Composition for forming organic film, method for forming organic film, patterning process, and polymer

Abstract

The present invention aims to provide a polymer that is useful as a film-forming material, has low environmental impact, and is not a PFAS (phosphorus esterase inhibitor). Furthermore, it provides an organic film material composition containing this polymer that exhibits excellent coating properties, such as no pinholes or other coating defects on the substrate (wafer), and excellent film-forming properties (in-plane uniformity) and filling properties, as well as a method for forming an organic film. Additionally, it provides a patterning method that provides excellent process tolerance for resist films using this organic film-forming composition. The solution to this problem is an organic film-forming composition characterized by containing: (A) an organic film-forming material, (B) a polymer having repeating units represented by the following formula (B1), and (C) a solvent. In the formula, R1 is a hydrogen atom or a methyl group, R2 and R3 are each independently a monovalent organic group with 10 to 20 carbon atoms and no fluorine atoms, X is a nitrogen atom or an oxygen atom, and W1 is a single bond or a divalent linker with 1 to 10 carbon atoms, which may also contain oxygen atoms and no fluorine atoms.

Description

Technical Field

[0001] This invention relates to an organic film forming composition for forming organic films used in microfabrication processes in the manufacture of semiconductor devices, an organic film planarization process in the manufacture of semiconductor devices, an organic film forming method using the composition, a pattern forming method using the aforementioned composition, and a polymer used in the aforementioned composition. Prior Technology

[0002] With the increasing integration and speed of LSI (Liquid Crystal Interchange) technology, the miniaturization of patterned patterns is also progressing rapidly. This is due to the widespread adoption of 5G high-speed communication and artificial intelligence (AI), which necessitates high-performance devices to process them. Regarding the most advanced miniaturization technology, mass production of 5nm node devices using 13.5nm extreme ultraviolet (EUV) lithography is already underway. Furthermore, the use of EUV lithography is being explored in the next generation of 3nm node devices and the generation after that, 2nm node devices.

[0003] If the fineness of resist patterns continues in this way, the pattern formation method in the single-layer resist method, which is a representative resist pattern formation method, will become difficult. In terms of fine pattern processing methods, it is known that the multilayer resist method, which stacks films with different dry etching characteristics to form patterns on substrates with high aspect ratios, is excellent in order to form patterns. A three-layer resist method (Patent Document 1) has been developed and put into practical use, which combines the photoresist layer of organic photosensitive polymer, the intermediate layer of silicone polymer or silicone CVD film, and the bottom layer of organic polymer used in the single-layer resist method.

[0004] In this three-layer resist method, an organic film, such as phenolic resin, is uniformly deposited on the substrate as the lower resist film (organic lower film), and a silicon-containing resist intermediate film is deposited on top of it as the resist intermediate film. Then, a conventional organic photoresist film is formed on top of it as the upper resist film. For dry etching using fluorine-based gas plasma, the organic resist upper film can achieve a better etching selectivity than the silicon-containing resist intermediate film. Therefore, the resist pattern is transferred to the silicon-containing resist intermediate film by dry etching using fluorine-based gas plasma. According to this method, even if a resist composition that is difficult to form a pattern with a film thickness sufficient to directly process the substrate is used, or a resist composition whose dry etching resistance is insufficient to process the substrate, a pattern can still be transferred onto a silicon-containing resist intermediate film. If a pattern transfer using dry etching with oxygen-based gas plasma is subsequently performed, a pattern of a phenolic varnish resin film (resistor underlayer film) with sufficient dry etching resistance can be obtained.

[0005] As mentioned above, many technologies for organic underlayer films are already known (e.g., patent document 2). However, with the recent advancements in miniaturization, in addition to dry etching characteristics, the necessity for excellent embedding characteristics has gradually increased. It is necessary to have an organic film material that can uniformly form a film on the substrate, even if the substrate has a complex shape and material, and has the embedding characteristics to fill the necessary patterns without gaps.

[0006] As described above, organic underlayer films can be formed using a coater / developer capable of performing spin coating, EBR (Edge Bead Removal), and calcination processes during the manufacture of semiconductor substrates. The EBR step refers to the process of removing the film from the ends of the substrate (wafer) with a removal solution after spin coating to prevent contamination by the substrate transport arm of the coater / developer. The removal solution used in the EBR step is a mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30% by mass: 70% by mass), and is widely used in the EBR steps of resist films or resist underlayer films (silicon-containing intermediate films, organic underlayer films).

[0007] Due to the effect of the remover in the EBR step, the outer periphery of the organic underlayer film sometimes forms a thicker state (hump). In the dry etching step of the above substrate processing, the hump can become a cause of defects, so an organic underlayer film that suppresses the hump is required.

[0008] Not only organic substrate films, but also photoresist materials used in photolithography employing organic photosensitive polymers, as mentioned above, are coated with solutions using methods such as spin coating, and then baked to evaporate the solvent to form the film. Similar to organic substrate films, the baked film thickness must be uniform and flat, and these requirements for uniformity and flatness have become increasingly stringent year by year.

[0009] In recent years, there has been a demand for thick resist films in 3D-NAND memory applications, with a requirement for even greater flatness. As the film thickness increases, achieving flatness within the film becomes more difficult. On the other hand, while miniaturization is progressing, thinning is also underway, which increases the risk of pinhole defects and other defects.

[0010] Examples of film materials using organic materials in semiconductor processing have been mentioned above. However, the ability to form films with in-plane uniformity of film thickness and without pinholes without using organic materials is a significant advantage for the industry.

[0011] In recent years, there have been criticisms regarding the health effects of perfluoroalkyl compounds (PFAS), and there are attempts to impose restrictions on the manufacture and sale of PFAS compounds under the European REACH agreement. Perfluoroalkyl compounds have a wide range of applications. Due to their hydrophobic, oleophobic, heat-resistant, chemical-resistant, and light-non-absorbent properties, they are widely used in water-repellent agents, surface treatment agents, emulsifiers, fire extinguishing agents, and coatings. Therefore, the development of alternative materials without the PFAS structure has become an urgent priority.

[0012] As exemplified by the materials using perfluoroalkyl compounds mentioned above, surfactants with fluoroalkyl or polysiloxane chains are highly effective at reducing surface tension. In particular, fluoroalkyl surfactants, which have a low risk of generating silicon particles after dry ashing of resist films, have been widely used (Patent Documents 3 and 4). Furthermore, fluorine-based surfactants are suitable not only for resist materials but also for top coats formed on top of resists and for lower antireflective films formed below resists (Patent Document 5).

[0013] Considering the future strengthening of regulations, materials not subject to PFAS regulations must be used. For example, regarding surfactants as mentioned above, surfactants containing trifluoromethoxy or pentafluorosulfane compounds and their uses have been proposed (Patent Document 6). Furthermore, in the field of inhibitor materials, inhibitor materials using photoacid generators have been proposed (Patent Document 7). In addition, fluorine-free surfactants have been proposed (Patent Document 8). [Previous Technical Documents] [Patent Literature]

[0014] [Patent Document 1] Japanese Patent Application Publication No. 2005-128509 [Patent Document 2] Japanese Patent Application Publication No. 2004-205685 [Patent Document 3] Japanese Patent Application Publication No. 6-186735 [Patent Document 4] Japanese Patent Application Publication No. 6-214380 [Patent Document 5] Japanese Patent Application Publication No. 2010-139822 [Patent Document 6] Japanese Patent Publication No. 2008-526792 [Patent Document 7] International Publication No. 2023-223624 [Patent Document 8] International Publication No. 2022-073921 Summary of the Invention

[0015] [The problem that the invention aims to solve] This invention addresses the aforementioned issues by providing a polymer characterized by being free of fluorine atoms. By using an organic film material composition containing this polymer, films with excellent coating properties, such as pinholes on a substrate (wafer), good film-forming properties (in-plane uniformity), and excellent filling performance, can be formed. Furthermore, by using this organic film-forming composition as an organic underlayer film material, an organic film with excellent process tolerance can be provided when used as an organic underlayer film for multilayer resists. Methods for forming organic films and patterning methods using this organic film-forming composition are also provided. The invention provides a film-forming material that is not a PFAS (phosphorus esterase inhibitor), making it useful as a film-forming material with a lower environmental impact. [Methods for solving problems]

[0016] To address the aforementioned issues, the present invention provides a composition for forming organic films, characterized by containing: (A) Materials for organic film formation, (B) Polymers having repeating units represented by the following formula (B1), and (C) Solvent. [Chemistry 1] In the formula, R1 is a hydrogen atom or a methyl group, R2 and R3 are independently monovalent organic groups with 10 to 20 carbon atoms and no fluorine atoms, X is a nitrogen atom or an oxygen atom, and W1 is a single bond or a divalent linker with 1 to 10 carbon atoms that may contain oxygen atoms and no fluorine atoms.

[0017] If the composition for forming an organic film is such, the long-chain alkyl groups in the branch of formula (B1) above will exert an interfacial activity effect, forming an organic film with excellent in-plane uniformity and landfill characteristics, and suppressing the formation of protrusions caused by the removal agent in the EBR step.

[0018] In this invention, W1 in the above formula (B1) should preferably be the basis of the following formula (B2). [Chemistry 2] In the formula, the dashed lines represent the atomic bonds of X in the above formula (B1) and the atomic bonds of carbon atoms bonded to R2 and R3, and may have one or two of the structures represented by the above formula (B2).

[0019] If the composition for forming an organic film contains such a polymer, an organic film with better in-plane uniformity can be formed, which is more ideal.

[0020] In this invention, the aforementioned polymer (B) preferably contains one or more repeating units represented by the following general formula (B3). [Chemistry 3] In the formula, R1 and X are the same as those mentioned above, and W2 is a monovalent organic group that may contain oxygen atoms but not fluorine atoms.

[0021] By including such units, solvent solubility can be improved.

[0022] In this invention, W2 in the above formula (B3) should preferably be based on the following formula (B4). [Chemistry 4] In the formula, R4 is a hydrogen atom or a methyl group, R5 is a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms that does not contain fluorine atoms, and m is an integer from 4 to 20.

[0023] By incorporating such units, thermal decomposition, interfacial activity, and polymer flowability can be adjusted, resulting in compounds that more reliably balance film-forming properties and filling properties, while also ensuring solubility in inhibitor solvents.

[0024] Furthermore, the weight average molecular weight of the aforementioned component (B) should preferably be between 1,000 and 30,000.

[0025] If the weight-average molecular weight is within such a range, an organic membrane with better film-forming and landfill properties can be formed.

[0026] Furthermore, the content of the aforementioned component (B) relative to the content of the aforementioned organic film forming material (A) in 100 parts by mass is preferably 0.01 to 5 parts by mass.

[0027] If the composition for forming an organic film contains such a content of the aforementioned component (B), the in-plane uniformity of the organic film after film formation will be better, and therefore more ideal.

[0028] Furthermore, the present invention provides an organic film forming method, which is a method for forming an organic film used in the manufacturing process of a semiconductor device. The method involves spin-coating the organic film forming composition of the present invention described above onto a substrate to obtain a coating film, and then heat-treating the aforementioned coating film at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to harden it and form an organic film.

[0029] The composition for forming organic films of the present invention is particularly useful in filling complex shaped patterns on a substrate by spin coating, forming an organic film with excellent in-plane uniformity, and in suppressing protrusions while removing the organic film at the ends during the EBR step. Therefore, according to the organic film forming method of the present invention, an organic film exhibiting excellent film-forming properties, excellent filling characteristics, excellent protrusion suppression during the EBR step, and excellent process tolerance when used as an organic film for multilayer resists can be formed.

[0030] Furthermore, the present invention provides a pattern forming method, characterized by: forming an organic film on a workpiece using the organic film forming composition of the present invention described above; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming a resist upper film on the silicon-containing resist intermediate film using a resist upper film material composed of a photoresist composition; forming a circuit pattern on the resist upper film; using the resist upper film with the circuit pattern as a mask and etching to transfer the pattern onto the silicon-containing resist intermediate film; using the silicon-containing resist intermediate film with the transferred pattern as a mask and etching to transfer the pattern onto the organic film; and then using the organic film with the transferred pattern as a mask and etching to form the pattern on the workpiece.

[0031] Furthermore, the present invention provides a pattern forming method, characterized by: forming an organic film on a workpiece using the organic film forming composition described above; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming an organic antireflective film or a sealing film on the silicon-containing resist intermediate film; forming a resist upper film on the organic antireflective film or the sealing film using a resist upper film material composed of a photoresist composition; forming a circuit pattern on the resist upper film; using the resist upper film with the circuit pattern as a mask and etching to transfer the pattern onto the organic antireflective film or the sealing film and the silicon-containing resist intermediate film; using the silicon-containing resist intermediate film with the transferred pattern as a mask and etching to transfer the pattern onto the organic film; and then using the organic film with the transferred pattern as a mask and etching to form the pattern on the workpiece.

[0032] Furthermore, the present invention provides a pattern forming method, characterized by: forming an organic film on a workpiece using the organic film forming composition described above; forming an inorganic hard mask selected from the group consisting of silicon oxide film, silicon nitride film, and silicon oxynitride film on the aforementioned organic film; forming a resist upper film on the aforementioned inorganic hard mask using a resist upper film material composed of a photoresist composition; forming a circuit pattern on the aforementioned resist upper film; using the resist upper film with the aforementioned circuit pattern as a mask and transferring the pattern to the aforementioned inorganic hard mask by etching; using the inorganic hard mask with the aforementioned pattern as a mask and transferring the pattern to the aforementioned organic film by etching; and then using the organic film with the aforementioned pattern as a mask and forming the pattern on the aforementioned workpiece by etching.

[0033] Furthermore, the present invention provides a pattern forming method, characterized by: forming an organic film on a workpiece using the organic film forming composition described above; forming an inorganic hard mask selected from the group consisting of silicon oxide film, silicon nitride film, and silicon oxynitride film on the aforementioned organic film; forming an organic antireflective film or a sealing film on the aforementioned inorganic hard mask; forming a resist upper film using a resist upper film material composed of a photoresist composition on the aforementioned organic antireflective film or sealing film; forming a circuit pattern on the aforementioned resist upper film; using the resist upper film with the aforementioned circuit pattern as a mask and etching to transfer the pattern onto the aforementioned organic antireflective film or sealing film and the aforementioned inorganic hard mask; using the inorganic hard mask with the aforementioned pattern as a mask and etching to transfer the pattern onto the aforementioned organic film; and then using the organic film with the aforementioned pattern as a mask and etching to form the pattern on the aforementioned workpiece.

[0034] Thus, the organic film forming composition of the present invention can be ideally used in various pattern forming methods, such as a three-layer resist process using a silicon-containing resist interlayer film or an inorganic hard mask interlayer film, or a four-layer resist process using an organic anti-reflective film or a sealing film. If the pattern forming method of the present invention is such, the circuit pattern of the resist upper layer film can be transferred and formed on the workpiece with high precision.

[0035] Furthermore, CVD or ALD methods are preferred for the formation of the aforementioned inorganic hard mask intermediate film.

[0036] The pattern forming method of the present invention can, for example, be used to form an inorganic hard mask intermediate film.

[0037] Furthermore, in the formation of the aforementioned circuit pattern, it is advisable to use photolithography, electron beam direct writing, nanoimprinting, or a combination thereof that uses light with a wavelength of 10 nm or more and 300 nm or less to form the circuit pattern.

[0038] Furthermore, in the formation of the aforementioned circuit patterns, it is advisable to use alkaline development or organic solvents to develop the circuit patterns.

[0039] In the pattern forming method of the present invention, such circuit pattern forming means and developing means can be ideally used.

[0040] Furthermore, the aforementioned processed body is preferably a semiconductor device substrate, or a semiconductor device substrate having 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 formed on the aforementioned semiconductor device substrate.

[0041] At this time, for the aforementioned workpiece, it is advisable to use a metal constituting the workpiece that is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or alloys thereof.

[0042] If it is the pattern forming method of the present invention, the workpiece as described above can be processed to form a pattern.

[0043] Furthermore, the present invention provides a polymer characterized by having repeating units represented by the following formula (B1). [Chemistry 5] In the formula, R1 is a hydrogen atom or a methyl group, R2 and R3 are independently monovalent organic groups with 10 to 20 carbon atoms and no fluorine atoms, X is a nitrogen atom or an oxygen atom, and W1 is a single bond or a divalent linker with 1 to 10 carbon atoms that may contain oxygen atoms and no fluorine atoms.

[0044] Such polymers are ideal because the long-chain alkyl groups in the branches of the above formula (B1) will have an interfacial activity effect, forming an organic film with excellent in-plane uniformity and landfill characteristics, and the formation of protrusions caused by the removal agent in the EBR step is suppressed.

[0045] In this invention, W1 in the above formula (B1) should preferably be the basis of the following formula (B2). [Chemistry 6] In the formula, the dashed lines represent the atomic bonds of X in the above formula (B1) and the atomic bonds of carbon atoms bonded to R2 and R3, and may have one or two of the structures represented by the above formula (B2).

[0046] If the composition for forming an organic film contains such a polymer, an organic film with better in-plane uniformity can be formed.

[0047] The aforementioned polymer is preferably a polymer containing one or more repeating units represented by the following general formula (B3). [Chemistry 7] In the formula, R1 and X are the same as those mentioned above, and W2 is a monovalent organic group that may contain oxygen atoms but not fluorine atoms.

[0048] By including such units, it is more desirable because it can improve solvent solubility.

[0049] In this invention, W2 in the above formula (B3) should preferably be based on the following formula (B4). [Chemistry 8] In the formula, R4 is a hydrogen atom or a methyl group, R5 is a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms that does not contain fluorine atoms, and m is an integer from 4 to 20.

[0050] By incorporating such units, the thermal decomposition, interfacial activity, and polymer flowability can be adjusted, resulting in a compound that more reliably balances film-forming properties and filling properties. Furthermore, it ensures solubility in inhibitor solvents, making it a more ideal compound.

[0051] The weight average molecular weight of the aforementioned polymer should preferably be between 1,000 and 30,000.

[0052] If the weight-average molecular weight falls within this range, an organic membrane with excellent film-forming and landfill properties can be formed. Furthermore, the weight-average molecular weight can be obtained using the method described later. [Effects of the Invention]

[0053] As explained above, the present invention provides an organic film forming composition and its contained polymer that exhibit excellent film-forming properties (in-plane uniformity) and filling characteristics on a substrate (wafer), excellent film-forming properties of the intermediate film on an organic film when used as an organic film, and excellent suppression of protrusions during the EBR step. Because the organic film forming composition of the present invention has excellent film-forming properties, filling characteristics, and suppression of protrusions generated during the EBR step, it provides a patterning method that can be ideally applied to two-layer resist processes, three-layer resist processes using silicon-containing resist intermediate films or inorganic hard mask intermediate films, or four-layer resist processes using silicon-containing resist intermediate films or inorganic hard mask intermediate films and organic anti-reflective films or sealing films, etc. In this patterning method, it is extremely useful as an organic film material or an organic film forming material for semiconductor device manufacturing. Furthermore, in the organic film formation method of the present invention, since an organic film with suppressed protrusions can be formed, semiconductor devices and the like can be manufactured efficiently. Also, the polymer of the present invention exhibits the above-mentioned properties by being configured as a branched long-chain alkyl group, thus it is useful as a composition system for organic film formation. Simple Explanation of the Diagram

[0054] [Figure 1] (A)~(F) are explanatory diagrams of an example of the pattern formation method of the three-layer resist process of the present invention. [Figure 2] is an example of a graph showing the height of a protrusion measured using a contact profilometer in Example 2. [Figure 3] is one example of a graph showing the height of a protrusion measured using a contact profilometer in Comparative Example 2. [Figure 4] (G)~(I) are explanatory diagrams of the landfill characteristic evaluation method in the embodiments. Implementation

[0055] As described above, we seek an organic film forming composition that can form an organic film on a substrate (wafer) with excellent film-forming properties (in-plane uniformity) and filling characteristics, and suppresses the protrusion of the organic film during the EBR step; an organic film forming method and a patterning method using the composition; and the development of polymers that can be used in the aforementioned organic film forming composition.

[0056] Typically, when forming an organic film, the resin and additives for forming the organic film are dissolved in an organic solvent to form a composition. This composition is then coated onto a substrate with structures and wiring using a coating machine and a developing machine. The composition is spread by rotating the substrate. The composition is then removed from the ends in the EBR step, followed by calcination to form the organic film.

[0057] It is believed that if the above-mentioned components have insufficient fluidity, voids will be generated when filling holes and trenches with very high aspect ratios. At the same time, if the resin and additives used to form the organic membrane have poor solubility in the removal agent used in the EBR step, protrusions will be generated on the outer periphery of the organic membrane.

[0058] After further and in-depth research into the above-mentioned issues, the inventors discovered that by incorporating polymers with specific repeating units into the composition for forming organic films, an organic film-forming composition can be provided that has both excellent film-forming properties and a high degree of landfill characteristics, while also exhibiting excellent protrusion suppression during the EBR step, thus completing the present invention.

[0059] That is, the present invention is a composition for forming an organic film, characterized by containing: (A) Materials for organic film formation, (B) Polymers having repeating units represented by the following formula (B1), and (C) Solvent. [Chemistry 9] In the formula, R1 is a hydrogen atom or a methyl group, R2 and R3 are independently monovalent organic groups with 10 to 20 carbon atoms and no fluorine atoms, X is a nitrogen atom or an oxygen atom, and W1 is a single bond or a divalent linker with 1 to 10 carbon atoms that may contain oxygen atoms and no fluorine atoms.

[0060] Furthermore, the present invention is a polymer characterized by having repeating units represented by the following formula (B1). [Chemistry 10] In the formula, R1 is a hydrogen atom or a methyl group, R2 and R3 are independently monovalent organic groups with 10 to 20 carbon atoms and no fluorine atoms, X is a nitrogen atom or an oxygen atom, and W1 is a single bond or a divalent linker with 1 to 10 carbon atoms that may contain oxygen atoms and no fluorine atoms.

[0061] The present invention will now be described in detail, but it is not limited thereto.

[0062] [Compositions for organic film formation] The organic film forming composition of the present invention contains: (A) Materials for organic film formation, (B) Polymers having repeating units represented by the following formula (B1), and (C) Solvent. [Chemistry 11] In the formula, R1 is a hydrogen atom or a methyl group, R2 and R3 are independently monovalent organic groups with 10 to 20 carbon atoms and no fluorine atoms, X is a nitrogen atom or an oxygen atom, and W1 is a single bond or a divalent linker with 1 to 10 carbon atoms that may contain oxygen atoms and no fluorine atoms.

[0063] Furthermore, in the composition for forming organic films of the present invention, the aforementioned (B) polymer, (A) organic film forming material, and (C) solvent can each be used individually or in combination of two or more.

[0064] Hereinafter, among the components of the above-mentioned organic film forming composition, the feature of the present invention, namely (B) polymer, will be described first, and then the above-mentioned (A) organic film forming material, (C) solvent, and other components will be described.

[0065] [(B) Polymer] The polymer system of the present invention (B) is a novel polymer having repeating units represented by the above general formula (B1) that can be ideally used in compositions for forming organic films. By incorporating this polymer into compositions for forming organic films, an ideal composition for forming organic films can be provided.

[0066] The (B) polymer of this invention is a compound containing branched long-chain alkyl groups. Coatings formed using an organic film-forming composition containing the (A) organic film-forming material described later and such a (B) polymer are less prone to protrusion during the EBR step. Furthermore, by introducing suitable branched long-chain alkyl groups such as those in formula (B1) above, surface tension reduction capability can be achieved, and this function can be imparted as a surfactant that provides excellent uniform coating properties (leveling) of the organic film. Therefore, when using the (B) polymer of this invention as a surfactant, its application is not limited to organic films, but can also be used in photolithography coating materials. Specifically, examples include photosensitizing resist materials and surface coating materials formed on resist films. Thus, the (B) polymer of this invention has the characteristic of functioning as a surfactant.

[0067] That is, according to the organic film forming composition of the present invention, which contains (A) an organic film forming material and (B) a polymer, an organic film with excellent film-forming and filling properties on a substrate, excellent protrusion suppression during the EBR step, and excellent process tolerance when used as an organic film for multilayer resists can be formed. For example, if the organic film forming composition of the present invention is used, an organic film that is excellent for microfabrication in the manufacture of semiconductor devices and the like, and an organic film that is excellent for planarization in the manufacture of semiconductor devices and the like can be formed.

[0068] In the above general formula (B1), R1 is a hydrogen atom or a methyl group. R2 and R3 are each independently a monovalent organogroup with 10 to 20 carbon atoms and no fluorine atoms. Examples of such monovalent organogroups include: decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, etc. Considering the availability of raw materials, R2 and R3 should preferably be decyl, dodecyl, or hexadecyl.

[0069] In the above formula (B1), X is a nitrogen atom or an oxygen atom. When W1 is a single bond or a divalent linkage group with 1 to 10 carbon atoms that may contain an oxygen atom but no fluorine atom, and when W1 is a divalent organic group with 1 to 10 carbon atoms that may contain an oxygen atom but no fluorine atom, examples of such divalent organic groups include: methylene, ethanediyl, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl, decanediyl, and divalent organic groups that may also contain an oxygen atom, a carbonyl group, and / or an ester group.

[0070] In the polymer of the present invention (B), W1 is preferably represented by the base of the following formula (B2). [Chemistry 12] In the formula, the dashed lines represent the atomic bonds of X in the above formula (B1) and the atomic bonds of carbon atoms bonded to R2 and R3, and may have one or two of the structures represented by the above formula (B2).

[0071] If the composition for forming an organic film contains such a polymer, the branched long-chain alkyl groups can improve film formation during coating by exerting interfacial activity. Moreover, the decomposition products generated during baking will not impair the in-plane uniformity of the film, nor will insoluble components be formed due to the reaction between the decomposition products. Therefore, the process tolerance when used as an organic film is not narrow, and there will be no equipment contamination or other adverse effects.

[0072] The polymer (B) described above preferably contains one or more repeating units represented by the following general formula (B3). [Chemistry 13] In the formula, R1 and X are the same as those mentioned above, and W2 is a monovalent organic group that may contain oxygen atoms but not fluorine atoms.

[0073] In the above formula (B3), X should preferably be an oxygen atom.

[0074] The above formula (B3) can be specifically exemplified as described below, but is not limited thereto. In the following examples, R1 is a hydrogen atom or a methyl group, R5 is a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms that does not contain fluorine atoms, and m is an integer from 4 to 20. [Chemistry 14]

[0075] By including such units, solvent solubility can be improved.

[0076] In the polymer of the present invention (B), W2 in the above formula (B3) is preferably a base represented by the following formula (B4). [Chemistry 15] In the formula, R4 is a hydrogen atom or a methyl group, R5 is a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms that does not contain fluorine atoms, and m is an integer from 4 to 20.

[0077] More ideal specific examples of the above formula (B3) may be illustrated as follows, but are not limited thereto. In the following examples, R1 is a hydrogen atom or a methyl group. [Chemistry 16]

[0078] By incorporating such units, thermal decomposition, interfacial activity, and polymer flowability can be adjusted, resulting in compounds that more reliably balance film-forming properties and filling properties, while also ensuring solubility in inhibitor solvents.

[0079] The weight-average molecular weight of the aforementioned polymer (B) is preferably 1,000 to 30,000, and more preferably 1,500 to 25,000. A weight-average molecular weight of 1,000 or higher can suppress the reduction in blending effect caused by volatilization and other factors, and ensure sufficient blending effect. Furthermore, a weight-average molecular weight of 30,000 or lower will not result in deterioration of flowability and will provide excellent landfill characteristics. Furthermore, regarding the amount of component (B) added, the content of component (B) relative to 100 parts by mass of the organic film forming material (A) should preferably be 0.01 parts by mass to 5 parts by mass.

[0080] In addition, in this invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) are polystyrene conversion values ​​obtained by gel permeation chromatography (GPC) at a measurement temperature of 40°C using tetrahydrofuran as the extraction solvent, and the dispersity (Mw / Mn) is calculated from Mw and Mn.

[0081] [(B) Polymer Manufacturing Method] Regarding the means of obtaining the polymer (B) of the present invention, it can be synthesized, for example, by methods such as: (1) introducing a branched long-chain alkyl unit from a (meth)acrylic acid monomer; synthesizing (meth)acrylic acid or (meth)acrylamide by free radical polymerization, etc.; or (2) subsequently modifying the introduction of a branched long-chain alkyl unit; or acting a carboxylic acid on an epoxy-containing polymer obtained by free radical polymerization, but not limited thereto. The (meth)acrylic acid or (meth)acrylamide used in the synthesis can be used alone or in combination of two or more. They can be appropriately selected and combined according to the desired properties. R1, R2, R3, X, W1 and W2 in the following formula are the same as those described above.

[0082] [Chemistry 17]

[0083] Examples of free radical initiators that can be used at this time include: 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl-2,2-azobis(2-methylpropionate), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, lauryl peroxide, etc., which can be used alone or in combination of two or more. The amount of these free radical initiators added relative to the total amount of monomers that cause the reaction should preferably be 0.01~25 mol%.

[0084] If the solvent used is inert to the above reaction, there are no particular restrictions. Examples include ether solvents such as diethyl ether, tetrahydrofuran, and dialkyl ethers; aromatic solvents such as benzene, toluene, and xylene; and esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tributyl acetate, tributyl propionate, and propylene glycol monotert-butyl ether acetate. These solvents can be used alone or in combination. For example, relative to 100 parts by weight of the reactants, these solvents can be used in the range of 0 to 2000 parts by weight. The reaction temperature is preferably 50 to 150°C, and more preferably 60 to 100°C. The reaction time should be appropriately selected from 0.1 to 100 hours.

[0085] Reaction methods include feeding (meth)acrylic acid or (meth)acrylamide into a solvent in one step; dispersing or dissolving (meth)acrylic acid or (meth)acrylamide in separate solvents and then adding them dropwise; or dispersing or dissolving one of (meth)acrylic acid or (meth)acrylamide in a solvent and then adding the other, which has already been dispersed or dissolved in the solvent, dropwise. Furthermore, when multiple (meth)acrylic acid or (meth)acrylamide) are fed separately, they can be mixed beforehand and allowed to react, or they can be reacted separately and sequentially. When using a free radical initiator, methods include feeding (meth)acrylic acid or (meth)acrylamide) in one step; dispersing or dissolving (meth)acrylic acid or (meth)acrylamide in a solvent and then adding or droppingwise the free radical initiator; or dispersing or dissolving the free radical initiator beforehand and then droppingwise the (meth)acrylic acid or (meth)acrylamide.

[0086] (2) When introducing branched long-chain alkyl units in subsequent modifications, in terms of the above-mentioned ratio of epoxy compound and carboxylic acid compound, the amount of carboxyl group in carboxylic acid compound should preferably be 0.3 to 2.0 mol, more preferably 0.5 to 1.5 mol, and even more preferably 0.75 to 1.25 mol, relative to 1 mol of epoxy group in epoxy compound. If the amount of carboxyl group relative to epoxy group is appropriate, there is no concern about residual unreacted epoxy group that could impair the storage stability of the composition for forming organic films, and it can also prevent the residual unreacted carboxylic acid compound from becoming a cause of escaping gas.

[0087] The compounds synthesized by introducing branched long-chain alkyl units as described above in this invention can generally be obtained by reacting an epoxide with a carboxylic acid in the absence of a solvent or in the presence of a reaction catalyst, at room temperature or under cooling or heating as needed.

[0088] Specific examples of solvents used at this time include: alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, methyl cellulose, ethyl cellulose, butyl cellulose, and propylene glycol monomethyl ether; ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dimethyl ether; 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; lactones such as γ-butyrolactone; and nonprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and hexamethyltrimethamide. These can be used alone or in combination of two or more. These solvents should preferably be used in the range of 0 to 2,000 parts by mass relative to 100 parts by mass of the reactants.

[0089] Catalysts can also be used in reactions that modify and introduce branched long-chain alkyl units. Specific examples of catalysts include: benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltrimethylammonium chloride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium hydroxide, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, trimethylbenzylammonium hydroxide, and N. - Quaternary ammonium salts such as laurylpyridine chloride, N-lauryl-4-methylpyridine chloride, N-laurylmethylpyridine chloride, trimethylphenylammonium bromide, and N-benzylmethylpyridine chloride; Quaternary phosphonium salts such as tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, and tetraphenylphosphonium chloride; Tertiary amines such as tris(2-(2-methoxyethoxy)ethyl)amine, tris(3,6-dioxaheptyl)amine, and tris(3,6-dioxaoctyl)amine. The amount of catalyst used relative to the raw materials should preferably be 0.001~100% by mass, preferably in the range of 0.005~50% by mass. The reaction temperature should preferably be -50℃ to approximately the boiling point of the solvent, preferably room temperature to 150℃. The reaction time should be appropriately selected from 0.1~100 hours.

[0090] Methods for modifying reactions involving branched long-chain alkyl units include: feeding the epoxide, carboxylic acid, and catalyst in a single step; dispersing or dissolving the epoxide and carboxylic acid in a solvent and then adding the catalyst in a single step, or diluting it with a solvent and adding it dropwise; or dispersing or dissolving the catalyst in a solvent and then adding the epoxide and carboxylic acid in a single step, or diluting it with a solvent and adding it dropwise. After the reaction, the product can be used directly as a composition for forming an organic film. However, to remove unreacted raw materials, catalyst, etc., present in the system, it can also be diluted in an organic solvent, separated, washed, and recovered.

[0091] In order to remove unreacted raw materials, catalysts, etc. present in the system, the reaction solution obtained by the method described above can be diluted with an organic solvent, and then the liquid-liquid washing can be performed to recover (B) polymer.

[0092] If the organic solvent used for separation cleaning is a soluble compound that separates into two layers when mixed with water, there are no particular restrictions. 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 pentyl ketone, cyclohexanone, and methyl isobutyl ketone; ethers such as diethyl ether, diisopropyl ether, methyl tributyl ether, and ethyl cyclopentyl methyl ether; chlorinated solvents such as dichloromethane, chloroform, dichloroethane, and trichloroethylene; and mixtures thereof. The cleaning water used in this case can be deionized water or ultrapure water. One or more cleaning cycles are sufficient, but since even 10 or more cycles may not achieve the desired cleaning effect, approximately 1 to 5 cycles are recommended.

[0093] During separation and cleaning, alkaline aqueous solutions can also be used to remove unreacted raw materials or acidic components from the system. Specific examples of alkalis include: alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, ammonia, and organic ammonium compounds.

[0094] In addition, during separation and cleaning, acidic aqueous solutions can also be used to remove unreacted raw materials, metallic impurities, or alkaline components from the system. Specific examples of acids 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.

[0095] The separation and cleaning process using the aforementioned alkaline and acidic aqueous solutions can be performed individually or in combination. Ideally, the separation and cleaning should proceed sequentially with the alkaline and acidic aqueous solutions to facilitate the removal of metallic impurities.

[0096] After the separation and cleaning with the alkaline and acidic aqueous solutions mentioned above, a subsequent cleaning with neutral water can be performed. Deionized water or ultrapure water, as described above, can be used for neutral water. One or more cleaning cycles are sufficient; fewer cycles may result in the inability to remove alkaline or acidic components. Even 10 or more cleaning cycles may not achieve the desired cleaning effect; therefore, approximately 1 to 5 cycles are recommended.

[0097] Furthermore, the reaction product after liquid-liquid separation can be concentrated and dried under reduced pressure or normal pressure, or subjected to crystallization, and recovered in powder form. To improve operability when preparing polymers with subsequent modification to introduce branched long-chain alkyl units, a solution of appropriate concentration can be prepared beforehand. The concentration should ideally be 0.1–50% by mass, with 0.5–30% by mass being more preferable. Such a concentration prevents operability issues caused by difficulty in increasing viscosity, and also avoids excessive solvent usage, thus being economical.

[0098] If the solvent is a solvent that can dissolve the compound, there are no particular restrictions. 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, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tributyl acetate, tributyl propionate, and propylene glycol monotert-butyl ether acetate. These can be used alone or in combination of two or more types.

[0099] [(A) Materials for organic film formation] The organic film forming material (resin or compound) used in the organic film forming composition of the present invention is not particularly limited if it is a resin or compound with satisfactory film-forming and curing properties for spin coating. However, from the viewpoints of etching resistance, optical properties, heat resistance, etc., it is more preferable to be a resin or compound containing an aromatic skeleton (different from (B) polymer).

[0100] Examples of aromatic skeletons mentioned above include: benzene, naphthalene, anthracene, pyrene, indene, fumonisin, furan, pyrrole, thiophene, phosphonazole, pyrazole, phosphonazole, isophosphonazole, thiazole, pyridine, pyridine, pyrimidine, triazine, carbazole, etc. Among them, benzene, naphthalene, fumonisin, and carbazole are particularly good.

[0101] The following are specific examples of materials for forming organic films as described in (A) above, but these are merely illustrative and not limited to this. Furthermore, the numbering of the formulas shown in the following examples is only applicable to illustrating the following formulas.

[0102] The organic film forming material (resin or compound) used in this invention can be exemplified by the resins containing the following structure described in Japanese Patent Application Publication No. 2012-001687 and Japanese Patent Application Publication No. 2012-077295.

[0103] [Chemistry 18] In formula (1), the ring structures Ar1 and Ar2 independently represent benzene rings or naphthalene rings, respectively. X represents a single bond or an alkyl group with 1 to 20 carbon atoms. m represents 0 or 1. n represents any natural number that makes the molecular weight less than 100,000. In addition, the definitions of the symbols in the formula apply only to this formula.

[0104] [Chemistry 19] In equation (2), the ring structures Ar1 and Ar2 independently represent benzene rings or naphthalene rings, respectively. n represents any natural number that makes the equivalent weight-average molecular weight of polystyrene obtained by gel permeation chromatography less than 100,000. In addition, the definitions of the symbols in the equation apply only to this equation.

[0105] The organic film forming material (A) used in this invention can be further exemplified by resins containing the following structure as described in Japanese Patent Application Publication No. 2004-264710, Japanese Patent Application Publication No. 2005-043471, Japanese Patent Application Publication No. 2005-250434, Japanese Patent Application Publication No. 2007-293294, and Japanese Patent Application Publication No. 2008-065303.

[0106] [Chemistry 20] In formulas (3) and (4), R1 and R2 independently represent hydrogen atoms or alkyl or aryl groups having 1 to 3 carbon atoms, R3 represents alkyl, vinyl, allyl, or aryl groups having 1 to 3 carbon atoms, n represents 0 or 1, and m represents 0, 1, or 2. In addition, the definitions of the symbols in the formulas apply only to the formulas themselves.

[0107] [Chemistry 21] In equation (5), R1 is a monovalent atom or base other than hydrogen, and n is an integer from 0 to 4. However, when n is 2 to 4, multiple R1s can be the same or different. R2 and R3 are each independently a monovalent atom or base. X is a divalent base. In addition, the definitions of the symbols in the equation only apply to this equation.

[0108] [Chemistry 22] In formula (6), R1 is a hydrogen atom or a methyl group. R2 is any one of a single bond, a straight-chain, branched, or cyclic alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 10 carbon atoms, and may also contain any one of an ether, ester, lactone, or acetylamine. R3 and R4 are each independently a hydrogen atom or an epoxypropyl group. X represents any one of a hydrocarbon containing an indene skeleton, a cyclic olefin with 3 to 10 carbon atoms, or a maleimide, and may also contain any one of an ether, ester, lactone, or carboxylic anhydride. R5 and R6 are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R7 is any one of a hydrogen atom, a straight-chain, branched, or cyclic alkyl group with 1 to 6 carbon atoms, a hydroxyl group, or an alkoxycarbonyl group. p and q are integers from 1 to 4. r is an integer from 0 to 4. a, b, and c are the ranges of 0.5≦a+b+c≦1, 0≦a≦0.8, 0≦b≦0.8, 0.1≦a+b≦0.8, and 0.1≦c≦0.8, respectively. Furthermore, the definitions of the symbols in the formula apply only to that specific formula.

[0109] [Chemistry 23] In equation (7), R1 represents a hydrogen atom or a monovalent organic group, and R2 and R3 independently represent a monovalent atom or a monovalent organic group, respectively. In addition, the definitions of the symbols in the equation apply only to this equation.

[0110] The organic film forming material (A) used in this invention can be further exemplified by resins containing the following structure as described in Japanese Patent Application Publication No. 2004-205685, Japanese Patent Application Publication No. 2007-171895, and Japanese Patent Application Publication No. 2009-014816.

[0111] [Chemistry 24] In formulas (8) and (9), R1 to R8 are independently hydrogen atoms, hydroxyl groups, substituted alkyl groups with 1 to 6 carbon atoms, substituted alkoxy groups with 1 to 6 carbon atoms, substituted alkoxycarboxyl groups with 2 to 6 carbon atoms, substituted aryl groups with 6 to 10 carbon atoms, hydroxyalkyl groups with 1 to 6 carbon atoms, isocyanate groups, or glycidyl groups. m and n are positive integers. In addition, the definitions of the symbols in the formulas apply only to the formulas themselves.

[0112] [Chemistry 25] In formula (10), R1 and R6 are each independently a hydrogen atom or a methyl group. R2, R3, and R4 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a hydroxyl group, an acetoxy group, an alkoxycarbonyl group, or an aryl group having 6 to 10 carbon atoms, R5 is a condensed polycyclic hydrocarbon group having 13 to 30 carbon atoms, -O-R7, -C(=O)-O-R7, -O-C(=O)-R7, or -C(=O)-NR8-R7, m is 1 or 2, n is an integer from 0 to 4, and p is an integer from 0 to 6. R7 is an organic group having 7 to 30 carbon atoms, and R8 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Z is any one of a methylene group, -O-, -S-, and -NH-. a, b, c, d, and e are in the ranges of 0 < a < 1.0, 0 ≤ b ≤ 0.8, 0 ≤ c ≤ 0.8, 0 ≤ d ≤ 0.8, 0 ≤ e ≤ 0.8, and 0 < b + c + d + e < 1.0. Additionally, the definitions of the symbols in the formula are only applicable within the formula.

[0113] [Chemical formula 26] In formula (11), n represents 0 or 1. R1 represents a methylene group that may be substituted, an alkylene group having 2 to 20 carbon atoms that may be substituted, or an arylene group having 6 to 20 carbon atoms that may be substituted. R2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may be substituted, or an aryl group having 6 to 20 carbon atoms that may be substituted. R3 to R7 each independently represent a hydroxyl group, an alkyl group having 1 to 6 carbon atoms that may be substituted, an alkoxy group having 1 to 6 carbon atoms that may be substituted, an alkoxycarbonyl group having 2 to 10 carbon atoms that may be substituted, an aryl group having 6 to 14 carbon atoms that may be substituted, or a glycidyl group having 2 to 6 carbon atoms that may be substituted. R9 represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched, or cyclic alkyl ether group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Additionally, the definitions of the symbols in the formula are only applicable within the formula.

[0114] The resin represented by formula (11) is exemplified by the following resins.

[0115] [Chemical formula 27]

[0116] [Chemical formula 28]

[0117] The organic film forming material (A) used in this invention can be further exemplified by resins containing the following structure as described in Japanese Patent Application Publication No. 2007-199653, Japanese Patent Application Publication No. 2008-274250, and Japanese Patent Application Publication No. 2010-122656.

[0118] [Chemistry 29] In formula (12), R1 and R2 are independently the same or different hydrogen atoms, straight-chain, branched, or cyclic alkyl groups with 1 to 10 carbon atoms, aryl groups with 6 to 10 carbon atoms, or alkenyl groups with 2 to 10 carbon atoms, respectively. R3 is a single bond, or a straight-chain, branched, or cyclic alkyl group with 1 to 30 carbon atoms, and may also have a bridged cyclic hydrocarbon group, a double bond, a heteroatom, or an aromatic group with 6 to 30 carbon atoms. R4 and R5 are independently hydrogen atoms or glycidyl groups, respectively, and n is an integer from 1 to 4. In addition, the definitions of the symbols in the formula are only applicable to this formula.

[0119] [Chemistry 30] In formula (13), R1 and R2 are independently the same or different hydrogen atoms, straight-chain, branched, or cyclic alkyl groups with 1 to 10 carbon atoms, aryl groups with 6 to 10 carbon atoms, or alkenyl groups with 2 to 10 carbon atoms, respectively. R3 is a single bond, or a straight-chain, branched, or cyclic alkyl group with 1 to 30 carbon atoms, and may also have a bridged cyclic hydrocarbon group, a double bond, a heteroatom, or an aromatic group with 6 to 30 carbon atoms. R4 and R5 are independently hydrogen atoms or glycidyl groups, respectively. R6 is a single bond, or a straight-chain or branched alkyl group with 1 to 10 carbon atoms. In addition, the definitions of the symbols in the formula are only applicable to this formula.

[0120] [Chemistry 31] In equation (14), rings Z1 and Z2 are condensed polycyclic aromatic hydrocarbon rings, and R1a, R1b, R2a, and R2b represent the same or different substituents. k1 and k2 can be the same or different and represent integers from 0 to 4, m1 and m2 represent integers greater than or equal to 1, and n1 and n2 represent integers greater than or equal to 1. However, n1 + n2 ≥ 1. Furthermore, the definitions of the symbols in the equation apply only to this specific equation.

[0121] [Chemistry 32] In formula (15), R1 and R2 are the same or different hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms. R3 and R4 are each independently a hydrogen atom or an epoxypropyl group, R5 is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, and R6 and R7 are each independently a benzene ring or a naphthalene ring. p and q are each 1 or 2. n is 0 < n ≦ 1. In addition, the definitions of the symbols in the formula are only applicable to that formula.

[0122] The resin represented by formula (15) is exemplified by the following resins.

[0123] [Chemical formula 33]

[0124] [Chemical formula 34]

[0125] [Chemical formula 35]

[0126] [Chemical formula 36]

[0127] The (A) organic film-forming material used in the present invention can be further exemplified by resins having the following structures described in Japanese Patent Application Laid-Open No. 2012-214720.

[0128] [Chemical formula 37] In formula (16), the ring structures Ar1 and Ar2 each independently represent a benzene ring or a naphthalene ring. x and z each independently represent 0 or 1. In addition, the definitions of the symbols in the formula are only applicable to that formula.

[0129] The (A) organic film-forming material used in the present invention can be further exemplified by resins described in Japanese Patent Application Laid-Open No. 2014-29435.

[0130] [Chemical formula 38] In formula (17), A represents a carbazole structure, B represents an aromatic ring structure, and C represents a hydrogen atom, an alkyl group, or an aromatic ring structure. B and C can also form rings with each other. The structure formed by combining A, B, and C has 1 to 4 carboxyl groups or their salts, or carboxylic acid ester groups. In addition, the definitions of the symbols in the formula only apply to this formula.

[0131] Furthermore, the organic film forming material (A) used in this invention can be further exemplified as a polymer containing the unit structure represented by formula (18) and the unit structure represented by formula (19) as described in International Publication No. 2012 / 077640, wherein the ratio of the unit structure represented by formula (18) to the unit structure represented by formula (19) is 3 to 97 to 97 to 3 in molar ratio.

[0132] [Chemistry 39] In formula (18), R1 and R2 independently represent hydrogen atoms, halogen atoms, nitro groups, amino groups, hydroxyl groups, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 40 carbon atoms, or combinations of these groups that may contain ether bonds, ketone bonds, or ester bonds. R3 represents hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 40 carbon atoms, or combinations of these groups that may contain ether bonds, ketone bonds, or ester bonds. R4 represents hydrogen atoms, or aryl groups with 6 to 40 carbon atoms that may be substituted with halogen atoms, nitro groups, amino groups, or hydroxyl groups, or heterocyclic groups. R5 represents hydrogen atoms, or alkyl groups with 1 to 10 carbon atoms, aryl groups with 6 to 40 carbon atoms that may be substituted with halogen atoms, nitro groups, amino groups, or hydroxyl groups, or heterocyclic groups. R4 and R5 may also form rings with each other. n1 and n2 represent integers from 1 to 3. Furthermore, the symbols in the formula are defined only within that formula.

[0133] [Chemistry 40] In formula (19), Ar represents an aromatic cyclic group with 6 to 20 carbon atoms, R6 represents a hydroxyl group, and R7 represents a combination of these groups, including hydrogen, halogen, nitro, amino, alkyl with 1 to 10 carbon atoms, alkenyl with 2 to 10 carbon atoms, aryl with 6 to 40 carbon atoms, or possibly containing ether, ketone, or ester bonds. R8 represents a hydrogen atom, or an aryl or heterocyclic group with 6 to 40 carbon atoms that may be substituted by a halogen, nitro, amino, or hydroxyl group. R9 represents a hydrogen atom, or an alkyl, aryl, or heterocyclic group with 1 to 10 carbon atoms that may be substituted by a halogen, nitro, amino, or hydroxyl group. R8 and R9 may also form rings with each other. n6 represents an integer from 1 to p, and n7 represents an integer from p to n6. Here, p represents the largest number of aromatic cyclic groups Ar that can be substituted. In addition, the definitions of the symbols in the formula apply only to this formula.

[0134] The organic film forming material (A) used in this invention can be further exemplified by the polymer containing the unit structure represented by the following formula (20) as described in International Publication No. 2010 / 147155.

[0135] [Chemistry 41] In formula (20), R1 and R2 independently represent groups selected from the group consisting of hydrogen atoms, halogen groups, nitro groups, amino groups, hydroxyl groups, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 40 carbon atoms, and combinations thereof, wherein the alkyl group, alkenyl group, or aryl group may also contain ether bonds, ketone bonds, or ester bonds, and R3 represents groups selected from the group consisting of hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 40 carbon atoms, and combinations thereof. In the group consisting of these compounds, the alkyl, alkenyl, or aryl groups may also contain ether, ketone, or ester bonds. R4 represents an aryl or heterocyclic group with 6 to 40 carbon atoms that may be substituted with a halogen, nitro, amino, or hydroxyl group. R5 represents a hydrogen atom, or an alkyl, aryl, or heterocyclic group with 1 to 10 carbon atoms that may be substituted with a halogen, nitro, amino, or hydroxyl group. R4 and R5 may also form a ring with the carbon atoms they are bonded to. n1 and n2 are integers from 1 to 3. Furthermore, the definitions of the symbols in the formula apply only to this specific formula.

[0136] The organic film forming material (A) used in this invention can be further exemplified by: phenolic varnish resin obtained by reacting one or more of the following phenols, such as phenol, cresol, xylenol, catechol, resorcinol, hydroquinone, gallol, hydroxyhydroquinone, and phloroglucinol, with one or more of the following aldehyde sources, such as formaldehyde, paraformaldehyde, and trimethylolpropionate, using an acidic catalyst; and resin containing the repeating unit structure represented by the following formula (21) as described in International Publication No. 2012 / 176767.

[0137] [Chemistry 42] In formula (21), A represents a hydroxyl-substituted phenyl group derived from polyhydroxybenzene, and B represents a monovalent condensed aromatic hydrocarbon cyclic group formed by the condensation of 2 to 6 benzene rings. Furthermore, the definitions of the symbols in the formula apply only to that specific formula.

[0138] The organic film forming material used in this invention can be further exemplified by: phenolic varnish resins having a fusiform or tetrahydrospirodiinden structure as described in Japanese Patent Application Publication Nos. 2005-128509, 2006-259249, 2006-259482, 2006-293298, and 2007-316282, and resins containing a repeating unit structure represented by the following formula (22-1) or (22-2), etc.

[0139] [Chemistry 43] In formulas (22-1) and (22-2), R1, R2, R6, and R7 are independently hydrogen atoms, linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms, aryl, allyl, or halogen atoms having 6 to 10 carbon atoms, respectively; R3, R4, R8, and R9 are independently hydrogen atoms, linear, branched, or cyclic alkyl groups having 1 to 6 carbon atoms, linear, branched, or cyclic alkenyl groups having 2 to 6 carbon atoms, aryl, or glycidyl groups having 6 to 10 carbon atoms, respectively; and R5 and R14 are independently hydrogen atoms, linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms, or aryl groups having 6 to 10 carbon atoms, respectively. n, m, p, and q are integers from 1 to 3. R10 to R13 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a straight-chain, branched, or cyclic alkoxy group having 1 to 6 carbon atoms. Furthermore, the definitions of the symbols in the formula apply only to that specific formula.

[0140] The organic film-forming material (A) used in this invention can be further exemplified by the reaction product obtained by the method described in Japanese Patent Application Publication No. 2012-145897. More specifically, it can be exemplified by a polymer obtained by condensation of one or more compounds represented by the following general formulas (23-1) and / or (23-2) with one or more compounds represented by the following general formulas (24-1) and / or (24-2) and / or their equivalents.

[0141] [Chemistry 44] In general formulas (23-1) and (23-2), R1 to R8 are independently hydrogen atoms, halogen atoms, hydroxyl groups, isocyanoxy groups, epoxypropyloxy groups, carboxyl groups, amino groups, alkoxy groups with 1 to 30 carbon atoms, alkoxycarbonyl groups with 1 to 30 carbon atoms, alkoxyloxy groups with 1 to 30 carbon atoms, or saturated or unsaturated organic groups with 1 to 30 carbon atoms that may be substituted. Furthermore, any two substituents selected from R1 to R4 or R5 to R8 within the molecule can be bonded together to further form cyclic substituents. Additionally, the definitions of the symbols in the formulas apply only to that specific formula.

[0142] [Chemistry 45] In general formulas (24-1) and (24-2), Q represents an organogroup with 1 to 30 carbon atoms that can be substituted. Furthermore, any two Qs chosen within the molecule can bond together to form a cyclic substituent. n1 to n6 represent the number of each substituent, where n1 to n6 are 0, 1, or 2. Hydroxybenzaldehyde is excluded from formula (24-1). Also, formula (24-2) conforms to the relationships 0≦n3+n5≦3, 0≦n4+n6≦4, and 1≦n3+n4≦4. Additionally, the definitions of the symbols in the formulas apply only to that specific formula.

[0143] Furthermore, examples can be given of polymers obtained by condensation of one or more compounds represented by the above general formula (23-1) and / or (23-2), one or more compounds and / or their equivalents represented by the above general formula (24-1) and / or (24-2), and one or more compounds and / or their equivalents represented by the following general formula (25).

[0144] [Chemistry 46] In formula (25), Y is a hydrogen atom or a monovalent organic group with 30 or fewer carbon atoms that may have substituents. Formula (25) is different from general formulas (24-1) and (24-2). In addition, the symbols in the formula are defined only in this formula.

[0145] The organic film forming material (A) used in this invention can be further exemplified by compounds containing the following structure as described in Japanese Patent Application Publication No. 2017-119671.

[0146] [Chemistry 47] In formula (26-1), R is a single bond or an organic group with 1 to 50 carbon atoms, X is a base represented by the following general formula (26-2), and m1 is an integer satisfying 2 ≤ m1 ≤ 10. Furthermore, the definitions of the symbols in the formula apply only to this formula.

[0147] [Chemistry 48] In the formula, X2 is a divalent organic group with 1 to 10 carbon atoms, n1 is 0 or 1, n2 is 1 or 2, X3 is a group represented by the following general formula (26-3), and n5 is 0, 1, or 2. In addition, the definitions of the symbols in the formula apply only to this formula.

[0148] [Chemistry 49] In the formula, R10 is a hydrogen atom or a saturated or unsaturated hydrocarbon group with 1 to 10 carbon atoms, and the hydrogen atom on the benzene ring can also be replaced by a methyl or methoxy group. Furthermore, the symbols in the formula are defined only for that specific formula.

[0149] Compounds containing the above structure, for example, are shown below.

[0150] [Transformation 50]

[0151] The organic film forming material (A) used in this invention can be further exemplified by polymers having repeating units represented by the following general formula (27-1) as described in Japanese Patent Application Publication No. 2019-044022.

[0152] [Chemistry 51] In formula (27-1), AR1 and AR2 are benzene rings or naphthalene rings that may also have substituents. R1 and R2 are independently hydrogen atoms or organic groups with 1 to 30 carbon atoms. When R1 and R2 are organic groups, they can also form cyclic organic groups by intramolecular bonding. n is 0 or 1. When n=0, AR1 and AR2 do not form a bridging structure with each other through Z and the aromatic rings of AR1 and AR2. When n=1, AR1 and AR2 form a bridging structure with each other through Z and the aromatic rings of AR1 and AR2. Z is a single bond or any of the following formula (27-2). Y is the base represented by the following formula (27-3). In addition, the definitions of the symbols in the formula only apply to this formula.

[0153] [Chemistry 52] In equation (27-3), R3 is a single bond or a divalent organic group with 1 to 20 carbon atoms, R4 is a hydrogen atom or a monovalent organic group with 1 to 20 carbon atoms, and the dashed line represents an atomic bond. Furthermore, the definitions of the symbols in the equation apply only to that specific equation.

[0154] Polymers having repeating units represented by the above general formula (27-1) are exemplified by the following polymers.

[0155] [Chemistry 53]

[0156] [Chemistry 54]

[0157] (A) Materials for organic membrane formation can be synthesized using known methods or commercially available products.

[0158] The amount of the aforementioned organic film-forming material in (A) is not particularly limited if it satisfies the film-forming properties of the spin-coating composition of the organic film-forming compound. If the aforementioned organic film-forming compound is 100 parts by mass, then the content of the aforementioned organic film-forming material in (A) is preferably 10-40 parts by mass, more preferably 10-30 parts by mass, and even more preferably 10-25 parts by mass. For example, when filling the very high aspect ratio holes and trenches of a 3D NAND memory architecture with the organic film-forming composition, it is necessary to increase the amount of the organic film-forming material. However, this increases the viscosity of the organic film-forming composition, deteriorating the in-plane uniformity and filling characteristics after spin-coating. Even with the aforementioned mixing ratio of the organic film-forming material in (A), the organic film-forming composition of the present invention can still form an organic film with excellent in-plane uniformity and filling characteristics, thus making it ideally applicable.

[0159] Furthermore, relative to 100 parts by mass of the organic film forming material (A) mentioned above, the content of the polymer mentioned above (B) should preferably be 0.01 parts by mass to 5 parts by mass. If the composition for forming an organic film contains such a content of polymer, the in-plane uniformity of the organic film after film formation will be better.

[0160] [(C) Solvent] Regarding the solvent (C) that can be used in the composition for forming the organic film of the present invention, there are no particular limitations if it is able to dissolve the aforementioned organic film-forming material (A) and the aforementioned polymer (B). It is preferable that it is also able to dissolve the acid generator, crosslinking agent, and surfactant described later. Specifically, for example, solvents with a boiling point not reaching 180°C, such as those described in paragraphs (0091) to (0092) of Japanese Patent Application Publication No. 2007-199653, can be used. Among them, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and mixtures of two or more thereof are preferable.

[0161] (C) The solvent content is preferably 200 to 10,000 parts by mass, or 300 to 5,000 parts by mass, relative to 100 parts by mass of the organic film-forming material in (A). By setting it within such a range, the concentration can be adjusted to match the thickness of the film consumed.

[0162] Furthermore, in the organic film-forming composition of the present invention, a high-boiling-point solvent (a mixture of a solvent with a boiling point below 180°C and a solvent with a boiling point above 180°C) can also be added to the solvent with a boiling point below 180°C as the organic solvent of (C). If the high-boiling-point organic solvent is capable of dissolving the organic film-forming material of (A) and the polymer of (B), it is not particularly limited to hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc. Specific examples can be given as follows: 1-Octanol, 2-Ethylhexanol, 1-Nonanol, 1-Decanol, 1-Undecylol, Ethylene glycol, 1,2-Propanediol, 1,3-Butanediol, 2,4-Pentanediol, 2-Methyl-2,4-Pentanediol, 2,5-Hexanediol, 2,4-Heptanediol, 2-Ethyl-1,3-Hexanediol, Diethylene glycol, Dipropylene glycol, Triethylene glycol, Tripropylene glycol, Glycerol, 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 monon-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 diethyl ether Ester, Tetraethylene glycol dimethyl ether, Dipropylene glycol monomethyl ether, Dipropylene glycol mono-n-propyl ether, Dipropylene glycol mono-n-butyl ether, Tripropylene glycol dimethyl ether, Tripropylene glycol monomethyl ether, Tripropylene glycol mono-n-propyl ether, Tripropylene glycol mono-n-butyl ether, Ethylene glycol monoethyl ether acetate, Ethylene glycol monobutyl ether acetate, Diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate, Triacetin, Propylene glycol diacetate, Dipropylene glycol monomethyl ether Acetates, dipropylene glycol methyl 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., and they can be used alone or in combination.

[0163] The boiling point of the high-boiling-point solvent mentioned above should be appropriately selected in conjunction with the heat treatment temperature of the material used to form the organic film (A). The boiling point of the added high-boiling-point solvent should preferably be between 180°C and 300°C, with 200°C to 300°C being even better. With such a boiling point, there is no concern that the solvent will evaporate too quickly during baking (heat treatment) due to a low boiling point, thus ensuring sufficient thermal fluidity. Furthermore, with such a high boiling point, there is no residue remaining in the film after baking, thus eliminating concerns about adverse effects on film properties such as etching resistance.

[0164] Furthermore, when using the aforementioned high-boiling-point solvents, the amount of high-boiling-point solvent added should preferably be 1 to 30 parts by mass relative to 100 parts by mass of solvents with a boiling point not reaching 180°C. If such an amount of addition is used, sufficient thermal fluidity can be imparted during baking due to the appropriate amount of addition, while there is no concern that residual material in the film will cause degradation of film properties such as etching resistance.

[0165] If it is such an organic film forming composition, then by imparting the above-mentioned (A) organic film forming material with thermal fluidity due to the addition of a high-boiling-point solvent, it becomes an organic film forming composition that has both a high degree of landfilling and excellent planarization characteristics.

[0166] [Other ingredients] Furthermore, various other components can be added to the composition for forming organic films of the present invention. [Acid generating agent] To further promote the cross-linking reaction, an acid-generating agent may be added. Acid-generating agents can be those that generate acid through thermal decomposition or those that generate acid through light exposure; either type may be added. Specific examples of acid-generating agents can be found in paragraphs

[0061] to

[0085] of Japanese Patent Application Publication No. 2007-199653. The aforementioned acid-generating agents may be used alone or in combination of two or more. The amount of acid-generating agent added should preferably be 0.05 to 50 parts by weight, and more preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of the organic film-forming material (A). Such an amount will promote the cross-linking reaction and form a dense film.

[0167] [Cross-linking agent] To further promote the crosslinking reaction, a crosslinking agent may be added. Examples of crosslinking agents include those described in paragraphs

[0055] to

[0060] of Japanese Patent Application Publication No. 2007-199653. One type of crosslinking agent may be used alone, or two or more may be used in combination. The amount of crosslinking agent added relative to 100 parts by weight of the organic film-forming material (A) is preferably 1 to 100 parts by weight, and more preferably 5 to 50 parts by weight. Such an amount improves curing properties and further inhibits mixing with the upper film.

[0168] [Surfactants] Furthermore, in order to further improve the in-plane uniformity during spin coating, a surfactant may be added to the composition for forming the organic film of the present invention in addition to the polymer (B) of the present invention. Specific examples of the surfactants to be added include those described in paragraphs

[0142] to

[0147] of Japanese Patent Application Publication No. 2009-269953. The aforementioned surfactants may be used alone or in combination of two or more. The amount of surfactant added is preferably 0.01 to 10 parts by weight, and more preferably 0.05 to 5 parts by weight, relative to 100 parts by weight of the organic film forming material. With such an amount, an organic film with excellent in-plane uniformity can be formed.

[0169] [Basic compounds] Furthermore, an alkaline compound for improving storage stability can be added to the composition for forming organic films of the present invention. The alkaline compound acts as an acid quencher, preventing cross-linking reactions caused by trace amounts of acid generated from the acid generator. Examples of such alkaline compounds include those described in paragraphs

[0086] to

[0090] of Japanese Patent Application Publication No. 2007-199653. One alkaline compound can be used alone or in combination of two or more. The amount of acid generator added is preferably 0.05 to 50 parts by weight, and more preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of the organic film forming material (A). Such an amount improves the storage stability of the composition for forming organic films.

[0170] As described above, the organic film forming composition of the present invention will become an organic film forming composition with excellent protrusion suppression properties during the EBR step. Therefore, the organic film forming composition of the present invention is extremely useful as a lower layer film material (organic film material) for multilayer resistive processes such as two-layer resistive processes, three-layer resistive processes using silicon-containing resistive intermediate films or silicon-containing inorganic hard mask intermediate films, and four-layer resistive processes using silicon-containing resistive intermediate films or silicon-containing inorganic hard mask intermediate films and organic antireflective films or sealing films.

[0171] [Organic Film Formation Methods] The present invention obtains a coating by spin-coating the organic film forming composition of the present invention onto a substrate to be processed, and then heat-treats the aforementioned coating at an appropriate temperature and time range to harden it, thereby forming an organic film.

[0172] The present invention provides an organic film forming method, which is a method for forming organic films used in the manufacturing process of semiconductor devices. The method is characterized by: spin-coating the aforementioned organic film forming composition onto a substrate to obtain a coating film, and then curing it by heat treatment to form an organic film. The heat treatment conditions for the aforementioned coating should be carried out at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds.

[0173] In this organic film formation method, the organic film formation composition of the present invention is first spin-coated onto the substrate to be processed. By using spin-coating, good filling characteristics can be obtained. After removing the end film in the EBR step, baking (heat treatment) is performed to promote the crosslinking reaction. Furthermore, this baking allows the solvent in the composition to evaporate, thus preventing mixing even when a resist upper layer and a silicon-containing resist intermediate layer are formed on the organic film.

[0174] Baking should ideally be performed at a temperature between 100°C and 600°C for 10 to 600 seconds, preferably between 200°C and 500°C for 10 to 300 seconds. Considering the potential for device damage and wafer deformation, the upper limit of the heating temperature for wafer processing in lithography should ideally be below 600°C, preferably below 500°C. Performing heat treatment under these conditions promotes the cross-linking reaction and forms an organic film that does not mix with the film formed on top.

[0175] [Pattern Formation Method] The following describes a pattern forming method using the composition for forming an organic film according to the present invention. The pattern forming method of the present invention uses the composition for forming an organic film described above and forms a pattern by using the organic film forming method described above to form an organic film.

[0176] [A three-layer resistive process using a silicon-containing resistive interlayer film] This invention provides a pattern forming method, characterized by: forming an organic film on a workpiece using the aforementioned organic film forming composition of the present invention; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming a resist upper film on the silicon-containing resist intermediate film using a resist upper film material composed of a photoresist composition; forming a circuit pattern on the resist upper film; using the resist upper film with the circuit pattern as a mask and etching to transfer the pattern onto the silicon-containing resist intermediate film; using the silicon-containing resist intermediate film with the transferred pattern as a mask and etching to transfer the pattern onto the organic film; and then using the organic film with the transferred pattern as a mask and etching to form the pattern on the workpiece.

[0177] The aforementioned workpiece is preferably formed using a semiconductor device substrate, or a semiconductor device substrate having a metal film, metal carbide film, metal oxide film, metal nitride film, metal oxide carbide film, and metal oxide nitride film formed thereon. More specifically, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, and Al, or substrates having the aforementioned metal films formed thereon as the workpiece layer, may be used, but are not limited thereto.

[0178] The processed layer can be made of various Low-k films and their barrier films, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, typically forming thicknesses of 50–10,000 nm, and especially 100–5,000 nm. Furthermore, different materials can be used for the substrate and the processed layer during film formation.

[0179] In addition, it is preferable to use metals that constitute the workpiece, including silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or alloys thereof.

[0180] When forming an organic film on a workpiece using the composition for forming an organic film according to the present invention, the organic film forming method of the present invention described above can be used, but is not limited thereto.

[0181] Then, a resistive intermediate film (silicon-containing resistive intermediate film) is formed on the organic film using a resistive intermediate film material containing silicon atoms. The resistive intermediate film material containing silicon atoms is preferably a polysiloxane-based intermediate film material. By giving the silicon-containing resistive intermediate film an anti-reflective effect, reflection can be suppressed. Especially for 193nm exposure, if the composition for forming the organic film uses a material containing a large number of aromatic groups and with high etching selectivity to the substrate, the k-value will increase and the substrate reflection will increase. However, by using a silicon-containing resistive intermediate film, by giving it absorption that results in an appropriate k-value, reflection can be suppressed, and the substrate reflection can be controlled below 0.5%. For silicon-containing resistive interlayer films with anti-reflective effects, polysiloxanes with anthracene groups that are cross-linked by acid or heat are preferred for 248nm or 157nm exposure, while polysiloxanes with light-absorbing groups having phenyl or silicon-silicon bonds in a pendant structure and cross-linked by acid or heat are preferred for 193nm exposure.

[0182] Then, a top resist film is formed on top of the silicon-containing resist intermediate film by using a top resist film material composed of a photoresist composition. The top resist film material can be either positive or negative, and can be the same as commonly used photoresist compositions. After spin-coating the top resist film material, pre-baking is preferably performed at 60–180°C for 10–300 seconds. Subsequently, exposure is performed following common methods, followed by post-exposure baking (PEB) and development to obtain the top resist film pattern. Furthermore, the thickness of the top resist film is not particularly limited, but is preferably 30–500 nm, with 50–400 nm being particularly desirable.

[0183] Then, a circuit pattern (resistor overlayer pattern) is formed on the resist overlayer film. When forming the circuit pattern, it is advisable to use lithography, electron beam writing, nanoimprinting, or a combination thereof that uses light with wavelengths of 10 nm or higher and 300 nm or lower to form the circuit pattern.

[0184] In addition, exposure light can include high-energy rays with wavelengths below 300nm, specifically: far ultraviolet light, KrF excimer laser light (248nm), ArF excimer laser light (193nm), F2 laser light (157nm), Kr2 laser light (146nm), Ar2 laser light (126nm), soft X-rays (EUV) of 3~20nm, electron beam (EB), ion beam, and X-rays, etc.

[0185] Furthermore, when forming circuit patterns, it is advisable to use alkaline development or organic solvents to develop the circuit patterns.

[0186] Then, using the resist top film with the circuit pattern as a mask, the pattern is transferred to the silicon-containing resist intermediate film by etching. The etching of the silicon-containing resist intermediate film using the resist top film pattern as a mask is preferably performed using a fluorocarbon-based gas. This transfers the pattern (silicon-containing resist intermediate film pattern) onto the silicon-containing resist intermediate film.

[0187] Then, using a patterned silicon-containing resist interlayer film (silicon-containing resist interlayer film pattern) as a mask, the pattern is transferred to the organic film by etching. Since the silicon-containing resist interlayer film exhibits etching resistance to oxygen or hydrogen, the etching of the organic film using the silicon-containing resist interlayer film pattern as a mask should preferably be performed using an etching gas primarily composed of oxygen or hydrogen. This is how the pattern (organic film pattern) is transferred to the organic film.

[0188] Then, an organic film with a transferred pattern (organic film pattern) is used as a mask and the pattern is formed on the workpiece by etching.

[0189] Subsequent etching of the workpiece (processed layer) can be performed using common methods. For example, if the workpiece is a low-dielectric-constant insulating film based on SiO2, SiN, or silicon dioxide, etching using fluorocarbon (Fluoron) based gases is performed; if it is p-Si, Al, or W, etching using chlorine or bromine based gases is performed. When substrate processing is performed using etching with fluorocarbon (Fluoron) based gases, the silicon-containing resist interlayer pattern is stripped off simultaneously with the processing of the workpiece. On the other hand, when the workpiece processing is performed using etching with chlorine or bromine based gases, dry etching with fluorocarbon (Fluoron) based gases is required after the processing of the workpiece in order to strip the silicon-containing resist interlayer pattern.

[0190] Organic films obtained using the organic film forming composition of the present invention can be made to exhibit excellent etching resistance during etching of the workpiece, as described above.

[0191] [A four-layer resist process using a silicon-containing resist interlayer and an organic antireflective film or sealing film] Furthermore, the present invention provides a pattern forming method, characterized by: forming an organic film on a workpiece using the organic film forming composition of the present invention described above; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming an organic anti-reflective film or a sealing film on the silicon-containing resist intermediate film; forming a resist upper film on the organic anti-reflective film or the sealing film using a resist upper film material composed of a photoresist composition; forming a circuit pattern on the resist upper film; using the resist upper film with the circuit pattern as a mask and etching to transfer the pattern onto the organic anti-reflective film or the sealing film and the silicon-containing resist intermediate film; using the silicon-containing resist intermediate film with the transferred pattern as a mask and etching to transfer the pattern onto the organic film; and then using the organic film with the transferred pattern as a mask and etching to form the pattern on the workpiece.

[0192] In addition, this method involves forming an organic antireflective film (BARC) or a sealing film between the silicon-containing resist intermediate film and the resist upper film. Otherwise, it can be implemented in the same way as the three-layer resist process using the silicon-containing resist intermediate film mentioned above.

[0193] Organic antireflective films and sealing films can be formed using known organic antireflective film materials by spin coating.

[0194] [A three-layer resist process using an inorganic hard mask interlayer] Furthermore, the present invention provides a pattern forming method, characterized by: forming an organic film on a workpiece using the organic film forming composition of the present invention described above; forming an inorganic hard mask selected from the group consisting of silicon oxide film, silicon nitride film, and silicon oxynitride film on the aforementioned organic film; forming a resist upper film on the aforementioned inorganic hard mask using a resist upper film material composed of a photoresist composition; forming a circuit pattern on the aforementioned resist upper film; using the resist upper film with the aforementioned circuit pattern as a mask and etching to transfer the pattern onto the aforementioned inorganic hard mask; using the inorganic hard mask with the aforementioned pattern as a mask and etching to transfer the pattern onto the aforementioned organic film; and then using the organic film with the aforementioned pattern as a mask and etching to form the pattern on the aforementioned workpiece.

[0195] In addition, this method involves replacing the silicon-containing resist intermediate film on top of the organic film with an inorganic hard mask intermediate film. Otherwise, it can be carried out in the same way as the three-layer resist process using the silicon-containing resist intermediate film mentioned above.

[0196] Inorganic hard masking interlayers are selected from the group consisting of silicon oxide films, silicon nitride films, and silicon oxynitride films (SiON films), and can be formed, for example, using CVD or ALD methods. Methods for forming silicon nitride films are described, for example, in Japanese Patent Application Publication No. 2002-334869 and International Publication No. 2004 / 066377. The thickness of the inorganic hard masking interlayer is preferably 5-200 nm, and more preferably 10-100 nm. SiON films, which are highly effective as anti-reflective films, are the best choice for inorganic hard masking interlayers.

[0197] [A four-layer resist process using an inorganic hard mask interlayer and an organic anti-reflective film or sealing film] Furthermore, the present invention provides a pattern forming method, characterized by: forming an organic film on a workpiece using the aforementioned composition for forming organic films; forming an inorganic hard mask selected from the group consisting of silicon oxide film, silicon nitride film, and silicon oxynitride film on the aforementioned organic film; forming an organic antireflective film or a sealing film on the aforementioned inorganic hard mask; forming a resist upper film using a resist upper film material composed of a photoresist composition on the aforementioned organic antireflective film or sealing film; forming a circuit pattern on the aforementioned resist upper film; using the resist upper film with the aforementioned circuit pattern as a mask and etching to transfer the pattern onto the aforementioned organic antireflective film or sealing film and the aforementioned inorganic hard mask; using the inorganic hard mask with the aforementioned pattern as a mask and etching to transfer the pattern onto the aforementioned organic film; and then using the organic film with the aforementioned pattern as a mask and etching to form the pattern on the aforementioned workpiece.

[0198] In addition, this method involves forming an organic antireflective film (BARC) or a sealing film between the inorganic hard mask intermediate film and the upper resist film. Otherwise, it can be implemented in the same way as the three-layer resist process using the inorganic hard mask intermediate film mentioned above.

[0199] Especially when using SiON film as the intermediate film in inorganic hard masking, the two-layer anti-reflection film of SiON film and BARC can suppress reflection even in immersion exposure with a high NA exceeding 1.0. Another advantage of forming BARC is that it reduces the trailing of the resist layer pattern located directly above the SiON film.

[0200] Here, an example of the pattern formation method of the three-layer resist process of the present invention is shown in Figures 1(A) to (F). In the three-layer resist process, as shown in Figure 1(A), an organic film 3 is formed on the workpiece 2 formed on the substrate 1 using the organic film forming composition of the present invention. Then, a silicon-containing resist intermediate film 4 is formed on the organic film 3, and a resist upper film 5 is formed thereon. Then, as shown in Figure 1(B), the exposure portion 6 of the resist upper film 5 is exposed, and then PEB (post-exposure baking) is performed. Then, as shown in Figure 1(C), development is performed to form the resist upper film pattern 5a. Then, as shown in Figure 1(D), using the resist upper film pattern 5a as a mask, the silicon-containing resist intermediate film 4 is dry-etched using a fluorocarbon (Fluoron) gas to form the silicon-containing resist intermediate film pattern 4a. Then, the resist upper film pattern 5a is removed. Then, as shown in Figure 1(E), the organic film 3 is etched with oxygen plasma using the silicon-containing resist intermediate film pattern 4a as a mask to form the organic film pattern 3a. Then, as shown in Figure 1(F), the silicon-containing resist intermediate film pattern 4a is removed. Then, the processed layer 2 is etched using the organic film pattern 3a as a mask to form the pattern 2a.

[0201] In this pattern formation method, by suppressing protrusions during the formation of the organic film 3, defects arising from protrusions in the organic film during the dry etching process of Figures 1(D), (E) and (F) can be reduced.

[0202] When forming an inorganic hard mask interlayer, the silicon-containing resist interlayer 4 can be replaced with an inorganic hard mask interlayer. When forming a BARC or sealing film, a BARC or sealing film can be formed between the silicon-containing resist interlayer 4 and the upper resist film 5. The etching of the BARC or sealing film can be carried out continuously before the etching of the silicon-containing resist interlayer 4, or the etching of the silicon-containing resist interlayer 4 can be carried out after the etching of only the BARC or sealing film, by changing the etching apparatus, etc.

[0203] As described above, if it is the pattern forming method of the present invention, the multilayer resist process can form fine patterns on the workpiece with high precision, and by suppressing the formation of protrusions in the organic film, defects originating from protrusions in the organic film can be reduced. [Example]

[0204] The present invention will be described in more detail below with examples of synthesis, comparative synthesis, examples, and comparative examples, but the present invention is not limited thereto. Furthermore, the method for determining molecular weight is specifically performed using the following method: Using tetrahydrofuran as the extraction solvent, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of polystyrene converted by gel permeation chromatography (GPC) are determined at a temperature of 40°C, and the dispersity (Mw / Mn) is also determined.

[0205] [Synthesis of polymers (B-1) to (B-10)] The compounds (B-1) to (B-10) used in the preparation of the organic film forming composition (UDL-1 to 65) of the examples were synthesized using the following compounds (a1) to (a4) containing branched long-chain alkyl groups and (b1) to (b5) containing oxygen atoms (meth)acrylic acid monomers.

[0206] (Compounds containing branched long-chain alkyl groups) [Chemistry 55]

[0207] (Methyl)acrylic acid monomers containing oxygen atoms [Chemistry 56]

[0208] [Synthesis Example 1] Synthesis of Polymer (B-1) [Chemistry 57]

[0209] 4.89 g of a branched long-chain alkyl compound (a1) and 2.21 g of an oxygen-containing (meth)acrylic acid monomer (b1) were mixed with 20.0 g of PGMEA (propylene glycol monoethyl ether acetate) to form a homogeneous solution, which was then bubbled under nitrogen for 15 minutes. Subsequently, 0.23 g of dimethyl-2,2-azobis(2-methylpropionate) was added to this homogeneous solution, and the mixture was heated to 85°C under nitrogen atmosphere and reacted at this internal temperature for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 47.3 g of a PGMEA solution of polymer (B-1) (compound concentration 15%).

[0210] When using GPC to determine the weight-average molecular weight (Mw) and dispersion (Mw / Mn), the results are as follows. (B-1): Mw=5370, Mw / Mn=3.51

[0211] [Synthesis Example 2] Synthesis of Polymer (B-2) [Chem.58]

[0212] 6.12 g of a branched long-chain alkyl compound (a1) and 1.38 g of an oxygen-containing (meth)acrylic acid monomer (b1) were mixed with 20.0 g of PGMEA (propylene glycol monoethyl ether acetate) to form a homogeneous solution. The solution was then bubbled under nitrogen for 15 minutes. Subsequently, 0.23 g of dimethyl-2,2-azobis(2-methylpropionate) was added to this homogeneous solution, and the mixture was heated to 85°C under nitrogen atmosphere and reacted at this internal temperature for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 50.0 g of a PGMEA solution of polymer (B-2) (compound concentration 15%).

[0213] When using GPC to determine the weight-average molecular weight (Mw) and dispersion (Mw / Mn), the results are as follows. (B-2): Mw=6150, Mw / Mn=3.78

[0214] [Synthesis Example 3] Synthesis of Polymer (B-3) [Chemistry 59]

[0215] 6.12 g of a branched long-chain alkyl compound (a1) and 2.41 g of an oxygen-containing (meth)acrylic acid monomer (b2) were mixed with 20.0 g of PGMEA (propylene glycol monoethyl ether acetate) to form a homogeneous solution, which was then bubbled under nitrogen for 15 minutes. Subsequently, 0.23 g of dimethyl-2,2-azobis(2-methylpropionate) was added to this homogeneous solution, and the mixture was heated to 85°C under nitrogen atmosphere and reacted at an internal temperature of 85°C for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 56.9 g of a PGMEA solution of polymer (B-3) (compound concentration 15%).

[0216] When using GPC to determine the weight-average molecular weight (Mw) and dispersion (Mw / Mn), the results are as follows. (B-3): Mw=9140, Mw / Mn=2.94

[0217] [Synthesis Example 4] Synthesis of Polymer (B-4) [Transformation 60]

[0218] 4.08 g of a branched long-chain alkyl compound (a1) and 1.56 g of an oxygen-containing (meth)acrylic acid monomer (b3) were mixed with 20.0 g of PGMEA (propylene glycol monoethyl ether acetate) to form a homogeneous solution, which was then bubbled under nitrogen for 15 minutes. Subsequently, 0.23 g of dimethyl-2,2-azobis(2-methylpropionate) was added to this homogeneous solution, and the mixture was heated to 85°C under nitrogen atmosphere and reacted at an internal temperature of 85°C for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 37.6 g of a PGMEA solution of polymer (B-4) (compound concentration 15%).

[0219] When using GPC to determine the weight-average molecular weight (Mw) and dispersion (Mw / Mn), the results are as follows. (B-4): Mw=4950, Mw / Mn=2.26

[0220] [Synthesis Example 5] Synthesis of Polymer (B-5) [Chemistry 61]

[0221] 6.12 g of a branched long-chain alkyl compound (a1) and 0.78 g of an oxygen-containing (meth)acrylic acid monomer (b3) were mixed with 20.0 g of PGMEA (propylene glycol monoethyl ether acetate) to form a homogeneous solution. The solution was then bubbled under nitrogen for 15 minutes. Subsequently, 0.23 g of dimethyl-2,2-azobis(2-methylpropionate) was added to this homogeneous solution, and the mixture was heated to 85°C under nitrogen atmosphere and reacted at this internal temperature for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 46.0 g of a PGMEA solution of polymer (B-5) (compound concentration 15%).

[0222] When using GPC to determine the weight-average molecular weight (Mw) and dispersion (Mw / Mn), the results are as follows. (B-5): Mw=4130, Mw / Mn=2.59

[0223] [Synthesis Example 6] Synthesis of Polymer (B-6) [Chemistry 62]

[0224] 6.12 g of a branched long-chain alkyl compound (a1) and 4.79 g of an oxygen-containing (meth)acrylic acid monomer (b4) were mixed with 20.0 g of PGMEA (propylene glycol monoethyl ether acetate) to form a homogeneous solution, which was then bubbled under nitrogen for 15 minutes. Subsequently, 0.23 g of dimethyl-2,2-azobis(2-methylpropionate) was added to this homogeneous solution, and the mixture was heated to 85°C under nitrogen atmosphere and reacted at this internal temperature for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 72.7 g of a PGMEA solution of polymer (B-6) (compound concentration 15%).

[0225] When using GPC to determine the weight-average molecular weight (Mw) and dispersion (Mw / Mn), the results are as follows. (B-6): Mw=4710, Mw / Mn=2.84

[0226] [Synthesis Example 7] Synthesis of Polymer (B-7) [Chemistry 63]

[0227] 6.93 g of a branched long-chain alkyl compound (a1) and 2.87 g of an oxygen-containing (meth)acrylic acid monomer (b4) were mixed with 20.0 g of PGMEA (propylene glycol monoethyl ether acetate) to form a homogeneous solution, which was then bubbled under nitrogen for 15 minutes. Subsequently, 0.23 g of dimethyl-2,2-azobis(2-methylpropionate) was added to this homogeneous solution, and the mixture was heated to 85°C under nitrogen atmosphere and reacted at an internal temperature of 85°C for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 65.3 g of a PGMEA solution of polymer (B-7) (compound concentration 15%).

[0228] When using GPC to determine the weight-average molecular weight (Mw) and dispersion (Mw / Mn), the results are as follows. (B-7): Mw=4840, Mw / Mn=2.75

[0229] [Synthesis Example 8] Synthesis of Polymer (B-8) [Chemistry 64]

[0230] 6.97 g of a branched long-chain alkyl compound (a2) and 1.38 g of an oxygen-containing (meth)acrylic acid monomer (b1) were mixed with 20.0 g of PGMEA (propylene glycol monoethyl ether acetate) to form a homogeneous solution, which was then bubbled under nitrogen for 15 minutes. Subsequently, 0.23 g of dimethyl-2,2-azobis(2-methylpropionate) was added to this homogeneous solution, and the mixture was heated to 85°C under nitrogen atmosphere and reacted at an internal temperature of 85°C for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 55.7 g of a PGMEA solution of polymer (B-8) (compound concentration 15%).

[0231] When using GPC to determine the weight-average molecular weight (Mw) and dispersion (Mw / Mn), the results are as follows. (B-8): Mw=6300, Mw / Mn=3.89

[0232] [Synthesis Example 9] Synthesis of Polymer (B-9) [Chemistry 65]

[0233] 5.50 g of a branched long-chain alkyl compound (a3) ​​and 1.38 g of an oxygen-containing (meth)acrylic acid monomer (b1) were mixed with 20.0 g of PGMEA (propylene glycol monoethyl ether acetate) to form a homogeneous solution. The solution was then bubbled under nitrogen for 15 minutes. Subsequently, 0.23 g of dimethyl-2,2-azobis(2-methylpropionate) was added to this homogeneous solution, and the mixture was heated to 85°C under nitrogen atmosphere and reacted at this internal temperature for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 45.9 g of a PGMEA solution of polymer (B-9) (compound concentration 15%).

[0234] When using GPC to determine the weight-average molecular weight (Mw) and dispersion (Mw / Mn), the results are as follows. (B-9): Mw=6050, Mw / Mn=3.57

[0235] [Synthesis Example 10] Synthesis of Polymer (B-10) [Chemistry 66]

[0236] 2.13 g of oxygen-containing (meth)acrylic monomer (b5) and 1.38 g of oxygen-containing (meth)acrylic monomer (b1) were mixed with 20.0 g of PGME (propylene glycol monomethyl ether) to form a homogeneous solution, which was then bubbled under nitrogen for 15 minutes. Subsequently, 0.23 g of dimethyl-2,2-azobis(2-methylpropionate) was added to this homogeneous solution, and the mixture was heated to 85°C under nitrogen atmosphere and reacted at an internal temperature of 85°C for 24 hours. The reaction solution was then cooled to room temperature.

[0237] Then, 7.63 g of a branched long-chain alkyl compound (a4) and 0.34 g of benzyltriethylammonium chloride were added to the obtained reaction solution, and the mixture was heated to 105 °C under nitrogen atmosphere and reacted at an internal temperature of 105 °C for 24 hours. After cooling to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution and homogenized. The separated aqueous layer was then removed. The organic layer was washed twice with 100 ml of 3% nitric acid aqueous solution and five times with 100 ml of pure water, and then dried under reduced pressure. 100 g of PGMEA was added to the residue and a homogeneous solution was prepared. The solution was dried under reduced pressure and then diluted with PGMEA to obtain 74.3 g of a PGMEA solution of polymer (B-10) (compound concentration 15%).

[0238] When using GPC to determine the weight-average molecular weight (Mw) and dispersion (Mw / Mn), the results are as follows. (B-10): Mw=11090, Mw / Mn=2.98

[0239] [Comparative synthesis of polymers (R-1) to (R-2)] The comparative polymers (R1) to (R2) used in the preparation of the organic film forming composition are synthesized using the following monomers (r1) to (r3). [Chemistry 67]

[0240] [Comparative Synthesis Example 1] Synthesis of Comparative Polymer (R-1) [Chemistry 68]

[0241] 5.06 g of monomer (r1) and 1.38 g of monomer (r3) were added to 20.0 g of PGMEA (propylene glycol monoethyl ether acetate), and the mixture was stirred to form a homogeneous solution. The solution was then bubbled under nitrogen for 15 minutes. Subsequently, 0.23 g of dimethyl-2,2-azobis(2-methylpropionate) was added to this homogeneous solution, and the mixture was heated to 85°C under nitrogen atmosphere and reacted at this internal temperature for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 42.9 g of a PGMEA solution of polymer (R-1) (compound concentration 15%).

[0242] When using GPC to determine the weight-average molecular weight (Mw) and dispersion (Mw / Mn), the results are as follows. (R-1): Mw=10120, Mw / Mn=3.95

[0243] [Comparative Synthesis Example 2] Synthesis of Comparative Polymer (R-2) [Chemistry 69]

[0244] 2.97 g of monomer (r2) and 1.38 g of monomer (r3) were mixed with 20.0 g of PGMEA (propylene glycol monoethyl ether acetate) to form a homogeneous solution, which was then bubbled under nitrogen for 15 minutes. Subsequently, 0.23 g of dimethyl-2,2-azobis(2-methylpropionate) was added to this homogeneous solution, and the mixture was heated to 85°C under nitrogen atmosphere and reacted at this internal temperature for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 29.1 g of a PGMEA solution of polymer (R-2) (compound concentration 15%).

[0245] When using GPC to determine the weight-average molecular weight (Mw) and dispersion (Mw / Mn), the results are as follows. (R-2): Mw=9770, Mw / Mn=3.65

[0246] [(A) Organic film forming materials (resins or compounds)] The organic film forming compositions (UDL-1~65 and comparative UDL-1~13) of the Examples and Comparative Examples were prepared by using the following resins or compounds as (A) organic film forming materials. M1: Resin represented by the following formula (M1) M2: Resin represented by the following formula (M2) M3: The compound represented by the following formula (M3) M4: The compound represented by the following formula (M4) M5: Resin represented by the following formula (M5) M6: Resin represented by the following formula (M6)

[0247] [Chemistry 70]

[0248] [(C) Solvent] The organic film forming compositions (UDL-1~65 and comparative UDL-1~13) of the Examples and Comparative Examples were prepared using the following solvents as solvent (C). (S1): Propylene glycol monomethyl ether acetate (S2): Propylene glycol monoethyl ether

[0249] [Preparation of Organic Film-Forming Components (UDL-1~65, Comparative UDL-1~13)] The above-mentioned compounds (B-1) to (B-10) and (R-1) to (R-2) as polymers, the above-mentioned organic film forming materials (M1) to (M6) as organic film forming resins, and one or two of the solvents mentioned in (C) are dissolved in the proportions shown in Tables 1 to 3. The resulting mixture is then filtered through a 0.1 μm fluoropolymer filter to obtain organic film forming compositions (UDL-1 to 65, comparative UDL-1 to 7). Furthermore, the above-mentioned organic film forming materials (M1) to (M6) and the above-mentioned solvent (S1) are dissolved in the proportions shown in Table 3. The resulting mixture is then filtered through a 0.1 μm fluoropolymer filter to obtain organic film forming compositions (comparative UDL-8 to 13). The results are shown in Tables 1 to 3.

[0250] [Table 1] Organic film formation Composition Organic membrane finished resin polymer Solvent 1 Solvent 2 type Quality type Quality type Quality type Parts by mass UDL-1 (M 1) 10.00 (B-1) 0.10 (S 1) 89.90 UDL-2 (M 1) 10.00 (B-2) 0.10 (S 1) 89.90 UDL-3 (M 1) 10.00 (B-3) 0.10 (S 1)[[ID=4I]] 89.90 UDL-4 (M 1) 10.00 (B-4) 0.10 (S 1) 89.90 UDL-5 (M 1) 10.00 (B-5) 0.10 (S 1) 89.90 UDL-6 (M 1) 10.00 (B-6) 0.10 (S 1) 89.90 UDL-7 (M I) 10.00 (B-7) 0.10 (S 1) 89.90 UDL-8 (M 1) 10.00 (B-8) 0.10 (S 1) 89.90 UDL-9 (M 1) 10.00 (B-9) 0.10 (S 1) 89.90 UDL-10 (M 1) 10.00 (B-10) 0.10 (S 1) 89.90 UDL-11 (M 1) 10.00 (B-2) 0.10 (S 1) 62.93 (S 2) 26.97 UDL-12 (M 1) 10.00 (B-9) 0.10 (S 1) 62.93 (S 2) 26.97 UDL-13 (M 1) 10.00 (B-10) 0.10 (S 1) 62.93 (S 2) 26.97 UDL-14 (M 1) 10.00 (B-5) 1.00 (S 1) 89.00 UDL-15 (M 1) 10.00 (B-5) 0.001 (S 1) 90.00 UDL-16 (M2) 10.00 (B-1) 0.10 (S 1) 89.90 UDL-17 (M2) 10.00 (B-2) 0.10 (S 1) 89.90 UDL-18 (M2) 10.00 (B-3) 0.10 (S 1) 89.90 UDL-19 (M2) 10.00 (B-4) 0.10 (S 1) 89.90 UDL-20 (M2) 10.00 (B-5) 0.10 (S 1) 89.90 UDL-21 (M2) 10.00 (B-6) 0.10 (S 1) 89.90 UDL-22 (M2) 10.00 (B-7) 0.10 (S 1) 89.90 UDL-23 (M2) 10.00 (B-8) 0.10 (S 1) 89.90 UDL-24 (M2) 10.00 (B-9) 0.10 (S 1) 89.90 UDL-25 (M2) 10.00 (B-10) 0.10 (S 1) 89.90

[0251] [Table 2] Organic film formation Composition Organic membrane finished resin polymer Solvent 1 Solvent 2 type Quality type Quality type Quality type Quality UDL-26 (M 3) 10.00 (B-1) 0.10 (S 1) 89.90 UDL-27 (M 3) 10.00 (B-2) 0.10 (S 1) 89.90 UDL-28 (M 3) 10.00 (B-3) 0.10 (S 1) 89.90 UDL-29 (M 3) 10.00 (B-4) 0.10 (S 1) 89.90 UDL-30 (M 3) 10.00 (B-5) 0.10 (S 1) 89.90 UDL-31 (M 3) 10.00 (B-6) 0.10 (S 1) 89.90 UDL-32 (M 3) 10.00 (B-7) 0.10 (S 1) 89.90 UDL-33 (M 3) 10.00 (B-8) 0.10 (S 1) 89.90 UDL-34 (M 3) 10.00 (B-9) 0.10 (S 1) 89.90 UDL-35 (M 3) 10.00 (B-10) 0.10 (S 1) 89.90 UDL-36 (M 4) 10.00 (B-1) 0.10 (S 1) 89.90 UDL-37 (M 4) 10.00 (B-2) 0.10 (S 1) 89.90 UDL-38 (M 4) 10.00 (B-3) 0.10 (S 1) 89.90 UDL-39 (M 4) 10.00 (B-4) 0.10 (S 1) 89.90 UDL-40 (M 4) 10.00 (B-5) 0.10 (S 1) 89.90 UDL-41 (M 4) 10.00 (B-6) 0.10 (S 1) 89.90 UDL-42 (M 4) 10.00 (B-7) 0.10 (S 1) 89.90 UDL-43 (M 4) 10.00 (B-8) 0.10 (S 1) 89.90 UDL-44 (M 4) 10.00 (B-9) 0.10 (S 1) 89.90 UDL-45 (M 4) 10.00 (B-10) 0.10 (S 1) 89.90 UDL-46 (M 5) 10.00 (B-1) 0.10 (S 1) 89.90 UDL-47 (M 5) 10.00 (B-2) 0.10 (S 1) 89.90 UDL-48 (M 5) 10.00 (B-3) 0.10 (S 1) 89.90 UDL-49 (M 5) 10.00 (B-4) 0.10 (S 1) 89.90 UDL-50 (M 5) 10.00 (B-5) 0.10 (S 1) 89.90

[0252] [Table 3] Organic film formation Composition Organic membrane finished resin polymer Solvent 1 Solvent 2 type Quality type Quality type Quality type Quality UDL-51 (M 5) 10.00 (B-6) 0.10 (S 1) 89.90 UDL-52 (M 5) 10.00 (B-7) 0.10 (S 1) 89.90 UDL-53 (M 5) 10.00 (B-8) 0.10 (S 1) 89.90 UDL-54 (M 5) 10.00 (B-9) 0.10 (S 1) 89.90 UDL-55 (M 5) 10.00 (B-10) 0.10 (S 1) 89.90 UDL-56 (M 6) 10.00 (B-1) 0.10 (S 1) 89.90 UDL-57 (M 6) 10.00 (B-2) 0.10 (S 1) 89.90 UDL-58 (M 6) 10.00 (B-3) 0.10 (S 1) 89.90 UDL-59 (M 6) 10.00 (B-4) 0.10 (S 1) 89.90 UDL-60 (M 6) 10.00 (B-5) 0.10 (S 1) 89.90 UDL-61 (M 6) 10.00 (B-6) 0.10 (S 1) 89.90 UDL-62 (M 6) 10.00 (B-7) 0.10 (S 1) 89.90 UDL-63 (M 6) 10.00 (B-8) 0.10 (S 1) 89.90 UDL-64 (M 6) 10.00 (B-9) 0.10 (S 1) 89.90 UDL-65 (M 6) 10.00 (B-10) 0.10 (S 1) 89.90 Comparison with UDL-1 (M 1) 10.00 (R-1) 0.10 (S 1) 89.9 Comparison of UDL-2 (M 2) 10.00 (R-1) 0.10 (S 1) 89.9 Comparison with UDL-3 (M 3) 10.00 (R-1) 0.10 (S 1) 89.9 Comparison with UDL-4 (M 4) 10.00 (R-1) 0.10 (S 1) 89.9 Comparison with UDL-5 (M 5) 10.00 (R-1) 0.10 (S 1) 89.9 Comparison with UDL-6 (M 6) 10.00 (R-1) 0.10 (S 1) 89.9 Comparison with UDL-7 (M 1) 10.00 (R-2) 0.10 (S 1) 89.9 Comparison with UDL-8 (M 1) 10.00 (S 1) 90.0 Comparison with UDL-9 (M 2) 10.00 (S 1) 90.0 Comparison with UDL-10 (M 3) 10.00 (S 1) 90.0 Comparison with UDL-11 (M 4) 10.00 (S 1) 90.0 Comparison with UDL-12 (M 5) 10.00 (S 1) 90.0 Comparison with UDL-13 (M 6) 10.00 (S 1) 90.0

[0253] [The fabrication of silicon wafers using organic curing films formed from organic film forming compositions (UDL-1~65, compared to UDL-1~13)] Using a coating / developing machine, "CLEAN TRACK LITHIUS Pro AP," manufactured by Tokyo Power Technology Co., Ltd., 2 ml of the aforementioned organic film-forming compositions (UDL-1~65, Comparative UDL-1~13) was sprayed onto the center of a silicon wafer. The wafer was rotated and spread at a speed equal to the average film thickness described in Tables 4~6, and then baked at 350°C to form a coating of the organic film-forming compositions. While rotating the silicon wafer at 1000 rpm, a removal solution (a mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30:70, mass ratio)) was sprayed from the removal solution nozzle at a rate of 2 mL / s. Simultaneously, the nozzle moved from the outer periphery of the silicon wafer towards the center at a speed of 5 mm / s to a position of 3 mm, where the removal solution was further sprayed at a rate of 2 mL / s for 5 seconds. Subsequently, the spraying of the spraying liquid was stopped, and the silicon wafer was rotated at 1000 rpm for 30 seconds. Then, the silicon wafer was heated at 350°C for 60 seconds to obtain a silicon wafer with an organic film (organic hardened film) of various types.

[0254] [Solvent resistance evaluation: Examples 1-1 to 1-65, Comparative Examples 1-1 to 1-13] Organic films were formed on silicon wafers using the above method using various organic film formation compositions (UDL-1~65, comparative UDL-1~13), and the film thickness was measured. Then, PGMEA solvent was dispensed onto each organic film, left to stand for 30 seconds, followed by rotary drying and baking at 100°C for 60 seconds to evaporate the PGMEA, and the film thickness was measured again. Let the film thickness before PGMEA solvent dispensing be X, and the film thickness after PGMEA solvent dispensing be X1. The absolute value of the value obtained by calculating [(X1-X) / X]×100 is defined as the film thickness change rate (%). A film thickness change rate of less than 0.5% is rated as good, and a rate of 0.5% or higher is rated as poor. The results are shown in Tables 4~6 below.

[0255] [Evaluation of in-plane uniformity: Examples 1-1 to 1-65, Comparative Examples 1-1 to 1-13] Organic films were formed on silicon wafers using the methods described above, employing various organic film formation compositions (UDL-1~65, comparative UDL-1~13). The film thickness within a radius of 145 mm from the center of the organic film was measured. The maximum film thickness was defined as Xmax, the minimum film thickness as Xmin, and the average film thickness as Xaverage. The in-plane uniformity (%) was calculated as [(Xmax-Xmin) / Xaverage]×100. In-plane uniformity less than 2% was rated A (Good), 2% to less than 3% as B, and 3% or more as C (Poor). The results are shown in Tables 4-6.

[0256] [Table 4] Organic film forming components average film thickness Solvent resistance In-plane uniformity Example 1-1 UDL-1 500nm good B Examples 1-2 UDL-2 500nm good A Examples 1-3 UDL-3 500nm good A Examples 1-4 UDL-4 500nm good B Examples 1-5 UDL-5 500nm good A Examples 1-6 UDL-6 500nm good A Examples 1-7 UDL-7 500nm good A Examples 1-8 UDL-8 500nm good A Examples 1-9 UDL-9 500nm good A Examples 1-10 UDL-10 500nm good A Examples 1-11 UDL-11 500nm good A Examples 1-12 UDL-12 500nm good A Examples 1-13 UDL-13 500nm good A Examples 1-14 UDL-14 500nm good A Examples 1-15 UDL-15 500nm good A Examples 1-16 UDL-16 500nm good B Examples 1-17 UDL-17 500nm good A Examples 1-18 UDL-18 500nm good A Examples 1-19 UDL-19 500nm good B Examples 1-20 UDL-20 500nm good A Examples 1-21 UDL-21 500nm good A Examples 1-22 UDL-22 500nm good A Examples 1-23 UDL-23 500nm good A Examples 1-24 UDL-24 500nm good A Examples 1-25 UDL-25 500nm good A

[0257] [Table 5] Organic film forming components average film thickness Solvent resistance In-plane uniformity Examples 1-26 UDL-26 500nm good B Examples 1-27 UDL-27 500nm good A Examples 1-28 UDL-28 500nm good A Examples 1-29 UDL-29 500nm good B Examples 1-30 UDL-30 500nm good A Examples 1-31 UDL-31 500nm good A Examples 1-32 UDL-32 500nm good A Examples 1-33 UDL-33 500nm good A Examples 1-34 UDL-34 500nm good A Examples 1-35 UDL-35 500nm good A Examples 1-36 UDL-36 500nm good B Examples 1-37 UDL-37 500nm good A Examples 1-38 UDL-38 500nm good A Examples 1-39 UDL-39 500nm good B Examples 1-40 UDL-40 500nm good A Examples 1-41 UDL-41 500nm good A Examples 1-42 UDL-42 500nm good A Examples 1-43 UDL-43 500nm good A Examples 1-44 UDL-44 500nm good A Examples 1-45 UDL-45 500nm good A Examples 1-46 UDL-46 500nm good B Examples 1-47 UDL-47 500nm good A Examples 1-48 UDL-48 500nm good A Examples 1-49 UDL-49 500nm good B Examples 1-50 UDL-50 500nm good A

[0258] [Table 6] Organic film forming components average film thickness Solvent resistance In-plane uniformity Examples 1-51 UDL-51 500nm good A Examples 1-52 UDL-52 500nm good A Examples 1-53 UDL-53 500nm good A Examples 1-54 UDL-54 500nm good A Examples 1-55 UDL-55 500nm good A Examples 1-56 UDL-56 500nm good B Examples 1-57 UDL-57 500nm good A Examples 1-58 UDL-58 500nm good A Examples 1-59 UDL-59 500nm good B Examples 1-60 UDL-60 500nm good A Examples 1-61 UDL-61 500nm good A Examples 1-62 UDL-62 500nm good A Examples 1-63 UDL-63 500nm good A Examples 1-64 UDL-64 500nm good A Examples 1-65 UDL-65 500nm good A Comparative Example 1-1 Comparison with UDL-1 500nm good C Comparative Examples 1-2 Comparison of UDL-2 500nm good C Comparative Examples 1-3 Comparison with UDL-3 500nm good C Comparative Examples 1-4 Comparison with UDL-4 500nm good C Comparative Examples 1-5 Comparison with UDL-5 500nm good C Comparative Examples 1-6 Comparison with UDL-6 500nm good C Comparative Examples 1-7 Comparison with UDL-7 500nm good C Comparative Examples 1-8 Comparison with UDL-8 500nm good C Comparative Examples 1-9 Comparison with UDL-9 500nm good C Comparative Examples 1-10 Comparison with UDL-10 500nm good C Comparative Examples 1-11 Comparison with UDL-11 500nm good C Comparative Examples 1-12 Comparison with UDL-12 500nm good C Comparative Examples 1-13 Comparison with UDL-13 500nm good C

[0259] As shown in Tables 4-6, Examples 1-1 to 1-65, which used organic film-forming compositions (UDL-1) to (UDL-65) containing (B-1) to (B-10) polymers (B) of the present invention, all exhibited good solvent resistance. Furthermore, the in-plane uniformity was evaluated as either A or B. On the other hand, Comparative Examples 1-1 to 1-7 (UDL-1 to UDL-7) which used organic film forming compositions containing polymers (R-1) and (R-2) that are outside the scope of the present invention, and Comparative Examples 1-8 to 1-13 (UDL-8 to 13) which used organic film forming compositions containing polymers (B) belonging to the present invention, all had poor in-plane uniformity (Evaluation C).

[0260] [Evaluation of protrusion inhibition: Examples 2-1 to 2-65, Comparative Examples 2-1 to 2-13] Organic films were formed on silicon wafers using the methods described above, employing various organic film formation compositions (UDL-1~65, comparative UDL-1~13). The height variation from the outer periphery of the organic film to a position 1000 μm from the center of the silicon wafer was measured using a KLA-TENCOR Alpha-Step D-600 (contact profilometer). With the silicon wafer height set to 0, as shown in Figure 2, a maximum height less than 110% of the film thickness was rated A (Good); a maximum height greater than 110% but less than 150% was rated B; and as shown in Figure 3, an area with a height greater than 150% was rated C (Poor). The results are shown in Tables 7~9.

[0261] [Landfill Evaluation: Examples 2-1 to 2-65, Comparative Examples 2-1 to 2-13] As shown in Figure 4, organic films 8, as shown in Figure 4(I) (cross-sectional view), were formed on a SiO2 wafer substrate with a dense hole pattern (hole diameter 0.2 μm, hole depth 1.0 μm, distance between the centers of two adjacent holes 0.4 μm). The organic film composition (UDL-1~65, comparative UDL-1~13) was used to form films on the substrate with a dense hole pattern as shown in Figure 4(G) (top view) and (H) (cross-sectional view). The substrate used was a SiO2 wafer substrate 7 with a dense hole pattern, as shown in Figure 4(G) (top view) and (H) (cross-sectional view). The cross-sectional shape of each wafer substrate was observed using a scanning electron microscope (SEM) to confirm whether the holes were filled with organic film without voids. When using organic film composition with poor filling properties, voids were generated inside the holes. When using organic film composition with good filling properties, in this evaluation, the holes were filled with organic film without voids, as shown in Figure 4(I). No voids were rated as good, and voids were rated as poor. The results are shown in Tables 7-9.

[0262] [Table 7] Organic film forming components Evaluation of protrusion inhibition Landfill Characteristic Evaluation Example 2-1 UDL-1 B good Example 2-2 UDL-2 A good Example 2-3 UDL-3 A good Examples 2-4 UDL-4 B good Examples 2-5 UDL-5 A good Examples 2-6 UDL-6 A good Examples 2-7 UDL-7 A good Examples 2-8 UDL-8 A good Examples 2-9 UDL-9 A good Example 2-10 UDL-10 A good Example 2-11 UDL-11 A good Example 2-12 UDL-12 A good Example 2-13 UDL-13 A good Example 2-14 UDL-14 A good Example 2-15 UDL-15 A good Example 2-16 UDL-16 B good Example 2-17 UDL-17 A good Example 2-18 UDL-18 A good Example 2-19 UDL-19 B good Example 2-20 UDL-20 A good Example 2-21 UDL-21 A good Example 2-22 UDL-22 A good Example 2-23 UDL-23 A good Example 2-24 UDL-24 A good Example 2-25 UDL-25 A good

[0263] [Table 8] Organic film forming components Evaluation of protrusion inhibition Landfill Characteristic Evaluation Example 2-26 UDL-26 B good Example 2-27 UDL-27 A good Example 2-28 UDL-28 A good Example 2-29 UDL-29 B good Examples 2-30 UDL-30 A good Example 2-31 UDL-31 A good Example 2-32 UDL-32 A good Example 2-33 UDL-33 A good Examples 2-34 UDL-34 A good Example 2-35 UDL-35 A good Examples 2-36 UDL-36 B good Example 2-37 UDL-37 A good Example 2-38 UDL-38 A good Example 2-39 UDL-39 B good Example 2-40 UDL-40 A good Example 2-41 UDL-41 A good Example 2-42 UDL-42 A good Examples 2-43 UDL-43 A good Example 2-44 UDL-44 A good Example 2-45 UDL-45 A good Example 2-46 UDL-46 B good Example 2-47 UDL-47 A good Example 2-48 UDL-48 A good Example 2-49 UDL-49 B good Example 2-50 UDL-50 A good

[0264] [Table 9] Organic film forming components Evaluation of protrusion inhibition Landfill Characteristic Evaluation Example 2-51 UDL-51 A good Example 2-52 UDL-52 A good Examples 2-53 UDL-53 A good Example 2-54 UDL-54 A good Example 2-55 UDL-55 A good Examples 2-56 UDL-56 B good Example 2-57 UDL-57 A good Example 2-58 UDL-58 A good Example 2-59 UDL-59 B good Example 2-60 UDL-60 A good Example 2-61 UDL-61 A good Example 2-62 UDL-62 A good Example 2-63 UDL-63 A good Example 2-64 UDL-64 A good Example 2-65 UDL-65 A good Comparative Example 2-1 Comparison with UDL-1 C bad Comparative Example 2-2 Comparison of UDL-2 C bad Comparative Examples 2-3 Comparison with UDL-3 C bad Comparative Examples 2-4 Comparison with UDL-4 C bad Comparative Examples 2-5 Comparison with UDL-5 C bad Comparative Examples 2-6 Comparison with UDL-6 C bad Comparative Examples 2-7 Comparison with UDL-7 C bad Comparative Examples 2-8 Comparison with UDL-8 C bad Comparative Examples 2-9 Comparison with UDL-9 C bad Comparative Example 2-10 Comparison with UDL-10 C bad Comparative Example 2-11 Comparison with UDL-11 C bad Comparative Example 2-12 Comparison with UDL-12 C bad Comparative Example 2-13 Comparison with UDL-13 C bad

[0265] As shown in Tables 7-9, Examples 2-1 to 2-65, which used the organic film forming composition (UDL-1 to 65) of the present invention, were found to have excellent protrusion suppression and landfill characteristics. On the other hand, Comparative Examples 2-1 to 2-7 (UDL-1 to UDL-7) which used organic film forming compositions containing polymers (R-1) and (R-2) that are outside the scope of the claims of this invention, and Comparative Examples 2-8 to 2-13 (UDL-8 to 13) which used organic film forming compositions that do not contain polymers (B) belonging to this invention, had a protrusion inhibition rating of C (poor) and a landfill characteristics rating of poor.

[0266] [Pattern Formation Experiments: Examples 3-1 to 3-65] An organic film is formed on a SiO2 wafer substrate using the above method (baking at 350°C) with each organic film formation composition (UDL-1~65). A silicon-containing resist intermediate film material (SOG1) is then coated onto the organic film, and the substrate is baked at 200°C for 60 seconds to form a silicon-containing resist intermediate film with a thickness of 35 nm. An ArF monolayer resist is then coated onto the intermediate film as the resist top layer, and the substrate is baked at 105°C for 60 seconds to form a photoresist film with a thickness of 100 nm. Finally, an immersion protective film material (TC-1) is coated onto the photoresist film, and the substrate is baked at 90°C for 60 seconds to form a protective film with a thickness of 50 nm.

[0267] A 2% solution of the following polymer in propylene glycol ethyl ether was prepared as a silicon-containing resistive intermediate film material (SOG1).

[0268] [Chemistry 71]

[0269] The upper membrane material of the inhibitor (single-layer inhibitor for ArF) is prepared by dissolving the polymer (RP1), acid generator (PAG1), and basic compound (Amine1) in a solvent (PGMEA) containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 10, and filtering it through a 0.1 μm fluororesin filter.

[0270] [Table 10] polymer (parts by weight) Acid generating agent (parts by weight) alkaline compounds (parts by weight) solvent (parts by weight) ArF uses Single-layer inhibitor RP1 (100) PAG1 (6.6) Aminel (0.8) PGMEA (2500)

[0271] The polymer (RP1), acid generator (PAG1), and basic compound (Amine1) are shown below.

[0272] [Chemistry 72]

[0273] The impregnated protective membrane material (TC-1) is prepared by dissolving polymer (PP1) in an organic solvent at the proportions shown in Table 11 and filtering it through a 0.1 μm fluororesin filter.

[0274] [Table 11] polymer (parts by weight) organic solvents (parts by weight) TC-1 PP1 (100) Diisopentyl ether (2700) 2-Methyl-1-butanol (270)

[0275] The polymer (PP1) is shown below. [Chemistry 73]

[0276] Then, the exposure was performed using an ArF immersion exposure apparatus (Nikon Corporation; NSR-S610C, NA1.30, σ0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% half-tone phase shift mask), baked at 100°C (PEB) for 60 seconds, and developed with 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a 1:1 positive line and space pattern (resistor upper film pattern) at 55 nm.

[0277] Then, using the Telius etching apparatus manufactured by Tokyo Powertech, the silicon-containing resist intermediate film was dry-etched (pattern transfer) using the resist upper film pattern as a mask to obtain a silicon-containing resist intermediate film pattern. The obtained silicon-containing resist intermediate film pattern was then used as a mask to dry-etch (pattern transfer) an organic film to obtain an organic film pattern. Finally, the obtained organic film pattern was used as a mask to dry-etch (pattern transfer) a SiO2 wafer substrate (SiO2 film). The etching conditions are as follows.

[0278] (Transfer conditions for the pattern of the upper resist film to the silicon-containing intermediate resist film) Chamber pressure 10.0 Pa RF power 1,500W CF4 gas flow rate 75 mL / min O2 gas flow rate 15 mL / min 15 seconds

[0279] (Transfer conditions for the pattern of the silicon-containing resistive intermediate film to the organic film) Chamber pressure 2.0 Pa RF power 500W Ar gas flow rate 75 mL / min O2 gas flow rate 45 mL / min 120 seconds

[0280] (Transfer conditions for organic film pattern to SiO2 wafer substrate) Chamber pressure 2.0 Pa RF power 2,200W C5F12 gas flow rate 20 mL / min C2F6 gas flow rate 10 mL / min Ar gas flow rate 300 mL / min O2 gas flow rate 60 mL / min 90 seconds

[0281] The results of cross-sectional observations of the patterns obtained using an electron microscope (S-4700) manufactured by Hitachi, Ltd. are shown in Tables 12-14.

[0282] [Table 12] Organic film forming components Shape after substrate transfer etching Example 3-1 UDL-1 good Example 3-2 UDL-2 good Example 3-3 UDL-3 good Examples 3-4 UDL-4 good Examples 3-5 UDL-5 good Examples 3-6 UDL-6 good Examples 3-7 UDL-7 good Examples 3-8 UDL-8 good Examples 3-9 UDL-9 good Examples 3-10 UDL-10 good Example 3-11 UDL-11 good Example 3-12 UDL-12 good Example 3-13 UDL-13 good Example 3-14 UDL-14 good Example 3-15 UDL-15 good Example 3-16 UDL-16 good Example 3-17 UDL-17 good Example 3-18 UDL-18 good Example 3-19 UDL-19 good Example 3-20 UDL-20 good Example 3-21 UDL-21 good Example 3-22 UDL-22 good Example 3-23 UDL-23 good Example 3-24 UDL-24 good Example 3-25 UDL-25 good

[0283] [Table 13] Organic film forming components Shape after substrate transfer etching Example 3-26 UDL-26 good Example 3-27 UDL-27 good Example 3-28 UDL-28 good Example 3-29 UDL-29 good Examples 3-30 UDL-30 good Example 3-31 UDL-31 good Example 3-32 UDL-32 good Example 3-33 UDL-33 good Examples 3-34 UDL-34 good Examples 3-35 UDL-35 good Examples 3-36 UDL-36 good Examples 3-37 UDL-37 good Examples 3-38 UDL-38 good Examples 3-39 UDL-39 good Examples 3-40 UDL-40 good Examples 3-41 UDL-41 good Examples 3-42 UDL-42 good Examples 3-43 UDL-43 good Examples 3-44 UDL-44 good Examples 3-45 UDL-45 good Examples 3-46 UDL-46 good Examples 3-47 UDL-47 good Examples 3-48 UDL-48 good Examples 3-49 UDL-49 good Examples 3-50 UDL-50 good

[0284] [Table 14] Organic film forming components Shape after substrate transfer etching Examples 3-51 UDL-51 good Example 3-52 UDL-52 good Examples 3-53 UDL-53 good Examples 3-54 UDL-54 good Examples 3-55 UDL-55 good Examples 3-56 UDL-56 good Examples 3-57 UDL-57 good Examples 3-58 UDL-58 good Examples 3-59 UDL-59 good Example 3-60 UDL-60 good Example 3-61 UDL-61 good Example 3-62 UDL-62 good Examples 3-63 UDL-63 good Examples 3-64 UDL-64 good Examples 3-65 UDL-65 good

[0285] As shown in Tables 12-14, Examples 3-1 to 3-65, which used the organic film formation composition (UDL-1 to 65) of the present invention, confirmed that the resist upper film pattern was well transferred to the SiO2 wafer substrate. The organic film formation composition of the present invention can be ideally used for micro-processing using the multilayer resist method.

[0286] As can be seen from the above, the organic film forming composition of the present invention has excellent film-forming properties, high filling characteristics, and excellent protrusion suppression properties, making it extremely useful as an organic film material used in multilayer resist processes. Furthermore, the pattern forming method of the present invention, which uses the organic film forming composition of the present invention, can fill holes and trenches with very high aspect ratios without gaps, while simultaneously forming fine patterns with high precision. Moreover, because it can form an organic film with suppressed protrusions, it can efficiently manufacture semiconductor devices, etc.

[0287] This specification contains the following specifications.

[0288] [1]: An organic film forming composition characterized by containing: (A) Materials for organic film formation, (B) Polymers having repeating units represented by the following formula (B1), and (C) Solvent. [Chemistry 74] In the formula, R1 is a hydrogen atom or a methyl group, R2 and R3 are independently monovalent organic groups with 10 to 20 carbon atoms and no fluorine atoms, X is a nitrogen atom or an oxygen atom, and W1 is a single bond or a divalent linker with 1 to 10 carbon atoms that may contain oxygen atoms and no fluorine atoms. [2]: The composition for forming organic films as in [1], wherein W1 in the above formula (B1) is a base represented by the following formula (B2). [Chemistry 75] In the formula, the dashed lines represent the atomic bonds of X in the above formula (B1) and the atomic bonds of carbon atoms bonded to R2 and R3, and may have one or two of the structures represented by the above formula (B2). [3]: Organic film forming composition such as [1] or [2], wherein the aforementioned polymer (B) further contains one or more repeating units represented by the following general formula (B3). [Chemistry 76] In the formula, R1 and X are the same as those mentioned above, and W2 is a monovalent organic group that may contain oxygen atoms but not fluorine atoms. [4]: The composition for forming organic films as in [3], wherein W2 in the above formula (B3) is a base represented by the following formula (B4). [Chemistry 77] In the formula, R4 is a hydrogen atom or a methyl group, R5 is a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms that does not contain fluorine atoms, and m is an integer from 4 to 20. [5]: An organic film forming composition as described in any of [1] to [4], wherein the weight average molecular weight of the aforementioned component (B) is 1,000 to 30,000. [6]: An organic film forming composition as described in any of [1] to [5], wherein the content of the aforementioned component (B) is 0.01 to 5 parts by mass relative to 100 parts by mass of the aforementioned organic film forming material (A). [7]: An organic film forming method, which is a method for forming an organic film used in the manufacturing process of a semiconductor device, characterized in that: an organic film forming composition of any one of [1] to [6] is spin-coated on a substrate to obtain a coating film, and the aforementioned coating film is heat-treated at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to harden and form an organic film. [8]: A pattern forming method, characterized in that: an organic film is formed on a workpiece using an organic film forming composition of any one of [1] to [6], a silicon-containing resist intermediate film is formed on the organic film using a silicon-containing resist intermediate film material, a resist upper film material composed of a photoresist composition is formed on the silicon-containing resist intermediate film to form a resist upper film, a circuit pattern is formed on the resist upper film, the resist upper film with the circuit pattern is used as a mask and the pattern is transferred to the silicon-containing resist intermediate film by etching, the silicon-containing resist intermediate film with the transferred pattern is used as a mask and the pattern is transferred to the organic film by etching, and the organic film with the transferred pattern is used as a mask and the pattern is formed on the workpiece by etching. [9]: A pattern forming method, characterized in that: an organic film is formed on a workpiece using an organic film forming composition of any one of [1] to [6], a silicon-containing resist intermediate film is formed on the organic film using a silicon-containing resist intermediate film material, an organic anti-reflective film or a sealing film is formed on the silicon-containing resist intermediate film, a resist upper film material composed of a photoresist composition is used on the organic anti-reflective film or the sealing film to form a resist upper film, a circuit pattern is formed on the resist upper film, the resist upper film with the circuit pattern is used as a mask and the pattern is transferred to the organic anti-reflective film or the sealing film and the silicon-containing resist intermediate film by etching, the silicon-containing resist intermediate film with the transferred pattern is used as a mask and the pattern is transferred to the organic film by etching, and the organic film with the transferred pattern is used as a mask and the pattern is formed on the workpiece by etching.

[10] : A pattern forming method, characterized in that: an organic film is formed on a workpiece using an organic film forming composition of any one of [1] to [6], an inorganic hard mask selected from the group consisting of silicon oxide film, silicon nitride film and silicon oxynitride film is formed on the organic film, an upper resistive film composed of a photoresist composition is used on the upper resistive film to form an upper resistive film, a circuit pattern is formed on the upper resistive film, the upper resistive film with the circuit pattern is used as a mask and the pattern is transferred to the upper inorganic hard mask by etching, the upper inorganic hard mask with the transferred pattern is used as a mask and the pattern is transferred to the organic film by etching, and the organic film with the transferred pattern is used as a mask and the pattern is formed on the workpiece by etching.

[11] : A pattern forming method, characterized in that: an organic film is formed on a workpiece using an organic film forming composition of any one of [1] to [6], an inorganic hard mask selected from the group consisting of silicon oxide film, silicon nitride film and silicon oxynitride film is formed on the organic film, an organic antireflective film or a sealing film is formed on the inorganic hard mask, an upper resistive film composed of a photoresist composition is used on the organic antireflective film or the sealing film to form an upper resistive film, a circuit pattern is formed on the upper resistive film, the upper resistive film with the circuit pattern is used as a mask and the pattern is transferred to the organic antireflective film or the sealing film and the inorganic hard mask by etching, the inorganic hard mask with the transferred pattern is used as a mask and the pattern is transferred to the organic film by etching, and the organic film with the transferred pattern is used as a mask and the pattern is formed on the workpiece by etching.

[12] : The pattern forming method of

[10] or

[11] is to form the aforementioned inorganic hard mask by means of CVD or ALD.

[13] : The pattern forming method of any one of [8] to

[12] , wherein the circuit pattern is formed by photolithography, electron beam direct writing, nanoimprinting or a combination thereof using light with a wavelength of 10 nm or more and 300 nm or less.

[14] : The pattern forming method of any one of [8] to

[13] , wherein the circuit pattern is formed by developing an alkaline developer or an organic solvent.

[15] : The pattern forming method of any one of [8] to

[14] , wherein the aforementioned workpiece is a semiconductor device substrate, or is formed on the aforementioned semiconductor device substrate by forming any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film.

[16] : The pattern forming method of any one of [8] to

[15] , wherein, with respect to the aforementioned workpiece, the metal constituting the workpiece is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or alloys thereof.

[17] : A polymer characterized by having repeating units represented by the following formula (B1). [Chemistry 78] In the formula, R1 is a hydrogen atom or a methyl group, R2 and R3 are independently monovalent organic groups with 10 to 20 carbon atoms and no fluorine atoms, X is a nitrogen atom or an oxygen atom, and W1 is a single bond or a divalent linker with 1 to 10 carbon atoms that may contain oxygen atoms and no fluorine atoms.

[18] : Polymers such as

[17] , wherein W1 in the above formula (B1) is the base represented by the following formula (B2). [Chemistry 79] In the formula, the dashed lines represent the atomic bonds of X in the above formula (B1) and the atomic bonds of carbon atoms bonded to R2 and R3, and may have one or two of the structures represented by the above formula (B2).

[19] : Polymers such as

[17] or

[18] , wherein the aforementioned polymers further contain one or more repeating units represented by the following general formula (B3). [Chemistry 80] In the formula, R1 and X are the same as those mentioned above, and W2 is a monovalent organic group that may contain oxygen atoms but not fluorine atoms.

[20] : Polymers such as

[19] , wherein W2 in the above formula (B3) is a base represented by the following formula (B4). [Chemistry 81] In the formula, R4 is a hydrogen atom or a methyl group, R5 is a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms that does not contain fluorine atoms, and m is an integer from 4 to 20.

[21] : The polymer of any one of

[17] to

[20] , wherein the weight average molecular weight of the aforementioned polymer is 1,000 to 30,000.

[0289] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are examples, and those having a structure that is substantially the same as the technical concept described in the claims of the present invention and performing the same function are all intended to be included within the technical scope of the present invention.

[0290] 1:Substrate 2: Processed layer 2a: Pattern (a pattern formed on the processed layer) 3: Organic membrane 3a: Organic film pattern 4: Silicon-containing inhibitor interlayer 4a: Pattern of silicon-containing inhibitor interlayer film 5: Upper layer film of inhibitor 5a: Pattern of the upper layer film of the inhibitor 6: Exposure section 7: Substrate 8: Organic membrane

Claims

1. An organic film forming composition, characterized by comprising: (A) an organic film forming material, (B) a polymer having repeating units represented by formula (B1), and (C) a solvent; wherein the polymer (B) further comprises one or more repeating units represented by general formula (B3); the content of component (B) is 0.01 to 5 parts by mass relative to 100 parts by mass of the organic film forming material (A); the content of solvent (C) is 200 to 10,000 parts by mass relative to 100 parts by mass of the organic film forming material (A); wherein R1 is a hydrogen atom or a methyl group, R2 and R3 are each independently a monovalent organic group with 10 to 20 carbon atoms that does not contain fluorine atoms, X is a nitrogen atom or an oxygen atom, and W1 is a single bond or a divalent linker group with 1 to 10 carbon atoms that may also contain oxygen atoms and does not contain fluorine atoms; In the formula, R1 and X are the same as those mentioned above, and W2 is a monovalent organic group that may contain oxygen atoms but not fluorine atoms.

2. The organic film-forming composition as claimed in claim 1, wherein, In formula (B1), W1 is the base represented by formula (B2); In the formula, the dashed line represents the atomic bond with X in formula (B1) and the atomic bond with carbon atoms bonded to R2 and R3, and can have one or two of the structures represented by formula (B2).

3. The organic film-forming composition as claimed in claim 1, wherein, In formula (B3), W2 is the base represented by formula (B4); where R4 is a hydrogen atom or a methyl group, R5 is a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms that does not contain fluorine atoms, and m is an integer from 4 to 20.

4. The organic film-forming composition as claimed in claim 1, wherein, The weight average molecular weight of component (B) is 1,000 to 30,000.

5. An organic film forming method, which is a method for forming an organic film used in the manufacturing process of a semiconductor device, characterized in that: an organic film forming composition of any one of claims 1 to 4 is spin-coated onto a substrate to obtain a coating film, and the coating film is heat-treated at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to harden and form an organic film.

6. A pattern forming method, characterized in that: an organic film is formed on a workpiece using an organic film forming composition as claimed in claim 1; a silicon-containing resist intermediate film is formed on the organic film using a silicon-containing resist intermediate film material; a resist upper film material composed of a photoresist composition is formed on the silicon-containing resist intermediate film; a circuit pattern is formed on the resist upper film; the resist upper film with the circuit pattern is used as a mask and the pattern is transferred to the silicon-containing resist intermediate film by etching; the silicon-containing resist intermediate film with the transferred pattern is used as a mask and the pattern is transferred to the organic film by etching; and the organic film with the transferred pattern is used as a mask and the pattern is formed on the workpiece by etching.

7. A pattern forming method, characterized by: forming an organic film on a workpiece using an organic film forming composition as claimed in claim 1; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming an organic antireflective film or a sealing film on the silicon-containing resist intermediate film; forming a resist upper film on the organic antireflective film or the sealing film using a resist upper film material composed of a photoresist composition; forming a circuit pattern on the resist upper film; using the resist upper film with the circuit pattern as a mask and etching to transfer the pattern onto the organic antireflective film or the sealing film and the silicon-containing resist intermediate film; using the silicon-containing resist intermediate film with the transferred pattern as a mask and etching to transfer the pattern onto the organic film; and then using the organic film with the transferred pattern as a mask and etching to form the pattern on the workpiece.

8. A pattern forming method, characterized in that: an organic film is formed on a workpiece using an organic film forming composition as claimed in claim 1; an inorganic hard mask selected from the group consisting of silicon oxide film, silicon nitride film, and silicon oxynitride film is formed on the organic film; an upper resist film is formed on the inorganic hard mask using an upper resist film material composed of a photoresist composition; a circuit pattern is formed on the upper resist film; the upper resist film with the circuit pattern is used as a mask and the pattern is transferred to the inorganic hard mask by etching; the inorganic hard mask with the transferred pattern is used as a mask and the pattern is transferred to the organic film by etching; and the organic film with the transferred pattern is used as a mask and the pattern is formed on the workpiece by etching.

9. A pattern forming method, characterized by: forming an organic film on a workpiece using an organic film forming composition as claimed in claim 1; forming an inorganic hard mask selected from the group consisting of silicon oxide film, silicon nitride film, and silicon oxynitride film on the organic film; forming an organic antireflective film or an adhesive film on the inorganic hard mask; forming an upper resistive film on the organic antireflective film or the adhesive film using an upper resistive film material composed of a photoresist composition; forming a circuit pattern on the upper resistive film; using the upper resistive film with the circuit pattern as a mask and etching to transfer the pattern onto the organic antireflective film or the adhesive film and the inorganic hard mask; using the inorganic hard mask with the transferred pattern as a mask and etching to transfer the pattern onto the organic film; and then using the organic film with the transferred pattern as a mask and etching to form the pattern on the workpiece.

10. The pattern forming method of claim 8 or 9 is to form the inorganic hard mask by means of CVD or ALD.

11. The pattern forming method as described in any of claims 6 to 9, wherein, The circuit pattern is formed by using lithography, electron beam writing, nanoimprinting, or a combination thereof, with wavelengths of 10 nm or more and 300 nm or less.

12. The pattern forming method as described in any of claims 6 to 9, wherein, In the formation of this circuit pattern, the circuit pattern is developed using alkaline development or organic solvents.

13. The pattern forming method as described in any of claims 6 to 9, wherein, The workpiece is a semiconductor device substrate, or is formed on the semiconductor device substrate by forming any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film.

14. The pattern forming method as described in claim 13, wherein, The workpiece being processed is made of silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or alloys thereof.

15. A polymer characterized by having a repeating unit represented by the following formula (B1), further containing one or more repeating units represented by the following general formula (B3), and free of fluorine atoms; wherein R1 is a hydrogen atom or a methyl group, R2 and R3 are each independently a monovalent organic group with 10 to 20 carbon atoms that does not contain fluorine atoms, X is a nitrogen atom or an oxygen atom, and W1 is a single bond or a divalent linker with 1 to 10 carbon atoms that may contain oxygen atoms and does not contain fluorine atoms; wherein R1 and X are the same as described above, and W2 is a monovalent organic group that may contain oxygen atoms and does not contain fluorine atoms.

16. The polymer as claimed in claim 15, wherein, In formula (B1), W1 is the base represented by formula (B2); In the formula, the dashed line represents the atomic bond with X in formula (B1) and the atomic bond with carbon atoms bonded to R2 and R3, and can have one or two of the structures represented by formula (B2).

17. The polymer as claimed in claim 15, wherein, In formula (B3), W2 is the base represented by formula (B4); where R4 is a hydrogen atom or a methyl group, R5 is a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms that does not contain fluorine atoms, and m is an integer from 4 to 20.

18. The polymer of any one of claims 15 to 17, wherein, The polymer has a weight-average molecular weight of 1,000 to 30,000.

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