Composition for forming adhesive film, pattern forming method, and method for forming adhesive film

Abstract

The invention relates to a composition for forming an adhesive film, a pattern forming method, and a method for forming an adhesive film. The present invention addresses the problem of providing a fine patterning process using a multilayer resist method in a semiconductor device manufacturing step, which exhibits good coating properties even on a hydrophobic underlayer film. The composition for forming an adhesive film can provide an adhesive film having good pattern collapse suppression performance and ability to remove resist residue at the bottom of a pattern. The solution of the present invention is a composition for forming an adhesive film, which is characterized by comprising (A) a resin containing a repeating unit represented by general formula (1) and a repeating unit having an organic sulfonyl anion structure, and (B) an organic solvent. In the formula, X is a single bond or an aromatic ring having 20 or less carbon atoms, R01 is a hydrogen atom or a methyl group, R02 is a hydrogen atom or a monovalent alkyl group having 1-10 carbon atoms, and when R02 is an alkyl group, the hydrogen atom constituting the alkyl group may be substituted by a hydroxyl group.

Description

Technical Field

[0001] The present invention relates to a composition for forming a sealing film, a method for forming a pattern using the composition for forming a sealing film, and a method for forming a sealing film using the aforementioned composition for forming a sealing film. Background Technology

[0002] With the increasing integration and speed of LSI (Lithium-ion Sensor), the miniaturization of pattern sizes is rapidly advancing. Photolithography, while achieving this miniaturization, utilizes appropriately selected short wavelengths of light sources and suitable resist compositions to form fine patterns. At the heart of this process is the positive photoresist composition used in a single layer. This single-layer positive photoresist composition consists of a resist resin with an etch-resistant framework against chlorine or fluorine-based gas plasmas, and a resist mechanism that dissolves the exposed area to form a pattern. The remaining resist pattern serves as an etching mask for dry etching of the substrate coated with the photoresist composition.

[0003] However, when the thickness of the photoresist film is directly reduced, that is, the pattern width is further reduced, the resolution of the photoresist film will decrease. Furthermore, if the photoresist film is to be patterned using a developer, the aspect ratio will become too large, resulting in pattern corruption. Therefore, with miniaturization, the thickness of the photoresist film also becomes thinner.

[0004] On the other hand, in the processing of substrates, a method typically uses a patterned photoresist film as an etching mask and employs dry etching to process the substrate. However, in reality, there is no dry etching method that can achieve complete etch selectivity between the photoresist film and the substrate. Therefore, the photoresist film is also damaged during substrate processing, and may even break down, making it impossible to correctly transfer the resist pattern to the substrate. Thus, with the miniaturization of patterns, higher dry etching resistance is required for the photoresist composition. Furthermore, due to the shortening of exposure wavelengths, the resin used in the photoresist composition needs to have low light absorption at the exposure wavelength. Therefore, changes from i-rays, KrF, and ArF to phenolic varnish resins, polyhydroxystyrene, and resins with aliphatic polycyclic skeletons have been made. However, in reality, the most recent photoresist compositions that offer fast etching speeds and high resolution under the aforementioned dry etching conditions tend to have weaker etching resistance.

[0005] Therefore, it has become necessary to use thinner photoresist films with weaker etching resistance to dry etch the substrate, and ensuring the quality of materials and processing in this step is of paramount importance.

[0006] One method to address this problem is the multilayer resist method. This method involves placing an intermediate resist film, with a different etching selectivity than the photoresist film (i.e., the upper resist film), between the upper resist film and the substrate being processed. After a pattern is obtained on the upper resist film, the pattern is used as a dry etching mask to transfer the pattern onto the intermediate resist film via dry etching. Then, the intermediate resist film is used as a dry etching mask to transfer the pattern onto the substrate being processed via dry etching.

[0007] One type of multilayer photoresist method is the three-layer photoresist method, which utilizes common photoresist compositions used in single-layer photoresist methods. In this three-layer photoresist method, for example, an organic film such as phenolic varnish is formed on the substrate as the lower photoresist film, a silicon-containing film is formed on it as a silicon-containing photoresist intermediate film, and a common organic photoresist film is formed on it as the upper photoresist film. For dry etching using fluorine-based gas plasma, the organic photoresist upper film exhibits good etch selectivity to the silicon-containing photoresist intermediate film; therefore, the pattern of the upper photoresist film is transferred to the silicon-containing photoresist intermediate film by dry etching using fluorine-based gas plasma. Furthermore, for etching using oxygen or hydrogen, the silicon-containing photoresist intermediate film exhibits good etch selectivity to the lower photoresist film; therefore, the pattern of the silicon-containing photoresist intermediate film can be transferred to the lower photoresist film by etching using oxygen or hydrogen. By means of this method, even if a photoresist composition with a sufficient film thickness is difficult to form for direct processing of the substrate, or a photoresist composition with insufficient dry etching resistance for processing the substrate is used, a pattern can still be transferred onto a silicon-containing film (silicon-containing photoresist intermediate film), and a pattern of an organic film (photoresist underlayer film) obtained by processing phenolic varnish or the like with sufficient dry etching resistance can be obtained.

[0008] In recent years, vacuum ultraviolet (EUV) lithography with a wavelength of 13.5 nm has attracted attention as a powerful alternative to ArF immersion lithography and multiple exposure processes. Using this technology, fine patterns with a half-pitch of less than 25 nm can be formed in a single exposure.

[0009] On the other hand, in EUV lithography, the resist material needs to be highly sensitive in order to compensate for insufficient light source output. However, with the increase of sensitivity, the increase of shot noise is related to the increase of edge roughness (LER, LWR) of the line pattern. Balancing high sensitivity and low edge roughness can be listed as one of the important issues in EUV lithography.

[0010] In recent years, attempts have been made to increase the sensitivity of photoresist materials and reduce the impact of shot noise. The use of metallic materials in photoresist materials has been explored. Compounds containing metallic elements such as barium, titanium, hafnium, zirconium, and tin exhibit higher absorbance for EUV light compared to metal-free organic materials, which is expected to improve the photosensitivity of the photoresist and suppress shot noise. Furthermore, photoresist patterns containing metals, when combined with a photoresist underlayer composed of non-metallic materials, are expected to enable high-selectivity etching processes.

[0011] For example, researchers have explored resist materials containing metal salts or organometallic complexes (Patent Documents 1 and 2), and non-chemically amplified resist materials using metal oxide nanoparticles (Patent Documents 3 and 4, Non-Patent Document 1). However, the resolution of these metal-containing resists has not yet reached the level required for practical application, and further improvements in resolution are needed.

[0012] Furthermore, the advent of ArF immersion lithography and EUV lithography has enabled the formation of finer patterns. However, ultra-fine patterns are very prone to collapse due to their small footprint, and suppressing pattern collapse is a significant challenge. On the other hand, insufficient light source output can lead to resist residue at the bottom of the pattern, which can negatively impact the processing.

[0013] As the miniaturization process increases, the difficulty of patterning also increases. Furthermore, the manufacturing process becomes more complex as the structure of semiconductor devices becomes more diverse, necessitating photolithography on various underlying films. To improve pattern adhesion and remove residue from the bottom of the pattern, attempts were made to form a resist-adhesive film directly beneath the resist layer. However, forming the adhesive film itself becomes particularly difficult when the underlying film has high hydrophobicity.

[0014] To suppress pattern collapse, materials have been reported that improve adhesion to the upper resist film by using a resist underlayer containing polar functional groups such as lactone or urea structures (Patent Documents 4 and 5), and that enhance the rectangularity of the resist pattern (Patent Documents 6 and 7). However, these materials cannot be formed on a hydrophobic underlayer, and even if they can be formed, their collapse suppression performance and ability to remove resist residue at the bottom of the pattern are still insufficient.

[0015] Existing technical documents

[0016] Patent documents

[0017] [Patent Document 1] Japanese Patent No. 5708521

[0018] [Patent Document 2] Japanese Patent No. 5708522

[0019] [Patent Document 3] US Patent No. 9,310,684

[0020] [Patent Document 4] International Publication No. 2003 / 017002

[0021] [Patent Document 5] International Publication No. 2018 / 143359

[0022] [Patent Document 6] Japanese Patent Application Publication No. 2023-094359

[0023] [Patent Document 7] Japanese Patent Application Publication No. 2024-027459

[0024] Non-patent literature

[0025] [Non-Patent Literature 1] Proc. SPIE Vol.7969,796915 (2011) Summary of the Invention

[0026] [The problem that the invention aims to solve]

[0027] The present invention is based on the foregoing circumstances and aims to provide a composition for forming an adhesive film, a pattern forming method using the composition, and the aforementioned method for forming an adhesive film. The composition for forming an adhesive film provides an adhesive film that exhibits good coatability even on a hydrophobic underlying film during the micro-patterning process using a multilayer resist method in the semiconductor device manufacturing process, while also having good pattern collapse suppression performance and the ability to remove resist residue at the bottom of the pattern.

[0028] [Methods for solving the problem]

[0029] To address the aforementioned issues, the present invention provides a composition for forming a tight-fitting film, comprising:

[0030] (A) A resin containing repeating units represented by the following general formula (1) and repeating units having an organic sulfonyl anionic structure, and

[0031] (B) Organic solvents;

[0032] [Chemistry 1]

[0033]

[0034] In the formula, X is a single bond or an aromatic ring with 20 or fewer carbon atoms, and R... 01 It is a hydrogen atom or a methyl group, R 02 It is a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, R 02 When it is an alkyl group, the hydrogen atoms constituting it can also be replaced by hydroxyl groups.

[0035] If such a composition is used for forming a tight film, good coatability can be ensured even on a hydrophobic underlying film, and residues at the bottom of the resist can be removed without increasing the pattern roughness.

[0036] Furthermore, in this invention, the ratio of repeating units represented by the general formula (1) in the repeating units of the (A) resin is preferably 70 mol% or more and 99.9 mol% or less.

[0037] Furthermore, in this invention, the ratio of repeating units having an organic sulfonyl anionic structure in the repeating units of the (A) resin is preferably 0.1 mol% to 30 mol%.

[0038] Such a composition for forming a tight film can ensure good coatability on various underlying films and remove residues at the bottom of the resist without increasing pattern roughness.

[0039] Furthermore, in this invention, the weight-average molecular weight of the (A) resin is preferably 1,000 to 70,000.

[0040] Such a composition for forming a tight film has excellent film-forming properties and can suppress the generation of sublimation products during heat curing, thereby suppressing device contamination caused by sublimation products.

[0041] Furthermore, in this invention, it is preferable that the (B) organic solvent is a mixture of one or more organic solvents with a boiling point of less than 150°C and one or more organic solvents with a boiling point of 150°C or higher and a boiling point of less than 220°C.

[0042] If the composition is such a tight-film forming material, it has sufficient solvent solubility, thus suppressing the generation of coating defects.

[0043] Furthermore, the present invention preferably contains one or more selected from (C) a hot acid generating agent, (D) a surfactant, and (E) a crosslinking agent.

[0044] By adjusting the presence or absence of these various additives, performance can be finely tuned to meet customer requirements such as film-forming properties, fillability, optical properties, and reduction of sublimation, making it ideal for practical use.

[0045] Furthermore, the present invention provides a pattern forming method, which is a method for forming a pattern on a substrate to be processed, comprising the following steps:

[0046] (I-1) After coating the above-described composition for forming an adhesive film onto the substrate to be processed, a heat treatment is performed to form an adhesive film.

[0047] (I-2) A photoresist material is used on the sealed film to form a photoresist top film.

[0048] (I-3) After patterning the upper layer of the photoresist film, it is developed with a developer to form a circuit pattern on the upper layer of the photoresist film.

[0049] (I-4) Using the resist film on which the circuit pattern has been formed as a mask, the pattern is transferred onto the sealing film by dry etching, and

[0050] (I-5) Using the patterned resist top layer film and / or sealing film as a mask, the substrate to be processed is processed to form a pattern on the substrate to be processed.

[0051] Furthermore, the present invention provides a pattern forming method, which is a method for forming a pattern on a substrate to be processed, comprising the following steps:

[0052] (II-1) Form a photoresist underlayer film on the substrate to be processed.

[0053] (II-2) A silicon-containing photoresist intermediate film is formed on the lower layer of the photoresist film.

[0054] (II-3) After coating the aforementioned adhesive film forming composition onto the silicon-containing photoresist interlayer film, heat treatment is performed to form an adhesive film.

[0055] (II-4) A photoresist material is used on the sealed film to form a photoresist top film.

[0056] (II-5) After patterning the upper layer of the photoresist film, it is developed with a developer to form a circuit pattern on the upper layer of the photoresist film.

[0057] (II-6) Using the resist film on which the circuit pattern is formed as a mask, the pattern is transferred to the sealing film by dry etching.

[0058] (II-7) Using the patterned upper resist film and / or sealing film as a mask, the pattern is transferred to the silicon-containing resist intermediate film by dry etching.

[0059] (II-8) Using the silicon-containing resist intermediate film with the transferred pattern as a mask, the pattern is transferred to the resist underlying film by dry etching.

[0060] (II-9) The patterned resist underlayer film is used as a mask to process the substrate and form a pattern on the substrate.

[0061] Furthermore, the present invention provides a pattern forming method, which is a method for forming a pattern on a substrate to be processed, comprising the following steps:

[0062] (III-1) Form a photoresist underlayer film on the substrate to be processed.

[0063] (III-2) An inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film is formed on the lower layer film of the photoresist.

[0064] (III-3) After coating the aforementioned composition for forming an adhesive film onto the intermediate film of the inorganic hard mask, heat treatment is performed to form an adhesive film.

[0065] (III-4) A photoresist material is used on the sealed film to form a photoresist top film.

[0066] (III-5) After patterning the upper layer of the photoresist film, develop it with a developer to form a circuit pattern on the upper layer of the photoresist film.

[0067] (III-6) Using the resist film on which the circuit pattern has been formed as a mask, the pattern is transferred to the sealing film by dry etching.

[0068] (III-7) Using the patterned resist upper layer film and / or sealing film as a mask, the pattern is transferred onto the inorganic hard mask intermediate film by dry etching.

[0069] (III-8) Using the inorganic hard mask intermediate film with the transferred pattern as a mask, the pattern is transferred to the resist underlayer film by dry etching.

[0070] (III-9) Using the resist underlayer film with the transferred pattern as a mask, the substrate to be processed is processed to form a pattern on the substrate to be processed.

[0071] Thus, the composition for forming the adhesive film of the present invention can be applied to various pattern forming methods, such as two-layer photoresist treatment, four-layer photoresist treatment on a silicon-containing intermediate film (silicon-containing photoresist intermediate film, inorganic hard mask intermediate film), and if it is one of these pattern forming methods, it is applicable to the optical lithography of the upper photoresist film.

[0072] At this point, it is preferable to form the aforementioned inorganic hard mask intermediate film using CVD or ALD methods.

[0073] Furthermore, in this invention, the method of forming circuit patterns on the resist film preferably uses optical lithography with a wavelength of 10 nm to 300 nm, direct electron beam lithography, nanoimprinting, or a combination thereof.

[0074] Furthermore, in this invention, it is preferable to use a photoresist material that contains at least an organometallic compound and a solvent.

[0075] Furthermore, in this invention, the developing method is preferably alkali developing or developing using organic solvents.

[0076] In this invention, pattern formation can be performed well and efficiently by using the pattern forming method described above.

[0077] Furthermore, in this invention, it is preferable that the substrate being processed is a semiconductor device substrate, or a substrate on which any one of a metal film, metal carbide film, metal oxide film, metal nitride film, metal oxide carbide film, and metal oxide nitride film has been formed.

[0078] At this time, it is preferable to use silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or alloys thereof.

[0079] If it is the pattern forming method of the present invention, the substrate to be processed as described above can be processed in the manner described above to form a pattern.

[0080] Furthermore, the present invention provides a method for forming an adhesive film, which is a method for forming an adhesive film used in the manufacturing process of a semiconductor device. The method involves spin-coating the adhesive film forming composition described above onto a substrate to be processed, and heat-treating the substrate coated with the adhesive film forming composition at a temperature of 100°C to 300°C for 10 to 600 seconds to form an adhesive film.

[0081] Furthermore, the present invention provides a method for forming an adhesive film, which is a method for forming an adhesive film used in the manufacturing process of a semiconductor device. The method involves spin-coating the adhesive film forming composition described above onto a substrate to be processed, and heat-treating the substrate coated with the adhesive film forming composition in an ambient gas with an oxygen concentration of 0.1% to 21% or less to form an adhesive film.

[0082] This method promotes the cross-linking reaction during the formation of the adhesive film, thereby suppressing mixing with the upper layer of the resist film to a higher degree. Furthermore, by appropriately adjusting the heat treatment temperature, time, and oxygen concentration within the aforementioned ranges, a pattern collapse suppression effect suitable for the application can be achieved, and the pattern shape adjustment characteristics of the upper layer of the resist film can be obtained.

[0083] Furthermore, the present invention provides a method for forming an adhesive film, which is a method for forming an adhesive film used in the manufacturing process of a semiconductor device. The method involves spin-coating the adhesive film forming composition described above onto a substrate to be processed, and heat-treating the substrate coated with the adhesive film forming composition in an ambient gas with an oxygen concentration of 0.0001% or more but less than 0.1% to form an adhesive film.

[0084] This method is useful because it promotes the cross-linking reaction during the formation of the adhesive film even when the substrate contains materials that are unstable when heated in an oxygen environment, without causing substrate degradation. It can also suppress mixing with the upper film to a higher level.

[0085] [The effects of the invention]

[0086] As explained above, the present invention provides a composition for forming an adhesive film that exhibits excellent coatability on various underlying films. Furthermore, this composition for forming an adhesive film can remove residue from the bottom of the resist without deteriorating the roughness of the resist pattern. Therefore, it is very useful, for example, in multilayer resist processing such as a four-layer resist processing in which the aforementioned adhesive film is formed on a silicon-containing resist intermediate film. Moreover, the adhesive film formation method of the present invention allows for sufficient curing on the processed substrate, resulting in an adhesive film with high adhesion to the upper resist film. Furthermore, the pattern formation method of the present invention enables the formation of fine patterns on the processed substrate with high precision in multilayer resist processing. Attached Figure Description

[0087] [ Figure 1 [A schematic diagram of an example of the pattern formation method performed by the four-layer resist treatment of the present invention.] Detailed Implementation

[0088] In this specification, when a component is referred to as being "directly below" another component, it is in direct contact with the other components without any intermediary elements. Conversely, when a component is referred to as being "below" another component, there may be an intermediary element between them. Similarly, when a component is referred to as being "directly above" another component, it is in direct contact with the other components without any intermediary elements; when a component is referred to as being "above" another component, there may be an intermediary element between them.

[0089] As mentioned above, in the micro-patterning process using the multilayer resist method in the semiconductor device manufacturing process, there is a need for a composition for forming an adhesive film that has good coating properties on various underlying films and can remove residues at the bottom of the resist without deteriorating the roughness of the resist pattern, a patterning method using the composition, and a method for forming an adhesive film.

[0090] The inventors of this application have repeatedly and thoroughly examined the above-mentioned problems and found that the above-mentioned problems can be solved and the present invention can be completed by using a composition for forming a sealing film containing a resin with a specific structure, a pattern forming method using the composition for forming a sealing film, and a method for forming a sealing film using the composition for forming a sealing film.

[0091] That is, the present invention is a composition for forming a tight-fitting film, comprising:

[0092] (A) A resin containing repeating units represented by the following general formula (1) and repeating units having an organic sulfonyl anionic structure, and

[0093] (B) Organic solvents;

[0094] [Chemistry 2]

[0095]

[0096] In the formula, X is a single bond or an aromatic ring with 20 or fewer carbon atoms, and R... 01 It is a hydrogen atom or a methyl group, R 02 It is a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, R 02 When it is an alkyl group, the hydrogen atoms constituting it can also be replaced by hydroxyl groups.

[0097] The present invention will now be described in detail, but it is not limited thereto.

[0098] [Composition for sealing film formation]

[0099] The present invention provides a composition for forming a tight film, comprising: (A) a resin containing repeating units represented by the following general formula (1) and repeating units having an organic sulfonyl anionic structure, and (B) an organic solvent.

[0100] [Chemistry 3]

[0101]

[0102] In the formula, X is a single bond or an aromatic ring with 20 or fewer carbon atoms, and R... 01 It is a hydrogen atom or a methyl group, R 02 It is a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, R 02 When it is an alkyl group, the hydrogen atoms constituting it can also be replaced by hydroxyl groups.

[0103] Furthermore, in the composition for forming a sealing film of the present invention, resin (A) can be used alone or in combination of two or more. Moreover, the composition for forming a sealing film may also include components other than those in (A) and (B). Each component will be described below.

[0104] [(A) Resin]

[0105] The (A) resin contained in the composition for forming a tight film of the present invention contains repeating units represented by the following general formula (1) and repeating units having an organic sulfonyl anionic structure.

[0106] [Chemistry 4]

[0107]

[0108] In the formula, X is a single bond or an aromatic ring with 20 or fewer carbon atoms, and R... 01 It is a hydrogen atom or a methyl group, R 02 It is a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, R 02 When it is an alkyl group, the hydrogen atoms constituting it can also be replaced by hydroxyl groups.

[0109] The structural unit represented by the above general formula (1) functions as a crosslinking group and a close-knit group with the underlying layer. Because it contains nitrogen-hydrogen bonds that act as hydrogen bond donors, it can efficiently form hydrogen bonds even on a hydrophobic underlying film, thereby suppressing coating errors. On the other hand, the structural unit itself is crosslinkable, so even if a large amount of this unit is introduced into the resin, the curability of the film will not be impaired.

[0110] In the above general formula (1), X is a single bond or an aromatic ring with 20 or fewer carbon atoms, preferably a single bond, a benzene ring, or a naphthalene ring. By using a structure with a smaller molecular weight as described above, the number of hydrogen bond donors per unit molecular weight will increase, and the coating properties on hydrophobic surfaces will be improved.

[0111] In the above general formula (1), R 01 It is either a hydrogen atom or a methyl group. However, when X is an aromatic ring, considering the polymerization reactivity during the synthesis of the starting materials, R... 01 It should be a hydrogen atom. When X is a single bond, R 01 The presence of hydrogen atoms or methyl groups ensures sufficient polymerization reactivity during the synthesis of raw materials, and the choice of this structure allows for effective adjustment of polymerization reactivity.

[0112] In the above general formula (1), R 02 It is a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, R 02 When it is an alkyl group, the hydrogen atoms constituting it can be replaced by hydroxyl groups. R 02 It is preferable to use a straight-chain or branched alkyl group with hydrogen atoms or 1 to 6 carbon atoms, and even more preferably a straight-chain or branched alkyl group with hydrogen atoms or 1 to 4 carbon atoms.

[0113] In the above general formula (1), R 02 Specifically, examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl, and organic groups in which the hydrogen atoms constituting these alkyl groups are substituted with hydroxyl groups.

[0114] In the above general formula (1), ΟR 02 The structure detaches during baking, generating carbocations. These carbocations react and bond with other structures, thereby forming cross-links. This is achieved by adding R... 02Setting the structure to a small molecular weight can suppress film shrinkage during baking and reduce coating errors during baking. On the other hand, if R... 02 By designing a structure with a large molecular weight, the volume of the resin structure increases, thereby increasing the resin viscosity during coating and suppressing coating errors during rotary drying. Considering the ease with which coating errors occur during rotary drying and baking, R... 02 It is preferred to use a straight-chain or branched alkyl group with hydrogen atoms or 1 to 6 carbon atoms, and even more preferred to use a straight-chain or branched alkyl group with hydrogen atoms or 1 to 4 carbon atoms.

[0115] A specific example of the repeating unit represented by the above general formula (1) is preferably illustrated by the following structure. R 01 Same as above.

[0116] [Chemistry 5]

[0117]

[0118] [Chemistry 6]

[0119]

[0120] [Chemistry 7]

[0121]

[0122] Furthermore, due to the presence of an organic sulfonyl anion structure in the resin, an acid derived from this organic sulfonyl anion structure is generated on the surface of the lower film, which helps to remove residues from the bottom of the resist film. On the other hand, this acid has bonds with the resin in the composition for forming the adhesive film, resulting in an extremely short diffusion length and minimal adverse effect on pattern roughness.

[0123] Furthermore, structural units having an organic sulfonyl anionic structure are suitable for use with known features. For example, the anion of a monomer providing an organic sulfonyl anionic structure may use the structure represented below, but is not limited thereto. And, in the following, R... A Each is independently a hydrogen atom or a methyl group, X BI Each atom can be independently an iodine atom, a bromine atom, or a fluorine atom.

[0124] [Chemistry 8]

[0125]

[0126] [Chemistry 9]

[0127]

[0128] [Chemistry 10]

[0129]

[0130] [Chemistry 11]

[0131]

[0132] [Chemistry 12]

[0133]

[0134] [Chemistry 13]

[0135]

[0136] [Chemistry 14]

[0137]

[0138] [Chemistry 15]

[0139]

[0140] [Chemistry 16]

[0141]

[0142] [Chemistry 17]

[0143]

[0144] [Chemistry 18]

[0145]

[0146] [Chemistry 19]

[0147]

[0148] [Chemistry 20]

[0149]

[0150] [Chemistry 21]

[0151]

[0152] [Chemistry 22]

[0153]

[0154] [Chemistry 23]

[0155]

[0156] [Chemistry 24]

[0157]

[0158] [Chemistry 25]

[0159]

[0160] [Chemistry 26]

[0161]

[0162] [Chemistry 27]

[0163]

[0164] [Chemistry 28]

[0165]

[0166] [Chemistry 29]

[0167]

[0168] [Chemistry 30]

[0169]

[0170] [Chemistry 31]

[0171]

[0172] [Chemistry 32]

[0173]

[0174] [Chemistry 33]

[0175]

[0176] [Chemistry 34]

[0177]

[0178] [Chemistry 35]

[0179]

[0180] [Chemistry 36]

[0181]

[0182] [Chemistry 37]

[0183]

[0184] [Chemistry 38]

[0185]

[0186] [Chemistry 39]

[0187]

[0188] [Chemistry 40]

[0189]

[0190] [Chemistry 41]

[0191]

[0192] [Chemistry 42]

[0193]

[0194] [Chemistry 43]

[0195]

[0196] [Chemistry 44]

[0197]

[0198] [Chemistry 45]

[0199]

[0200] [Chemistry 46]

[0201]

[0202] [Chemistry 47]

[0203]

[0204] [Chemistry 48]

[0205]

[0206] Furthermore, the relative cation of the aforementioned anion can be a known ammonium cation, sulfonium cation, or monazine cation. For example, the structure described in paragraphs

[0043] to

[0045] of Japanese Patent No. 5415982, or the structure described below, can be used, but it is not limited thereto.

[0207] The aforementioned sulfonium cation is preferably represented by the following general formula (2), and the aforementioned monium cation is preferably represented by the following general formula (3).

[0208] [Chemistry 49]

[0209]

[0210] In the above general formulas (2) and (3), R 4 ~R 8Each is an independent hydrocarbon group consisting of halogen atoms or may contain heteroatoms, and has 1 to 20 carbon atoms.

[0211] R 4 ~R 8 Specific examples of halogen atoms can be listed, such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0212] R 4 ~R 8 The hydrocarbon group represented by these groups, having 1 to 20 carbon atoms, can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, decadecyl, heptadecyl, octadecyl, nonadecanyl, and icosyl; cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, and adamantyl; and alkenyl groups with 2 to 20 carbon atoms such as vinyl, propenyl, butenyl, and hexenyl. ; alkynyl groups with 2 to 20 carbon atoms, such as ethynyl, propynyl, and butynyl; cyclic unsaturated hydrocarbon groups with 3 to 20 carbon atoms, such as cyclohexenyl and norcamphenyl; aryl groups with 6 to 20 carbon atoms, such as phenyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, sec-butylnaphthyl, and tert-butylnaphthyl; aralkyl groups with 7 to 20 carbon atoms, such as benzyl and phenethyl; and groups obtained by combining these.

[0213] Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon group can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it can also contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, nitro groups, mercapto groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0214] Also, R 4 and R 5 They can also bond to each other and form rings together with the sulfur atoms of these bonds. In this case, the aforementioned rings should preferably have the structure shown below.

[0215] [Transformation 50]

[0216]

[0217] In the formula, the dashed lines represent atomic bonds.

[0218] Specific examples of sulfonium cations represented by the above general formula (2) are shown below, but are not limited to these.

[0219] [Chemistry 51]

[0220]

[0221] [Chemistry 52]

[0222]

[0223] [Chemistry 53]

[0224]

[0225] [Chemistry 54]

[0226]

[0227] [Chemistry 55]

[0228]

[0229] [Chemistry 56]

[0230]

[0231] [Chemistry 57]

[0232]

[0233] [Chem.58]

[0234]

[0235] [Chemistry 59]

[0236]

[0237] [Transformation 60]

[0238]

[0239] [Chemistry 61]

[0240]

[0241] [Chemistry 62]

[0242]

[0243] [Chemistry 63]

[0244]

[0245] [Chemistry 64]

[0246]

[0247] [Chemistry 65]

[0248]

[0249] [Chemistry 66]

[0250]

[0251] [Chemistry 67]

[0252]

[0253] [Chemistry 68]

[0254]

[0255] [Chemistry 69]

[0256]

[0257] [Chemistry 70]

[0258]

[0259] [Chemistry 71]

[0260]

[0261] [Chemistry 72]

[0262]

[0263] [Chemistry 73]

[0264]

[0265] [Chemistry 74]

[0266]

[0267] [Chemistry 75]

[0268]

[0269] [Chemistry 76]

[0270]

[0271] [Chemistry 77]

[0272]

[0273] [Chemistry 78]

[0274]

[0275] [Chemistry 79]

[0276]

[0277] [Chemistry 80]

[0278]

[0279] Specific examples of citric cations represented by the above general formula (3) are shown below, but are not limited to these.

[0280] [Chemistry 81]

[0281]

[0282] [Chemistry 82]

[0283]

[0284] The aforementioned structural unit with an organic sulfonyl anion structure preferably includes an iodine atom. Because iodine atoms have high atomic absorption under EUV light, they have a sensitizing effect on EUV light, which improves the removal of residues at the bottom of the pattern and reduces pattern roughness.

[0285] In the repeating units of the above-mentioned (A) resin, the ratio of repeating units represented by the above general formula (1) is preferably 70 mol% or more and 99.9 mol% or less.

[0286] Furthermore, in the repeating units of the resin described above (A), the ratio of repeating units represented by the general formula (1) is preferably 80 mol% to 99.9 mol%, and even more preferably 80 mol% to 99 mol%, but is not limited thereto. As mentioned above, the nitrogen-hydrogen bonds of the repeating units represented by the general formula (1) contribute to coatability, so a high content of these bonds is preferable from the viewpoint of ensuring coatability.

[0287] Furthermore, in the repeating units of the above-mentioned (A) resin, the ratio of the repeating units having the organic sulfonyl anionic structure is preferably 0.1 mol% to 30 mol%, more preferably 0.1 mol% to 20 mol%, and even more preferably 1 mol% to 20 mol%, but is not limited thereto.

[0288] By adjusting the ratio of the aforementioned organic sulfonyl anionic structures in the repeating units of the above-mentioned (A) resin, the appropriate patterning properties required in each step can be provided.

[0289] Furthermore, when the total molar fraction of the repeating unit represented by the above general formula (1) and the repeating unit having an organic sulfonyl anionic structure is not 100%, resin (A) contains other structural units. In this case, existing structural units are suitable. For example, combinations of α,β-unsaturated carboxylic acid esters such as other acrylates, other methacrylates, other acrylamides, other methacrylamides, crotonates, maleates, and isoconates can be used; α,β-unsaturated carboxylic acids such as methacrylic acid, acrylic acid, maleic acid, and isoconic acid; acrylonitrile; methacrylonitrile; α,β-unsaturated lactones such as 5,5-dimethyl-3-methylene-2-oxotetrahydrofuran; norcamphene derivatives, tetracyclic [4.4.0.1] 2,5 .1 7,10 [Any structural unit in, but not limited to, dodecene derivatives and other cyclic alkenes; maleic anhydride, itaconic anhydride and other α,β-unsaturated carboxylic anhydrides; allyl ethers; vinyl ethers; vinyl esters; vinyl silanes.]

[0290] When the top layer of the resist film is exposed using EUV light, it is preferable that other structural units contain iodine atoms. Iodine atoms have a strong atomic absorption effect on EUV light, thus enhancing its sensitization. Therefore, considering the removal of residues at the bottom of the pattern and the improvement of pattern roughness is preferable.

[0291] In cases where it is desirable to suppress the collapse of the upper resist film, it is preferable for other structural units to contain phenolic hydroxyl groups. The formation of hydrogen bonds between the phenolic hydroxyl groups and the upper resist composition helps to suppress collapse. Structural units containing phenolic hydroxyl groups include, for example, those contained in resins described in paragraphs

[0058] to

[0059] of Japanese Patent Application Publication No. 2023-094359, but are not limited thereto. Phenolic hydroxyl groups can also act as hydrogen bond donors; therefore, even if such structural units are present, the adverse effects on coatability are minimal, which is ideal from the perspective of coatability on hydrophobic surfaces.

[0292] Furthermore, (A) resins that do not contain epoxide structures or oxobutane structures are preferred.

[0293] If epoxide or oxobutane structures that cannot serve as hydrogen bond donors are included in the resin, hydrogen bonding between the sealed film and the underlying film from the composition for forming the sealed film of the present invention will be hindered, potentially leading to coating errors. Therefore, it is ideal to ensure coatability on hydrophobic surfaces if these structures are not included in the resin.

[0294] Furthermore, the weight-average molecular weight (Mw) of the aforementioned resin (A) is preferably 1,000 to 70,000, and more preferably 10,000 to 50,000. If Mw is 1,000 or higher, it exhibits excellent film-forming properties and suppresses the formation of sublimation products during heat curing, thus preventing device contamination caused by sublimation. On the other hand, if Mw is 70,000 or lower, it can suppress poor coatability and coating defects caused by insufficient solubility in organic solvents. Furthermore, in the aforementioned resin (A), the molecular weight distribution (Mw / Mn) is preferably 1.0 to 2.8, and more preferably 1.0 to 2.5. Moreover, in this invention, Mw and molecular weight distribution are polystyrene-converted values ​​obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. The measurement temperature is set to 40°C.

[0295] By using a composition for forming a sealing film containing such a resin in the microprocessing stage of manufacturing semiconductor devices, a composition for forming a sealing film, a method for forming a sealing film, and a method for forming a pattern can be provided that have good coatability even on a hydrophobic underlying film, maintain good pattern roughness, and improve the removal of residues at the bottom of the resist.

[0296] The resin described above (A) can be synthesized by polymerizing monomers protected by protecting groups as needed using known methods, followed by a deprotection reaction as required. The polymerization reaction is not particularly limited, but free radical polymerization and anionic polymerization are preferred. Japanese Patent Application Publication No. 2004-115630 can be referenced for these methods.

[0297] [(B) Organic solvents]

[0298] The organic solvent (B) contained in the composition for forming the sealing film of the present invention is not particularly limited as long as the above-mentioned resin (A) and other additives are present and the other additives are soluble. It is preferred that the above-mentioned organic solvent (B) is a mixture of one or more organic solvents with a boiling point of less than 150°C and one or more organic solvents with a boiling point of 150°C or higher and a boiling point of less than 220°C. Specifically, the following can be used: ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentanone, and 2-heptanone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate, and lactones such as γ-butyrolactone. For organic solvents with a boiling point below 150°C, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, cyclopentanone, and mixtures of one or more thereof are preferred. For organic solvents with a boiling point above 150°C but below 220°C, cyclohexanone, diacetone alcohol, ethyl lactate, γ-butyrolactone, and mixtures of one or more thereof are preferred.

[0299] (B) The amount of organic solvent added is preferably 5,000 parts by weight or more, more preferably 8,000 parts by weight or more, relative to 100 parts by weight of resin in (A) above.

[0300] [additive]

[0301] In addition to components (A) and (B) described above, the composition for forming a tight-film according to the present invention may further include one or more components selected from (C) a thermal acid generating agent, (D) a surfactant, and (E) a crosslinking agent. By adjusting the type and amount of these additives, various properties of the composition for forming a tight-film can be optimized, such as curing temperature, coatability, and patterning performance. The following descriptions will be provided for each component.

[0302] [(C) Thermal acid generating agent]

[0303] In the composition for forming a tight film of the present invention, (C) a thermal acid generator may be added to promote the thermal crosslinking reaction.

[0304] The hot acid generating agent (C) that can be used in the composition for forming a tight film according to the present invention can be represented by the following general formula (4), etc.

[0305] [Chemistry 83]

[0306]

[0307] In the formula, K - Indicates non-nucleophilic relative ions. R8, R9, R 10 and R 11 These groups represent hydrogen atoms, linear, branched, or cyclic alkyl groups (1-12 carbon atoms), alkenyl groups (2-12 carbon atoms), aryl groups (6-20 carbon atoms), aralkyl groups (7-12 carbon atoms), or aryloxoalkyl groups. Some or all of the hydrogen atoms in these groups may be substituted with alkoxy groups, etc. Also, R8 and R9, R8, R9 and R... 10 They can bond together to form a loop. When a loop is formed, R8 and R9, and R8, R9 and R 10 It represents an alkylene group having 3 to 10 carbon atoms, or a heteroaromatic ring having a nitrogen atom in the ring.

[0308] The above refers to R8, R9, and R 10 and R 11 These can be the same as or different from each other. Specifically, alkyl groups can include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, adamantyl, etc. Alkenyl groups can include vinyl, allyl, propenyl, butenyl, hexenyl, cyclohexenyl, etc. Oxyalkyl groups can include 2-oxocyclopentyl, 2-oxocyclohexyl, etc., and can also include 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, 2-(4-methylcyclohexyl)-2-oxoethyl, etc. Oxyalkenyl groups can include 2-oxo-4-cyclohexenyl, 2-oxo-4-propenyl, etc. Aryl groups include phenyl, naphthyl, p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, m-tert-butoxyphenyl, alkoxyphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, alkylphenyl, methylnaphthyl, ethylnaphthyl, alkylnaphthyl, methoxynaphthyl, ethoxynaphthyl, dialkylnaphthyl, dimethylnaphthyl, diethylnaphthyl, dialkoxynaphthyl, diethoxynaphthyl, etc. Arylalkyl groups include benzyl, phenylethyl, phenethyl, etc. Aryloxoalkyl groups include 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, 2-(2-naphthyl)-2-oxoethyl, etc.

[0309] Also, R8 and R9, and R8, R9 and R 10The ring in the formula is a heteroaromatic ring containing a nitrogen atom. Examples include imidazole derivatives (e.g., imidazole, 4-methylimidazolium, 4-methyl-2-phenylimidazolium, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazoline idine derivatives, and pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone). 4-Pyrrolidinylpyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminepyridine, etc.), pyridazine derivatives, pyrazine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoleline derivatives, quinoline derivatives (e.g., quinoline, 3-quinoline carboxynitrile, etc.), isoquinoline derivatives, cyclophosphine derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-o-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, ureosine derivatives, etc.

[0310] The above K - Non-nucleophilic relative ions can be listed as halogen ions such as chloride ions and bromide ions, fluoroalkyl sulfonates such as trifluoromethanesulfonate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutyrate, toluenesulfonate, benzenesulfonate, 4-fluorobenzenesulfonate, aryl sulfonates such as 1,2,3,4,5-pentafluorobenzenesulfonate, methanesulfonate, butyrate, alkyl sulfonates such as bis(trifluoromethanesulfonyl)imide, bis(perfluoroethanesulfonyl)imide, and bis(perfluorobutyrate)imide, methyl acids such as tri(trifluoromethanesulfonyl)methyl and tri(perfluoroethanesulfonyl)methyl, and further examples include sulfonates with fluorine substitution at the α-position shown in the following general formula (5) and sulfonates with fluorine substitution at the α and β positions shown in the following general formula (6).

[0311] [Chemistry 84]

[0312]

[0313] R 13 -CF2-CF2-SO3 - (6)

[0314] In the above general formula (5), R12 It is a hydrogen atom, a straight-chain, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, an alkenyl group, an aryl group having 6 to 20 carbon atoms, or an aryloxy group. In the above general formula (6), R 13 It is a hydrogen atom, a straight-chain, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0315] The above-mentioned (C) hot acid generating agents can be specifically exemplified by the following.

[0316] [Chemistry 85]

[0317]

[0318] The hot acid generating agent (C) contained in the composition for forming the adhesive film of the present invention can be used alone or in combination of two or more. The amount of hot acid generating agent (C) added is preferably 0.05 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of the above-mentioned resin (A). If it is 0.05 parts by weight or more, the acid generation becomes sufficient and the crosslinking reaction proceeds fully; if it is 30 parts by weight or less, the mixing phenomenon caused by acid migrating to the upper resist layer will not occur.

[0319] [(D) Surfactant]

[0320] In the composition for forming a tight-film according to the present invention, a surfactant (D) may be added to improve the coatability during spin coating. The surfactant (D) may be used alone or in combination of two or more. For example, the surfactant (D) described in paragraphs

[0142] to

[0147] of Japanese Patent Application Publication No. 2009-269953 may be used. The amount of surfactant (D) added is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, relative to 100 parts by weight of the aforementioned resin (A).

[0321] [(E) Crosslinking agent]

[0322] Furthermore, in order to improve curability and further suppress miscibility with the upper layer of the resist film, a crosslinking agent (E) may be added to the composition for forming the adhesive film of the present invention. The crosslinking agent is not particularly limited, and various known crosslinking agents can be widely used. Examples include melamine-based crosslinking agents, glycourea-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, epoxy-based crosslinking agents, and polyphenol-based crosslinking agents.

[0323] Melamine is a crosslinking agent, specifically, examples include hexamethoxymethylated melamine, hexabutoxymethylated melamine, their alkoxy and / or hydroxyl-substituted derivatives, and some of their self-condensates.

[0324] Glycourea is a crosslinking agent, specifically, examples include tetramethoxymethylated glycourea, tetrabutoxymethylated glycourea, their alkoxy and / or hydroxyl-substituted derivatives, and some of their self-condensates.

[0325] Benzoguanidine is a crosslinking agent, specifically, examples include tetramethoxymethylated benzoguanidine, tetrabutoxymethylated benzoguanidine, their alkoxy and / or hydroxy substituted derivatives, and their partial self-condensates.

[0326] Urea crosslinking agents, specifically, can be exemplified by dimethoxymethylated dimethoxyethylene urea, its alkoxy and / or hydroxyl-substituted derivatives, and some of their self-condensates.

[0327] β-hydroxyalkylamide crosslinking agents, specifically, N,N,N',N'-tetra(2-hydroxyethyl)adipic acid amide.

[0328] Isocyanurates are crosslinking agents; examples include triglycidyl isocyanurate and triallyl isocyanurate.

[0329] Aziridine is a crosslinking agent, specifically, examples include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-dihydroxymethylbutanol-tris[3-(1-aziridine)propionate].

[0330] Oxazoline crosslinking agents, specifically, examples include 2,2'-isopropylidene bis(4-benzyl-2-oxazoline), 2,2'-isopropylidene bis(4-phenyl-2-oxazoline), 2,2'-methylene bis(4,5-diphenyl-2-oxazoline), 2,2'-methylene bis(4-phenyl-2-oxazoline), 2,2'-methylene bis(4-tert-butyl-2-oxazoline), 2,2'-bis(2-oxazoline), 1,3-phenylidene bis(2-oxazoline), 1,4-phenylidene bis(2-oxazoline), and 2-isopropylidene oxazoline copolymers.

[0331] Epoxy crosslinking agents, specifically, may include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanediethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and neopentyl tertetrol tetraglycidyl ether.

[0332] Polyphenolic crosslinking agents, specifically, can be exemplified by compounds represented by the following general formula (7).

[0333] [Chemistry 86]

[0334]

[0335] In the formula, Q is a single bond or a q-valent hydrocarbon group with 1 to 20 carbon atoms. R 14 It is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. q is an integer from 1 to 5.

[0336] Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. q is an integer from 1 to 5, preferably 2 or 3. Specifically, Q can be exemplified by groups that have removed q hydrogen atoms from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, methylbenzene, dimethylbenzene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. R 14 It is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specifically, examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, and eicosyl, with hydrogen atoms or methyl being preferred.

[0337] Examples of compounds represented by the above general formula (7) can be specifically exemplified by the following compounds. Among them, considering the curability of the sealing film and the improvement of film thickness uniformity, triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and hexamethoxymethylated derivatives of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred.

[0338] [Chemistry 87]

[0339]

[0340] [Chemistry 88]

[0341]

[0342] The aforementioned (E) crosslinking agent can be used alone or in combination of two or more. The amount of (E) crosslinking agent added, relative to 100 parts by weight of the aforementioned (A) resin, is preferably 10% to 50% by weight, more preferably 10% to 30% by weight. If the addition amount is 10% by weight or more, sufficient curing properties are achieved, suppressing miscibility with the upper layer of the resist film. On the other hand, if the addition amount is 50% by weight or less, the proportion of (A) resin in the composition remains high, thus the coatability of the hydrophobic surface will not deteriorate.

[0343] The thickness of the film formed by the composition for forming the sealing film of the present invention can be appropriately selected, preferably 2 to 100 nm, and more preferably 5 to 20 nm.

[0344] Furthermore, the composition for forming a sealing film according to the present invention is extremely useful as a sealing film material for multilayer photoresist treatment, such as a 2-layer photoresist treatment or a 4-layer photoresist treatment using a photoresist lower layer film and a silicon-containing intermediate film.

[0345] The aforementioned silicon-containing interlayer film, depending on the pattern formation method described later, can be used as a silicon-containing photoresist interlayer film or an inorganic hard mask interlayer film. The aforementioned inorganic hard mask interlayer film is preferably selected from silicon oxide films, silicon nitride films, and silicon oxide nitride films.

[0346] Furthermore, in this invention, the film formed using a composition containing components (A) and (B) is referred to as a "sealing film." As mentioned above, the film formed by this invention can also be referred to as a "lower layer film" or "intermediate film" in the multilayer resist method. If it is an organic film formed by curing a composition containing components (A) and (B) using heat treatment or the like, regardless of its name, it is included within the scope of this invention.

[0347] [Methods for forming a sealing membrane]

[0348] The present invention provides a method for forming an adhesive film that, using the above-described composition for forming an adhesive film, in the micro-patterning process performed by the multilayer resist method in the semiconductor device manufacturing step, has good coatability even on a hydrophobic lower layer film, maintains good pattern roughness, and improves the residue at the bottom of the resist.

[0349] The method for forming the adhesive film of the present invention involves coating the aforementioned adhesive film forming composition onto a substrate to be processed using a spin coating method or the like. After spin coating, the organic solvent is evaporated, and to prevent mixing of the upper resist film and the silicon-containing intermediate film, a baking (heat treatment) is performed to promote the crosslinking reaction. The baking is preferably performed at a temperature between 100°C and 300°C for 10 to 600 seconds, more preferably at a temperature between 200°C and 250°C for 10 to 300 seconds. Considering the potential damage to the adhesive film and the impact on wafer deformation, the upper limit of the heating temperature for photolithography during wafer processing is preferably 300°C or lower, more preferably 250°C or lower.

[0350] That is, the present invention provides a method for forming an adhesive film, which is a method for forming an adhesive film used in the manufacturing process of a semiconductor device. The method involves spin-coating the adhesive film forming composition described above onto a substrate to be processed, and heat-treating the substrate coated with the adhesive film forming composition at a temperature of 100°C to 300°C for 10 to 600 seconds to form an adhesive film.

[0351] Furthermore, the method for forming the sealing film of the present invention can also involve coating the sealing film forming composition of the present invention onto a substrate using a spin coating method or similar method, as described above, and then hardening the sealing film forming composition by firing it in an ambient gas with an oxygen concentration of 0.1% to 21% to form the sealing film. By firing the sealing film forming composition of the present invention in such an oxygen environment, a sufficiently hardened sealing film can be obtained. Furthermore, the baking temperature and other parameters can be the same as described above.

[0352] That is, the present invention provides a method for forming an adhesive film, which is a method for forming an adhesive film used in the manufacturing process of a semiconductor device. The adhesive film forming composition described above is spin-coated onto a substrate to be processed, and the substrate coated with the adhesive film forming composition is heat-treated in an ambient gas with an oxygen concentration of 0.1% to 21% or less, thereby forming an adhesive film.

[0353] The ambient gas during baking is not limited to air; inert gases such as N2, Ar, and He can also be introduced. In this case, the ambient gas can have an oxygen concentration of 0.0001% or higher but less than 0.1%. Furthermore, the baking temperature and other parameters can be the same as described above. By firing the composition for forming the adhesive film of the present invention in such an oxygen environment, even if the substrate being processed is an unstable material when heated in an oxygen-containing environment, the cross-linking reaction during adhesive film formation will be promoted without causing substrate degradation.

[0354] That is, the present invention provides a method for forming an adhesive film, which is a method for forming an adhesive film used in the manufacturing process of a semiconductor device. The method involves spin-coating the adhesive film forming composition described above onto a substrate to be processed, and heat-treating the substrate coated with the adhesive film forming composition in an ambient gas with an oxygen concentration of 0.0001% or more but less than 0.1% to form an adhesive film.

[0355] [Pattern Formation Method]

[0356] This invention provides a pattern forming method, which is a method for forming a pattern on a substrate to be processed, comprising the following steps:

[0357] (I-1) After coating the above-described composition for forming an adhesive film onto the substrate to be processed, a heat treatment is performed to form an adhesive film.

[0358] (I-2) A photoresist material is used on the aforementioned sealing film to form a photoresist top film.

[0359] (I-3) After patterning the aforementioned upper resist film, develop it with a developer to form a circuit pattern on the aforementioned upper resist film.

[0360] (I-4) Using the aforementioned resist film with the circuit pattern as a mask, the pattern is transferred to the aforementioned sealing film by dry etching, and

[0361] (I-5) Using the aforementioned patterned resist upper layer film and / or sealing film as a mask, the aforementioned substrate is processed to form a pattern on the aforementioned substrate.

[0362] Regarding the pattern forming method of the present invention, the following description uses a four-layer resist treatment as an example, but is not limited to this treatment. The present invention provides a pattern forming method, which firstly involves forming a pattern on a substrate. At least, an organic film material is used to form a lower resist layer on the substrate; a silicon-containing intermediate film (silicon-containing resist intermediate film) is formed on the lower resist layer using a resist intermediate film material containing silicon atoms; an adhesive film is formed on the silicon-containing resist intermediate film using a composition for forming an adhesive film according to the present invention; and an upper resist film is formed on the adhesive film using a resist upper film material composed of a photoresist composition, thus forming a multilayer resist film. After exposing the patterned circuit area of ​​the upper resist film, development is performed using a developing solution. The upper resist film is used to form a resist upper film pattern. The obtained resist upper film pattern is used as an etching mask to etch the sealing film to form the sealing film pattern. The resist upper film pattern and / or sealing film pattern remaining after etching are used as an etching mask to etch the silicon-containing resist intermediate film to form a silicon-containing resist intermediate film pattern. The obtained silicon-containing resist intermediate film pattern is used as an etching mask to etch the lower resist film to form a resist lower film pattern. Next, the obtained resist lower film pattern is used as an etching mask to etch the substrate to be processed to form a pattern on the substrate to be processed.

[0363] That is, the present invention provides a pattern forming method, which is a method for forming a pattern on a substrate to be processed, characterized by having the following steps:

[0364] (II-1) Form a photoresist underlayer film on the substrate to be processed.

[0365] (II-2) A silicon-containing photoresist intermediate film is formed on the aforementioned lower photoresist film.

[0366] (II-3) After coating the aforementioned silicone resist intermediate film with the composition for forming the adhesive film described above, heat treatment is performed to form the adhesive film.

[0367] (II-4) A photoresist material is used on the aforementioned sealing film to form a photoresist top film.

[0368] (II-5) After patterning the aforementioned upper resist film, develop it with a developer to form a circuit pattern on the aforementioned upper resist film.

[0369] (II-6) Using the aforementioned resist film with the circuit pattern as a mask, the pattern is transferred to the aforementioned sealing film by dry etching.

[0370] (II-7) Using the aforementioned patterned upper resist film and / or sealing film as a mask, the pattern is transferred onto the aforementioned silicon-containing resist intermediate film by dry etching.

[0371] (II-8) Using the aforementioned silicon-containing resist intermediate film with the transferred pattern as a mask, the pattern is transferred to the aforementioned resist lower layer film by dry etching, and

[0372] (II-9) Using the aforementioned resist lower layer film with the transferred pattern as a mask, the aforementioned substrate is processed to form a pattern on the aforementioned substrate.

[0373] The aforementioned four-layer photoresist treatment with a silicon-containing photoresist interlayer is also suitable for use with a polysilicon silsesquioxane-based interlayer. The silicon-containing photoresist interlayer has an anti-reflective effect, which can suppress reflection. Especially for 193nm exposure, if the lower photoresist layer uses a material containing a large number of aromatic groups and with high substrate etching resistance, the k-value will increase, and the substrate reflection will increase. However, by using a silicon-containing photoresist interlayer to suppress reflection, the substrate reflection can be reduced to below 0.5%. For 248nm and 157nm exposure, a polysilicon silsesquioxane with an anthracene-based overhang structure that is cross-linked by acid or heat is ideally suitable for the silicon-containing photoresist interlayer with an anti-reflective effect. For 193nm exposure, a polysilicon silsesquioxane with a light-absorbing group possessing phenyl or silicon-silicon bonds and cross-linked by acid or heat is ideally suitable.

[0374] At this point, compared to CVD, spin coating is simpler and has a cost advantage in forming silicon-containing photoresist intermediate films.

[0375] Alternatively, an inorganic hard mask intermediate film can be formed as a silicon-containing intermediate film. In this case, at least an organic film material is used to form a lower resist film on the substrate being processed, and an inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film is formed on the lower resist film. An adhesive film is formed on the inorganic hard mask intermediate film using the adhesive film forming composition of the present invention. An upper resist film is formed on the upper resist film using a photoresist composition, and the patterned circuit area of ​​the upper resist film is exposed. Then, development is performed using a developer. A resist upper layer film is formed to create a resist upper layer film pattern. Using the obtained resist upper layer film pattern as an etching mask, the adhesive film is etched to form an adhesive film pattern. Using the obtained adhesive film pattern as an etching mask, the inorganic hard mask intermediate film is etched to form an inorganic hard mask intermediate film pattern. Using the obtained inorganic hard mask intermediate film pattern as an etching mask, the resist lower layer film is etched to form a resist lower layer film pattern. Next, using the obtained resist lower layer film pattern as an etching mask, the substrate to be processed is etched to form a pattern on the substrate to be processed.

[0376] That is, the present invention is a pattern forming method, which is a method for forming a pattern on a substrate to be processed, comprising the following steps:

[0377] (III-1) Form a photoresist underlayer film on the substrate to be processed.

[0378] (III-2) An inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film is formed on the aforementioned photoresist lower layer film.

[0379] (III-3) After coating the aforementioned inorganic hard mask intermediate film with the composition for forming the sealing film described above, heat treatment is performed to form the sealing film.

[0380] (III-4) A photoresist material is used on the aforementioned sealing film to form a photoresist top film.

[0381] (III-5) After patterning the aforementioned upper resist film, develop it with a developer to form a circuit pattern on the aforementioned upper resist film.

[0382] (III-6) Using the aforementioned resist film on which the circuit pattern has been formed as a mask, the pattern is transferred onto the aforementioned sealing film by dry etching.

[0383] (III-7) Using the aforementioned patterned resist upper layer film and / or sealing film as a mask, the pattern is transferred onto the aforementioned inorganic hard mask intermediate film by dry etching.

[0384] (III-8) Using the aforementioned inorganic hard mask intermediate film with the transferred pattern as a mask, the pattern is transferred to the aforementioned resist underlayer film by dry etching, and

[0385] (III-9) Using the aforementioned resist lower layer film with the transferred pattern as a mask, the aforementioned substrate is processed to form a pattern on the aforementioned substrate.

[0386] As described above, when forming an inorganic hard mask interlayer film on top of the resist underlayer film, silicon oxide films, silicon nitride films, and silicon oxide nitride films (SiON films) can be formed using methods such as CVD and ALD. That is, it is preferable to form the aforementioned inorganic hard mask interlayer film using CVD or ALD methods. For example, a method for forming a silicon nitride film is described in Japanese Patent Application Publication No. 2002-334869 and International Publication No. 2004 / 066377. The thickness of the inorganic hard mask interlayer film is preferably 5–200 nm, and more preferably 10–100 nm. Furthermore, SiON films, which have high anti-reflection properties, are most suitable as the inorganic hard mask interlayer film. Since the substrate temperature during SiON film formation is 300–500°C, the resist underlayer film needs to be able to withstand temperatures of 300–500°C.

[0387] The upper resist film in the above-mentioned four-layer photoresist treatment can be either positive or negative, and can use the same photoresist composition as commonly used as a photoresist material. Furthermore, it is preferable to use a photoresist material containing at least an organometallic compound and a solvent; the aforementioned organometallic compound preferably includes at least one selected from titanium, cobalt, copper, zinc, zirconium, lead, indium, tin, antimony, and hafnium, but is not limited thereto. After spin-coating the photoresist composition, pre-baking is performed, preferably in the range of 60–180°C for 10–300 seconds. Subsequently, exposure is performed according to conventional methods, followed by post-exposure baking (PEB) and development to obtain the upper resist film pattern. The thickness of the upper resist film is not particularly limited, but 30–500 nm is preferred, and more preferably 50–400 nm.

[0388] When photoresist materials contain at least organometallic compounds and solvents, they exhibit a micro-pattern collapse suppression effect and allow for appropriate adjustment of the pattern shape and exposure sensitivity of the upper layer of the photoresist film. Simultaneously, they prevent contamination of the processed substrate caused by metal compounds when using photoresist materials containing organometallic compounds and solvents.

[0389] A circuit pattern (resist overlayer pattern) is formed on the resist overlayer film. The method for forming the circuit pattern on the aforementioned resist overlayer film preferably uses optical lithography with a wavelength of 10 nm to 300 nm, direct electron beam lithography, nanoimprinting, or a combination thereof.

[0390] Furthermore, the exposure light can include high-energy rays with wavelengths below 300nm, specifically far ultraviolet light, KrF excimer laser (248nm), ArF excimer laser (193nm), F2 laser (157nm), Kr2 laser (146nm), Ar2 laser (126nm), soft X-rays (EUV) with wavelengths of 3-20nm, electron beams (EB), ion beams, and X-rays.

[0391] Furthermore, for developing circuit patterns, alkaline development or development using organic solvents is preferred.

[0392] Next, the obtained upper resist film pattern is used as a mask for etching. The etching of the sealing film in the 4-layer resist treatment is performed using an oxygen-based gas and with the upper resist film pattern as a mask. This forms the sealing film pattern.

[0393] Next, the remaining resist upper film pattern and / or adhesive film pattern are used as a mask for etching. The etching of the silicon-containing resist intermediate film and the inorganic hard mask intermediate film is performed using a chlorofluorocarbon (CFC) gas, with the remaining resist upper film pattern and / or adhesive film pattern used as a mask. This forms the silicon-containing resist intermediate film pattern and the inorganic hard mask intermediate film pattern.

[0394] The etching of the seal film can sometimes be performed continuously before the etching of the silicon-containing intermediate film, or the etching of the silicon-containing intermediate film can be performed by changing the etching apparatus only after the seal film is etched.

[0395] Next, the obtained silicon-containing resist intermediate film pattern and inorganic hard mask intermediate film pattern are used as masks to perform etching of the lower resist film.

[0396] The subsequent etching of the substrate can also be performed using conventional methods. For example, if the substrate is a low-dielectric-constant insulating film based on SiO2, SiN, or silicon dioxide, etching with a chlorofluorocarbon (CFC) gas is performed; if it is p-Si, Al, or W, etching with a chlorine or bromine gas is performed. When etching the substrate with a CFC gas, the silicon-containing interlayer pattern in the three-layer resist treatment is stripped off simultaneously with the substrate processing. When etching the substrate with chlorine or bromine gases, the stripping of the silicon-containing interlayer pattern requires a separate dry etching stripping process with a CFC gas after the substrate processing.

[0397] Furthermore, the substrate being processed is not particularly limited and can be a semiconductor device substrate, or a substrate on which any of the following films—metal film, metal carbide film, metal oxide film, metal nitride film, metal oxide carbide film, and metal oxide nitride film—has been formed. The aforementioned metal can be silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or alloys thereof.

[0398] Specifically, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, and Al, or substrates on which the processed layer is formed, can be used. The processed layer can be various Low-k films and their barrier films, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, and can be formed with a thickness typically of 50–10,000 nm, particularly 100–5,000 nm. Furthermore, when forming the processed layer, the substrate and the processed layer can be made of different materials.

[0399] In one example of a four-layer resist treatment, if using Figure 1 The specific details are as follows. In the case of a 4-layer resist treatment, such as... Figure 1 As shown in (A), after forming a lower resist film 3 on the processed layer 2 stacked on the substrate 1 using an organic film material, a silicon-containing intermediate film 4 is formed, and an adhesive film 5 is formed thereon using the adhesive film forming composition of the present invention, and an upper resist film 6 is formed thereon.

[0400] Then, as Figure 1 As shown in (B), the exposed portion 7 of the upper resist film is exposed, and PEB and development are performed to form the upper resist film pattern 6a. Figure 1 (C)). Using the obtained upper resist film pattern 6a as a mask, the sealing film 5 is etched with O2-based gas to form the sealing film pattern 5a. Figure 1 (D)). Using the obtained tight-fitting film pattern 5a as a mask, the silicon-containing intermediate film 4 is etched using CF-based gas to form the silicon-containing intermediate film pattern 4a. Figure 1 (E)). After removing the sealing film pattern 5a, the obtained silicon-containing intermediate film pattern 4a is used as a mask, and the resist underlayer film 3 is etched using O2-based gas to form the resist underlayer film pattern 3a. Figure 1 (F)). Next, after removing the silicon-containing intermediate film pattern 4a, the resist lower film pattern 3a is used as a mask to etch the processed layer 2 to form pattern 2a. Figure 1 (G)).

[0401] Thus, in the pattern forming method of the present invention, fine patterns can be formed on the substrate being processed at a high level during multilayer resist treatment.

[0402] Example

[0403] The present invention will be further described below with reference to synthetic examples, comparative synthetic examples, examples, and comparative examples, but the invention is not limited thereto. Furthermore, the molecular weight was determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) in the dissolution solution, and the dispersity (Mw / Mn) was obtained from the weight-average molecular weight (Mw) and number-average molecular weight (Mn) converted from polystyrene. The measurement temperature was set to 40°C.

[0404] The synthesis of polymers (A1) to (A24) and comparative polymers (R1) to (R5) used in the (A) resin as a sealing film forming material uses monomers (B1) to (B21) as shown below.

[0405] [Chemistry 89]

[0406]

[0407] [Synthesis Example 1] Synthesis of Polymer (A1)

[0408] Under nitrogen atmosphere, 64.9 g of monomer (B1), 35.1 g of monomer (B17), 4.13 g of V-601 (dimethyl 2,2'-azobis(isobutyrate), manufactured by Wako Pure Chemical Industries, Ltd.), and 340 g of DAA (diacetone alcohol) were weighed into a 1 L flask and degassed while stirring to prepare a monomer-polymerization initiator solution. In another 1 L flask under nitrogen atmosphere, 60 g of DAA was weighed, degassed while stirring, and heated to an internal temperature of 80°C. The aforementioned monomer-polymerization initiator solution was added dropwise over 4 hours, and the polymerization solution was maintained at 80°C with stirring for 16 hours, then cooled to room temperature. The obtained polymerization solution was added dropwise to 1,500 g of vigorously stirred hexane, and the precipitated polymer was filtered. Next, the obtained polymer was washed twice with 600g of hexane and then vacuum dried at 50°C for 20 hours to obtain a white powder polymer (A1) (yield 98.4g, 95% yield). The average molecular weight (Mw) and dispersion (Mw / Mn) of polymer (A1) were determined by GPC, and the results were Mw = 27,900 and Mw / Mn = 1.92.

[0409] [Chemistry 90]

[0410]

[0411] [Synthetic Examples 2-24, Comparative Synthetic Examples 1-2] Synthesis of polymers (A2)-(A24) and comparative polymers (R1)-(R2)

[0412] Using the monomers and polymerization initiators shown in Table 1, and except for the same reaction and post-treatment conditions as in Synthesis Example 1, polymers (A2) to (A24) and comparative polymers (R1) to (R2) were obtained as products. The weight-average molecular weight (Mw), dispersity (Mw / Mn), and polymer (A1) obtained by GPC are also shown.

[0413] [Table 1]

[0414]

[0415] [Comparative Synthesis Example 3] Synthesis of Comparative Polymer (R3)

[0416] Under nitrogen atmosphere, 62.8 g of monomer (B9), 37.2 g of monomer (B10), 1.45 g of V-601, and 340 g of PGMEA were weighed into a 1 L flask and degassed while stirring to prepare a monomer-polymerization initiator solution. In another 1 L flask under nitrogen atmosphere, 60 g of PGMEA was weighed, degassed while stirring, and heated to an internal temperature of 80 °C. The aforementioned monomer-polymerization initiator solution was added dropwise over 4 hours, and the polymerization solution was maintained at 80 °C with stirring for 16 hours, then cooled to room temperature. The obtained polymerization solution was added dropwise to 1,500 g of vigorously stirred hexane, and the precipitated polymer was filtered. Next, the obtained polymer was washed twice with 600 g of hexane and then vacuum dried at 50 °C for 20 hours to obtain a white powdery comparative polymer (R3) (yield 97.5 g, 96% yield). The average molecular weight (Mw) and dispersion (Mw / Mn) of polymer (R3) were obtained by GPC, and the results were Mw = 33,500 and Mw / Mn = 1.88.

[0417] [Chemistry 91]

[0418]

[0419] [Comparative Synthesis Example 4] Synthesis of Comparative Polymer (R4)

[0420] Under nitrogen atmosphere, 64.3 g of monomer (B9), 35.7 g of monomer (B11), 1.49 g of V-601, and 340 g of PGMEA were weighed into a 1 L flask and degassed while stirring to prepare a monomer-polymerization initiator solution. In another 1 L flask under nitrogen atmosphere, 60 g of PGMEA was weighed, degassed while stirring, and heated to an internal temperature of 80 °C. The aforementioned monomer-polymerization initiator solution was added dropwise over 4 hours, and the polymerization solution was maintained at 80 °C with stirring for 16 hours, then cooled to room temperature. The obtained polymerization solution was added dropwise to 1,500 g of vigorously stirred hexane, and the precipitated polymer was filtered. Next, the obtained polymer was washed twice with 600 g of hexane and then vacuum dried at 50 °C for 20 hours to obtain a white powdery comparative polymer (R4) (yield 96.5 g, 95% yield). The average molecular weight (Mw) and dispersion (Mw / Mn) of polymer (R4) were obtained by GPC, and the results were Mw = 32,200 and Mw / Mn = 1.80.

[0421] [Chemistry 92]

[0422]

[0423] [Comparative Synthesis Example 5] Synthesis of Comparative Polymer (R5)

[0424] Under nitrogen atmosphere, 66.1 g of monomer (B9), 33.9 g of monomer (B16), 1.49 g of V-601, and 340 g of PGMEA were weighed into a 1 L flask and degassed while stirring to prepare a monomer-polymerization initiator solution. In another 1 L flask under nitrogen atmosphere, 60 g of PGMEA was weighed, degassed while stirring, and heated to an internal temperature of 80 °C. The aforementioned monomer-polymerization initiator solution was added dropwise over 4 hours, and the polymerization solution was maintained at 80 °C with stirring for 16 hours, then cooled to room temperature. The obtained polymerization solution was added dropwise to 1,500 g of vigorously stirred hexane, and the precipitated polymer was filtered. Next, the obtained polymer was washed twice with 600 g of hexane and then vacuum dried at 50 °C for 20 hours to obtain a white powdery comparative polymer (R5) (yield 97.0 g, 96% yield). The average molecular weight (Mw) and dispersion (Mw / Mn) of polymer (R5) were obtained by GPC, and the results were Mw = 31,200 and Mw / Mn = 1.82.

[0425] [Chemistry 93]

[0426]

[0427] [Comparative Synthesis Example 6] Synthesis of Comparative Polymer (R6)

[0428] The comparative polymer (R6) was synthesized according to the method described in paragraph

[0136] of Patent Document 6.

[0429] [Chemistry 94]

[0430]

[0431] [Comparative Synthesis Example 7] Synthesis of Comparative Polymer (R7)

[0432] The comparative polymer (R7) was synthesized according to the method described in paragraph

[0155] of Patent Document 7.

[0433] [Chemistry 95]

[0434]

[0435] Preparation of sealing membrane materials (AL-1~33, comparative AL-1~7)

[0436] Using the polymers (A1) to (A24), comparative polymers (R1) to (R7), propylene glycol monomethyl ether acetate (PGMEA), diacetone alcohol (DAA), or ethyl lactate (EL) containing the additives (AD1) to (AD7) shown below, 0.01% by mass of PF6320 (manufactured by OMNOVA), and dissolved in the proportions shown in Table 2, the materials were filtered through a 0.1 μm fluoropolymer filter to prepare sealing membrane materials (AL-1 to 33, comparative AL-1 to 7). Furthermore, comparative AL-7 was prepared to have the same composition as AL8 described in paragraph

[0165] of Patent Document 7.

[0437] [Chemistry 96]

[0438]

[0439] [Table 2]

[0440]

[0441]

[0442] The components in Table 2 are as follows.

[0443] Organic solvents:

[0444] PGMEA (Propylene Glycol Monomethyl Ether Acetate)

[0445] DAA (diacetone alcohol)

[0446] EL (ethyl lactate)

[0447] Example 1 includes wafer coating tests for various films (Examples 1-1 to 1-33, Comparative Examples 1-1 to 1-7).

[0448] The aforementioned adhesive film materials (AL-1 to 33, comparative AL-1 to 7) were coated onto substrates treated with hexamethyldisilazane (HMDS) at 120°C for 60 seconds, or substrates with films formed of CVD-SiO2, CVD-SiON, CVD-amorphous Si, CVD-amorphous carbon, or CVD-SiN, and then baked at 250°C for 60 seconds to form adhesive films with a thickness of 5 nm (AL-1 to 2, 4 to 33, comparative AL-1 to 7) or 20 nm (AL-3). Subsequently, the film surface was observed using an optical microscope to confirm the presence and number of coating errors. The results are shown in Table 3. The labels in the table correspond as follows.

[0449] ++: No exceptions

[0450] +: Confirm coating error of 1-5 pinholes.

[0451] - Confirm coating errors of 6-10 pinholes.

[0452] --: Coating errors of 11 or more pinholes or numerous coating errors that prevent film formation

[0453] [Table 3]

[0454]

[0455] As shown in Table 3, Examples 1-1 to 1-33, which used the sealing film materials (AL-1 to 33) of the sealing film forming composition of the present invention, all exhibited minimal pinhole-like coating errors. It is evident that coating properties are particularly superior for those containing more structural units represented by general formula (1). On the other hand, Comparative Examples 1-3 to 1-6, which used comparative AL-3 to 6 and did not contain structural units represented by general formula (1), showed slightly inferior coating properties compared to the others.

[0456] Example 2: Coating performance test on silicon-containing photoresist interlayer (Examples 2-1 to 2-33, Comparative Examples 2-1 to 2-7)

[0457] A silicon resist intermediate film composition SHB-A940 manufactured by Shin-Etsu Chemical Industry Co., Ltd. was coated onto a silicon wafer substrate and baked at 215°C for 60 seconds to form a silicon resist intermediate film with a thickness of 20 nm. Further, the aforementioned bonding film materials (AL-1 to 33, comparative AL-1 to 7) were coated onto this substrate and baked at 250°C for 60 seconds to form bonding films with a thickness of 5 nm (AL-1 to 2, 4 to 33, comparative AL-1 to 7) or 20 nm (AL-3). Subsequently, the film surface was observed using an optical microscope to confirm the presence and number of coating errors. The results are shown in Table 4. The labels in the table correspond as follows.

[0458] ++: No exceptions

[0459] +: Confirm coating error of 1-5 pinholes.

[0460] - Confirm coating errors of 6-10 pinholes.

[0461] --: Coating errors of 11 or more pinholes or numerous coating errors that prevent film formation

[0462] [Table 4]

[0463]

[0464]

[0465] As shown in Table 4, Examples 2-1 to 2-33, which used the sealing film materials (AL-1 to 33) of the sealing film forming composition of the present invention, still exhibited good coating properties even on the silicon resist interlayer. Furthermore, Comparative Examples 2-3 to 2-6, which used the structure without the structure represented by general formula (1), produced a large amount of coating error compared to other examples, indicating that the coating properties were improved by introducing this structural unit.

[0466] Example 3: ArF Immersion Exposure Pattern Formation Experiment (Examples 3-1 to 3-23, Comparative Examples 3-1 to 3-3)

[0467] A 200 nm thick lower resist film is formed by coating a spin-coated carbon ODL-301 (88% by mass) manufactured by Shin-Etsu Chemical Industry Co., Ltd. onto a silicon wafer substrate and baking it at 350°C for 60 seconds. A CVD-SiON hard mask intermediate film is formed on this film, and then the above-mentioned bonding film materials (AL-1~6, 8, 10~16, 23~27, 30~33, comparative AL-1~2, 7) are coated and baked at 250°C for 60 seconds to form a bonding film with a thickness of 5 nm (AL-1~2, 4~6, 8, 10~16, 23~27, 30~33, comparative AL-1~2, 7) or 20 nm (AL-3). A positive resist upper film material (a single layer of resist for ArF) is coated on this film and baked at 105°C for 60 seconds to form a 100 nm thick upper resist film. A protective film with a thickness of 50 nm is formed by coating a protective film material (TC-1) onto the upper layer of the resist film and baking it at 90°C for 60 seconds.

[0468] The positive resist upper film material (ArF single-layer resist) is prepared by dissolving the polymer (PRP-A1), acid generator (PAG1), and basic compound (Amine1) in a solvent containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 5, and filtering the solution using a 0.1 μm fluororesin filter.

[0469] [Table 5]

[0470]

[0471] Polymer: PRP-A1

[0472] Molecular weight (Mw) = 8,600

[0473] Dispersion (Mw / Mn) = 1.88

[0474] [Chemistry 97]

[0475]

[0476] Acid generator: PAG1

[0477] [Chem. 98]

[0478]

[0479] Basic compound: Amine1

[0480] [Chemistry 99]

[0481]

[0482] The impregnated protective film material (TC-1) is prepared by dissolving the protective film polymer (PP1) in an organic solvent at the proportions shown in Table 6 and filtering it using a 0.1 μm fluororesin filter.

[0483] [Table 6]

[0484]

[0485] Protective film polymer: PP1

[0486] Molecular weight (Mw) = 8,800

[0487] Dispersion (Mw / Mn) = 1.69

[0488] [Chemistry 100]

[0489]

[0490] Then, exposure was performed using an ArF immersion exposure apparatus (Nikon, NSR-S610C, NA1.30, σ0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% half-step phase shift mask), followed by baking at 100°C (PEB) for 60 seconds and development with a 2.38% (w / w) tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds, yielding a 40 nm 1:1 line and spacing pattern. This pattern was used as the object, and its cross-sectional shape and roughness were observed using an electron microscope. Furthermore, by increasing the exposure, the minimum size at which the image could be resolved without line collapse when the line size became thinner was determined, defined as the collapse limit (nm). A smaller value indicates higher collapse resistance, which is preferable.

[0491] The obtained pattern cross-sectional shape was evaluated using a Hitachi S-4700 electron microscope, and the pattern roughness was evaluated using a Hitachi Advanced Electron Microscope (CG4000). The results are shown in Table 7.

[0492] [Table 7]

[0493]

[0494] As shown in Table 7, it can be seen that Examples 3-1 to 3-23, which use the sealing film materials (AL-1 to 6, 8, 10 to 16, 23 to 27, 30 to 33) of the sealing film forming composition of the present invention, have lower pattern roughness and better pattern shape compared to the comparative examples. Looking at the collapse limit, an improvement was observed in Examples 3-18 to 3-19, which use structural units containing phenolic hydroxyl groups, indicating that this structure contributes to the collapse suppression capability.

[0495] Example 4: EUV exposure pattern formation test using positive resist (Examples 4-1 to 4-15, Comparative Example 4-) 1～4-4)

[0496] A 100 nm thick photoresist lower layer film is formed by coating a spin-coating carbon ODL-301 (88% by mass) manufactured by Shin-Etsu Chemical Industry Co., Ltd. onto a silicon wafer substrate and baking it at 350°C for 60 seconds. A silicon-containing spin-coating hard mask SHB-A940 (43% by mass) manufactured by Shin-Etsu Chemical Industry Co., Ltd. is then coated onto the substrate and baked at 215°C for 60 seconds to form a 15 nm thick silicon-containing intermediate film. Furthermore, the aforementioned bonding film materials (AL-4, 5, 8, 10, 14–16, 23–29, 32, and comparative AL-1, 2, 7) are coated and baked at 250°C for 60 seconds to form a bonding film with a 5 nm thick. A positive photoresist upper layer film forming composition (EUV single-layer photoresist) is then coated onto the substrate and baked at 100°C for 60 seconds to form a 40 nm thick photoresist upper layer film. Furthermore, after forming a silicon-containing intermediate film using the same method as described above, a positive resist upper layer film forming composition (EUV single-layer resist) is coated on the silicon-containing intermediate film without forming a sealed film.

[0497] The composition for forming the upper layer of positive resist (single-layer resist for EUV) is prepared by dissolving the polymer compound PRP1 and quencher Q1 in the proportions shown in Table 8 in a solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), and filtering it through a 0.1 μm fluororesin filter.

[0498] [Table 8]

[0499]

[0500] Polymer compound: PRP1

[0501] Molecular weight (Mw) = 9,200

[0502] Dispersion (Mw / Mn) = 1.8

[0503] [Chemistry 101]

[0504]

[0505] Quenching agent: Q1

[0506] [Chemistry 102]

[0507]

[0508] Then, using an EUV exposure apparatus (ASML EUV scanning exposure machine NXE3400, NA 0.33, σ 0.9, 90-degree dipole illumination), a 1:1 line-to-spacing (LS) pattern of 18 nm was exposed, baked at 90°C (PEB) for 60 seconds, and developed with a 2.38% (w / w) tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds, resulting in a line-to-spacing pattern with a spacing width of 18 nm and a pitch of 36 nm. This pattern was used as the object, and its cross-sectional shape and roughness were observed using an electron microscope. Furthermore, by gradually increasing the exposure amount used to form the above line-to-spacing pattern, the smallest resolvable size without line collapse when the line size becomes thinner was determined, defined as the collapse limit (nm). The smaller the value, the higher the collapse resistance, which is preferable.

[0509] The obtained pattern cross-sectional shape was evaluated using a Hitachi S-4700 electron microscope, and the pattern roughness was evaluated using a Hitachi Advanced Technology electron microscope (CG6300). The results are shown in Table 9. Furthermore, Comparative Example 4-4 is the result of patterning by applying a positive resist upper film formation composition (EUV single-layer resist) onto the silicon-containing intermediate film without forming a seal film after forming a silicon-containing intermediate film.

[0510] [Table 9]

[0511]

[0512] As shown in Table 9, it can be seen that Examples 4-1 to 4-15, which use the sealing film materials (AL-4, 5, 8, 10, 14-16, 23-29, 32) of the sealing film forming composition of the present invention, have lower pattern roughness and better pattern shape compared to the comparative examples. It can be seen that Examples 4-9 to 4-11, which use AL-24 to 26, which contain iodine atoms in the structural units of the organic sulfonyl anion structure, and Examples 4-13 to 4-14, which use AL-28 to 29, which incorporate iodine-containing structural units, have particularly low pattern roughness. Regarding the comparative examples, it can be seen that Comparative Example 4-3, which uses the composition described in Patent Document 7 (Comparative AL-7), shows good results, but Comparative Examples 4-1 and 4-2, which use comparative AL-1 and 2, which do not contain the organic sulfonyl anion structure, have a trailing pattern and deteriorate pattern roughness. Furthermore, considering the case of Comparative Example 4-4, in which a positive resist upper film forming composition (EUV single-layer resist) is coated on the positive side of a silicon-containing intermediate film and then patterned, the pattern shape is slightly trailed and the pattern roughness is also high. It can be seen that the four-layer resist treatment using the adhesive film forming composition of the present invention improves the patterning performance compared to the three-layer resist treatment without using it.

[0513] Example 5: EUV exposure pattern formation test 2 using positive resist (Examples 5-1 to 5-12, Comparative Examples) 5-1～5-4)

[0514] A 100 nm thick photoresist lower layer film is formed by coating a spin-coating carbon ODL-301 (88% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. onto a silicon wafer substrate and baking it at 350°C for 60 seconds. A silicon-containing spin-coating hard mask SHB-A940 (43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. is then coated onto the lower layer and baked at 215°C for 60 seconds to form a 15 nm thick silicon-containing intermediate film. Next, the aforementioned bonding film materials (AL-14-16, 23-29, 32, 33, and comparative AL-1, 2, 7) are coated and baked at 250°C for 60 seconds to form a bonding film with a thickness of 5 nm. A positive photoresist upper layer film forming composition-2 is then coated onto the bonding film and baked at 105°C for 60 seconds to form a 50 nm thick photoresist upper layer film. Furthermore, after forming a silicon-containing intermediate film using the same method as described above, a positive resist upper film forming composition-2 is also coated on the positive side of the silicon-containing intermediate film without forming an adhesive film.

[0515] Composition 2 for forming the upper layer of positive resist (single-layer resist for EUV) is prepared by dissolving polymeric compound PRP2, hot acid generator PAG2, and quencher Q2 in a solvent containing 0.01% by mass of propylene glycol monomethyl ether acetate (PGMEA) and diacetone alcohol (DAA) at the proportions shown in Table 10, and filtering the solution through a 0.1 μm fluoropolymer filter.

[0516] [Table 10]

[0517]

[0518] Polymer compound: PRP2 Molecular weight (Mw) = 5,200 Dispersion (Mw / Mn) = 1.45

[0519] [Chemistry 103]

[0520]

[0521] Hot acid generator: PAG2

[0522] [Chemistry 104]

[0523]

[0524] Quenching agent: Q2

[0525] [Chemistry 105]

[0526]

[0527] Then, the aforementioned upper resist film was exposed using an ASML NXE3400 EUV scanning exposure machine (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, mask for a hole pattern with a pitch of 40 nm on the wafer, +20% deviation). PEB was applied at 80°C for 60 seconds on a heated plate, followed by development with a 2.38% TMAH aqueous solution for 30 seconds, forming a hole pattern with a size of 20 nm. This pattern was used as the object for cross-sectional shape and CDU observation using an electron microscope. Furthermore, the size of 50 holes at the exposure level with a hole size of 20 nm was measured, and the CDU was expressed as three times the standard deviation (σ) calculated from the results (3σ).

[0528] The obtained pattern profile shapes were evaluated using a Hitachi S-4700 electron microscope, and CDUs were evaluated using a Hitachi Advanced Technology electron microscope (CG6300). The results are shown in Table 11.

[0529] [Table 11]

[0530] As shown in Table 11, it can be seen that Examples 5-1 to 5-12, which use the sealing film materials (AL-14 to 16, 23 to 29, 32, 33) of the sealing film forming composition of the present invention, have smaller CDU and better pattern shape compared to the comparative examples. It can be seen that Examples 5-5 to 5-7, which use AL-24 to 26 containing iodine atoms in the structural units containing the organic sulfonyl anion structure, and Examples 5-9 to 5-10, which use AL-28 to 29 incorporating iodine-containing structural units, have particularly small CDU. Regarding the comparative examples, it can be seen that Comparative Example 5-3, which uses the composition described in Patent Document 7, which showed good results in Comparative Examples 4-3, also has a trailing pattern, and the organic sulfonyl anion structure is effective in improving the trailing shape of the pattern. Furthermore, in Comparative Examples 5-4, where a positive resist upper film forming composition is coated on the positive side of a silicon-containing intermediate film for patterning, the pattern shape is a trailing shape and the CDU is also large. Therefore, the patterning performance is significantly improved by using the four-layer resist treatment of the adhesive film forming composition of the present invention compared to the three-layer resist treatment without using it.

[0531] Example 6 Electron Beam Pattern Formation Experiment (Examples 6-1 to 6-12, Comparative Examples 6-1 to 6-3)

[0532] The above-mentioned adhesive film materials (AL-14~16, 23~29, 32, 33, comparative AL-1, 6, 7) are coated on a silicon wafer substrate and baked at 250°C for 60 seconds to form an adhesive film with a film thickness of 5 nm. A photoresist top layer film material (containing metal photoresist) is coated on it and baked at 180°C for 60 seconds to form a photoresist top layer film with a film thickness of 50 nm.

[0533] The top layer of the resist film (containing metal resist) is prepared by dissolving a titanium-containing compound (AM-1) and a metal salt sensitizer (S-1) in a solution containing 0.1% by mass of 4-methyl-2-pentanol (MIBC) of FC-4430 (manufactured by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 12, and then filtering the solution using a 0.1 μm fluororesin filter.

[0534] [Table 12]

[0535]

[0536] Synthesis of titanium-containing compound (AM-1)

[0537] A solution of 27 g of deionized water in 500 g of IPA was added dropwise over 2 hours at room temperature while stirring, to a solution of 284 g of isopropyl titanate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 500 g of 2-propanol (IPA). 180 g of 2,4-dimethyl-2,4-octanediol was added to the resulting solution, and the mixture was stirred at room temperature for 30 minutes. The solution was concentrated under reduced pressure at 30°C, then heated to 60°C, and heated under reduced pressure until no distillate was observed. After no distillate was observed, 1,200 g of 4-methyl-2-pentanol (MIBC) was added, and the mixture was heated at 40°C under reduced pressure until no more IPA distilled off, yielding 1,000 g of a MIBC solution containing titanium compound AM-1 (compound concentration 25% by mass). The polystyrene-converted molecular weight of this compound was determined to be Mw = 1,200.

[0538] Metal salt sensitizer: S-1

[0539] [Chemistry 106]

[0540]

[0541] Then, a vacuum chamber pattern was created using a JBX-9000MV (manufactured by Nippon Electron Ltd.) with an accelerating voltage of 50 kV. Immediately after patterning, the pattern was baked at 200°C (PEB) for 60 seconds and then developed with butyl acetate for 20 seconds to obtain a negative pattern.

[0542] The obtained negative patterns were evaluated as follows. Sensitivity was defined as the exposure at which the line-to-spacing (LS) ratio of 100 nm was resolved at a 1:1 ratio. The smallest size that could be resolved without line collapse at the aforementioned exposure was defined as the collapse limit (nm). A smaller value indicates higher collapse tolerance, which is considered better. The results are shown in Table 13.

[0543] [Table 13]

[0544]

[0545]

[0546] As shown in Table 13, Examples 6-1 to 6-12, which use the adhesive film materials (AL-14 to 16, 23 to 29, 32, 33) of the adhesive film formation composition of the present invention, have smaller collapse limit values ​​than Comparative Examples 6-1 to 6-3, which use Comparative Examples 6-1, 6, and 7. This is believed to be because the nitrogen-hydrogen bonds in the structure represented by general formula (1) interact with the metal oxides in the metal-containing resist pattern. Therefore, it can be seen that the present invention is also applicable to photolithography steps containing metal resists.

[0547] Based on the above, the composition for forming a sealing film of the present invention exhibits good coating properties even on a hydrophobic underlying film, and can form a sealing film with good pattern collapse suppression performance and the ability to remove resist residue at the bottom of the pattern. Therefore, it is extremely useful as a composition for forming a sealing film in a multilayer resist method. Furthermore, the pattern forming method of the present invention using this composition can form fine patterns on a processed substrate with high precision.

[0548] This specification contains the following specifications.

[0549] [1]: A composition for forming a tight-fitting film, characterized by comprising:

[0550] (A) A resin containing repeating units represented by the following general formula (1) and repeating units having an organic sulfonyl anionic structure, and

[0551] (B) Organic solvents;

[0552] [Chemistry 107]

[0553]

[0554] In the formula, X is a single bond or an aromatic ring with 20 or fewer carbon atoms, and R... 01 It is a hydrogen atom or a methyl group, R 02 It is a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, R 02 When it is an alkyl group, the hydrogen atoms constituting it can also be replaced by hydroxyl groups.

[0555] [2]: The composition for forming a tight film as described in [1] above, wherein the ratio of repeating units represented by the general formula (1) in the repeating units of the (A) resin is 70 mol% or more and 99.9 mol% or less.

[0556] [3]: The composition for forming a tight film as described in [1] or [2] above, wherein the ratio of repeating units having an organic sulfonyl anionic structure in the repeating units of the (A) resin is 0.1 mol% or more and 30 mol% or less.

[0557] [4]: A composition for forming a tight film as described in any of [1] to [3] above, wherein the weight-average molecular weight of the (A) resin is 1,000 to 70,000.

[0558] [5]: The composition for forming a tight film as described in any one of [1] to [4] above, wherein the (B) organic solvent is a mixture of one or more organic solvents with a boiling point of less than 150°C and one or more organic solvents with a boiling point of 150°C or higher and a boiling point of less than 220°C.

[0559] [6]: The composition for forming a tight film as described in any of [1] to [5] above further contains one or more selected from (C) a hot acid generating agent, (D) a surfactant, and (E) a crosslinking agent.

[0560] [7]: A pattern forming method, characterized by comprising the following steps:

[0561] (I-1) After coating the substrate with the composition for forming an adhesive film as described in any one of [1] to [6] above, heat treatment is performed to form an adhesive film.

[0562] (I-2) A photoresist material is used on the sealed film to form a photoresist top film.

[0563] (I-3) After patterning the upper layer of the photoresist film, it is developed with a developer to form a circuit pattern on the upper layer of the photoresist film.

[0564] (I-4) Using the resist film on which the circuit pattern has been formed as a mask, the pattern is transferred onto the sealing film by dry etching, and

[0565] (I-5) Using the patterned resist top layer film and / or sealing film as a mask, the substrate to be processed is processed to form a pattern on the substrate to be processed.

[0566] [8]: A method for forming a pattern on a substrate being processed, characterized by comprising the following steps:

[0567] (II-1) Form a photoresist underlayer film on the substrate to be processed.

[0568] (II-2) A silicon-containing photoresist intermediate film is formed on the lower layer of the photoresist film.

[0569] (II-3) After coating the silicone resist intermediate film with any one of the above [1] to [6] compositions, heat treatment is performed to form the adhesive film.

[0570] (II-4) A photoresist material is used on the sealed film to form a photoresist top film.

[0571] (II-5) After patterning the upper layer of the photoresist film, it is developed with a developer to form a circuit pattern on the upper layer of the photoresist film.

[0572] (II-6) Using the resist film on which the circuit pattern is formed as a mask, the pattern is transferred to the sealing film by dry etching.

[0573] (II-7) Using the patterned upper resist film and / or sealing film as a mask, the pattern is transferred to the silicon-containing resist intermediate film by dry etching.

[0574] (II-8) Using the silicon-containing resist intermediate film with the transferred pattern as a mask, the pattern is transferred to the resist underlying film by dry etching.

[0575] (II-9) The patterned resist underlayer film is used as a mask to process the substrate and form a pattern on the substrate.

[0576] [9]: A method for forming a pattern on a substrate being processed, characterized by comprising the following steps:

[0577] (III-1) Form a photoresist underlayer film on the substrate to be processed.

[0578] (III-2) An inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film is formed on the lower layer film of the photoresist.

[0579] (III-3) After coating the inorganic hard mask intermediate film with any one of the above [1] to [6] compositions for forming a tight film, heat treatment is performed to form a tight film.

[0580] (III-4) A photoresist material is used on the sealed film to form a photoresist top film.

[0581] (III-5) After patterning the upper layer of the photoresist film, develop it with a developer to form a circuit pattern on the upper layer of the photoresist film.

[0582] (III-6) Using the resist film on which the circuit pattern has been formed as a mask, the pattern is transferred to the sealing film by dry etching.

[0583] (III-7) Using the patterned resist upper layer film and / or sealing film as a mask, the pattern is transferred onto the inorganic hard mask intermediate film by dry etching.

[0584] (III-8) Using the inorganic hard mask intermediate film with the transferred pattern as a mask, the pattern is transferred to the resist underlayer film by dry etching.

[0585] (III-9) Using the resist underlayer film with the transferred pattern as a mask, the substrate to be processed is processed to form a pattern on the substrate to be processed.

[0586]

[10] : The pattern forming method described in [9] above, wherein the inorganic hard mask intermediate film is formed by CVD or ALD.

[0587]

[11] : The pattern forming method of any one of [7] to

[10] above, wherein the method of forming a circuit pattern on the resist film uses optical lithography, direct electron beam drawing, nanoimprinting, or a combination thereof with a wavelength of 10 nm to 300 nm.

[0588]

[12] : The pattern forming method of any one of [7] to

[11] above, wherein the photoresist material uses a material containing at least an organometallic compound and a solvent.

[0589]

[13] : The pattern forming method of any one of [7] to

[12] above, wherein the developing method is alkali developing or developing with an organic solvent.

[0590]

[14] : The pattern forming method of any one of [7] to

[13] above, wherein the substrate to be processed is a semiconductor device substrate, or a substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film has been formed.

[0591]

[15] : The pattern forming method described above

[14] , wherein the metal is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or alloys thereof.

[0592]

[16] : A method for forming an adhesive film, which is a method for forming an adhesive film used in the manufacturing process of a semiconductor device, characterized in that:

[0593] A sealing film is formed by spin-coating a composition for forming a sealing film as described in any one of [1] to [6] above onto a substrate to be processed, and by heat-treating the substrate coated with the composition for forming a sealing film at a temperature of 100°C to 300°C for 10 to 600 seconds.

[0594]

[17] : A method for forming an adhesive film, which is a method for forming an adhesive film used in the manufacturing process of a semiconductor device, characterized in that:

[0595] A sealing film is formed by spin-coating a composition for forming a sealing film as described in any one of [1] to [6] above onto a substrate to be processed, and by heat-treating the substrate coated with the composition for forming a sealing film in an ambient gas with an oxygen concentration of 0.1% to 21%.

[0596]

[18] : A method for forming an adhesive film, which is a method for forming an adhesive film used in the manufacturing process of a semiconductor device, characterized in that:

[0597] A sealing film is formed by spin-coating a composition for forming a sealing film as described in any one of [1] to [6] above onto a substrate to be processed, and by heat-treating the substrate coated with the composition for forming a sealing film in an ambient gas with an oxygen concentration of 0.0001% or more but less than 0.1%.

[0598] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and those having a substantially identical structure to the technical concept described in the claims of the present invention and achieving the same effect are all covered within the technical scope of the present invention.

[0599] Explanation of symbols in attached drawings

[0600] 1:Substrate

[0601] 2: Processed layer

[0602] 2a: Pattern (the pattern formed on the processed layer)

[0603] 3: Underlayer film of resist

[0604] 3a: Pattern of the underlayer resist film

[0605] 4: Silicon-containing interlayer

[0606] 4a: Pattern of silicon-containing interlayer film

[0607] 5: Sealing film

[0608] 5a: Sealing film pattern

[0609] 6: Top layer of resist film

[0610] 6a: Pattern of the upper layer of the resist film

[0611] 7: Exposure section

Claims

1. A composition for forming a tight-fitting film, characterized by comprising: (A) A resin containing repeating units represented by the following general formula (1) and repeating units having an organic sulfonyl anionic structure, and (B) Organic solvents; In the formula, X is a single bond or an aromatic ring with 20 or fewer carbon atoms, and R... 01 It is a hydrogen atom or a methyl group, R 02 It is a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, R 02 When it is an alkyl group, the hydrogen atoms constituting it can also be replaced by hydroxyl groups.

2. The composition for forming a tight-fitting film according to claim 1, wherein, In the repeating units of the (A) resin, the ratio of repeating units represented by the general formula (1) is more than 70 mol% and less than 99.9 mol%.

3. The composition for forming a tight-fitting film according to claim 1, wherein, In the repeating units of the (A) resin, the ratio of repeating units having an organic sulfonyl anionic structure is more than 0.1 mol% and less than 30 mol%.

4. The composition for forming a tight-fitting film according to claim 1, wherein, The weight-average molecular weight of the (A) resin is 1,000 to 70,000.

5. The composition for forming a tight-fitting film according to claim 1, wherein, The (B) organic solvent is a mixture of one or more organic solvents with a boiling point of less than 150°C and one or more organic solvents with a boiling point of more than 150°C and a boiling point of less than 220°C.

6. The composition for forming a tight film according to claim 1 further comprises one or more selected from (C) a hot acid generating agent, (D) a surfactant, and (E) a crosslinking agent.

7. A pattern forming method, characterized in that it forms a pattern on a substrate to be processed. It has the following steps: (I-1) After coating the substrate with the composition for forming an adhesive film according to any one of claims 1 to 6, heat treatment is performed to form an adhesive film. (I-2) A photoresist material is used on the sealed film to form a photoresist top film. (I-3) After patterning the upper layer of the photoresist film, it is developed with a developer to form a circuit pattern on the upper layer of the photoresist film. (I-4) Using the resist film on which the circuit pattern has been formed as a mask, the pattern is transferred onto the sealing film by dry etching, and (I-5) Using the patterned resist top layer film and / or sealing film as a mask, the substrate to be processed is processed to form a pattern on the substrate to be processed.

8. A pattern forming method, characterized in that it forms a pattern on a substrate to be processed. It has the following steps: (II-1) Form a photoresist underlayer film on the substrate to be processed. (II-2) A silicon-containing photoresist intermediate film is formed on the lower layer of the photoresist film. (II-3) After coating the silicone resist intermediate film with the composition for forming a sealing film according to any one of claims 1 to 6, heat treatment is performed to form a sealing film. (II-4) A photoresist material is used on the sealed film to form a photoresist top film. (II-5) After patterning the upper layer of the photoresist film, it is developed with a developer to form a circuit pattern on the upper layer of the photoresist film. (II-6) Using the resist film on which the circuit pattern is formed as a mask, the pattern is transferred to the sealing film by dry etching. (II-7) Using the patterned upper resist film and / or sealing film as a mask, the pattern is transferred to the silicon-containing resist intermediate film by dry etching. (II-8) Using the silicon-containing resist intermediate film with the transferred pattern as a mask, the pattern is transferred to the resist underlying film by dry etching. (II-9) The patterned resist underlayer film is used as a mask to process the substrate and form a pattern on the substrate.

9. A pattern forming method, characterized in that it forms a pattern on a substrate to be processed. It has the following steps: (III-1) Form a photoresist underlayer film on the substrate to be processed. (III-2) An inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film is formed on the lower layer film of the photoresist. (III-3) After coating the inorganic hard mask intermediate film with the composition for forming a sealing film according to any one of claims 1 to 6, heat treatment is performed to form a sealing film. (III-4) A photoresist material is used on the sealed film to form a photoresist top film. (III-5) After patterning the upper layer of the photoresist film, develop it with a developer to form a circuit pattern on the upper layer of the photoresist film. (III-6) Using the resist film on which the circuit pattern has been formed as a mask, the pattern is transferred to the sealing film by dry etching. (III-7) Using the patterned resist upper layer film and / or sealing film as a mask, the pattern is transferred onto the inorganic hard mask intermediate film by dry etching. (III-8) Using the inorganic hard mask intermediate film with the transferred pattern as a mask, the pattern is transferred to the resist underlayer film by dry etching. (III-9) Using the resist underlayer film with the transferred pattern as a mask, the substrate to be processed is processed to form a pattern on the substrate to be processed.

10. The pattern forming method according to claim 9, wherein, The inorganic hard mask intermediate film is formed by CVD or ALD.

11. The pattern forming method according to claim 7, wherein, The method of forming circuit patterns on the upper layer of the resist film uses optical lithography with a wavelength of 10 nm to 300 nm, direct drawing by electron beam, nanoimprinting, or a combination thereof.

12. The pattern forming method according to claim 7, wherein, The photoresist material uses materials containing at least organometallic compounds and solvents.

13. The pattern forming method according to claim 7, wherein, The developing methods are alkali development or development using organic solvents.

14. The pattern forming method according to claim 7, wherein, The substrate being processed is a semiconductor device substrate, or a substrate on which any of the following films are formed: a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film.

15. The pattern forming method according to claim 14, wherein, The metal used is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or alloys thereof.

16. A method for forming an adhesive film, which is a method for forming an adhesive film used in the manufacturing process of a semiconductor device, characterized in that: An adhesive film is formed by spin-coating a composition for forming an adhesive film according to any one of claims 1 to 6 onto a substrate to be processed, and then heat-treating the substrate coated with the composition for forming an adhesive film at a temperature of 100°C to 300°C for 10 to 600 seconds.

17. A method for forming an adhesive film, which is a method for forming an adhesive film used in the manufacturing process of a semiconductor device, characterized in that: A sealing film is formed by spin-coating a composition for forming a sealing film according to any one of claims 1 to 6 onto a substrate to be processed, and then heat-treating the substrate coated with the composition for forming a sealing film in an ambient gas with an oxygen concentration of 0.1% to 21%.

18. A method for forming an adhesive film, which is a method for forming an adhesive film used in the manufacturing process of a semiconductor device, characterized in that: A sealing film is formed by spin-coating a composition for forming a sealing film according to any one of claims 1 to 6 onto a substrate to be processed, and then heat-treating the substrate coated with the composition for forming a sealing film in an ambient gas with an oxygen concentration of 0.0001% or more but less than 0.1%.

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