Polymer removal composition and removal method

Abstract

To provide a removal composition which is capable of satisfactorily removing a strong resist, and a polymer residue and a resist residue on a substrate for semiconductor device production, while reducing the toxicity to humans, and which is also capable of suppressing damage to a wiring metal.SOLUTION: The present invention relates to a nonaqueous composition which is used for removing a polymer residue, a resist, and / or a resist residue on a substrate for semiconductor device production by applying ultrasonic waves thereto, and which contains 80-100 mass% of diethylene glycol monoethyl ether or triethylene glycol monomethyl ether.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a composition used for removing 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. [Background technology]

[0002] In the photolithography process for forming metal wiring patterns such as copper (Cu) on silicon or glass substrates in the manufacture of semiconductor devices, it is necessary to remove the photoresist film that is no longer needed after the etching or plating process. In particular, in the etching or plating process, a composition is required that can remove resists that are difficult to remove, such as hardened resists and dry film resists (DFR). In addition, copper (Cu) and aluminum (Al) are often used as metals for wiring, and a composition is required that can remove strong resists without damaging these wiring metals. In addition, in the manufacturing of semiconductor devices, organic polymers such as polyimide, which are used as insulating or protective films for substrates, are processed or reworked, resulting in the generation of 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 for substrates, a deposit (CF polymer) consisting of silicon (Si), carbon (C) and fluorine (F) remains on the substrate. The CF polymers must also be removed from the substrate in a later process. These polymer residues must also be removed without damaging metals such as copper (Cu) and aluminum (Al).

[0003] The most widely used resist removal compositions are those containing N-methylpyrrolidone (NMP) (Patent Document 1). In the case of resists that are easy to remove, the resist can be removed by simply immersing the resist in N-methylpyrrolidone (NMP), while in the case of resists that are difficult to remove, such as hardened resists and dry film resists (DFR), the resist can be removed by applying ultrasonic waves to N-methylpyrrolidone (NMP). In particular, the process of applying ultrasonic waves to N-methylpyrrolidone (NMP) has been used as a very powerful tool that can remove strong resists without damaging the wiring metal. However, the use of removal compositions containing N-methylpyrrolidone (NMP) is limited due to toxicity to the human body.

[0004] As a resist removal composition that does 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 study has been conducted, an embodiment in which ultrasonic waves are applied to the resist removal composition has also been described (Patent Documents 2 to 3, 5). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2013-501958 [Patent Document 2] Special Publication No. 2012-526295 [Patent Document 3] International Publication No. 2019 / 187868 [Patent Document 4] International Publication No. 2021 / 020410 [Patent Document 5] JP 2006-251786 A Summary of the Invention [Problem to be solved by the invention]

[0006] 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. In addition, 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. Therefore, the present inventors have carried out research with the objective of providing a removal composition that does not contain N-methylpyrrolidone (NMP), which can effectively remove resists that are difficult to remove, such as hardened resists and dry film resists (DFR), polymer residues on substrates for manufacturing semiconductor devices, resist residues, etc., and furthermore can suppress damage to wiring metal. That is, the objective of the present invention is to provide a removal composition that can effectively remove strong resists, polymer residues on substrates for manufacturing semiconductor devices, and resist residues, while reducing toxicity to the human body, and can suppress damage to wiring metal. [Means for solving the problem]

[0007] In the course of intensive research to achieve the above-mentioned object, the present inventors discovered that a non-aqueous composition containing diethylene glycol monoethyl ether (EDG) or triethylene glycol monomethyl ether (TEGME) can effectively remove tough resist, polymer residues and resist residues on substrates for manufacturing semiconductor devices 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, which contains 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 remainder. [4] The composition according to any one of the above [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.

[0009] [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. [7] 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 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 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. Effect of the Invention

[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 resist, and resist residues on substrates used for manufacturing semiconductor devices. 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. [Brief description of the drawings]

[0011] [Figure 1] 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. [Diagram 2] 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 in the compositions of Example 1, Comparative Example 2, and Comparative Example 5 while applying ultrasonic waves. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, the present invention will be described in detail based on preferred embodiments of the present invention. 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.

[0013] 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. Polymer residues refer 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 silicon dry etching processing. 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. In one embodiment, 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 oxygen plasma.

[0014] The substrate having the polymer residue, resist, and / or resist residue is a substrate for semiconductor device manufacture. 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, etc. In one embodiment, a substrate for manufacturing a semiconductor device has wiring, contacts, electrodes, and the like. 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 manufacturing a semiconductor device has copper (Cu) wiring and / or aluminum (Al) wiring.

[0015] The composition of the present invention is applied with 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, the removability is significantly improved by applying ultrasonic waves.

[0016] The compositions of the present invention include 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 cavitation effect when ultrasonic waves are applied, so that polymer residues, resist, and / or resist residues can be removed well.

[0017] Conventionally, compositions free of N-methylpyrrolidone (NMP) and having high removability contain tetramethylammonium hydroxide (TMAH), potassium hydroxide (KOH), water, etc., and have insufficient removability, causing damage to the wiring metal. When ultrasonic waves are applied to these, the removability improves, but the damage to the wiring metal is dramatically worsened. In contrast, the composition of the present invention contains an organic solvent called diethylene glycol monoethyl ether (EDG) and / or triethylene glycol monomethyl ether (TEGME), and almost no damage occurs to the wiring metal even when ultrasonic waves are applied. As device materials become more diverse in the future, it is very important that various metals are not damaged.

[0018] 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.

[0019] The compositions of the present invention, in one embodiment, may comprise, as the balance excluding diethylene glycol monoethyl ether (EDG) or triethylene glycol monomethyl ether (TEGME), at least one additive. Examples of additives 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, surfactants, etc. As additives, from the viewpoints of removability of polymer residues, resist, and / or resist residues, suppression of reattachment thereof, and suppression of damage to wiring metal, glycol ethers other than diethylene glycol monoethyl ether (EDG) and triethylene glycol monomethyl ether (TEGME), sulfolane, and tetrahydrofurfuryl alcohol are preferred.

[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 additive is 0 to 20% by mass relative to 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 relative to the total mass of the composition.

[0024] The composition of the present invention is a non-aqueous composition. As used herein, the term "non-aqueous" refers to not containing water. When 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.

[0025] From the viewpoint of suppressing toxicity to the human body, 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. From the viewpoint of suppressing damage to the wiring metal, 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. From the viewpoint of suppressing damage to the wiring metal, 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.

[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 addition, 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 each component. 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, the resist, and the resist residue.

[0028] The present invention also relates to a method for removing polymer residues, resist, and / or resist residues on a substrate for manufacturing semiconductor devices, comprising contacting the substrate for manufacturing semiconductor devices 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 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 thereof 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 or the like.

[0030] 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. When the composition of the present invention is sprayed onto the substrate by shower or the like, a single-wafer type apparatus or the like can be used. In this manner, the method of the present invention can appropriately adjust 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.).

[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), 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.

[0032] The method of the present invention, in one embodiment, comprises contacting a composition of the present invention with a copper (Cu) interconnect and / or an aluminum (Al) interconnect having polymer residue, resist, and / or resist residue thereon. The method of the present invention, in one embodiment, 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. In one aspect, 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 (?) drying the substrate for semiconductor device production.

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

[0034] The 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 thereto.

[0035] 1. Preparation of polymer removal liquid composition 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 compositions according to Examples 1 to 5 and Comparative Examples 1 to 14, respectively.

[0036] 2. Evaluation 2.1.Evaluation of resist removal A dry film resist (100 μm) was attached onto a copper (Cu) sputtered film, and after patterning, a silicon (Si) substrate on which a copper (Cu) bump was 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 completion of the immersion, water was overflow rinsed for 1 minute, and the substrate was dried by nitrogen blowing. The resist removability was evaluated by observing the dried substrate with an optical microscope (Olympus Corporation, model number: LEXT OLS5000).

[0037] The removability of the resist was evaluated according to the following criteria, and the results are shown in Table 1. ○: Good removability △: 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 damage suppression for copper (Cu) and aluminum (Al) (evaluation of corrosion rate) A silicon (Si) substrate with a 100 nm copper (Cu) or aluminum (Al) sputtered film was immersed in each composition shown in Table 1 for 60 minutes at 85°C while applying ultrasonic waves (38 kHz, 300 W). After the immersion, the substrate was rinsed with water overflow for 1 minute and dried by nitrogen blowing. The copper (Cu) or aluminum (Al) film thickness of the dried substrate was analyzed using a wavelength dispersive X-ray fluorescence spectrometer (Rigaku Corporation, model number: PrimusIV), 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 occurred (corrosion rate was 0.6-0.9 nm / hr) ×: Corroded (corrosion rate was 1.0 nm / hr or more)

[0040] 2.3. Evaluation of damage suppression for copper (Cu) and aluminum (Al) (evaluation of metal surface roughness) A silicon (Si) substrate with a 100 nm copper (Cu) or aluminum (Al) sputtered film was immersed in each composition listed in Table 1 with ultrasonic waves (38 kHz, 300 W) applied at 85°C for 60 minutes. After immersion, water overflow rinse was performed for 1 minute, and the substrate was dried by nitrogen blowing. The dried substrate surface was observed with FE-SEM (manufactured by Hitachi High-Tech Corporation, model number: SU8220) to evaluate the suppression of surface roughness of copper (Cu) or aluminum (Al). By observing the surface roughness, it is possible to evaluate small metal damage that cannot be estimated by the 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. 〇: No surface roughness (metal damage) △: Slight surface roughness (metal damage) ×: Significant surface roughness (metal damage) occurs 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.

[0042] 2.4. Evaluation of Water Rinseability of Composition A dry film resist (100 μm) was attached onto a copper (Cu) sputtered film, and after patterning, a silicon (Si) substrate on which a copper (Cu) bump was 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 completion of the immersion, water was overflow rinsed for 1 minute, and the substrate was dried by nitrogen blowing. The dried substrate was observed with an optical microscope (Olympus Corporation, model number: LEXT OLS5000) to evaluate whether the composition remained on the substrate surface.

[0043] The water rinsability of the compositions was evaluated using the following criteria, and the results are shown in Table 1. Good: Good water rinsability △: Generally good water rinsability ×: Insufficient water rinsability

[0044] 2.5. Evaluation of 2-propanol (IPA) rinsability of the composition A dry film resist (100 μm) was attached onto a copper (Cu) sputtered film, and after patterning, a silicon (Si) substrate on which a copper (Cu) bump was 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 completion of the immersion, the substrate was immersed in 2-propanol (IPA) for 1 minute, then rinsed with water overflow for 1 minute, and dried by nitrogen blowing. The dried substrate was observed with an optical microscope (Olympus Corporation, model number: LEXT OLS5000) to evaluate whether the composition remained on the substrate surface.

[0045] The 2-propanol (IPA) rinsability of the compositions was evaluated using the following criteria, and the results are shown in Table 1. 〇: Good IPA rinsability △: Generally good IPA rinsability ×: Insufficient IPA rinsing ability

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

[0047] As shown in Table 1, the compositions according to 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 surface roughness of copper (Cu) and aluminum (Al), and good water rinsability and 2-propanol (IPA) rinsability of the compositions. In contrast, the compositions of Comparative Examples 1 to 14 showed insufficient results in one or more of the following: dry film resist (DFR) removability, inhibition of the corrosion rate of (Cu) and aluminum (Al), inhibition of surface roughness of (Cu) and aluminum (Al), 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), the resist removal was insufficient (Comparative Example 1). When diethylene glycol monoethyl ether (EDG) was mixed with water, the resist removal 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 %, the resist removal was insufficient, and damage occurred to copper (Cu) (Comparative Examples 13 to 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) and 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 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. 2. The composition according to claim 1, comprising 90 to 100% by mass of diethylene glycol monoethyl ether or triethylene glycol monomethyl ether.

3. 3. The composition according to claim 1, further comprising, 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 a semiconductor device, 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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