Composition for forming silicon-containing antireflection film, and method for forming pattern

Abstract

To provide a composition for forming silicon-containing antireflection film for forming a silicon-containing antireflection film having both excellent antireflection function and good process selectivity in dry etching in a fine patterning process in a production process of a semiconductor device, and a method for forming a pattern.SOLUTION: A composition for forming a silicon-containing antireflection film includes (A) a silicon-containing polymer, (B) an organic polymer, and (C) an organic solvent, where (A) the silicon-containing polymer includes any polymer selected from polysiloxane, polycarbosilane, and polysilane, and (B) the organic polymer includes a polymer including two hydroxyl groups and no silicon in a repeating unit of the polymer.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a composition for forming a silicon-containing antireflection film and a pattern forming method using the same.

Background Art

[0002] With the high integration and high speed of LSIs, the miniaturization of pattern dimensions has been rapidly progressing. Along with this miniaturization, lithography technology has achieved the formation of fine patterns by shortening the wavelength of the light source and appropriately selecting a resist composition therefor. At the center has been the positive photoresist composition used as a single layer. This single-layer positive photoresist composition has a skeleton in the resist resin that has etching resistance against dry etching with chlorine-based or fluorine-based gas plasmas, and has a switching mechanism such that the exposed portion dissolves, thereby dissolving the exposed portion to form a pattern and dry-etching the substrate to be processed using the remaining resist pattern as an etching mask.

[0003] However, when the film thickness of the photoresist film used is directly miniaturized, that is, when the pattern width is made smaller, the resolution performance of the photoresist film deteriorates, and when trying to develop the photoresist film into a pattern with a developer, the so-called aspect ratio becomes too large, resulting in a problem that pattern collapse occurs. For this reason, the photoresist film has been thinned as the pattern is miniaturized.

[0004] On one hand, for processing a substrate to be processed, usually, a method of processing the substrate by dry etching using a photoresist film with a formed pattern as an etching mask is used. However, in reality, there is no dry etching method that can achieve complete etching selectivity between the photoresist film and the substrate to be processed. Therefore, during the processing of the substrate, the photoresist film is also damaged and collapses, resulting in the problem that the resist pattern cannot be accurately transferred to the substrate to be processed. Thus, with the miniaturization of patterns, higher dry etching resistance has been required for the resist composition. However, on the other hand, in order to improve the resolution, the resin used in the photoresist composition has been required to be a resin with little light absorption at the exposure wavelength. Therefore, as the exposure light becomes shorter in wavelength, such as i-line, KrF, and ArF, the resin has also changed from novolak resin, polyhydroxystyrene, to a resin having an aliphatic polycyclic skeleton. However, in reality, the etching rate under the dry etching conditions during substrate processing has become faster, and recent photoresist compositions with high resolution tend to have weaker etching resistance.

[0005] From this, it becomes necessary to dry-etch the substrate to be processed with a thinner and weaker etching-resistant photoresist film, and ensuring the materials and processes in this processing step has become an urgent task.

[0006] As one method to solve such problems, there is a multilayer resist method. This method involves interposing a resist lower layer film with different etching selectivity from the photoresist film (i.e., the resist upper layer film) between the resist upper layer film and the substrate to be processed. After obtaining a pattern on the resist upper layer film, the resist upper layer film pattern is used as a dry etching mask to transfer the pattern to the resist lower layer film by dry etching, and further, the resist lower layer film is used as a dry etching mask to transfer the pattern to the substrate to be processed by dry etching.

[0007] One of the multilayer resist methods is a three-layer resist method that can be performed using a general resist composition used in the single-layer resist method. In this three-layer resist method, for example, an organic film made of novolak resin or the like is formed as a resist lower layer film on a substrate to be processed, a silicon-containing resist intermediate film is formed as a resist intermediate film thereon, and a normal organic photoresist film is formed as a resist upper layer film thereon. When performing dry etching using a fluorine-based gas plasma, the organic resist upper layer film has a good etching selectivity with respect to the silicon-containing resist intermediate film, so the resist upper layer film pattern can be transferred to the silicon-containing resist intermediate film by dry etching using a fluorine-based gas plasma. According to this method, even when using a resist composition that is difficult to form a pattern with a sufficient film thickness for directly processing the substrate to be processed or a resist composition that does not have sufficient dry etching resistance for substrate processing, a pattern can be transferred to the silicon-containing resist intermediate film (resist intermediate film), and then, if pattern transfer is performed by dry etching using an oxygen-based or hydrogen-based gas plasma, a pattern of an organic film (resist lower layer film) made of novolak resin or the like that has sufficient dry etching resistance for substrate processing can be obtained. As the resist lower layer film as described above, many are already known, such as those described in Patent Document 1 for example.

[0008] As the silicon-containing resist intermediate film used in the three-layer resist method as described above, as an inorganic hard mask intermediate film by CVD, for example, a SiO2 film (for example, Patent Document 2 etc.) or a SiON film (for example, Patent Document 3 etc.), as those obtained by spin coating, a SOG (spin-on glass) film (for example, Patent Document 4 etc., Non-Patent Document 1) or a crosslinkable silsesquioxane film (for example, Patent Document 5 etc.) etc. are used, and a polysilane film (for example, Patent Document 6 etc.) could also be used. In the advanced three-layer resist method, a SOG film is often used because it is easy to adjust the antireflection function.

[0009] There are several problems with the SOG film that has been conventionally used in such a three-layer resist method. For example, when attempting to form a resist pattern by photolithography, it is well known that the exposure light is reflected by the substrate and interferes with the incident light, causing the so-called standing wave problem. In order to obtain a fine pattern without edge roughness of the resist film under the state-of-the-art ArF immersion and high-NA exposure conditions, an antireflection function is essential as a resist intermediate film. Furthermore, in the state-of-the-art semiconductor processes as described above, the thinning of the photoresist has been further progressing, so the resist intermediate film is also required to be thinned. In the next-generation exposure process, it is required to impart an antireflection effect with a film thickness of 30 nm or less. Also, the dry etching rate with respect to the oxygen gas plasma generally used when processing the resist lower layer film is preferably smaller in order to increase the etching selectivity between the SOG film and the resist lower layer film. From the trend of thinning, improvement in dry etching resistance is required for the SOG film.

[0010] In the three-layer resist method, it is difficult to develop a SOG film having high-dimensional antireflection function and dry etching resistance. In order to improve the antireflection function, it is necessary to use polysiloxane having an organic group with a high refractive index. However, when the introduction rate of the organic group is increased, the silicon component in the film decreases, so the dry etching resistance to oxygen gas deteriorates. On the other hand, there is a four-layer resist method in which the functions of antireflection and dry etching resistance are imparted to two different films. In Patent Document 7, a four-layer resist method consisting of an organic lower layer film (resist lower layer film), a silicon-containing hard mask (resist intermediate film), an organic antireflection film, and a photoresist (resist upper layer film) has been reported.

[0011] The antireflection film is required to have functions such as a layer for preventing the interaction between the substrate to be processed and the photoresist, a layer having a function of preventing the adverse effects of the material used in the photoresist or the substances generated during the exposure of the photoresist on the substrate, a layer having a function of preventing the diffusion of the substances generated from the substrate during heat baking into the upper photoresist, and a function as a barrier layer for reducing the poisoning of the photoresist layer by the semiconductor substrate dielectric layer. However, in the case of the organic antireflection film, these functions are insufficient, and further improvement is considered necessary.

[0012] In Patent Document 8, a four-layer resist method using a silicon-containing antireflection film has been reported. It has been reported that it is effective in suppressing poisoning against the organic antireflection film. However, the silicon-containing antireflection film used in the examples is 50 nm. As described above, in the most advanced semiconductor processes, the thinning of the photoresist is further progressing. Therefore, the silicon-containing antireflection film is also required to be thinned. In the next-generation exposure process, a composition for forming a silicon-containing antireflection film that exhibits excellent film-forming properties in forming a thin film with a thickness of 12 nm or less is required.

Prior Art Documents

Patent Documents

[0013]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Non-Patent Document

[0014]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0015] The present invention has been made in view of the above circumstances, and in the fine patterning process in the semiconductor device manufacturing process, a silicon-containing antireflection film forming composition for forming a silicon-containing antireflection film having an excellent antireflection function and good processing selectivity in dry etching, and a pattern forming method using the same are provided.

Means for Solving the Problems

[0016] In order to solve the above problems, the present invention provides a silicon-containing antireflection film forming composition containing (A) a silicon-containing polymer, (B) an organic polymer, and (C) an organic solvent, wherein the (A) silicon-containing polymer contains any one selected from polysiloxane, polycarbosilane, and polysilane, and the (B) organic polymer contains two or more hydroxyl groups in the repeating unit structure of the polymer and does not contain silicon, to provide a silicon-containing antireflection film forming composition.

[0017] For such a composition for forming a silicon-containing antireflection film, by combining the silicon-containing antireflection film formed using this composition with a resist intermediate film such as a silicon-containing hard mask or a resist underlayer film such as an organic resist underlayer film, a high antireflection effect can be exhibited under ArF immersion and high NA exposure conditions, and thus a fine pattern without edge roughness can be obtained. Further, since the composition for forming a silicon-containing antireflection film contains (B) an organic polymer, it can exhibit an excellent poisoning suppression effect against conventional antireflection films and has good adhesion to the resist pattern, and thus is also effective in preventing the collapse of fine patterns. Further, by containing a (B) organic polymer that contains two or more hydroxyl groups in the repeating unit structure of the polymer and does not contain silicon, the affinity with a hydrophilic substrate becomes good, and excellent film-forming properties are exhibited in the formation of a thin film of 12 nm or less. Therefore, the pattern formation method of the present invention can transfer the resist pattern shape onto a substrate to be processed with high precision.

[0018] Further, in the present invention, it is preferable that the (B) organic polymer contains the following general formula (1B) or (2B). [Chemical formula] (In the formula, R 01 is a hydrogen atom or a methyl group, R 02 is an alkyl group having 1 to 3 carbon atoms or a halogen atom, m is an integer of 2 to 5, n is an integer of 0 to 3, m + n is an integer of 2 or more and 5 or less. X represents a single bond or an alkylene group that may contain one or more selected from oxygen atoms and nitrogen atoms having 1 to 10 carbon atoms.) [Chemical formula] (In the formula, R 1 is any one selected from a saturated monovalent organic group having 1 to 30 carbon atoms, an unsaturated monovalent organic group having 2 to 30 carbon atoms, and a halogen atom, Y is a divalent organic group having 1 to 30 carbon atoms, p is an integer of 0 to 5, q1 is an integer of 2 to 6, p + q1 is an integer of 2 or more and 6 or less, and q2 is 0 or 1.)

[0019] By containing such (B) organic polymer, when applying the composition for forming a silicon-containing antireflection film to a substrate, the affinity with the substrate is improved, and a silicon-containing antireflection film with excellent film-forming properties and forming a thin film can be formed.

[0020] In addition, in the present invention, it is preferable that the polysiloxane contains any one or more selected from a repeating unit represented by the following general formula (Sx-1), a repeating unit represented by the following general formula (Sx-2), and a partial structure represented by the following general formula (Sx-3).

Chemical formula

[0021] A composition for forming a silicon-containing antireflection film containing such a polysiloxane is preferable because the effects of the present invention can be improved.

[0022] At this time, in the general formulas (Sx-1) to (Sx-3), it is preferable that at least one of R a to R c is an organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds.

[0023] By using such a composition for forming a silicon-containing resist antireflection film, it becomes possible to improve the adhesion to a resist pattern and prevent the collapse of a fine pattern.

[0024] In addition, in the present invention, it is preferable that the polycarbosilane contains a unit structure represented by the following general formula (Sy-1).

Chemical formula

[0025] By using such a composition for forming a silicon-containing resist antireflective film, it becomes possible to improve the adhesion to the resist pattern and to prevent the collapse of the fine pattern.)

[0026] In the present invention, it is preferable that the content of the (B) organic polymer is in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the (A) silicon-containing polymer.)

[0027] Since the composition for forming a silicon-containing antireflective film contains the (B) organic polymer in such a range, it becomes possible to highly balance the dry etching resistance of the silicon-containing antireflective film formed using this and the film forming property of the thin film.)

[0028] In the present invention, it is preferable that the weight average molecular weight Mw in terms of polystyrene of the (B) organic polymer by gel permeation chromatography is in the range of 1,500 ≦ Mw ≦ 20,000.)

[0029] Due to the molecular weight range of the above (B) organic polymer being as described above, it is possible to form a silicon-containing antireflective film that exhibits excellent film forming property in thin film formation. Also, it is possible to form a silicon-containing antireflective film that is excellent in film thickness uniformity and defect suppression property derived from sublimates.)

[0030] In the present invention, it is preferable that the composition for forming a silicon-containing antireflective film further contains a (D) crosslinking agent.)

[0031] For such a composition for forming a silicon-containing antireflection film, the density of the silicon-containing antireflection film formed using the composition can be improved, and the basic components generated from the inorganic hard mask intermediate film can be prevented from migrating to the photoresist film (resist upper layer film), thereby further improving the ability to suppress the poisoning that reduces the sensitivity and resolution of the resist. In addition, the adhesion to the resist pattern can be further improved, and it becomes possible to prevent the collapse of the fine pattern. Furthermore, the refractive index of the silicon-containing antireflection film can be improved, and an excellent antireflection function can be imparted.

[0032] At this time, it is preferable that the crosslinking agent (D) is a compound containing an isocyanuric acid structure.

[0033] For such a composition for forming a silicon-containing antireflection film, the above effects can be further improved.

[0034] In addition, in the present invention, it is preferable that the composition for forming a silicon-containing antireflection film further contains at least one selected from (E) an acid generator, (F) a surfactant, and (H) a pigment.

[0035] By the presence or absence and selection of these various additives, fine adjustment of the performance according to customer requirements is possible in terms of film-forming properties, reduction of sublimates, and further various characteristics of resist patterning, which is practically preferable.

[0036] In addition, in the present invention, it is preferable that the organic solvent (C) contains at least one organic solvent having a boiling point of 180°C or higher as a high-boiling solvent (C1).

[0037] By including such a high-boiling solvent, sufficient thermal fluidity can be obtained during film formation, so that the substrate affinity effect of the organic polymer (B) can be further improved in thin film formation. In addition, the occurrence of defects due to drying of the composition for forming a silicon-containing antireflection film can be suppressed, which is practically preferable.

[0038] Also, the present invention provides a method for forming a pattern on a substrate to be processed, comprising: (I-1) a step of forming a silicon-containing antireflection film by applying the composition for forming a silicon-containing antireflection film described above on the substrate to be processed and then performing a heat treatment; (I-2) a step of forming a resist upper layer film on the silicon-containing antireflection film using a photoresist material; (I-3) a step of forming a pattern on the resist upper layer film by performing pattern exposure on the resist upper layer film and then developing it with a developer; (I-4) a step of transferring the pattern to the silicon-containing antireflection film by dry etching using the resist upper layer film having the pattern as a mask; and (I-5) a step of processing the substrate to be processed using the silicon-containing antireflection film having the pattern transferred thereto to form a pattern on the substrate to be processed. The present invention provides a pattern forming method having the above steps.

[0039] By the pattern forming method using the two-layer resist process described above, a fine pattern can be formed on a workpiece (substrate to be processed).

[0040] Also, the present invention provides a method for forming a pattern on a substrate to be processed, comprising: (II-1) a step of forming a resist lower layer film on the substrate to be processed; (II-2) a step of forming a silicon-containing antireflection film by applying the composition for forming a silicon-containing antireflection film described above on the resist lower layer film and then performing a heat treatment; (II-3) a step of forming a resist upper layer film on the silicon-containing antireflection film using a photoresist material; (II-4) a step of forming a pattern on the resist upper layer film by performing pattern exposure on the resist upper layer film and then developing it with a developer; (II-5) a step of transferring the pattern to the silicon-containing antireflection film by dry etching using the resist upper layer film having the pattern formed thereon as a mask; (II-6) A step of transferring a pattern onto the silicon-containing antireflection film onto which the pattern has been transferred using it as a mask by dry etching, and (II-7) A step of processing the substrate to be processed using the resist underlayer film onto which the pattern has been transferred as a mask to form a pattern on the substrate to be processed provided is a pattern formation method having.

[0041] By the pattern formation method using the above three-layer resist process, a fine pattern can be formed on a workpiece (substrate to be processed).

[0042] A method of forming a pattern on a substrate to be processed, (III-1) A step of forming a resist underlayer film on the substrate to be processed, (III-2) A step of forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film, (III-3) A step of forming a silicon-containing antireflection film by applying the composition for forming a silicon-containing antireflection film described above on the inorganic hard mask intermediate film and then performing heat treatment, (III-4) A step of forming a resist upper layer film using a photoresist material on the silicon-containing antireflection film, (III-5) A step of forming a pattern on the resist upper layer film by performing pattern exposure on the resist upper layer film and then developing it with a developer, (III-6) A step of transferring a pattern onto the silicon-containing antireflection film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask, (III-7) A step of transferring a pattern onto the resist underlayer film by dry etching using the inorganic hard mask intermediate film onto which the pattern has been transferred as a mask, and (III-8) A step of processing the substrate to be processed using the resist underlayer film onto which the pattern has been transferred as a mask to form a pattern on the substrate to be processed provided is a pattern formation method having.

[0043] By the pattern formation method using the above four-layer resist process, a fine pattern can be formed on a workpiece (workpiece substrate).

[0044] At this time, it is preferable that the film thickness of the silicon-containing antireflection film is 12 nm or less.

[0045] By using a silicon-containing antireflection film having such a film thickness range, it becomes possible to transfer the resist pattern shape to the silicon-containing antireflection film at high speed. Therefore, a pattern shape with small roughness can be transferred onto the workpiece substrate.

Advantages of the Invention

[0046] As described above, with the composition for forming a silicon-containing antireflection film of the present invention, in the fine patterning process in the semiconductor device manufacturing process, a silicon-containing antireflection film having an excellent antireflection function and good processing selectivity in dry etching can be formed.

[0047] In addition, a pattern formation method using the above composition for forming a silicon-containing antireflection film can also be provided.

Brief Description of the Drawings

[0048]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0049] As described above, in the fine patterning process using ArF immersion and high NA exposure conditions in the semiconductor device manufacturing process, there has been a demand for the development of a silicon-containing antireflection film-forming composition having an excellent antireflection function capable of forming a fine resist pattern without edge roughness and exhibiting excellent thin film formability, and a patterning method using the same.

[0050] In microfabrication using an ArF excimer laser (wavelength 193 nm) and an EUV excimer laser (wavelength 13 nm), etc., the wiring width becomes narrower, and as a result, pattern collapse of the photoresist film (simply referred to as resist) occurs. In order to prevent pattern collapse of the resist, the thickness of the resist layer has also been decreasing as the wiring width decreases. When such a thin film resist is used, further improvement in the dry etching rate is also required for the resist underlayer film. However, in the case of an organic resist underlayer film for an organic photoresist film, film loss of the organic photoresist film occurs due to the dry etching gas (for example, fluorine-based gas, oxygen gas, etc.) of the organic resist underlayer film. On the other hand, when a silicon-containing hard mask layer is used under the organic resist film, when dry etching the silicon-containing hard mask (resist intermediate film) with a fluorine-based gas, the film loss of the organic photoresist film (resist film on which a resist pattern is formed (resist upper layer film)) is small with the fluorine-based gas, and the resist pattern formed by the thin film resist can be accurately transferred to the silicon-containing hard mask (resist intermediate film). Then, if the organic underlayer film (resist underlayer film) is dry-etched with an oxygen-based dry etching gas, the film loss of the silicon-containing hard mask (resist intermediate film) is small, and the resist pattern can be accurately transferred to the organic underlayer film (resist underlayer film), and the semiconductor substrate can be processed with a fluorine-based gas using the organic underlayer film (resist underlayer film) to which the resist pattern has been transferred.

[0051] However, in the three-layer process of the organic underlayer film (resist underlayer film), silicon-containing hard mask (resist intermediate film), and resist film (resist upper layer film) shown above, there has been a technical problem that it is difficult to achieve both high refractive index and dry etching resistance of the silicon-containing hard mask.

[0052] To prevent pattern collapse of the photoresist film, the silicon-containing hard mask also needs to be thinned by thinning. As a result, under the state-of-the-art ArF immersion and high-NA exposure conditions, it is necessary to increase the refractive index of the silicon-containing hard mask in order to further improve the antireflection effect. In order to form a silicon-containing hard mask with a high refractive index, generally, a SOG material containing polysiloxane with an organic group having a high refractive index is used. However, since these have a high introduction rate of organic groups and the silicon component in the film decreases, the dry etching resistance to oxygen gas becomes insufficient. In order to transfer a fine pattern without edge roughness onto the substrate to be processed with high precision, a silicon-containing hard mask with excellent dry etching resistance is required.

[0053] In response to such problems, the solution to the above problems was considered by providing a silicon-containing antireflection film between the silicon-containing hard mask (resist intermediate film) and the photoresist film (resist upper layer film). On the other hand, in Patent Document 8, a four-layer resist method using a silicon-containing antireflection film has been reported, but the silicon-containing antireflection film used in the examples is 50 nm. As described above, in the state-of-the-art semiconductor process, the thinning of the photoresist has advanced further, so the silicon-containing antireflection film also needs to be thinned. In the next-generation exposure process, a composition for forming a silicon-containing antireflection film that exhibits excellent film-forming properties in forming a thin film with a thickness of 12 nm or less is required.

[0054] As a result of intensive studies on the above problems, the inventors of the present invention have found that a composition for forming a silicon-containing antireflection film containing (A) a silicon-containing polymer, (B) an organic polymer, and (C) an organic solvent, wherein the (A) silicon-containing polymer contains any one selected from polysiloxane, polycarbosilane, and polysilane, and the (B) organic polymer contains two or more hydroxyl groups in the repeating unit structure of the polymer and does not contain silicon. A composition for forming a silicon-containing antireflection film and a pattern forming method using the same have a high effect of suppressing poisoning from the underlying film and also have excellent thin film formability, so that a fine resist pattern can be formed and the above problems can be solved, and the present invention has been completed.

[0055] That is, the present invention is a composition for forming a silicon-containing antireflection film containing (A) a silicon-containing polymer, (B) an organic polymer, and (C) an organic solvent, wherein the (A) silicon-containing polymer contains any one selected from polysiloxane, polycarbosilane, and polysilane, and the (B) organic polymer is a composition for forming a silicon-containing antireflection film that contains two or more hydroxyl groups in the repeating unit structure of the polymer and does not contain silicon.

[0056] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0057] [Composition for Forming Silicon-Containing Antireflection Film] The composition for forming a silicon-containing antireflection film of the present invention is a composition for forming a silicon-containing antireflection film containing (A) a silicon-containing polymer, (B) an organic polymer, and (C) an organic solvent, wherein the (A) silicon-containing polymer contains any one selected from polysiloxane, polycarbosilane, and polysilane, and the (B) organic polymer is a composition for forming a silicon-containing antireflection film that contains two or more hydroxyl groups in the repeating unit structure of the polymer and does not contain silicon.

[0058] <(A) Silicon-containing polymer> The (A) silicon-containing polymer contained in the composition for forming a silicon-containing antireflection film of the present invention contains any one selected from polysiloxane (Sx), polycarbosilane (Sy), and polysilane (Sz).

[0059] (Polysiloxane (Sx)) When the (A) silicon-containing polymer of the composition for forming a silicon-containing antireflection film of the present invention contains polysiloxane, the polysiloxane (Sx) preferably contains any one or more selected from the repeating unit represented by the following general formula (Sx-1), the repeating unit represented by the following general formula (Sx-2), and the partial structure represented by the following general formula (Sx-3). [Chemical formula] (In the formula, R a , R b , R c are each independently a monovalent organic group having 1 to 30 carbon atoms which may be the same or different.)

[0060] The above polysiloxane (Sx) is preferably a thermally crosslinkable polysiloxane and can be produced, for example, by hydrolytic condensation of the following hydrolyzable monomer (Sm).

[0061] Specific examples of the hydrolyzable monomer (Sm) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltriisopropoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltripropoxysilane, isopropyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, butyltriisopropoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyltripropoxysilane, sec-butyltriisopropoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltripropoxysilane, t-butyltriisopropoxysilane, cyclopropyltrimethoxysilane, cyclopropyltriethoxysilane, cyclopropyltripropoxysilane, cyclopropyltriisopropoxysilane, cyclobutyltrimethoxysilane, cyclobutyltriethoxysilane, cyclobutyltripropoxysilane, cyclobutyltriisopropoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyltripropoxysilane, cyclopentyltriisopropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltripropoxysilane, cyclohexyltriisopropoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, cyclohexenyltripropoxysilane, cyclohexenyltriisopropoxysilane, cyclohexenylethyltrimethoxysilane,Cyclohexenylethyltriethoxysilane, cyclohexenylethyltripropoxysilane, cyclohexenylethyltriisopropoxysilane, cyclooctyltrimethoxysilane, cyclooctyltriethoxysilane, cyclooctyltripropoxysilane, cyclooctyltriisopropoxysilane, cyclopentadienylpropyltrimethoxysilane, cyclopentadienylpropyltriethoxysilane, cyclopentadienylpropyltripropoxysilane, cyclopentadienylpropyltriisopropoxysilane, bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenyltripropoxysilane, bicycloheptenyltriisopropoxysilane, bicycloheptyltrimethoxysilane, bicycloheptyltriethoxysilane, bicycloheptyltripropoxysilane, bicycloheptyltriisopropoxysilane, adamantyltrimethoxysilane, adamantyltriethoxysilane, adamantyltripropoxysilane, adamantyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, benzyltripropoxysilane, benzyltriisopropoxysilane, anisyltrimethoxysilane, anisyltriethoxysilane, anisyltripropoxysilane, anisyltriisopropoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, tolyltripropoxysilane, tolyltriisopropoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, phenethyltripropoxysilane, phenethyltriisopropoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltripropoxysilane, naphthyltriisopropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiisopropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiisopropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane,Dipropyldipropoxysilane, dipropyldiisopropoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldipropoxysilane, diisopropyldiisopropoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dibutyldipropoxysilane, dibutyldiisopropoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldipropoxysilane, di-sec-butyldiisopropoxysilane, di-t-butyldimethoxysilane, di-t-butyldiethoxysilane, di-t-butyldipropoxysilane, di-t-butyldiisopropoxysilane, dicyclopropyldimethoxysilane, dicyclopropyldiethoxysilane, dicyclopropyldipropoxysilane, dicyclopropyldiisopropoxysilane, dicyclobutyldimethoxysilane, dicyclobutyldiethoxysilane, dicyclobutyldipropoxysilane, dicyclobutyldiisopropoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclopentyldipropoxysilane, dicyclopentyldiisopropoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclohexyldipropoxysilane, dicyclohexyldiisopropoxysilane, dicyclohexenyldimethoxysilane, dicyclohexenyldiethoxysilane, dicyclohexenyldipropoxysilane, dicyclohexenyldiisopropoxysilane, dicyclohexenylethyldimethoxysilane, dicyclohexenylethyldiethoxysilane, dicyclohexenylethyldipropoxysilane, dicyclohexenylethyldiisopropoxysilane, dicyclooctyldimethoxysilane, dicyclooctyldiethoxysilane, dicyclooctyldipropoxysilane, dicyclooctyldiisopropoxysilane, dicyclopentadienylpropyldimethoxysilane, dicyclopentadienylpropyldiethoxysilane, dicyclopentadienylpropyldipropoxysilane, dicyclopentadienylpropyldiisopropoxysilane, bis(bicycloheptenyl)dimethoxysilane, bis(bicycloheptenyl)diethoxysilane, bis(bicycloheptenyl)dipropoxysilane,Examples thereof include bis(bicycloheptenyl)diisopropoxysilane, bis(bicycloheptyl)dimethoxysilane, bis(bicycloheptyl)diethoxysilane, bis(bicycloheptyl)dipropoxysilane, bis(bicycloheptenyl)diisopropoxysilane, diadamantyldimethoxysilane, diadamantyldiethoxysilane, diadamantyldipropoxysilane, diadamantyldiisopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldiisopropoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, dimethylbenzylmethoxysilane, dimethylbenzylethoxysilane, dimethylphenethylmethoxysilane, dimethylphenethylethoxysilane, etc.

[0062] As the above compound, preferably, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, trimethylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane, dimethylphenethylmethoxysilane, etc. can be exemplified.

[0063] As the hydrolyzable monomer (Sm), the above R corresponding to the compounds exemplified above a , R b , R c As another example of the organic group represented by, an organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds can be mentioned. That is, in the general formulas (Sx-1) to (Sx-3), the above R a ~R cAt least one of them can be an organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds. Specifically, it is an organic group having one or more groups selected from the group consisting of an ether bond, an ester bond, an alkoxy group, a hydroxy group, and the like. As an example of this, those represented by the following general formula (Sm-R) can be mentioned.

[0064]

Chemical formula

[0065] Examples of the alicyclic ring, aromatic ring, or heterocyclic ring that may contain a heteroatom such as an oxygen atom as T are shown below. The position where Q2 and Q3 are bonded in T is not particularly limited, but it can be appropriately selected in consideration of the reactivity due to steric factors and the availability of commercially available reagents used in the reaction.

[0066]

Chemical formula

[0067] Preferred examples of the organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds in the general formula (Sm-R) include the following. In the following formulas, (Si) is described to indicate the bonding position with Si.

[0068] [Chemical formula]

[0069] [Chemical formula]

[0070] Also, as examples of the organic groups of R a , R b , R c , organic groups containing a silicon-silicon bond can also be used. Specifically, the following can be mentioned. [Chemical formula]

[0071] Also, as examples of the organic groups of R a , R b , R c , organic groups having a protecting group that decomposes with an acid can also be used. Specifically, the organic groups listed from paragraph

[0043] to paragraph

[0048] of JP-A No. 2013-167669 and the organic groups obtained from the silicon compounds shown in paragraph

[0056] of JP-A No. 2013-224279 can be mentioned.

[0072] Furthermore, as examples of the organic groups of R a , R b , R c , organic groups having a fluorine atom can also be used. Specifically, the organic groups obtained from the silicon compounds shown in paragraphs

[0059] to

[0065] of JP-A No. 2012-053253 can be mentioned.

[0073] In the above hydrolyzable monomer (Sm), one, two, or three chlorine, bromine, iodine, acetoxy group, methoxy group, ethoxy group, propoxy group, or butoxy group, etc. are bonded as hydrolyzable groups to the silicon shown in the above partial structure (Si).

[0074] [Synthesis Method of Thermally Crosslinkable Polysiloxane (Sx)] (Synthesis Method 1: Acid Catalyst) The thermally crosslinkable polysiloxane (Sx) used in the present invention can be produced by subjecting one or a mixture of two or more hydrolyzable monomers (Sm) to hydrolysis and condensation in the presence of an acid catalyst.

[0075] Examples of the acid catalyst used at this time include organic acids such as formic acid, acetic acid, oxalic acid, maleic acid, methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid, and inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, and phosphoric acid. The amount of the catalyst used is 1×10 -6 ~10 moles, preferably 1×10 -5 ~5 moles, more preferably 1×10 -4 ~1 mole per mole of the monomer.

[0076] When obtaining the thermally crosslinkable polysiloxane (Sx) by hydrolysis and condensation from these monomers, the amount of water added is preferably 0.01 to 100 moles, more preferably 0.05 to 50 moles, and still more preferably 0.1 to 30 moles per mole of the hydrolyzable substituent bonded to the monomer. If it is 100 moles or less, the apparatus used for the reaction becomes smaller and more economical. If it is 0.01 mole or more, the reaction proceeds.

[0077] As an operation method, the monomer is added to the aqueous catalyst solution to initiate the hydrolysis and condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, or the monomer may be diluted with an organic solvent, or both may be performed. The reaction temperature is 0 to 100°C, preferably 5 to 80°C. A method of maintaining the temperature at 5 to 80°C during the dropping of the monomer and then aging at 20 to 80°C is preferable.

[0078] Examples of the organic solvent that can be added to the catalyst aqueous solution or dilute the monomer include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, and mixtures thereof, etc. are preferred.

[0079] Among these solvents, preferred ones are water-soluble ones. For example, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, polyhydric alcohols such as ethylene glycol, propylene glycol, polyhydric alcohol condensate derivatives such as butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, acetone, acetonitrile, tetrahydrofuran, etc. can be mentioned. Particularly preferred among these are those having a boiling point of 100 °C or lower.

[0080] In addition, the amount of the organic solvent used is preferably 0 to 1,000 ml, particularly preferably 0 to 500 ml, per mole of the monomer. When the amount of the organic solvent used is reduced, the reaction vessel becomes smaller, which is economical.

[0081] Thereafter, if necessary, a neutralization reaction of the catalyst is carried out to obtain an aqueous solution of the reaction mixture. At this time, the amount of the alkaline substance that can be used for neutralization is preferably 0.1 to 2 equivalents with respect to the acid used in the catalyst. This alkaline substance may be any substance as long as it shows alkalinity in water.

[0082] Subsequently, it is preferable to remove by-products such as alcohol produced by the hydrolysis condensation reaction from the reaction mixture by means of vacuum removal or the like. At this time, the temperature at which the reaction mixture is heated depends on the types of the added organic solvent and the alcohol generated by the reaction, etc., but is preferably 0 to 100 °C, more preferably 10 to 90 °C, and still more preferably 15 to 80 °C. Also, the degree of vacuum at this time varies depending on the types of the organic solvent and alcohol to be removed, the exhaust device, the condensation device, and the heating temperature, but is preferably below atmospheric pressure, more preferably 80 kPa or less in absolute pressure, and still more preferably 50 kPa or less in absolute pressure. Although it is difficult to accurately know the amount of alcohol removed at this time, it is desirable that approximately 80% by mass or more of the generated alcohol or the like is removed.

[0083] Next, the acid catalyst used for hydrolysis condensation may be removed from the reaction mixture. As a method for removing the acid catalyst, water is mixed with the reaction mixture, which is a thermally crosslinkable polysiloxane solution, and the thermally crosslinkable polysiloxane is extracted with an organic solvent. The organic solvent used at this time is preferably one that can dissolve the thermally crosslinkable polysiloxane and separates into two layers when mixed with water. For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof, etc. can be mentioned.

[0084] Furthermore, it is also possible to use a mixture of a water-soluble organic solvent and a water-insoluble organic solvent. For example, methanol-ethyl acetate mixture, ethanol-ethyl acetate mixture, 1-propanol-ethyl acetate mixture, 2-propanol-ethyl acetate mixture, butanediol monomethyl ether-ethyl acetate mixture, propylene glycol monomethyl ether-ethyl acetate mixture, ethylene glycol monomethyl ether-ethyl acetate mixture, butanediol monoethyl ether-ethyl acetate mixture, propylene glycol monoethyl ether-ethyl acetate mixture, ethylene glycol monoethyl ether-ethyl acetate mixture, butanediol monopropyl ether-ethyl acetate mixture, propylene glycol monopropyl ether-ethyl acetate mixture, ethylene glycol monopropyl ether-ethyl acetate mixture, methanol-methyl isobutyl ketone mixture, ethanol-methyl isobutyl ketone mixture, 1-propanol-methyl isobutyl ketone mixture, 2-propanol-methyl isobutyl ketone mixture, propylene glycol monomethyl ether-methyl isobutyl ketone mixture, ethylene glycol monomethyl ether-methyl isobutyl ketone mixture, propylene glycol monoethyl ether-methyl isobutyl ketone mixture, ethylene glycol monoethyl ether-methyl isobutyl ketone mixture, propylene glycol monopropyl ether-methyl isobutyl ketone mixture, ethylene glycol monopropyl ether-methyl isobutyl ketone mixture, methanol-cyclopentyl methyl ether mixture, ethanol-cyclopentyl methyl ether mixture, 1-propanol-cyclopentyl methyl ether mixture, 2-propanol-cyclopentyl methyl ether mixture, propylene glycol monomethyl ether-cyclopentyl methyl ether mixture, ethylene glycol monomethyl ether-cyclopentyl methyl ether mixture, propylene glycol monoethyl ether-cyclopentyl methyl ether mixture, ethylene glycol monoethyl ether-cyclopentyl methyl ether mixture, propylene glycol monopropyl ether-cyclopentyl methyl ether mixture, ethylene glycol monopropyl ether-cyclopentyl methyl ether mixture,Methanol-propylene glycol methyl ether acetate mixture, ethanol-propylene glycol methyl ether acetate mixture, 1-propanol-propylene glycol methyl ether acetate mixture, 2-propanol-propylene glycol methyl ether acetate mixture, propylene glycol monomethyl ether-propylene glycol methyl ether acetate mixture, ethylene glycol monomethyl ether-propylene glycol methyl ether acetate mixture, propylene glycol monoethyl ether-propylene glycol methyl ether acetate mixture, ethylene glycol monoethyl ether-propylene glycol methyl ether acetate mixture, propylene glycol monopropyl ether-propylene glycol methyl ether acetate mixture, ethylene glycol monopropyl ether-propylene glycol methyl ether acetate mixture, etc. are preferred, but the combination is not limited thereto.

[0085] In addition, the mixing ratio of the water-soluble organic solvent and the water-insoluble organic solvent is appropriately selected. However, with respect to 100 parts by mass of the water-insoluble organic solvent, 0.1 to 1,000 parts by mass, more preferably 1 to 500 parts by mass, and still more preferably 2 to 100 parts by mass of the water-soluble organic solvent are preferred.

[0086] Subsequently, it may be washed with neutral water. As this water, what is usually called deionized water or ultrapure water may be used. The amount of this water is preferably 0.01 to 100 L, more preferably 0.05 to 50 L, and still more preferably 0.1 to 5 L with respect to 1 L of the thermally crosslinkable polysiloxane solution. For this washing method, both may be put in the same container, stirred, and then left standing to separate the aqueous layer. The number of washing times may be 1 or more, but even if washed 10 or more times, the effect of just washing may not be obtained. Therefore, it is preferably about 1 to 5 times.

[0087] As other methods for removing the acid catalyst, there may be mentioned a method using an ion exchange resin, and a method of neutralizing with an epoxy compound such as ethylene oxide or propylene oxide and then removing it. These methods can be appropriately selected according to the acid catalyst used in the reaction.

[0088] In this case, due to the water washing operation at this time, a part of the thermally crosslinkable polysiloxane may escape into the aqueous layer, and an effect equivalent to a fractionation operation may be obtained. Therefore, the number of water washing times and the amount of washing water may be appropriately selected in view of the catalyst removal effect and the fractionation effect.

[0089] In both the thermally crosslinkable polysiloxane solution in which the acid catalyst remains and the thermally crosslinkable polysiloxane solution from which the acid catalyst has been removed, the final solvent is added and solvent exchange is carried out under reduced pressure to obtain a desired thermally crosslinkable polysiloxane solution. The temperature of the solvent exchange at this time depends on the type of the reaction solvent or extraction solvent to be removed, but is preferably 0 to 100 °C, more preferably 10 to 90 °C, and still more preferably 15 to 80 °C. Also, the degree of reduced pressure at this time varies depending on the type of the extraction solvent to be removed, the exhaust device, the condensation device, and the heating temperature, but is preferably below atmospheric pressure, more preferably 80 kPa or less in absolute pressure, and still more preferably 50 kPa or less in absolute pressure.

[0090] At this time, the thermally crosslinkable polysiloxane may become unstable due to the change of the solvent. This is caused by the compatibility between the final solvent and the thermally crosslinkable polysiloxane. To prevent this, as a stabilizer, a monohydric or polyhydric alcohol having a cyclic ether described in paragraphs

[0181] to

[0182] of JP-A-2009-126940 as a substituent may be added. The amount to be added is 0 to 25 parts by mass, preferably 0 to 15 parts by mass, more preferably 0 to 5 parts by mass with respect to 100 parts by mass of the thermally crosslinkable polysiloxane in the solution before the solvent exchange. However, when adding, 0.5 part by mass or more is preferable. If necessary, a monohydric or polyhydric alcohol having a cyclic ether as a substituent may be added to the solution before the solvent exchange to carry out the solvent exchange operation.

[0091] When the thermosetting polysiloxane is concentrated above a certain concentration, the condensation reaction may further proceed, and there is a risk of changing to a state where it cannot be redissolved in an organic solvent. Therefore, it is preferable to keep it in a solution state with an appropriate concentration. Also, if it is too dilute, the amount of solvent becomes excessive, so it is economically preferable to keep it in a solution state with an appropriate concentration. The concentration at this time is preferably 0.1 to 20% by mass.

[0092] The preferred final solvent to be added to the thermosetting polysiloxane solution is an alcohol-based solvent, and particularly preferred are monoalkyl ether derivatives such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and butanediol. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, diacetone alcohol, etc. are preferred.

[0093] If these solvents are the main components, it is also possible to add a non-alcohol-based solvent as an auxiliary solvent. Examples of this auxiliary solvent include acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc.

[0094] As another reaction operation using an acid catalyst, water or a water-containing organic solvent is added to a monomer or an organic solution of the monomer to initiate a hydrolysis reaction. At this time, the catalyst may be added to the monomer or the organic solution of the monomer, or may be added to water or the water-containing organic solvent. The reaction temperature is 0 to 100°C, preferably 10 to 80°C. A method of heating to 10 to 50°C when dropping water and then raising the temperature to 20 to 80°C for aging is preferred.

[0095] When using an organic solvent, a water-soluble one is preferred, and examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether, and polyhydric alcohol condensate derivatives such as these and mixtures thereof.

[0096] The amount of the organic solvent used is preferably 0 to 1,000 ml, particularly 0 to 500 ml, per 1 mol of the monomer. When the amount of the organic solvent used is smaller, the reaction vessel becomes smaller and it is more economical. The post-treatment of the obtained reaction mixture is the same as the above method, and a thermally crosslinkable polysiloxane can be obtained.

[0097] (Synthesis Method 2: Alkali Catalyst) Further, the thermally crosslinkable polysiloxane (Sx) can be produced by performing hydrolysis and condensation of one or a mixture of two or more hydrolyzable monomers (Sm) in the presence of an alkali catalyst.

[0098] The alkali catalysts used at this time include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononene, diazabicycloundecene, hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and the like. The amount of the catalyst used is 1×10 -6 mol to 10 mol, preferably 1×10 -5 mol to 5 mol, more preferably 1×10 -4 mol to 1 mol.

[0099] When obtaining a thermally crosslinkable polysiloxane by hydrolysis and condensation from the above monomers, the amount of water is preferably 0.1 to 50 mol per mol of the hydrolyzable substituent bonded to the monomer. If it is 50 mol or less, the apparatus used for the reaction becomes smaller and more economical.

[0100] As an operation method, the monomer is added to the aqueous catalyst solution to initiate a hydrolysis and condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, or the monomer may be diluted with an organic solvent, or both may be performed. The reaction temperature is 0 to 100°C, preferably 5 to 80°C. A method of maintaining the temperature at 5 to 80°C during the dropping of the monomer and then aging at 20 to 80°C is preferred.

[0101] As the organic solvent that can be added to the aqueous alkali catalyst solution or can dilute the monomer, those similar to the organic solvents exemplified as those that can be added to the aqueous acid catalyst solution are preferably used. The amount of the organic solvent used is preferably 0 to 1,000 ml per mole of the monomer in order to carry out the reaction economically.

[0102] Subsequently, if necessary, a neutralization reaction of the catalyst is carried out to obtain an aqueous reaction mixture solution. At this time, the amount of the acidic substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the alkaline substance used as the catalyst. This acidic substance can be any substance as long as it shows acidity in water.

[0103] Subsequently, it is preferable to remove by-products such as alcohol generated by the hydrolysis condensation reaction from the reaction mixture by distillation under reduced pressure or the like. The temperature at which the reaction mixture is heated depends on the types of the added organic solvent and the alcohol generated by the reaction, but is preferably 0 to 100 ° C, more preferably 10 to 90 ° C, and still more preferably 15 to 80 ° C. Also, the degree of reduced pressure at this time varies depending on the types of the organic solvent and alcohol to be removed, the exhaust device, the condensation device, and the heating temperature, but is preferably below atmospheric pressure, more preferably 80 kPa or less in absolute pressure, and still more preferably 50 kPa or less in absolute pressure. Although it is difficult to accurately know the amount of alcohol removed at this time, it is desirable that approximately 80 mass% or more of the generated alcohol is removed.

[0104] Next, in order to remove the alkali catalyst used in the hydrolysis condensation, the thermally crosslinkable polysiloxane is extracted with an organic solvent. As the organic solvent used at this time, those that can dissolve the thermally crosslinkable polysiloxane and separate into two layers when mixed with water are preferable. For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, and mixtures thereof, etc. can be mentioned.

[0105] Furthermore, it is also possible to use a mixture of a water-soluble organic solvent and a water-insoluble organic solvent.

[0106] Specific examples of the organic solvent used when removing the alkali catalyst can be the same as those specifically exemplified above for the organic solvents used when removing the acid catalyst, and mixtures of water-soluble organic solvents and water-insoluble organic solvents.

[0107] Note that the mixing ratio of the water-soluble organic solvent and the water-insoluble organic solvent is appropriately selected, but it is 0.1 to 1,000 parts by mass, preferably 1 to 500 parts by mass, and more preferably 2 to 100 parts by mass of the water-soluble organic solvent with respect to 100 parts by mass of the water-insoluble organic solvent.

[0108] Subsequently, wash with neutral water. As this water, usually deionized water or ultrapure water can be used. The amount of this water is 0.01 to 100 L, preferably 0.05 to 50 L, more preferably 0.1 to 5 L, per 1 L of the thermally crosslinkable polysiloxane solution. For this washing method, both can be put in the same container, stirred, and then left to stand to separate the aqueous layer. The number of washing times may be one or more, but even if washed 10 times or more, the effect of just washing may not be obtained, so preferably it is about 1 to 5 times.

[0109] Add the final solvent to the washed thermally crosslinkable polysiloxane solution and perform solvent exchange under reduced pressure to obtain the desired thermally crosslinkable polysiloxane solution. The temperature of the solvent exchange at this time depends on the type of extraction solvent to be removed, but is preferably 0 to 100 °C, more preferably 10 to 90 °C, still more preferably 15 to 80 °C. Also, the degree of reduced pressure at this time varies depending on the type of extraction solvent to be removed, the exhaust device, the condensation device, and the heating temperature, but is preferably below atmospheric pressure, more preferably 80 kPa or less in absolute pressure, still more preferably 50 kPa or less in absolute pressure.

[0110] Preferred as the final solvent to be added to the thermally crosslinkable polysiloxane solution are alcohol-based solvents, and particularly preferred are monoalkyl ethers such as ethylene glycol, diethylene glycol, and triethylene glycol, and monoalkyl ethers such as propylene glycol and dipropylene glycol. Specifically, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, diacetone alcohol, etc. are preferred.

[0111] As another reaction operation using an alkali catalyst, water or a water-containing organic solvent is added to a monomer or an organic solution of the monomer to initiate a hydrolysis reaction. At this time, the catalyst may be added to the monomer or the organic solution of the monomer, or may be added to water or the water-containing organic solvent. The reaction temperature is 0 to 100°C, preferably 10 to 80°C. A method of heating to 10 to 50°C when dropping water and then raising the temperature to 20 to 80°C for aging is preferred.

[0112] The organic solvent that can be used as the organic solution of the monomer or the water-containing organic solvent is preferably water-soluble, and examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and polyhydric alcohol condensate derivatives such as these and mixtures thereof.

[0113] The molecular weight of the thermally crosslinkable polysiloxane obtained by the above synthesis method 1 or 2 can be adjusted by controlling the reaction conditions during polymerization as well as by the selection of the monomer. However, it is preferable to use those having a weight average molecular weight of 100,000 or less, more preferably 200 to 50,000, and still more preferably 300 to 30,000. If the weight average molecular weight is 100,000 or less, foreign substances and coating spots do not occur. The data regarding the above weight average molecular weight is represented by the molecular weight in terms of polystyrene using polystyrene as a standard substance by gel permeation chromatography (GPC) using RI as a detector and tetrahydrofuran as an elution solvent.

[0114] The physical properties of the thermosetting polysiloxane used in the present invention vary depending on the type of acid or alkali catalyst used during hydrolysis and condensation and the reaction conditions. Therefore, it can be appropriately selected according to the performance of the target silicon-containing antireflection film.

[0115] Furthermore, a mixture of one or more hydrolyzable monomers (Sm) and a hydrolyzable metal compound represented by the following general formula (Mm) can be used as a component of the composition for forming a silicon-containing antireflection film, which is produced under conditions using the above-mentioned acid or alkali catalyst.

Chemical formula

[0116] In the general formula (Mm), R 7 , R 8 are organic groups having 1 to 30 carbon atoms, m7 + m8 is the same number as the valence determined by the type of U, m7 and m8 are integers of 0 or more, and U is an element of Group III, Group IV, or Group V of the periodic table excluding carbon and silicon.

[0117] Examples of the hydrolyzable metal compound represented by the general formula (Mm) include metal alkoxides such as boron, aluminum, gallium, yttrium, germanium, titanium, and hafnium. Specifically, those described in paragraphs

[0107] to

[0123] of the pamphlet of JP-A No. 2020-118960 can be used.

[0118] (Polysilane (Sy)) When the silicon-containing polymer (A) of the composition for forming a silicon-containing antireflection film of the present invention contains polysilane, the polysilane preferably contains a unit structure represented by the following general formula (Sy-1).

Chemical formula

[0119] Examples of Z in the general formula (Sy-1) include a substituted or unsubstituted divalent chain hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent aliphatic cyclic hydrocarbon group having 3 to 20 carbon atoms, and a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. In the present specification, the chain hydrocarbon group includes both a linear hydrocarbon group and a branched hydrocarbon group.)

[0120] Examples of the unsubstituted divalent chain hydrocarbon group having 1 to 20 carbon atoms include a chain saturated hydrocarbon group such as a methanediyl group or an ethanediyl group, and a chain unsaturated hydrocarbon group such as an ethenediyl group or a propenediyl group.)

[0121] Examples of the unsubstituted divalent aliphatic cyclic hydrocarbon group having 3 to 20 carbon atoms include a monocyclic saturated hydrocarbon group such as a cyclobutanediyl group, a monocyclic unsaturated hydrocarbon group such as a cyclobutenediyl group, a polycyclic saturated hydrocarbon group such as a bicyclo[2.2.1]heptanediyl group, and a polycyclic unsaturated hydrocarbon group such as a bicyclo[2.2.1]heptenediyl group.)

[0122] Examples of the unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenylene group, a biphenylene group, a phenyleneethylene group, and a naphthylene group.)

[0123] Examples of the substituent in the substituted divalent chain hydrocarbon group having 1 to 20 carbon atoms, the substituted divalent aliphatic cyclic hydrocarbon group having 3 to 20 carbon atoms, and the substituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by Z include a halogen atom, a hydroxy group, a cyano group, a nitro group, an alkoxy group, an acyl group, an acyloxy group, etc.)

[0124] As Z, an unsubstituted chain saturated hydrocarbon group is preferable, and a methanediyl group or an ethanediyl group is more preferable.

[0125] R in the above formula (Sy-1) d or R e Examples of the monovalent organic group having 1 to 30 carbon atoms represented by include a monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, a monovalent group (α) having a divalent heteroatom-containing group between carbon-carbon atoms of this hydrocarbon group, and a monovalent group (β) obtained by substituting a part or all of the hydrogen atoms of the monovalent group (α) having the above hydrocarbon group or the above divalent heteroatom-containing group with a monovalent heteroatom-containing group.

[0126] Examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms include a monovalent chain hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms.

[0127] Examples of the monovalent chain hydrocarbon group having 1 to 30 carbon atoms include an alkyl group such as a methyl group and an ethyl group, an alkenyl group such as an ethenyl group, and an alkynyl group such as an ethynyl group.

[0128] Examples of the monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms include a monovalent monocyclic alicyclic saturated hydrocarbon group such as a cyclopentyl group and a cyclohexyl group, a monovalent monocyclic alicyclic unsaturated hydrocarbon group such as a cyclopentenyl group and a cyclohexenyl group, a monovalent polycyclic alicyclic saturated hydrocarbon group such as a norbornyl group and an adamantyl group, and a monovalent polycyclic alicyclic unsaturated hydrocarbon group such as a norbornenyl group and a tricyclodecenyl group.

[0129] Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a methylnaphthyl group, and an anthryl group, and an aralkyl group such as a benzyl group, a naphthylmethyl group, and an anthrylmethyl group.

[0130] R in the above formula (Sy-1) e Examples of the divalent organic group having 1 to 30 carbon atoms represented by include a divalent chain hydrocarbon group having 1 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, and the like.

[0131] Examples of the hetero atom constituting the divalent or monovalent hetero atom-containing group include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a halogen atom, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0132] Examples of the divalent hetero atom-containing group include -O-, -CO-, -S-, -CS-, -NR'-, and a group formed by combining two or more of these. R' is a hydrogen atom or a monovalent hydrocarbon group.

[0133] Examples of the monovalent hetero atom-containing group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxy group, a carboxy group, a cyano group, an amino group, a sulfanyl group, and the like.

[0134] R d or R e As the monovalent organic group having 1 to 30 carbon atoms represented by, a monovalent hydrocarbon group is preferred, a monovalent chain hydrocarbon group and a monovalent aromatic hydrocarbon group are more preferred, and an alkyl group and an aryl group are even more preferred.

[0135] R d or R e The number of carbon atoms of the monovalent organic group represented by is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

[0136] R d or R e Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. As this halogen atom, a chlorine atom or a bromine atom is preferred.

[0137] The lower limit of the content ratio of the structural unit (Sy-1) to all the structural units constituting the polycarbosilane (Sy) is preferably 5 mol%, more preferably 30 mol%, still more preferably 60 mol%, and particularly preferably 80 mol%. On the other hand, the upper limit of the content ratio of the structural unit (Sy-1) is not particularly limited and may be 100 mol%. By setting the content ratio of the structural unit (Sy-1) within the above range, the resist pattern collapse suppression property, oxygen-based gas etching resistance, and solvent resistance of the silicon-containing antireflection film formed by the composition for forming a silicon-containing antireflection film of the present invention can be further improved.

[0138] In addition to the repeating unit represented by the above general formula (Sy-1), the polycarbosilane (Sy) may contain a repeating unit represented by the following formula (Sy-2) and / or the following general formula (Sy-3).

[0139] [Chemical formula]

[0140] When the polycarbosilane (Sy) has a repeating unit represented by the above formula (Sy-2), the lower limit of the content ratio of the structural unit (Sy-2) to all the structural units constituting the polycarbosilane (Sy) is preferably 0.1 mol%, more preferably 1 mol%, and still more preferably 5 mol%. On the other hand, the upper limit of the content ratio of the structural unit (Sy-2) is preferably 50 mol%, more preferably 40 mol%, still more preferably 30 mol%, and particularly preferably 20 mol%.

[0141] [Chemical formula]

[0142] In the above general formula (Sy-3), R f is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. c is 1 or 2. When c is 2, the two R f are the same as or different from each other.

[0143] As for the above c, 1 is preferable.

[0144] R f As R, for example, the same groups as the monovalent hydrocarbon groups having 1 to 20 carbon atoms exemplified in R of the above general formula (Sy-1) d or R e are mentioned. Further, as substituents of the monovalent hydrocarbon groups having 1 to 20 carbon atoms, for example, the same groups as the monovalent heteroatom-containing groups exemplified in R of the above general formula (Sy-1) d or R e are mentioned.

[0145] R f As R, a substituted or unsubstituted monovalent chain hydrocarbon group or a substituted or unsubstituted monovalent aromatic hydrocarbon group is preferable, an alkyl group or an aryl group is more preferable, and a methyl group or a phenyl group is even more preferable.

[0146] When the polycarbosilane (Sy) has the structural unit (Sy-3), the lower limit of the content ratio of the structural unit (Sy-3) to all the structural units constituting the polycarbosilane (Sy) is preferably 0.1 mol%, more preferably 1 mol%, and even more preferably 5 mol%. The upper limit of the content ratio of the structural unit (Sy-3) is preferably 50 mol%, more preferably 40 mol%, even more preferably 30 mol%, and particularly preferably 20 mol%.

[0147] Further, in addition to the above structural units, the polycarbosilane (Sy) may contain a structural unit containing a Si—O—Si structure formed by dehydration condensation or the like from the hydroxy group represented by R d or R e in the above general formula (Sy-1).

[0148] Preferred solvents for the polycarbosilane are alcohol solvents or ether solvents. Particularly preferred alcohol solvents include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, diacetone alcohol, and the like. Specific examples of ether solvents preferably include propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, and the like.

[0149] In addition, commercially available polycarbosilanes can be used in the present invention. For example, polycarbosilanes having a unit structure represented by the following formula (Sy-4) (for example, manufactured by NGS Advanced Fiber Co., Ltd., trade name NIPSY TypeS (Mn = 2,716 (GPC UV detector / polystyrene conversion)), trade name NIPSY TypeL (number average molecular weight 1,000, weight average molecular weight 4,500), etc.) can be used. The weight average molecular weight of the polycarbosilane used in the present invention is preferably from 400 to 12,000, more preferably from 2,000 to 12,000.

Chemical formula

[0150] (Polysilane (Sz)) When the silicon-containing polymer (A) used in the composition for forming a silicon-containing antireflection film of the present invention contains polysilane, the polysilane preferably contains a repeating unit represented by the following general formula (Sz-1). (R 9 R 10 R 11 Si) a2 (R 12 R 13 Si) a3 (R 14 Si) a4 (Si) a5 (Sz-1) (In the formula, R 9, R 10 , R 11 , R 12 , R 13 , and R 14 are each a methyl group, a phenyl group, or a hydroxyl group. a2, a3, a4, and a5 are molar fractions, and a2 + a3 + a4 + a5 = 1, 0 ≤ a2 ≤ 1, 0 ≤ a3 ≤ 1, 0 ≤ a4 ≤ 1, 0 ≤ a5 ≤ 1.)

[0151] Furthermore, it may be one or more polymers selected from the hydrolyzates, condensates, and hydrolytic condensates of the above polysilane compound. Also, it may be a hydrolyzate, condensate, or hydrolytic condensate with polysiloxane, and may undergo hydrolytic condensation with a hydrolyzable monomer (Sm).

[0152] Examples of the polysilane compound represented by the above general formula (Sz-1) include Ogsoal SI-10-10 (polymethylphenylsilane), SI-10-20 (polymethylphenylsilane), SI-20-10 (polyphenylsilane), SI-20-10 modified (polyphenylsilane), SI-30-10 (cyclic polydiphenylsilane), etc. manufactured by Osaka Gas Chemical. Also, those obtained by reacting these under alkaline conditions to reduce the molecular weight may be used.

[0153] In particular, it is preferable that the weight average molecular weight of the polysilane compound represented by the above general formula (Sz-1) is 1,000 or less. By setting the weight average molecular weight to 1,000 or less, the hydrolyzate, condensate, or hydrolytic condensate of the mixture containing the polysilane compound represented by the above general formula (Sz-1) is easily dissolved in the solvent component of the composition for forming a silicon-containing antireflection film, and the generation of particles during film formation can be prevented.

[0154] Here, various solvents can be used for the reaction under the above alkaline conditions. For example, hydrocarbon solvents such as benzene, toluene, and xylene; glycol solvents such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, and 1,4-dioxane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone, and cyclohexanone; and alcohol solvents such as ethanol, isopropyl alcohol, and butanol. One or more solvents selected from these can be used.

[0155] Also, various bases can be used as the base to be added. For example, inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, ammonia, tetramethylammonium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, lithium hydride, sodium hydride, potassium hydride, and calcium hydride; alkyl metals such as methyl lithium, n-butyl lithium, methyl magnesium chloride, and ethyl magnesium bromide; alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide; and organic bases such as triethylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 4-dimethylaminopyridine, and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The reaction temperature is preferably from -50°C to about the boiling point of the solvent, more preferably from room temperature to 100°C.

[0156] The hydrolysis, condensation, or hydrolysis-condensation reaction can be carried out using one or more compounds selected from inorganic acids, aliphatic sulfonic acids, and aromatic sulfonic acids as an acid catalyst. Examples of the acid catalyst used at this time include hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid. The amount of the catalyst used is preferably 10 -6 to 10 moles per mole of the monomer, more preferably 10 -5 to 5 moles, and even more preferably 10 -4It is 0 to 1 mol.

[0157] When hydrolytically condensing these monomers to synthesize a polymer, the amount of water is preferably 0.01 to 100 mol, more preferably 0.05 to 50 mol, and still more preferably 0.1 to 30 mol per 1 mol of the hydrolyzable substituent bonded to the monomer. By setting the addition amount to 100 mol or less, the apparatus used for the reaction does not become excessive, which is economical. Further, if the addition amount is 0.01 mol or more, the reaction proceeds.

[0158] As an operation method, a monomer can be added to an aqueous catalyst solution to initiate a hydrolytic condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, or the monomer may be diluted with an organic solvent, or both may be performed. The reaction temperature is preferably 0 to 100°C, more preferably 5 to 80°C. A method of maintaining the temperature at 5 to 80°C during the dropping of the monomer and then aging at 20 to 80°C is preferred.

[0159] Examples of the organic solvent that can be added to the aqueous catalyst solution or that can dilute the monomer include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, and mixtures thereof, etc. are preferred.

[0160] Among these solvents, more preferable ones are water-soluble ones. For example, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, polyhydric alcohols such as ethylene glycol and propylene glycol, polyhydric alcohol condensate derivatives such as butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, acetone, acetonitrile, tetrahydrofuran, etc. can be mentioned. Among these, particularly preferable ones are those having a boiling point of 100 °C or lower.

[0161] In addition, the amount of the organic solvent used is preferably 0 to 1,000 mL, particularly preferably 0 to 500 mL, per 1 mol of the monomer. If the amount of the organic solvent used is 1,000 mL or less, the reaction vessel will not become too large, which is economical.

[0162] Thereafter, if necessary, a neutralization reaction of the catalyst is carried out, the alcohol produced by the hydrolysis condensation reaction is removed under reduced pressure, and an aqueous solution of the reaction mixture is obtained. At this time, the amount of the basic substance that can be used for neutralization is preferably 0.1 to 2 equivalents with respect to the acid used in the catalyst. Any substance may be used as long as this basic substance shows alkalinity in water.

[0163] Subsequently, it is preferable to remove by-products such as alcohol generated by the hydrolysis condensation reaction from the reaction mixture. At this time, the temperature for heating the reaction mixture depends on the types of the added organic solvent and alcohol generated by the reaction, but is preferably 0 to 100 °C, more preferably 10 to 90 °C, and still more preferably 15 to 80 °C. Further, the degree of reduced pressure at this time varies depending on the types of the organic solvent and alcohol to be removed, the exhaust device, the condensation device, and the heating temperature, but is preferably below atmospheric pressure, more preferably 80 kPa or less in absolute pressure, and still more preferably 50 kPa or less in absolute pressure. Although it is difficult to accurately know the amount of alcohol removed at this time, it is desirable that approximately 80% by mass or more of the generated alcohol or the like is removed.

[0164] Next, the acid catalyst used for hydrolysis condensation may be removed from the reaction mixture. As a method for removing the acid catalyst, water and the polymer are mixed, and the polymer is extracted with an organic solvent. The organic solvent used at this time is preferably one that can dissolve the polymer and separates into two layers when mixed with water. For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc., and mixtures thereof can be mentioned.

[0165] Furthermore, it is also possible to use a mixture of a water-soluble organic solvent and a water-insoluble organic solvent. For example, methanol + ethyl acetate, ethanol + ethyl acetate, 1-propanol + ethyl acetate, 2-propanol + ethyl acetate, butanediol monomethyl ether + ethyl acetate, propylene glycol monomethyl ether + ethyl acetate, ethylene glycol monomethyl ether + ethyl acetate, butanediol monoethyl ether + ethyl acetate, propylene glycol monoethyl ether + ethyl acetate, ethylene glycol monoethyl ether + ethyl acetate, butanediol monopropyl ether + ethyl acetate, propylene glycol monopropyl ether + ethyl acetate, ethylene glycol monopropyl ether + ethyl acetate, methanol + methyl isobutyl ketone, ethanol + methyl isobutyl ketone, 1-propanol + methyl isobutyl ketone, 2-propanol + methyl isobutyl ketone, propylene glycol monomethyl ether + methyl isobutyl ketone, ethylene glycol monomethyl ether + methyl isobutyl ketone, propylene glycol monoethyl ether + methyl isobutyl ketone, ethylene glycol monoethyl ether + methyl isobutyl ketone, propylene glycol monopropyl ether + methyl isobutyl ketone, ethylene glycol monopropyl ether + methyl isobutyl ketone, methanol + cyclopentyl methyl ether, ethanol + cyclopentyl methyl ether, 1-propanol + cyclopentyl methyl ether, 2-propanol + cyclopentyl methyl ether, propylene glycol monomethyl ether + cyclopentyl methyl ether, ethylene glycol monomethyl ether + cyclopentyl methyl ether, propylene glycol monoethyl ether + cyclopentyl methyl ether, ethylene glycol monoethyl ether + cyclopentyl methyl ether, propylene glycol monopropyl ether + cyclopentyl methyl ether, ethylene glycol monopropyl ether + cyclopentyl methyl ether, methanol + propylene glycol methyl ether acetate, ethanol + propylene glycol methyl ether acetate, 1-propanol + propylene glycol methyl ether acetate,2-propanol + propylene glycol methyl ether acetate, propylene glycol monomethyl ether + propylene glycol methyl ether acetate, ethylene glycol monomethyl ether + propylene glycol methyl ether acetate, propylene glycol monoethyl ether + propylene glycol methyl ether acetate, ethylene glycol monoethyl ether + propylene glycol methyl ether acetate, propylene glycol monopropyl ether + propylene glycol methyl ether acetate, ethylene glycol monopropyl ether + propylene glycol methyl ether acetate, etc. are preferred, but the combination is not limited thereto.

[0166] Incidentally, the mixing ratio of the water-soluble organic solvent and the water-insoluble organic solvent is appropriately selected. However, with respect to 100 parts by mass of the water-insoluble organic solvent, 0.1 to 1,000 parts by mass of the water-soluble organic solvent is preferable, more preferably 1 to 500 parts by mass, and still more preferably 2 to 100 parts by mass.

[0167] Subsequently, it may be washed with neutral water. As this water, what is usually called deionized water or ultrapure water may be used. The amount of this water is preferably 0.01 to 100 L, more preferably 0.05 to 50 L, and still more preferably 0.1 to 5 L with respect to 1 L of the polymer solution. For this washing method, after putting both in the same container and stirring, it may be left to stand and the aqueous layer may be separated. The number of washings may be one or more, but since no effect of just washing can be obtained even if washed 10 times or more, it is preferably about 1 to 5 times.

[0168] At this time, due to the water washing operation, a part of the polymer may escape into the aqueous layer, and in some cases, an effect substantially equivalent to the fractionation operation may be obtained. Therefore, the number of water washings and the amount of washing water may be appropriately selected in view of the catalyst removal effect and the fractionation effect.

[0169] As other methods for removing the acid catalyst, methods using an ion exchange resin and methods of neutralizing with an epoxy compound such as ethylene oxide or propylene oxide and then removing can be mentioned. These methods can be appropriately selected according to the acid catalyst used in the reaction.

[0170] In both the case of the polymer in which the acid catalyst remains and the polymer solution from which the acid catalyst has been removed, a final solvent is added and the solvent is exchanged under reduced pressure to obtain a polymer solution. The temperature of the solvent exchange at this time depends on the type of reaction solvent or extraction solvent to be removed, but is preferably 0 to 100°C, more preferably 10 to 90°C, and still more preferably 15 to 80°C. Also, the degree of reduced pressure at this time varies depending on the type of extraction solvent to be removed, the exhaust device, the condensation device, and the heating temperature, but is preferably below atmospheric pressure, more preferably 80 kPa or less in absolute pressure, and still more preferably 50 kPa or less in absolute pressure.

[0171] At this time, the polymer may become unstable due to the change of the solvent. This is caused by the compatibility between the final solvent and the polymer. To prevent this, a monohydric or polyhydric alcohol having a cyclic ether as a substituent, or an ether compound may be added as a stabilizer. The amount to be added is preferably 0 to 25 parts by mass, more preferably 0 to 15 parts by mass, and still more preferably 0 to 5 parts by mass with respect to 100 parts by mass of the polymer in the solution before the solvent exchange. However, when adding, 0.5 parts by mass or more is preferable. If necessary, a stabilizer may be added to the solution before the solvent exchange and the solvent exchange operation may be performed.

[0172] Also, the concentration of the polymer is preferably 0.1 to 20% by mass. By setting the concentration in this way, the condensation reaction of the polymer proceeds and it does not change to a state where it is insoluble in the organic solvent again. Also, by setting the concentration in this way, the amount of the solvent is appropriate and it is economical.

[0173] The preferred final solvent to be added to the polymer is an alcohol-based solvent, and particularly preferred are monoalkyl ether derivatives such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, etc. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, etc. are preferred.

[0174] If these solvents are the main components, it is also possible to add a non-alcohol-based solvent as an auxiliary solvent. Examples of this auxiliary solvent include acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, cyclopentyl methyl ether, etc.

[0175] Also, as another reaction operation, water or a water-containing organic solvent may be added to the monomer or the organic solution of the monomer to initiate a hydrolysis reaction. At this time, the acid catalyst may be added to the monomer or the organic solution of the monomer, or may be added to the water or the water-containing organic solvent. The reaction temperature is preferably 0 to 100°C, more preferably 10 to 80°C. A method of heating to 10 to 50°C during the dropping of water and then raising the temperature to 20 to 80°C for aging is preferred.

[0176] When using an organic solvent, a water-soluble one is preferred. Specifically, examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether, and polyhydric alcohol condensate derivatives such as these and mixtures thereof.

[0177] At this time, the amount of the organic solvent used may be the same as the above amount. The obtained reaction mixture can be post-treated in the same manner as above to obtain a polymer.

[0178] In addition, the hydrolysis, condensation, or hydrolysis-condensation reaction for synthesizing the polymer can also be carried out using a basic catalyst. The basic catalysts used at this time include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, ethylmethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, dicyclohexylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononene, diazabicycloundecene, hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, tetramethylammonium hydroxide, choline hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and the like. The amount of the catalyst used may be the same as that when using the above acid catalyst.

[0179] When obtaining the polymer from these monomers, it is preferable to add 0.1 to 50 moles of water per mole of the hydrolyzable substituent bonded to the monomer. By setting the addition amount to 50 moles or less, the apparatus used for the reaction does not become excessive, which is economical. If the addition amount is 0.1 mole or more, the reaction proceeds.

[0180] The operation method of the reaction may be the same as that when using the above acid catalyst.

[0181] The organic solvent that can be added to the catalyst aqueous solution or can dilute the monomer is preferably the same as that when using the above acid catalyst. The amount of the organic solvent used is preferably 0 to 1,000 mL per mole of the monomer. By setting the amount in this way, the reaction vessel does not become excessive, which is economical.

[0182] Subsequently, if necessary, a neutralization reaction of the catalyst is carried out, and the alcohol produced by the hydrolysis condensation reaction is removed under reduced pressure to obtain an aqueous solution of the reaction mixture. At this time, the amount of the acidic substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the basic substance used in the catalyst. Any substance may be used as long as it shows acidity in water.

[0183] Subsequently, it is preferable to remove by-products such as alcohol produced by the hydrolysis condensation reaction from the reaction mixture. At this time, the temperature and degree of reduced pressure for heating the reaction mixture may be the same as those when using the above acid catalyst.

[0184] Next, the basic catalyst used for the hydrolysis condensation may be removed from the reaction mixture. The organic solvent used for removing the basic catalyst can be the same as that used when using the above acid catalyst. Also, the basic catalyst can be removed using a mixture of a water-soluble organic solvent and a water-insoluble organic solvent similar to that used when using the above acid catalyst. The mixing ratio of the water-soluble organic solvent and the water-insoluble organic solvent may also be the same as that used when using the above acid catalyst.

[0185] Subsequently, washing with neutral water may be performed. The washing method may be the same as that used when using the above acid catalyst.

[0186] A final solvent is added to the washed polymer, and the solvent is exchanged under reduced pressure to obtain a polymer solution. The temperature and degree of reduced pressure for the solvent exchange may be the same as those when using the above acid catalyst.

[0187] Also, at this time, a monohydric or polyhydric alcohol having a cyclic ether as a substituent or an ether compound may be added as a stabilizer in the same manner as when using the above acid catalyst. Also, the polymer solution is preferably adjusted to a concentration of 0.1 to 20% by mass.

[0188] Preferred final solvents to be added to the polymer are alcohol solvents or ether solvents. Particularly preferred alcohol solvents are ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc. Specific examples of ether solvents preferably include propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, etc.

[0189] If these solvents are the main components, it is also possible to add a non-alcohol solvent as an auxiliary solvent. As this auxiliary solvent, the same auxiliary solvents as those used when using the above acid catalyst can be used.

[0190] Also, as another reaction operation, water or a water-containing organic solvent may be added to the monomer or the organic solution of the monomer to initiate a hydrolysis reaction. At this time, the basic catalyst may be added to the monomer or the organic solution of the monomer, or may be added to the water or the water-containing organic solvent. The reaction temperature is preferably 0 to 100°C, more preferably 10 to 80°C. A method of heating to 10 to 50°C during the dropping of water and then raising the temperature to 20 to 80°C for aging is preferred.

[0191] When using an organic solvent, a water-soluble one is preferred. Specifically, examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether, and polyhydric alcohol condensate derivatives such as these and mixtures thereof.

[0192] At this time, the amount of the organic solvent used may be the same as the above amount. The obtained reaction mixture can be post-treated in the same manner as above to obtain a polymer.

[0193] The molecular weight of the polymer obtained by the reaction as described above can be adjusted not only by the selection of the monomer but also by controlling the reaction conditions during polymerization. The molecular weight of the obtained polymer is not particularly limited, but those having a weight average molecular weight of 100,000 or less are preferred, more preferably 200 to 50,000, and even more preferably 300 to 30,000. By using those having a weight average molecular weight of 100,000 or less, the generation of foreign matters and coating irregularities can be suppressed. The data regarding the above weight average molecular weight is represented by the molecular weight in terms of polystyrene using gel permeation chromatography (GPC) with RI as the detector and tetrahydrofuran as the eluent solvent, using polystyrene as the standard substance.

[0194] From the viewpoints of antireflection performance and raw material procurement, the silicon-containing polymer (A) contained in the composition for forming a silicon-containing antireflection film of the present invention preferably contains polysiloxane (Sx).

[0195] <(B) Organic polymer> The (B) organic polymer contained in the composition for forming a silicon-containing antireflection film of the present invention contains two or more hydroxyl groups in the repeating unit structure of the polymer, does not contain silicon, and preferably contains the following general formula (1B) or (2B). [Chemical formula] (In the formula, R 01 is a hydrogen atom or a methyl group, R 02 is an alkyl group having 1 to 3 carbon atoms or a halogen atom, m is an integer of 2 to 5, n is an integer of 0 to 3, m + n is an integer of 2 or more and 5 or less. X represents a single bond or an alkylene group which may contain one or more selected from oxygen atoms and nitrogen atoms having 1 to 10 carbon atoms.) [Chemical formula] (In the formula, R 1 is any one selected from a saturated monovalent organic group having 1 to 30 carbon atoms, an unsaturated monovalent organic group having 2 to 30 carbon atoms, and a halogen atom, Y is a divalent organic group having 1 to 30 carbon atoms, p is an integer of 0 to 5, q1 is an integer of 2 to 6, p + q1 is an integer of 2 or more and 6 or less, and q2 is 0 or 1.)

[0196] The (B) organic polymer contained in the composition for forming a silicon-containing antireflection film of the present invention may contain a structural unit different from the structure of the above general formula (1B) or (2B). However, in order to minimize the deterioration of the antireflection effect and thin film formability of the silicon-containing antireflection film formed using the composition for forming a silicon-containing antireflection film, the content of the structural units of the above general formula (1B) and (2B) contained in the (B) organic polymer is preferably 50% or more, more preferably 75% or more, and particularly preferably 100%.

[0197] (Organic polymer (1B)) It is preferable that the (B) organic polymer is a high molecular compound containing a repeating unit represented by the following general formula (1B). [Chemical formula] (wherein, R 01 is a hydrogen atom or a methyl group, R 02 is an alkyl group having 1 to 3 carbon atoms or a halogen atom, m is an integer of 2 to 5, n is an integer of 0 to 3, m + n is an integer of 2 or more and 5 or less. X represents a single bond or an alkylene group which may contain one or more selected from oxygen atoms and nitrogen atoms having 1 to 10 carbon atoms.)

[0198] In the general formula (1B), R 01 is a hydrogen atom or a methyl group, preferably a methyl group. R 02 is an alkyl group having 1 to 3 carbon atoms or a halogen atom, m is an integer of 2 to 5, n is an integer of 0 to 3, m + n is an integer of 2 or more and 5 or less, preferably, m is an integer of 2, n is an integer of 0 or 1, m + n is an integer of 2 or more and 3 or less, and more preferably, m is 2, n is 0, m + n is 2.)

[0199] In the general formula (1B), X is a single bond or an alkylene group which may contain one or more selected from oxygen atoms and nitrogen atoms having 1 to 10 carbon atoms. The oxygen atom in X can form a carbonyl group, a hydroxyl group, or an ether bond. For example, an ester bond is an alkylene group containing an oxygen atom having 1 carbon atom. Also, the nitrogen atom in X can form an amino group. Furthermore, X may contain an oxygen atom and a nitrogen atom. For example, an amide bond is an alkylene group containing an oxygen atom and a nitrogen atom having 1 carbon atom.) Specific examples of X include, but are not limited to, the following.)

[0200]

Chemical formula

[0201] Examples of R 02 in the general formula (1B) include a methyl group, an ethyl group, a propyl group, and an isopropyl group, but a methyl group is preferred from the viewpoint of adhesion to the resist upper layer film.)

[0202] Examples of the resin represented by the general formula (1B) include, but are not limited to, the following. In the following formula, R 01 and R 02 are the same as those described above.

[0203]

Chemical formula

[0204] For a silicon-containing antireflection film-forming composition containing these resins, a silicon-containing antireflection film excellent in thin film formability can be formed.

[0205] The organic polymer (B) may further contain one or both of the repeating unit represented by the following general formula (1B-1) and the repeating unit represented by the following general formula (1B-2).

Chemical formula

[0206] By the organic polymer (B) further containing one or both of the repeating unit represented by the general formula (1B-1) and the repeating unit represented by the general formula (1B-2), it is possible to further improve the adhesion to the underlying substrate and exhibit excellent thin film formability.

[0207] The above R3 is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and is preferably a hydrogen atom.

[0208] It is preferable that the heterocyclic structure contained in R2 of the high molecular compound containing any one of the repeating units represented by the general formula (1B-1) and the formula (1B-2) is a heterocyclic structure containing an oxygen atom.

[0209] By including such a complex ring structure, higher adhesion to the underlying substrate can be obtained.

[0210] It is preferable that R2 is a monovalent organic group containing a group selected from the following formulas (R2-1) to (R2-3).

Chemical formula

[0211] By including such a structure, higher adhesion to the underlying substrate can be obtained.

[0212] As specific examples of the repeating unit represented by the above general formula (1B-1) or (1B-2), the following structures can be preferably exemplified.

Chemical formula

[0213] The above (B) organic polymer is a high molecular compound containing the repeating unit represented by the above general formula (1B). When it contains any of the repeating units represented by the above general formulas (1B-1) and (1B-2), the content of the repeating units represented by the above general formulas (1B-1) and (1B-2) is preferably 5 mol% or more and 50 mol% or less with respect to all the repeating units. More preferably, it is 10 mol% or more and 30 mol% or less.

[0214] (Organic polymer (2B)) It is preferable that the above (B) organic polymer is a high molecular compound containing the repeating unit represented by the following general formula (2B).

Chemical formula

[0215] In the general formula (2B), R 1 is any one selected from a saturated monovalent organic group having 1 to 30 carbon atoms, an unsaturated monovalent organic group having 2 to 30 carbon atoms, and a halogen atom, Y is a divalent organic group having 1 to 30 carbon atoms, p is an integer from 0 to 5, q1 is an integer from 2 to 6, p + q1 is an integer from 2 or more to 6 or less, and q2 is 0 or 1.)

[0216] Here, when q2 is 0, p is an integer from 0 to 2, q1 is an integer from 2 to 4, and p + q1 is an integer from 2 or more to 4 or less. When q2 is 1, p is an integer from 0 to 5, q1 is an integer from 2 to 6, and p + q1 is an integer from 2 or more to 6 or less.)

[0217] In the general formula (2B), q1 is preferably 2 or 3, more preferably 2. q2 is 0 or 1, and 0 is preferable from the viewpoint of dry etching resistance.)

[0218] In the above general formula (2B), R 1 Examples of the saturated monovalent organic group having 1 to 30 carbon atoms represented by include an alkyl group having 1 to 10 carbon atoms. R 1 Examples of the unsaturated monovalent organic group having 2 to 30 carbon atoms represented by include a vinyl group, an allyl group, an ethynyl group, an allyloxy group, a propargyl group, etc. R 1 Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.)

[0219] In the general formula (2B) above, examples of the divalent organic group having 1 to 30 carbon atoms represented by Y include alkane diyl groups such as methylene group, ethanediyl group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, octanediyl group, decanediyl group, etc.; monocyclic cycloalkane diyl groups such as cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cycloheptanediyl group, cyclooctanediyl group, cyclodecanediyl group, methylcyclohexanediyl group, ethylcyclohexanediyl group, etc.; polycyclic cycloalkane diyl groups such as bicyclo[2.2.1]heptane diyl group, bicyclo[2.2.2]octane diyl group, tricyclo[5.2.1.0 2,6 decane diyl group (dicyclopentylene group), tricyclo[3.3.1.1 3,7 decane diyl group, tetracyclo[6.2.1.1 3,6 .0 2,7 dodecane diyl group, adamantane diyl group, etc.; arene diyl groups such as phenylene group, naphthylene group, etc.

[0220] Examples of the alkanediyl oxy group represented by the above Y include groups formed by combining the above alkanediyl group and an oxygen atom. Examples of the cycloalkanediyl oxy group represented by the above Y include groups formed by combining the above cycloalkanediyl group and an oxygen atom.

[0221] Some or all of the hydrogen atoms of the above alkanediyl group, cycloalkanediyl group, alkanediyl oxy group, cycloalkanediyl oxy group, and arene diyl group may be substituted, and examples of the substituents include the same groups as the examples of the substituents that the organic group represented by R a1 described later may have.

[0222] Examples of the organic group represented by the above Y include groups represented by the following formula.

Chemical formula

[0223] As the above Y, from the viewpoint of raw material availability, a methylene group can preferably be mentioned.

[0224] As the resin having the structural unit represented by the general formula (2B), specifically, the following can be exemplified.

[0225] [Chemical formula] (In the above formula, the hydrogen atom on the aromatic ring having a hydroxyl group may be substituted with the above R 1 .)

[0226] The content of the (B) organic polymer contained in the silicon-containing antireflection film-forming composition of the present invention is preferably in the range of 1 to 50 parts by mass, more preferably in the range of 3 to 30 parts by mass, and still more preferably in the range of 5 to 15 parts by mass with respect to 100 parts by mass of the (A) silicon-containing polymer.

[0227] By including the (B) organic polymer in such a range in the silicon-containing antireflection film-forming composition, it becomes possible to highly balance the dry etching resistance and thin film formability of the silicon-containing antireflection film formed using this. If the content of the (B) organic polymer is 1 part by mass or more, the thin film formability of the silicon-containing antireflection film-forming composition does not deteriorate. If the content of the (B) organic polymer is 50 parts by mass or less, the antireflection function and etching resistance of the silicon-containing antireflection film formed by the silicon-containing antireflection film-forming composition do not deteriorate.

[0228] The weight average molecular weight Mw in terms of polystyrene of the (B) organic polymer contained in the silicon-containing antireflection film-forming composition of the present invention by gel permeation chromatography is preferably in the range of 1,500 ≤ Mw ≤ 20,000, more preferably 3,000 ≤ Mw ≤ 15,000, and particularly preferably 4,000 ≤ Mw ≤ 9,000.

[0229] Since the molecular weight range of the above-mentioned (B) organic polymer is as described above, a silicon-containing antireflection film showing excellent film-forming properties in thin film formation can be formed. Further, a silicon-containing antireflection film excellent in film thickness uniformity and defect suppression property derived from sublimates can be formed. If the weight average molecular weight Mw of the (B) organic polymer is 1,500 or more, the outgas components of the (B) organic polymer are reduced, and the thin film-forming property and film thickness uniformity of the silicon-containing antireflection film do not deteriorate. Also, the defects derived from sublimates are reduced. If the weight average molecular weight Mw of the (B) organic polymer is 20,000 or less, the thermal fluidity of the (B) organic polymer and the composition for forming a silicon-containing antireflection film of the present invention containing the same does not deteriorate, and the thin film-forming property of the silicon-containing antireflection film does not deteriorate.

[0230] The organic polymer (B) may further contain a repeating unit represented by the following general formula (2B-1).

[0231]

Chemical formula

[0232] In the general formula (2B-1), R 1 is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms, Y is a divalent organic group having 1 to 30 carbon atoms, R a1 is an optionally substituted saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms. p is an integer of 0 to 5, q3 is an integer of 1 to 6, p + q3 is an integer of 1 or more and 6 or less, and q4 is 0 or 1.

[0233] Here, when q4 is 0, p is an integer from 0 to 3, q3 is an integer from 1 to 4, and p + q3 is an integer from 2 to 4. When q4 is 1, p is an integer from 0 to 5, q3 is an integer from 1 to 6, and p + q3 is an integer from 1 to 6.

[0234] In the general formula (2B-1), R 1 Examples of the saturated monovalent organic group having 1 to 30 carbon atoms and the unsaturated monovalent organic group having 2 to 30 carbon atoms represented by are the same as R 1 in the general formula (2B).

[0235] In the general formula (2B-1), examples of the divalent organic group having 1 to 30 carbon atoms represented by Y include alkane diyl groups such as methylene group, ethanediyl group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, octanediyl group, and decanediyl group; monocyclic cycloalkane diyl groups such as cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cycloheptanediyl group, cyclooctanediyl group, cyclodecanediyl group, methylcyclohexanediyl group, and ethylcyclohexanediyl group; polycyclic cycloalkane diyl groups such as bicyclo[2.2.1]heptane diyl group, bicyclo[2.2.2]octane diyl group, tricyclo[5.2.1.0 2,6 decane diyl group (dicyclopentylene group), tricyclo[3.3.1.1 3,7 decane diyl group, tetracyclo[6.2.1.1 3,6 .0 2,7 dodecane diyl group, adamantane diyl group, etc.; arene diyl groups such as phenylene group and naphthylene group.

[0236] Examples of the alkanediyl oxy group represented by the above Y include groups formed by combining the above alkanediyl group and an oxygen atom. Examples of the cycloalkanediyl oxy group represented by the above Y include groups formed by combining the above cycloalkanediyl group and an oxygen atom.

[0237] Some or all of the hydrogen atoms in the above-mentioned alkandiyl group, cycloalkandiyl group, alkandiyl-oxy group, cycloalkandiyl-oxy group, arenediyl group, etc. may be substituted, and examples of the substituent include, for example, R described later. a1 Examples of the substituent that the organic group represented by may have include the same groups as those exemplified for the substituent that the organic group represented by R may have.

[0238] Examples of the organic group represented by the above Y include groups represented by the following formula. [Chemical formula] (In the above formula, * represents a bond.)

[0239] From the viewpoint of raw material availability, the above Y preferably includes a methylene group.

[0240] Specific examples of the resin having the structural unit represented by the above general formula (2B-1) include the following.

[0241] [Chemical formula]

[0242] [Chemical formula] (In the above formula, R a1 is the same as described above.)

[0243] R a1 Examples of the substituent that the organic group represented by may have include a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms that may be substituted.

[0244] From the viewpoint of thermosetting properties, the above R a1 is preferably either an alkyl group having 1 to 10 carbon atoms or a structure represented by the following general formula (b-1). [Chemical formula] (In the above general formula (b-1), * represents the bonding site to the oxygen atom, and R A is an optionally substituted divalent organic group having 1 to 10 carbon atoms, and R B is a hydrogen atom or an optionally substituted monovalent organic group having 1 to 10 carbon atoms.)

[0245] From the viewpoint of thermal fluidity, the above general formula (b-1) preferably has the following structure.

Chemical formula

[0246] Since the organic polymer (B) contains the repeating unit represented by the above structure, its thermal fluidity is improved, and thus it becomes possible to further improve the thin film forming property of the silicon-containing antireflection film.

[0247] (B) The organic polymer is a high molecular compound containing the repeating unit represented by the above general formula (2B). When it contains the repeating unit represented by the above general formula (2B-1), the content of the repeating unit represented by the general formula (2B-1) is preferably 5 mol% or more and 50 mol% or less with respect to all the repeating units. More preferably, it is 10 mol% or more and 30 mol% or less.

[0248] <(C) Organic solvent> As the (C) organic solvent that can be used in the composition for forming a silicon-containing antireflection film of the present invention, there is no particular limitation as long as it can dissolve or disperse the above (A) silicon-containing polymer, (B) organic polymer, and when included, the following (D) crosslinking agent, (E) acid generator, (F) surfactant, (H) dye, and other additives.

[0249] Specifically, for example, an organic solvent described in paragraphs

[0091] to

[0092] of JP-A-2007-199653 can be added. More specifically, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and γ-butyrolactone, or a mixture containing one or more of these is preferably used.

[0250] (C) The blending amount of the organic solvent is preferably 200 to 10,000 parts by mass, more preferably 250 to 5,000 parts by mass, relative to 100 parts by mass of the (B) organic polymer.

[0251] <(C1) High-boiling solvent> In the composition for forming a silicon-containing antireflection film of the present invention, it is preferable that the (C) organic solvent contains one or more organic solvents having a boiling point of 180°C or higher as the (C1) high-boiling solvent.

[0252] For example, as the (C) organic solvent, a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher ((C1) high-boiling solvent) may be used.

[0253] (C1) As the high-boiling solvent, there are no particular restrictions as long as it can dissolve or disperse each component of the silicon-containing antireflection film-forming composition of the present invention, and examples include hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc. Specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3 - hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, n-nonyl acetate, monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol - n-butyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4 - butanediol diacetate, 1,3 - butylene glycol diacetate, 1,Examples thereof include 6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, triethanolamine, etc., and these may be used alone or in combination.

[0254] (C1) The high-boiling solvent may be appropriately selected from the above examples, etc., according to the temperature for heat-treating the silicon-containing antireflection film-forming composition of the present invention. The boiling point of the high-boiling solvent is preferably 180°C to 300°C, and more preferably 200°C to 300°C. At such a boiling point, the volatilization during baking (heat treatment) does not become too fast, so the occurrence of defects caused by drying during film formation can be suppressed. Also, at such a boiling point, it volatilizes after baking and does not remain in the film, so it does not adversely affect the film physical properties such as etching resistance.

[0255] Also, when using (C1) the high-boiling solvent, the blending amount is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the organic solvent having a boiling point of less than 180°C. At such a blending amount, sufficient heat fluidity can be imparted during baking, and it does not remain in the film and does not lead to deterioration of film physical properties such as etching resistance, so it is preferable.

[0256] <Other components> It is preferable that the silicon-containing antireflection film-forming composition contains one or more selected from (D) a crosslinking agent, (E) an acid generator, (F) a surfactant, and (H) a pigment.

[0257] Hereinafter, components other than the above (A) silicon-containing polymer, (B) organic polymer, and (C) organic solvent that may be included in the silicon-containing antireflection film-forming composition of the present invention will be described.

[0258] <(D) Crosslinking agent> In the composition for forming a silicon-containing antireflection film of the present invention, in order to enhance the density of the silicon-containing antireflection film and improve the poisoning suppression effect of preventing the base component generated from the silicon-containing hard mask (resist intermediate film) from migrating to the photoresist film (resist upper layer film) and degrading the sensitivity and resolution of the resist, it is preferable to add (D) a crosslinking agent. (D) The crosslinking agent is not particularly limited, and various known types of crosslinking agents can be widely used. As an example, a melamine-based crosslinking agent, a glycoluril-based crosslinking agent, a benzoguanamine-based crosslinking agent, a urea-based crosslinking agent, a β-hydroxyalkylamide-based crosslinking agent, an isocyanurate-based crosslinking agent, an aziridine-based crosslinking agent, an oxazoline-based crosslinking agent, an epoxy-based crosslinking agent, and a phenol-based crosslinking agent can be exemplified. The above (D) crosslinking agent can be used alone or in combination of two or more. When adding the (D) crosslinking agent, the addition amount is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, and still more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the composition for forming a silicon-containing antireflection film. If the addition amount is 5 parts by mass or more, sufficient curability can be exhibited, and poisoning to the photoresist film can be suppressed. On the other hand, if the addition amount is 50 parts by mass or less, the ratio of (A) the silicon-containing polymer in the composition for forming a silicon-containing antireflection film does not decrease, so the dry etching resistance does not deteriorate.

[0259] It is preferable that the above (D) crosslinking agent is a compound containing an isocyanuric acid structure, and more preferably has the structure of the following general formula (D-1). [Chemical formula] (In the above formula, X1, X2 and R 3 represent a methyl group, an ethyl group, a propyl group, an allyl group, a propargyl group, a group represented by the following general formula (D-2) or (D-3).)

[0260] [Chemical formula] (In the above formula, R 5represents a methyl group, an ethyl group, a propyl group, an allyl group, or a propargyl group, and R 6 represents a hydrogen atom, an acetyl group, an acryloyl group, a methacryloyl group, a benzoyl group, a toluoyl group, a naphthoyl group, or an anthranoyl group, and * represents a bonding site.)

[0261]

Chemical Structure

[0262] (D) If the crosslinking agent is a compound containing the above structure, when added to the composition for forming a silicon-containing antireflection film, it can form a dense film by crosslinking with polysiloxane during baking. Therefore, it becomes possible to form a silicon-containing antireflection film showing an excellent poisoning suppression effect. Also, it is possible to further improve the adhesion to the resist upper layer film, has a high effect of suppressing the collapse of ultra-fine patterns, and can form a resist pattern with a good pattern shape.)

[0263] Examples of the structure represented by the general formula (D-2) include the following.

[0264]

Chemical Structure

[0265]

Chemical Structure

[0266] Examples of the preferred structure of the crosslinking agent containing the general formula (D-2) include the following structure. R 3 is the same as above.)

[0267] [Chemical formula]

[0268] [Chemical formula]

[0269] [Chemical formula]

[0270] [Chemical formula]

[0271] [Chemical formula]

[0272] Preferred examples of the crosslinking agent containing the structure represented by the general formula (D-3) above can be exemplified by the following structures.

[0273] [Chemical formula]

[0274] [Chemical formula]

[0275] [Chemical formula]

[0276] Preferred examples of the compound represented by the general formula (D-1) above can be exemplified by the following, specifically, R 5 is an allyl group or a propargyl group, R 6 is a hydrogen atom, an acetyl group, or an acryloyl group, R 3is preferably an allyl group or a group represented by the above general formula (D-2), R 5 is an allyl group or a propargyl group, R 6 is a hydrogen atom or an acetyl group, R 3 is more preferably an allyl group.

[0277] [Chemical formula]

[0278] [Chemical formula]

[0279] [(E) Acid generator] One or more acid generators may be further blended in the composition for forming a silicon-containing antireflection film of the present invention. As the (E) acid generator, any substance that acts as an acid precursor such as a thermal acid generator, a photoacid generator, or an acid proliferator may be used. However, in the present invention, it is more preferable that the acid generator to be blended is a sulfonium salt and is a photoacid generator that generates an acid by the action of high-energy rays. Specifically, the materials described in paragraphs

[0061] to

[0085] of JP-A-2007-199653 can be added, but are not limited thereto.

[0280] The above (E) acid generator can be used alone or in combination of two or more. When the (E) acid generator is blended, the blending amount is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the (A) silicon-containing polymer.

[0281] [(F) Surfactant] Furthermore, a (F) surfactant can be incorporated into the composition for forming a silicon-containing antireflection film of the present invention. Specifically, materials described in paragraph

[0185] of JP-A-2009-126940 can be added. When the (F) surfactant is incorporated, the amount thereof is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the (A) silicon-containing polymer.

[0282] <(H) dye> In addition, a (H) dye can be incorporated into the composition for forming a silicon-containing antireflection film of the present invention in order to further improve the resolution during patterning in multilayer lithography. The (H) dye is not particularly limited as long as it is a compound having appropriate absorption at the exposure wavelength, and various known compounds can be widely used. As an example, benzenes, naphthalenes, anthracenes, phenanthrenes, pyrenes, isocyanuric acids, and triazines can be exemplified. When the (H) dye is incorporated, the amount thereof is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the above (A) silicon-containing polymer.

[0283] [Other components] (Crosslinking catalyst) In the present invention, a crosslinking catalyst (Xc) may be incorporated into the composition for forming a silicon-containing antireflection film. Examples of the crosslinking catalyst that can be incorporated include compounds represented by the following general formula (Xc0). L a H b A (Xc0) (In the formula, L is lithium, sodium, potassium, rubidium, cesium, sulfonium, iodonium, phosphonium, or ammonium. A is a non-nucleophilic counter ion. a is an integer of 1 or more, b is 0 or an integer of 1 or more, and a + b is the valence of the non-nucleophilic counter ion.)

[0284] As the crosslinking catalyst used in the present invention for specific (Xc0), there are sulfonium salts of the following general formula (Xc-1), iodonium salts of the following general formula (Xc-2), phosphonium salts of the following general formula (Xc-3), ammonium salts of the following general formula (Xc-4), alkali metal salts, etc., and polysiloxanes (Xc-10) having ammonium salts, sulfonium salts, phosphonium salts, and iodonium salts as part of the structure. Specifically, materials described in paragraphs

[0124] to

[0163] of JP-A-2020-118960 can be added, etc. [Chemical formula] [Chemical formula] (In the formula, R 204 , R 205 , R 206 , and R 207 each represent a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms, and part or all of the hydrogen atoms of these groups may be substituted by an alkoxy group or the like. Also, R 205 and R 206 may form a ring, and when forming a ring, R 205 , R 206 each represent an alkylene group having 1 to 6 carbon atoms. A - represents a non-nucleophilic counter ion. R 208 , R 209 , R 210 , and R 211 are the same as R 204 , R 205 , R 206 , and R 207 but may be a hydrogen atom. R 208 and R 209 , or R 208 and R 209 and R 210 may form a ring, and when forming a ring, R 208 and R 209and R 208 and R 209 and R 210 represents an alkylene group having 3 to 10 carbon atoms.)

[0285] The above crosslinking catalysts (Xc-1), (Xc-2), (Xc-3), (Xc-4), and (Xc-10) can be used alone or in combination of two or more. The compounding amount of the crosslinking catalyst is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, based on 100 parts by mass of the base polymer (for example, (A) silicon-containing polymer).

[0286] The composition for forming a silicon-containing antireflection film of the present invention may further contain the following components.

[0287] (Organic acid) In order to improve the stability of the composition for forming a silicon-containing antireflection film of the present invention, it is preferable to blend a monovalent or divalent or higher organic acid having 1 to 30 carbon atoms. Examples of the acid to be added at this time include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, citric acid, etc. Particularly, oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid, etc. are preferable. Also, in order to maintain stability, two or more acids may be mixed and used.

[0288] The compounding amount of the organic acid is 0.001 to 25 parts by mass, preferably 0.01 to 15 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the (A) silicon-containing polymer contained in the composition for forming a silicon-containing antireflection film of the present invention.

[0289] Alternatively, when the above organic acid is converted to pH of the composition for forming a silicon-containing antireflection film of the present invention, it is preferably formulated so that 0 ≦ pH ≦ 7, more preferably 0.3 ≦ pH ≦ 6.5, and still more preferably 0.5 ≦ pH ≦ 6.

[0290] (Stabilizer) Furthermore, a stabilizer can be blended in the composition for forming a silicon-containing antireflection film of the present invention. As the stabilizer, a monohydric or polyhydric alcohol having a cyclic ether as a substituent can be added. In particular, blending the stabilizer described in paragraphs

[0181] to

[0182] of JP-A-2009-126940 can improve the stability of the composition for forming a silicon-containing antireflection film.

[0291] Furthermore, a basic compound for improving storage stability can be added to the composition for forming a resist underlayer film of the present invention. The basic compound serves as a quencher for an acid to prevent the acid generated in a trace amount from the acid generator from promoting the crosslinking reaction. Specific examples of such a basic compound include those described in paragraphs

[0086] to

[0090] of JP-A-2007-199653.

[0292] <Method for forming a silicon-containing antireflection film> In the present invention, there is provided a method for forming a film that functions as a silicon-containing antireflection film of a multilayer resist film used in lithography, using the above-described composition for forming a silicon-containing antireflection film.

[0293] In the method for forming a silicon-containing antireflection film using the composition for forming a silicon-containing antireflection film of the present invention, the above-described composition for forming a silicon-containing antireflection film is coated on a substrate to be processed by a spin coating method or the like. By using a spin coating method or the like, a silicon-containing antireflection film excellent in thin film formability can be obtained. After spin coating, the solvent is evaporated, and baking (heat treatment) is performed to promote the crosslinking reaction in order to prevent mixing with the resist upper layer film. The baking is preferably performed in the range of 100°C or higher and 600°C or lower for 10 to 600 seconds, more preferably in the range of 200°C or higher and 500°C or lower for 10 to 300 seconds. Considering the influence on device damage and wafer deformation, the upper limit of the heating temperature in the wafer process of lithography is preferably 500°C or lower, more preferably 400°C or lower.

[0294] Also, in the method for forming a silicon-containing antireflection film using the composition for forming a silicon-containing antireflection film of the present invention, the composition for forming a silicon-containing antireflection film of the present invention is coated on a substrate to be processed by the spin coating method or the like as described above, and the composition for forming a silicon-containing antireflection film is fired and cured in an atmosphere having an oxygen concentration of 0.1% by volume or more and 21% by volume or less to form a silicon-containing antireflection film.

[0295] By firing the composition for forming a silicon-containing antireflection of the present invention in such an oxygen atmosphere, a sufficiently cured film can be obtained. The atmosphere during baking may be air, but it is preferable to enclose an inert gas such as N2, Ar, or He to reduce oxygen in order to prevent oxidation of the silicon-containing antireflection film. In order to prevent oxidation, it is necessary to control the oxygen concentration, preferably 1,000 ppm or less, more preferably 100 ppm or less (volume basis). Preventing oxidation of the silicon-containing antireflection film during baking is preferable because it does not increase absorption or reduce etching resistance.

[0296] <Pattern formation method using a silicon-containing antireflection film> In the present invention, as a pattern formation method by a two-layer resist process using the above-described composition for forming a silicon-containing antireflection film, (I-1) A step of forming a silicon-containing antireflection film by applying the composition for forming a silicon-containing antireflection film described above on a substrate to be processed and then performing heat treatment, (I-2) A step of forming a resist upper layer film on the silicon-containing antireflection film using a photoresist material, (I-3) A step of forming a pattern in the resist upper layer film by performing pattern exposure on the resist upper layer film and then developing it with a developer, (I-4) A step of transferring the pattern to the silicon-containing antireflection film by dry etching using the resist upper layer film having the pattern as a mask, and (I-5) A step of processing the substrate to be processed using the silicon-containing antireflection film having the pattern transferred thereto as a mask to form a pattern on the substrate to be processed A pattern formation method having the above steps is provided.

[0297] Since the resist upper layer film of the two-layer resist process exhibits etching resistance to a fluorine-based gas, in the two-layer resist process, it is preferable to perform dry etching of the silicon-containing antireflection film using the resist upper layer film as a mask using an etching gas mainly composed of a fluorine-based gas.

[0298] In the present invention, as a pattern formation method by a three-layer resist process using such a composition for forming a silicon-containing antireflection film, (II-1) A step of forming a resist lower layer film on a substrate to be processed, (II-2) A step of forming a silicon-containing antireflection film by applying the composition for forming a silicon-containing antireflection film described above on the resist lower layer film and then performing heat treatment, (II-3) A step of forming a resist upper layer film on the silicon-containing antireflection film using a photoresist material, (II-4) A step of forming a pattern in the resist upper layer film by performing pattern exposure on the resist upper layer film and then developing it with a developer, (II-5) A step of transferring a pattern to the silicon-containing antireflection film by dry etching using the resist upper layer film on which the pattern is formed as a mask. (II-6) A step of transferring a pattern to the resist lower layer film by dry etching using the silicon-containing antireflection film on which the pattern is transferred as a mask, and (II-7) A step of processing the substrate to be processed using the resist lower layer film on which the pattern is transferred as a mask to form a pattern on the substrate to be processed. provided is a patterning method having the above steps.

[0299] Since the resist lower layer film in the above three-layer resist process exhibits etching resistance to fluorine-based gases, in the above three-layer resist process, it is preferable to perform dry etching of the substrate to be processed using the resist lower layer film as a mask using an etching gas mainly composed of a fluorine-based gas.

[0300] A method for forming a pattern by a three-layer resist process will be described with reference to FIG. 2. In the present invention, as a method for forming a pattern by a three-layer resist process using such a composition for forming a silicon-containing antireflection film, as shown in FIG. 2(G), a resist lower layer film 3 is formed on a layer to be processed 2 on a substrate to be processed 1 using a resist lower layer film material. A silicon-containing antireflection film 4 is formed on the resist lower layer film using the above-described composition for forming a silicon-containing antireflection film. A resist upper layer film 6 is formed on the silicon-containing antireflection film using a photoresist material. Subsequently, as shown in FIG. 2(H), after the exposed portion 7 of the resist upper layer film is pattern-exposed, as shown in FIG. 2(I), it is developed with a developer to form a resist upper layer film pattern 6a on the resist upper layer film. As shown in FIG. 2(J), using the resist upper layer film on which the pattern is formed as a mask, a silicon-containing antireflection film pattern 4a is transferred to the silicon-containing antireflection film by dry etching. As shown in FIG. 2(K), using the silicon-containing antireflection film on which the pattern is transferred as a mask, a resist lower layer film pattern 3a is transferred to the resist lower layer film by dry etching. As shown in FIG. 2(L), using the resist lower layer film on which the pattern is formed as a mask, the layer to be processed on the substrate to be processed is processed to form a pattern 2a on the substrate to be processed 1, thereby providing a pattern forming method.

[0301] In addition, in the present invention, as a method for forming a pattern by a four-layer resist process using such a composition for forming a silicon-containing antireflection film, (III-1) a step of forming a resist lower layer film on a substrate to be processed, (III-2) a step of forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist lower layer film, (III-3) a step of forming a silicon-containing antireflection film by applying the composition for forming a silicon-containing antireflection film described above on the inorganic hard mask intermediate film and then performing heat treatment, (III-4) a step of forming a resist upper layer film on the silicon-containing antireflection film using a photoresist material, (III-5) After pattern-exposing the resist upper layer film, developing it with a developer to form a pattern in the resist upper layer film; (III-6) Using the resist upper layer film on which the pattern is formed as a mask, transferring the pattern to the silicon-containing antireflection film and the inorganic hard mask intermediate film by dry etching; (III-7) Using the inorganic hard mask intermediate film on which the pattern is transferred as a mask, transferring the pattern to the resist lower layer film by dry etching, and (III-8) Using the resist lower layer film on which the pattern is transferred as a mask to process the substrate to be processed and form a pattern on the substrate to be processed provided is a patterning method having the above steps.

[0302] With the above patterning method, in a fine patterning process using ArF immersion and high-NA exposure conditions in a semiconductor device manufacturing process, it becomes possible to transfer a resist pattern shape onto a substrate to be processed with high precision.

[0303] A method for forming a pattern by a four-layer resist process will be described with reference to FIG. 1. In the present invention, as a method for forming a pattern by a three-layer resist process using such a composition for forming a silicon-containing antireflection film, as shown in FIG. 1(A), a resist underlayer film 3 is formed on a layer to be processed 2 on a substrate to be processed 1 using a resist underlayer film material. An inorganic hard mask intermediate film 5 is formed on the resist underlayer film using an inorganic hard mask intermediate film material. A silicon-containing antireflection film 4 is formed on the inorganic hard mask intermediate film using the composition for forming a silicon-containing antireflection film. A resist upper layer film 6 is formed on the silicon-containing antireflection film using a photoresist material. Subsequently, as shown in FIG. 1(B), after the exposed portion 7 of the resist upper layer film is pattern-exposed, as shown in FIG. 1(C), it is developed with a developer to form a resist upper layer film pattern 6a on the resist upper layer film. As shown in FIG. 1(D), using the resist upper layer film on which the pattern is formed as a mask, a silicon-containing antireflection film pattern 4a and an inorganic hard mask intermediate film pattern 5a are transferred to the silicon-containing antireflection film and the inorganic hard mask intermediate film by dry etching. As shown in FIG. 1(E), using the silicon-containing antireflection film and the inorganic hard mask intermediate film on which the pattern is transferred as a mask, a resist underlayer film pattern 3a is transferred to the resist underlayer film by dry etching. As shown in FIG. 1(F), using the resist underlayer film on which the pattern is formed as a mask, the layer to be processed on the substrate to be processed is processed to form a pattern 2a on the substrate to be processed 1, thereby providing a pattern formation method.

[0304] As an example of the above pattern formation method, using the resist pattern as an etching mask, the silicon-containing antireflection film and the inorganic hard mask intermediate film (resist intermediate film) are processed by dry etching using a fluorine-based gas, using the inorganic hard mask intermediate film pattern as an etching mask, the organic resist underlayer film (resist underlayer film) is processed by dry etching using an oxygen-based gas, a method of processing the substrate to be processed by dry etching using a fluorine-based gas with the organic resist underlayer film pattern as an etching mask, may be mentioned.

[0305] <Organic resist underlayer film (resist underlayer film)> Examples of the organic resist underlayer film material that can be used for the organic resist underlayer film (resist underlayer film) include those that are already known as the underlayer film for the three-layer resist method or the two-layer resist method using a silicon resist composition. For example, the resins and compositions disclosed in JP-A-2012-001687, JP-A-2012-077295, JP-A-2004-264710, JP-A-2005-043471, JP-A-2005-250434, JP-A-2007-293294, JP-A-2008-065303, JP-A-2004-205685, JP-A-2007-171895, JP-A-2009-014816, JP-A-2007-199653, JP-A-2008-274250, JP-A-2010-122656, JP-A-2012-214720, JP-A-2014-029435, WO2012 / 077640, WO2010 / 147155, WO2012 / 176767, JP-A-2005-128509, JP-A-2006-259249, JP-A-2006-259482, JP-A-2006-293298, JP-A-2007-316282, JP-A-2012-145897, JP-A-2017-119671, JP-A-2019-044022, etc. can be exemplified.

[0306] The above resist underlayer film can be formed on a substrate to be processed, for example, by using a composition solution containing the above organic resist underlayer film material and a spin coating method or the like. After forming the organic resist underlayer film by a spin coating method or the like, it is desirable to bake it to evaporate the organic solvent. The baking temperature is preferably in the range of 100 to 600°C, and the baking time is preferably in the range of 10 to 300 seconds.

[0307] Instead of the above organic resist underlayer film material, it is also possible to apply an organic hard mask formed by CVD method or ALD method. In the pattern forming method of the present invention, it is preferable to apply an organic hard mask formed by CVD method.

[0308] By using an organic hard mask formed by CVD method on the organic resist underlayer film, it becomes possible to process the resist pattern shape with high precision on the substrate to be processed. The organic hard mask formed by CVD method shows higher resistance to dry etching using fluorine-based gas than the organic resist underlayer film formed of the organic resist underlayer film material, and thus is useful for forming fine patterns.

[0309] It is preferable that the organic resist underlayer film contains any one of a graphene film, an amorphous carbon film, and a diamond-like carbon film.

[0310] In the pattern formation method using the resist underlayer film, since the organic resist underlayer film shows high resistance to the fluorine-based gas used when processing the substrate to be processed by dry etching, it becomes possible to process the resist pattern shape with high precision on the substrate to be processed.

[0311] The thickness of the resist underlayer film is preferably 10 to 1,000 nm, more preferably 15 nm to 100 nm, and still more preferably 20 nm to 50 nm.

[0312] <Silicon-containing hard mask (resist intermediate film)> Examples of the silicon-containing hard mask material that can be used for the silicon-containing hard mask (resist intermediate film) include polysiloxane-based resist intermediate film materials. For example, those described in Japanese Patent No. 471603 can be cited.

[0313] In conventional silicon-containing hard mask materials, polysiloxanes having pendant phenyl groups or light-absorbing groups having silicon-silicon bonds to provide an antireflection effect and crosslinked by acid or heat are preferably used. Since they contain many organic groups, there is a risk of deteriorating the pattern shape when dry-etching the organic resist underlayer film with an oxygen-based gas. On the other hand, in the pattern formation method of the present invention, by providing the silicon-containing antireflection film with an antireflection function, reflection can be suppressed. Therefore, the silicon-containing hard mask material can be designed to minimize organic groups that deteriorate dry-etching resistance, and high-precision processing of the substrate to be processed can be realized.

[0314] The above silicon-containing hard mask can be formed on a substrate to be processed by, for example, a spin coating method or the like using a composition solution containing the above silicon-containing hard mask material. After forming the silicon-containing hard mask by a spin coating method or the like, it is desirable to bake it to evaporate the organic solvent. The baking temperature is preferably in the range of 100 to 600 °C, and the baking time is preferably in the range of 10 to 300 seconds.

[0315] Instead of the above silicon-containing hard mask material, it is also possible to apply an inorganic hard mask intermediate film formed by a CVD method or an ALD method. Specifically, it is preferably a layer selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film. For example, as a method for forming a silicon nitride film, it is described in JP-A-2002-334869 and WO 2004 / 066377.

[0316] In the pattern formation method of the present invention, it is preferable to apply an inorganic hard mask intermediate film (a layer selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film) formed by a CVD method.

[0317] In the case of the pattern formation method using the above inorganic hard mask intermediate film, since it shows high resistance to the oxygen-based gas used when processing the organic resist lower layer film by dry etching, it becomes possible to process the resist pattern shape with high precision onto the substrate to be processed. Further, in the pattern formation method of the present invention, when the above inorganic hard mask is used, it exhibits an excellent effect from the viewpoint of suppressing poisoning from the resist lower layer film and the substrate to the photoresist layer (resist upper layer film), and thus is useful in the formation of fine patterns.

[0318] The film thickness of the silicon-containing hard mask is preferably 5 to 200 nm, more preferably 10 to 100 nm. Further, as the silicon-containing hard mask, a silicon oxynitride film (SiON) having a high effect as an antireflection film is most preferably used. Since the substrate temperature when forming the SiON film is 300 to 500 °C, the organic resist lower layer film needs to withstand a temperature of 300 to 500 °C.

[0319] <Silicon-containing antireflection film> It is preferable to form a silicon-containing antireflection film using the composition for forming a silicon-containing antireflection film of the present invention.

[0320] The ratio (b) of silicon in the silicon-containing antireflection film measured by RBS (Rutherford backscattering spectrometry) is preferably 5 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 5 to 20% by mass. If the ratio (b) of silicon in the silicon-containing antireflection film is 5% by mass or more, a film with a high refractive index can be formed, and the antireflection function can be improved. If the ratio (b) of silicon in the silicon-containing antireflection film is 30% by mass or less, the acceleration of the etching rate with respect to the fluorine-based gas can be suppressed, and the selectivity with respect to the silicon-containing hard mask (resist intermediate film) can be improved.

[0321] In the case of the silicon-containing antireflection film as described above, since the etching rate of the silicon-containing antireflection film with respect to the fluorine-based gas is slower than that of the silicon-containing hard mask (resist intermediate film), it becomes possible to transfer the resist pattern shape to the silicon-containing hard mask (resist intermediate film) with high precision.

[0322] It is preferable that the film thickness of the silicon-containing antireflection film is 12 nm or less.

[0323] <Photoresist film (resist upper layer film)> In the pattern forming method of the present invention, the composition for the resist upper layer film is not particularly limited as long as it is composed of a chemically amplified photoresist composition. In the present invention, since either positive development using an alkaline developer or negative development using an organic solvent developer can be employed, a positive resist upper layer film material or a negative resist upper layer film material may be appropriately selected according to the developing method.

[0324] The thickness of the resist upper layer film is not particularly limited, but is preferably 10 to 500 nm, particularly preferably 20 to 200 nm.

[0325] In the positive pattern forming method, after forming the resist upper layer film and performing heat treatment, exposure is performed, and usually, alkaline development is performed using an alkaline developer to obtain a positive resist pattern. Further, it is preferable to perform post-exposure bake (PEB) after exposure.

[0326] As the alkaline developer, an aqueous solution of tetramethylammonium hydroxide (TMAH) or the like can be used.

[0327] In the negative pattern forming method, after forming the resist upper layer film and performing heat treatment, exposure is performed, and usually, organic solvent development is performed using an organic solvent to obtain a negative resist pattern. Further, it is preferable to perform PEB after exposure.

[0328] As the developer of the organic solvent, a developer containing one or more selected from 4-methyl-2-pentanol, 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butenyl acetate, isoamyl acetate, phenyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, 2-phenylethyl acetate, etc. as components can be used.

[0329] In addition, the photoresist composition may contain metal atoms such as Sn, In, Ga, Ge, Al, Ce, La, Cs, Zr, Hf, Ti, Bi, and Sb. When forming a resist upper layer film with the above photoresist composition, it may be formed by a spin coating method or a vapor deposition treatment method by CVD method or ALD method.

[0330] When forming a resist upper layer film by vapor deposition treatment by CVD method or ALD method, the photoresist composition is an EUV photosensitive metal oxide, the metal is selected from Sn, Zr, Hf, Ti, Bi, and Sb, etc., and among them, Sn with excellent EUV photosensitivity is preferable. The metal oxide may be a photosensitive organometallic oxide such as an organotin oxide (for example, haloalkyl Sn, alkoxyalkyl Sn, or amidoalkyl Sn). Some specific examples of suitable precursors include trimethyltin chloride, dimethyltin dichloride, methyltin trichloride, tris(dimethylamino)methyltin(IV), and (dimethylamino)trimethyltin(IV).

[0331] The metal oxide may be deposited, for example, by PECVD or PEALD using a Lam Vector (registered trademark) tool. In the ALD example, the Sn oxide precursor is separated from the O precursor / plasma. The deposition temperature preferably ranges from 50°C to 600°C. The deposition pressure preferably ranges between 100 and 6,000 mTorr. The flow rate of the metal oxide precursor liquid (e.g., an organic tin oxide precursor) may be 0.01 to 10 cmm, and the gas flow rate (CO2, CO, Ar, N2) may be 100 to 10,000 sccm. The plasma power may be 200 to 1,000 W per 300 mm wafer station using a high-frequency plasma (e.g., 13.56 MHz, 27.1 MHz, or a higher frequency). The deposition thickness is preferably 100 to 2,000 Å.

[0332] Examples of the exposure light include high-energy rays with a wavelength of 300 nm or less, specifically, excimer lasers of 248 nm, 193 nm, and 157 nm, soft X-rays of 3 to 20 nm, electron beams, X-rays, and the like.

[0333] As the method for forming the pattern of the resist upper layer film, it is preferable to form a pattern by photolithography with a wavelength of 5 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination thereof.

[0334] The workpiece (workpiece substrate) is not particularly limited, and substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., and those with a processed layer formed on the substrate are used. As the processed layer, various Low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, etc., and their stopper films are used, and they can usually be formed to a thickness of 30 to 10,000 nm, particularly 50 to 5,000 nm. When forming the processed layer, the substrate and the processed layer are made of different materials.

Example

[0335] The present invention will be described in more detail below with reference to synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited thereto. The weight average molecular weight and dispersity were determined in terms of polystyrene by gel permeation chromatography (GPC) using RI as a detector and tetrahydrofuran as an eluent solvent, with polystyrene as a standard substance.

[0336] [Synthesis Examples 1 to 10] Synthesis of polysiloxanes (A1) to (A4) for silicon-containing antireflection films, polycarbosilane (A5) for silicon-containing antireflection films, and polysilanes (A6) to (A10) for silicon-containing antireflection films

[0337] (Synthesis Example 1) Synthesis of polysiloxane (A1) for silicon-containing antireflection film

Chemical formula

[0338] (Synthesis Example 2) Synthesis of polysiloxane (A2) for silicon-containing antireflection film

Chemical formula

[0339] (Synthesis Example 3) Synthesis of polysiloxane (A3) for silicon-containing antireflection film [Chemical formula] 120 g of methanol, 0.1 g of 10% nitric acid, and 60 g of ultrapure water were added and made into a uniform solution at 40°C under a nitrogen atmosphere. Then, a mixture of 38.1 g of tetramethoxysilane, 30.6 g of methyltrimethoxysilane, and 5.9 g of 3-glycidoxypropyltrimethoxysilane was slowly dropped. After dropping, a hydrolysis and condensation reaction was carried out at 40°C for 12 hours. After the reaction was completed, 600 g of PGEE (propylene glycol monoethyl ether) was added, and water and by-produced alcohol were distilled off to recover 440 g of a PGEE solution of the polysiloxane compound (A3) for a silicon-containing antireflection film (compound concentration 10%). When the polystyrene-reduced molecular weight of the polysiloxane compound (A3) for a silicon-containing antireflection film was measured, Mw = 2,900.

[0340] (Synthesis Example 4) Synthesis of polysiloxane (A4) for silicon-containing antireflection film [Chemical formula] To a mixture of 120 g of methanol, 0.1 g of 10% nitric acid, and 60 g of deionized water, a mixture of 20.4 g of methyltrimethoxysilane, 45.7 g of tetramethoxysilane, and 20.1 g of the compound of the following formula (A4-1) was added, and the mixture was maintained at 40 °C for 12 hours for hydrolysis and condensation. After completion of the reaction, 500 g of PGEE (propylene glycol monoethyl ether) was added, and the water and by-produced alcohol used for hydrolysis and condensation were distilled off under reduced pressure to obtain 450 g of a PGEE solution (compound concentration: 10%) of the polysiloxane compound (A4) for a silicon-containing antireflection film. When the polystyrene-equivalent molecular weight of the polysiloxane compound (A4) for a silicon-containing antireflection film was measured, Mw = 2,200. [Chemical formula]

[0341] (Synthesis Example 5) Synthesis of polycarbosilane (A5) for a silicon-containing antireflection film In a nitrogen-filled reaction vessel, 2.9 g of magnesium and 5.5 g of tetrahydrofuran were added and stirred at 20 °C. Next, 8.7 g of the compound represented by the following formula (Z-1), 2.2 g of the compound represented by the following formula (Z-2), and 4.7 g of the compound represented by the following formula (Z-3) were dissolved in 56 g of tetrahydrofuran to prepare a monomer solution. The temperature inside the reaction vessel was set to 20 °C, and while stirring, the above monomer solution was added dropwise over 1 hour. The end of the dropwise addition was taken as the start time of the reaction, and the reaction was carried out at 40 °C for 1 hour and then at 60 °C for 3 hours. After completion of the reaction, 33 g of tetrahydrofuran was added, and the polymerization solution was ice-cooled and cooled to 10 °C or lower. After adding 15.2 g of triethylamine to the cooled polymerization solution, 4.8 g of methanol was added dropwise from a dropping funnel over 10 minutes while stirring. The end of the dropwise addition was taken as the start time of the reaction, and the reaction was carried out at 20 °C for 1 hour. The polymerization solution was poured into 110 g of diisopropyl ether, and the precipitated salt was filtered off. Next, using an evaporator, tetrahydrofuran, excess triethylamine, and excess methanol in the filtrate were removed. The obtained residue was poured into 28 g of diisopropyl ether, the precipitated salt was filtered off, and 20 g of cyclohexanone was added to the filtrate. By removing diisopropyl ether in the solution using an evaporator, a cyclohexanone solution of polycarbosilane (A5) for a silicon-containing antireflection film with a solid content concentration of 8% by mass was obtained. The Mw of polycarbosilane (A5) for a silicon-containing antireflection film was 1,960. [Chemical formula]

[0342] (Synthesis Example 6) Synthesis of polysilane (A6) for a silicon-containing antireflection film 10.0 g of Ogsoal SI-10-20 (Mw 1,900) manufactured by Osaka Gas Chemical Co., Ltd. was dissolved in 100.0 g of tetrahydrofuran, and 6.0 g of triethylamine and 16.0 g of ultrapure water were added. After reacting this solution under reflux for 7 hours, 375 g of propylene glycol monoethyl ether (PGEE) was added and concentrated under reduced pressure to obtain 91.3 g of a PGEE solution of polysilane (A6) for a silicon-containing antireflection film (polymer concentration 11%). The Mw was 980.

[0343] (Synthesis Example 7) Synthesis of polysilane (A7) for silicon-containing antireflection film 10.0 g of Ogsoal SI-20-10 (Mw 1,300) manufactured by Osaka Gas Chemical Co., Ltd. was dissolved in 100.0 g of tetrahydrofuran, and 2.0 g of 29% aqueous ammonia and 6.0 g of ultrapure water were added. After reacting this solution under reflux for 6.5 hours, 250 g of propylene glycol monoethyl ether (PGEE) was added and concentrated under reduced pressure to obtain 70.3 g of a PGEE solution of polysilane (A7) for silicon-containing antireflection film (polymer concentration 15%). Mw was 870.

[0344] (Synthesis Example 8) Synthesis of polysilane (A8) for silicon-containing antireflection film 10.0 g of Ogsoal SI-20-10 modified (Mw 1,400) manufactured by Osaka Gas Chemical Co., Ltd. was dissolved in 100.0 g of tetrahydrofuran, and 6.0 g of triethylamine and 16.0 g of ultrapure water were added. After reacting this solution under reflux for 12 hours, 250 g of propylene glycol monoethyl ether (PGEE) was added and concentrated under reduced pressure to obtain 71.3 g of a PGEE solution of polysilane (A8) for silicon-containing antireflection film (polymer concentration 14%). Mw was 830.

[0345] (Synthesis Example 9) Synthesis of polysilane (A9) for silicon-containing antireflection film A mixture of 120 g of PGEE, 1 g of 70% nitric acid, and 60 g of deionized water was added to a mixture of 17.0 g of methyltrimethoxysilane, 5.0 g of phenyltrimethoxysilane, 45.7 g of tetramethoxysilane, and 54.6 g of a PGEE solution of polysilane (A6) for silicon-containing antireflection film, and the mixture was held at 40 °C for 12 hours for hydrolysis and condensation. After completion of the reaction, 300 g of PGEE was added, and by-products alcohol and excess water were distilled off under reduced pressure to obtain 300 g of a PGEE solution of polysilane (A9) for silicon-containing antireflection film (polymer concentration 12%). Mw was 3,000.

[0346] (Synthesis Example 10) Synthesis of polysilane (A10) for silicon-containing antireflection film To a mixture of 80 g of PGEE, 1 g of 70% nitric acid, and 60 g of deionized water, a mixture of 17.0 g of methyltrimethoxysilane, 5.0 g of phenyltrimethoxysilane, 45.7 g of tetramethoxysilane, and 43.6 g of a PGEE solution of polysilane (A8) for silicon-containing antireflection film was added, and the mixture was maintained at 40 °C for 12 hours for hydrolysis and condensation. After completion of the reaction, 300 g of PGEE was added, and by-produced alcohol and excess water were distilled off under reduced pressure to obtain 320 g of a PGEE solution of polysilane (A10) for silicon-containing antireflection film (polymer concentration: 11%). Mw was 2,900.

[0347] [Synthesis of (B) organic polymers (B1) to (B9) and polymer compounds (R1) to (R2)] (B) As polymer compounds of organic polymers, (B1) to (B9) and comparative polymer compounds (R1) to (R2) were synthesized. The following monomers (J1) to (J9) were used for the preparation of these polymer compounds. [Chemical formula]

[0348] (Synthesis Example 11) Synthesis of organic polymer (B1) 37.5 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80 °C under a nitrogen atmosphere. To this, a mixture of 50.0 g of (J1) and 82.5 g of PGMEA and a mixture of 4.2 g of dimethyl 2,2-azobis(2-methylpropionate) and 30.0 g of PGMEA were added simultaneously and separately over 2 hours. After further heating and stirring for 24 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (B1). As a result of analysis, the weight average molecular weight (Mw) of the polymer (B-1) was 10,100, and the dispersity (Mw / Mn) was 2.1.

[0349] [Synthesis of organic polymers (B2) to (B9) and polymer compounds (R1) to (R2) (Synthesis Examples 12 to 19, Comparative Synthesis Examples 1 and 2)] (B1) was synthesized under the same conditions, using the raw materials shown in Table 1, to synthesize organic polymers (B2) to (B9) and polymer compounds (R1) to (R2), and the target products were obtained respectively. The results are shown in Table 1.

[0350]

Table 1

[0351] [Synthesis of (B) Organic Polymers (B10) to (B14)] (B) Resins of organic polymers (B10) to (B14) and comparative resins (R3) to (R5) were synthesized. The following resin raw materials (K1) to (K9), which are monomers, were used for the preparation of these resins.

[0352]

Chemical formula

[0353] (Synthesis Example 20) Synthesis of Resin (B10)

Chemical formula

[0354] (Synthesis Example 21) Synthesis of Resin (B11) [Chemistry] Under a nitrogen atmosphere, 144.2 g of resin raw material (K2), 95.8 g of resin raw material (K6), and 250 g of PGME (propylene glycol monomethyl ether) were added and homogenized at an internal temperature of 100°C. Then, a mixed solution of 3.0 g of paratoluenesulfonic acid monohydrate and 7.1 g of PGME, which had been previously mixed and homogenized, was slowly added dropwise, and the reaction was carried out at an internal temperature of 120°C for 8 hours. After the reaction was completed, it was cooled to room temperature, 2,000 ml of MIBK was added, and it was washed 6 times with 500 ml of pure water. The organic layer was dried under reduced pressure to obtain resin (B11). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B11): Mw = 8,500, Mw / Mn = 2.65

[0355] (Synthesis Example 22) Synthesis of organic polymer (B12) [Chemistry] Under a nitrogen atmosphere, 160.2 g of resin raw material (K3), 40.6 g of resin raw material (K6), and 250 g of PGME (propylene glycol monomethyl ether) were added and homogenized at an internal temperature of 100°C. Then, a mixed solution of 3.2 g of paratoluenesulfonic acid monohydrate and 8.0 g of PGME, which had been previously mixed and homogenized, was slowly added dropwise, and the reaction was carried out at an internal temperature of 120°C for 8 hours. After the reaction was completed, it was cooled to room temperature, 2,000 ml of MIBK was added, and it was washed 6 times with 500 ml of pure water. The organic layer was dried under reduced pressure to obtain resin (B12). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B12): Mw = 3,400, Mw / Mn = 2.54

[0356] (Synthesis Example 23) Synthesis of resin (B13) [Chemistry] Under a nitrogen atmosphere, 160.2 g of resin raw material (K4), 40.6 g of resin raw material (K6), and 300 g of PGME (propylene glycol monomethyl ether) were added and homogenized at an internal temperature of 100°C. Then, a mixed solution of 3.2 g of p-toluenesulfonic acid monohydrate and 8.0 g of PGME, which had been previously mixed and homogenized, was slowly added dropwise, and the reaction was carried out at an internal temperature of 120°C for 8 hours. After the reaction was completed, it was cooled to room temperature, 2,000 ml of MIBK was added, washed 6 times with 500 ml of pure water, and the organic layer was dried under reduced pressure to obtain resin (B13). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B13): Mw = 3,300, Mw / Mn = 2.41

[0357] (Synthesis Example 24) Synthesis of resin (B14)

Chemical formula

[0358] (Synthesis Example 25) Synthesis of resin (B15)

Chemical formula

[0359] (Comparative Synthesis Example 3) Synthesis of Comparative Example Resin (R3)

Chemical formula

[0360] (Comparative Synthesis Example 4) Synthesis of Comparative Example Resin (R4)

Chemical formula

[0361] (Comparative Synthesis Example 5) Synthesis of the resin for comparative example (R5) [Chemical formula] Under a nitrogen atmosphere, 20.0 g of resin (B11), 45.3 g of potassium carbonate, and 100 g of DMF were added to form a homogeneous dispersion at an internal temperature of 50°C. 40.3 g of 3-bromo-1-propyne was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. 300 ml of methyl isobutyl ketone and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, then the separated aqueous layer was removed. The obtained organic layer was added to 1,500 g of hexane, and the upper layer was removed. Then it was dissolved again with 300 ml of methyl isobutyl ketone, washed 6 times with 100 g of 3% aqueous nitric acid solution and 100 g of pure water, and the organic layer was dried under reduced pressure to obtain the resin for comparative example (R5). When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (R5): Mw = 7,800, Mw / Mn = 3.05

[0362] Preparation of compositions for forming silicon-containing antireflection films (UDL-1 to 22, Comparative Examples UDL-1 to 6) (A) Silicon-containing polymers (A1) to (A10), (B) organic polymers (B1) to (B15), organic polymers for comparative examples (R1) to (R5), crosslinking agents (D1) to (D3), a crosslinking catalyst, photoacid generators (AG1) to (AG4), and a high-boiling solvent (C-1) were dissolved in an organic solvent containing 0.1% by mass of FC-4430 (purified by the company itself, manufactured by 3M Corporation) at the ratios shown in Tables 2 to 4, and filtered through a 0.1-μm fluororesin filter to prepare silicon-containing antireflection film-forming compositions (UDL-1 to 22, comparative example UDL-1 to 6).

[0363]

Table 2

[0364]

Table 3

[0365]

Table 4

[0366] The crosslinking agents (D1) to (D3) used were as follows.

Chemical formula

[0367] The crosslinking catalyst used was as follows. TPSNO3... Triphenylsulfonium nitrate QBANO3... Tetrabutylammonium nitrate

[0368] The solvents used were as follows. PGEE... Propylene glycol monoethyl ether PGMEA... Propylene glycol monomethyl ether acetate CyHO... Cyclohexanone

[0369] The photoacid generator used is as shown in Table 5 below. [Table 5]

[0370] [Solvent resistance evaluation (Examples 1-1 to 1-22, Comparative Examples 1-1 to 1-6)] The silicon-containing antireflection film-forming composition (UDL-1 to 22, Comparative Example UDL-1 to 6) prepared above was applied onto a silicon substrate and baked at 220°C for 60 seconds. After that, the film thickness from the center part to the outer peripheral part of the substrate was measured to calculate the average film thickness (a [nm]). Subsequently, PGMEA solvent was dispensed thereon, left standing for 30 seconds, spin-dried, baked at 100°C for 60 seconds to evaporate PGMEA, and the film thickness (b [nm]) was measured. The film thickness difference before and after PGMEA treatment (remaining film ratio: (b / a)×100) was determined. The results are shown in Table 6.

[0371] [Table 6]

[0372] In Examples 1-1 to 1-22 using the silicon-containing antireflection film-forming composition (UDL-1 to 22) of the present invention, the remaining film ratio ((b / a)×100) after PGMEA rinse treatment was 99% or more, indicating that a crosslinking reaction occurred and sufficient solvent resistance was exhibited.

[0373] [Thin film formability (Examples 2-1 to 2-22, Comparative Examples 2-1 to 2-6)] The silicon-containing antireflection film-forming composition (UDL-1 to 22, Comparative Example UDL-1 to 6) prepared above was applied onto a silicon substrate and baked at 220°C for 60 seconds. By this operation, silicon-containing antireflection films with film thicknesses adjusted to 12 nm, 10 nm, and 7 nm respectively were formed. After that, a single-layer resist for ArF of the resist upper layer film material was applied thereon and baked at 105°C for 60 seconds to form a photoresist film with a film thickness of 100 nm. A liquid immersion protective film material (TC-1) was applied onto the photoresist film and baked at 90°C for 60 seconds to form a protective film with a film thickness of 50 nm.

[0374] As a resist upper layer film material (single-layer resist for ArF), a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) were dissolved in a solvent containing 0.1% by mass of surfactant FC-4430 (manufactured by Sumitomo 3M Limited) at the ratios shown in Table 7, and filtered through a 0.1-μm fluororesin filter.

[0375] [Table 7]

[0376] The polymer (RP1), acid generator (PAG1), and basic compound (Amine1) used in the resist upper layer film material (single-layer resist for ArF) are shown below. [Chemical formula]

[0377] As an immersion protective film material (TC-1), a protective film polymer (PP1) was dissolved in an organic solvent at the ratios shown in Table 8, and filtered through a 0.1-μm fluororesin filter.

[0378] [Table 8]

[0379] The polymer (PP1) used in the immersion protective film material (TC-1) is shown below. [Chemical formula]

[0380] Next, it was exposed using an ArF immersion exposure apparatus (manufactured by Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% halftone phase shift mask), baked at 100 °C for 60 seconds (PEB), developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds, and a 10-μm 1:1 positive line-and-space pattern (resist pattern) was obtained. Using a length-measuring SEM (CG5000) manufactured by Hitachi High-Technologies Corporation, the film-forming property of the silicon-containing antireflection film was evaluated. Specifically, the focus was adjusted using the line pattern obtained above, and the film-forming property of the silicon-containing antireflection film on which the space pattern was formed was observed. When no film-forming defect such as a sea-island structure occurred, it was rated "good", and when a sea-island structure was observed, it was rated "bad". The results are shown in Table 9.

[0381] Also shown in Table 9 are the results of evaluation when the underlayer of the silicon-containing antireflection film was changed from a silicon substrate to a silicon oxynitride film (SiON).

[0382] The structural formulas of the ArF silicon-containing intermediate film polymer (SiP1) and the crosslinking catalyst (CAT1) used for the formation of the silicon oxynitride film (SiON) are shown below.

Chemical formula

[0383]

Table 9

[0384] The silicon-containing antireflection film formed using the composition for forming a silicon-containing antireflection film of the present invention showed excellent film-forming property in the formation of a thin film with a thickness of 12 nm.

[0385] On the other hand, different from the composition for forming a silicon-containing antireflection film of the present invention, Comparative Examples 2-1 to 2-6 using Comparative Examples UDL-1 to 6 which do not contain an (B) organic polymer that is a polymer containing two or more hydroxyl groups in the repeating unit structure of the polymer and does not contain silicon, observed a sea-island structure that seems to be derived from aggregation in the formation of a thin film with a film thickness of 12 nm. It is presumed that this is because the affinity with the underlying substrate was insufficient and aggregation of the silicon-containing polymer occurred.

[0386] Among the (B) organic polymers to be added, the silicon-containing antireflection films formed using UDL-1 to 6, 10 to 15, and 22 which contain only a polymer containing two or more hydroxyl groups in the repeating unit structure of the polymer and do not contain silicon showed excellent film-forming properties even in the formation of a thin film with a film thickness of 10 nm. It is considered that the higher the proportion of the polymer containing two or more hydroxyl groups in the repeating unit structure of the polymer and not containing silicon in the (B) organic polymer, the better the affinity with the underlying substrate and the better the film-forming properties of the silicon-containing antireflection film.

[0387] In addition, the silicon-containing antireflection films formed using UDL-10 to 14 and 22 with the polymer having the structure of the general formula (2B) used in the (B) organic polymer showed excellent film-forming properties even in the further formation of a thin film with a film thickness of 7 nm. Although the cause is not clear, since the polymer having the structure of the general formula (2B) has excellent heat resistance, it is presumed that the thermosetting property and the heat fluidity are improved with respect to the composition for forming a silicon-containing antireflection film using the polymer having the structure of the general formula (1B), and the aggregation of the silicon-containing polymer during baking is suppressed.

[0388] [Optical Constant Evaluation (Examples 3-1 to 3-5, Comparative Example 3-1)] The composition for forming a silicon-containing antireflection film (UDL-2, 6, 10, 14, 22, Comparative Example UDL-1) prepared above was applied onto a silicon substrate, baked at 220 °C for 60 seconds, and then the optical constants (refractive index n, extinction coefficient k) at a wavelength of 193 nm were determined using a variable angle spectroscopic ellipsometer (VASE) manufactured by J.A. Woollam Co., Ltd. The results are shown in Table 10 below.

[0389]

Table 10

[0390] For Examples 3-1 to 3-5 using the composition for forming a silicon-containing antireflection film containing the silicon-containing polymer (A2), all the optical constants were between an n value of 1.70 to 1.85 and a k value of 0.3 to 0.40. The composition for forming a silicon-containing antireflection film of the present invention is a composition containing (B) an organic polymer in order to improve the thin film forming property. However, it can be seen that the change in the optical constants from the composition of the (A) silicon-containing polymer alone is small, and the deterioration of the antireflection performance essential for the antireflection film can be suppressed to a minimum. On the other hand, the higher the content of the (B) organic polymer contained in the composition for forming a silicon-containing antireflection film, the lower the optical constant n. Therefore, it can be said that the addition amount is preferably 50 parts by mass or less with respect to 100 parts by mass of the (A) silicon-containing polymer.

[0391] Regarding the optical constants, although they also depend on the film thickness, the type of laminated film, etc., generally, if they are between an n value of 1.70 to 2.05 and a k value of 0.2 to 0.4, even when an antireflection film is formed with a thin film of 10 nm or less, the reflected light from the substrate in ArF immersion and high NA exposure can be suppressed to a considerable extent, and it is applicable as an underlayer film for photoresist patterning (Figure 3). In the above examples, it can be seen that all the optical constants are in a suitable range and applicable for photoresist patterning as an antireflection film.

[0392] [ArF Patterning Test (Examples 4-1 to 4-5, Comparative Examples 4-1 to 4-2)] An amorphous carbon film (carbon content: 73 atomic%) with a film thickness of 35 nm was formed as an organic underlayer film, and a silicon oxynitride film (SiON) with a film thickness of 15 nm was formed as a silicon-containing hard mask on a silicon wafer on which a silicon oxide film with a film thickness of 200 nm was formed. A composition for forming a silicon-containing antireflection film (UDL-2, 6, 10, 14, 22, and Comparative Example UDL-1) was applied onto the SiON film and heated at 220°C for 60 seconds to form a silicon-containing antireflection film with a film thickness of 10 nm.

[0393] Subsequently, a negative-tone ArF resist solution (PR1) containing the following ArF resist polymer (P-1), photoacid generator (PAG-A), amine quencher (Q-1), surfactant (F-1), and solvent in the composition described in Table 11 was applied onto the silicon-containing antireflection film and baked at 110°C for 60 seconds to form a photoresist film (PR-1) with a film thickness of 70 nm. [Chemical formula]

[0394] [Photoacid generator] (PAG-A): Triphenylsulfonium 2-(adamantan-1-carbonyloxy)-1,1,3,3,3-pentafluoropropane-1-sulfonate (compound described in JP-A-2007-145797)

[0395] [Amine quencher] (Q-1): 2-Morpholinoethyl laurate

[0396] [Surfactant] Alkali-soluble surfactant (F-1): Poly(methacrylic acid-3,3,3-trifluoro-2-hydroxy-1,1-dimethyl-2-trifluoromethylpropyl·methacrylic acid-1,1,1-trifluoro-2-hydroxy-6-methyl-2-trifluoromethylhept-4-yl) (compound described in JP-A-2008-122932) Weight-average molecular weight (Mw) = 7,300, dispersity (Mw / Mn) = 1.86 [Chemical]

[0397] [Solvent] PGMEA: Propylene Glycol Monomethyl Ether Acetate CyHO: Cyclohexanone

[0398] [Table 11]

[0399] Using an ArF immersion excimer laser stepper (manufactured by ASML, XT1900i, NA1.35, σ0.98 / 0.80, cross-pole aperture 30 degrees, 6% halftone phase shift mask), exposure was performed using a mask with hole patterns arranged on the wafer with a pitch of 90 nm and a width of 36 nm. After heat treatment (PEB) for 60 seconds after exposure, butyl acetate was ejected from the development nozzle while rotating at 30 rpm for 3 seconds, and then stationary paddle development was performed for 27 seconds to obtain a negative pattern.

[0400] The hole dimensions of the pattern created under the above conditions were measured using an electron microscope (CG5000) manufactured by Hitachi High-Technologies Corporation. Also, the cross-sectional shape (pattern shape) was observed using an electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and it was considered good when no trailing shape or undercut shape was seen, and was evaluated as bad when an obvious trailing shape or undercut shape was seen. The reflectivity was calculated using PROLITH 2020a (Lithotech Japan Co., Ltd.). The film thickness of the silicon-containing antireflection film was fixed at 10 nm, and the results of calculating the reflectivity when n of the silicon-containing antireflection film was 1.60 - 2.10 and k was 0.20 - 0.40 are shown in Figure 3. An optical constant (n / k) that can reduce the reflected light from the underlying substrate during pattern exposure to 1.0% or less is preferred.

[0401] Using the resist pattern (D layer) as a mask, the silicon-containing antireflection film (C layer) and the silicon-containing hard mask (B layer) were processed by dry etching under the following conditions (1), and then the pattern was transferred to the organic underlayer film (A layer) under the following conditions (2). Finally, the pattern was transferred to the oxide film (substrate to be processed) under the following conditions (3).

[0402] (1) Processing conditions for the silicon-containing antireflection film (C layer) and the silicon-containing hard mask (B layer) Equipment: Dry etching equipment Telius SP manufactured by Tokyo Electron Limited Chamber pressure: 80 mT RF power (upper): 500 W RF power (lower): 300 W CF4 gas flow rate: 150 sccm CHF3 gas flow rate: 50 sccm Time: 15 sec

[0403] (2) Processing conditions for the organic underlayer film (A layer) Equipment: Dry etching equipment Telius SP manufactured by Tokyo Electron Limited Chamber pressure: 80 mT RF power (upper): 500 W RF power (lower): 300 W CO2 gas flow rate: 320 sccm N2 gas flow rate: 80 sccm Time: 45 sec

[0404] (3) Processing conditions for the oxide film (substrate to be processed) Equipment: Dry etching equipment Telius SP manufactured by Tokyo Electron Limited Chamber pressure: 10 mT RF power (upper): 100 W RF power (lower): 800 W CF4 gas flow rate: 25 sccm CHF3 gas flow rate: 15 sccm O2 gas flow rate: 5 sccm Time: 60 sec

[0405] The hole sizes of the patterns created under the above conditions were measured using an electron microscope (CG5000) manufactured by Hitachi High-Technologies Corporation. Additionally, the hole diameters at 50 different locations within the same exposure shot were measured, and the 3σ value of the dimensional variation was defined as the CDU. The results are shown in Table 12. A smaller CDU value indicates better dimensional controllability, which is preferable.

[0406]

Table 12

[0407] From the results in Table 12, it was found that the pattern formation method (Examples 4-1 to 4-5) using the silicon-containing antireflection film-forming composition of the present invention had a good cross-sectional pattern shape after exposure and exhibited good CDU after processing the substrate to be processed. In particular, the silicon-containing antireflection films formed using the silicon-containing antireflection film-forming compositions UDL-2, 6, and 10 containing crosslinking agents (D1, D3) showed excellent CDU for the resist pattern after exposure, presumably because of their excellent poisoning suppression effect.

[0408] In Comparative Example 4-1, the cross-sectional pattern shape after exposure was an undercut shape. It is presumed that this was because the base component generated from the SiON film migrated to the photoresist film and the resolution of the resist decreased since no silicon-containing antireflection was used. Additionally, combined with the insufficient reflection light suppression effect, it is presumed that the CDU of the resist pattern after exposure deteriorated and the CDU after processing the substrate to be processed was also insufficient.

[0409] In Comparative Example 4-2, the cross-sectional pattern shape after exposure was an undercut shape. It is presumed that this was because the poisoning suppression effect of Comparative Example UDL-1 used as the silicon-containing antireflection was insufficient and the base component generated from the SiON film migrated to the photoresist film, resulting in a decrease in the resolution of the resist. Additionally, combined with the insufficient thin film forming property, it is presumed that the CDU of the resist pattern after exposure deteriorated and the CDU after processing the substrate to be processed was also insufficient.

[0410] From the above, the silicon-containing antireflection film formed using the composition for forming a silicon-containing antireflection film of the present invention has excellent thin film formability, antireflection effect, and an effect of suppressing poisoning from the resist underlayer to the photoresist film, and gives a pattern shape of a resist upper layer film with high rectangularity. Therefore, it is particularly preferably used in a multilayer resist process and is extremely useful in fine patterning for manufacturing semiconductor devices.

[0411] This specification includes the following aspects. [1]: A composition for forming a silicon-containing antireflection film, comprising (A) a silicon-containing polymer, (B) an organic polymer, and (C) an organic solvent, wherein the (A) silicon-containing polymer contains any one selected from polysiloxane, polycarbosilane, and polysilane, and the (B) organic polymer contains two or more hydroxyl groups in the repeating unit structure of the polymer and does not contain silicon. A composition for forming a silicon-containing antireflection film characterized by this. [2]: The composition for forming a silicon-containing antireflection film according to the above [1], wherein the (B) organic polymer contains the following general formula (1B) or (2B). [Chemical formula] (In the formula, R 01 is a hydrogen atom or a methyl group, R 02 is an alkyl group having 1 to 3 carbon atoms or a halogen atom, m is an integer of 2 to 5, n is an integer of 0 to 3, and m + n is an integer of 2 or more and 5 or less. X represents a single bond or an alkylene group that may contain one or more selected from oxygen atoms and nitrogen atoms having 1 to 10 carbon atoms.) [Chemical formula] (In the formula, R 1 is any one selected from a saturated monovalent organic group having 1 to 30 carbon atoms, an unsaturated monovalent organic group having 2 to 30 carbon atoms, and a halogen atom, Y is a divalent organic group having 1 to 30 carbon atoms, p is an integer of 0 to 5, q1 is an integer of 2 to 6, p + q1 is an integer of 2 or more and 6 or less, and q2 is 0 or 1.) [3]: The silicon-containing antireflection film-forming composition according to [1] or [2] above, wherein the polysiloxane contains any one or more selected from the repeating unit represented by the following general formula (Sx-1), the repeating unit represented by the following general formula (Sx-2), and the partial structure represented by the following general formula (Sx-3).

Chemical formula

Chemical formula

[10] : The silicon-containing antireflection film-forming composition is characterized in that it further contains one or more selected from (E) an acid generator, (F) a surfactant, and (H) a pigment, and is the silicon-containing antireflection film-forming composition according to any one of [1] to [9] above.

[11] : The silicon-containing antireflection film-forming composition according to any one of [1] to

[10] above, wherein the (C) organic solvent contains one or more organic solvents having a boiling point of 180 °C or higher as (C1) a high-boiling solvent.

[12] : A method for forming a pattern on a substrate to be processed, comprising: (I-1) A step of forming a silicon-containing antireflection film by applying a silicon-containing antireflection film-forming composition according to any one of [1] to

[11] above on a substrate to be processed and then performing heat treatment; (I-2) A step of forming a resist upper layer film on the silicon-containing antireflection film using a photoresist material; (I-3) A step of performing pattern exposure on the resist upper layer film and then developing with a developer to form a pattern on the resist upper layer film; (I-4) A step of transferring the pattern to the silicon-containing antireflection film by dry etching using the resist upper layer film having the pattern as a mask, and (I-5) A step of processing the substrate to be processed using the silicon-containing antireflection film having the pattern transferred thereto as a mask to form a pattern on the substrate to be processed. The pattern forming method is characterized by comprising the above steps.

[13] : A method for forming a pattern on a substrate to be processed, comprising: (II-1) A step of forming a resist lower layer film on a substrate to be processed. (II-2) A step of forming a silicon-containing antireflection film by applying any one of the compositions for forming a silicon-containing antireflection film from [1] to

[11] onto the resist underlayer film and then performing heat treatment. (II-3) A step of forming a resist upper layer film on the silicon-containing antireflection film using a photoresist material. (II-4) A step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern in the resist upper layer film. (II-5) A step of transferring the pattern to the silicon-containing antireflection film by dry etching using the resist upper layer film with the pattern formed thereon as a mask. (II-6) A step of transferring the pattern to the resist underlayer film by dry etching using the silicon-containing antireflection film with the pattern transferred thereon as a mask, and (II-7) A step of processing the substrate to be processed using the resist underlayer film with the pattern transferred thereon as a mask to form a pattern on the substrate to be processed. A pattern forming method characterized by comprising the above steps.

[14] : A method of forming a pattern on a substrate to be processed, (III-1) A step of forming a resist underlayer film on the substrate to be processed. (III-2) A step of forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film. (III-3) A step of forming a silicon-containing antireflection film by applying any one of the compositions for forming a silicon-containing antireflection film from [1] to

[11] onto the inorganic hard mask intermediate film and then performing heat treatment. (III-4) A step of forming a resist upper layer film on the silicon-containing antireflection film using a photoresist material. (III-5) A step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern in the resist upper layer film. (III-6) A step of transferring the pattern to the silicon-containing antireflection film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film with the pattern formed thereon as a mask. (III-7) Using the inorganic hard mask intermediate layer onto which the pattern has been transferred as a mask, transferring the pattern to the resist underlayer film by dry etching, and (III-8) Using the resist underlayer film onto which the pattern has been transferred as a mask to process the substrate to be processed and forming a pattern on the substrate to be processed A pattern forming method characterized by comprising the above steps.

[15] : The pattern forming method according to any one of

[12] to

[14] above, characterized in that the film thickness of the silicon-containing antireflection film is 12 nm or less.

[0412] Note that the present invention is not limited to the above embodiments. The above embodiments are illustrative, and any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same operational effects is included in the technical scope of the present invention.

Explanation of reference numerals

[0413] 1... Substrate to be processed, 2... Layer to be processed, 2a... Pattern (pattern formed on the layer to be processed), 3... Resist underlayer film, 3a... Resist underlayer film pattern, 4... Silicon-containing antireflection film, 4a... Silicon-containing antireflection film pattern, 5... Inorganic hard mask intermediate layer, 5a... Inorganic hard mask intermediate layer pattern, 6... Resist upper layer film, 6a... Resist upper layer film pattern, 7... Exposed portion.

Claims

1. A composition for forming a silicon-containing antireflection film, comprising (A) a silicon-containing polymer, (B) an organic polymer, and (C) an organic solvent, wherein the (A) silicon-containing polymer contains any one selected from polysiloxane, polycarbosilane, and polysilane, and the (B) organic polymer contains two or more hydroxyl groups in the repeating unit structure of the polymer and does not contain silicon, characterized in that it is a composition for forming a silicon-containing antireflection film.

2. The composition for forming a silicon-containing antireflection film according to claim 1, wherein the (B) organic polymer contains the following general formula (1B) or (2B). 【Chemical 1】 (wherein, R ０１ is a hydrogen atom or a methyl group, R ０２ is an alkyl group having 1 to 3 carbon atoms or a halogen atom, m is an integer of 2 to 5, n is an integer of 0 to 3, and m + n is an integer of 2 or more and 5 or less. X represents a single bond or an alkylene group which may contain one or more selected from oxygen atoms and nitrogen atoms having 1 to 10 carbon atoms.) 【Chemical 2】 (wherein R １ is any one selected from a saturated monovalent organic group having 1 to 30 carbon atoms, an unsaturated monovalent organic group having 2 to 30 carbon atoms, and a halogen atom, Y is a divalent organic group having 1 to 30 carbon atoms, p is an integer of 0 to 5, q １ is an integer of 2 to 6, p + q １ is an integer of 2 or more and 6 or less, q ２ is 0 or 1.)

3. The composition for forming a silicon-containing antireflection film according to claim 1, wherein the polysiloxane contains any one or more selected from the repeating unit represented by the following general formula (Sx-1), the repeating unit represented by the following general formula (Sx-2), and the partial structure represented by the following general formula (Sx-3). 【Chemical Formula 3】 (wherein R ａ , R ｂ , R ｃ are each independently a monovalent organic group having 1 to 30 carbon atoms which may be the same or different.)

4. In the general formulas (Sx-1) to (Sx-3), the R ａ ~R ｃ The silicon-containing antireflection film-forming composition according to claim 3, wherein at least one of them is an organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds.

5. The composition for forming a silicon-containing antireflection film according to claim 1, wherein the polycarbosilane contains a unit structure represented by the following general formula (Sy-1). 【Chemical Formula 4】 (wherein R ｄ and R ｅ are each independently a hydrogen atom, a hydroxy group, a halogen atom, or a monovalent organic group having 1 to 30 carbon atoms, and Z is a divalent hydrocarbon group having 1 to 20 carbon atoms which is substituted or unsubstituted.)

6. The composition for forming a silicon-containing antireflection film according to claim 1, wherein the content of the (B) organic polymer is in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the (A) silicon-containing polymer.

7. The composition for forming a silicon-containing antireflection film according to claim 1, wherein the weight average molecular weight Mw in terms of polystyrene of the (B) organic polymer by gel permeation chromatography is in the range of 1,500 ≤ Mw ≤ 20,000.

8. The composition for forming a silicon-containing antireflection film according to claim 1, further comprising (D) a crosslinking agent.

9. The composition for forming a silicon-containing antireflection film according to claim 8, wherein the (D) crosslinking agent is a compound containing an isocyanuric acid structure.

10. The composition for forming a silicon-containing antireflection film according to claim 1, further containing one or more selected from (E) an acid generator, (F) a surfactant, and (H) a pigment.

11. The silicon-containing antireflection film-forming composition according to claim 1, wherein the organic solvent (C) contains at least one organic solvent having a boiling point of 180 ° C. or higher as the high-boiling solvent (C1).

12. A method of forming a pattern on a substrate to be processed, comprising: (I-1) A step of forming a silicon-containing antireflection film by applying the silicon-containing antireflection film-forming composition according to any one of claims 1 to 11 on a substrate to be processed and then performing heat treatment; (I-2) A step of forming a resist upper layer film on the silicon-containing antireflection film using a photoresist material; (I-3) A step of forming a pattern on the resist upper layer film by pattern exposure and then developing with a developer; (I-4) A step of transferring the pattern to the silicon-containing antireflection film by dry etching using the resist upper layer film having the pattern as a mask, and (I-5) A step of processing the substrate to be processed using the silicon-containing antireflection film having the pattern transferred thereto as a mask to form a pattern on the substrate to be processed A pattern forming method characterized by comprising the steps of:

13. A method of forming a pattern on a substrate to be processed, comprising: (II-1) A step of forming a resist lower layer film on a substrate to be processed; (II-2) A step of forming a silicon-containing antireflection film by applying the silicon-containing antireflection film-forming composition according to any one of claims 1 to 11 on the resist lower layer film and then performing heat treatment; (II-3) A step of forming a resist upper layer film on the silicon-containing antireflection film using a photoresist material; (II-4) A step of forming a pattern on the resist upper layer film by pattern exposure and then developing with a developer; (II-5) A step of transferring the pattern to the silicon-containing antireflection film by dry etching using the resist upper layer film having the pattern as a mask; (II-6) A step of transferring the pattern to the resist lower layer film by dry etching using the silicon-containing antireflection film having the pattern transferred thereto as a mask, and (II-7) A step of processing the substrate to be processed using the resist lower layer film having the pattern transferred thereto as a mask to form a pattern on the substrate to be processed A pattern forming method characterized by comprising the steps of:

14. A method of forming a pattern on a substrate to be processed, comprising: (III-1) A step of forming a resist lower layer film on a substrate to be processed; Step (III-2): Forming an inorganic hard mask intermediate layer selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film; Step (III-3): Applying the composition for forming a silicon-containing antireflection film according to any one of claims 1 to 11 on the inorganic hard mask intermediate layer and then performing heat treatment to form a silicon-containing antireflection film; Step (III-4): Forming a resist upper layer film using a photoresist material on the silicon-containing antireflection film; Step (III-5): After pattern-exposing the resist upper layer film, developing the film with a developer to form a pattern in the resist upper layer film; Step (III-6): Using the resist upper layer film having the pattern formed thereon as a mask and transferring the pattern to the silicon-containing antireflection film and the inorganic hard mask intermediate layer by dry etching; Step (III-7): Using the inorganic hard mask intermediate layer having the pattern transferred thereto as a mask and transferring the pattern to the resist underlayer film by dry etching; and Step (III-8): Using the resist underlayer film having the pattern transferred thereto as a mask to process the substrate to be processed and form a pattern on the substrate to be processed A pattern forming method characterized by comprising the above steps.

15. The pattern forming method according to claim 12, wherein the film thickness of the silicon-containing antireflection film is 12 nm or less.

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