Processing solution for semiconductor devices, method for processing substrates, and method for manufacturing semiconductor devices

Abstract

The present invention provides a processing solution for semiconductor devices that excels in suppressing defects, a method for processing substrates, and a method for manufacturing semiconductor devices. [Solution] The present invention provides a processing solution for semiconductor devices, a method for processing substrates, and a method for manufacturing semiconductor devices, each containing a quaternary ammonium hydroxide compound and at least one nonionic surfactant selected from the group consisting of a surfactant having the structure represented by the following formula (1) and a surfactant having the structure represented by the following formula (2), wherein the content of the nonionic surfactant is 0.001 ppm or more and 40 ppm or less.

Description

[Technical Field]

[0001] This invention relates to a processing solution for semiconductor devices, a method for processing substrates, and a method for manufacturing semiconductor devices. Regarding. [Background technology]

[0002] Semiconductor elements such as ICs and LSIs, as well as liquid crystal panel elements, are manufactured by, for example, uniformly coating an insulating film such as a metal film or SiO2 film deposited on a substrate using CVD (Chemical Vapor Deposition) technology, selectively exposing and developing the resist to form a resist pattern, using this pattern as a mask to selectively etch the substrate on which the CVD-deposited metal film or SiO2 film or other insulating film is formed to form a fine circuit, and then removing the unwanted resist layer. In the pattern formation of such fine circuits, a processing solution is used to remove the resist layer.

[0003] As an example related to such processing solutions, Patent Document 1 discloses a resist developer composition characterized by adding at least one selected from polyoxypropylene monoalkyl ether, polypropylene glycol, and polyoxyethylene monoalkyl ether to a resist developer mainly composed of an organic base that does not contain metal ions. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 07-128865 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, the above-described prior art still requires further improvement in defect suppression of the processed wafer. Therefore, the present invention has been made in view of such demands, and an object thereof is to provide a processing liquid for semiconductor devices, a method for processing a substrate, and a method for manufacturing a semiconductor device, which are excellent in defect suppression.

Means for Solving the Problems

[0006] As a result of intensive studies to achieve the above object, the present inventors have found that a quaternary ammonium hydroxide compound and a nonionic surfactant, which is a surfactant having a specific structure, are contained, and the content of the nonionic surfactant is 0.001 ppm or more and 40 ppm or less, and have obtained a finding that a processing liquid for semiconductor devices is obtained, and the present invention has been completed.

[0007] That is, the present invention is as follows. <1> A processing liquid for semiconductor devices, which contains a quaternary ammonium hydroxide compound and at least one nonionic surfactant selected from the group consisting of a surfactant having a structure represented by the following formula (1) and a surfactant having a structure represented by the following formula (2), and the content of the nonionic surfactant is 0.001 ppm or more and 40 ppm or less.

Chemical Formula

Chemical Formula

Chemical formula

Chemical formula

[0008] According to the present invention, it is possible to provide a processing solution for semiconductor devices that is excellent in suppressing defects, a method for processing a substrate, and a method for manufacturing a semiconductor device. [Modes for carrying out the invention]

[0009] The following describes in detail embodiments for carrying out the present invention (hereinafter simply referred to as "these embodiments"). These embodiments are illustrative for explaining the present invention and are not intended to limit the present invention to the following content. The present invention can be appropriately modified and implemented within the scope of its gist. Furthermore, the configurations and parameters disclosed herein can be any combination unless otherwise specified. Moreover, the upper and lower limits of the values ​​disclosed herein can be any combination unless otherwise specified.

[0010] <Processing solution for semiconductor devices>

[0011] The semiconductor device processing solution according to this embodiment (hereinafter sometimes simply referred to as "processing solution") contains a quaternary ammonium hydroxide compound and at least one nonionic surfactant selected from the group consisting of a surfactant (1) having the structure represented by the following formula (1) and a surfactant (2) having the structure represented by the following formula (2), wherein the content of the nonionic surfactant is 0.001 ppm or more and 40 ppm or less. Unless otherwise specified in this specification, "ppm" is a numerical value based on mass.

[0012] [ka]

[0013] (In the formula, R 1 , R 2 , R 3 , and R 4 Each of these independently represents a hydrocarbon group with 1 to 5 carbon atoms.

[0014] [ka]

[0015] (In the formula, R 5 , and R 6 Each of these independently represents a hydrocarbon group with 1 to 5 carbon atoms.

[0016] The processing solution according to this embodiment is excellent at suppressing defects in wafers after processing. The reason for this is not entirely clear, but for example, if a silicon wafer is etched, and the substrate is treated with the processing solution according to this embodiment after etching, the surface of the substrate becomes hydrophilic, and hydroxyl groups are present on the surface. It is thought that nonionic surfactants and the like in the processing solution according to this embodiment are weakly adsorbed onto these hydroxyl groups, thereby suppressing the adhesion of defects (however, the effects and benefits of this embodiment are not limited to these).

[0017] The components of the processing solution according to this embodiment will be described below.

[0018] (a) Quaternary ammonium hydroxide compounds

[0019] (a) The quaternary ammonium hydroxide compound is not particularly limited, but it is preferably at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and tetrapropylammonium hydroxide. Using such a compound can further improve defect suppression.

[0020] (a) The content of component (a) is preferably 0.2% by mass or more and 13% by mass or less. The lower limit of the content of component (a) is more preferably 1% by mass or more, even more preferably 1.3% by mass or more, even more preferably 1.7% by mass or more, and even more preferably 2% by mass or more. The upper limit of the content of component (a) is more preferably 4% by mass or less, even more preferably 3.5% by mass or less, even more preferably 3% by mass or less, and even more preferably 2.8% by mass or less. By setting the content of component (a) within the above range, defect suppression can be further improved.

[0021] (b) Nonionic surfactants

[0022] (b) The nonionic surfactant is at least one selected from the group consisting of surfactant (1) having the structure represented by formula (1) and surfactant (2) having the structure represented by formula (2).

[0023] [ka]

[0024] (In the formula, R 1 , R 2 , R 3 , and R 4 Each of these independently represents a hydrocarbon group with 1 to 5 carbon atoms.

[0025] [ka]

[0026] (In the formula, R 5 , and R 6 Each of these independently represents a hydrocarbon group with 1 to 5 carbon atoms.

[0027] R in equation (1) 1 , R 2 , R 3 , and R 4It is preferably a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a hydrocarbon group having 1 to 2 carbon atoms. 1 , R 2 , R 3 , and R 4 Specific examples of these groups include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, etc., with methyl groups and ethyl groups being more preferred.

[0028] As a specific example of surfactant (1), it is preferable that it be at least one selected from the group consisting of surfactant (1-1) having a structure represented by the following formula (1-1) and surfactant (1-2) having a structure represented by the following formula (1-2). By using such a compound, defect suppression can be further improved.

[0029] [ka]

[0030] [ka]

[0031] R in equation (2) 5 It is preferably a hydrocarbon group having 1 to 4 carbon atoms. 6 It is preferably a hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrocarbon group having 1 to 3 carbon atoms, and even more preferably a hydrocarbon group having 1 to 2 carbon atoms. 5 Specific examples of preferred groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl groups, with n-butyl and isobutyl groups being more preferred. 6 Specific examples of preferred groups include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, and isobutyl groups, with methyl groups and ethyl groups being more preferred, and methyl groups being even more preferred.

[0032] A specific example of the surfactant (2) is preferably a surfactant (2-1) having the structure represented by the following formula (2-1). By using such a compound, defect suppression can be further improved.

[0033] [ka]

[0034] (b) Commercially available nonionic surfactants can also be used. Examples include "Surfinol® 82", "Surfinol® 104", "Surfinol® 61" (all manufactured by Nisshin Chemical Industry Co., Ltd.), and "Acetylenel® E00" (manufactured by Kawaken Fine Chemical Co., Ltd.).

[0035] (b) The content of component (b) is 0.001 ppm or more and 40 ppm or less. The lower limit of the content of component (b) is preferably 0.01 ppm or more, more preferably 0.1 ppm or more, even more preferably 0.2 ppm or more, even more preferably 5 ppm or more, and even more preferably 10 ppm or more. The upper limit of the content of component (b) is preferably 45 ppm or less, more preferably 40 ppm or less, even more preferably 35 ppm or less, and even more preferably 30 ppm or less. By setting the content of component (b) within the above range, defect suppression can be further improved.

[0036] The mass ratio of the content of (a) quaternary ammonium hydroxide compound to the content of (b) nonionic surfactant (quaternary ammonium hydroxide compound / nonionic surfactant, (a) / (b)) is preferably 500 or more and 130,000 or less. The lower limit of this mass ratio is more preferably 550 or more, even more preferably 800 or more, and even more preferably 900 or more. The upper limit of this mass ratio is more preferably 120,000 or less, even more preferably 50,000 or less, even more preferably 30,000 or less, even more preferably 10,000 or less, and even more preferably 5,000 or less. By setting this mass ratio within the above range, defect suppression can be further improved.

[0037] (c) Cyclic ether compounds

[0038] The treatment solution according to this embodiment may further contain (c) a cyclic ether compound as needed. In this embodiment, sufficient effects can be expected even without necessarily containing component (c), but if component (c) is included, it is preferable that the (c) cyclic ether compound contains one ring containing an oxygen atom in its molecule. Furthermore, it is preferable that the number of carbon atoms forming the ring in the (c) cyclic ether compound is 2 or more and 4 or less. The number of carbon atoms forming the ring here refers to the number of carbon atoms forming one ring. In addition, it is preferable that the number of oxygen atoms forming the ring in the cyclic ether compound is 1 or more and 2 or less.

[0039] (c) Specific examples of component are not particularly limited, but it is preferable that it be at least one selected from the group consisting of ethylene oxide (ethylene oxide, oxirane), 1,4-dioxane, tetrahydrofuran (THF), and 4-methyltetrahydropyran (MTHP). Among these, ethylene oxide and 1,4-dioxane are more preferred, and ethylene oxide is even more preferred.

[0040] Furthermore, component (c) may be used alone or in combination of two or more. For example, when two or more components of (c) are included, it is preferable to include only ethylene oxide and / or 1,4-dioxane. When ethylene oxide and 1,4-dioxane are used in combination, the mass ratio (ethylene oxide:1,4-dioxane) is preferably, for example, 10:90 to 90:10, preferably 15:85 to 85:15, more preferably 15:85 to 60:40, and even more preferably 15:85 to 55:45.

[0041] The treatment solution according to this embodiment can be expected to produce sufficient effects even if it does not necessarily contain component (c). However, if component (c) is included, the content of component (c) may be between 0.0005 ppm and 4.5 ppm. The lower limit of the content of component (c) may be 0.001 ppm or more, 0.01 ppm or more, or 0.1 ppm or more. The upper limit of the content of component (c) may be 4 ppm or less, 3 ppm or less, 2.5 ppm or less, 2 ppm or less, or 1.5 ppm or less.

[0042] (d) Alkyl ketones

[0043] The treatment solution according to this embodiment may further contain (d) alkyl ketone as needed. While the treatment solution according to this embodiment can be expected to provide sufficient effects even without necessarily containing component (d), if component (d) is included, the (d) alkyl ketone is not particularly limited, but is preferably at least one selected from the group consisting of acetone, methyl isobutyl ketone, methyl ethyl ketone, dimethyl ketone, diethyl ketone, and ethyl isobutyl ketone. Such a compound can further improve defect suppression.

[0044] (d) The content of component (d) is preferably 0.001 ppm or more and 4 ppm or less. The lower limit of the content of component (d) is more preferably 0.01 ppm or more, even more preferably 0.01 ppm or more, and even more preferably 0.1 ppm or more. The upper limit of the content of component (d) is more preferably 3 ppm or less, even more preferably 2.5 ppm or less, even more preferably 2 ppm or less, and even more preferably 1.8 ppm or less. By setting the content of component (d) within the above range, defect suppression can be further improved.

[0045] The processing solution according to this embodiment has a total content of (c) cyclic ether compounds and (d) alkyl ketones of 0.001 ppm or more and less than 5 ppm. The lower limit of this total is preferably 0.01 ppm or more, more preferably 0.02 ppm or more, even more preferably 0.1 ppm or more, and even more preferably 0.2 ppm or more. The upper limit of this total is preferably 4 ppm or less, more preferably 3 ppm or less, even more preferably 2 ppm or less, even more preferably 1 ppm or less, and even more preferably 0.6 ppm or less. By setting this total within the above range, defect suppression can be further improved.

[0046] (e) Water-soluble organic solvents other than cyclic ether compounds

[0047] The treatment solution according to this embodiment may further contain a water-soluble organic solvent other than (e) the cyclic ether compound. Component (e) can be any water-soluble organic solvent that is miscible with the other components contained in the treatment solution, and an appropriate water-soluble organic solvent can be selected considering the type and amount of the other components used. It is preferable that component (e) is a solvent other than the compound corresponding to component (d).

[0048] (e) Specific examples of components include, for example, sulfoxides such as dimethyl sulfoxide (DMSO); sulfones such as dimethyl sulfone, diethyl sulfone, bis(2-hydroxyethyl) sulfone, and tetramethylene sulfone; amides such as N,N-dimethylformamide (DMF), N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, and N,N-diethylacetamide; lactams such as N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, and N-hydroxyethyl-2-pyrrolidone; and 1,3-dimethyl-2-imidazolidino Examples include imidazolidinones such as 1,3-diethyl-2-imidazolidinone and 1,3-diisopropyl-2-imidazolidinone; lactones such as γ-butyrolactone and δ-valerolactone; and polyhydric alcohols and their derivatives such as ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.

[0049] In this embodiment, it is expected that sufficient effects can be obtained even without necessarily containing component (e), so component (e) does not need to be included. However, if component (e) is included, the content of component (e) may be 50% by mass or more and 80% by mass or less. The lower limit of the content of component (e) may be 60% by mass or more and 65% by mass or more. The upper limit of the content of component (e) may be 75% by mass or less and 70% by mass or less. By setting the content of component (e) within the above range, defect suppression can be further improved.

[0050] (Other additives)

[0051] The treatment solution according to this embodiment may further contain any additional components other than those described above, as long as the effects of this embodiment are obtained. Examples include corrosion inhibitors and surfactants.

[0052] The corrosion inhibitor is preferably at least one selected from the group consisting of aromatic hydroxy compounds, acetylene alcohol, carboxyl group-containing organic compounds and their anhydrides, triazole compounds, and sugars.

[0053] Furthermore, it is preferable that the semiconductor device processing solution according to this embodiment does not contain a water-insoluble organic solvent as a solvent. Examples of water-insoluble organic solvents include halogen-substituted or unsubstituted hydrocarbon solvents.

[0054] The semiconductor device processing solution according to this embodiment, having the composition described above, can be suitably used as an aqueous processing solution containing water. Such a semiconductor device processing solution can be suitably used as a substrate processing solution as described below. Furthermore, it can be suitably used in the substrate processing methods described below. Below, preferred examples of how the semiconductor device processing solution can be used will be described.

[0055] <Method for processing circuit boards>

[0056] The semiconductor device processing solution according to this embodiment is suitable for removing residue generated after etching treatment has been performed on a substrate equipped with a metal layer, which is used in the manufacture of semiconductor devices. More specifically, the substrate can be etched using the resist pattern (e.g., photoresist) provided on the substrate as a mask. Furthermore, an ashing treatment may be performed thereafter. After that, the substrate can be processed using the semiconductor device processing solution according to this embodiment. Alternatively, it may be used as a processing solution (cleaning solution) after the chemical mechanical polishing (CMP) process. The substrate may be processed using a single-wafer method. As for the processing, for example, immersion in the processing solution or application of the processing solution can be performed.

[0057] Regarding the substrate configuration, the semiconductor device processing solution according to this embodiment is suitable for use in a semiconductor device that includes a substrate with a metal layer, and where the processing solution is used for processing the metal layer. In other words, the semiconductor device processing solution according to this embodiment is suitable for use in a semiconductor device that includes a substrate with a metal layer, and where the processing solution is used for processing the substrate. Examples of the metal layer include a metal layer containing Cu, Co, W, Al, Mo, Ru, and alloys containing one or more of these.

[0058] The semiconductor device processing solution according to this embodiment can be suitably used in substrate processing methods. A suitable example of a substrate processing method according to this embodiment is a substrate processing method comprising a processing step of processing a substrate having a metal layer using a semiconductor device processing solution containing a quaternary ammonium hydroxide compound, a cyclic ether compound, an alkyl ketone, and a water-soluble organic solvent other than the cyclic ether compound, wherein the total content of the cyclic ether compound and the alkyl ketone is 0.001 ppm or more and less than 5 ppm. As the semiconductor device processing solution, for example, a processing solution having the above-described composition can be used.

[0059] The processing conditions using the semiconductor device processing solution according to this embodiment can be selected based on the configuration, materials, and characteristics of the target semiconductor device, as well as the etching and ashing conditions. For example, when processing by immersion in the processing solution, the immersion time is preferably 1 to 60 minutes, and more preferably 1 to 15 minutes. The temperature during immersion is preferably 5 to 70°C, more preferably 10 to 50°C, and even more preferably 20 to 30°C.

[0060] Examples of the above-mentioned processes include residue removal and / or wet etching. According to this embodiment, the process may consist of either residue removal or wet etching, or both may be performed simultaneously.

[0061] In other words, the processing step is preferably a residue removal step in which residues on the substrate are removed using a processing solution for semiconductor devices. In this case, the conditions for residue removal include, for example, immersing the substrate in the processing solution for 1 minute at room temperature.

[0062] Alternatively, the processing step is preferably an etching step in which the substrate is wet-etched using a processing solution for semiconductor devices. In this case, the conditions for wet etching include, for example, immersing the substrate in the processing solution for 1 minute at room temperature.

[0063] Furthermore, it goes without saying that the processing step may also be a step that performs the wet etching described above while simultaneously removing the residue described above. For example, the processing step may be a step that performs the residue removal and wet etching described above.

[0064] After processing with a semiconductor device processing solution, the substrate can be rinsed as needed. For example, the substrate (or semiconductor device) can be rinsed with at least one selected from the group consisting of methanol, isopropanol, ethylene glycol, water, a mixture of water and a surfactant, and mixtures thereof. After rinsing, it can be dried by nitrogen gas, spin-dry cycle, steam drying, etc.

[0065] <Manufacturing methods for semiconductor devices>

[0066] A preferred example of a semiconductor device manufacturing method according to this embodiment is a semiconductor device manufacturing method including a substrate having a metal layer, which includes a processing step of processing the substrate using a semiconductor device processing solution containing a quaternary ammonium hydroxide compound, a cyclic ether compound, an alkyl ketone, and a water-soluble organic solvent other than the cyclic ether compound, wherein the total content of the cyclic ether compound and the alkyl ketone is 0.001 ppm or more and less than 5 ppm. It goes without saying that the contents and conditions of each step of the manufacturing method and the processing solution used can be appropriately adopted from the matters described in the above-mentioned semiconductor device processing solution and substrate processing method.

[0067] The processing step is preferably a residue removal step in which residues on the substrate are removed using a processing solution for semiconductor devices.

[0068] Alternatively, the processing step is preferably an etching step in which the substrate is wet-etched using a processing solution for semiconductor devices.

[0069] As described above, the semiconductor device processing solution according to this embodiment is excellent in suppressing defects. Furthermore, by adopting a suitable embodiment, it can be expected to exhibit excellent residue removal and / or etching properties. Moreover, even when the semiconductor device processing solution according to this embodiment is used after etching and ashing, it can exhibit excellent effects. It can efficiently remove not only residue generated from the resist (resist residue) but also residue generated from the substrate and metal layer (metal oxide residue), etc.

[0070] Furthermore, since the semiconductor device processing solution according to this embodiment can be an aqueous processing solution, it is not only possible to reduce the environmental burden, but it is also expected that the processing solution can be efficiently removed from the processed substrate (semiconductor device) in the subsequent rinsing process.

[0071] Furthermore, the semiconductor device processing solution according to this embodiment can also be used in a form that does not contain metal ions (metal-free processing solution). Moreover, the semiconductor device processing solution according to this embodiment can exert sufficient effects on defect suppression, etc., even without containing strong bases other than quaternary ammonium hydroxide compounds and / or strong acids. Examples of strong bases other than quaternary ammonium hydroxide compounds include sodium hydroxide (NaOH) and potassium hydroxide (KOH). Examples of strong acids include sulfuric acid, hydrogen peroxide, and hydrofluoric acid. [Examples]

[0072] The present invention will be described in more detail by the following examples and comparative examples, but the present invention is not limited in any way by the following examples. Unless otherwise specified below, quantities are by mass, and the actual measurements were taken under conditions of 25°C and atmospheric pressure.

[0073] <Ingredients used> The quaternary ammonium hydroxide compound, cyclic ether compound, and alkyl ketone used in this example are as follows:

[0074] • Quaternary ammonium hydroxide compounds: Tetramethylammonium hydroxide (TMAH) • Surfactants: "Surfactant (1-1)": A nonionic surfactant (1-1) having a structure represented by the following formula (1-1).

[0075] [ka]

[0076] "Surfactant (1-2)": A nonionic surfactant (1-2) having a structure represented by the following formula (1-2).

[0077] [ka]

[0078] <Example 1>

[0079] [Preparation of the treatment solution]

[0080] Each component was prepared to the concentrations shown in Table 1, and 20 L of treatment solution was obtained. Water was prepared as the remainder of the treatment solution. For example, the treatment solution of Example 1 contained 2.38% by mass of TMAH and 1 ppm of the nonionic surfactant (1-2), with the remainder being water. The mass ratio of the quaternary ammonium hydroxide compound content to the surfactant content of the treatment solution (quaternary ammonium hydroxide compound / surfactant, a / b) was 23800. Then, 20 L of the treated liquid was filtered through a filtration filter made of ultra-high molecular weight polyethylene with a pore size of 10 nm at a pressure of 0.04 MPa, and then sealed in a container made of high-density polyethylene (HDPE) for use in subsequent processes.

[0081] Then, after forming a resist film on the evaluation wafer, the wafer was treated with the processing solution from Example 1, and the wafer after treatment was evaluated for defects. The defect evaluation was performed in accordance with the following procedure.

[0082] [Defect inspection of wafers for testing] Prior to evaluating defects in the resist film, a 12-inch (300 mm diameter) silicon wafer (inspection wafer) used for inspection was inspected using a dark-field defect inspection system (KLA-Tencor, Surfscan® SP5), and the number of defects larger than 19 nm on the surface of the silicon wafer was measured ("E: Original substrate defect count").

[0083] [Formation of resist film] A positive-type resist composition (TARF-PI6-144ME, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was connected to the resist line (a separate line from the solvent line) of a coater (CLEAN TRACK® ACT® 12, manufactured by Tokyo Electron Ltd.) (Note that no filter was connected to the connection piping during the connection; a dummy capsule was used instead). Next, the resist composition connected using the method described above was applied to a 12-inch (300 mm diameter) silicon wafer, whose defect count had been previously inspected in the [Wafer Defect Inspection for Inspection] described above, using the coater described above. The coating was then baked at 100°C for 60 seconds to form a film. The thickness of the resist film (coating) was adjusted to 100 nm.

[0084] [Resist film removal process] Next, the resist film is removed from the silicon wafer with the resist film obtained by performing the above-described procedure for [formation of resist film] using the processing solution from Example 1.

[0085] The removal was performed using a coater (Tokyo Electron Ltd., CLEAN TRACK® ACT® 12) connected to a removal solvent after filtration. Specifically, the processing solution from Example 1, connected to the resist line of the coater using the method described above, was applied to a silicon wafer with a resist film using the coater (discharged at a flow rate of 1 mL / S for 10 seconds), and then baked at 100°C for 60 seconds.

[0086] [Inspection of defects in the circuit board after removal] (Calculation of [B: Number of defects after removal]) After the resist film removal process described above, the wafer was subjected to a dark-field defect inspection using a Surfscan® SP5 (manufactured by KLA-Tencor) to measure the number of defects (defect count) present on the silicon wafer surface that were 19 nm or larger ([D: Total number of defects after solvent removal treatment]). Next, based on the results of "E: Number of defects in the original substrate" and "D: Total number of defects after solvent removal treatment" obtained above, "B: Number of defects after removal" was calculated using the following formula. [B: Number of defects after removal] = [D: Total number of defects after solvent removal] - [E: Number of defects in the original substrate]

[0087] The defects were then evaluated based on the following criteria. A: The number of defects was 500 or less. B: The number of defects was between 500 and 1000. C: The number of defects exceeded 1000.

[0088] <Examples 2-11, Comparative Examples 1-4>

[0089] The treatment solution was prepared in the same manner as in Example 1, except for the changes in composition shown in Table 1. Then, defect evaluation was performed using the same method as in Example 1.

[0090] Table 1 shows the compositions and evaluation results of Examples 1-11 and Comparative Examples 1-4.

[0091] [Table 1]

[0092] Based on the above, it has been confirmed that the processing solution of this embodiment is excellent in suppressing defects.

Claims

1. Quaternary ammonium hydroxide compounds, It contains at least one nonionic surfactant selected from the group consisting of a surfactant having the structure represented by the following formula (1) and a surfactant having the structure represented by the following formula (2), The content of the nonionic surfactant is 0.001 ppm or more and 40 ppm or less. Processing solution for semiconductor devices. 【Chemistry 1】 (In the formula, R １ , R ２ , R ３ , and R ４ Each of these independently represents a hydrocarbon group having 1 to 5 carbon atoms. 【Chemistry 2】 (In the formula, R ５ , and R ６ Each of these independently represents a hydrocarbon group having 1 to 5 carbon atoms.

2. The quaternary ammonium hydroxide compound is at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and tetrapropylammonium hydroxide. The processing solution for semiconductor devices according to claim 1.

3. The content of the quaternary ammonium hydroxide compound is 0.2% by mass or more and 13% by mass or less. The semiconductor device processing solution according to claim 1 or 2.

4. The mass ratio of the content of the quaternary ammonium hydroxide compound to the content of the nonionic surfactant (quaternary ammonium hydroxide compound / nonionic surfactant) is 500 or more and 130,000 or less. The semiconductor device processing solution according to claim 1 or 2.

5. The semiconductor device includes a substrate having a metal layer, The aforementioned semiconductor device processing solution is used for processing the substrate. The semiconductor device processing solution according to claim 1 or 2.

6. A method for processing a substrate having a metal layer, The process includes a step of processing the substrate using a semiconductor device processing solution containing a quaternary ammonium hydroxide compound and at least one nonionic surfactant selected from the group consisting of a surfactant having the structure represented by the following formula (1) and a surfactant having the structure represented by the following formula (2), wherein the content of the nonionic surfactant is 0.001 ppm or more and 40 ppm or less. Method for processing circuit boards. 【Transformation 3】 (wherein, R １ , R ２ , R ３ , and R ４ each independently represents a hydrocarbon group having 1 to 5 carbon atoms.) 【Chemistry 4】 (In the formula, R ５ , and R ６ Each of these independently represents a hydrocarbon group having 1 to 5 carbon atoms.

7. The processing step is a residue removal step in which residue is removed from the substrate using the semiconductor device processing solution. The method for processing a substrate according to claim 6.

8. The processing step is an etching step in which the substrate is wet-etched using the semiconductor device processing solution. The method for processing a substrate according to claim 6.

9. A method for manufacturing a semiconductor device including a substrate with a metal layer, The process includes a step of processing the substrate using a semiconductor device processing solution containing a quaternary ammonium hydroxide compound and at least one nonionic surfactant selected from the group consisting of a surfactant having the structure represented by the following formula (1) and a surfactant having the structure represented by the following formula (2), wherein the content of the nonionic surfactant is 0.001 ppm or more and 40 ppm or less. A method for manufacturing semiconductor devices. 【Transformation 5】 (In the formula, R １ , R ２ , R ３ , and R ４ Each of these independently represents a hydrocarbon group having 1 to 5 carbon atoms. 【Transformation 6】 (In the formula, R ５ , and R ６ Each of these independently represents a hydrocarbon group having 1 to 5 carbon atoms.

10. The processing step is a residue removal step in which residue is removed from the substrate using the semiconductor device processing solution. A method for manufacturing a semiconductor device according to claim 9.

11. The processing step is an etching step in which the substrate is wet-etched using the semiconductor device processing solution. A method for manufacturing a semiconductor device according to claim 9.

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