Inspection method, method for manufacturing resin composition, and method for manufacturing resist composition or thermosetting composition

Abstract

To provide an inspection method with which a minute defect can be found, a resin solution in which the number of defects is reduced by the inspection method, a resist composition in which the number of defects is reduced by the inspection method, a method for manufacturing a resin composition, and a method for manufacturing the resist composition.SOLUTION: An inspection method includes: a step V of filtering a precursor composition V containing a polymer compound and a solvent V; a step X1 of applying a resin composition X including the precursor composition to a substrate X to form a coating X; a step X2 of removing the coating X from the substrate X by using a solvent for removal X including at least one selected from the group consisting of an organic solvent X, an alkaline developing solution X, and water; and a step X3 of measuring the number of defects on the substrate X after the coating X is removed by using a defect inspection device.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an inspection method, a resin solution, a resist composition or a thermosetting composition, a method for producing a resin composition, and a method for producing a resist composition or a thermosetting composition.

Background Art

[0002] Semiconductor devices are known to be manufactured by forming a fine electronic circuit pattern on a substrate using photolithography technology. Specifically, after forming a resist film obtained using a radiation-sensitive or radiation-sensitive composition (hereinafter also referred to as a "resist composition") on a substrate, the resist film is subjected to various treatments such as an exposure treatment of irradiating light, a development treatment using a developer, and a rinse treatment using a rinse solution as necessary, whereby a patterned resist film is obtained. Using the patterned resist film thus obtained as a mask, various treatments are performed to form an electronic circuit pattern. In such a semiconductor device forming process, in order to further improve the yield of the obtained semiconductor device, a pattern forming method capable of suppressing the occurrence of defects is required. In recent years, the manufacture of semiconductor devices with a node size of 10 nm or less has been under consideration, and this tendency has become even more prominent.

[0003] By the way, one of the causes of defects occurring in the pattern is foreign matter contained in the resist composition. For example, Patent Document 1 proposes a method of automatically inspecting whether foreign matter is attached to a member to be coated such as a substrate before and / or after coating a coating material, selecting good and bad, and preventing defective products from being conveyed to the next process.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

[0005] However, in recent years, further miniaturization of electronic circuit patterns has advanced, and even a tiny foreign object can cause minute defects, which may significantly affect the performance of semiconductor devices. Therefore, in the manufacturing process of semiconductor devices, an inspection method capable of detecting minute defects has been demanded.

[0006] The present invention has been made in view of the above circumstances, and an object thereof is to provide an inspection method capable of detecting minute defects, a resin solution with a reduced number of defects by the inspection method, a resist composition or a thermosetting composition with a reduced number of defects by the inspection method, a method for producing the resin composition, and a method for producing the resist composition or the thermosetting composition. [Means for Solving the Problems]

[0007] In order to solve the above problems, the present invention employs the following configuration. That is, a first aspect of the present invention includes a step V of filtering a precursor composition V containing a polymer compound and a solvent V, a step X1 of applying a resin composition X containing the precursor composition onto a substrate X to form a coating film X, a step X2 of removing the coating film X from the substrate X using a removal solvent X containing at least one selected from the group consisting of an organic solvent X, an alkaline developer X, and water, and a step X3 of measuring the number of defects on the substrate X after removing the coating film X using a defect inspection apparatus.

[0008] A second aspect of the present invention is a resin solution containing a polymer compound and a solvent V, wherein the number of defects having a size of 12.5 nm or more per 1 cm 2 is 2 or less under the following measurement conditions. (Measurement Conditions) (1) Filter a precursor composition containing a polymer compound and a solvent V. (2) Apply a resin composition X containing the precursor composition onto a substrate X to form a coating film X. (3) The coating film X is removed from the substrate X using a removal solvent X containing at least one selected from the group consisting of an organic solvent, an alkaline developer, and water. (4) The number of defects on the substrate X after removing the coating film X is measured using a defect inspection apparatus.

[0009] A third aspect of the present invention is a resist composition or a thermosetting composition containing the resin solution according to the second aspect.

[0010] A fourth aspect of the present invention includes a step V of filtering a precursor composition containing a polymer compound and a solvent V, a step X1 of applying a resin composition X containing the precursor composition to a substrate X to form a coating film X, a step X2 of removing the coating film X from the substrate X using a removal solvent X containing at least one selected from the group consisting of an organic solvent, an alkaline developer, and water, a step X3 of measuring the number of defects on the substrate X after removing the coating film X using a defect inspection apparatus, and a step R1 of providing a resin composition that satisfies a predetermined number of defects in the step X3, which is a method for producing a resin composition.

[0011] A fifth aspect of the present invention includes a step R11 of providing a resin composition by the method for producing a resin composition according to the fourth aspect, and a step R12 of providing a resist composition or a thermosetting composition containing the resin composition, which is a method for producing a resist composition or a thermosetting composition.

Advantages of the Invention

[0012] According to the present invention, it is possible to provide an inspection method capable of detecting fine defects, a resin solution with a reduced number of defects by the inspection method, a resist composition or a thermosetting composition with a reduced number of defects by the inspection method, a method for producing the resin composition, and a method for producing the resist composition or the thermosetting composition.

Brief Description of the Drawings

[0013]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0014] <First Aspect: Inspection Method> The inspection method according to the present embodiment includes a step V of filtering a precursor composition V containing a polymer compound and a solvent V, a step X1 of applying a resin composition X containing the precursor composition to a substrate X to form a coating film X, a step X2 of removing the coating film X from the substrate X using a removal solvent X containing at least one selected from the group consisting of an organic solvent X, an alkaline developer X, and water, and a step X3 of measuring the number of defects on the substrate X after removing the coating film X using a defect inspection apparatus. Hereinafter, each step will be described.

[0015] [Step V] The method for filtering the precursor composition V is not particularly limited, and examples thereof include filtration using a filter. The filter pore size and material are not particularly limited and can be appropriately adjusted according to the composition. The filter may be one that has been washed in advance with a solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel and used. When using a plurality of types of filters, filters having at least one of different pore sizes and materials may be combined and used. Further, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulation filtration step.

[0016] As the filter, for example, a filter made of at least one porous membrane of polyimide, polyamideimide, polyimide, polyamideimide, and polyethylene may be used to filter the precursor composition V. Examples of the polyimide porous membrane and the polyamideimide porous membrane include those described in JP-A-2016-155121. Also, as the filter, one with reduced eluate as disclosed in JP-A-2016-201426 may be used.

[0017] The pore diameter of the filter is not particularly limited, but is preferably 50 nm or less, more preferably 20 nm or less, and even more preferably 10 nm or less.

[0018] In this embodiment, the filter may be in one stage or two or more stages, but two or more stages are preferred. The pore diameter of the first-stage filter is preferably 20 nm or less, more preferably 10 nm or less, and even more preferably 6 nm or less. The pore diameter of the filters after the second stage is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 2 nm or less.

[0019] In addition to filter filtration, removal of impurities by an adsorbent may be performed, or filter filtration and an adsorbent may be used in combination. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel or zeolite, or organic adsorbents such as activated carbon can be used. Examples of the metal adsorbent include those disclosed in JP-A-2016-206500.

[0020] Also, as a method for removing impurities such as metals, a raw material with a low metal content is selected as the raw material, filter filtration is performed on the raw material, or distillation is performed under conditions where contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene, etc. Preferred conditions for filter filtration performed on the raw material are the same as the conditions described above.

[0021] (High molecular compound) The high molecular compound is not particularly limited, and examples thereof include high molecular compounds contained in coating materials to be applied to materials to be coated such as substrates in the manufacturing process of semiconductor devices. Specifically, examples of the high molecular compound include a base material component of a resist composition, a thermosetting composition for forming an antireflection film, a material for forming a dicing protective film, and the like.

[0022] (Solvent) The solvent is not particularly limited as long as it can dissolve the high molecular compound. Specifically, examples of the solvent include water, lactone solvents, ketone solvents, alcohol solvents, ester solvents, ether solvents, aromatic organic solvents, hydrocarbon solvents, and polar solvents such as dimethyl sulfoxide (DMSO).

[0023] The solid content concentration of the precursor composition is not particularly limited, but is preferably 50% by mass or less, more preferably 35% by mass or less, still more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0024] [Process X1] Examples of the method for forming a coating film X on substrate X using the precursor composition include, for example, a method of applying the precursor composition onto substrate X. Another example of the coating method includes a coating method using a coater cup and a coating method using an organic developing unit. Also preferred is a coating method using a spin coating method using a spinner. The rotation speed during spin coating using a spinner is preferably 500 to 3000 rpm. When using a coater, the discharge time is not particularly limited and may be appropriately changed according to the solid content concentration of the composition.

[0025] After applying the precursor composition onto substrate X, it is preferable to dry substrate X. Examples of the drying method include a method of drying by heating. The heating can be carried out by means provided in a normal exposure machine and / or a developing machine, or it may be carried out using a hot plate or the like. The heating temperature is preferably 80 to 150 °C, more preferably 80 to 140 °C, and even more preferably 80 to 130 °C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds. As one aspect, it is preferable to carry out heating at 100 °C for 60 seconds.

[0026] The film thickness of the coating film X is not particularly limited, but is preferably 10 to 1000 nm, and more preferably 10 to 120 nm. Among them, it is preferable to consider the film thickness for each use purpose of the precursor composition. For example, when the precursor composition is a base material component for a resist composition and is used for pattern formation by EUV exposure or EB exposure, the film thickness of the coating film X is more preferably 10 to 100 nm, and even more preferably 15 to 70 nm. Further, for example, when the precursor composition is a base material component for a resist composition and is used for pattern formation by ArF exposure, the film thickness of the coating film X is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0027] (Resin composition X) The resin composition X is not particularly limited as long as it contains the precursor composition. For example, the precursor composition itself may be used as the resin composition X, or the precursor composition may be mixed with optional components to form the resin composition X. In the present embodiment, from the viewpoint of more accurately inspecting defects derived from the precursor composition, it is preferable that the resin composition is non-photosensitive. Further, in the present embodiment, from the viewpoint of more accurately inspecting defects derived from the precursor composition, it is preferable that the resin composition X is composed of a polymer compound and the solvent V.

[0028] (Substrate X) Examples of the substrate X include substrates used in the manufacture of integrated circuit elements, and silicon wafers are preferred. The substrate X may be a recycled wafer. In terms of further improving the inspection accuracy, the substrate X used in process X1 preferably has the number of defects (original substrate defect number) existing on the substrate X before being applied to process X1 of 2.00 defects / cm 2 or less, more preferably 1.20 defects / cm 2 or less, even more preferably 0.75 defects / cm 2 or less, still more preferably 0.15 defects / cm 2 or less, and particularly preferably so. Note that as the lower limit value, for example, it is 0.00 defects / cm 2 or more. Among them, in terms of further improving the inspection accuracy, the substrate X used in process X1 preferably has the number of defects with a size of 12.5 nm or more existing on the substrate X before being applied to process X1 of 2.00 defects / cm2 or less, more preferably 1.20 defects / cm2 or less, even more preferably 0.75 defects / cm2 or less, and particularly preferably 0.15 defects / cm2 or less. Note that as the lower limit value, for example, it is 0.00 defects / cm 2 or more. Regarding the size of the defects, there is no particular upper limit, but for example, it is 5 μm or less, and the same applies to the defects described in each process described later. When the number of defects of the substrate X used in process X1 is large, scattering may occur during the defect inspection on the substrate performed in process X3, which may prevent accurate measurement of the number of defects. Therefore, in terms of the point that the accuracy of the defect inspection on the substrate in process X3 is more excellent (and thus the inspection accuracy of this inspection method is further improved), it is preferable to use a substrate X with high cleanliness (a substrate with a small number of original substrate defects) in process X1. The defect inspection on the substrate X can be measured by a defect inspection apparatus (for example, a dark field defect inspection apparatus: Surfscan (registered trademark) SP7 manufactured by KLA-Tencor Corporation XP etc.).

[0029] [Process X2] The removal solvent X used in process X2 contains at least one selected from the group consisting of organic solvent X, alkaline developer X, and water (hereinafter also referred to as "X component"). The X component may be a single type or a mixture of multiple types. The content of component X (total when mixing multiple types) in the removal solvent is preferably 60 to 100% by mass, more preferably 85 to 100% by mass, still more preferably 90 to 100% by mass, particularly preferably 95 to 100% by mass, and most preferably 98 to 100% by mass with respect to the total amount of the removal solvent X. Among them, the organic solvent X preferably contains substantially no water in terms of improving inspection accuracy. "The organic solvent X contains substantially no water" means that the water content in the organic solvent X is intended to be 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably contains no water.

[0030] (organic solvent X) The above-mentioned organic solvent X is not particularly limited as long as it can remove the coating film X formed in step X1 from the substrate X. Among them, it is preferably an organic solvent contained in the precursor composition (for example, when the precursor composition is a base component of a resist composition, the organic solvent diluting the resist component corresponds). It preferably contains one or more selected from the group consisting of ester-based organic solvents, alcohol-based organic solvents, and ketone-based organic solvents, and more preferably consists of these groups.

[0031] Examples of the ester-based organic solvent include propylene glycol monoalkyl ether carboxylate, lactate ester, acetate ester, lactone, and alkoxypropionate ester.

[0032] Examples of propylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, or propylene glycol monoethyl ether acetate, with propylene glycol monomethyl ether acetate (PGMEA) being more preferred. Examples of the lactate ester include ethyl lactate, butyl lactate, or propyl lactate. As the acetate ester, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate is preferable. As the alkoxypropionate ester, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable. As the lactone, γ-butyrolactone is preferable.

[0033] Examples of the alcoholic organic solvent include propylene glycol monoalkyl ether and the like. As the propylene glycol monoalkyl ether, propylene glycol monomethyl ether (PGME) or propylene glycol monoethyl ether (PGEE) is preferable.

[0034] Examples of the ketonic organic solvent include chain ketones and cyclic ketones and the like. As the chain ketone, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone is preferable. As the cyclic ketone, methylcyclohexanone, isophorone, or cyclohexanone is preferable.

[0035] The organic solvent X may be used alone or in combination of two or more. As the organic solvent X, it is preferably to contain one or more selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), methyl amyl ketone, cyclohexanone, ethyl lactate, butyl acetate, and γ-butyrolactone, and more preferably to consist of these groups.

[0036] (Alkaline developer X) Examples of the alkaline developer X include an aqueous solution of 0.1 to 10% by mass of tetramethylammonium hydroxide (TMAH).

[0037] In this embodiment, the step X2 may be applied in a state where the coating film X has not been subjected to an exposure process by irradiation with actinic rays or radiation, or may be applied in a state where the coating film X has been subjected to an exposure process by irradiation with actinic rays or radiation. From the viewpoint of more accurately inspecting defects derived from the precursor composition, the step X2 is preferably applied in a state where the coating film X has not been subjected to an exposure process by irradiation with actinic rays or radiation.

[0038] [Step X3] The step X3 is a step of measuring the number of defects on the substrate X after the coating film X has been removed in the step X2 using a defect inspection apparatus. Specifically, the number of defects present on the substrate X (preferably, the number of defects having a size of 12.5 nm or more) is measured. The defect inspection of the substrate X in the step X3 can be measured with a defect inspection apparatus (for example, a dark field defect inspection apparatus: Surfscan (registered trademark) SP7 manufactured by KLA-Tencor Corporation XP etc.). By carrying out the above step X3, the number of defects (preferably, the number of defects having a size of 12.5 nm or more) present on the substrate X after removal by the removing solvent is measured.

[0039] [Optional step] The inspection method according to this embodiment may include steps other than the step V, the step X1, the step X2, and the step X3. The following describes each optional step.

[0040] [Step X2A] The removal solvent X may be used after filtration (Step X2A). The method of filtering the removal solvent X is the same as the method of filtering the precursor composition V in the above Step V.

[0041] [Step Z] The inspection method according to this embodiment includes: Step Z1 of applying a resist composition or a thermosetting composition containing the precursor composition V onto a substrate Z to form a coating film Z; Step Z2 of removing the coating film Z from the substrate Z using a removal solvent Z containing at least one selected from the group consisting of an organic solvent Z, an alkali developer Z, and water; and Step Z3 of measuring the number of defects on the substrate Z after removing the coating film Z using the defect inspection apparatus. Step Z may be performed. By performing Step Z, not only defects derived from the precursor composition V but also defects derived from other components of the resist composition or the thermosetting composition can be inspected, making it easier to judge the results for defects derived from the resist composition or the thermosetting composition actually used in the manufacture of semiconductor devices.

[0042] [Step Z1] The method of applying a resist composition or a thermosetting composition onto a substrate Z to form a coating film Z is the same as the method of forming a coating film X on a substrate X using the precursor composition in Step X1.

[0043] (Resist composition or thermosetting composition) The resist composition or the thermosetting composition used in Step Z1 is not particularly limited as long as it contains the precursor composition V. For example, as the resist composition, it may contain the precursor composition V as a base material component and other optional components. Typically, it contains the precursor composition V as a base material component, a photoacid generator, an acid diffusion controller, a solvent, and other additives (crosslinking agents, fluorine additives, organic acids, additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halation agents, dyes, etc.). Alternatively, the resist composition may contain, as a hydrophobic resin, a precursor composition V, a substrate component, a photoacid generator, an acid diffusion controller, a solvent, and other additives (a crosslinking agent, a fluorine additive, an organic acid, an additional resin for improving the performance of the resist film, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, etc.). As the thermosetting composition, it may contain a precursor composition V, a solvent, a crosslinking agent, and a surfactant.

[0044] The solid content concentration of the resist composition or the thermosetting composition is not particularly limited, but is preferably 50% by mass or less, more preferably 35% by mass or less, still more preferably 10% by mass or less, and still more preferably 3% by mass or less.

[0045] (Substrate Z) As the substrate Z, any one of the substrates X described in the step X1 can be used. From the viewpoint of accurately measuring defects derived from the resist composition or the thermosetting composition, the substrate Z is of the same type as the substrate X, and it is preferable not to use the substrate X itself used in the step X1 as the substrate Z.

[0046] [Step Z2] The removing solvent Z used in the step Z2 can be selected from the removing solvents X described in the step X2, and is preferably of the same type as the removing solvent X used in the step X2. [Step Z2A] The removing solvent Z may be used after filtration (step Z2A). The method of filtering the removing solvent Z is the same as the method of filtering the precursor composition V in the step V.

[0047] [Step Z3] The step Z3 can be carried out in the same manner as the step X3.

[0048] [Step Y1] The inspection method according to this embodiment may further include, before the step X1 or step Z1, a step Y1 of measuring the number of defects on the substrate X or substrate Z using the defect inspection apparatus with respect to the substrate X or substrate Z used in the step X1 or step Z1. By performing the step Y1, defects derived from the substrate X or substrate Z can be grasped in advance, making it easier to judge the results regarding defects derived from the precursor composition V, the resist composition, or the thermosetting composition in the step X3 or step Z3.

[0049] Defect inspection on the substrate X or substrate Z can be measured with a defect inspection apparatus (for example, a dark field defect inspection apparatus: Surfscan (registered trademark) SP7 manufactured by KLA-Tencor Corporation) XP etc.).

[0050] [Step Y2] The inspection method according to this embodiment may perform a step Y2 including a step Y2A of applying a removal solvent used in the step X2 or step Z2 to the substrate Y, and a step Y2B of measuring the number of defects on the substrate X or substrate Z after the application of the removal solvent using a defect inspection apparatus. By performing the step Y, the number of defects derived from the removal solvent can be measured, making it easier to judge the results regarding defects derived from the precursor composition V in the step X3.

[0051] The step Y2A can be performed in the same manner as the step X1 or step Z1. The step Y2B can be performed in the same manner as the step X3 or step Z3.

[0052] The inspection method according to this embodiment may perform both the step Y1 and the step Y2. When performing both the step Y1 and the step Y2, the number of defects derived from the substrate X or substrate Z measured in the step Y1 and the number of defects derived from the removal solvent measured in the step Y2 may be subtracted from the number of defects measured in the step X3 or step Z3. By this subtraction, it becomes easier to judge the results regarding defects derived from the precursor composition V. In addition, when the number of defects derived from the removal solvent (the number of removal solvent defects) is already known from the description in a catalog or the like, step Y2 may not be performed and such a nominal value may be used as "the number of defects derived from the removal solvent measured in step Y2".

[0053] [Step X4] The inspection method according to this embodiment may include a step X4 of overlapping the position coordinates of the defect detection results in the step Y1 and the defect detection results in the step X3, subtracting the number of defects obtained in the step Y1 from the number of defects in the step X3, and measuring the number of defects derived from the resin composition X. By performing step X4, it becomes easier to judge the results regarding the defects derived from the resin composition X.

[0054] An example of the procedure of step X4 will be described with reference to the drawings. First, as shown in FIG. 1, the defect positions in the substrate X are measured (step X41). In FIG. 1, the defect 41 is a defect derived from the substrate X. Next, as shown in FIG. 2, in the substrate X after applying the removal solvent X, the defect positions in the substrate X are measured (step X42). In FIG. 2, the defect 41' is a defect derived from the substrate X, and the defect 42 is a defect derived from the resin composition X. Furthermore, as shown in FIG. 3, from the defects 41' and 42 measured in step X42, the defect 41' at the same position as the defect measured in step X41 is subtracted, and the number of defects 43 derived from the removal solvent X is measured (step X43).

[0055] Since the defects detected at the same position in step X41 and step X42 are derived from the substrate X, by subtracting the defects detected at the same position, the number of defects derived from the resin composition can be appropriately measured in step X43.

[0056] In addition, in step X42, all of the defect positions in substrate X measured in step 41 may not be detected. Therefore, in step X43, if the total number of defects in step X41 is subtracted from the number of defects measured in step X42, rather than the number of defects detected at the same positions in steps X41 and X42, the defects detected in step X41 but not detected in step X42 will be subtracted additionally, and the accurate number of defects cannot be measured.

[0057] [Step Y3] The inspection method according to this embodiment may include a step Y3 of superimposing the position coordinates of the defect detection results obtained in the step Y1 and the defect detection results obtained in the step Y2, subtracting the number of defects obtained in the step Y1 from the number of defects obtained in the step Y2, and measuring the number of defects derived from the removal solvent Y. By performing step Y3, it becomes easier to judge the results regarding the defects derived from the resin composition X. Step Y3 can be performed in the same manner as step X4.

[0058] [Step Z4] The inspection method according to this embodiment may include a step Z4 of superimposing the position coordinates of the defect detection results obtained in the step Y1 and the defect detection results obtained in the step Z3, subtracting the number of defects obtained in the step Y1 from the number of defects obtained in the step Z3, and measuring the number of defects derived from the resist composition or the thermosetting composition. By performing step Z4, it becomes easier to judge the results regarding the defects derived from the resist composition or the thermosetting composition. Step Z4 can be performed in the same manner as step X4.

[0059] In the inspection method according to this embodiment, the minimum value of the measurable defect is preferably 20 nm or less, more preferably 19 nm or less, still more preferably 17 nm or less, and most preferably 12.5 nm or less. That is, in the inspection method according to this embodiment, it is most preferable that the size of the defect measured in at least one selected from the group consisting of the step X3, the step Z3, and the step Y1 is 12.5 nm or more.

[0060] According to the inspection method according to this embodiment, by evaluating the resin raw material for defects before preparing the resist composition or the thermosetting composition, defective resins can be discriminated. Therefore, by applying the inspection method according to this embodiment, an improvement in the productivity of semiconductor devices can be expected. In addition, by previously inspecting the number of defects in the resin composition X, it is easier to more accurately investigate the cause of the defects in the resist composition or the thermosetting composition.

[0061] <Second Aspect: Resin Solution> The resin solution according to this embodiment contains a polymer compound and a solvent V, and the number of defects having a size of 12.5 nm or more per 1 cm 2 is 2 or less when measured under the following measurement conditions. (Measurement Conditions) (1) Filter the precursor composition containing the polymer compound and the solvent V. (2) Apply the resin composition X containing the precursor composition to the substrate X to form a coating film X. (3) Remove the coating film X from the substrate X using a removal solvent X containing at least one selected from the group consisting of an organic solvent, an alkaline developer, and water. (4) Measure the number of defects on the substrate X after removing the coating film X using a defect inspection apparatus.

[0062] In this embodiment, (1) to (4) of the above measurement conditions can be performed in the same manner as steps V, X1, X2, and X3 in the inspection method according to the first aspect.

[0063] Since the resin solution according to this embodiment has reduced defects, it is useful as a resin raw material for various materials used in the manufacture of semiconductor devices.

[0064] <Third Aspect: Resist Composition or Thermosetting Composition> The resist composition or the thermosetting composition according to this embodiment contains the resin solution according to the second aspect. The resist composition according to this embodiment contains, for example, the resin solution according to the second aspect as a base material component, and may contain other optional components. Typically, it contains the resin solution according to the second aspect as a base material component, a photoacid generator, an acid diffusion controller, a solvent, and other additives (crosslinking agents, fluorine additives, organic acids, additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halation agents, dyes, etc.). Alternatively, the resist composition may contain the resin solution according to the second aspect as a hydrophobic resin, a base material component, a photoacid generator, an acid diffusion controller, a solvent, and other additives (crosslinking agents, fluorine additives, organic acids, additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halation agents, dyes, etc.). The thermosetting composition according to this embodiment may contain a precursor composition V, a solvent, a crosslinking agent, and a surfactant.

[0065] Since the resist composition or thermosetting composition according to this embodiment contains a resin solution with reduced defects, it is suitable for the manufacture of semiconductor devices.

[0066] <Fourth Aspect: Method for Producing Resin Composition> The method for producing a resin composition according to this embodiment includes a step V of filtering a precursor composition containing a polymer compound and a solvent V, a step X1 of applying a resin composition X containing the precursor composition onto a substrate X to form a coating film X, a step X2 of removing the coating film X from the substrate X using a removal solvent X containing at least one selected from the group consisting of an organic solvent, an alkaline developer, and water, a step X3 of measuring the number of defects on the substrate X after removing the coating film X using a defect inspection apparatus, and a step R1 of providing a resin composition that satisfies a predetermined number of defects in the step X3.

[0067] In this embodiment, the step V, step X1, step X2, and step X3 are the same as the step V, step X1, step X2, and step X3 in the inspection method according to the first aspect. In Step R1, as the resin composition satisfying the number of predetermined defects, it is preferable that the number of defects having a size of 12.5 nm or more per 1 cm 2 is 2 or less as measured in Step X3.

[0068] According to the method for producing a resin composition according to the present embodiment, since a resin composition with reduced defects can be obtained, it can be applied to resin raw materials of various materials used in the manufacture of semiconductor devices.

[0069] <Method for producing a resist composition or a thermosetting composition> The method for producing a resist composition or a thermosetting composition according to the present embodiment includes Step R11 of providing a resin composition by the method for producing a resin composition, and Step R12 of providing a resist composition or a thermosetting composition containing the resin composition. According to the method for producing a resist composition or a thermosetting composition according to the present embodiment, since defects can be reduced, a resist composition or a thermosetting composition suitable for the manufacture of semiconductor devices can be provided.

Examples

[0070] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0071] (Step Y1: Step of measuring the number of defects on the substrate X with respect to the substrate X used in Step X1) Using a dark field defect inspection apparatus (manufactured by KLA-Tencor, Surfscan (registered trademark) SP7 XP ), defect inspection of a 12-inch (diameter 300 mm) silicon wafer used for inspection was carried out, and the number of defects (defect count) having a size of 12.5 nm or more present on the surface of the silicon wafer per 1 cm 2 or more was measured. The result is designated as "E: number of defects on the original substrate".

[0072] (Steps X2A and Z2A: Filtration of the removal solvent) Each removal solvent was filtered using a 10 nm pore size polyethylene filter, and the filtered liquid was filled into a gallon bottle.

[0073] (Process Y2: Measurement of the number of defects derived from the solvent for removal used in Process X2) The above-mentioned solvent for removal after filtration was respectively connected to the line of a coater (Tokyo Electron Limited, CLEAN TRACK (registered trademark) ACT (registered trademark) 12) (Note that no filter was connected to the connection piping during connection). Subsequently, on a 12-inch (diameter 300 mm) silicon wafer whose number of defects had been inspected in advance in the above-mentioned [Defect inspection of the wafer for inspection], the solvent for removal connected by the above-mentioned method was applied with the coater (discharged for 10 seconds at a flow rate of 75 mL / min), and then baked at 100 °C for 45 seconds. For the wafer after application of the solvent for removal obtained by the above procedure, using a dark-field defect inspection apparatus (manufactured by KLA-Tencor Corporation, Surfscan (registered trademark) SP7 XP ), the number of defects (number of defects) with a size of 12.5 nm or more present on the surface of the silicon wafer per 1 cm 2 or more was measured. The result was designated as "F: Number of defects after shaking off the solvent for removal". Next, based on the results of "E: Number of defects on the original substrate" and "F: Number of defects after shaking off the solvent for removal" obtained by the above various inspections, "C: Number of defects of the solvent for removal" was determined by the following calculation formula. Formula (A1): [C: Number of defects of the solvent for removal] = [F: Number of defects after shaking off the solvent for removal] - [E: Number of defects on the original substrate]

[0074] [Preparation of the precursor composition, resist composition, and thermosetting composition] The following components were used for the preparation of the precursor composition, resist composition, and thermosetting composition. (Polymer compound) The structures of the polymer compounds used are shown below. For each polymer compound, 13 The copolymerization composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by C-NMR is shown in Table 1. The composition ratios in Table 1 correspond in order from the left of each polymer compound. Also, for each polymer compound, the weight-average molecular weight (Mw) and molecular weight dispersity (Mw / Mn) in terms of standard polystyrene determined by GPC measurement are shown in Table 1.

[0075] [Chemistry]

[0076] [Chemistry]

[0077] [Chemistry]

[0078] [Table 1]

[0079] (Compound 1: Photoacid Generator, Near-Infrared Absorbing Dye) The structures of each photoacid generator and near-infrared absorbing dye used as Compound 1 are shown below.

[0080] [Chemistry]

[0081] (Compound 2: Acid Diffusion Controller) The structures of each acid diffusion controller used as Compound 2 are shown below.

[0082] [Chemistry]

[0083] (Compound 3: Fluorine Additive, Photoacid Generator) The structures of each fluorine additive and photoacid generator used as Compound 3 are shown below.

[0084] [Chemistry]

[0085] The weight-average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 15,000, and the molecular weight distribution (Mw / Mn) was 1.5. 13 The copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by C-NMR was l / m = 50 / 50.

[0086]

Chemical formula

[0087]

Chemical formula

[0088] The weight-average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 10,000, and the molecular weight distribution (Mw / Mn) was 1.4. 13 The copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) determined by C-NMR was l / m = 60 / 40.

[0089]

Chemical formula

[0090] (Solvent) The solvents used for the composition are as follows. s1: Propylene glycol monomethyl ether acetate (hereinafter, "PGMEA") s2: Propylene glycol monomethyl ether (hereinafter, "PGME") s3: Gamma-butyrolactone

[0091] The solvents used for removal are as follows. c1: A mixed solution of PGMEA / PGME = 3 / 7 c2: 2.38% aqueous solution of tetramethylammonium hydroxide (NMD-3: manufactured by Tokyo Ohka Kogyo Co., Ltd.) c3: PGMEA

[0092] [Step V: Preparation of the precursor composition] For Examples 01 to 04, 11 to 28, and Comparative Examples 01 to 04, 11 to 18, a solution composed of the polymer compound shown in Table 2 and the composition solvent was prepared so that the solid content concentration was 10% by mass. Next, it was filtered once through a two-stage filter with a pore size nylon filter in the first stage and a polyethylene filter with a pore size of 1 nm in the second stage to obtain a precursor composition.

[0093]

Table 2

[0094] (Step X1: Step of applying the precursor composition to substrate X to form a coating film X) The prepared precursor compositions were respectively connected to the lines of a coater (Tokyo Electron Limited, CLEAN TRACK (registered trademark) LITHIUSPro (registered trademark) Z) (however, it is a line different from the solvent line). Note that no filter was connected to the connection piping during connection. Subsequently, on a 12-inch (diameter 300 mm) silicon wafer whose defect count had been inspected in advance in the above-mentioned [Defect inspection of the test wafer], the precursor composition connected by the above-mentioned method was applied at 1500 rpm with the above-mentioned coater, and then baked at 110 °C for 60 seconds to form a coating film.

[0095] (Step X2: Step of removing the coating film X from the substrate X using the removal solvent X) In Examples 01 to 04, 11 to 28, then, a removal solvent was used to remove the coating film from the silicon wafer with the coating film obtained in Step X1. The removal solvents used here are various solvents prepared in Step X2 and Step Z2.

[0096] (Step X3: Step of measuring the number of defects on the substrate X after removing the coating film X using the defect inspection device X) For the wafer after the above-mentioned coating film removal step, defect inspection was carried out using a dark field defect inspection device (manufactured by KLA-Tencor Corporation, Surfscan (registered trademark) SP7 XP ) and the defect inspection was carried out, and for 1 cm 2The number of defects (defect count) with a size of 12.5 nm or more present on the surface of the silicon wafer as described above was measured ([D: Total defect count after solvent removal treatment]). Subsequently, based on the results of "E: Original substrate defect count" and [D: Total defect count after solvent removal treatment] obtained by the above various inspections, "B: Defect count after removal" was determined using the following calculation formula. Formula (A2): [B: Defect count after removal] = [D: Total defect count after solvent removal treatment] - [E: Original substrate defect count]

[0097] <Defect evaluation after peeling (calculation of [A: Defect count after peeling])>As the defect count after peeling, the value obtained by subtracting the defect count derived from the removal solvent ([C: Defect count of removal solvent]) from the defect count after removal was defined as "[A: Defect count after peeling]". Specifically, "[A: Defect count after peeling]" was determined using the following calculation formula. Note that [C: Defect count of removal solvent] is based on the above description. Formula (A3): [A: Defect count after peeling] = [B: Defect count after removal] - [C: Defect count of removal solvent]. 1 cm 2 The defect count of the defects after peeling per 1 cm was evaluated according to the following evaluation criteria. The results are shown in Tables 4 and 5. (Evaluation criteria) A: 1 cm 2 The defect count of the defects after peeling per 1 cm is less than 0.1 B: 1 cm 2 The defect count of the defects after peeling per 1 cm is 0.5 or more and less than 2 C: 1 cm 2 The defect count of the defects after peeling per 1 cm is 2 or more and less than 10 D: 1 cm 2 The defect count of the defects after peeling per 1 cm is 10 or more

[0098] (Coating film defect evaluation) For the above wafer with a coating film, defect inspection was carried out using a dark field defect inspection device (manufactured by KLA-Tencor, Surfscan (registered trademark) SP7 XP ). As a result, since the inspection target is the coating film, defects less than 30 nm cannot be evaluated. Therefore, as the coating film defect count, 1 cm 2The value obtained by subtracting the number of defects ([E: number of defects derived from the original substrate]) derived from the original substrate defects from the number of defects on the surface of the coating film and the number of defects with a size of 30 nm or more in the film ([B’: number of defects after coating]) was defined as the “A’: number of coating film defects”. Specifically, the “A’: number of coating film defects” was obtained by the following calculation formula. Formula (A3’): [A’: number of coating film defects] = [B’: number of defects after coating] - [E: number of defects derived from the original substrate]. Per 1 cm 2 Table 4 shows the number of defects of the coating film defects per 2 .

[0099] (Process X4: A process of overlapping the position coordinates of the defect detection results by Process Y1 and the defect detection results by Process X3, subtracting the number of defects obtained in Process Y1 from the number of defects by Process X3, and measuring the number of defects derived from Resin Composition X) First, as shown in FIG. 1, the defect positions in Substrate X are measured (Process X41). Next, as shown in FIG. 2, in Substrate X after applying Resin Composition X, the defect positions in Substrate X are measured (Process X42). Further, as shown in FIG. 3, from the defects measured in Process X42, the defects at the same positions as the defects measured in Process X41 are subtracted to measure the number of defects derived from Resin Composition X (Process X43).

[0100] Since the defects detected at the same positions in Process X41 and Process X42 are derived from Substrate X, by subtracting the defects detected at the same positions, the number of defects derived from Resin Composition X in Process X43 can be appropriately measured. Regarding the defects derived from the solvent for removal and the defects derived from the resist composition or the thermosetting composition, the number of defects derived from Substrate Y or Substrate Z is also subtracted and measured by the same method as in Process X4 (Process Y3, Process Z4).

[0101] (Preparation of a resist composition or a thermosetting composition using a precursor composition) In Examples 01, 03, 11 to 28 and Comparative Examples 01 to 04, the precursor composition, Compound 1, Compound 2, Compound 3, and Composition Solvents 1 to 2 shown in Table 3 were mixed to prepare a solution with a solid content concentration of 2% by mass. Next, filtration was performed once through a two-stage filter with a 5-nm pore size nylon filter in the first stage and a 1-nm pore size polyethylene filter in the second stage as described in Tables 4 and 5 to obtain a resist composition or a thermosetting composition. In addition, in Examples 02 and 04, since it was found that the number of defects would be poor when used as a resist composition due to defects after peeling of the precursor composition, a resist composition was not prepared.

[0102] In Comparative Examples 11 to 18, the precursor composition shown in Table 2 and Compounds 1 to 3 shown in Table 3 were mixed to prepare a solution with a solid content concentration of 2% by mass. Next, filtration was performed twice through a two-stage filter with a 5-nm pore size nylon filter in the first stage and a 1-nm pore size polyethylene filter in the second stage as described in Table 5 to obtain a resist composition or a thermosetting composition. In addition, Compounds 1 to 3 in Table 3 are values relative to 100% by mass of the content of the polymer compound contained in the resist composition or the thermosetting composition.

[0103]

Table 3

[0104] (Step Z1: A step of applying a resist composition or a thermosetting composition containing the precursor composition V onto a substrate Z to form a coating film Z) A resist composition or a thermosetting composition was applied onto a substrate in the same manner as in Step X1 to form a coating film.

[0105] (Step Z1A: A step of exposing the coating film) In Example 28, the coating film Z formed in Step Z1 was selectively irradiated with an ArF excimer laser (193 nm) using an ArF liquid immersion exposure apparatus 1900i (NA 1.35 Closspole (in / o = 0.78 / 0.97) with Pol., liquid immersion medium: water). Then, post-exposure bake (PEB) treatment was performed at a temperature of 90°C for 60 seconds. Subsequently, at 23°C, solvent development was performed with butyl acetate for 13 seconds. Thereafter, rinsing was carried out for 5 seconds using methyl isobutyl carbinol (MIBC).

[0106] (Step Z2: Step of removing the coating film Z from the substrate Z using a solvent for removal) In the same manner as in Step X2, the coating film Z formed in Step Z1 was removed from the substrate Z.

[0107] (Step Z3: Step of measuring the number of defects on the substrate Z after removing the coating film Z using a defect inspection apparatus) In the same manner as in Step X3, the number of defects on the substrate Z after Step Z2 was measured using a defect inspection apparatus.

[0108] [Table 4]

[0109] As shown in Table 4, in a resin composition containing precursor compositions of the same composition but different lots after Step V2 of filtering a precursor composition composed of a polymer compound and PGMEA, in the inspection method having Step X2 of removing the coating film from the substrate X using a solvent for removal and Step X3 of measuring the number of defects on the substrate after removing the coating film using a defect inspection apparatus, in the "defects after peeling" measured, differences between lots could be found in the number of defects per 1 cm² for defects with a size of 12.5 nm or more. However, in the "coating film defects" where the number of defects of the wafer with a coating film was measured without performing Step V2 of filtering a solution composed of a polymer compound and a solvent for the composition, only the number of defects per unit area for defects with a size of 30 nm or more could be evaluated, and differences between lots could not be found. 2 In the "coating film defects" where the number of defects of the wafer with a coating film was measured without performing Step V2 of filtering a solution composed of a polymer compound and a solvent for the composition, only the number of defects per unit area for defects with a size of 30 nm or more could be evaluated, and differences between lots could not be found.

[0110] From the above results, it was confirmed that the inspection method of the present invention can easily determine whether the polymer compound used in the resist composition is good or bad, compared with the coating film defect in which the step X2 of removing the coating film from the substrate X using the removing solvent is not performed.

[0111]

Table 5

[0112] As shown in Table 5, by applying the inspection method of the present invention, a resist composition with a small number of defects could be prepared by filtering the resist composition or the thermosetting composition once thereafter. On the other hand, when the step V2 of filtering the precursor composition composed of the polymer compound and the solvent was not performed, even if the resist composition or the thermosetting composition was filtered twice thereafter, the number of defects in the resist composition or the thermosetting composition was large. Also, it was better not to expose the resist composition or the thermosetting composition. Furthermore, by performing coordinate alignment, the number of defects derived from the removal solvent or the composition could be appropriately measured by suppressing the mixing of the detected components derived from the original substrate that is irrelevant to the composition for evaluation purposes. In addition, since the number of defects to be obtained by subtraction by coordinate alignment can be accurately obtained, the cleanliness of the initial state of the wafer to be used does not particularly need to be required.

Explanation of Reference Signs

[0113] Substrate X 41, 41’, 42, 43 Defects

Claims

1. Step V of filtering the precursor composition V containing a polymer compound and a solvent V; Step X1 of applying a resin composition X containing the precursor composition to a substrate X to form a coating film X; Step X2 of removing the coating film X from the substrate X using a removal solvent X containing at least one selected from the group consisting of an organic solvent X, an alkaline developer X, and water; A inspection method including Step X3 of measuring the number of defects on the substrate X after removing the coating film X using a defect inspection apparatus.

2. Further, Step Z1 of applying a resist composition or a thermosetting composition containing the precursor composition V to a substrate Z to form a coating film Z; Step Z2 of removing the coating film Z from the substrate Z using a removal solvent Z containing at least one selected from the group consisting of an organic solvent Z, an alkaline developer Z, and water; The inspection method according to Claim 1, further including Step Z3 of measuring the number of defects on the substrate Z after removing the coating film Z using the defect inspection apparatus.

3. Further, before Step X1 or Step Z1, Step Y1 of measuring the number of defects on the substrate X or the substrate Z using the defect inspection apparatus with respect to the substrate X or the substrate Z used in Step X1 or Step Z1 is included. The inspection method according to Claim 1 or 2.

4. Step X4 of measuring the number of defects derived from the resin composition X by overlapping the position coordinates of the defect detection results by Step Y1 and the defect detection results by Step X3, and subtracting the number of defects obtained in Step Y1 from the number of defects by Step X3. The inspection method according to Claim 3.

5. The inspection method according to Claim 1 or 2, wherein the size of the defect measured in at least one selected from the group consisting of Step X3, Step Z3, and Step Y1 is 12.5 nm or more.

6. The inspection method according to claim 1 or 2, wherein the resin composition is non-photosensitive.

7. The inspection method according to claim 1 or 2, wherein the resin composition comprises the polymer compound and the solvent V.

8. The inspection method according to claim 1 or 2, wherein the step X2 is applied in a state where the coating film X has not been subjected to an exposure treatment by irradiation with actinic rays or radiation.

9. The inspection method according to claim 1 or 2, wherein the step X2 is applied in a state where the coating film X has been subjected to an exposure treatment by irradiation with actinic rays or radiation.

10. A resin solution containing a polymer compound and a solvent V, Measured under the following measurement conditions, 1 cm ２ The resin solution has 2 or less defects having a size of 12.5 nm or more per. (Measurement conditions) (1) Filter a precursor composition containing a polymer compound and a solvent V. (2) Apply a resin composition X containing the precursor composition to a substrate X to form a coating film X. (3) Remove the coating film X from the substrate X using a removal solvent X containing at least one selected from the group consisting of an organic solvent, an alkaline developer, and water. (4) Measure the number of defects on the substrate X after removing the coating film X using a defect inspection apparatus.

11. A resist composition or a thermosetting composition containing the resin solution according to claim 10.

12. A step V of filtering a precursor composition containing a polymer compound and a solvent V, A step X1 of applying a resin composition X containing the precursor composition to a substrate X to form a coating film X, A step X2 of removing the coating film X from the substrate X using a removal solvent X containing at least one selected from the group consisting of an organic solvent, an alkaline developer, and water, Step X3 of measuring the number of defects on the substrate X after removing the coating film X using a defect inspection apparatus; A method for producing a resin composition, comprising step R1 of providing a resin composition that satisfies a predetermined number of defects in step X3.

13. Step R11 of providing a resin composition by the method for producing a resin composition according to claim 12; A method for producing a resist composition or a thermosetting composition, comprising step R12 of providing a resist composition or a thermosetting composition containing the resin composition.

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