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, all of which contain a quaternary ammonium hydroxide compound, a cyclic ether compound, and an alkyl ketone, wherein the total content of the cyclic ether compound and the alkyl ketone is 0.001 ppm or more and less than 5 ppm.

Description

Technical Field

[0001] The present invention relates to a processing liquid for semiconductor devices, a method for processing a substrate, and a method for manufacturing a semiconductor device. It relates thereto.

Background Art

[0002] Semiconductor elements such as ICs and LSIs, and liquid crystal panel elements are manufactured, for example, by uniformly applying a resist on an insulating film such as a metal film or a SiO2 film CVD-deposited on a substrate, selectively exposing and developing this to form a resist pattern, selectively etching the substrate on which the insulating film such as the CVD-deposited metal film or SiO2 film is formed using this pattern as a mask to form a fine circuit, and then removing an unnecessary resist layer. In the formation of such a fine circuit pattern, a processing liquid is used to remove the resist layer.

[0003] As an example related to such a processing liquid, Patent Document 1 discloses a resist developer composition characterized in that at least one selected from polyoxypropylene monoalkyl ether, polypropylene glycol, and polyoxyethylene monoalkyl ether is added to a resist developer containing an organic base not containing metal ions as a main agent.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] 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. [Means for solving the problem]

[0006] As a result of diligent research to achieve the above-mentioned objectives, the present inventors have found that a processing solution for semiconductor devices containing a quaternary ammonium hydroxide compound, a cyclic ether compound, and an alkyl ketone, wherein the total content of the cyclic ether compound and the alkyl ketone is 0.001 ppm or more and less than 5 ppm, has been created, and thus the present invention has been completed.

[0007] In other words, the present invention is as follows. <1> This is a processing solution for semiconductor devices, containing a quaternary ammonium hydroxide compound, a cyclic ether compound, and an alkyl ketone, wherein the total content of the cyclic ether compound and the alkyl ketone is 0.001 ppm or more and less than 5 ppm. <2> The quaternary ammonium hydroxide compound is at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. <1> This is a processing solution for semiconductor devices as described above. <3> The cyclic ether compound is at least one selected from the group consisting of ethylene oxide, 1,4-dioxane, tetrahydrofuran, and 4-methyltetrahydropyran. <1> or <2> This is a processing solution for semiconductor devices as described above. <4> The alkyl ketone is at least one selected from the group consisting of acetone, methyl isobutyl ketone, methyl ethyl ketone, dimethyl ketone, diethyl ketone, and ethyl isobutyl ketone. <1> ~ <3> This is a processing solution for semiconductor devices as described in any of the following. <5> The content of the quaternary ammonium hydroxide compound is 0.2% by mass or more and 13% by mass or less. <1> ~ <4> This is a processing solution for semiconductor devices as described in any of the following. <6> The mass ratio of the content of the quaternary ammonium hydroxide compound to the total content of the cyclic ether compound and the alkyl ketone (quaternary ammonium hydroxide compound / (cyclic ether compound + alkyl ketone)) is 11,000 or more and 1,300,000 or less. <1> ~ <5> This is a processing solution for semiconductor devices as described in any of the following. <7> The mass ratio of the alkyl ketone content to the cyclic ether compound content (alkyl ketone / cyclic ether compound) is 0.01 or more and 100 or less. <1> ~ <6> This is a processing solution for semiconductor devices as described in any of the following. <8> The semiconductor device includes a substrate having a metal layer, and the processing solution for the semiconductor device is used for processing the substrate. <1> ~ <7> This is a processing solution for semiconductor devices as described in any of the following. <9> A method for processing 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, a cyclic ether compound, and an alkyl ketone, wherein the total content of the cyclic ether compound and the alkyl ketone is 0.001 ppm or more and less than 5 ppm. <10> The processing step is a residue removal step in which residue is removed from the substrate using the semiconductor device processing solution. <9> This is the method for processing the substrate as described above. <11> The processing step is an etching step in which the substrate is wet-etched using the semiconductor device processing solution. <9> This is the method for processing the substrate as described above. <12> 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, a cyclic ether compound, and an alkyl ketone, wherein the total content of the cyclic ether compound and the alkyl ketone is 0.001 ppm or more and less than 5 ppm. <13> The processing step is a residue removal step in which residue is removed from the substrate using the semiconductor device processing solution. <12> This is a method for manufacturing semiconductor devices as described above. <14> The processing step is an etching step in which the substrate is wet-etched using the semiconductor device processing solution. <12> This is a method for manufacturing semiconductor devices as described above. [Effects of the Invention]

[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, 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 addition, unless otherwise specified herein, "ppm" is a numerical value based on mass.

[0010] <Processing solution for semiconductor devices>

[0011] The processing liquid for semiconductor devices according to this embodiment (hereinafter, may be simply abbreviated as "processing liquid") contains a quaternary ammonium hydroxide compound, a cyclic ether compound, and an alkyl ketone, and the total content of the cyclic ether compound and the alkyl ketone is 0.001 ppm or more and less than 5 ppm. It is a processing liquid for semiconductor devices. 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 weak adsorption of the cyclic ether, alkyl ketone, etc. in the processing liquid of this embodiment 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).

[0012] Hereinafter, the components, etc. of the processing liquid according to this embodiment will be described.

[0013] (a) Quaternary ammonium hydroxide compound

[0014] (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, and tetrabutylammonium hydroxide. By being such a compound, the defect suppression can be further improved.

[0015] (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 10% by mass or less, even 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.

[0016] (b) Cyclic ether compounds

[0017] (b) The cyclic ether compound preferably contains one ring containing an oxygen atom in its molecule. Furthermore, the number of carbon atoms forming the ring in the (b) cyclic ether compound is preferably 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, the number of oxygen atoms forming the ring in the cyclic ether compound is preferably 1 or more and 2 or less. By having such a compound, defect suppression can be further improved.

[0018] (b) The molecular weight of the cyclic ether compound is not particularly limited, but is preferably 200 or less, more preferably 150 or less, even more preferably 105 or less, and even more preferably 90 or less. Furthermore, the lower limit of the molecular weight of component (b) is preferably 40 or more. By setting the molecular weight within the above range, defect suppression can be further improved.

[0019] (b) 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; molecular weight 44.5), 1,4-dioxane (molecular weight 88.1), tetrahydrofuran (THF, molecular weight 72.1), and 4-methyltetrahydropyran (MTHP, molecular weight 100). Among these, ethylene oxide and 1,4-dioxane are more preferred. Such a compound can further improve defect suppression.

[0020] Furthermore, component (b) may be used alone or in combination of two or more. For example, it is preferable that component (b) contains 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. Such a ratio can further improve defect suppression.

[0021] (b) The content of component (b) is preferably 0.0005 ppm or more and 4.5 ppm or less. The lower limit of the content of component (b) is more preferably 0.001 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 (b) is more preferably 4 ppm or less, even 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 1.5 ppm or less. By setting the content of component (b) within the above range, defect suppression can be further improved.

[0022] (c) Alkyl ketones

[0023] (c) The alkyl ketone is not particularly limited, but it 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. Using such a compound can further improve defect suppression.

[0024] (c) The content of component (c) is preferably 0.0005 ppm or more and 4 ppm or less. The lower limit of the content of component (c) is more preferably 0.001 ppm or more, even more preferably 0.01 ppm or more, and even more preferably 0.1 ppm or more. Furthermore, the upper limit of the content of component (c) 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 (c) within the above range, defect suppression can be further improved.

[0025] The processing solution according to this embodiment has a total content of (b) cyclic ether compounds and (c) 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.

[0026] The mass ratio of the content of (a) quaternary ammonium hydroxide compound to the sum of the content of (b) cyclic ether compound and (c) alkyl ketone (quaternary ammonium hydroxide compound / (cyclic ether compound + alkyl ketone)) is preferably 11,000 to 1,300,000. The lower limit of this mass ratio is more preferably 11,500 or more, and even more preferably 11,700 or more. The upper limit of this mass ratio is more preferably 1,250,000 or less, and even more preferably 1,200,000 or less. By blending the ratio of component (a) to component (b) and component (c) (a / (b+c)) in the above proportions, defect suppression can be further improved.

[0027] (d) Water-soluble organic solvents other than cyclic ether compounds

[0028] The treatment solution according to this embodiment may further contain a water-soluble organic solvent other than the cyclic ether compound (d). Component (d) may be any water-soluble organic solvent that is miscible with components (a), (b), and (c), and an appropriate water-soluble organic solvent can be selected considering the types and content of components (a), (b), and (c) used. It is preferable that component (d) is a solvent other than the compound corresponding to component (c).

[0029] (d)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.

[0030] Furthermore, if component (d) is included, the combination of the cyclic ether compound (b) and the water-soluble organic solvent (d) preferably includes only at least one selected from the group consisting of ethylene oxide and 1,4-dioxane as component (b) and at least one selected from the group consisting of dimethyl sulfoxide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone as component (d); more preferably includes only ethylene oxide and / or 1,4-dioxane as component (b) and at least one selected from the group consisting of dimethyl sulfoxide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone as component (d).

[0031] In this embodiment, sufficient effects can be expected even without necessarily including component (d). However, if component (d) is included, its content may be 50 to 80% by mass. The lower limit of the content of component (d) may be 60% by mass or more, or 65% by mass or more. The upper limit of the content of component (d) may be 75% by mass or less, or 70% by mass or less.

[0032] The mass ratio of the content of (c) alkyl ketone to the content of (b) cyclic ether compound (alkyl ketone / cyclic ether compound, c / b) is preferably 0.01 or more and 100 or less. The lower limit of this mass ratio is more preferably 0.05 or more, even more preferably 0.1 or more, and even more preferably 0.2 or more. The upper limit of this mass ratio is more preferably 50 or less, even more preferably 30 or less, and even more preferably 10 or less. By setting the ratio of component (c) to component (b) (c / b) to the above ratio, defect suppression can be further improved.

[0033] (Other additives)

[0034] 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.

[0035] 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.

[0036] Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Among these, nonionic surfactants are preferred. More preferably, the surfactant is at least one nonionic surfactant selected from the group consisting of surfactants having the structure represented by formula (1) below and surfactants having the structure represented by formula (2) below.

[0037] [ka]

[0038] (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.

[0039] [ka]

[0040] (In the formula, R 5 , and R 6 Each of these independently represents a hydrocarbon group with 1 to 5 carbon atoms.

[0041] 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.

[0042] 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.

[0043] <Method for processing circuit boards>

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] <Manufacturing methods for semiconductor devices>

[0054] 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.

[0055] The processing step is preferably a residue removal step in which residues on the substrate are removed using a processing solution for semiconductor devices.

[0056] Alternatively, the processing step is preferably an etching step in which the substrate is wet-etched using a processing solution for semiconductor devices.

[0057] 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.

[0058] 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.

[0059] 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 a strong base containing a metal element and / or a strong acid. Examples of strong bases containing a metal element include sodium hydroxide (NaOH) and potassium hydroxide (KOH). Examples of strong acids include sulfuric acid, hydrogen peroxide, and hydrofluoric acid. [Examples]

[0060] 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.

[0061] <Ingredients used> The quaternary ammonium hydroxide compound, cyclic ether compound, and alkyl ketone used in this example are as follows:

[0062] • Quaternary ammonium hydroxide compounds: Tetramethylammonium hydroxide (TMAH) • Cyclic ether compounds: 1,4-Dioxane (DO: 6-membered ring, 2 oxygen atoms) Ethylene oxide (EO: ethylene oxide, 3-membered ring, 1 oxygen atom) • alkyl ketones: Methyl isobutyl ketone (MIBK)

[0063] <Example 1>

[0064] [Preparation of the treatment solution]

[0065] 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, 0.1 ppm of DO, and 0.1 ppm of MIBK, with the remainder being water. The mass ratio of the alkyl ketone content to the cyclic ether compound content of the treatment solution ((c) alkyl ketone / (b) cyclic ether compound, c / b) was 1, and the content of the quaternary ammonium hydroxide compound ((a) quaternary ammonium hydroxide / ((b) cyclic ether compound + (c) alkyl ketone), a / ((b+c)) relative to the sum of the cyclic ether compound content and the alkyl ketone content was 119000. 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.

[0066] 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.

[0067] [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").

[0068] [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.

[0069] [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.

[0070] 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.

[0071] [Inspection of defects in the circuit board after removal] <[B: Calculation of the 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]

[0072] 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.

[0073] <Examples 2-10, Comparative Examples 1 and 2>

[0074] 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.

[0075] Table 1 shows the compositions and evaluation results of Examples 1-10 and Comparative Examples 1 and 2.

[0076] [Table 1]

[0077] 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, Cyclic ether compounds and It contains alkyl ketones, The sum of the content of the cyclic ether compound and the content of the alkyl ketone is 0.001 ppm or more and less than 5 ppm. Processing solution for semiconductor devices.

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

3. The cyclic ether compound is at least one selected from the group consisting of ethylene oxide, 1,4-dioxane, tetrahydrofuran, and 4-methyltetrahydropyran. The semiconductor device processing solution according to claim 1 or 2.

4. The alkyl ketone is at least one selected from the group consisting of acetone, methyl isobutyl ketone, methyl ethyl ketone, dimethyl ketone, diethyl ketone, and ethyl isobutyl ketone. The semiconductor device processing solution according to claim 1 or 2.

5. 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.

6. The mass ratio of the content of the quaternary ammonium hydroxide compound to the total content of the cyclic ether compound and the alkyl ketone (quaternary ammonium hydroxide compound / (cyclic ether compound + alkyl ketone)) is 11,000 or more and 1,300,000 or less. The semiconductor device processing solution according to claim 1 or 2.

7. The mass ratio of the alkyl ketone content to the cyclic ether compound content (alkyl ketone / cyclic ether compound) is 0.01 or more and 100 or less. The semiconductor device processing solution according to claim 1 or 2.

8. 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.

9. 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, a cyclic ether compound, and an alkyl ketone, wherein the total content of the cyclic ether compound and the alkyl ketone is 0.001 ppm or more and less than 5 ppm. Method for processing circuit boards.

10. 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 9.

11. 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 9.

12. 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, a cyclic ether compound, and an alkyl ketone, wherein the total content of the cyclic ether compound and the alkyl ketone is 0.001 ppm or more and less than 5 ppm. A method for manufacturing semiconductor devices.

13. 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 12.

14. 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 12.

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