a semiconductor substrate having a metal wiring made of aluminum (Al) or an Al alloy containing 90 mass% or more of Al, a resist residue remaining after dry etching and ashing to form a via hole The present invention also relates to a composition suitably used for stripping metal residues derived from wiring materials and a cleaning method for stripping resist residues and wiring material-derived residues using a residue stripping solution composition.
- lithography technology is applied when forming a wiring or forming a via hole in an interlayer insulating layer. That is, a resist is uniformly applied on a conductive metal film such as Al, copper (Cu), Al alloy, etc. formed on a substrate, or an insulating film such as a silicon oxide (SiOx) film, and a pattern is formed by exposure and development processing. Then, using the resist as a mask, the conductive metal film and the insulating film are dry-etched, and then unnecessary resist and the resist residue altered by the dry etching are removed, thereby forming a wiring and forming a via hole in the interlayer insulating film. Is done.
- a metal residue derived from an interlayer insulating material or a wiring material (which may be referred to as a residue, including these) remains altered by the gas.
- the resist residue is the substrate after dry etching and ashing.
- Residue residue derived from the resist remaining on the surface, and metal residue derived from the wiring material altered by the plasma gas is a metal component remaining on the side and bottom surfaces of the via hole: Al, Cu, Ti, among these, oxidation containing Ti in particular This is a product (hereinafter referred to as titanium (Ti) -derived residue).
- the composition containing the above-mentioned fluorine compound and a water-soluble organic solvent has a property that the etching rate with respect to the Al alloy increases when diluted with water. If the water replacement is not performed quickly, the liquid diluted with water and having increased corrosiveness to the Al alloy comes into contact with the substrate and has a disadvantage that the Al alloy wiring portion is corroded.
- Patent Document 5 proposes a “fluorine compound-containing liquid composed of a fluorine compound and a sulfonic acid”, but this chemical solution does not have sufficient anticorrosion properties on the interlayer insulating film and the bottom of the via hole. (See Comparative Example 34).
- Patent Document 6 proposes an “acidic aqueous solution containing an organic phosphonic acid and a fluorine compound”. However, this chemical solution does not have sufficient removal of residues and does not have sufficient anticorrosive properties at the bottom of the via hole (comparison). See Example 35).
- Patent Document 7 proposes a “fluorine compound and orthoboric acid or orthophosphoric acid and a water-soluble organic solvent”, but this chemical solution did not have sufficient residue removability (see Comparative Example 36).
- a water-soluble organic solvent is often contained for anticorrosion.
- a fluorine compound and a water-soluble organic solvent are used. Similar to the composition containing Al, there is a property that the etching rate for the Al alloy increases when diluted with water, and as a result, the Al alloy wiring portion is corroded.
- Patent Document 8 proposes a “semiconductor substrate cleaning solution containing a fluorinated compound and a water-soluble or water-miscible organic solvent containing acetylene alcohol to remove metal contamination”, but acetylene alcohol was added. There is no description about the effect of the anticorrosion property to the metal wiring.
- Patent Document 9 discloses that “a cleaning agent for manufacturing a semiconductor device comprising an aqueous solution containing a fluorine-containing compound, boric acid and a water-soluble organic solvent, which contains acetylene alcohol to improve the removal rate of the deposited polymer”. "Includes acetylene alcohol to improve the removal rate of the deposited polymer, organic carboxylic acid ammonium salt and / or organic carboxylic acid amine salt, fluorine-containing compound, water-soluble or water-miscible organic solvent, inorganic acid and / or Alternatively, a “cleaning solution for manufacturing a semiconductor device comprising an aqueous solution containing an organic acid” has been proposed. However, there is no description regarding the effect of anticorrosion on the metal wiring due to the addition of acetylene alcohol.
- Patent Document 11 includes “at least one of an acetylene alcohol compound and an organic sulfonic acid compound, and at least one of a polyhydric alcohol and a derivative thereof, and further a fluorine compound and a quaternary ammonium hydroxide salt.
- a composition containing at least one of them has been proposed, but this composition has been proposed as relating to the production of a semiconductor circuit element having a metal wiring mainly composed of Cu as a wiring material.
- evaluation is performed using wiring using tantalum as a barrier metal, and there is no description regarding a Ti-derived residue.
- An object of the present invention is derived from a resist residue and titanium (Ti) remaining after dry etching and ashing to form a via hole in a manufacturing process of a semiconductor substrate having a metal wiring made of aluminum (Al) or an Al alloy.
- An object of the present invention is to provide a residue stripping solution composition that can completely remove residues in a low temperature in a short time and does not corrode members such as interlayer insulating materials and wiring materials, and a method for cleaning a semiconductor device using the same.
- the present inventors have found that as a corrosion inhibitor for Al alloy wiring containing 90% by mass or more of Al in a release agent containing ammonium fluoride and methanesulfonic acid as an acidic compound. Addition of a compound having a carbon-carbon triple bond gives an anticorrosive effect to the Al alloy when the undiluted solution and the undiluted solution are diluted with water, and provides corrosion resistance to interlayer insulating materials and wiring materials while having residue removability The knowledge that it was possible to suppress the sex was obtained.
- the present invention relates to a method for cleaning a semiconductor element, and the gist thereof is as follows. 1.
- a compound having a carbon-carbon triple bond which is at least one selected from 2-butyn-1-ol, 3,5-dimethyl-1-hexyn-3-ol, and 3-hexyne-2,5-diol
- (D) A residual stripping liquid composition containing a water-soluble organic solvent that is at least one selected from poly
- Residual stripping solution composition comprising -38% by mass and (B) containing 0.9 to 1.5 times (molar ratio) with respect to (A).
- a barrier metal layer made of SiOx and TiN / Ti on a silicon substrate, an Al alloy layer made of Al—Cu, Al—Si or Al—Si—Cu containing 90% by mass or more of Al, and a barrier metal layer made of TiN / Ti Are sequentially laminated, and after applying the resist (1) to form the resist (1) layer, exposure and development are performed, dry etching is performed using the resist (1) layer as a mask to form an Al alloy wiring body, Further, the resist (1) layer is removed by ashing with plasma gas, the resist (1) residue is removed by chemical treatment, an interlayer insulating film layer made of SiOx is further laminated thereon, and then the resist (2) is applied.
- the residue removal described in 1 above A cleaning method in which at least a residue in a via hole is removed using a liquid composition.
- residue stripping liquid composition and cleaning method of the present invention dry etching and ashing are performed to form via holes in the manufacturing process of a semiconductor substrate having a metal wiring made of Al or Al alloy containing 90 mass% or more of Al. Resist residue and Ti-derived residue remaining after performing the process can be completely removed at a low temperature in a short time, and the product yield in the manufacture of semiconductor devices is improved without corroding members such as interlayer insulation materials and wiring materials. Can do.
- the residue stripping composition of the present invention comprises (A) ammonium fluoride, (B) methanesulfonic acid, (C) a compound having a carbon-carbon triple bond, (D) a polyhydric alcohol, a glycol ether, and an amide.
- a water-soluble organic solvent that is at least one selected from the group, and (E) water, and the contents of (A), (C), (D), and (E) in the residual stripping solution composition are each 0.005 to 2% by mass, 0.1 to 10% by mass, 60 to 75% by mass, and 5 to 38% by mass, and (B) is 0.9 to 1.5 times (A) ( (Molar ratio).
- the residue remover composition of the present invention contains (A) ammonium fluoride.
- the content of ammonium fluoride in the residue stripping solution composition is used in a concentration range of 0.005 to 2.0% by mass, preferably 0.01 to 1.8% by mass, particularly 0.1 to 1.%. 5 mass% is preferable.
- concentration of ammonium fluoride is higher than 2.0% by mass, the corrosiveness to the material is high, and when it is less than 0.005% by mass, the peeling rate of the residue is slow.
- the residue stripping solution composition of the present invention contains (B) methanesulfonic acid.
- Methanesulfonic acid has a small acid dissociation constant (pKa) in water or in a water-soluble organic solvent, and further, compatibility when mixed into the residue stripping solution composition, stability, balance of residue stripping and material corrosion
- pKa acid dissociation constant
- the residue stripping solution composition of the present invention is employed.
- Methanesulfonic acid needs to be contained in an amount of 0.9 to 1.5 times, preferably 0.9 to 1.4 times the molar ratio of ammonium fluoride contained. More preferably, the amount is 0.95 times to 1.3 times.
- the amount is less than 0.9 times, the peelability of the residue is not sufficient, or the corrosiveness of the interlayer insulating material is increased. On the other hand, if the amount is more than 1.5 times, the releasability of the residue is not sufficient or the corrosivity of the metal wiring material is increased.
- the residue stripping composition of the present invention contains (C) a compound having a carbon-carbon triple bond.
- (C) a compound having a carbon-carbon triple bond includes 3-methyl-1-pentyn-3-ol, 1-ethynyl-1-cyclohexanol, 2-propyn-1-ol, 2-butyne- 1,4-diol, 4-ethyl-1-octin-3-ol, 3-methyl-1-butyn-3-ol, 1-octin-3-ol, ethynylbenzene, 3,3-dimethyl-1-butyne , 2-butyn-1-ol, 3,5-dimethyl-1-hexyne-3-ol, and 3-hexyne-2,5-diol, and contains a plurality of the above compounds. May be.
- the content of the compound having a carbon-carbon triple bond in the residue stripping solution composition needs to be 0.1% by mass to 10% by mass, and preferably 0.15% by mass to 8% by mass. More preferably, the content is 0.2% by mass to 5% by mass. If the amount is less than 0.1% by mass, the anti-corrosion effect on the Al stripper composition containing 90% by mass or more of Al when the composition is diluted with water is insufficient, and if the amount is more than 10% by mass, the residue There is a possibility that the removability of the resin may deteriorate or the mixing property may deteriorate.
- the water-soluble organic solvent (D) used in the present invention is at least one selected from polyhydric alcohols, glycol ethers and amides. By using these organic solvents, residue removability can be improved.
- Preferred examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, glycerin, diglycerin, polyglycerin, and 1,3-butylene glycol.
- glycol ethers ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene Glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, dipropylene glycol monopro Ethers, such as tripropylene glycol dimethyl ether preferably.
- amides include dimethylformamide, dimethylacetamide, acetamide, methylacetamide, ethylacetamide, formamide, methylformamide, dimethylformamide, ethylformamide, diethylformamide and the like.
- the (D) water-soluble organic solvent in the present invention can be used in combination with other organic solvents.
- organic solvents include lactones such as ⁇ -butyrolactone, sulfoxides such as diethyl sulfoxide and diphenyl sulfoxide, nitriles such as acetonitrile and benzonitrile, alcohols such as methanol, ethanol, isopropanol and ethylene glycol, methyl acetate, Preference is given to esters such as ethyl acetate.
- the organic solvent may be used alone or in combination of two or more from the above.
- the content of the water-soluble organic solvent in the residue stripping composition needs to be 60 to 75% by mass, and preferably 65 to 75% by mass.
- the content of the water-soluble organic solvent is less than 60% by mass, the material corrosion becomes large, and when it is more than 75% by mass, the peelability of the residue is lowered.
- the residue stripping solution composition of the present invention contains (E) water.
- the water content in the residue stripping solution composition needs to be 5 to 38% by mass, preferably 20 to 38% by mass, and more preferably 20 to 31% by mass. When the water content is less than 5% by mass, the releasability of the residue is lowered, and when it is more than 38% by mass, the material corrosion is increased.
- the cleaning method of the present invention includes a barrier metal layer made of SiOx and TiN / Ti on a silicon substrate, an Al alloy layer made of Al—Cu, Al—Si or Al—Si—Cu containing 90% by mass or more of Al, and TiN.
- a barrier metal layer made of / Ti is laminated in order, and a resist (1) is applied to form a resist (1) layer. Then, exposure and development are performed, and dry etching is performed using the resist (1) layer as a mask.
- An alloy wiring body is formed, and the resist (1) layer is removed by ashing with a plasma gas. Resist (1) residue is removed by a chemical treatment, and an interlayer insulating film layer made of SiOx is laminated thereon.
- the residue of the present invention A stripping solution composition is used to strip at least the residue in the via hole.
- FIG. 1 is a process diagram of manufacturing an aluminum alloy circuit in which the residue remover composition of the present invention is suitably used.
- the residue stripping solution composition of the present invention is subjected to dry etching of an interlayer insulating film layer and a barrier metal layer using a resist on a substrate in semiconductor element manufacturing as a mask, forming a via hole, and ashing by plasma It is used for peeling off the resist residue remaining after the etching and the Ti-derived residue remaining in the via hole.
- the Ti-derived residue is a residue derived from Ti contained in the TiN / Ti barrier metal layer shown in the third stage in FIG. 1 and the second “right” from the right.
- the residue stripping solution composition of the present invention strips and removes the resist residue existing on the surface of the SiOx oxide film simultaneously with the Ti-derived residue in the via hole.
- the Al or Al alloy wiring provided for the cleaning method of the present invention is an Al alloy containing 90% by mass or more of Al, and includes alloys such as Al—Cu, Al—Si, and Al—Si—Cu.
- the Al alloy is preferably an Al alloy containing 95% by mass or more, more preferably 98% by mass or more.
- the barrier metal layer is a layer laminated on the wiring layer for the purpose of improving the reliability of the wiring, and TiN / Ti is a material widely used for Al alloy wiring.
- the cleaning method of the present invention can be applied to a Ti-derived residue derived from TiN / Ti without limitation as long as it is a TiN / Ti barrier metal layer generally used for Al alloy wiring.
- the temperature at which the residue is peeled is preferably 0 ° C. to 50 ° C., more preferably 10 ° C. to 40 ° C., and further preferably 15 ° C. to 35 ° C.
- the treatment time for removing the residue is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes.
- the rinsing liquid used after the treatment with the residue stripping liquid composition has no problem with rinsing with pure water alone, but methyl alcohol, ethyl alcohol, isopropanol, dimethylacetamide, dimethyl sulfoxide, glycol Water-soluble organic solvents such as ether and ethanolamine can also be used. Moreover, the mixture of said water-soluble organic solvent and pure water can also be used as a rinse liquid.
- FIG. 2 shows a cross-sectional view of an Al alloy circuit element containing 90% by mass or more of aluminum (Al) to be peeled.
- a base oxide film 2 made of silicon oxide (SiOx) or the like is formed on a silicon substrate 1, and then a barrier metal layer 3 made of titanium nitride (TiN) / titanium (Ti) is formed.
- An Al alloy layer 4 made of Al-copper (Cu), Al-silicon (Si) or Al-Si-Cu (sometimes referred to as Al alloy wiring) is formed thereon as a wiring, and a barrier metal layer made of TiN / Ti. 5 is applied, and then a resist (1) is applied to form a resist (1) layer.
- the Al alloy layer is exposed at the bottom of the via hole, and the Ti-derived residue 7 remains on the side wall of the via hole, and the resist (2) residue 8 remains on the interlayer insulating film layer 6.
- cleaning was performed using the following residue stripping solution composition.
- Example 1 Comparative Examples 1-9 and 16-24 According to the blending composition (% by mass) shown in Table 1, the residue stripping solution compositions of Example 1, Comparative Examples 1 to 9 and 16 to 24 were prepared.
- ammonium fluoride was used in the residue stripping solution composition of Example 1.
- hydrofluoric acid was used as a fluorine compound instead of ammonium fluoride.
- tetrafluoride was used in Comparative Examples 6 to 8 and 21 to 23, tetrafluoride was used. Methylammonium was used. Comparative Examples 9 and 24 did not contain a fluorine compound.
- the stripping compositions of Example 1 and Comparative Examples 1 to 9 contained 2.00% by mass of 3-methyl-1-pentyn-3-ol as a compound having a carbon-carbon triple bond (anticorrosive). 16-24 did not contain an anticorrosive. All the reagents used here were reagent special grades.
- the evaluation sample wafer shown in FIG. 1 is immersed in the residue stripping liquid compositions of Example 1, Comparative Examples 1 to 9 and 16 to 24 at 25 ° C. for 2 minutes, respectively, and then rinsed with ultrapure water. Nitrogen gas was blown to dry.
- Example 2 Comparative Examples 10-12 and 25-27 According to Table 1, the residue stripping solution compositions of Example 2, Comparative Examples 10 to 12 and 25 to 27 were prepared.
- the molar ratio of methanesulfonic acid / fluorine compound was 1.00 for the residue stripping solution composition of Example 2, 0.75 for Comparative Examples 10 and 25, 1.69 for Comparative Examples 11 and 26, and Comparative Examples 12 and 27. Then, it was set to 2.42.
- the residue stripping liquid compositions of Example 2 and Comparative Examples 10 to 12 contain 0.50% by mass of ethynylbenzene as a compound having a carbon-carbon triple bond (anticorrosive), and in Comparative Examples 25 to 27, the anticorrosive agent was not included.
- the liquid composition was not sufficiently peelable from the resist residue and corroded the material at the bottom of the via hole.
- Examples 3 to 9, Comparative Examples 13 and 28 According to Table 1, the residual stripping solution compositions of Examples 3 to 9 and Comparative Examples 13 and 28 were prepared.
- the residue remover compositions of Examples 3 to 9 contain a water-soluble organic solvent selected from polyhydric alcohols, glycol ethers and amides in the composition, and the residue remover compositions of Comparative Examples 13 and 28 are: A predetermined amount of water-soluble organic solvent was not included.
- Examples 3 to 7 and Comparative Example 13 contain 0.30% by mass of 3,5-dimethyl-1-hexyn-3-ol as a compound having a carbon-carbon triple bond (anticorrosive), and Examples 8 to 9 contained 0.20% by mass of 3-methyl-1-pentyn-3-ol as an anticorrosive agent, and Comparative Example 28 contained no anticorrosive agent. All the reagents used here were reagent special grades. Others were performed according to Example 1, and the results are shown in Table 1. In the residue remover compositions of Examples 3 to 9, the Ti-derived residue and the resist residue were peeled off and the material was not corroded. However, in the residue remover compositions of Comparative Examples 13 and 28, the Ti-derived residue and the resist residue were sufficient. The result was not peeled off.
- Comparative Examples 14-15, 29-30 According to Table 1, the residual stripping solution compositions of Comparative Examples 14 to 15 and 29 to 30 were prepared.
- the residue stripping liquid compositions of Comparative Examples 14 and 29 contained 76.75% by mass of the water-soluble organic solvent, and Comparative Examples 15 and 30 contained 56.75% by mass of the water-soluble organic solvent.
- the residual stripping solution compositions of Comparative Examples 14 to 15 contain 2.00% by mass of 3-methyl-1-pentyn-3-ol as a compound having a carbon-carbon triple bond (anticorrosive), and Comparative Examples 29 to 30. Did not contain anticorrosives. All the reagents used here were reagent special grades. Others were performed according to Example 1, and the results are shown in Table 1.
- the residue stripping liquid compositions of Comparative Examples 14 and 29 were not sufficient in the strippability of Ti-derived residues and strippability of resist residues.
- the residue stripping liquid compositions of Comparative Examples 15 and 30 corroded the material.
- the residue remover composition of Example 1 (66.75% by mass) containing the water-soluble organic solvent in the range of 60 to 75% by mass defined in the present invention, and the residue remover composition of Example 9 (72 .94 mass%) showed good results with no material corrosion and peeling of Ti-derived residues and resist residues.
- Examples 10 to 13 and Comparative Examples 31 to 33 According to Table 1, the residue stripping liquid compositions of Examples 10 to 13 and Comparative Examples 31 to 33 were prepared.
- the basic composition of the stripping composition excluding a compound containing a carbon-carbon triple bond (anticorrosive) is 0.80% by mass of ammonium fluoride, 2.20% by mass of methanesulfonic acid, 20% by mass of diethylene glycol, propylene Glycol monomethyl ether was 51% by mass, and the balance was water.
- no anticorrosive was added, and in the residue remover compositions of Comparative Examples 32-33, 1.00% by mass of an additive other than the compound containing a carbon-carbon triple bond of the present invention was added. .
- Example 14 According to Table 1, the residue stripping solution composition of Example 14 was prepared.
- the basic composition of the residue stripping liquid composition excluding a compound containing a carbon-carbon triple bond (anticorrosive) is 1.00 mass% ammonium fluoride, 3.00 mass% methanesulfonic acid, 30 mass% diethylene glycol, propylene Glycol monomethyl ether was 35% by mass and the balance of water, and the molar ratio of methanesulfonic acid / fluorine compound was 1.16.
- the residue stripping liquid compositions of Examples 15 to 25 were prepared by replacing the compound (corrosion inhibitor) containing a carbon-carbon triple bond in the preparation composition of Example 14. All the reagents used here were reagent special grades. Others were performed according to Example 1, and the results are shown in Table 1. In the residue remover compositions of Examples 14 to 25, Ti-derived residues and resist residues were peeled off, and there was no material corrosivity, and good results were obtained.
- Comparative Examples 34 to 39 According to Table 1, the residue remover compositions of Comparative Examples 34 to 39 were prepared.
- the residue stripping solution composition of Comparative Example 34 has a methanesulfonic acid / ammonium fluoride molar ratio outside the scope of the present invention and does not contain a compound containing a carbon-carbon triple bond (anticorrosive).
- 35 does not contain ammonium fluoride, methanesulfonic acid and anticorrosive
- Comparative Example 36 does not contain methanesulfonic acid and anticorrosive
- Comparative Example 37 does not contain ammonium fluoride and methanesulfonic acid
- Comparative Example No Comparative Example No.
- Comparative Example 38 does not contain ammonium fluoride and anticorrosive agent
- Comparative Example 39 does not contain methanesulfonic acid and contains an excessive amount of water-soluble organic solvent. All the reagents used here were reagent special grades. Others were performed according to Example 1, and the results are shown in Table 1.
- the residue stripping solution composition of Comparative Example 34 is not sufficient in terms of material corrosivity
- Comparative Example 35 is not sufficiently peelable, corrodes the bottom of the via hole
- Comparative Examples 36 to 39 are sufficient in terms of peelability. It wasn't.
- Examples 26 to 37, Comparative Examples 40 to 51 Residue stripping liquid compositions of Examples 26 to 37 and Comparative Examples 40 to 51 were prepared according to the blending composition (% by mass) shown in Table 2.
- the basic composition of the residue stripping liquid composition excluding the compound containing a carbon-carbon triple bond (anticorrosive agent) in these compositions was the same as that of Example 14.
- Comparative Example 40 no anticorrosive was added, and in Comparative Examples 41 to 51, 0.50% by mass of an agent other than the compound containing a carbon-carbon triple bond of the present invention was added. All the reagents used here were reagent special grades.
- the corrosiveness to Al—Cu of the obtained water dilution of the residue stripping solution composition was evaluated.
- the Al—Cu film is obtained by immersing a silicon wafer slice having an Al—Cu film (containing 0.5 mass% of Cu) on the entire surface in a residue stripping solution composition to obtain a film thickness before and after the immersion.
- SEA2110L manufactured by SII Nano Technology Co., Ltd. was used as the fluorescent X-ray analyzer.
- the results of the etching rate are also shown in Table 2.
- the etching rate of Al—Cu in the water dilution solution was obviously reduced to 80% or less as compared with Comparative Example 40 without the anticorrosive agent.
- the etching rate of Al—Cu in the water dilution solution was 85% to 100% as compared with Comparative Example 40 without the anticorrosive agent. Judged that there was no rate reduction effect.
- residue stripping liquid composition and cleaning method of the present invention dry etching and ashing are performed to form via holes in the manufacturing process of a semiconductor substrate having a metal wiring made of Al or Al alloy containing 90 mass% or more of Al. Resist residue and Ti-derived residue remaining after performing the process can be completely removed at a low temperature in a short time, and the product yield in the manufacture of semiconductor devices is improved without corroding members such as interlayer insulation materials and wiring materials. Can do.
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Abstract
Description
2.SiOx酸化膜
3.TiN/Tiバリアメタル層
4.Al合金配線層
5.TiN/Tiバリアメタル層
6.SiOx酸化膜
7.Ti由来残渣
8.レジスト残渣
1.(A)フッ化アンモニウム、(B)メタンスルホン酸、(C)3-メチル-1-ペンチン-3-オール、1-エチニル-1-シクロヘキサノール、2-プロピン-1-オール、2-ブチン-1,4-ジオール、4-エチル-1-オクチン-3-オール、3-メチル-1-ブチン-3-オール、1-オクチン-3-オール、エチニルベンゼン、3,3-ジメチル-1-ブチン、2-ブチン-1-オール、3,5-ジメチル-1-ヘキシン-3-オール、および3-ヘキシン-2,5-ジオールから選択される少なくとも一種である炭素-炭素三重結合を有する化合物、(D)多価アルコール類、グリコールエーテル類、およびアミド類から選ばれる少なくとも一種である水溶性有機溶剤、及び(E)水を含有する残渣剥離液組成物であって、該残渣剥離液組成物中の(A)、(C)、(D)及び(E)の含有量が各々0.005~2質量%、0.1~10質量%、60~75質量%及び5~38質量%であり、(B)が(A)に対して0.9~1.5倍量(モル比)含むものである残渣剥離液組成物。
2.シリコン基板上にSiOx、TiN/Tiからなるバリアメタル層、Alを90質量%以上含むAl-Cu,Al-SiまたはAl-Si-CuからなるAl合金層、及びTiN/Tiからなるバリアメタル層を順に積層し、レジスト(1)を塗布してレジスト(1)層を形成した後、露光、現像を行い、該レジスト(1)層をマスクとしてドライエッチングを行いAl合金配線体を形成し、さらにプラズマガスにより該レジスト(1)層をアッシング除去し、薬液処理によってレジスト(1)残渣を除去し、さらにその上にSiOxからなる層間絶縁膜層を積層し、その後レジスト(2)を塗布してレジスト(2)層を形成した後、露光、現像を行い、該レジスト(2)層をマスクとしてドライエッチングを行い、Al合金配線体上の層間絶縁膜層とバリアメタル層にビアホールを形成し、さらにプラズマガスにより該レジスト(2)層をアッシング除去した電子材料基板より残留する残渣を剥離して洗浄する方法において、上記1に記載の残渣剥離液組成物を用いて、少なくともビアホール内の残渣を剥離する洗浄方法。
本発明の残渣剥離液組成物は、(A)フッ化アンモニウム、(B)メタンスルホン酸、(C)炭素-炭素三重結合を有する化合物、(D)多価アルコール類、グリコールエーテル類、およびアミド類から選ばれる少なくとも一種である水溶性有機溶剤、及び(E)水を含有し、該残渣剥離液組成物中の(A)、(C)、(D)及び(E)の含有量が各々0.005~2質量%、0.1~10質量%、60~75質量%及び5~38質量%であり、(B)が(A)に対して0.9~1.5倍量(モル比)含むものであることを特徴とするものである。
本発明の残渣剥離液組成物は、(A)フッ化アンモニウムを含む。残渣剥離液組成物中のフッ化アンモニウムの含有量は、0.005~2.0質量%の濃度範囲で使用され、好ましくは0.01~1.8質量%、特に0.1~1.5質量%が好ましい。フッ化アンモニウムの濃度が2.0質量%より高い場合には、材質に対する腐食性が高く、0.005質量%より少ない場合には残渣の剥離速度が遅くなってしまう。
本発明の残渣剥離液組成物は、(B)メタンスルホン酸を含む。メタンスルホン酸は、水中あるいは水溶性有機溶剤中の酸解離定数(pKa)が小さく、さらに残渣剥離液組成物中へ混合したときの相溶性、安定性、残渣の剥離性と材質腐食性のバランスなどを考慮して、本発明の残渣剥離液組成物に採用されるものである。
メタンスルホン酸は、含有されるフッ化アンモニウムに対してモル比で0.9倍~1.5倍量含有することを要し、好ましくは、0.9倍~1.4倍量であり、より好ましくは0.95倍~1.3倍量である。0.9倍量未満では、残渣の剥離性が十分ではない、あるいは層間絶縁材料の腐食性が大きくなってしまう。また、1.5倍量より多いと、残渣の剥離性が十分ではない、あるいは金属配線材料の腐食性が大きくなってしまう。
本発明の残渣剥離液組成物は、(C)炭素-炭素三重結合を有する化合物を含む。本発明において、(C)炭素-炭素三重結合を有する化合物は、3-メチル-1-ペンチン-3-オール、1-エチニル-1-シクロヘキサノール、2-プロピン-1-オール、2-ブチン-1,4-ジオール、4-エチル-1-オクチン-3-オール、3-メチル-1-ブチン-3-オール、1-オクチン-3-オール、エチニルベンゼン、3,3-ジメチル-1-ブチン、2-ブチン-1-オール、3,5-ジメチル-1-ヘキシン-3-オール、および3-ヘキシン-2,5-ジオールから選択される少なくとも一種であり、上記の化合物の複数を含有してもよい。
本発明で使用される(D)水溶性有機溶剤は、多価アルコール類、グリコールエーテル類及びアミド類から選ばれる少なくとも一種である。これらの有機溶剤を用いることで、残渣物除去性を向上させることができる。
多価アルコール類としては、エチレングリコール、ジエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール、グリセリン、ジグリセリン、ポリグリセリン、1,3-ブチレングリコールなどが好ましく挙げられる。
グリコールエーテル類としては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノブチルエーテル、トリエチレングリコールジメチルエーテル、ジプロピレングリコールモノプロピルエーテル、トリプロピレングリコールジメチルエーテルなどが好ましく挙げられる。
アミド類としては、ジメチルホルムアミド、ジメチルアセトアミド、アセトアミド、メチルアセトアミド、エチルアセトアミド、ホルムアミド、メチルホルムアミド、ジメチルホルムアミド、エチルホルムアミド、ジエチルホルムアミドなどが好ましく挙げられる。
本発明の残渣剥離液組成物は、(E)水を含む。残渣剥離液組成物中の水の含有量は、5~38質量%であることを要し、20~38質量%であることが好ましく、より好ましくは20~31質量%である。
水の含有量が5質量%より少ない場合は、残渣の剥離性が低下し、38質量%より多い場合は、材質腐食が大きくなってしまう。
本発明の洗浄方法は、シリコン基板上にSiOx、TiN/Tiからなるバリアメタル層、Alを90質量%以上含むAl-Cu,Al-SiまたはAl-Si-CuからなるAl合金層、及びTiN/Tiからなるバリアメタル層を順に積層し、レジスト(1)を塗布してレジスト(1)層を形成した後、露光、現像を行い、該レジスト(1)層をマスクとしてドライエッチングを行いAl合金配線体を形成し、さらにプラズマガスにより該レジスト(1)層をアッシング除去し、薬液処理によってレジスト(1)残渣を除去し、さらにその上にSiOxからなる層間絶縁膜層を積層し、その後レジスト(2)を塗布してレジスト(2)層を形成した後、露光、現像を行い、該レジスト(2)層をマスクとしてドライエッチングを行い、Al合金配線体上の層間絶縁膜層とバリアメタル層にビアホールを形成し、さらにプラズマガスにより該レジスト(2)層をアッシング除去した電子材料基板より残留する残渣を剥離する方法において、本発明の残渣剥離液組成物を用いて、少なくともビアホール内の残渣を剥離するものである。
また、残渣を剥離する際の処理時間は、好ましくは10秒~5分であり、より好ましくは30秒~3分である。
各実施例及び比較例における洗浄の結果、Ti由来残渣及びレジスト残渣の剥離状態、層間絶縁膜材質及びビアホール底の材質の腐食性について、走査型電子顕微鏡(SEM)による観察を行い、下記の基準で行った。走査型電子顕微鏡による観察は、日立高分解能電界放出形走査電子顕微鏡S-4700を用いた。
<Ti由来残渣およびレジスト残渣の剥離性の判定基準>
○:良好。
△:剥離残りがあった。
×:全く剥離できていなかった。
<層間絶縁膜層の材質腐食性の判定基準>
○:良好。
×:腐食し、形状が変化していた。
<ビアホール底の材質腐食性の判定基準>
○:良好。
×:腐食し、形状が変化していた。
図2に、剥離対象であるアルミニウム(Al)を90質量%以上含むAl合金回路素子の断面図を示す。図2に示すように、シリコン基板1に酸化シリコン(SiOx)などからなる下地酸化膜2を形成し、次に窒化チタン(TiN)/チタン(Ti)からなるバリアメタル層3を形成し、その上に配線としてAl-銅(Cu),Al-シリコン(Si)またはAl-Si-Cu(Al合金配線という場合がある)からなるAl合金層4を形成し、TiN/Tiからなるバリアメタル層5を積層し、その後レジスト(1)を塗布してレジスト(1)層を形成した後、露光、現像を行い、該レジスト(1)層をマスクとしてドライエッチングを行い、Al合金配線体を形成し、さらにプラズマガスにより該レジスト(1)層をアッシング除去し、薬液処理によってレジスト(1)残渣を除去した。さらにその上にSiOxからなる層間絶縁膜層6を積層し、その後レジスト(2)を塗布してレジスト(2)層を形成した後、露光、現像を行い、該レジスト(2)層をマスクとしてドライエッチングを行い、層間絶縁膜層6とバリアメタル層5にビアホールを形成し、さらに酸素のプラズマガスによりレジスト(2)層をアッシング除去した。ビアホールの底はAl合金層が露出しており、ビアホール側壁にはTi由来残渣7、層間絶縁膜層6の上部にはレジスト(2)残渣8が残存している。上記のアルミニウム合金回路素子(評価用サンプルウェハ)を用いて下記の残渣剥離液組成物を用いて洗浄を行なった。
表1に示される配合組成(質量%)に従い、実施例1、比較例1~9および16~24の残渣剥離液組成物を調合した。実施例1の残渣剥離液組成物ではフッ化アンモニウムを、比較例1~5および16~20ではフッ化アンモニウムにかわるフッ素化合物としてフッ酸を、比較例6~8および21~23ではフッ化テトラメチルアンモニウムを用いた。比較例9および24ではフッ素化合物を含まなかった。また実施例1、比較例1~9の剥離液組成物は炭素-炭素三重結合を有する化合物(防食剤)として3-メチル-1-ペンチン-3-オールを2.00質量%含み、比較例16~24では防食剤を含まなかった。ここで用いた試薬はすべて試薬特級を用いた。
図1に示される評価用サンプルウェハを、実施例1、比較例1~9および16~24の残渣剥離液組成物にそれぞれ25℃にて2分間浸漬し、その後、超純水でリンスを行い、窒素ガスを吹き付けて乾燥した。処理後のチタン由来残渣7およびレジスト残渣8の剥離性、ならびに層間絶縁膜層6およびビアホール底の材質腐食性について走査型電子顕微鏡(SEM)観察を行い、その結果を表1に記載した。
実施例1の残渣剥離液組成物ではTi由来残渣、レジスト残渣が剥離され、材質腐食性も無く良好な結果であった。比較例1~5および16~20のフッ酸を含む剥離液組成物では、残渣の剥離性およびビアホール底の材質腐食性が十分ではなかった。比較例6~8および21~23のフッ化テトラメチルアンモニウムを含む剥離液組成物では、残渣の剥離性および/または材質腐食性が十分ではなかった。比較例9および24のフッ素化合物を含まない剥離液組成物では、残渣の剥離性が十分ではなかった。
表1に従い、実施例2、比較例10~12および25~27の残渣剥離液組成物を調合した。メタンスルホン酸/フッ素化合物のモル比は、実施例2の残渣剥離液組成物では1.00、比較例10および25では0.75、比較例11および26では1.69、比較例12および27では2.42とした。また、実施例2および比較例10~12の残渣剥離液組成物は、炭素-炭素三重結合を有する化合物(防食剤)としてエチニルベンゼンを0.50質量%含み、比較例25~27では防食剤を含まなかった。ここで用いた試薬はすべて試薬特級を用いた。その他は実施例1に準じて行ない、結果を表1に記載した。
実施例2のメタンスルホン酸/フッ素化合物(モル比)=1.00の残渣剥離液組成物はTi由来残渣、レジスト残渣が剥離され、材質腐食も無く良好な結果を示した。比較例10および25のメタンスルホン酸/フッ素化合物[モル比]=0.75の残渣剥離液組成物は、層間絶縁膜を腐食した。比較例11および26のメタンスルホン酸/フッ素化合物[モル比]=1.69の残渣剥離液組成物ならびに比較例12および27のメタンスルホン酸/フッ素化合物[モル比]=2.42の残渣剥離液組成物は、レジスト残渣の剥離性が十分でなく、ビアホール底の材質を腐食した。
表1に従い、実施例3~9、比較例13および28の残渣剥離液組成物を調合した。実施例3~9の残渣剥離液組成物は、組成中に多価アルコール類、グリコールエーテル類およびアミド類から選ばれる水溶性有機溶剤を含み、比較例13および28の残渣剥離液組成物は、所定量の水溶性有機溶剤を含まなかった。また、実施例3~7および比較例13は炭素-炭素三重結合を有する化合物(防食剤)として3,5-ジメチル-1-ヘキシン-3-オールを0.30質量%含み、実施例8~9は防食剤として3-メチル-1-ペンチン-3-オールを0.20質量%含み、比較例28は防食剤を含まなかった。ここで用いた試薬はすべて試薬特級を用いた。その他は実施例1に準じて行ない、結果を表1に記載した。
実施例3~9の残渣剥離液組成物ではTi由来残渣およびレジスト残渣が剥離され材質も腐食しなかったが、比較例13、28の残渣剥離液組成物ではTi由来残渣およびレジスト残渣が十分に剥離されない結果となった。
表1に従い、比較例14~15および29~30の残渣剥離液組成物を調合した。比較例14および29の残渣剥離液組成物は水溶性有機溶剤を76.75質量%含み、比較例15および30では水溶性有機溶剤を56.75質量%含んでいた。また比較例14~15の残渣剥離液組成物は炭素-炭素三重結合を有する化合物(防食剤)として3-メチル-1-ペンチン-3-オールを2.00質量%含み、比較例29~30は防食剤を含まなかった。ここで用いた試薬はすべて試薬特級を用いた。その他は実施例1に準じて行ない、結果を表1に記載した。
比較例14および29の残渣剥離液組成物は、Ti由来残渣の剥離性およびレジスト残渣の剥離性が十分ではなかった。比較例15および30の残渣剥離液組成物は、材質を腐食した。一方、水溶性有機溶剤を本発明で規定する60~75質量%の範囲で含む実施例1の残渣剥離液組成物(66.75質量%)や、実施例9の残渣剥離液組成物(72.94質量%)は、Ti由来残渣およびレジスト残渣が剥離され、材質腐食性もなく良好な結果を示した。
表1に従い、実施例10~13および比較例31~33の残渣剥離液組成物を調合した。炭素-炭素三重結合を含む化合物(防食剤)を除く該剥離液組成物の基本的な組成は、フッ化アンモニウム0.80質量%、メタンスルホン酸2.20質量%、ジエチレングリコール20質量%、プロピレングリコールモノメチルエーテル51質量%、水残部とした。比較例31の残渣剥離液組成物では防食剤無し、比較例32~33の残渣剥離液組成物では、本発明の炭素-炭素三重結合を含む化合物以外の添加剤を1.00質量%加えた。ここで用いた試薬はすべて試薬特級を用いた。その他は実施例1に準じて行い、結果を表1に記載した。
実施例10~13の残渣剥離液組成物では、Ti由来残渣、レジスト残渣が剥離され、材質腐食性も無く良好な結果であった。比較例31~33の残渣剥離液組成物ではビアホール底を腐食した。
表1に従い、実施例14の残渣剥離液組成物を調合した。炭素-炭素三重結合を含む化合物(防食剤)を除く残渣剥離液組成物の基本的な組成は、フッ化アンモニウム1.00質量%、メタンスルホン酸3.00質量%、ジエチレングリコール30質量%、プロピレングリコールモノメチルエーテル35質量%、および水残部であり、メタンスルホン酸/フッ素化合物のモル比は、1.16であった。実施例15~25の残渣剥離液組成物は、実施例14の調合組成において、炭素-炭素三重結合を含む化合物(防食剤)を代えたものである。ここで用いた試薬はすべて試薬特級を用いた。その他は実施例1に準じて行い、結果を表1に記載した。
実施例14~25の残渣剥離液組成物では、Ti由来残渣、レジスト残渣が剥離され、材質腐食性も無く良好な結果であった。
表1に従い、比較例34~39の残渣剥離液組成物を調合した。比較例34の残渣剥離液組成物は、メタンスルホン酸/フッ化アンモニウムのモル比が本発明の範囲外であり、かつ炭素-炭素三重結合を含む化合物(防食剤)を含有せず、比較例35ではフッ化アンモニウム、メタンスルホン酸および防食剤を含有せず、比較例36ではメタンスルホン酸および防食剤を含有せず、比較例37ではフッ化アンモニウムおよびメタンスルホン酸を含有せず、比較例38ではフッ化アンモニウムおよび防食剤を含有せず、比較例39ではメタンスルホン酸を含有せず、過剰に水溶性有機溶剤を含有するものである。ここで用いた試薬はすべて試薬特級を用いた。その他は実施例1に準じて行い、結果を表1に記載した。
比較例34の残渣剥離液組成物は材質腐食性の点で十分ではなく、比較例35では剥離性が十分ではなく、ビアホール底を腐食し、比較例36~39では、剥離性の点で十分ではなかった。
[略称]
DMAc:N,N-ジメチルアセトアミド、DEG:ジエチレングリコール、DPG:ジプロピレングリコール、TEG:テトラエチレングリコール、DGME:ジエチレングリコールモノメチルエーテル、MFDG:ジプロピレングリコールモノメチルエーテル、MFG:プロピレングリコールモノメチルエーテル、DGBE:ジエチレングリコールモノブチルエーテル、DMSO:ジメチルスルホキシド、HEDP:1-ヒドロキシエチリデン-1,1-ジスルホン酸、
EG:1,2-エタンジオール、PGE:1-エトキシ-2-プロパノール、1,3-BDO:1,3-ブタンジオール
表2に示される配合組成(質量%)に従い、実施例26~37および比較例40~51の残渣剥離液組成物を調合した。これらの組成物の炭素-炭素三重結合を含む化合物(防食剤)を除く残渣剥離液組成物の基本的な組成は、実施例14の組成物と同じとした。比較例40では防食剤無し、比較例41~51では本発明の炭素-炭素三重結合を含む化合物以外の剤を0.50質量%加えた。ここで用いた試薬はすべて試薬特級を用いた。
得られた残渣剥離液組成物の水希釈液(実施例あるいは比較例の残渣剥離液組成物10gと超純水10gを混合して調製)のAl-Cuに対する腐食性を評価した。Al-Cu膜は、表面全面にAl-Cu膜(Cuを0.5質量%含有する)が成膜されたシリコンウェハ切片を、残渣剥離液組成物中に浸漬して、浸漬前後の膜厚を蛍光X線分析装置にて測定し、エッチングレートを求めた。蛍光X線分析装置はエスアイアイ・ナノテクノロジー株式会社製 SEA2110Lを使用した。エッチングレートの結果を表2に併せて記載した。
Claims (4)
- (A)フッ化アンモニウム、(B)メタンスルホン酸、(C)3-メチル-1-ペンチン-3-オール、1-エチニル-1-シクロヘキサノール、2-プロピン-1-オール、2-ブチン-1,4-ジオール、4-エチル-1-オクチン-3-オール、3-メチル-1-ブチン-3-オール、1-オクチン-3-オール、エチニルベンゼン、3,3-ジメチル-1-ブチン、2-ブチン-1-オール、3,5-ジメチル-1-ヘキシン-3-オール、および3-ヘキシン-2,5-ジオールから選択される少なくとも一種である炭素-炭素三重結合を有する化合物、(D)多価アルコール類、グリコールエーテル類、およびアミド類から選ばれる少なくとも一種である水溶性有機溶剤、及び(E)水を含有する残渣剥離液組成物であって、該残渣剥離液組成物中の(A)、(C)、(D)及び(E)の含有量が各々0.005~2質量%、0.1~10質量%、60~75質量%及び5~38質量%であり、(B)が(A)に対して0.9~1.5倍量(モル比)含むものである残渣剥離液組成物。
- シリコン基板上にSiOx、TiN/Tiからなるバリアメタル層、Alを90質量%以上含むAl-Cu,Al-SiまたはAl-Si-CuからなるAl合金層、及びTiN/Tiからなるバリアメタル層を順に積層し、レジスト(1)を塗布してレジスト(1)層を形成した後、露光、現像を行い、該レジスト(1)層をマスクとしてドライエッチングを行いAl合金配線体を形成し、さらにプラズマガスにより該レジスト(1)層をアッシング除去し、薬液処理によってレジスト(1)残渣を除去し、さらにその上にSiOxからなる層間絶縁膜層を積層し、その後レジスト(2)を塗布してレジスト(2)層を形成した後、露光、現像を行い、該レジスト(2)層をマスクとしてドライエッチングを行い、Al合金配線体上の層間絶縁膜層とバリアメタル層にビアホールを形成し、さらにプラズマガスにより該レジスト(2)層をアッシング除去した電子材料基板より残留する残渣を剥離して洗浄する方法において、請求項1に記載の残渣剥離液組成物を用いて、少なくともビアホール内の残渣を剥離する洗浄方法。
- 残渣の剥離を10~40℃で行う請求項2に記載の洗浄方法。
- 残渣の剥離を30秒~3分で行う請求項2又は3に記載の洗浄方法。
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JP6412377B2 (ja) * | 2013-09-11 | 2018-10-24 | 花王株式会社 | 樹脂マスク層用洗浄剤組成物及び回路基板の製造方法 |
KR102261638B1 (ko) * | 2013-11-15 | 2021-06-08 | 삼성디스플레이 주식회사 | 세정제 조성물 및 이를 이용한 금속배선 제조방법 |
CN103887230B (zh) * | 2014-03-28 | 2016-08-31 | 中国电子科技集团公司第二十四研究所 | 等离子体刻蚀AlSi的方法 |
US10170296B2 (en) | 2014-05-13 | 2019-01-01 | Basf Se | TiN pull-back and cleaning composition |
JP6840041B2 (ja) * | 2017-06-21 | 2021-03-10 | 東京エレクトロン株式会社 | エッチング方法 |
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