Organic film forming composition, pattern forming method, and organic film forming compound and polymer

Abstract

The present invention provides an organic film-forming composition, a pattern-forming method, and an organic film-forming compound and polymer. The solution provided by the present invention is an organic film-forming composition characterized by containing an organic film-forming material represented by the following general formula and an organic solvent. In the general formula, R1 is a hydrogen atom, an allyl group, or a propargyl group; R2 is a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group; m = 0, 1, n = 1, 2, l = 0, 1, k is an integer from 0 to 2, W is a divalent organic group having 1 to 40 carbon atoms; and V each independently represents a hydrogen atom or a linking moiety.

Description

Technical Field

[0001] The present invention relates to an organic film-forming composition that can be used for fine patterning by a multilayer resist method in a semiconductor device manufacturing process, a pattern forming method using the composition, and a compound and a polymer used in the organic film-forming composition. Existing technology

[0002] With the increasing integration and speed of LSIs, pattern sizes are rapidly becoming smaller. Photolithography technology, along with this miniaturization, has achieved the formation of fine patterns through the shortening of light sources and the appropriate selection of corresponding resist compositions. Central to this development is a single-layer positive photoresist composition. This single-layer positive photoresist composition incorporates a resist resin with a backbone resistant to dry etching using chlorine- or fluorine-based gas plasma, and a switching mechanism that dissolves the exposed portion. This allows the exposed portion to dissolve to form a pattern, and the remaining resist pattern serves as an etching mask for dry etching of the substrate being processed.

[0003] However, when miniaturization is performed while maintaining the film thickness of the photoresist film being used, that is, when the pattern width is further reduced, the resolution performance of the photoresist film decreases. In addition, when the photoresist film is used to develop the pattern with a developer, the aspect ratio becomes too large, resulting in pattern collapse. Therefore, as the pattern becomes miniaturized, the photoresist film thickness is gradually reduced.

[0004] On the other hand, processing of substrates typically involves using a patterned photoresist film as an etching mask and dry etching to process the substrate. However, there is no dry etching method that can achieve complete etching selectivity between the photoresist film and the substrate being processed. Consequently, the resist film can be damaged and broken during processing of the substrate, preventing the resist pattern from being properly transferred to the substrate. Consequently, with the increasing miniaturization of patterns, photoresist compositions are also being sought to have higher dry etching resistance. However, to improve resolution, the resins used in photoresist compositions are required to have low light absorption at the exposure wavelength. Consequently, as exposure light becomes shorter, such as i-rays, KrF, and ArF, resins have shifted to novolac resins, polyhydroxystyrene, and resins with aliphatic polycyclic backbones. These resins, which exhibit faster etching speeds under the dry etching conditions used during substrate processing, tend to have lower etching resistance. Recent photoresist compositions with higher resolution have, in fact, exhibited a tendency to have lower etching resistance.

[0005] Due to this fact, it becomes necessary to dry-etch the substrate to be processed through a thinner photoresist film with weaker etching resistance, and it is important to ensure the materials and processing in this processing step.

[0006] One method for solving this problem is the multilayer resist method. This method involves inserting an interlayer film, which has a different etching selectivity from the photoresist film (i.e., the resist upper layer), between the resist upper layer and the substrate being processed. After a pattern is formed on the resist upper layer, the pattern is transferred to the interlayer film by dry etching, using the resist upper layer pattern as a dry etching mask. Furthermore, the pattern is transferred to the substrate being processed by dry etching, using the interlayer film as a dry etching mask.

[0007] One type of multilayer resist method is the three-layer resist method, which can be performed using the typical resist compositions used in the single-layer resist method. This three-layer resist method involves forming an organic film, such as a novolac, as a resist lower layer on a substrate to be processed, forming a silicon-containing film as a silicon-containing resist intermediate film on top of the organic film, and then forming a conventional organic photoresist film as a resist upper layer on top of the organic film. When dry-etched with fluorine-based gas plasma, the organic resist upper layer exhibits a good etching selectivity relative to the silicon-containing resist intermediate film, allowing the resist upper layer pattern to be transferred to the silicon-containing resist intermediate film through dry etching with the fluorine-based gas plasma. According to this method, even when using a resist composition that is difficult to form a pattern having a sufficient film thickness for direct processing of a substrate, or when using a resist composition that does not have sufficient dry etching resistance for processing a substrate, if the pattern can be transferred to a silicon-containing film (resist intermediate film) and then the pattern transfer is performed by dry etching using oxygen-based or hydrogen-based gas plasma, a pattern of an organic film (resist underlayer film) such as novolac having sufficient dry etching resistance for substrate processing can be obtained. As such resist underlayer films, many types are known, such as those described in Patent Document 1.

[0008] On the other hand, in recent years, the manufacture of semiconductor devices with new structures such as multi-gate structures has been actively studied. In response to this, the requirements for the planarization and filling characteristics of the resist lower layer film are becoming increasingly better than before. For example, when the base substrate to be processed has micro-pattern structures such as holes, trenches, and fins, it is necessary to utilize the characteristics of the resist lower layer film to fill the pattern with the film without gaps. In addition, when the base substrate to be processed has height differences, and when the pattern-dense parts and the areas without patterns exist on the same wafer, it is necessary to use the resist lower layer film to flatten the film surface (planarization). By flattening the surface of the lower layer film, the film thickness variation of the resist intermediate film and the resist upper film formed thereon can be suppressed, and the focus tolerance of the lithography and the reduction in tolerance in the subsequent processing steps of the processed substrate can be suppressed.

[0009] Furthermore, organic film materials with excellent filling and planarizing properties are not limited to use as underlayer films for multilayer resists. For example, they can be used as planarizing materials for semiconductor device manufacturing, for example, for substrate planarization prior to patterning using nanoimprint lithography. Furthermore, while CMP is currently the most common method for planarizing the entire surface of a semiconductor device during manufacturing, this is a costly process, leading to the development of materials that can replace it and achieve this goal.

[0010] To form a planarizing film for flattening uneven semiconductor substrates, a resist underlayer film material comprising a polymer obtained by reacting an aromatic compound with a compound having a carbon-oxygen double bond, such as a carbonyl group, has been proposed (Patent Document 2). However, this material is insufficient to meet the requirements of state-of-the-art devices, such as those for flattening wide trenches in substrates. Consequently, a resist underlayer film material with excellent flatness over a wider range of substrate structures is sought.

[0011] Furthermore, as the structure of the substrate being processed becomes more complex, research is underway to utilize novel materials with high electron mobility, such as strained silicon and gallium arsenide, as well as ultra-thin polysilicon with angstrom-level control. This allows for film formation to accommodate a wide variety of substrate surface shapes and materials. Therefore, to ensure process latitude, not only are excellent fill and planarization characteristics crucial, but also the ability to form films independently of the substrate's material and shape is crucial.

[0012] Prior art literature

[0013] Patent Literature

[0014] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-205685

[0015] [Patent Document 2] International Publication No. 2019 / 225615 Summary of the Invention

[0016] [Problems to be Solved by the Invention]

[0017] The present invention was developed in light of the above circumstances and aims to provide a compound and a polymer capable of forming an organic film having excellent heat resistance, excellent filling and planarization properties for a pattern formed on a substrate, and good film-forming properties and adhesion to the substrate, as well as an organic film-forming composition containing the compound and / or polymer. Furthermore, the present invention aims to provide a pattern-forming method using the composition.

[0018] [Methods for solving the problem]

[0019] In order to solve the above-mentioned problems, the present invention provides an organic film-forming composition characterized by containing an organic film-forming material represented by the following general formula and an organic solvent.

[0020] [Chemistry 1]

[0021]

[0022] (In this general formula, R1 is a hydrogen atom, an allyl group, or a propargyl group; R2 represents a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group; m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and when l=1, the aromatic rings form a cyclic ether structure; k represents an integer of 0 to 2, W represents a divalent organic group having 1 to 40 carbon atoms; and V each independently represents a hydrogen atom or a linking moiety.)

[0023] Such an organic film-forming composition can form an organic film having excellent heat resistance, filling properties of a pattern formed on a substrate, and planarization properties, as well as good film-forming properties and adhesion properties to the substrate.

[0024] In this case, the organic film-forming material may be a compound represented by the following general formula (1).

[0025] [Chemistry 2]

[0026]

[0027] (In the above general formula (1), R1, R2, m, n, l, k, and W are the same as those described above.)

[0028] The compound of the present invention represented by the general formula (1) has excellent heat resistance and solubility, so it can be made into an organic film material as a single compound. Because it has better thermal fluidity than high molecular weight compounds, it also has excellent filling / flattening properties for patterned substrates when used as a resist underlayer film. In addition, the presence of a cyclic amide structure in the molecule does not impair heat resistance, and improves adhesion to the substrate and film-forming properties. In addition, by appropriately selecting the connecting portion represented by W, it is possible to adjust the various physical properties required when using the organic film as a resist underlayer film, such as optical properties and etching resistance.

[0029] Furthermore, the compound represented by the above-mentioned general formula (1) is preferably a compound represented by the following general formula (2).

[0030] [Chemistry 3]

[0031]

[0032] (In the above general formula (2), R1, W, and n are the same as those described above.)

[0033] By introducing such a structure, thermal fluidity can be improved, and the filling / planarization performance can be further improved.

[0034] Furthermore, the ratio Mw / Mn of the polystyrene-equivalent weight average molecular weight Mw to the number average molecular weight Mn of the compound as determined by gel permeation chromatography is preferably 1.00≤Mw / Mn≤1.10.

[0035] By controlling the Mw / Mn ratio of the compound for the organic film-forming composition within such a range, an organic film having excellent filling characteristics and flatness can be formed.

[0036] Furthermore, in the present invention, the organic film-forming material may be a polymer having a repeating unit represented by the following general formula (3).

[0037] [Chemistry 4]

[0038]

[0039] (In the above general formula (3), R1, R2, W, n, m, l, and k are the same as those described above, and L is a divalent organic group having 1 to 40 carbon atoms.)

[0040] By using a polymer having such a repeating unit, a dense organic film can be formed without deteriorating etching resistance and with improved curability, and an organic film-forming composition having excellent film formation regardless of substrate material or shape dependency can be obtained.

[0041] In this case, the polymer is preferably a polymer having a repeating unit represented by the following general formula (4).

[0042] [Chemistry 5]

[0043]

[0044] (In the above general formula (4), R1, W, L, and n are the same as those described above.)

[0045] By using a polymer having such a repeating unit, handling properties such as solubility in organic solvents can also be improved.

[0046] Furthermore, the above-mentioned L is preferably a divalent organic group represented by the following general formula (5).

[0047] [Chemistry 6]

[0048]

[0049] (In the above general formula (5), R3 is a hydrogen atom or an aromatic ring-containing organic group having 1 to 20 carbon atoms, and the dotted line represents an atomic bond.)

[0050] By constituting a repeating unit with such a linking group, properties such as hardenability and etching resistance can be improved.

[0051] Furthermore, the weight average molecular weight of the above polymer is preferably 1,000 to 5,000.

[0052] An organic film-forming composition containing a polymer having a weight average molecular weight within such a range can suppress outgassing during baking without impairing solubility in organic solvents.

[0053] In the present invention, the organic film-forming material may contain one or more compounds selected from the group consisting of compounds represented by the following general formula (1) and polymers having a repeating unit represented by the following general formula (3).

[0054] [Chemistry 7]

[0055]

[0056] (In the above general formula (1), R1, R2, m, n, l, k, and W are the same as those described above.)

[0057] [Chemistry 8]

[0058]

[0059] (In the above general formula (3), R1, R2, W, n, m, l, and k are the same as those described above, and L is a divalent organic group having 1 to 40 carbon atoms.)

[0060] Such a mixture can adjust various physical properties required when using an organic film, such as filling / planarization characteristics and dissipated gas caused by sublimation, to appropriate ranges.

[0061] Furthermore, the organic solvent is preferably 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 less than 180°C.

[0062] When the organic solvent is the mixture, the organic film-forming composition has high filling and planarizing properties by imparting thermal fluidity to the compound and / or polymer due to the addition of the high-boiling-point solvent.

[0063] Furthermore, the organic film-forming composition preferably contains one or more of a surfactant and a plasticizer.

[0064] When the organic film-forming composition contains the above-mentioned additives, coating properties and filling / planarization characteristics are further improved.

[0065] In addition, the present invention provides a pattern forming method, characterized in that it includes the following steps: using the above-mentioned organic film forming composition to form an organic film on a workpiece, using a silicon-containing resist intermediate film material to form a silicon-containing resist intermediate film on the organic film, using a photoresist composition to form a resist upper layer film on the silicon-containing resist intermediate film, forming a circuit pattern on the resist upper layer film, using the patterned resist upper layer film as a mask to transfer the pattern to the silicon-containing resist intermediate film by etching, using the silicon-containing resist intermediate film with the transferred pattern as a mask to transfer the pattern to the organic film by etching, and further, using the organic film with the transferred pattern as a mask to form a pattern on the workpiece by etching.

[0066] By using the pattern forming method using the three-layer resist process, a fine pattern can be formed on a workpiece with high precision.

[0067] In addition, the present invention provides a pattern forming method, characterized by comprising the following steps:

[0068] An organic film is formed on a workpiece using the above-mentioned organic film-forming composition, a silicon-containing resist interlayer is formed on the organic film using a silicon-containing resist interlayer material, an organic antireflective film (BARC) is formed on the silicon-containing resist interlayer, a photoresist composition is used to form a resist upper layer film on the BARC to form a four-layer film structure, a circuit pattern is formed on the resist upper layer film, the patterned resist upper layer film is used as a mask to transfer the pattern to the BARC film and the silicon-containing resist interlayer by etching, the pattern-transferred silicon-containing resist interlayer is used as a mask to transfer the pattern to the organic film by etching, and further, the workpiece is etched using the organic film with the transferred pattern as a mask to form a pattern on the workpiece.

[0069] By using the pattern forming method using the four-layer resist process, a fine pattern can be formed on a workpiece with higher precision.

[0070] In addition, the present invention provides a pattern forming method, characterized by comprising the following steps:

[0071] An organic film is formed on a workpiece using the above-mentioned organic film-forming composition, an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film is formed on the organic film, a photoresist composition is used to form a resist upper layer film on the inorganic hard mask, a circuit pattern is formed on the resist upper layer film, the inorganic hard mask is etched using the patterned resist upper layer film as a mask, the organic film is etched using the patterned inorganic hard mask as a mask, and further, the workpiece is etched using the patterned organic film as a mask to form a pattern on the workpiece.

[0072] By using the pattern forming method using the three-layer resist process, a fine pattern can be formed on a workpiece with high precision.

[0073] In addition, the present invention provides a pattern forming method, characterized by comprising the following steps:

[0074] An organic film is formed on a workpiece using the above-mentioned organic film-forming composition, an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film is formed on the organic film, a BARC is formed on the inorganic hard mask, a photoresist composition is used to form a resist upper layer film on the BARC to form a four-layer film structure, a circuit pattern is formed on the resist upper layer film, the BARC film and the inorganic hard mask are etched using the patterned resist upper layer film as a mask, the organic film is etched using the patterned inorganic hard mask as a mask, and further, the workpiece is etched using the patterned organic film as a mask to form a pattern on the workpiece.

[0075] By using the pattern forming method using the four-layer resist process, a fine pattern can be formed on a workpiece with high precision.

[0076] In this case, the inorganic hard mask is preferably formed by a CVD method or an ALD method.

[0077] If the inorganic hard mask is formed by a CVD method or an ALD method, a fine pattern can be formed on a workpiece with higher precision.

[0078] Furthermore, the patterning of the resist upper layer film is preferably performed by optical lithography with a wavelength of 10 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0079] If the above method is used as a method for forming a circuit pattern on the resist upper layer film, a fine pattern can be formed on the workpiece with higher precision.

[0080] In the above-mentioned pattern forming method, exposure and development are performed to form a circuit pattern on the resist upper layer film. The development is performed by alkali development or development using an organic solvent.

[0081] When alkali development or development using an organic solvent is used as a development method, a fine pattern can be formed on a workpiece with higher precision.

[0082] Furthermore, as the above-mentioned object to be processed, a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film is preferably used.

[0083] In the present invention, as the workpiece, for example, those described above can be used.

[0084] In this case, the metal is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, cobalt, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, manganese, molybdenum, ruthenium, or an alloy thereof.

[0085] As the metal, these can be used. In this manner, when patterning is performed using the organic film-forming material of the present invention, the pattern of the upper photoresist layer can be transferred with high precision to form the pattern on the workpiece.

[0086] Furthermore, the present invention provides a compound represented by the following general formula (1).

[0087] [Chemistry 9]

[0088]

[0089] (In the general formula (1), R1 is a hydrogen atom, an allyl group, or a propargyl group; R2 is a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group; m is 0 or 1, n is an integer of 1 or 2, l is 0 or 1, and when l=1, the aromatic rings form a cyclic ether structure; k is an integer of 0 to 2, and W is a divalent organic group having 1 to 40 carbon atoms.)

[0090] The compound represented by the general formula (1) can provide a compound for an organic film-forming composition capable of forming an organic film having excellent heat resistance, filling / planarization characteristics, and film-forming properties.

[0091] In this case, the compound is preferably a compound represented by the following general formula (2).

[0092] [Chemistry 10]

[0093]

[0094] (In the above general formula (2), R1, W, and n are the same as those described above.)

[0095] Such a compound can further improve the filling and planarizing properties of the compound for forming an organic film composition.

[0096] Furthermore, the present invention provides a polymer having a repeating unit represented by the following general formula (3).

[0097] [Chemistry 11]

[0098]

[0099] (In the general formula (3), R1 is a hydrogen atom, an allyl group, or a propargyl group; R2 is a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group; m is 0 or 1, n is an integer of 1 or 2, l is 0 or 1, and when l=1, the aromatic rings form a cyclic ether structure; k is an integer of 0 to 2, W is a divalent organic group having 1 to 40 carbon atoms; and L is a divalent organic group having 1 to 40 carbon atoms.)

[0100] The polymer represented by the general formula (3) can provide a polymer for an organic film-forming composition capable of forming an organic film having excellent curability.

[0101] In this case, a polymer having a repeating unit represented by the following general formula (4) is preferred.

[0102] [Chemistry 12]

[0103]

[0104] (In the above general formula (4), R1, W, L, and n are the same as those described above.)

[0105] A polymer having the above-mentioned repeating unit can be a polymer for an organic film-forming composition having excellent solvent solubility.

[0106] Furthermore, the above-mentioned L is preferably a divalent organic group represented by the following general formula (5).

[0107] [Chemistry 13]

[0108]

[0109] (In the above general formula (5), R3 is a hydrogen atom or an organic group containing an aromatic ring and having 1 to 20 carbon atoms, and the dotted line represents an atomic bond)

[0110] By introducing such a linking group L, various physical properties of the polymer, such as curability and etching resistance, can be improved.

[0111] [Effects of the Invention]

[0112] As described above, the compound or polymer of the present invention can be used to form an organic film having excellent heat resistance, excellent filling / planarization performance and excellent film-forming properties. In addition, the organic film-forming composition containing the compound and / or polymer is a useful material that can form an organic film that can form a film without relying on a processing substrate, and has various properties such as heat resistance and filling / planarization properties. Therefore, it is extremely useful as an organic film-forming composition in a multilayer resist process such as a two-layer resist process, a three-layer resist process using a silicon-containing resist intermediate film, or a four-layer resist process using a silicon-containing resist intermediate film and an organic anti-reflective film, or a planarizing material for semiconductor device manufacturing. In addition, if it is the pattern forming method of the present invention, in the multilayer resist process, a fine pattern can be formed on the workpiece with high precision. BRIEF DESCRIPTION OF THE DRAWINGS

[0113] [ Figure 1 ](A) to (F) are explanatory diagrams of an example of a pattern forming method using a three-layer resist process according to the present invention.

[0114] [ Figure 2 ](G) to (I) Illustrations of the landfill characteristic evaluation method in the examples and comparative examples.

[0115] [ Figure 3 ](J), (K) Illustrations of the planarization characteristic evaluation method in the embodiment and comparative example.

[0116] [ Figure 4 ] Illustrations showing the method for measuring adhesion in Examples and Comparative Examples. DETAILED DESCRIPTION

[0117] As mentioned above, there are organic film-forming compositions that are capable of forming an organic film having excellent film-forming properties and flatness even on a workpiece (workpiece substrate) having a portion particularly difficult to flatten, such as a wide trench structure, in fine patterning processing using a multilayer resist method in the manufacturing steps of semiconductor devices, pattern-forming methods using the organic film-forming compositions, and compounds and polymers suitable for such organic film-forming compositions.

[0118] The inventors of the present application have found that the compound or polymer of the present invention, in which the main skeleton is formed by a specific heterocyclic structure, is useful for forming an organic film having excellent filling / planarization properties, and have completed the present invention.

[0119] That is, the present invention is an organic film-forming composition characterized by containing an organic film-forming material represented by the following general formula and an organic solvent.

[0120] [Chemistry 14]

[0121]

[0122] (In this general formula, R1 is a hydrogen atom, an allyl group, or a propargyl group; R2 represents a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group; m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and when l=1, the aromatic rings form a cyclic ether structure; k represents an integer of 0 to 2, W represents a divalent organic group having 1 to 40 carbon atoms; and V each independently represents a hydrogen atom or a linking moiety.)

[0123] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto.

[0124] [Organic film forming composition]

[0125] The organic film-forming composition of the present invention contains an organic film-forming material represented by a specific general formula described below and an organic solvent.

[0126] The organic film-forming composition may contain the organic film-forming material represented by the general formula and an organic solvent, and may contain additives such as a surfactant and a plasticizer as needed.

[0127] [Organic film-forming material]

[0128] The organic film-forming composition of the present invention is characterized by containing an organic film-forming material represented by the following general formula.

[0129] [Chemistry 15]

[0130]

[0131] (In this general formula, R1 is a hydrogen atom, an allyl group, or a propargyl group; R2 represents a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group; m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and when l=1, the aromatic rings form a cyclic ether structure; k represents an integer of 0 to 2, W represents a divalent organic group having 1 to 40 carbon atoms; and V each independently represents a hydrogen atom or a linking moiety.)

[0132] In the above general formula, R1 is a hydrogen atom, an allyl group, or a propargyl group. From the viewpoint of thermosetting properties, a hydrogen atom or a propargyl group is preferred, and from the viewpoint of imparting thermal fluidity, a propargyl group is particularly preferred.

[0133] R2 represents a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group, an alkynyloxy group having 2 to 4 carbon atoms such as a propargyloxy group, an alkenyloxy group having 2 to 4 carbon atoms such as an allyloxy group, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms such as a methyl group, an isobutyl group, a cyclohexyl group, a trifluoromethyl group, or a trifluoromethyloxy group.

[0134] m represents 0 or 1, n represents an integer of 1 or 2, and l represents 0 or 1, where l=1, meaning that the aromatic rings form a cyclic ether structure. Furthermore, n and l satisfy the relationship 1≤n+l≤3. k represents an integer of 0 to 2. m is preferably 0, l is preferably 0, and k is preferably 0.

[0135] W in the above general formula is a divalent organic group having 1 to 40 carbon atoms, preferably a divalent organic group having 2 to 30 carbon atoms, and specifically includes the following structures. Among these, an alkylene group is preferred from the viewpoint of easy availability of raw materials and imparting thermal fluidity.

[0136] [Chemistry 16]

[0137]

[0138] (The dotted lines represent atomic bonds)

[0139] V each independently represents a hydrogen atom or a linking moiety. When all Vs are hydrogen atoms (without a linking moiety), the organic film-forming material represented by the above general formula is a monomolecular compound, corresponding to the compound represented by the general formula (1) described later. When V is a linking moiety, the organic film-forming material is a polymer. The linking moiety is a portion that connects the structures represented by the above general formula to each other, and examples thereof include a single bond and the linking group L described later. That is, the polymer includes a polymer having a repeating unit represented by the general formula (3) described later.

[0140] The organic film-forming material may be a compound represented by the general formula (1) described below, a compound represented by the general formula (2) (hereinafter, these compounds are also referred to as "compounds for an organic film-forming composition"), or a polymer having a repeating unit represented by the general formula (3) described below, or a polymer having a repeating unit represented by the general formula (4) (hereinafter, these polymers are also referred to as "polymers for an organic film-forming composition"). Furthermore, the organic film-forming material may contain one or more compounds each selected from the group consisting of compounds represented by the general formula (1) and polymers each selected from the group consisting of repeating units represented by the general formula (3).

[0141] <Compounds for Organic Film-Forming Compositions>

[0142] The organic film-forming composition of the present invention may contain a compound represented by the following general formula (1) (compound for the organic film-forming composition) as an organic film-forming material.

[0143] [Chemistry 17]

[0144]

[0145] (In the above general formula (1), R1, R2, m, n, l, k, and W are the same as above.)

[0146] W in the general formula (1) is a divalent organic group having 1 to 40 carbon atoms, preferably a divalent organic group having 2 to 30 carbon atoms, and specifically includes the above structures. Among these, an alkylene group is preferred from the viewpoint of easy availability of raw materials and imparting thermal fluidity.

[0147] R1 in the general formula (1) is a hydrogen atom, an allyl group, or a propargyl group. From the viewpoint of thermosetting properties, a hydrogen atom or a propargyl group is preferred, and from the viewpoint of imparting thermal fluidity, a propargyl group is particularly preferred.

[0148] R2 represents a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group, an alkynyloxy group having 2 to 4 carbon atoms such as a propargyloxy group, an alkenyloxy group having 2 to 4 carbon atoms such as an allyloxy group, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms such as a methyl group, an isobutyl group, a cyclohexyl group, a trifluoromethyl group, or a trifluoromethyloxy group.

[0149] m represents 0 or 1, n represents an integer of 1 or 2, and l represents 0 or 1, where l=1, meaning that the aromatic rings form a cyclic ether structure. Furthermore, n and l satisfy the relationship 1≤n+l≤3. k represents an integer of 0 to 2. m is preferably 0, l is preferably 0, and k is preferably 0.

[0150] Specific examples of the general formula (1) include the following, wherein R1, R2, W, and k are the same as those described above.

[0151] [Chemistry 18]

[0152]

[0153] Furthermore, the compound is preferably a compound represented by the following general formula (2).

[0154] [Chemistry 19]

[0155]

[0156] Specific examples of compounds (2) in the general formula include the following. Among these, compounds having a propargyl group as a substituent are particularly preferred from the viewpoint of thermal fluidity and curability. W in the general formula below is the same as described above.

[0157] [Chemistry 20]

[0158]

[0159] In addition, the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn of the compound represented by the general formula (1) in terms of polystyrene by gel permeation chromatography is preferably 1.00≤Mw / Mn≤1.10. By definition, if it is a monomolecular compound, Mw / Mn becomes 1.00, but due to the separation properties of gel permeation chromatography, there are cases where the measured value exceeds 1.00. Generally speaking, it is extremely difficult for a polymer having repeating units to approach Mw / Mn=1.00 without using a special polymerization method, and it will become a value with a distribution of Mw and Mw / Mn exceeding 1. In the present invention, 1.00≤Mw / Mn≤1.10 is defined as an indicator of monomolecularity for distinguishing monomolecular compounds from polymers.

[0160] By controlling the Mw / Mn ratio of the compound for the organic film-forming composition within such a range, an organic film having excellent filling characteristics and flatness can be formed.

[0161] The compound of the present invention contains a structure with a large number of aromatic rings, and therefore has excellent heat resistance and etching resistance. It can further be combined with substituents that impart fluidity and hardening properties, heterocyclic structures that impart film-forming properties and adhesion, or linking structures for further improving fluidity, and can be used as an organic film-forming compound.

[0162] [Method for producing compound]

[0163] As an example of a method for producing a compound represented by general formula (1) of the present invention, there can be exemplified a step (STEP 1) of using a compound represented by XWX having two leaving groups X and indole-2,3-diones as raw materials, obtaining a bis(indole-2,3-diones) as an intermediate by a substitution reaction using a base catalyst, and then obtaining a product by a dehydration condensation reaction using an acid catalyst using benzene or naphthalene having OR1 as a substituent as a raw material (STEP 2). The reactions used in STEP 1 and STEP 2 can use either a single raw material or two or more raw materials, which can be appropriately selected and combined according to the desired properties.

[0164] [Chemistry 21]

[0165]

[0166] (R1, R2, W, n, m, l, k are the same as above, and X is a halide, toluenesulfonate, or mesylate.)

[0167] Examples of base catalysts for the reaction to obtain the intermediate bis(indole-2,3-diones) shown in STEP 1 include inorganic base compounds such as sodium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, and potassium phosphate, and organic amine compounds such as triethylamine, pyridine, and N-methylmorpholine. These can be used alone or in combination of two or more. The amount of these catalysts used is, for example, 0.1 to 20 moles, preferably 0.2 to 10 moles, relative to the molar number of the indole-2,3-diones as a raw material.

[0168] The solvent used in this step is not particularly limited as long as it is inert in the above reaction. Examples include ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; aromatic solvents such as benzene, toluene, and xylene; acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone; and water. These can be used alone or in combination. These solvents can be used in an amount of 0 to 2000 parts by mass per 100 parts by mass of the reaction starting materials. The reaction temperature is preferably between -50°C and about the boiling point of the solvent, more preferably between room temperature and 150°C. The reaction time is appropriately selected from 0.1 to 100 hours.

[0169] Reaction methods include adding the indole-2,3-diones and the compound represented by XWX together to a solvent, adding the indole-2,3-diones and the compound represented by XWX separately or separately, dispersed, or dissolved, and then adding dropwise. Dispersing or dissolving one of the indole-2,3-diones and the compound represented by XWX in a solvent and then adding the other dispersed or dissolved in the solvent dropwise. Furthermore, when adding multiple indole-2,3-diones and the compound represented by XWX, they can be premixed and reacted, or they can be reacted sequentially. When using a catalyst, examples include adding the indole-2,3-diones and the compound represented by XWX together, and adding the catalyst dropwise after predispersing or dissolving it. The intermediate bis(indole-2,3-dione)s obtained can be maintained in the state of the reaction solution to continue the dehydration condensation reaction of STEP 2, or can be diluted with an organic solvent to remove unreacted raw materials, catalysts, etc. present in the system as reaction intermediates, and then recovered as a powder by liquid separation and washing or crystallization with a poor solvent.

[0170] As the acid catalyst used in the dehydration condensation reaction shown in STEP 2, inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acids; organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) isopropoxide, and titanium (IV) oxide can be used. The amount of the catalyst used is 0.1 to 20 mol, preferably 0.2 to 10 mol, relative to the molar number of the intermediate bis(indole-2,3-dione).

[0171] The solvent to be used is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane; chlorinated solvents such as dichloromethane, chloroform, dichloroethane, and trichloroethylene; hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and cumene; nitriles such as acetonitrile; ketones such as acetone, ethyl methyl ketone, and isobutyl methyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and hexamethylphosphoric triamide. These solvents may be used alone or in combination of two or more. These solvents can be used in an amount of 0 to 2000 parts by mass based on 100 parts by mass of the reaction raw materials. The reaction temperature is preferably -50°C to about the boiling point of the solvent, more preferably room temperature to 150°C. The reaction time is appropriately selected from 0.1 to 100 hours.

[0172] The reaction method includes adding the bis(indole-2,3-dione), benzene, or naphthalene together with the acid catalyst; dispersing or dissolving the bis(indole-2,3-dione), benzene, or naphthalene and then adding the catalyst all at once or in portions; diluting with a solvent and adding dropwise; dispersing or dissolving the catalyst and then adding the bis(indole-2,3-dione), benzene, or naphthalene all at once or in portions; or diluting with a solvent and adding dropwise. The reactivity of benzene or naphthalene depends on this; however, the amount of benzene or naphthalene used is preferably 2 or more moles per 1 mole of the bis(indole-2,3-dione). After the reaction is completed, the catalyst is removed by dilution in an organic solvent, followed by separation and washing to recover the desired product.

[0173] The organic solvent used at this time is not particularly limited as long as it can dissolve the target substance and separate into two layers when mixed with water. Examples include hydrocarbons such as hexane, heptane, benzene, toluene, and xylene; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and methyl isobutyl ketone; ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, and ethylcyclopentyl methyl ether; chlorinated solvents such as dichloromethane, chloroform, dichloroethane, and trichloroethylene; and mixtures thereof. The washing water used at this time is generally deionized water or ultrapure water. The number of washes may be one or more, but even 10 or more washes may not necessarily achieve the desired cleaning effect. Therefore, the washing time is preferably about one to five.

[0174] In order to remove the acidic components in the system during liquid separation and cleaning, an alkaline aqueous solution can be used for cleaning. Specific examples of the base include alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, ammonia, and organic ammonium.

[0175] Furthermore, in order to remove metal impurities or alkaline components in the system during liquid separation and cleaning, cleaning with an acidic aqueous solution may be performed. Specific examples of the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acids, and organic acids such as oxalic acid, fumaric acid, maleic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

[0176] The liquid separation cleaning using the alkaline aqueous solution or the acidic aqueous solution may be performed alone or in combination. From the perspective of removing metal impurities, the liquid separation cleaning is preferably performed in the order of the alkaline aqueous solution and the acidic aqueous solution.

[0177] After the aforementioned separation and cleaning using an alkaline or acidic aqueous solution, the product may be subsequently cleaned with neutral water. The cleaning frequency may be one or more, preferably about one to five times. Neutral water can be deionized water, ultrapure water, or the like. One or more cleaning cycles are sufficient, but fewer cycles may not remove the alkaline or acidic components. Even 10 or more cleaning cycles may not necessarily achieve the desired cleaning effect, so approximately one to five cycles are preferred.

[0178] Furthermore, the reaction product after the separation operation can be recovered as a powder by concentrating the solvent to dryness or crystallizing it under reduced pressure or normal pressure. This can also be converted into a solution of appropriate concentration to improve workability during the preparation of the organic film-forming composition. The concentration in this case is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass. This concentration prevents the viscosity from increasing, thus preventing impairment of workability. Furthermore, the amount of solvent does not become excessive, which is economically preferable.

[0179] The solvent in this case is not particularly limited as long as it can dissolve the compound. Specific examples include ketones such as cyclohexanone and methyl-2-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, and propylene glycol mono-t-butyl ether acetate. These can be used alone or in combination of two or more.

[0180] <Polymer for Organic Film-Forming Composition>

[0181] The organic film-forming composition of the present invention may contain a polymer (polymer for organic film-forming composition) having a repeating unit represented by the following general formula (3), preferably a polymer having a repeating unit represented by the general formula (4).

[0182] [Chemistry 22]

[0183]

[0184] (In the above general formula (3), R1, R2, W, n, m, l, and k are the same as those described above, and L is a divalent organic group having 1 to 40 carbon atoms.)

[0185] These polymers obtained using the compounds represented by the general formula (1) have excellent heat resistance, flatness, and thermosetting properties. Furthermore, since they are polymers having repeating units rather than monomers (single-molecule compounds), they contain less dissipated gas components. Furthermore, since they have a molecular weight distribution, they have moderate crystallinity and are expected to have improved film-forming properties.

[0186] L, which is a linking group constituting the repeating units of the general formulae (3) and (4), is a divalent organic group having 1 to 40 carbon atoms, and specific examples thereof include the following.

[0187] [Chemistry 23]

[0188]

[0189] (The dotted lines represent atomic bonds)

[0190] Furthermore, the above L is preferably represented by the following general formula (5).

[0191] [Chemistry 24]

[0192]

[0193] (In the above general formula (5), R3 is a hydrogen atom or an aromatic ring-containing organic group having 1 to 20 carbon atoms, and the dotted line represents an atomic bond.)

[0194] Specific examples of the general formula (5) include the following. In the following, a methylene group is preferable in view of the availability of raw materials, that is, R3 is a hydrogen atom.

[0195] [Chemistry 25]

[0196]

[0197] (The dotted lines represent atomic bonds)

[0198] The Mw (weight average molecular weight) of the above-mentioned polymer is preferably 1000 to 5000, more preferably 1000 to 4000. The molecular weight can be determined as the polystyrene-equivalent weight average molecular weight (Mw) by gel permeation chromatography (GPC) using tetrahydrofuran as the eluent.

[0199] This molecular weight range ensures solubility in organic solvents and suppresses the generation of sublimates during baking. Furthermore, the polymer used in the organic film-forming composition has excellent thermal fluidity. Therefore, when incorporated into a material, it not only effectively fills the fine structures formed on the substrate but also forms an organic film that is flat across the entire substrate.

[0200] [Method for producing polymer]

[0201] As a means of obtaining the polymer used in the organic film-forming composition of the present invention, it can be obtained by a condensation reaction of a compound represented by the general formula (1) with an aldehyde, a ketone, or a benzyl alcohol. In the following formula, R1, R2, W, n, m, l, and k are the same as those described above (where either or both of R4 and R5 are hydrogen atoms, it represents a condensation reaction with an aldehyde; otherwise, it represents a condensation reaction with a ketone. In addition, AR represents an aromatic compound such as benzene or naphthalene, and the substituent represented by -CH2-OH is a substituent of an aromatic ring.).

[0202] [Chemistry 26]

[0203]

[0204] The polycondensation reaction described above can generally be carried out in an organic solvent in the presence of an acid catalyst at room temperature or, as required, under cooling or heating. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acids; organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) isopropoxide, and titanium (IV) oxide.

[0205] Examples of the solvent include alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane; chlorinated solvents such as dichloromethane, chloroform, dichloroethane, and trichloroethylene; hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and cumene; nitriles such as acetonitrile; ketones such as acetone, ethyl methyl ketone, and isobutyl methyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and hexamethylphosphoric triamide. These solvents may be used alone or in combination of two or more.

[0206] The reaction method and the recovery method of the polymer can be carried out by the method described in the method for producing the compound represented by the above general formula (1).

[0207] [Another Method for Producing Compounds and Polymers]

[0208] In addition, when R1 of the compound represented by the general formula (1) or the polymer represented by the general formula (3) used in the organic film-forming composition of the present invention is not a hydrogen atom, another method for producing the compound can be exemplified by the following method: a step of using bis(indole-2,3-diones) and benzene or naphthalene having a hydroxyl group, i.e., phenols or naphthols, as raw materials and subjecting them to a dehydration condensation reaction using an acid catalyst to obtain an intermediate (STEP 1). A monomolecular compound can be obtained by a method comprising the following steps: using a raw material represented by R1-X having a leaving group X converted to OR1 and performing a substitution reaction using a base catalyst (STEP 2-1); a polymer can be obtained by a method comprising the following steps: performing a polycondensation reaction using the compound obtained in (STEP 1) (STEP 2-2), and then performing a substitution reaction using a raw material represented by R1-X having a leaving group X converted to OR1 and performing a base catalyst (STEP 3). In this case, R1-X can be used alone or in combination of two or more. Furthermore, the ratio of hydroxyl groups to OR1 can be controlled by controlling the reaction rate. By partially introducing a polar structure such as a hydroxyl group, the film-forming properties and the adhesion of the film to the substrate can also be controlled.

[0209] [Chemistry 27]

[0210]

[0211] (R1, R2, W, X, n, m, l, k are the same as above.)

[0212] The dehydration condensation reaction (STEP 1) and the polycondensation reaction (STEP 2-2) can be carried out by the methods described in the above-mentioned methods for producing the compound (1) and the polymer (3), respectively.

[0213] The reaction method and the method for recovering the compound or polymer can be carried out by the method described in the method for producing the compound represented by the above general formula (1).

[0214] Examples of the base catalyst used in the substitution reaction of (STEP2-1) and (STEP3) include inorganic base compounds such as sodium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, and potassium phosphate; and organic amine compounds such as triethylamine, pyridine, and N-methylmorpholine. These can be used alone or in combination of two or more.

[0215] The solvent used at this time is not particularly limited as long as it is an inert solvent in the above reaction. Examples include ether solvents such as diethyl ether, tetrahydrofuran, and dioxane, aromatic solvents such as benzene, toluene, and xylene, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and water. These can be used alone or in combination.

[0216] The reaction method and the method for recovering the compound or polymer can be carried out by the method described in the method for producing the compound represented by the above-mentioned general formula (1).

[0217] In preparing the compounds or polymers used in the organic film-forming composition obtained by this method, various halides, tosylates, and mesylates can be used alone or in combination to achieve the desired performance. For example, those having side chain structures that contribute to improved planarization properties, and rigid aromatic ring structures that contribute to etch resistance and heat resistance, can be combined in any proportion. Consequently, organic film-forming compositions using these compounds or polymers can achieve both high levels of fill / planarization properties and etch resistance.

[0218] As described above, the compound or polymer for an organic film-forming composition of the present invention can provide an organic film-forming composition that exhibits high etching resistance and excellent warp resistance.

[0219] [Compounds and / or polymers for organic film-forming compositions]

[0220] In the organic film-forming composition of the present invention containing the organic film-forming compound and / or polymer and an organic solvent as an organic film-forming material, the organic film-forming compound or polymer may be used alone or in combination of two or more.

[0221] In addition, in the present invention, the organic film forming material preferably contains one or more compounds and polymers selected from the above-mentioned compounds and polymers for forming the organic film. Specifically, the organic film forming material preferably contains one or more compounds selected from the above-mentioned general formula (1) and polymers having repeating units represented by the above-mentioned general formula (3).

[0222] With such a mixture, various physical properties required when using an organic film, such as filling / planarization characteristics and dissipated gas resulting from sublimation, can be adjusted to appropriate ranges.

[0223] [Organic solvents]

[0224] As for the organic solvent that can be used in the organic film forming material of the present invention, there is no particular limitation as long as it can dissolve the above-mentioned compound and / or polymer (base polymer), and if contained, the surfactant, crosslinking agent, and other additives described below. Specifically, solvents having a boiling point of less than 180°C, such as the solvents described in paragraphs

[0091] to

[0092] of Japanese Patent Application Laid-Open No. 2007-199653, can be used. Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and mixtures of two or more thereof are preferably used. The amount of the above-mentioned organic solvent to be added is preferably 200 to 10,000 parts, more preferably 300 to 5,000 parts, relative to 100 parts of the above-mentioned compound and / or polymer (A).

[0225] Such an organic film forming composition can be applied by spin coating, and because it contains the compound and / or polymer for the organic film forming composition of the present invention as described above, it has both heat resistance and high filling / planarization properties.

[0226] In the organic film-forming composition of the present invention, a high-boiling-point solvent (a mixture of a solvent having a boiling point of less than 180°C and a solvent having a boiling point of 180°C or higher) of 180°C or higher may be added to the above-mentioned solvent having a boiling point of less than 180°C as an organic solvent. The high-boiling-point organic solvent is not particularly limited as long as it can dissolve the compound and / or polymer for the organic film-forming composition. Examples thereof include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, and the like. Glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, n-nonyl acetate, ethylene glycol 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, triethylene glycol diacetate, 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 , glycerol triacetate, propylene glycol diacetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, etc., which can be used alone or in combination.

[0227] The boiling point of the high-boiling-point solvent can be appropriately selected to match the temperature at which the organic film-forming composition is heat-treated. The boiling point of the added high-boiling-point solvent is preferably 180°C to 300°C, more preferably 200°C to 300°C. This boiling point prevents the risk of excessively rapid volatilization during baking (heat treatment) due to a low boiling point, thereby achieving sufficient thermal fluidity. Furthermore, this boiling point prevents the boiling point from being too high, preventing the solvent from remaining in the film after baking without volatilization, thereby minimizing the risk of adversely affecting film properties such as etching resistance.

[0228] When a high-boiling-point solvent is used, the amount of the high-boiling-point solvent blended is preferably 1 to 30 parts by mass relative to 100 parts by mass of the solvent having a boiling point below 180° C. This blending amount provides sufficient thermal fluidity during baking and prevents the solvent from remaining in the film and deteriorating film properties such as etching resistance.

[0229] If such an organic film-forming composition is provided with thermal fluidity by adding a high-boiling-point solvent to the organic film-forming composition, the organic film-forming composition can have both high filling and planarizing properties.

[0230] [Acid generator]

[0231] An acid generator may be added to the organic film-forming composition of the present invention to further promote the curing reaction. Acid generators include those that generate acid by thermal decomposition and those that generate acid by light irradiation; either type can be added. Specifically, the materials described in paragraphs

[0061] to

[0085] of JP-A-2007-199653 may be added, but are not limited to these.

[0232] The acid generators may be used alone or in combination of two or more. The amount of the acid generator added is preferably 0.05 to 50 parts, more preferably 0.1 to 10 parts, based on 100 parts of the compound and / or polymer.

[0233] [Surfactant]

[0234] The organic film-forming composition of the present invention may contain a surfactant to improve the coating properties during spin coating. Examples of the surfactant include those described in

[0142] to

[0147] of Japanese Patent Application Laid-Open No. 2009-269953. The amount of the surfactant added is preferably 0.01 to 10 parts, more preferably 0.05 to 5 parts, relative to 100 parts of the compound and / or polymer.

[0235] In the present invention, the organic film-forming composition preferably further contains one or more of a surfactant and a plasticizer.

[0236] [Crosslinking agent]

[0237] In addition, in order to improve the curability and suppress the intermixing with the upper film, a crosslinking agent may be added to the organic film-forming composition of the present invention. There is no particular limitation on the crosslinking agent, and a wide range of known crosslinking agents can be used. As an example, hydroxymethyl or alkoxymethyl type crosslinking agents of polynuclear phenols, melamine-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, and epoxy-based crosslinking agents can be exemplified. The amount of the crosslinking agent added is preferably 1 to 100 parts, more preferably 5 to 50 parts, relative to 100 parts of the above-mentioned compound and / or polymer.

[0238] As melamine-based crosslinking agents, specifically, hexamethoxymethylated melamine, hexabutoxymethylated melamine, their alkoxy and / or hydroxyl substitutions, and their partial self-condensation products can be exemplified. As glycoluril-based crosslinking agents, specifically, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, their alkoxy and / or hydroxyl substitutions, and their partial self-condensation products can be exemplified. As benzoguanamine-based crosslinking agents, specifically, tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxyl substitutions, and their partial self-condensation products can be exemplified. As urea-based crosslinking agents, specifically, dimethoxymethylated dimethoxyethylene urea, its alkoxy and / or hydroxyl substitutions, and their partial self-condensation products can be exemplified. As β-hydroxyalkylamide-based crosslinking agents, specifically, N,N,N',N'-tetrakis(2-hydroxyethyl)adipamide can be exemplified. Specific examples of isocyanurate-based crosslinking agents include triglycidyl isocyanurate and triallyl isocyanurate. Specific examples of aziridine-based crosslinking agents include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate]. Specific examples of the oxazoline-based crosslinking agent include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis-4,5-diphenyl-2-oxazoline, 2,2'-methylenebis-4-phenyl-2-oxazoline, 2,2'-methylenebis-4-tert-butyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), and 2-isopropenyloxazoline copolymers. Specific examples of the epoxy crosslinking agent include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0239] Specific examples of the polynuclear phenol-based crosslinking agent include compounds represented by the following general formula (6).

[0240] [Chemistry 28]

[0241]

[0242] (In the formula, Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. R6 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. q is an integer of 1 to 5.)

[0243] Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. q is an integer of 1 to 5, more preferably 2 or 3. Specific examples of Q include groups obtained by removing q hydrogen atoms from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. R6 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, and eicosane, preferably a hydrogen atom or a methyl group.

[0244] Specific examples of the compound represented by the general formula (6) include the following compounds. Among these, trisphenolmethane, trisphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and hexamethoxymethylated tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred from the perspective of improving the curability and thickness uniformity of the organic film. R6 is the same as described above.

[0245] [Chemistry 29]

[0246]

[0247] [Chemistry 30]

[0248]

[0249] [Plasticizer]

[0250] In addition, in order to further improve the flattening / burying characteristics, a plasticizer may be added to the organic film-forming composition of the present invention. There is no particular limitation on the plasticizer, and plasticizers of various known systems can be widely used. As an example, low molecular weight compounds such as phthalates, adipates, phosphates, trimellitic acid esters, and citrates, polyethers, polyesters, and polymers such as polyacetal polymers described in Japanese Patent Application Laid-Open No. 2013-253227 can be exemplified. The amount of the plasticizer added is preferably 1 to 100 parts, more preferably 5 to 30 parts, relative to 100 parts of the above-mentioned compounds and / or polymers.

[0251] In the organic film-forming composition of the present invention, as an additive for imparting filling / planarizing properties similar to a plasticizer, a liquid additive having a polyethylene glycol or polypropylene glycol structure, or a pyrolyzable polymer having a weight loss rate of 40% by mass or greater between 30°C and 250°C and a weight-average molecular weight of 300 to 200,000 is preferably used. The pyrolyzable polymer preferably contains repeating units having an acetal structure represented by the following general formulas (DP1) and (DP1a).

[0252] [Chemistry 31]

[0253]

[0254] (In the formula, R7 is a hydrogen atom or an optionally substituted saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms. Y is a saturated or unsaturated divalent organic group having 2 to 30 carbon atoms.)

[0255] [Chemistry 32]

[0256]

[0257] (In the formula, R8 is an alkyl group having 1 to 4 carbon atoms. Z is a saturated or unsaturated divalent hydrocarbon group having 4 to 10 carbon atoms, which may also have an ether bond. j represents the average number of repeating units, which is 3 to 500.)

[0258] [Other ingredients]

[0259] The organic film-forming composition of the present invention may also be blended with other compounds or polymers. The blending compound or polymer mixed with the organic film-forming composition of the present invention has the effect of improving the film-forming property of spin coating and the filling property of substrates with uneven surfaces.

[0260] Examples of such materials include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3,5-diphenylphenol, 2-naphthylphenol, 3-naphthylphenol, 4-naphthylphenol, 4-tritylphenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, catechol, 4-tert-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, Phenol, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-tert-butyl-5-methylphenol, gallol, thymol, isothymol, 4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2'-dimethyl-4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2 'Diallyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'difluoro-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'diphenyl-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,2'dimethoxy-4,4'-(9H-fluorene-9-ylidene)bisphenol, 2,3,2',3'-tetrahydro-(1,1' )-spirobiindene-6,6'-diol, 3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 3,3,3',3',4,4'-hexamethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 2,3,2',3'-tetrahydro -(1,1')-spirobiindene-5,5'-diol, 5,5'-dimethyl-3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol and 1,5-dihydroxy Naphthalene, dihydroxynaphthalene such as 1,7-dihydroxynaphthalene and 2,6-dihydroxynaphthalene, methyl 3-hydroxynaphthalene-2-carboxylate, indene, hydroxyindene, benzofuran, hydroxyanthracene, vinylnaphthalene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborn-2-ene, α-pinene, β-pinene, novolac resins such as limonene, polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyvinylnaphthalene, polynorbornene, polycyclodecene, polytetracyclododecene, polytricyclo[2.2.1.0(2,6)]heptane (poly-nortricyclene), poly(meth)acrylates, and copolymers thereof.In addition, naphthol dicyclopentadiene copolymers described in JP-A-2004-205685, fluorene bisphenol novolac resins described in JP-A-2005-128509, ethylene naphthalene copolymers described in JP-A-2005-250434, fullerenes having a phenol group described in JP-A-2006-227391, bisphenol compounds and novolac resins thereof described in JP-A-2006-293298, novolac resins of adamantaneol compounds described in JP-A-2006-285095, bisnaphthol compounds and novolac resins described in JP-A-2010-122656, and fullerene resin compounds described in JP-A-2008-158002 may also be blended.

[0261] The amount of the compound or polymer for doping is preferably 0 to 1,000 parts by mass, more preferably 0 to 500 parts by mass, based on 100 parts by mass of the organic film-forming composition of the present invention.

[0262] The organic film-forming material of the present invention can be used alone or in combination of two or more. The organic film-forming material can be used as an organic film material or a planarizing material for manufacturing a semiconductor device.

[0263] Furthermore, the organic film-forming composition of the present invention is extremely useful as an organic film material for multilayer resist processing, such as two-layer resist processing, three-layer resist processing using a silicon-containing intermediate film, and four-layer resist processing using a silicon-containing inorganic hard mask and an organic antireflective film.

[0264] (Organic film formation method)

[0265] The present invention provides a method for forming an organic film that functions as an organic film of a multilayer resist film used in photolithography or a planarizing film for semiconductor manufacturing, using the above-mentioned organic film-forming composition.

[0266] The method for forming an organic film using the organic film-forming composition of the present invention is to apply the organic film-forming composition to a substrate to be processed by a spin coating method or the like. By using a spin coating method or the like, good filling characteristics can be obtained. After spin coating, the solvent is evaporated, and baking (heat treatment) is performed to promote a cross-linking reaction in order to prevent mixing with the resist upper film and the resist intermediate film. The baking is preferably performed at a temperature of 100°C to 600°C for 10 to 600 seconds, more preferably at a temperature of 200°C to 500°C for 10 to 300 seconds. Considering the influence on device damage and wafer deformation, the upper limit of the heating temperature in the wafer processing of photolithography is preferably 600°C or less, more preferably 500°C or less.

[0267] In addition, the organic film forming method using the organic film forming composition of the present invention can also apply the organic film forming composition of the present invention on the processed substrate by the same spin coating method as mentioned above, and calcine the above-mentioned organic film forming composition in an environment with an oxygen concentration of not less than 0.1 volume % and not more than 21 volume % to harden it, thereby forming an organic film.

[0268] By forming the organic film of the present invention and calcining the composition in such an oxygen environment, a fully hardened film can be obtained. As the environment in the baking, it is also fine in air. In order to reduce oxygen, inert gases such as N , Ar, He are enclosed, preferably in order to prevent the oxidation of the organic film. In order to prevent oxidation, it is necessary to control the oxygen concentration, preferably below 1000ppm, more preferably below 100ppm (volume basis). If the oxidation of the organic film in the baking is prevented, then absorption will not increase or etching resistance will not reduce so preferably.

[0269] The organic film formation method using the organic film-forming composition of the present invention can obtain a flat cured film regardless of the unevenness of the processed substrate due to its excellent filling / planarization properties. Therefore, it is extremely useful for forming a flat cured film on a processed substrate having structures with a height of 30 nm or more or having height differences.

[0270] The thickness of the organic film or the organic film such as the planarization film for manufacturing a semiconductor device is appropriately selected and is preferably 30 to 20,000 nm, particularly preferably 50 to 15,000 nm.

[0271] (Pattern Formation Method)

[0272] The present invention provides a pattern forming method as a pattern forming method using a three-layer resist using such an organic film-forming composition. The method is a method for forming a pattern on a workpiece, and has at least the following steps: using the above-mentioned organic film-forming composition to form an organic film on the workpiece, using a silicon-containing resist intermediate film material to form a silicon-containing resist intermediate film on the organic film, using a photoresist composition to form a resist upper film on the silicon-containing resist intermediate film, forming a circuit pattern on the resist upper film, using the patterned resist upper film as a mask, transferring the pattern to the silicon-containing resist intermediate film by etching, using the silicon-containing resist intermediate film with the transferred pattern as a mask, transferring the pattern to the organic film by etching, and further using the organic film with the transferred pattern as a mask, etching the workpiece to form a pattern.

[0273] The silicon-containing resist interlayer film in the three-layer resist process exhibits etching resistance by oxygen or hydrogen. Therefore, in the three-layer resist process, it is preferable to use an etching gas mainly composed of oxygen or hydrogen to perform dry etching of the organic film using the silicon-containing resist interlayer film as a mask.

[0274] A polysiloxane-based interlayer is preferably used as the silicon-containing resist interlayer for the three-layer resist treatment. By providing the silicon-containing resist interlayer with an antireflection effect, reflection can be suppressed. Especially for 193nm exposure, using an organic film made of a material containing a large number of aromatic groups and having high etching selectivity with the substrate results in a high k value and increased substrate reflection. However, by providing the silicon-containing resist interlayer with an absorption function that achieves an appropriate k value, reflection can be suppressed, reducing substrate reflection to less than 0.5%. For silicon-containing resist interlayers with an antireflection effect, it is preferable to use an acid- or heat-crosslinked polysiloxane with pendant anthracene-based light-absorbing groups for 248nm and 157nm exposure, and pendant phenyl-based or silicon-silicon-based light-absorbing groups for 193nm exposure.

[0275] Furthermore, it is also suitable for a four-layer resist process using an organic antireflective film. In this case, a semiconductor device circuit pattern can be formed on a substrate by a pattern forming method having at least the following steps:

[0276] An organic film is formed on a workpiece using the above-mentioned organic film-forming composition, a silicon-containing resist interlayer is formed on the organic film using a silicon-containing resist interlayer material, an organic antireflective film (BARC) is formed on the silicon-containing resist interlayer, a photoresist composition is formed on the BARC to form a resist upper layer film to form a four-layer film structure, a circuit pattern is formed on the resist upper layer film, the patterned resist upper layer film is used as a mask to transfer the pattern to the BARC film and the silicon-containing resist interlayer by etching, the patterned silicon-containing resist interlayer is used as a mask to transfer the pattern to the organic film by etching, and further, the organic film with the transferred pattern is used as a mask to etch the workpiece to form a pattern on the workpiece.

[0277] In addition, an inorganic hard mask can also be formed to replace the silicon-containing resist intermediate film. In this case, a semiconductor device circuit pattern can be formed on a substrate by a pattern forming method having at least the following steps: using the above-mentioned organic film forming composition to form an organic film on a workpiece, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the organic film, using a photoresist composition to form a resist upper film on the inorganic hard mask, forming a circuit pattern on the resist upper film, using the patterned resist upper film as a mask to etch the inorganic hard mask, using the patterned inorganic hard mask as a mask to etch the organic film, and further, using the patterned organic film as a mask to etch the workpiece to form a pattern on the workpiece.

[0278] As described above, when forming an inorganic hard mask on an organic film, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) can be formed by CVD, ALD, or the like. For example, methods for forming a silicon nitride film are described in Japanese Patent Application Publication No. 2002-334869 and International Publication No. 2004 / 066377. The thickness of the inorganic hard mask is preferably 5 to 200 nm, more preferably 10 to 100 nm. Furthermore, SiON film, which is highly effective as an antireflective film, is most preferably used as the inorganic hard mask. The substrate temperature during SiON film formation is 300 to 500°C, so the organic film must be able to withstand temperatures of 300 to 500°C. The organic film-forming composition used in the present invention has high heat resistance and can withstand high temperatures of 300 to 500°C, making it possible to combine an inorganic hard mask formed by CVD or ALD with an organic film formed by spin coating.

[0279] In addition, it is also suitable for a four-layer resist process using an organic anti-reflective film. In this case, a semiconductor device circuit pattern can be formed on a substrate by at least a pattern forming method having the following steps: using the above-mentioned organic film forming composition to form an organic film on a workpiece, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the organic film, forming a BARC on the inorganic hard mask, using a photoresist composition to form a resist upper film on the BARC to form a four-layer film structure, forming a circuit pattern on the resist upper film, using the patterned resist upper film as a mask, etching the BARC film and the inorganic hard mask, using the patterned inorganic hard mask as a mask, etching the organic film, and further, using the patterned organic film as a mask, etching the workpiece to form a pattern on the workpiece.

[0280] As described above, a photoresist film can be formed on an inorganic hard mask as a resist upper layer. Alternatively, an organic antireflective coating (BARC) can be formed on the inorganic hard mask by spin coating, and a photoresist film formed thereon. In particular, when a SiON film is used as the inorganic hard mask, the dual-layer antireflective coating of the SiON film and the BARC can suppress reflections even during immersion exposure with a high NA exceeding 1.0. Another advantage of forming a BARC is that it reduces the tailing of the photoresist pattern directly above the SiON film.

[0281] The resist top layer in the three-layer resist process can be either positive or negative, and the same photoresist composition as commonly used can be used. After spin coating the photoresist composition, a pre-bake is performed, preferably at 60-180°C for 10-300 seconds. Exposure is then performed according to conventional methods, followed by a post-exposure bake (PEB) and development to obtain a resist pattern. The thickness of the resist top layer is not particularly limited, but is preferably 30-500 nm, particularly 50-400 nm.

[0282] The exposure light is high-energy radiation having a wavelength of 300 nm or less, and specifically includes excimer lasers of 248 nm, 193 nm, and 157 nm, soft X-rays of 3 to 20 nm, electron beams, and X-rays.

[0283] As a method for forming a pattern of the resist upper layer film, optical lithography with a wavelength of 10 nm to 300 nm, direct writing using an electron beam, nanoimprinting, or a combination thereof is preferably used.

[0284] Furthermore, the development method in the above-mentioned pattern forming method is preferably alkali development or development using an organic solvent.

[0285] Then, etching is performed using the resulting resist pattern as a mask. Etching of the silicon-containing resist interlayer and the inorganic hard mask in the three-layer resist process is performed using a fluorocarbon-based gas and the upper resist pattern as a mask. This forms a silicon-containing resist interlayer pattern and an inorganic hard mask pattern.

[0286] Then, the organic film is etched using the obtained silicon-containing resist intermediate film pattern and the inorganic hard mask pattern as masks.

[0287] Subsequent etching of the substrate can also be performed using conventional methods. For example, if the substrate is SiO2, SiN, or a silicon dioxide-based low-k dielectric film, etching is performed primarily using chlorofluorocarbon-based gases; if it is p-Si, Al, or W, etching is performed primarily using chlorine-based or bromine-based gases. When etching the substrate using chlorofluorocarbon-based gases, the silicon-containing resist interlayer pattern in the three-layer resist process is stripped simultaneously with substrate processing. When etching the substrate using chlorine-based or bromine-based gases, stripping the silicon-containing resist interlayer pattern requires a separate dry etching stripping process using chlorofluorocarbon-based gases after substrate processing.

[0288] The organic film obtained by using the organic film-forming composition of the present invention is characterized by excellent etching resistance when etching these substrates to be processed.

[0289] Furthermore, the workpiece (substrate to be worked) is not particularly limited, and substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, and Al, and a workpiece layer formed on such a substrate, can be used. The workpiece layer can be made of various low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, as well as barrier films thereof. Typically, a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm, can be formed. Furthermore, when forming the workpiece layer, the substrate and the workpiece layer can be made of different materials.

[0290] As the object to be processed, it is preferable to use a semiconductor device substrate, or a film formed on the semiconductor device substrate of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film. More specifically, there is no particular limitation, and substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., and a film formed on the substrate of the above-mentioned metal film as the object to be processed, etc.

[0291] As the processing layer, various low-k films and barrier films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si can be used. Typically, thicknesses of 50 to 10,000 nm, particularly 100 to 5,000 nm, can be formed. Furthermore, when forming the processing layer, the substrate and the processing layer can be made of different materials.

[0292] In addition, the metal constituting the workpiece is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, ruthenium, or an alloy thereof.

[0293] Furthermore, as the object to be processed, it is preferable to use an object to be processed having a structure with a height of 30 nm or more or an object with a height difference.

[0294] For an example of 3-layer resist processing, use Figure 1 Specifically, it is shown as follows. Figure 1 As shown in (A), an organic film 3 is formed on a workpiece layer 2 laminated on a substrate 1 using the organic film-forming composition of the present invention, and then a silicon-containing resist intermediate film 4 is formed, and a resist upper film 5 is formed thereon.

[0295] Then, if Figure 1 As shown in (B), the portion 6 of the resist upper layer film 5 is exposed, PEB and developed to form a resist pattern 5a ( Figure 1(C)). The obtained resist pattern 5a is used as a mask, and the silicon-containing resist intermediate film 4 is etched using CF-based gas to form a silicon-containing resist intermediate film pattern 4a ( Figure 1 After removing the resist pattern 5a, the obtained silicon-containing resist intermediate film pattern 4a is used as a mask to perform oxygen plasma etching on the organic film 3 to form an organic film pattern 3a ( Figure 1 (E)). Further, after removing the silicon-containing resist intermediate film pattern 4a, the organic film pattern 3a is used as a mask to etch the processed layer 2 to form a pattern 2a ( Figure 1 (F)).

[0296] When an inorganic hard mask is used, the silicon-containing resist interlayer film 4 serves as the inorganic hard mask, and when applying BARC, a BARC layer is provided between the silicon-containing resist interlayer film 4 and the resist upper layer film 5. BARC etching may be performed continuously before etching the silicon-containing resist interlayer film 4. Alternatively, etching of the silicon-containing resist interlayer film 4 may be performed after etching the BARC alone, and then etching of the silicon-containing resist interlayer film 4 may be performed by changing the etching equipment.

[0297] As described above, according to the pattern forming method of the present invention, a fine pattern can be formed on a substrate to be processed with high precision in a multilayer resist process.

[0298] In particular, the present invention uses an organic film forming composition containing an organic solvent and a compound represented by the above-mentioned general formula (1) as an organic film forming material and / or a polymer having a repeating unit represented by the above-mentioned general formula (3), so that in multilayer resist processing, a fine pattern can be formed on the processed object with higher precision.

[0299] [Example]

[0300] The present invention will be described in more detail below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. Furthermore, as molecular weight and dispersity, the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene were determined by gel permeation chromatography (GPC) using tetrahydrofuran as the eluent, and the dispersity (Mw / Mn) was determined.

[0301] [Synthesis Example] Synthesis of Compounds and Polymers for Organic Film-Forming Materials]

[0302] In the synthesis of compounds (A1) to (A16), polymers (A17) to (A19), and comparative polymers (R1) to (R3) for organic film-forming materials, compounds (B1) to (B7) were used as phenols or naphthols, compounds (C1) to (C3) were used as bis(indole-2,3-dione)s, and compounds (D1) and (D2) were used as aldehydes. (D-1) was used as a 37% aqueous solution.

[0303] Phenols or naphthols:

[0304] [Chemistry 33]

[0305]

[0306] Bis(indole-2,3-diones):

[0307] [Chemistry 34]

[0308]

[0309] Aldehydes:

[0310] [Chemistry 35]

[0311]

[0312] The bis(indole-2,3-diones) shown above were synthesized as follows.

[0313] (Synthesis example 1)

[0314] Synthesis of compound (C1)

[0315] [Chemistry 36]

[0316]

[0317] Under a nitrogen environment, 73.6 g of indole-2,3-dione, 207.3 g of potassium carbonate, and 900 g of DMF (dimethylformamide) were added to form a uniform dispersion at an internal temperature of 50°C. 205.1 g of 1,4-dibromobutane was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. After the reaction was completed, the reaction solution was added to 5000 ml of pure water to precipitate crystals. The settled crystals were filtered and separated, washed 3 times with 1000 ml of pure water, then washed twice with 1000 ml of methanol and recovered. The recovered crystals were vacuum dried at 70°C to obtain compound (C1).

[0318] (Synthesis example 2)

[0319] Synthesis of compound (C2)

[0320] [Chemistry 37]

[0321]

[0322] Under a nitrogen environment, 73.6 g of indole-2,3-dione, 207.3 g of potassium carbonate, and 900 g of DMF were added to form a uniform dispersion at an internal temperature of 50°C. 231.8 g of 1,6-dibromohexane was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. After the reaction was completed, the reaction solution was added to 5000 ml of pure water to precipitate crystals. The settled crystals were filtered and separated, washed 3 times with 1000 ml of pure water, then washed twice with 1000 ml of methanol and recovered. The recovered crystals were vacuum dried at 70°C to obtain compound (C2).

[0323] (Synthesis example 3)

[0324] Synthesis of compound (C3)

[0325] [Chemistry 38]

[0326]

[0327] Under a nitrogen environment, 107.6 g of 7-(trifluoromethyl)indole-2,3-dione, 207.3 g of potassium carbonate, and 900 g of DMF were added to form a uniform dispersion at an internal temperature of 50°C. 205.1 g of 1,4-dibromobutane was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. After the reaction was completed, the reaction solution was added to 6000 ml of pure water to precipitate crystals. The settled crystals were separated by filtration, washed 3 times with 1000 ml of pure water, then washed twice with 1000 ml of methanol and recovered. The recovered crystals were vacuum dried at 70°C to obtain compound (C3).

[0328] Compounds (A1) to (A16), polymers (A17) to (A19), and polymers (R1) to (R3) for comparative examples were synthesized as follows.

[0329] (Synthesis Example 4)

[0330] Synthesis of compound (A1)

[0331] [Chemistry 39]

[0332]

[0333] Under a nitrogen environment, 11.9 g of compound (B1), 10.0 g of compound (C1), 8.3 g of methanesulfonic acid, and 100 g of dichloromethane were added, and a uniform dispersion was prepared at room temperature. Then, 0.3 g of 3-mercaptopropionic acid was added and the mixture was reacted at room temperature for 8 hours. After the reaction was completed, 200 ml of MIBK (methyl isobutyl ketone) was added at room temperature, washed 6 times with 100 ml of pure water, and the organic layer was dried under reduced pressure. After 60 g of MIBK was added to the residue to prepare a uniform solution, crystals were precipitated in 300 g of IPE (diisopropyl ether). The settled crystals were separated by filtration, washed twice with 100 g of IPE, and recovered. The recovered crystals were vacuum dried at 70°C to obtain compound (A1).

[0334] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0335] (A1): Mw=740, Mw / Mn=1.02

[0336] (Synthesis Example 5)

[0337] Synthesis of compound (A2)

[0338] [Chemistry 40]

[0339]

[0340] Under a nitrogen atmosphere, 13.9 g of compound (B2), 10.0 g of compound (C1), 8.3 g of methanesulfonic acid, and 100 g of dichloromethane were added to form a uniform dispersion at room temperature. 0.3 g of 3-mercaptopropionic acid was then added and the mixture was reacted at room temperature for 8 hours. After the reaction was completed, the mixture was cooled in an ice bath to precipitate crystals. 300 g of IPE was added and stirred to disperse the mixture. The settled crystals were separated by filtration and washed five times with 100 g of IPE for recovery. The recovered crystals were vacuum dried at 70 ° C to obtain compound (A2).

[0341] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0342] (A2): Mw=820, Mw / Mn=1.01

[0343] (Synthesis Example 6)

[0344] Synthesis of compound (A3)

[0345] [Chemistry 41]

[0346]

[0347] Under a nitrogen environment, 18.2 g of compound (B3), 10.0 g of compound (C1) and 120 g of dichloromethane were added, and a uniform dispersion was prepared at room temperature. Then, 12.9 g of trifluoromethanesulfonic acid was slowly added dropwise, and the reaction was carried out at room temperature for 8 hours. After the reaction was completed, 200 ml of MIBK was added, and the mixture was washed 6 times with 100 ml of pure water, and the organic layer was dried under reduced pressure. After 60 g of MIBK was added to the residue to prepare a uniform solution, crystals were precipitated in IPE300 g. The settled crystals were separated by filtration, washed twice with 100 g of IPE and recovered. The recovered crystals were vacuum dried at 70 ° C to obtain compound (A3).

[0348] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0349] (A3): Mw=910, Mw / Mn=1.03

[0350] (Synthesis Example 7)

[0351] Synthesis of compound (A4)

[0352] [Chemistry 42]

[0353]

[0354] Under a nitrogen environment, 20.2 g of compound (B4), 10.0 g of compound (C1), and 120 g of dichloromethane were added, and a uniform dispersion was prepared at room temperature. Then, 12.9 g of trifluoromethanesulfonic acid was slowly added dropwise, and the reaction was carried out at room temperature for 8 hours. After the reaction was completed, 200 ml of MIBK was added, and the mixture was washed 6 times with 100 ml of pure water. The organic layer was dried under reduced pressure. 80 g of MIBK was added to the residue to prepare a uniform solution, and crystals were precipitated in 300 g of IPE. The settled crystals were separated by filtration, washed twice with 100 g of IPE, and recovered. The recovered crystals were vacuum dried at 70 ° C to obtain compound (A4).

[0355] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0356] (A4): Mw=960, Mw / Mn=1.05

[0357] (Synthesis Example 8)

[0358] Synthesis of compound (A5)

[0359] [Chemistry 43]

[0360]

[0361] Under a nitrogen environment, 11.0 g of compound (B1), 10.0 g of compound (C2), 7.7 g of methanesulfonic acid, and 100 g of dichloromethane were added, and a uniform dispersion was prepared at room temperature. Then, 0.3 g of 3-mercaptopropionic acid was added, and the reaction was carried out at room temperature for 8 hours. After the reaction was completed, 200 ml of MIBK was added, and the mixture was washed 6 times with 100 ml of pure water. The organic layer was dried under reduced pressure. After 60 g of MIBK was added to the residue to prepare a uniform solution, crystals were precipitated in 300 g of IPE. The settled crystals were separated by filtration, washed twice with 100 g of IPE, and recovered. The recovered crystals were vacuum dried at 70 ° C to obtain compound (A5).

[0362] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0363] (A5): Mw=760, Mw / Mn=1.02

[0364] (Synthesis Example 9)

[0365] Synthesis of compound (A6)

[0366] [Chemistry 44]

[0367]

[0368] Under a nitrogen atmosphere, 12.9 g of compound (B2), 10.0 g of compound (C2), 7.7 g of methanesulfonic acid, and 100 g of dichloromethane were added to form a uniform dispersion at room temperature. 0.3 g of 3-mercaptopropionic acid was then added, and the mixture was reacted at room temperature for 8 hours. After the reaction was completed, the mixture was cooled in an ice bath to precipitate crystals. 300 g of IPE was added and stirred to disperse the mixture. The settled crystals were separated by filtration, washed five times with 100 g of IPE, and recovered. The recovered crystals were vacuum dried at 70°C to obtain compound (A6).

[0369] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0370] (A6): Mw=820, Mw / Mn=1.01

[0371] (Synthesis Example 10)

[0372] Synthesis of compound (A7)

[0373] [Chemistry 45]

[0374]

[0375] Under a nitrogen environment, 10.0 g of compound (B2), 10.0 g of compound (C3), 6.0 g of methanesulfonic acid and 100 g of dichloromethane were added, and a uniform dispersion was prepared at room temperature. Then, 0.2 g of 3-mercaptopropionic acid was added and the mixture was reacted at room temperature for 8 hours. After the reaction was completed, 100 ml of MIBK and 100 ml of THF were added, and the mixture was washed 6 times with 100 ml of pure water, and the organic layer was dried under reduced pressure. After 60 g of THF was added to the residue to prepare a uniform solution, crystals were precipitated in 300 g of hexane. The settled crystals were separated by filtration, washed twice with 100 g of hexane and recovered. The recovered crystals were dried in vacuo at 70 ° C to obtain compound (A7).

[0376] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0377] (A7): Mw=890, Mw / Mn=1.01

[0378] (Synthesis Example 11)

[0379] Synthesis of compound (A8)

[0380] [Chemistry 46]

[0381]

[0382] Under a nitrogen environment, 13.1 g of compound (B3), 10.0 g of compound (C3) and 100 g of dichloromethane were added, and a uniform dispersion was prepared at room temperature. Then, 9.3 g of trifluoromethanesulfonic acid was slowly added dropwise, and the reaction was carried out at room temperature for 8 hours. After the reaction was completed, 200 ml of MIBK was added, and the mixture was washed 6 times with 100 ml of pure water. The organic layer was dried under reduced pressure. After 60 g of THF was added to the residue to prepare a uniform solution, crystals were precipitated in 300 g of IPE. The settled crystals were separated by filtration, washed twice with 100 g of IPE and recovered. The recovered crystals were vacuum dried at 70 ° C to obtain compound (A8).

[0383] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0384] (A8): Mw=1030, Mw / Mn=1.04

[0385] (Synthesis Example 12)

[0386] Synthesis of compound (A9)

[0387] [Chemistry 47]

[0388]

[0389] Under a nitrogen environment, 10.0 g of compound (A1), 12.0 g of potassium carbonate, and 60 g of DMF were added to prepare a uniform dispersion at an internal temperature of 50°C. 8.6 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was completed, 100 ml of MIBK was added, and the mixture was washed 6 times with 50 ml of pure water, and the organic layer was dried under reduced pressure. 40 g of MIBK was added to the residue to prepare a uniform solution, and then crystals were precipitated in 200 g of MeOH (methanol). The settled crystals were separated by filtration, washed twice with 100 g of MeOH, and recovered. The recovered crystals were vacuum dried at 70°C to obtain compound (A9).

[0390] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0391] (A9): Mw=880, Mw / Mn=1.02

[0392] (Synthesis Example 13)

[0393] Synthesis of compound (A10)

[0394] [Chemistry 48]

[0395]

[0396] Under a nitrogen environment, 10.0 g of compound (A2), 22.0 g of potassium carbonate, and 80 g of DMF were added to prepare a uniform dispersion at an internal temperature of 50°C. 15.8 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. After the reaction was completed, 100 ml of MIBK was added, and the mixture was washed 6 times with 50 ml of pure water, and the organic layer was dried under reduced pressure. 40 g of MIBK was added to the residue to prepare a uniform solution, and then crystals were precipitated in 200 g of MeOH (methanol). The settled crystals were separated by filtration, washed twice with 100 g of MeOH, and recovered. The recovered crystals were vacuum dried at 70°C to obtain compound (A10).

[0397] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0398] (A10): Mw=1060, Mw / Mn=1.03

[0399] (Synthesis Example 14)

[0400] Synthesis of compound (A11)

[0401] [Chemistry 49]

[0402]

[0403] Under a nitrogen environment, 10.0 g of compound (A3), 9.3 g of potassium carbonate, and 40 g of DMF were added to prepare a uniform dispersion at an internal temperature of 50°C. 6.7 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was completed, 100 ml of MIBK was added, and the mixture was washed 6 times with 50 ml of pure water, and the organic layer was dried under reduced pressure. 40 g of MIBK was added to the residue to prepare a uniform solution, and then crystals were precipitated in 200 g of MeOH (methanol). The settled crystals were separated by filtration, washed twice with 100 g of MeOH, and recovered. The recovered crystals were vacuum dried at 70°C to obtain compound (A11).

[0404] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0405] (A11): Mw=1080, Mw / Mn=1.05

[0406] (Synthesis Example 15)

[0407] Synthesis of compound (A12)

[0408] [Chemistry 50]

[0409]

[0410] Under a nitrogen environment, 10.0 g of compound (A4), 9.0 g of potassium carbonate, and 40 g of DMF were added to prepare a uniform dispersion at an internal temperature of 50°C. 6.5 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was completed, 100 ml of MIBK was added, and the mixture was washed 6 times with 50 ml of pure water, and the organic layer was dried under reduced pressure. 40 g of MIBK was added to the residue to prepare a uniform solution, and then crystals were precipitated in 200 g of MeOH (methanol). The settled crystals were separated by filtration and recovered by washing twice with 100 g of MeOH. The recovered crystals were vacuum dried at 70°C to obtain compound (A12).

[0411] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0412] (A12): Mw=1110, Mw / Mn=1.05

[0413] (Synthesis Example 16)

[0414] Synthesis of compound (A13)

[0415] [Chemistry 51]

[0416]

[0417] Under a nitrogen environment, 10.0 g of compound (A5), 11.6 g of potassium carbonate, and 60 g of DMF were added to prepare a uniform dispersion at an internal temperature of 50°C. 8.6 g of allyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was completed, 100 ml of MIBK was added, and the mixture was washed 6 times with 50 ml of pure water, and the organic layer was dried under reduced pressure. After adding 40 g of MIBK to the residue to prepare a uniform solution, crystals were precipitated in 200 g of MeOH (methanol). The settled crystals were separated by filtration, washed twice with 100 g of MeOH, and recovered. The recovered crystals were vacuum dried at 70°C to obtain compound (A13).

[0418] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0419] (A13): Mw=900, Mw / Mn=1.02

[0420] (Synthesis Example 17)

[0421] Synthesis of compound (A14)

[0422] [Chemistry 52]

[0423]

[0424] Under a nitrogen environment, 10.0 g of compound (A6), 21.4 g of potassium carbonate, and 80 g of DMF were added to prepare a uniform dispersion at an internal temperature of 50°C. 15.2 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. After the reaction was completed, 100 ml of MIBK was added, and the mixture was washed 6 times with 50 ml of pure water, and the organic layer was dried under reduced pressure. 40 g of MIBK was added to the residue to prepare a uniform solution, and then crystals were precipitated in 200 g of MeOH (methanol). The settled crystals were separated by filtration, washed twice with 100 g of MeOH, and recovered. The recovered crystals were vacuum dried at 70°C to obtain compound (A14).

[0425] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0426] (A14): Mw=1130, Mw / Mn=1.03

[0427] (Synthesis Example 18)

[0428] Synthesis of compound (A15)

[0429] [Chemistry 53]

[0430]

[0431] Under a nitrogen environment, 10.0 g of compound (A7), 18.7 g of potassium carbonate, and 80 g of DMF were added to prepare a uniform dispersion at an internal temperature of 50°C. 13.3 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. After the reaction was completed, 100 ml of MIBK was added, and the mixture was washed 6 times with 50 ml of pure water, and the organic layer was dried under reduced pressure. 40 g of MIBK was added to the residue to prepare a uniform solution, and then crystals were precipitated in 200 g of MeOH (methanol). The settled crystals were separated by filtration, washed twice with 100 g of MeOH, and recovered. The recovered crystals were vacuum dried at 70°C to obtain compound (A15).

[0432] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0433] (A15): Mw=1130, Mw / Mn=1.03

[0434] (Synthesis Example 19)

[0435] Synthesis of compound (A16)

[0436] [Chemistry 54]

[0437]

[0438] Under a nitrogen environment, 10.0 g of compound (A8), 8.1 g of potassium carbonate, and 60 g of DMF were added to prepare a uniform dispersion at an internal temperature of 50°C. 5.9 g of allyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 16 hours. After the reaction was completed, 100 ml of MIBK was added, and the mixture was washed 6 times with 50 ml of pure water, and the organic layer was dried under reduced pressure. 40 g of MIBK was added to the residue to prepare a uniform solution, and then crystals were precipitated in 200 g of MeOH (methanol). The settled crystals were separated by filtration, washed twice with 100 g of MeOH, and recovered. The recovered crystals were vacuum dried at 70°C to obtain compound (A16).

[0439] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0440] (A16): Mw=1220, Mw / Mn=1.05

[0441] (Synthesis Example 20)

[0442] Synthesis of polymer (A17)

[0443] [Chemistry 55]

[0444]

[0445] Under a nitrogen environment, 5.0 g of compound (A9), 0.19 g of compound (D1), and 50 g of 1,2-dichloroethane were added to prepare a uniform solution at an internal temperature of 50°C. 0.5 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 50°C for 8 hours. After the reaction was completed, it was cooled to room temperature and 100 ml of MIBK was added. The mixture was washed 6 times with 50 ml of pure water, and the organic layer was dried under reduced pressure. 20 g of THF was added to the residue to prepare a uniform solution, and crystals were precipitated in 100 g of hexane. The settled crystals were separated by filtration, washed twice with 50 g of hexane, and recovered. The recovered crystals were vacuum dried at 70°C to obtain polymer (A17).

[0446] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0447] (A17): Mw=2700, Mw / Mn=1.58

[0448] (Synthesis Example 21)

[0449] Synthesis of polymer (A18)

[0450] [Chemistry 56]

[0451]

[0452] Under a nitrogen environment, 5.0 g of compound (A11), 0.12 g of compound (D1), and 50 g of 1,2-dichloroethane were added to prepare a uniform solution at an internal temperature of 50°C. 0.5 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 50°C for 8 hours. After the reaction was completed, it was cooled to room temperature and 100 ml of MIBK was added. The mixture was washed 6 times with 50 ml of pure water, and the organic layer was dried under reduced pressure. 20 g of THF was added to the residue to prepare a uniform solution, and crystals were precipitated in 100 g of hexane. The settled crystals were separated by filtration, washed twice with 50 g of hexane, and recovered. The recovered crystals were vacuum dried at 70°C to obtain polymer (A18).

[0453] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0454] (A18): Mw=3300, Mw / Mn=1.45

[0455] (Synthesis Example 22)

[0456] Synthesis of polymer (A19)

[0457] [Chemistry 57]

[0458]

[0459] Under a nitrogen environment, 5.0 g of compound (A14), 0.29 g of compound (D2), and 50 g of 1,2-dichloroethane were added to prepare a uniform solution at an internal temperature of 50°C. 0.5 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 50°C for 8 hours. After the reaction was completed, it was cooled to room temperature and 100 ml of MIBK was added. The mixture was washed 6 times with 50 ml of pure water, and the organic layer was dried under reduced pressure. 20 g of THF was added to the residue to prepare a uniform solution, and crystals were precipitated in 100 g of hexane. The settled crystals were separated by filtration, washed twice with 50 g of hexane, and recovered. The recovered crystals were vacuum dried at 70°C to obtain a polymer (A19).

[0460] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0461] (A19): Mw=3600, Mw / Mn=1.59

[0462] (Synthesis Example 23)

[0463] Synthesis of polymer (R1) for comparative example

[0464] [Chemistry 58]

[0465]

[0466] Under a nitrogen atmosphere, 31.8 g of compound (B5), 4.9 g of compound (D1), 5.0 g of oxalic acid, and 50 g of dioxane were added, and the reaction was allowed to proceed at an internal temperature of 100°C for 24 hours. After the reaction, 500 ml of MIBK was added at room temperature, and the mixture was washed six times with 100 ml of pure water. The organic layer was recovered, and the water and solvent were removed under reduced pressure at an internal temperature of 150°C and 2 mmHg to obtain a polymer (R1) for comparative example.

[0467] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0468] (R1): Mw=3200, Mw / Mn=4.88

[0469] (Synthesis Example 24)

[0470] Synthesis of polymer (R2) for comparative example

[0471] [Chemistry 59]

[0472]

[0473] Under a nitrogen atmosphere, 42.3 g of compound (B6), 5.7 g of compound (D1), 5.0 g of oxalic acid, and 60 g of dioxane were added and reacted at an internal temperature of 100°C for 24 hours. After the reaction, 500 ml of MIBK was added at room temperature and the mixture was washed six times with 100 ml of pure water. The organic layer was recovered and the water and solvent were removed under reduced pressure at an internal temperature of 150°C and 2 mmHg to obtain a polymer (R2) for comparative example.

[0474] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0475] (R2): Mw=2600, Mw / Mn=3.55

[0476] (Synthesis Example 25)

[0477] Synthesis of polymer (R3) for comparative example

[0478] [Chemistry 60]

[0479]

[0480] Under nitrogen, add 3.1 g of indole-2,3-dione, 10.0 g of compound (B7), 3.0 g of methane sulfone, 16.1 g of propylene glycol monomethyl ether, and 3.4 g of 3-mercaptopropionic acid, heat to 140 ° C and react under reflux for 4 hours. After the reaction is completed, 200 g of methanol / pure water = 1 / 1 (weight ratio) is added dropwise to precipitate crystals. The settled crystals are separated by filtration, washed twice with 100 g of pure water and recovered. The recovered crystals are vacuum dried at 60 ° C to obtain a polymer (R3) for comparative example.

[0481] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC, and the results were as follows.

[0482] (R3): Mw=8500, Mw / Mn=2.30

[0483] Tables 1 to 4 list the Mw and Mw / Mn results of compounds (A1) to (A16), polymers (A17) to (A19), and polymers (R1) to (R3) for comparative examples used in the examples.

[0484] [Table 1]

[0485]

[0486]

[0487] [Table 2]

[0488]

[0489]

[0490] [Table 3]

[0491]

[0492]

[0493] [Table 4]

[0494]

[0495] [Preparation of Organic Film-Forming Compositions (UDL-1 to 26, Comparative UDL-1 to 9)]

[0496] The above-mentioned compounds and polymers (A1) to (A19), comparative polymers (R1) to (R3), compounds (B5) and (B6) described in the above-mentioned synthesis examples, a crosslinking agent (XL), a thermal acid generator (TAG), and (S1) 1,6-diacetoxyhexane (boiling point 260°C) and (S2) tripropylene glycol monomethyl ether (boiling point 242°C) as high boiling point solvents were dissolved in propylene glycol monomethyl ether acetate (PGMEA) containing 0.1% by mass of PF-6320 (manufactured by OMNOVA) in the proportions shown in Table 5, and the mixture was filtered through a 0.1 μm fluororesin filter to prepare organic film-forming compositions (UDL-1 to 26, comparative UDL-1 to 9).

[0497] The structural formulas of the compound, cross-linking agent, and thermal acid generator used in the organic film-forming composition are shown below.

[0498] (Compound)

[0499] [Chemistry 61]

[0500]

[0501] (cross-linking agent)

[0502] [Chemistry 62]

[0503]

[0504] (Thermal Acid Generator)

[0505] [Chemistry 63]

[0506]

[0507] [Table 5]

[0508]

[0509]

[0510] <Evaluation>

[0511] [Solvent Resistance Measurement (Examples 1-1 to 1-26, Comparative Examples 1-1 to 1-9)]

[0512] UDLs 1 to 26 and comparative UDLs 1 to 9 prepared above were coated on a silicon substrate and baked in air at the temperatures listed in Table 6 for 60 seconds. The film thickness was then measured. A PGMEA solvent was dispensed onto the substrate, spin-dried for 30 seconds, and baked at 100°C for 60 seconds to evaporate the PGMEA. The film thickness before and after the PGMEA treatment was measured. The residual film rate was calculated using the film thickness after deposition and the film thickness after the PGMEA treatment. The results are shown in Table 6.

[0513] [Table 6]

[0514]

[0515]

[0516] As shown in Table 6, the organic films (Examples 1-1 to 1-26) using the compounds and / or polymers of the present invention exhibited a residual film rate of 99.5% or higher after PGMEA treatment, and exhibited sufficient solvent resistance through crosslinking reactions caused by heat treatment. Comparing Examples 1-1 to 1-16 with Comparative Examples 1-1 to 1-4 and 1-7 to 1-9, the compounds of the present invention exhibited sufficient curability regardless of the single molecule. However, Comparative Examples 1-7 and 1-8, which used only single-molecule compounds, exhibited insufficient curability, insufficient heat resistance, or low molecular weight, resulting in failure to achieve solvent resistance due to factors such as sublimation. As with Comparative Example 1-9, the addition of a crosslinker was required to ensure solvent resistance. Furthermore, in Comparative Examples 1-2 and 1-4, which incorporated polymers, while the polymers alone achieved curability, as described above, solvent resistance was likely not achieved due to insufficient curability, heat resistance, and sublimation. Furthermore, in Comparative Examples 1-5 and 1-6, regardless of the polymer used, the polymer alone did not exhibit curability, and the addition of a crosslinking agent and a thermal acid generator was necessary to ensure solvent resistance.

[0517] [Evaluation of Heat Resistance Characteristics (Examples 2-1 to 2-26, Comparative Examples 2-1 to 2-9)]

[0518] The organic film-forming compositions (UDL-1 to 26, comparative UDL-1 to 9) were each coated on a silicon substrate and baked in air at the temperature listed in Table 7 for 60 seconds to form a coating film of approximately 200 nm. The film thickness A was then measured. The substrate was further calcined at 400°C for 20 minutes under a nitrogen flow with an oxygen concentration controlled to 0.2% by volume or less, and the film thickness B was measured. These results are shown in Table 7.

[0519] [Table 7]

[0520]

[0521] As shown in Table 7, the organic film-forming compositions of the present invention (Examples 2-1 to 2-26) exhibited a film thickness reduction of less than 2% even after prolonged baking at 400°C, demonstrating excellent heat resistance. In particular, compounds and polymers incorporating a propargyloxy group as a substituent maintained a residual film rate of over 99%, demonstrating particularly excellent heat resistance.

[0522] On the other hand, in Comparative Examples 2-1 to 2-9, where solvent resistance was not achieved in the solvent resistance measurement, the residual film ratio was low. Comparative Examples 2-7 and 2-8, which used monomolecular compounds, showed almost no residual organic film. Comparative Examples 2-1, 2-3, and 2-6, which achieved solvent resistance by adding a crosslinker or using a polymer, showed lower residual film ratios than the examples of the present invention. This demonstrates that the organic films using the compounds and polymers of the present invention have excellent heat resistance.

[0523] [Evaluation of film-forming properties (Examples 3-1 to 3-26, Comparative Examples 3-1 to 3-9)]

[0524] The organic film-forming compositions prepared above (UDL-1 to 26, Comparative Examples UDL-1 to 9) were coated onto the bare-Si substrates, hexamethyldisilazane (HMDS)-treated substrates, and SiON-treated substrates shown in Table 8, respectively. These were then baked in air at the temperatures listed in Table 8 for 60 seconds to form organic films with a thickness of 100 nm. The formed organic films were then observed using an optical microscope (ECLIPSE L200 manufactured by Nikon Corporation) to determine whether coating abnormalities were present. In this evaluation, the film thickness was reduced to assess coating properties, creating stringent evaluation conditions that are prone to film formation abnormalities.

[0525] [Table 8]

[0526]

[0527] As shown in Table 8, it can be seen that the organic film-forming composition of the present invention (Examples 3-1 to 3-26) has no substrate dependence and can ensure film-forming properties. In contrast, Comparative Examples 3-7 and 3-8, as in the solvent resistance measurement and heat resistance evaluation, cannot ensure film-forming properties due to insufficient hardening and heat resistance of the monomolecular compound and the generation of sublimates. In addition, as in Comparative Examples 3-1 to 3-4 and 3-9, even with the addition of a crosslinker or polymer, the polymer alone still depends on the substrate and cannot ensure film-forming properties. From the comparison of these results, it can be inferred that the compounds and polymers of the present invention contribute to the improvement of film-forming properties by virtue of the cyclic amide structure functioning as an adhesion group. In terms of the same tendency, it can also be inferred that Comparative Examples 3-5 and 3-6 using polymers having a cyclic amide structure cannot ensure film-forming properties when the polymer alone has no hardening properties and poor heat resistance, but the film-forming properties of Comparative Example 3-6, in which a crosslinker is added to form a cured film, are improved.

[0528] [Evaluation of Landfill Characteristics (Examples 4-1 to 4-26, Comparative Examples 4-1 to 4-9)]

[0529] The organic film-forming compositions (UDL-1 to 26, comparative UDL-1 to 9) prepared above were coated on SiO2 wafer substrates having a dense hole pattern (hole diameter 0.16 μm, hole depth 0.50 μm, and distance between the centers of two adjacent holes 0.32 μm), and calcined in air at the temperature listed in Table 9 for 60 seconds to form organic films. The substrate used was as follows: Figure 2 The base substrate 7 (SiO2 wafer substrate) with a dense hole pattern is shown in (G) (top view) and (H) (cross-sectional view). The cross-sectional shape of each wafer substrate obtained was observed using a scanning electron microscope (SEM) to confirm whether the holes were filled with the organic film 8 without any gaps. The results are shown in Table 9. When an organic film-forming composition with poor filling characteristics was used, gaps were generated inside the holes in this evaluation. When an organic film-forming composition with good filling characteristics was used, as shown in this evaluation, Figure 2 As shown in (I), the organic film is filled in the voids.

[0530] [Table 9]

[0531]

[0532] As shown in Examples 4-1 to 4-26 in Table 9, when the compounds and polymers of the present invention were used, all organic film-forming compositions were able to fill the hole pattern without voids, demonstrating excellent filling properties. On the other hand, in Comparative Examples 4-1 to 4-5, 4-7, and 4-8, as shown by the results of solvent resistance measurements and heat resistance evaluations, it is believed that solvent resistance could not be ensured and heat resistance was insufficient, resulting in poor filling. Furthermore, in Comparative Example 4-6, solvent resistance was ensured, but due to the use of a polymer, thermal fluidity was inferior to that of a monomolecular compound, and a rapid curing reaction occurred due to the action of a thermal acid generator. This resulted in insufficient thermal fluidity and poor filling, leading to the formation of voids. On the other hand, in Comparative Example 4-9, the monomolecular compound contributed to thermal fluidity, ensuring filling properties.

[0533] [Evaluation of Flattening Characteristics (Examples 5-1 to 5-26, Comparative Examples 5-1 to 5-9)]

[0534] The organic film-forming compositions (UDL-1 to 26, comparative UDL-1 to 9) prepared above were applied to a substrate having a large isolated trench pattern ( Figure 3 The organic film 10 was baked in the atmosphere at the temperature described in Table 10 for 60 seconds, and the height difference between the organic film 10 in the groove part and the non-groove part was observed using an NX10 atomic force microscope (AFM) manufactured by Park Systems. Figure 3 The results are shown in Table 10. In this evaluation, smaller height differences indicate better planarization properties. Furthermore, this evaluation employed a strict evaluation condition for flattening a trench pattern with a depth of 0.10 μm using an organic film-forming composition typically having a film thickness of approximately 0.2 μm.

[0535] [Table 10]

[0536]

[0537] As shown in Table 10, Examples 5-1 to 5-26 using the compounds and polymers of the present invention demonstrate that, regardless of the organic film material, the height difference between the trench portion and the non-trench portion of the organic film is smaller than in Comparative Examples 5-1 to 5-9, resulting in excellent planarization properties. In particular, dehydrated condensates of phenol or catechol with bis(indole-2,3-diones) containing propargyl substituents, such as in Examples 5-9, 5-10, 5-14, and 5-15, exhibited excellent results. This is believed to be due to the excellent heat resistance results obtained in the heat resistance test for heat resistance evaluation, and to the reduced viscosity of the hydroxyl-terminated compounds due to etherification. Comparative Examples 5-1 to 5-5, 5-7, and 5-8, as shown in the heat resistance test for heat resistance evaluation, exhibited insufficient heat resistance, resulting in significant film shrinkage during baking. This, in turn, resulted in differences in height difference and film thickness, leading to poor planarization properties. In addition, in Comparative Examples 5-6 and 5-9, it is believed that because a cross-linking agent is used to ensure solvent resistance, a rapid hardening reaction is caused, and the benefits of thermal fluidity cannot be benefited, resulting in deterioration of the planarization characteristics. The polymer used in Comparative Example 5-6 originally lacks thermal fluidity, which can be inferred from the obvious results of Comparative Example 5-9, which is a single-molecule compound. If Examples 5-23 to 5-26 are compared with Examples 5-1, 5-10, 5-11, and 5-18 without addition, it can be seen that the flatness is further improved by adding a high-boiling point solvent. In addition, if Examples 5-20 to 5-22, which are a mixture of the compound of the present invention and the polymer, are compared with Examples 5-17 to 5-19, which are only polymers, the planarization characteristics are improved. By adjusting the blending amount, the flatness can be improved without compromising the various physical properties required of the organic film, such as heat resistance, distortion resistance, and etching resistance.

[0538] [Adhesion Test (Examples 6-1 to 6-26, Comparative Examples 6-1 to 6-4)]

[0539] The above-mentioned organic film-forming composition (UDL-1 to 26, comparative UDL1, 3, 6, and 9) was applied to a SiO2 wafer substrate and baked in the atmosphere at the temperature described in Table 11 for 60 seconds using a hot plate to form an organic film with a thickness of 200 nm. The wafer with the organic film was cut into 1×1 cm squares, and the wafer was cut using a special jig and aluminum pins with epoxy adhesive were attached to it. After that, the aluminum pins were bonded to the substrate by heating at 150°C for 1 hour in an oven. After cooling to room temperature, the initial adhesion was evaluated by resistance using a thin film adhesion strength tester (Sebastian Five-A). In addition, the comparative UDL-2, 4, 5, 7, and 8, which could not ensure solvent resistance in the solvent resistance test, could not be subjected to adhesion testing.

[0540] Figure 4 This is an explanatory diagram showing the adhesion measurement method. Figure 411 represents the silicon wafer (substrate), 12 represents the hardened film, 13 represents the support base, 14 represents the aluminum pin with adhesive, 15 represents the clamp, and 16 represents the direction of tension. Adhesion strength is the average value of the 12-point measurements. A higher value indicates greater adhesion of the adhesive film to the substrate. Adhesion was evaluated by comparing the obtained values. The results are shown in Table 11.

[0541] [Table 11]

[0542]

[0543]

[0544] As shown in Examples 6-1 to 6-26 in Table 11, the organic film materials using the compounds and polymers of the present invention exhibited higher adhesion compared to Comparative Examples 6-1, 6-2, and 6-4. Furthermore, Comparative Example 6-3 exhibited high adhesion due to its similar cyclic amide structure. These results suggest that the heterocyclic structure introduced into the compounds and polymers of the present invention improves adhesion, demonstrating excellent film-forming properties, as shown in the film-forming property evaluation results.

[0545] [Pattern Formation Test (Examples 7-1 to 7-26, Comparative Examples 7-1 to 7-4)]

[0546] The organic film-forming compositions (UDL-1 to 26, comparative UDLs 1, 3, 6, and 9) were applied to a bare Si substrate with a 200 nm thick SiO2 film formed thereon, and a trench pattern (10 μm in width and 0.10 μm in depth) formed thereon. These organic films were then calcined in air under the conditions shown in Table 15 to achieve a 200 nm film thickness on the bare Si substrate. A silicon-containing resist interlayer material (SOG-1) was then applied thereto and baked at 220°C for 60 seconds to form a 35 nm thick resist interlayer. A photoresist composition (SL resist for ArF) was then applied and baked at 105°C for 60 seconds to form a 100 nm thick resist top layer. A wet-protective film (TC-1) was applied to the resist top layer and baked at 90°C for 60 seconds to form a 50 nm thick protective film. Furthermore, in the comparative examples UDL-2, 4, 5, 7, and 8, which could not ensure solvent resistance in the solvent resistance measurement, the patterning test could not be performed because a silicon-containing resist interlayer film could not be formed.

[0547] As a photoresist composition (SL resist for ArF), a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) are dissolved in a solvent containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M Co., Ltd.) according to the proportions shown in Table 12, and the mixture is filtered through a 0.1 μm fluororesin filter to prepare the composition.

[0548] [Table 12]

[0549]

[0550] The structural formulas of the polymer (RP1), acid generator (PAG1), and basic compound (Amine1) used are shown below.

[0551] [Chemistry 64]

[0552]

[0553] As a wet protective film material (TC-1), the protective film polymer (PP1) was dissolved in an organic solvent according to the ratio shown in Table 13, and filtered through a 0.1 μm fluororesin filter to prepare the wet protective film material (TC-1).

[0554] [Table 13]

[0555]

[0556] The structural formula of the polymer (PP1) used is shown below.

[0557] [Chemistry 65]

[0558]

[0559] As a silicon-containing anti-etching intermediate film material (SOG-1), a polymer represented by ArF silicon-containing intermediate film polymer (SiP1) and a cross-linking catalyst (CAT1) are dissolved in an organic solvent containing 0.1% by mass of FC-4430 (produced by Sumitomo 3M Co., Ltd.) according to the proportions in Table 14, and filtered through a fluororesin filter with a pore size of 0.1 μm to prepare a silicon-containing anti-etching intermediate film material (SOG-1).

[0560] [Table 14]

[0561]

[0562] The structural formulas of the ArF silicon-containing interlayer polymer (SiP1) and the crosslinking catalyst (CAT1) used are shown below.

[0563] [Chemistry 66]

[0564]

[0565] Then, exposure was performed while changing the exposure amount using an ArF immersion exposure device (manufactured by Nikon Corporation; NSR-S610C, NA1.30, σ0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% half-step phase shift mask), baked (PEB) at 100°C for 60 seconds, and developed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a positive line and space pattern with a pitch of 100 nm and a resist line width of 50 nm to 30 nm.

[0566] Then, dry etching was performed using a Telius etching apparatus manufactured by Tokyo Electron Corporation to process the silicon-containing interlayer film using the resist pattern as a mask, process the organic film using the silicon-containing interlayer film as a mask, and process the SiO2 film using the organic film as a mask.

[0567] The etching conditions are as follows.

[0568] (Transfer Conditions of Resist Pattern to SOG Film)

[0569]

[0570] (Transfer Conditions of SOG Film to Organic Film)

[0571]

[0572]

[0573] (Transfer conditions for SiO2 films)

[0574]

[0575] The pattern cross-section was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the shapes were compared. The results are summarized in Table 15.

[0576] [Table 15]

[0577]

[0578]

[0579] As shown in Table 15, similar to the results of the organic film-forming compositions of the present invention (Examples 7-1 to 7-26), the resist upper layer pattern was successfully transferred to the substrate in all cases, confirming that the organic film-forming compositions of the present invention are suitable for microfabrication using the multilayer resist method. On the other hand, in Comparative Examples 7-1, 7-2, and 7-3, as in the film-forming property evaluation, pinholes generated during film formation caused pattern collapse during pattern processing, resulting in failure to form a pattern. In Comparative Example 7-4, similar to the film-forming property evaluation results, pinholes generated during film formation caused pattern collapse during pattern processing, resulting in failure to form a pattern.

[0580] Based on the above facts, it is clear that the organic film-forming composition of the present invention has good film-forming properties and excellent filling / planarization characteristics, and is therefore extremely useful as an organic film material for use in a multilayer resist method. In addition, the pattern forming method of the present invention using the organic film-forming composition of the present invention can form a fine pattern with high precision even if the workpiece is a substrate with height differences.

[0581] The present invention is not limited to the above-described embodiments, which are merely illustrative, and any technology having substantially the same configuration and exhibiting the same effects as those described in the claims of the present invention is encompassed within the technical scope of the present invention.

[0582] Description of Reference Numerals

[0583] 1:Substrate

[0584] 2: Processed layer

[0585] 2a: Pattern formed on the processed layer

[0586] 3: Organic film

[0587] 3a: Organic film pattern

[0588] 4: Silicon-containing resist interlayer

[0589] 4a: Silicon-containing resist interlayer pattern

[0590] 5: Resist upper film

[0591] 5a: Resist pattern

[0592] 6: Used part (exposed part)

[0593] 7: Base substrate with dense hole pattern

[0594] 8: Organic film

[0595] 9: Base substrate with large isolated trench patterns

[0596] 10: Organic film

[0597] Delta 10: The difference in film thickness between the trench and non-trench areas.

[0598] 11: Silicon wafer

[0599] 12: Hardened film

[0600] 13: Support Desk

[0601] 14: Aluminum pin with adhesive

[0602] 15: Fixture

[0603] 16: stretching direction

Claims

1. A composition for forming an organic film, characterized in that: Contains an organic film-forming material represented by the following general formula and an organic solvent; In the general formula, R1 is a hydrogen atom, an allyl group, or a propargyl group; R2 is a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group; m is 0 or 1, n is an integer of 1 or 2, l is 0 or 1, and when l=1, the aromatic rings form a cyclic ether structure; k is an integer of 0 to 2, and W is any of the following structures: V each independently represents a hydrogen atom or a linking portion. When V is a linking portion, the organic film-forming material is a polymer having a repeating unit represented by the general formula (3). In the general formula (3), R1, R2, W, n, m, l, and k are the same as those described above, and L is any of the following structures:

2. The organic film-forming composition according to claim 1, wherein The organic film forming material is a compound represented by the following general formula (1); In the general formula (1), R1, R2, m, n, l, k, and W are the same as those described above.

3. The organic film-forming composition according to claim 2, wherein The compound represented by the general formula (1) is a compound represented by the following general formula (2); In the general formula (2), R1, W, and n are the same as those described above.

4. The organic film-forming composition according to claim 2 or 3, wherein The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn of the compound in terms of polystyrene determined by gel permeation chromatography is 1.00≤Mw / Mn≤1.

10.

5. The organic film-forming composition according to claim 1, wherein The organic film forming material is a polymer having a repeating unit represented by the following general formula (3); In the general formula (3), R1, R2, W, n, m, l, k and L are the same as those described above.

6. The organic film-forming composition according to claim 5, wherein The polymer is a polymer having a repeating unit represented by the following general formula (4); In the general formula (4), R1, W, L, and n are the same as those described above.

7. The organic film-forming composition according to claim 5 or 6, wherein The L is a divalent organic group represented by the following general formula (5); The general formula (5) is any of the following structures: Dashed lines represent atomic bonds.

8. The organic film-forming composition according to claim 5 or 6, wherein The weight average molecular weight of the polymer is 1,000 to 5,000.

9. The organic film-forming composition according to claim 1, wherein The organic film forming material contains one or more compounds selected from the group consisting of compounds represented by the following general formula (1) and polymers having a repeating unit represented by the following general formula (3); In the general formula (1), R1, R2, m, n, l, k, and W are the same as those described above; In the general formula (3), R1, R2, W, n, m, l, k and L are the same as those described above.

10. The organic film-forming composition according to any one of claims 1 to 3, wherein The organic solvent is 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.

11. The organic film-forming composition according to any one of claims 1 to 3, wherein The organic film-forming composition further contains one or more of a surfactant and a plasticizer.

12. A pattern forming method comprising the following steps: forming an organic film on a workpiece using the organic film-forming composition according to any one of claims 1 to 11, A silicon-containing resist interlayer film is formed on the organic film using a silicon-containing resist interlayer material. Using a photoresist composition to form a resist upper layer film on the silicon-containing resist intermediate film, forming a circuit pattern on the upper layer of the resist, The pattern is transferred to the silicon-containing resist intermediate film by etching using the patterned resist upper layer film as a mask. The pattern is transferred to the organic film by etching using the silicon-containing resist intermediate film with the transferred pattern as a mask. Furthermore, a pattern is formed on the workpiece by etching using the organic film to which the pattern has been transferred as a mask.

13. A pattern forming method comprising the following steps: forming an organic film on a workpiece using the organic film-forming composition according to any one of claims 1 to 11, A silicon-containing resist interlayer film is formed on the organic film using a silicon-containing resist interlayer material. An organic anti-reflective film BARC is formed on the silicon-containing resist intermediate film. A photoresist composition is used to form a resist upper layer film on the BARC to form a 4-layer film structure. forming a circuit pattern on the upper layer of the resist, The patterned resist upper layer film is used as a mask to transfer the pattern to the BARC film and the silicon-containing resist intermediate film by etching. The pattern is transferred to the organic film by etching using the silicon-containing resist intermediate film with the transferred pattern as a mask. Furthermore, the object to be processed is etched using the organic film to which the pattern has been transferred as a mask to form a pattern on the object to be processed.

14. A pattern forming method comprising the following steps: forming an organic film on a workpiece using the organic film-forming composition according to any one of claims 1 to 11, forming an inorganic hard mask film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the organic film; Using a photoresist composition to form a resist upper layer film on the inorganic hard mask, forming a circuit pattern on the upper layer of the resist, The inorganic hard mask is etched using the patterned resist upper layer film as a mask. The organic film is etched using the patterned inorganic hard mask as a mask. Furthermore, the object to be processed is etched using the patterned organic film as a mask to form a pattern on the object to be processed.

15. A pattern forming method comprising the following steps: forming an organic film on a workpiece using the organic film-forming composition according to any one of claims 1 to 11, forming an inorganic hard mask film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the organic film; An organic anti-reflective film BARC is formed on the inorganic hard mask. A photoresist composition is used to form a resist upper layer film on the BARC to form a 4-layer film structure. forming a circuit pattern on the upper layer of the resist, The BARC film and the inorganic hard mask are etched using the patterned resist upper layer film as a mask. The organic film is etched using the patterned inorganic hard mask as a mask. Furthermore, the object to be processed is etched using the patterned organic film as a mask to form a pattern on the object to be processed.

16. The pattern forming method according to claim 14 or 15, wherein The inorganic hard mask is formed by a CVD method or an ALD method.

17. The pattern forming method according to any one of claims 12 to 15, wherein The patterning of the resist upper layer film is performed by optical lithography with a wavelength of 10 nm to 300 nm, direct writing using an electron beam, nanoimprinting, or a combination thereof.

18. The pattern forming method according to any one of claims 12 to 15, wherein In this pattern forming method, exposure and development are performed to form a circuit pattern on a resist upper layer film. The development is performed by alkali development or development using an organic solvent.

19. The pattern forming method according to any one of claims 12 to 15, wherein As the workpiece, a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film is used.

20. The pattern forming method according to claim 19, wherein The metal is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, cobalt, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, manganese, molybdenum, ruthenium or an alloy thereof.

21. A compound represented by the following general formula (1): In the general formula (1), R1 is a hydrogen atom, an allyl group, or a propargyl group; R2 represents a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group; m represents 0 or 1, n represents an integer of 1 or 2, l represents 0 or 1, and when l=1, the aromatic rings form a cyclic ether structure; k represents an integer of 0 to 2, and W represents any of the following structures:

22. The compound according to claim 21, wherein The compound is represented by the following general formula (2): In the general formula (2), R1, W, and n are the same as those described above.

23. A polymer having a repeating unit represented by the following general formula (3): In the general formula (3), R1 is a hydrogen atom, an allyl group, or a propargyl group; R2 is a nitro group, a halogen atom, a hydroxyl group, an alkyloxy group having 1 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a trifluoromethyl group, or a trifluoromethyloxy group; m is 0 or 1, n is an integer of 1 or 2, l is 0 or 1, and when l=1, the aromatic rings form a cyclic ether structure; k is an integer of 0 to 2, and W is any of the following structures: L is any of the following structures:

24. The polymer according to claim 23, wherein The polymer has a repeating unit represented by the following general formula (4); In the general formula (4), R1, W, L, and n are the same as those described above.

25. The polymer according to claim 23 or 24, wherein The L is a divalent organic group represented by the following general formula (5); The general formula (5) is any of the following structures: Dashed lines represent atomic bonds.

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