Classifications

• • 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
  • C11D7/26—Organic compounds containing oxygen
• • 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
• • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices

Definitions

• the present invention relates to a composition used to remove polymer residues, resist, and/or resist residues on a substrate for manufacturing semiconductor devices by applying ultrasonic waves, and a method for removing polymer residues, resist, and/or resist residues on a substrate for manufacturing semiconductor devices by applying ultrasonic waves using such a composition.
• organic polymer residues are generated on the substrate.
• the organic polymer residues must be removed from the substrate in the next process.
• a deposit (CF polymer) composed of silicon (Si), carbon (C) and fluorine (F) remains on the substrate.
• the CF polymer also needs to be removed from the substrate in a later process. It is also required that these polymer residues be removed without damaging metals such as copper (Cu) and aluminum (Al).
• NMP N-methylpyrrolidone
• Patent Document 1 The most commonly used resist removal compositions are those containing N-methylpyrrolidone (NMP) (Patent Document 1).
• NMP N-methylpyrrolidone
• DFR dry film resists
• the resist can be removed by applying ultrasound to N-methylpyrrolidone (NMP).
• NMP N-methylpyrrolidone
• the process of applying ultrasound to N-methylpyrrolidone (NMP) has been used as an extremely powerful tool that can remove stubborn resists without damaging the wiring metal.
• the use of removal compositions containing N-methylpyrrolidone (NMP) is restricted due to its toxicity to the human body.
• Patent Documents 2 to 5 As resist removal compositions that do not contain N-methylpyrrolidone (NMP), those containing components such as tetramethylammonium hydroxide (TMAH), water, and alkylene glycol monoalkyl ether have been proposed (Patent Documents 2 to 5). In addition, although no specific studies have been conducted, there is also a description of an embodiment in which ultrasonic waves are applied to the resist removal composition (Patent Documents 2 to 3, 5).
• NMP N-methylpyrrolidone
• TMAH tetramethylammonium hydroxide
• water alkylene glycol monoalkyl ether
• the present inventors have encountered the problem that the conventional removal compositions containing the above-mentioned tetramethylammonium hydroxide (TMAH) or water have insufficient removability for excessively hardened resist, causing damage (corrosion, erosion, etc.) to wiring metals such as copper (Cu) and aluminum (Al), and in addition, that applying ultrasonic waves to these removal compositions improves the removability but worsens the damage to the wiring metal. Also, the present inventors have encountered the problem that compositions containing dipropylene glycol monomethyl ether, an example of alkylene glycol monoalkyl ether, have insufficient resist removal ability.
• TMAH tetramethylammonium hydroxide
• the present inventors have carried out research with the objective of providing a removal composition that does not contain N-methylpyrrolidone (NMP), which can satisfactorily remove resists that are difficult to remove, such as hardened resists and dry film resists (DFR), polymer residues and resist residues on substrates for manufacturing semiconductor devices, and can further suppress damage to wiring metal.
• NMP N-methylpyrrolidone
• DFR dry film resists
• the objective of the present invention is to provide a removal composition that can satisfactorily remove strong resists, polymer residues and resist residues on substrates for manufacturing semiconductor devices, while reducing toxicity to the human body, and can suppress damage to wiring metal.
• a non-aqueous composition containing diethylene glycol monoethyl ether (EDG) or triethylene glycol monomethyl ether (TEGME) can effectively remove stubborn resist, polymer residues on substrates used in semiconductor device manufacturing, and resist residues while applying ultrasonic waves, and can also suppress damage to wiring metal.
• EDG diethylene glycol monoethyl ether
• TOGME triethylene glycol monomethyl ether
• the present invention relates to the following.
• a non-aqueous composition used for removing polymer residues, resist, and/or resist residues on a substrate for manufacturing a semiconductor device by applying ultrasonic waves the composition containing 80 to 100 mass % of diethylene glycol monoethyl ether or triethylene glycol monomethyl ether.
• the additive is selected from glycol ethers other than diethylene glycol monoethyl ether and triethylene glycol monomethyl ether, sulfolane, and tetrahydrofurfuryl alcohol.
• [5] The composition according to any one of [1] to [4] above, which is used after being heated to 40° C. or higher.
• [6] The composition according to any one of [1] to [5] above, wherein the semiconductor substrate has copper wiring and/or aluminum wiring.
• a method for removing polymer residues, resist, and/or resist residues on a substrate for manufacturing a semiconductor device comprising contacting the substrate for manufacturing a semiconductor device having the polymer residues, resist, and/or resist residues with the composition according to any one of [1] to [6] above while applying ultrasonic waves.
• a method for cleaning a substrate for use in the manufacture of semiconductor devices comprising rinsing the substrate for use in the manufacture of semiconductor devices with water or 2-propanol after the method according to [7] above.
• the composition of the present invention does not use N-methylpyrrolidone (NMP), which is highly toxic to humans, and can effectively remove polymer residues, strong resist, and resist residues on substrates used in manufacturing semiconductor devices by applying ultrasonic waves. Furthermore, the composition of the present invention does not corrode or erode the wiring metal even when ultrasonic waves are applied to the wiring metal, and can effectively suppress damage to the wiring metal.
• NMP N-methylpyrrolidone
• FIG. 1 is a diagram showing the state of the substrate surface before immersion and the state of the substrate surface after immersion (resist removal) in the compositions of Example 1, Comparative Example 2, and Comparative Example 5 while applying ultrasonic waves.
• FIG. 2 is a diagram showing the state of the Cu film surface before immersion and the state of damage (surface roughness) on the Cu film surface after immersion while applying ultrasonic waves to the compositions of Example 1, Comparative Example 2, and Comparative Example 5.
• the present invention relates to a non-aqueous composition used for removing polymer residues, resist, and/or resist residues on a substrate for manufacturing a semiconductor device by applying ultrasonic waves, the composition containing 80 to 100 mass % of diethylene glycol monoethyl ether or triethylene glycol monomethyl ether.
• the composition of the present invention is used to remove polymer residues, resist, and/or resist residues on substrates for semiconductor device manufacturing by applying ultrasonic waves.
• the polymer residue refers to organic polymer residues generated during semiconductor device manufacturing, such as polyimide residues, polybenzoxazole residues, and acrylic polymer residues, as well as CF polymer residues generated during dry etching of silicon.
• the resist refers to, for example, a resist applied to a substrate for manufacturing a semiconductor device having copper (Cu) wiring and aluminum (Al) wiring formed in a copper (Cu) bump forming process or an aluminum (Al) wiring forming process.
• the resist includes a resist that is difficult to remove, such as a hardened resist or a dry film resist (DFR).
• the resist residue refers to resist remaining on a substrate used for manufacturing a semiconductor device after resist removal is performed before contacting the composition of the present invention with the substrate, and includes, for example, resist remaining on a substrate after rough removal (ashing) of the resist with
• the substrate having the polymer residue, resist, and/or resist residue is a substrate for semiconductor device manufacturing.
• the substrate for semiconductor device manufacturing refers to a substrate used in semiconductor device manufacturing, and is made of, but is not limited to, silicon (Si), silicon oxide, silicon carbide, titanium oxide, aluminum oxide, gallium oxide, gallium nitride, indium phosphide, gallium arsenide, or the like.
• a substrate for manufacturing a semiconductor device has wiring, contacts, electrodes, and the like.
• Metals and metal alloys used for wiring, contacts, electrodes, and the like are not particularly limited, but include copper (Cu), aluminum (Al), aluminum (Al) alloyed with copper (Cu), aluminum (Al) alloyed with silicon, titanium, tungsten, cobalt, ruthenium, nickel, chromium, molybdenum, palladium, gold, silver, indium tin oxide, IGZO, and the like.
• a substrate for manufacturing a semiconductor device has copper (Cu) wiring and/or aluminum (Al) wiring.
• Ultrasound is applied to the composition of the present invention.
• shock waves are generated (cavitation effect), and these shock waves pulverize the polymer residue, resist, and/or resist residue.
• the composition of the present invention penetrates between the substrate and the polymer residue, resist, and/or resist residue, and is able to remove these from the substrate. Therefore, by applying ultrasound, removability is significantly improved.
• compositions of the present invention include diethylene glycol monoethyl ether (EDG) and/or triethylene glycol monomethyl ether (TEGME).
• EDG diethylene glycol monoethyl ether
• TOGME triethylene glycol monomethyl ether
• compositions that are N-methylpyrrolidone (NMP)-free and have high removability contain tetramethylammonium hydroxide (TMAH), potassium hydroxide (KOH), water, etc., and have insufficient removability, causing damage to the wiring metal.
• TMAH tetramethylammonium hydroxide
• KOH potassium hydroxide
• water etc.
• the composition of the present invention contains organic solvents called diethylene glycol monoethyl ether (EDG) and/or triethylene glycol monomethyl ether (TEGME), and causes almost no damage to the wiring metal even when ultrasound is applied.
• EDG diethylene glycol monoethyl ether
• TEGME triethylene glycol monomethyl ether
• the content of diethylene glycol monoethyl ether (EDG) or triethylene glycol monomethyl ether (TEGME) is 80 to 100% by mass based on the total mass of the composition. From the viewpoints of solubility and removability of polymer residues, resist, and/or resist residues, and suppression of damage to wiring metals, the content of diethylene glycol monoethyl ether (EDG) or triethylene glycol monomethyl ether (TEGME) is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, and even more preferably 98 to 100% by mass based on the total mass of the composition.
• the composition of the present invention may comprise, as the balance excluding diethylene glycol monoethyl ether (EDG) or triethylene glycol monomethyl ether (TEGME), at least one additive.
• the additive include glycol ethers other than diethylene glycol monoethyl ether or triethylene glycol monomethyl ether, glycols, amines, sulfolane, tetrahydrofurfuryl alcohol, benzyl alcohol, phenoxyethanol, glycerin, 1,3-dimethylimidazolidinone, ⁇ -butyrolactone, 2-pyrrolidinone, 1-(2-hydroxyethyl)-2-pyrrolidone, benzotriazole, adenine, carboxylbenzotriazole, 1-hydroxybenzotriazole, triazole, surfactants, etc.
• glycol ethers other than diethylene glycol monoethyl ether (EDG) and triethylene glycol monomethyl ether (TEGME), sulfolane, and tetrahydrofurfuryl alcohol are preferred.
• glycol ethers than diethylene glycol monoethyl ether (EDG) and triethylene glycol monomethyl ether (TEGME) include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol phenyl ether, and diethylene glycol monobutyl ether (BDG).
• EDG diethylene glycol monoethyl ether
• TMGME triethylene glycol monomethyl ether
• BDG diethylene glycol monobutyl ether
• Glycols include ethylene glycol and propylene glycol.
• Amines include ethanolamine, diethanolamine, triethanolamine, propanolamine, 4-(2-hydroxyethyl)morpholine, 1-(2-dimethylaminoethyl)-4-methylpiperazine, N-(2-aminoethyl)piperazine, 2-(2-aminoethoxy)ethanol, etc.
• the additives can be used alone or in combination of two or more.
• the content of the additive is 0 to 20% by mass, based on the total mass of the composition. From the viewpoint of removability of polymer residues, resist, and/or resist residues, the content of the additive is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 2% by mass, based on the total mass of the composition.
• the composition of the present invention is a non-aqueous composition.
• non-aqueous refers to not containing water.
• the composition of the present invention contains water, the removability of the polymer residue, resist, and/or resist residue decreases, and the wiring metal corrodes.
• the composition of the present invention preferably does not contain N-methylpyrrolidone. From the viewpoints of suppressing toxicity to the human body and suppressing damage to wiring metals, the composition of the present invention preferably does not contain dimethyl sulfoxide (DMSO). From the viewpoint of suppressing damage to the wiring metal, the composition of the present invention preferably does not contain tetramethylammonium hydroxide (TMAH). From the viewpoint of suppressing damage to the wiring metal, the composition of the present invention preferably does not contain an inorganic alkali, such as potassium hydroxide, sodium hydroxide, ammonia, potassium carbonate, and sodium carbonate.
• DMSO dimethyl sulfoxide
• TMAH tetramethylammonium hydroxide
• an inorganic alkali such as potassium hydroxide, sodium hydroxide, ammonia, potassium carbonate, and sodium carbonate.
• the composition of the present invention preferably does not contain an organic acid, such as oxalic acid, citric acid, malic acid, acetic acid, succinic acid, tartaric acid, or methanesulfonic acid.
• the composition of the present invention preferably does not contain an inorganic acid, such as sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid, or hydrochloric acid.
• the compositions of the present invention in one embodiment, are free of aromatic hydrocarbons.
• the composition of the present invention is used after being heated to 25°C or higher. From the viewpoint of removability, the composition of the present invention is used after being heated to preferably 40°C or higher, more preferably 60°C or higher, and even more preferably 80°C or higher. In one embodiment, the composition of the present invention is used after being heated to 100°C or lower. From the viewpoints of preventing damage to the wiring metal and safety and management, the composition of the present invention is used after being heated to preferably 130°C or lower, more preferably 110°C or lower, and even more preferably 100°C or lower.
• the method for producing the composition of the present invention is not particularly limited.
• the composition of the present invention may be prepared, for example, by mixing the components.
• the composition of the present invention does not need to be prepared in advance, and may be prepared, for example, immediately before removing the polymer residue, resist, and resist residue.
• the present invention also relates to a method for removing polymer residues, resist, and/or resist residues on a substrate for semiconductor device production, comprising contacting the substrate for semiconductor device production having the polymer residues, resist, and/or resist residues with a composition of the present invention.
• the method of the present invention can remove polymer residues, resist, and/or resist residues on a substrate for semiconductor device production by contacting the composition of the present invention with the substrate for semiconductor device production having polymer residues, resist, and/or resist residues.
• the contact method is not particularly limited, but examples include immersing the substrate together with the composition of the present invention, spraying the composition of the present invention onto the substrate by a shower, etc.
• a batch type apparatus or the like When the substrate is immersed in the composition of the present invention together with the substrate, a batch type apparatus or the like can be used.
• a single-wafer type apparatus or the like When the substrate is immersed in the composition of the present invention together with the substrate, a batch type apparatus or the like can be used.
• the composition of the present invention When the composition of the present invention is sprayed onto the substrate by a shower or the like, a single-wafer type apparatus or the like can be used.
• the method of the present invention allows the components of the composition of the present invention and the processing conditions (e.g., temperature, time, the fluidity of the composition of the present invention during immersion, the oscillation speed of the substrate, the pressure and/or flow rate of the shower, etc.) to be appropriately adjusted.
• the processing conditions e.g., temperature, time, the fluidity of the composition of the present invention during immersion, the oscillation speed of the substrate, the pressure and/or flow rate of the shower, etc.
• the method of the present invention is carried out while applying ultrasonic waves.
• ultrasonic waves When ultrasonic waves are applied to the composition of the present invention, shock waves are generated (cavitation effect), and the shock waves pulverize the polymer residue, resist, and/or resist residue, and the composition of the present invention penetrates between the substrate and the polymer residue, resist, and/or resist residue, and can remove them from the substrate. Therefore, by applying ultrasonic waves, the removability can be significantly improved compared to the case where the composition of the present invention is removed alone.
• the frequency of the ultrasonic waves is preferably 20 to 1000 KHz from the viewpoint of removability of polymer residues, resist, and/or resist residues and suppression of erosion of wiring metals. From the same viewpoint, the output of the ultrasonic waves is preferably 50 to 1200 W.
• the method of the present invention comprises contacting a composition of the present invention with copper (Cu) and/or aluminum (Al) interconnects having polymer residues, resist, and/or resist residues.
• the method of the present invention in one aspect, comprises contacting a composition of the present invention with a silicon (Si) substrate having polymer residues, resist, and/or resist residues for semiconductor device manufacture.
• the present invention includes the steps of: (A) providing a substrate for semiconductor device production having polymer residue, resist, and/or resist residue; (B) contacting the substrate for semiconductor device production having polymer residue, resist, and/or resist residue with a composition of the present invention to remove the polymer residue, resist, and/or resist residue; (C) rinsing the substrate for semiconductor device production with water or 2-propanol (IPA); and (D) drying the substrate for semiconductor device production.
• the present invention further relates to a method for cleaning a substrate for use in the manufacture of semiconductor devices, comprising contacting the composition of the present invention with a substrate for use in the manufacture of semiconductor devices having polymer residues, resist, and/or resist residues, and then rinsing the substrate for use in the manufacture of semiconductor devices with water or 2-propanol (IPA).
• IPA 2-propanol
• composition of the present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these.
• compositions according to Examples 1 to 5 and Comparative Examples 1 to 14 were prepared. Specifically, the components shown in Table 1 were mixed to prepare the compositions according to Examples 1 to 5 and Comparative Examples 1 to 14, respectively.
• FIG. 1 shows the state of the substrate surface before immersion and the state of the substrate surface after immersion (resist removal) in the compositions of Example 1, Comparative Example 2, and Comparative Example 5 while applying ultrasonic waves.
• FIG. 2 shows the state of the copper (Cu) film surface before immersion and the state of damage (surface roughness) on the copper (Cu) film surface after immersion while applying ultrasonic waves to the compositions of Example 1, Comparative Example 2, and Comparative Example 5.
• IPA 2-propanol
• EDG diethylene glycol monoethyl ether (ethyl carbitol)
• TEGME triethylene glycol monomethyl ether
• NMP stands for N-methylpyrrolidone
• DMSO dimethyl sulfoxide
• BDG diethylene glycol monobutyl ether (butyl carbitol)
• MDG diethylene glycol monomethyl ether (methyl carbitol)
• DPGME dipropylene glycol monomethyl ether
• BnOH stands for benzyl alcohol
• PhOEtOH stands for phenoxyethanol
• THFA tetrahydrofurfuryl alcohol.
• the compositions according to Examples 1 to 5 exhibited good dry film resist (DFR) removability, good inhibition of the corrosion rates of copper (Cu) and aluminum (Al), good inhibition of surface roughness of copper (Cu) and aluminum (Al), and good water rinsability and 2-propanol (IPA) rinsability of the compositions.
• the compositions according to Comparative Examples 1 to 14 showed insufficient results in one or more of the dry film resist (DFR) removability, the inhibition of the corrosion rate of (Cu) and aluminum (Al), the inhibition of surface roughness of (Cu) and aluminum (Al), and the water rinsability and 2-propanol (IPA) rinsability of the composition.

Landscapes

• Chemical & Material Sciences (AREA)
• Wood Science & Technology (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• General Physics & Mathematics (AREA)
• Health & Medical Sciences (AREA)
• Physics & Mathematics (AREA)
• Emergency Medicine (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Cleaning Or Drying Semiconductors (AREA)
• Detergent Compositions (AREA)
• Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=93939181

Family Applications (1)

Country Status (3)

Citations (5)

• 2023
  • 2023-06-28 JP JP2023105693A patent/JP2025005509A/ja active Pending
• 2024
  • 2024-06-27 TW TW113123954A patent/TW202505318A/zh unknown
  • 2024-06-27 WO PCT/JP2024/023322 patent/WO2025005178A1/ja not_active Ceased

Patent Citations (5)

Also Published As

Similar Documents

Legal Events