Semiconductor device processing liquid, substrate processing method, and semiconductor device manufacturing method

Abstract

Provided are: a semiconductor device processing liquid which comprises a quaternary ammonium hydroxide compound and at least one nonionic surfactant selected from the group consisting of surfactants having a specific structure and surfactants having a specific structure, and in which the contained amount of the nonionic surfactant is 0.001-40 ppm; a substrate processing method: and a semiconductor device manufacturing method.

Description

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

[0001] Cross-reference to Related Applications This application claims priority to Japanese Patent Application No. 2024-228062, filed with the Japan Patent Office on 24 December 2024, which is incorporated herein by reference in its entirety.

[0002] This invention relates to a processing solution for semiconductor devices, a method for processing substrates, and a method for manufacturing semiconductor devices.

[0003] Semiconductor elements such as ICs and LSIs, and liquid crystal panel elements, for example, are metal films or SiO2 deposited on a substrate using CVD. ２ A resist is uniformly coated onto an insulating film, and this is selectively exposed and developed to form a resist pattern. This pattern is then used as a mask to form the CVD-deposited metal film or SiO ２ The process involves selectively etching a substrate on which an insulating film, such as a thin film, has been formed to create a microcircuit, and then removing the unwanted resist layer. In the pattern formation of such microcircuits, a processing solution is used to remove the resist layer.

[0004] 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.

[0005] Japanese Patent Application Publication No. 07-128865

[0006] However, the conventional technologies described above require further improvement in suppressing defects in wafers after processing. Therefore, the present invention has been made in response to this need, and aims to provide a semiconductor device processing solution, a substrate processing method, and a semiconductor device manufacturing method that are excellent in suppressing defects.

[0007] As a result of diligent research to achieve the above-mentioned objectives, the present inventors have found that a processing solution for semiconductor devices contains a quaternary ammonium hydroxide compound and a nonionic surfactant having a specific structure, wherein the content of the nonionic surfactant is 0.001 ppm or more and 40 ppm or less, and have thus completed the present invention.

[0008] In other words, the present invention encompasses the following aspects: <1> A processing solution for semiconductor devices, comprising 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. (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. (In the formula, R ５ , and R ６Each 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, and is the processing liquid for semiconductor devices according to <1>. <3> The content of the quaternary ammonium hydroxide compound is 0.2% by mass or more and 13% by mass or less, and it is the processing liquid for semiconductor devices according to <1> or <2>. <4> The mass ratio (quaternary ammonium hydroxide compound / nonionic surfactant) of the content of the quaternary ammonium hydroxide compound to the content of the nonionic surfactant is 500 or more and 130,000 or less, and it is the processing liquid for semiconductor devices according to any one of <1> to <3>. <5> The semiconductor device includes a substrate provided with a metal layer, and the processing liquid for semiconductor devices is used for processing the substrate, and it is the processing liquid for semiconductor devices according to any one of <1> to <4>. <6> A method for processing a substrate provided with a metal layer, including a processing step of processing the substrate using a processing liquid for semiconductor devices containing 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. (In the formula, R １ , R ２ , R ３ , and R ４ each independently represents a hydrocarbon group having 1 to 5 carbon atoms.) (In the formula, R ５ , and R ６Each of these independently represents a hydrocarbon group having 1 to 5 carbon atoms.) <7> The processing step is a residue removal step in which residues on the substrate are removed using the semiconductor device processing solution, the method for processing a substrate according to <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 <6>. <9> A method for manufacturing a semiconductor device including a substrate having a metal layer, comprising a processing step of processing the substrate using a semiconductor device processing solution that 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), wherein the content of the nonionic surfactant is 0.001 ppm or more and 40 ppm or less. (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. (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 of removing residue from the substrate using the semiconductor device processing liquid, as described in <9>. <11> The processing step is an etching step of wet etching the substrate using the semiconductor device processing liquid, as described in <9>.

[0009] 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.

[0010] 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, each configuration and parameter 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. In this specification, unless otherwise specified, "ppm" is a numerical value based on mass.

[0011] Furthermore, in this specification, “comprise” may be replaced with “is,” “consist essentially of,” or “consist of,” as needed. In addition, “A and / or B” means “A, B, or both,” unless otherwise specified.

[0012] In this specification, "doing or to do" as in "doing..." may be replaced with "process" or "step," and "process" may be replaced with "doing or to do" or "step," and "step" may be replaced with "doing" or "process." Furthermore, in this specification, "process" as in "process," may be "an apparatus or part configured to perform a process," "apparatus" may be "a mechanism or part," and "part" may be "a part or apparatus for being provided in a mechanism, apparatus, or system, etc."

[0013] <Processing solution for semiconductor devices>

[0014] The processing liquid for semiconductor devices according to this embodiment (hereinafter, may be simply abbreviated as "processing liquid") contains a quaternary ammonium hydroxide compound, at least one nonionic surfactant selected from the group consisting of a surfactant (1) having a structure represented by the following formula (1) and a surfactant (2) 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. Here, unless otherwise specified in this specification, "ppm" is a numerical value based on a mass basis.

[0015]

[0016] (In the formula, R １ 、R ２ 、R ３ 、and R ４ each independently represents a hydrocarbon group having 1 to 5 carbon atoms.)

[0017]

[0018] (In the formula, R ５ 、and R ６ each independently represents a hydrocarbon group having 1 to 5 carbon atoms.)

[0019] According to the processing liquid of this embodiment, it is excellent in suppressing defects of the wafer after processing. Although the reason is not clear, for example, when etching a silicon wafer, if the substrate is processed with the processing liquid according to this embodiment after the etching, the surface of the substrate is hydrophilized and hydroxyl groups exist on the surface. As a result of the nonionic surfactant in the processing liquid of this embodiment being weakly adsorbed to the hydroxyl groups, it is considered that the adhesion of defects can be suppressed (however, the actions and effects of this embodiment are not limited to these).

[0020] Hereinafter, the components and the like of the processing liquid according to this embodiment will be described.

[0021] (a) Quaternary ammonium hydroxide compound

[0022] (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. By being such a compound, defect suppression can be further improved.

[0023] 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, still more preferably 1.3% by mass or more, even more preferably 1.7% by mass or more, and even still more preferably 2% by mass or more. Also, the upper limit of the content of component (a) is more preferably 4% by mass or less, still more preferably 3.5% by mass or less, even more preferably 3% by mass or less, and even still 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.

[0024] (b) Nonionic surfactant

[0025] The nonionic surfactant (b) is at least one selected from the group consisting of surfactant (1) having a structure represented by formula (1) and surfactant (2) having a structure represented by formula (2).

[0026]

[0027] (In the formula, R １ , R ２ , R ３ , and R ４ each independently represent a hydrocarbon group having 1 to 5 carbon atoms.)

[0028]

[0029] (In the formula, R ５ , and R ６ each independently represent a hydrocarbon group having 1 to 5 carbon atoms.)

[0030] R in formula (1) １ , R ２ , R ３, and R ４ R 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.

[0031] 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.

[0032]

[0033]

[0034] R in equation (2) ５ It is preferably a hydrocarbon group having 1 to 4 carbon atoms. ６ R 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.

[0035] A specific example of surfactant (2) is preferably a surfactant (2-1) having the structure represented by the following formula (2-1). Such a compound can further improve defect suppression.

[0036]

[0037] (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.).

[0038] 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 35 ppm or less, and more preferably 30 ppm or less. By setting the content of component (b) within the above range, defect suppression can be further improved.

[0039] 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.

[0040] (c) Cyclic ether compounds

[0041] 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, the number of carbon atoms forming the ring in the (c) cyclic ether compound is preferably 2 to 5, and more preferably 2 to 4. 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 to 2.

[0042] (c) Specific examples of the 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.

[0043] 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, 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.

[0044] The processing solution according to this embodiment is expected to provide 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.

[0045] (d) Alkyl ketones

[0046] 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.

[0047] 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 0.05 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.

[0048] In this embodiment, the processing solution preferably 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 more preferably 0.01 ppm or more, even 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 more preferably 4 ppm or less, even 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.

[0049] (e) Water-soluble organic solvents other than cyclic ether compounds

[0050] 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).

[0051] (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; 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.

[0052] 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.

[0053] (Other additives)

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] <Method for processing circuit boards>

[0059] 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.

[0060] 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.

[0061] The semiconductor device processing solution according to this embodiment can be suitably used in substrate processing methods. A preferred example of a substrate processing method according to this embodiment is a substrate processing method 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 and at least one nonionic surfactant selected from the group consisting of a surfactant having the structure represented by formula (1) and a surfactant having the structure represented by formula (2), wherein the content of the nonionic surfactant is 0.001 ppm or more and 40 ppm or less. As the semiconductor device processing solution, for example, a processing solution having the above-described composition can be used.

[0062] 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.

[0063] 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.

[0064] In other words, the processing step is preferably a residue removal step in which residue is removed from the substrate 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 one minute at room temperature.

[0065] 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 one minute at room temperature.

[0066] 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.

[0067] 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.

[0068] <Methods for manufacturing semiconductor devices>

[0069] 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 and at least one nonionic surfactant selected from the group consisting of a surfactant having the structure represented by formula (1) and a surfactant having the structure represented by formula (2), wherein the content of the nonionic surfactant is 0.001 ppm or more and 40 ppm or less. 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.

[0070] The processing step is preferably a residue removal step in which residues on the substrate are removed using a processing solution for semiconductor devices.

[0071] Alternatively, the processing step is preferably an etching step in which the substrate is wet-etched using a processing solution for semiconductor devices.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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 based on mass, and the experiments were conducted under conditions of 25°C and atmospheric pressure.

[0076] <Ingredients Used> The ingredients used in this example are as follows:

[0077] • Quaternary ammonium hydroxide compound: Tetramethylammonium hydroxide (TMAH) • Surfactant: "Surfactant (1-1)": Nonionic surfactant (1-1) having the structure represented by the following formula (1-1)

[0078]

[0079] "Surfactants (1-2)": Nonionic surfactants (1-2) having a structure represented by the following formula (1-2)

[0080]

[0081] <Example 1>

[0082] [Preparation of the treatment solution]

[0083] 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 surfactant (1-1), which is a nonionic surfactant, 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. The 20 L of the treatment solution was filtered through an ultra-high molecular weight polyethylene filter 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.

[0084] 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.

[0085] [Defect Inspection of Test Wafers] Prior to evaluating defects in the resist film, a 12-inch (300 mm diameter) silicon wafer (test wafer) used for inspection was inspected using a dark-field defect inspection system (Surfscan® SP5, manufactured by KLA-Tencor), and the number of defects larger than 19 nm on the surface of the silicon wafer was measured ("E: Number of defects in the original substrate").

[0086] [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). Subsequently, the resist composition connected in the manner 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] described above, using the coater. After that, the wafer was baked at 100°C for 60 seconds to form a coating film. The thickness of the resist film (coating film) at this time was adjusted to 100 nm.

[0087] [Resist film removal step] Next, the resist film was removed from the silicon wafer with the resist film obtained by performing the above-described procedure for [resist film formation] using the processing solution from Example 1.

[0088] 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 the silicon wafer with the 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.

[0089] [Defect Inspection of Substrate After Removal] (Calculation of [B: Number of Defects After Removal]) After the resist film removal process described above, a dark-field defect inspection was performed on the wafer using a dark-field defect inspection device (Surfscan® SP5, manufactured by KLA-Tencor), and the number of defects with a size of 19 nm or larger on the surface of the silicon wafer was measured ([D: Total Number of Defects After Solvent Removal]). Then, based on the results of "E: Number of Defects in the Original Substrate" and [D: Total Number of Defects After Solvent Removal] 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]

[0090] The defects were then evaluated based on the following criteria: A: The number of defects was less than 500. B: The number of defects was 500 or more but less than 1000. C: The number of defects was 1000 or more.

[0091] <Examples 2-11, Comparative Examples 1-4>

[0092] 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.

[0093] Table 1 shows the compositions and evaluation results of Examples 1 to 11 and Comparative Examples 1 to 4.

[0094]

[0095] Based on the above, it has been confirmed that the processing solution of this embodiment is excellent in suppressing defects.

Claims

1. A processing solution for semiconductor devices, comprising 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. (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. (In the formula, R ５ , and R ６ Each of these independently represents a hydrocarbon group having 1 to 5 carbon atoms.

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

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

4. The semiconductor device processing solution according to claim 1 or 2, wherein 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.

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

6. A method for treating a substrate provided with a metal layer, comprising a treatment step of treating the substrate with a treatment liquid for a semiconductor device, the treatment liquid containing 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 being 0.001 ppm or more and 40 ppm or less. (In the formula, R １ , R ２ , R ３ , and R ４ each independently represents a hydrocarbon group having 1 to 5 carbon atoms.) (In the formula, R ５ , and R ６ each independently represents a hydrocarbon group having 1 to 5 carbon atoms.) 7. The substrate processing method according to claim 6, wherein the processing step is a residue removal step in which residue is removed from the substrate using the semiconductor device processing liquid.

8. The method for processing a substrate according to claim 6, wherein the processing step is an etching step of wet etching the substrate using the processing solution for semiconductor devices.

9. A method for manufacturing a semiconductor device including a substrate having a metal layer, comprising a processing 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 a structure represented by the following formula (1) and a surfactant having a 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. (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. (In the formula, R ５ , and R ６ Each of these independently represents a hydrocarbon group having 1 to 5 carbon atoms.

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

11. The method for manufacturing a semiconductor device according to claim 9, wherein the processing step is an etching step of wet etching the substrate using the processing solution for semiconductor devices.

Images