Polymer removal composition and removal method

Abstract

The present invention addresses the problem of providing a removal composition which is capable of satisfactorily removing a strong resist, and a polymer residue and a resist residue on a substrate for the semiconductor device production, while reducing the toxicity to humans, and which is also capable of suppressing damage on a wiring metal.　The present invention relates to a nonaqueous composition which is used for the purpose of removing a polymer residue, a resist, and / or a resist residue on a substrate for the semiconductor device production by applying ultrasonic waves thereto, and which contains 80% by mass to 100% by mass of diethylene glycol monoethyl ether or triethylene glycol monomethyl ether.

Description

Polymer removal compositions and removal methods

[0001] The present invention relates to a composition used to remove polymer residues, resist, and / or resist residues on a substrate for manufacturing a semiconductor device by applying ultrasonic waves, and a method for removing polymer residues, resist, and / or resist residues on a substrate for manufacturing a semiconductor device by applying ultrasonic waves using such a composition.

[0002] In the manufacture of semiconductor devices, photolithography processes for forming metal wiring patterns, such as copper (Cu), on silicon or glass substrates require the removal of unnecessary photoresist coatings after etching or plating processes. In particular, etching and plating processes require compositions capable of removing difficult-to-remove resists, such as hardened resists and dry film resists (DFRs). In addition, copper (Cu) and aluminum (Al) are often used as metals for wiring, and compositions capable of removing tough resists without damaging these wiring metals are needed. Furthermore, in semiconductor device manufacturing, processing and reworking organic polymers, such as polyimides used as insulating or protective films on substrates, generates organic polymer residues on the substrate. These organic polymer residues must be removed from the substrate in the next process. Similarly, after plasma etching of a silicon oxide film used as an insulating film on a substrate, 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 subsequent process. These polymer residues are also required to be removed without damaging metals such as copper (Cu) and aluminum (Al).

[0003] The most commonly used resist removal compositions include those containing N-methylpyrrolidone (NMP) (see Patent Document 1). Resists that are easy to remove can be removed by simply immersing them in N-methylpyrrolidone (NMP). Resists that are difficult to remove, such as hardened resists and dry film resists (DFR), can be removed by applying ultrasound to N-methylpyrrolidone (NMP). In particular, the process of applying ultrasound to N-methylpyrrolidone (NMP) has been used as a very powerful tool for removing stubborn resists without damaging the wiring metal. However, the use of removal compositions containing N-methylpyrrolidone (NMP) is restricted due to its toxicity to humans.

[0004] 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 has also been described an embodiment in which ultrasonic waves are applied to the resist removal composition (Patent Documents 2 to 3 and 5).

[0005] JP 2013-501958 A JP 2012-526295 A International Publication No. 2019 / 187868 International Publication No. 2021 / 020410 Japanese Patent Application Laid-Open No. 2006-251786

[0006] The present inventors have encountered the problem that conventional removal compositions containing tetramethylammonium hydroxide (TMAH) or water have insufficient removability for overly hardened resist, causing damage (e.g., corrosion, erosion) to wiring metals such as copper (Cu) and aluminum (Al). Furthermore, applying ultrasonic waves to these removal compositions improves removability but worsens damage to the wiring metal. Furthermore, the present inventors have encountered the problem that compositions containing dipropylene glycol monomethyl ether, an example of an alkylene glycol monoalkyl ether, have insufficient resist removal. Therefore, the present inventors have conducted research aimed at providing a removal composition that does not contain N-methylpyrrolidone (NMP) and can effectively remove hard-to-remove resists such as cured resists and dry film resists (DFR), as well as polymer residues and resist residues on substrates used in semiconductor device manufacturing, while also suppressing damage to the wiring metal. That is, an object of the present invention is to provide a removal composition that can effectively remove tough resist, polymer residues on substrates used for manufacturing semiconductor devices, and resist residues while reducing toxicity to the human body and suppressing damage to wiring metal.

[0007] In the course of intensive research to achieve the above object, the present inventors have found that a non-aqueous composition containing diethylene glycol monoethyl ether (EDG) or triethylene glycol monomethyl ether (TEGME) can effectively remove tough resist, polymer residues on substrates used in semiconductor device production, and resist residues while applying ultrasonic waves, and can also suppress damage to wiring metal. As a result of further research, the present inventors have completed the present invention.

[0008] That is, the present invention relates to the following: [1] 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. [2] The composition according to [1] above, containing 90 to 100 mass % of diethylene glycol monoethyl ether or triethylene glycol monomethyl ether. [3] The composition according to [1] or [2] above, containing at least one additive as the balance. [4] The composition according to any of [1] to [3] above, wherein the additive is selected from glycol ethers other than diethylene glycol monoethyl ether and triethylene glycol monomethyl ether, sulfolane, and tetrahydrofurfuryl alcohol.

[0009] [5] The composition according to any one of [1] to [4] above, which is used after heating 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. [7] 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 polymer residues, resist, and / or resist residues with the composition according to any one of [1] to [6] above, while applying ultrasonic waves. [8] A method for cleaning a substrate for semiconductor device production, comprising rinsing the substrate for semiconductor device production with water or 2-propanol after the method according to [7] above.

[0010] The composition of the present invention does not use N-methylpyrrolidone (NMP), which is highly toxic to humans, and by applying ultrasonic waves, it can effectively remove polymer residues, strong resists, and resist residues from substrates used in manufacturing semiconductor devices. Furthermore, even when ultrasonic waves are applied, the composition of the present invention does not corrode or erode the wiring metal, and can effectively suppress damage to the wiring metal.

[0011] 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) while applying ultrasonic waves to the compositions of Example 1, Comparative Example 2, and Comparative Example 5. 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.

[0012] The present invention relates to a non-aqueous composition used for removing polymer residues, resist, and / or resist residues from a substrate used in 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.

[0013] The composition of the present invention is used to remove polymer residues, resist, and / or resist residues on semiconductor device manufacturing substrates by applying ultrasonic waves. Polymer residues refer to organic polymer residues, such as polyimide residues, polybenzoxazole residues, and acrylic polymer residues, which are generated during semiconductor device manufacturing, as well as CF polymer residues generated during silicon dry etching. Resist refers to, for example, resists applied to semiconductor device manufacturing substrates having copper (Cu) wiring and aluminum (Al) wiring formed in copper (Cu) bump formation processes or aluminum (Al) wiring formation processes. In one embodiment, resists include hardened resists and dry film resists (DFRs) that are difficult to remove. Resist residue refers to resists remaining on substrates after resist removal before contacting the composition of the present invention with the semiconductor device manufacturing substrate, such as resists remaining on substrates after rough resist removal (ashing) with oxygen plasma.

[0014] A substrate having polymer residue, resist, and / or resist residue is a substrate for semiconductor device manufacturing. The term "substrate for semiconductor device manufacturing" refers to a substrate used in semiconductor device manufacturing, and is composed of, for example, but not limited to, silicon (Si), silicon oxide, silicon carbide, titanium oxide, aluminum oxide, gallium oxide, gallium nitride, indium phosphide, gallium arsenide, etc. In one embodiment, the substrate for semiconductor device manufacturing has wiring, contacts, electrodes, etc. Metals and metal alloys used for wiring, contacts, electrodes, etc. include, but are not limited to, 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, etc. In one embodiment, the substrate for semiconductor device manufacturing has copper (Cu) wiring and / or aluminum (Al) wiring.

[0015] Ultrasonic waves are applied to the composition of the present invention. When ultrasonic waves are 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. Furthermore, the composition of the present invention penetrates between the substrate and the polymer residue, resist, and / or resist residue, thereby removing them from the substrate. Therefore, the application of ultrasonic waves significantly improves removability.

[0016] The composition of the present invention contains diethylene glycol monoethyl ether (EDG) and / or triethylene glycol monomethyl ether (TEGME). Diethylene glycol monoethyl ether (EDG) and triethylene glycol monomethyl ether (TEGME) have both high dissolving ability and a cavitation effect when ultrasonic waves are applied, and therefore can effectively remove polymer residues, resists, and / or resist residues.

[0017] Conventional compositions that are N-methylpyrrolidone (NMP)-free and have high removability contain tetramethylammonium hydroxide (TMAH), potassium hydroxide (KOH), water, etc., but these contain insufficient removability and cause damage to the wiring metal. Applying ultrasound to these compositions improves removability, but significantly worsens the damage to the wiring metal. In contrast, the composition of the present invention contains organic solvents, 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. As device materials become increasingly diverse in the future, it will be extremely important to avoid damage to various metals.

[0018] The content of diethylene glycol monoethyl ether (EDG) or triethylene glycol monomethyl ether (TEGME) is 80 to 100 mass% relative to 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 metal, the content of diethylene glycol monoethyl ether (EDG) or triethylene glycol monomethyl ether (TEGME) is preferably 90 to 100 mass%, more preferably 95 to 100 mass%, and even more preferably 98 to 100 mass%, relative to the total mass of the composition.

[0019] In one embodiment, the composition of the present invention may contain at least one additive as the remainder excluding diethylene glycol monoethyl ether (EDG) or triethylene glycol monomethyl ether (TEGME). Examples of 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, γ-butyrolactone, 2-pyrrolidinone, 1-(2-hydroxyethyl)-2-pyrrolidone, benzotriazole, adenine, carboxylbenzotriazole, 1-hydroxybenzotriazole, triazole, and surfactants. From the viewpoints of removability of polymer residues, resist, and / or resist residues, suppression of their redeposition, and suppression of damage to the wiring metal, preferred additives are glycol ethers other than diethylene glycol monoethyl ether (EDG) and triethylene glycol monomethyl ether (TEGME), sulfolane, and tetrahydrofurfuryl alcohol.

[0020] Examples of glycol ethers other 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).

[0021] Examples of glycols include ethylene glycol and propylene glycol.

[0022] Examples of the amine include ethanolamine, diethanolamine, triethanolamine, propanolamine, 4-(2-hydroxyethyl)morpholine, 1-(2-dimethylaminoethyl)-4-methylpiperazine, N-(2-aminoethyl)piperazine, and 2-(2-aminoethoxy)ethanol.

[0023] The additives can be used alone or in combination of two or more. The content of the additives 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 additives 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.

[0024] The composition of the present invention is a non-aqueous composition. As used herein, "non-aqueous" refers to a composition that does not contain water. If the composition of the present invention contains water, the removability of polymer residue, resist, and / or resist residue will be reduced, and the wiring metal will corrode.

[0025] The composition of the present invention preferably does not contain N-methylpyrrolidone from the viewpoint of suppressing toxicity to the human body. The composition of the present invention preferably does not contain dimethyl sulfoxide (DMSO) from the viewpoint of suppressing toxicity to the human body and 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 from the viewpoint of suppressing damage to the wiring metal. Examples of inorganic alkalis include potassium hydroxide, sodium hydroxide, ammonia, potassium carbonate, and sodium carbonate. The composition of the present invention preferably does not contain an organic acid from the viewpoint of suppressing damage to the wiring metal. Examples of organic acids include oxalic acid, citric acid, malic acid, acetic acid, succinic acid, tartaric acid, and methanesulfonic acid. The composition of the present invention preferably does not contain an inorganic acid from the viewpoint of suppressing damage to the wiring metal. Examples of inorganic acids include sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid, and hydrochloric acid. In one embodiment, the composition of the present invention does not contain an aromatic hydrocarbon.

[0026] In one embodiment, 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 suppressing 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.

[0027] 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. In addition, 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, or resist residue.

[0028] The present invention also relates to a method for removing polymer residues, resist, and / or resist residues on a substrate for semiconductor device production, which method comprises contacting the substrate for semiconductor device production having the polymer residues, resist, and / or resist residues with a composition of the present invention.

[0029] The method of the present invention can remove polymer residues, resist, and / or resist residues from a substrate for semiconductor device production by contacting the substrate having the polymer residues, resist, and / or resist residues with the composition of the present invention. The contact method is not particularly limited, but examples thereof include immersing the substrate together with the composition of the present invention, or spraying the composition of the present invention onto the substrate using a shower or the like.

[0030] When a substrate is immersed in the composition of the present invention, a batch-type apparatus or the like can be used. When the composition of the present invention is sprayed onto a substrate by shower or the like, a single-wafer apparatus or the like can be used. In this way, the method of the present invention allows for appropriate adjustment of the components of the composition of the present invention and treatment conditions (e.g., temperature, time, fluidity of the composition of the present invention during immersion, oscillation speed of the substrate, shower pressure and / or flow rate, etc.).

[0031] The method of the present invention is carried out while applying ultrasonic waves. When ultrasonic waves are applied to the composition of the present invention, shock waves are generated (cavitation effect), which pulverize the polymer residue, resist, and / or resist residue. Furthermore, the composition of the present invention penetrates between the substrate and the polymer residue, resist, and / or resist residue, thereby removing them from the substrate. Therefore, by applying ultrasonic waves, removability can be significantly improved compared to removal using the composition of the present invention alone. The frequency of the ultrasonic waves is preferably 20 to 1,000 kHz from the viewpoints of removability of the polymer residue, resist, and / or resist residue and suppression of erosion of the wiring metal. From the same viewpoint, the ultrasonic output is preferably 50 to 1,200 W.

[0032] In one aspect, the method of the present invention comprises contacting a copper (Cu) wiring and / or aluminum (Al) wiring having polymer residue, resist, and / or resist residue with a composition of the present invention. In one aspect, the method of the present invention comprises contacting a silicon (Si) substrate having polymer residue, resist, and / or resist residue for use in semiconductor device manufacturing with the composition of the present invention. In one aspect, the method of the present invention comprises the steps of: (A) providing a substrate for semiconductor device manufacturing having polymer residue, resist, and / or resist residue; (B) contacting the substrate for semiconductor device manufacturing having polymer residue, resist, and / or resist residue with the composition of the present invention to remove the polymer residue, resist, and / or resist residue; (C) rinsing the substrate for semiconductor device manufacturing with water or 2-propanol (IPA); and (D) drying the substrate for semiconductor device manufacturing.

[0033] The present invention also relates to a method for cleaning a substrate for semiconductor device production, comprising contacting a substrate for semiconductor device production having polymer residue, resist, and / or resist residue with the composition of the present invention, and then rinsing the substrate for semiconductor device production with water or 2-propanol (IPA).

[0034] The composition of the present invention will be described in more detail below with reference to the following examples and comparative examples, but the present invention is not limited thereto.

[0035] 1. Preparation of Polymer Removal Liquid Compositions First, 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.

[0036] 2. Evaluation 2.1. Resist Removability Evaluation A silicon (Si) substrate on which a dry film resist (100 μm) was attached to a copper (Cu) sputtered film and patterned, and then copper (Cu) bumps were formed by copper (Cu) plating, was immersed in each composition listed in Table 1 at 85° C. for 10 minutes while applying ultrasonic waves (38 kHz, 300 W). After immersion, a water overflow rinse was performed for 1 minute, and the substrate was dried by nitrogen blowing. Resist removability was evaluated by observing the dried substrate with an optical microscope (Olympus Corporation, Model: LEXT OLS5000).

[0037] The resist removability was evaluated using the following criteria. The results are shown in Table 1. ◯: Good removability Δ: Generally good removability ×: Insufficient removability 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.

[0038] 2.2. Evaluation of copper (Cu) and aluminum (Al) damage suppression (evaluation of corrosion rate) Silicon (Si) substrates with 100 nm copper (Cu) or aluminum (Al) sputtered films were immersed in each composition listed in Table 1 at 85°C for 60 minutes while applying ultrasonic waves (38 kHz, 300 W). After immersion, the substrates were rinsed with water overflow for 1 minute and dried by nitrogen blowing. The copper (Cu) or aluminum (Al) film thickness on the dried substrates was analyzed using a wavelength-dispersive X-ray fluorescence spectrometer (Rigaku Corporation, model number: Primus IV), and the corrosion rate (nm / min) was calculated.

[0039] The corrosion rate inhibition of copper (Cu) and aluminum (Al) was evaluated using the following criteria. The results are shown in Table 1. ◯: No corrosion (corrosion rate was 0.5 nm / hr or less) △: Almost no corrosion (corrosion rate was 0.6 to 0.9 nm / hr) ×: Corrosion (corrosion rate was 1.0 nm / hr or more)

[0040] 2.3. Evaluation of Copper (Cu) and Aluminum (Al) Damage Suppression (Evaluation of Metal Surface Roughness) Silicon (Si) substrates with a 100 nm copper (Cu) or aluminum (Al) sputtered film were immersed in each composition listed in Table 1 at 85°C for 60 minutes while applying ultrasonic waves (38 kHz, 300 W). After immersion, the substrates were rinsed with water overflow for 1 minute and dried by nitrogen blow. The dried substrate surfaces were observed with an FE-SEM (Hitachi High-Tech Corporation, Model No. SU8220) to evaluate the surface roughness suppression of copper (Cu) or aluminum (Al). Observing surface roughness allows evaluation of small metal damage levels that cannot be estimated by corrosion rate.

[0041] The damage (surface roughness) suppression properties of copper (Cu) and aluminum (Al) were evaluated using the following criteria. The results are shown in Table 1. ◯: No surface roughness (metal damage) Δ: Slight surface roughness (metal damage) occurred ×: Significant surface roughness (metal damage) occurred. Furthermore, Figure 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 in the compositions of Example 1, Comparative Example 2, and Comparative Example 5 while applying ultrasonic waves.

[0042] 2.4. Evaluation of Water Rinse Ability of Compositions A silicon (Si) substrate on which a dry film resist (100 μm) was attached to a copper (Cu) sputtered film and patterned, followed by copper (Cu) plating to form copper (Cu) bumps, was immersed in each of the compositions listed in Table 1 at 85°C for 10 minutes while applying ultrasonic waves (38 kHz, 300 W). After immersion, a water overflow rinse was performed for 1 minute, and the substrate was dried by nitrogen blowing. The dried substrate was observed with an optical microscope (Olympus Corporation, Model: LEXT OLS5000) to evaluate whether any composition remained on the substrate surface.

[0043] The water rinsability of the composition was evaluated using the following criteria. The results are shown in Table 1. ◯: Good water rinsability Δ: Generally good water rinsability ×: Insufficient water rinsability

[0044] 2.5. Evaluation of 2-propanol (IPA) Rinse Ability of Compositions A silicon (Si) substrate was prepared by attaching a dry film resist (100 μm) to a copper (Cu) sputtered film, patterning it, and then forming copper (Cu) bumps by copper (Cu) plating. The substrate was then immersed in each of the compositions listed in Table 1 at 85°C for 10 minutes while applying ultrasonic waves (38 kHz, 300 W). After immersion, the substrate was immersed in 2-propanol (IPA) for 1 minute, followed by a 1-minute water overflow rinse and drying with nitrogen blow. The dried substrate was observed with an optical microscope (Olympus Corporation, Model: LEXT OLS5000) to evaluate whether any composition remained on the substrate surface.

[0045] The 2-propanol (IPA) rinsing properties of the compositions were evaluated using the following criteria. The results are shown in Table 1. ◯: Good IPA rinsing properties Δ: Generally good IPA rinsing properties ×: Insufficient IPA rinsing properties

[0046] In Table 1, EDG represents diethylene glycol monoethyl ether (ethyl carbitol), TEGME represents triethylene glycol monomethyl ether, NMP represents N-methylpyrrolidone, DMSO represents dimethyl sulfoxide, BDG represents diethylene glycol monobutyl ether (butyl carbitol), MDG represents diethylene glycol monomethyl ether (methyl carbitol), DPGME represents dipropylene glycol monomethyl ether, BnOH represents benzyl alcohol, PhOEtOH represents phenoxyethanol, and THFA represents tetrahydrofurfuryl alcohol.

[0047] As shown in Table 1, the compositions of Examples 1 to 5 exhibited good dry film resist (DFR) removability, good inhibition of the corrosion rate of copper (Cu) and aluminum (Al), good inhibition of copper (Cu) and aluminum (Al) surface roughness, and good water rinsability and 2-propanol (IPA) rinsability of the composition. In contrast, the compositions of Comparative Examples 1 to 14 exhibited insufficient results in one or more of the dry film resist (DFR) removability, inhibition of the corrosion rate of (Cu) and aluminum (Al), inhibition of (Cu) and aluminum (Al) surface roughness, and water rinsability and 2-propanol (IPA) rinsability of the composition.

[0048] As can be seen from Table 1, when ultrasonic waves were not applied to diethylene glycol monoethyl ether (EDG), resist removability was insufficient (Comparative Example 1). When diethylene glycol monoethyl ether (EDG) was mixed with water, resist removability was insufficient and damage occurred to copper (Cu) and aluminum (Al) (Comparative Example 2). When diethylene glycol monoethyl ether (EDG) was limited to 60 mass % or 70 mass %, resist removability was insufficient and damage occurred to copper (Cu) (Comparative Examples 13 and 14).

[0049] Furthermore, when diethylene glycol monoethyl ether (ethyl carbitol) (EDG) was used at 100% by mass, the desired effect was achieved (Example 1), but when diethylene glycol monobutyl ether (butyl carbitol) (BDG) was used at 100% by mass (Comparative Example 5) or when diethylene glycol monomethyl ether (methyl carbitol) (MDG) was used at 100% by mass (Comparative Example 6), the desired effect was not achieved. This shows that diethylene glycol (carbitol) does not necessarily achieve the desired effect, and that whether or not an effect is achieved depends on the number of carbon atoms in the terminal alkyl group.

Claims

1. A non-aqueous composition used to remove polymer residues, resist, and / or resist residues on a substrate for manufacturing a semiconductor device by applying ultrasonic waves, said composition containing 80 to 100% by mass of diethylene glycol monoethyl ether or triethylene glycol monomethyl ether.

2. The composition according to claim 1, which contains 90 to 100% by mass of diethylene glycol monoethyl ether or triethylene glycol monomethyl ether.

3. The composition according to claim 1 or 2, which contains, as the balance, at least one additive.

4. The composition according to any one of claims 1 to 3, wherein 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 claims 1 to 4, which is used after being heated to 40°C or higher.

6. The composition according to any one of claims 1 to 5, wherein the semiconductor substrate has copper wiring and / or aluminum wiring.

7. A method for removing polymer residues, resist, and / or resist residues on a substrate for manufacturing semiconductor devices, comprising contacting the substrate having the polymer residues, resist, and / or resist residues with the composition according to any one of claims 1 to 6 while applying ultrasonic waves.

8. 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 claim 7.

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