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

Abstract

The invention relates to a composition for forming an organic film, an organic film forming method, and a pattern forming method. The present invention addresses the problem of providing a composition for forming an organic film, which is characterized by containing (A) a resin that contains an aromatic ring, (B) a polymer that contains a repeating unit that contains a [beta]-diketone structure represented by formula (1), and (C) a solvent. In formula (1), L1 is a C2-20 saturated or unsaturated linear or branched divalent hydrocarbon group. RA and RB each represents a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1-20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3-20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2-20 carbon atoms and having one or more double bonds or triple bonds, a substituted or unsubstituted hetero-alkyl group having 1-30 carbon atoms, or a substituted or unsubstituted hetero-alkyl group having 6-6 carbon atoms 30 is an aryl group, a thiol group, a hydroxyl group, an amino group, a carboxyl group or a halogen group.

Description

Technical Field

[0001] The present invention relates to an organic film for a multilayer photoresist used in the microfabrication of semiconductor devices, an organic film forming composition for forming an organic film for planarization of semiconductor devices, a method for forming an organic film using the composition, and a pattern forming method using the aforementioned composition. Background Technology

[0002] The improvement in the processing performance of semiconductor devices has been driven by the miniaturization of pattern sizes resulting from the shortening of light source wavelengths in photolithography. However, since the advent of ArF light sources, the trend of wavelength shortening has slowed down, necessitating alternative methods to achieve high performance instead of miniaturization. Therefore, technologies that enhance semiconductor device performance by making the structure three-dimensional and arranging transistors at higher densities are under active development.

[0003] In semiconductor device substrates with such three-dimensional structures, the circuit patterns are formed into deeper and finer structures compared to conventional substrates. Therefore, conventional photolithography techniques optimized for planar structures cannot ensure practical process margins. Thus, it is necessary to use a material capable of planarizing the substrate with the three-dimensional structure to form a flat surface, and then pattern the surface using photolithography to ensure process margins.

[0004] Several techniques for forming planarization films using spin-coated organic films are known (Patent Documents 1-5), but organic films formed with such materials cannot accommodate all patterns on substrates used in semiconductor device manufacturing. Other proposals include adding thermally degradable polyacetals (Patent Document 6), but these methods raise concerns about poor film formation and deteriorated packing properties due to film shrinkage induced by thermal decomposition. Furthermore, a method for planarization using chemical mechanical polishing (CMP) after packing in the unevenness of the substrate (Patent Document 7) is already practical, but CMP is a costly process. Therefore, there is a need for a method to achieve high-level planarization of substrates used in semiconductor device manufacturing using organic films at a low cost.

[0005] Existing technical documents

[0006] Patent documents

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2005-292528

[0008] [Patent Document 2] Japanese Patent Application Publication No. 2008-65081

[0009] [Patent Document 3] Japanese Patent Application Publication No. 2008-242492

[0010] [Patent Document 4] Japanese Patent Application Publication No. 2014-24831

[0011] [Patent Document 5] Japanese Patent Application Publication No. 2014-219559

[0012] [Patent Document 6] International Publication No. WO2008 / 026468 (Supplementary Booklet)

[0013] [Patent Document 7] Japanese Patent Application Publication No. 2004-335873 Summary of the Invention

[0014] [The problem the invention aims to solve]

[0015] In view of the above, the present invention aims to provide an organic film forming composition that takes into account a high degree of landfill / planarization characteristics, and a pattern forming method using the composition.

[0016] [Methods for solving problems]

[0017] To address the aforementioned issues, the present invention provides a composition for forming organic films, characterized by containing:

[0018] (A) Resins containing aromatic rings

[0019] (B) Polymers containing repeating units with a β-diketone structure as represented by formula (1)

[0020] (C) Solvent.

[0021] [Chemistry 1]

[0022]

[0023] In equation (1) above, L1 is a saturated or unsaturated straight-chain or branched divalent hydrocarbon group with 2 to 20 carbon atoms, which may be interrupted once or multiple times by atoms selected from oxygen, nitrogen, and sulfur. R A and R B They may be the same or different from each other, and may be hydrogen atoms, substituted or unsubstituted straight-chain alkyl groups with 1 to 20 carbon atoms, substituted or unsubstituted branched or cyclic alkyl groups with 3 to 20 carbon atoms, substituted or unsubstituted aliphatic unsaturated hydrocarbon groups with 2 to 20 carbon atoms containing one or more double or triple bonds, substituted or unsubstituted heteroalkyl groups with 1 to 30 carbon atoms, or substituted or unsubstituted aryl, thiol, hydroxyl, amino, carboxyl, or halogen groups with 6 to 30 carbon atoms.

[0024] If a resin containing an aromatic ring, such as in (A), is included, etching resistance and processing resistance become excellent. Furthermore, in (B), the repeating unit contains a polymer with a β-diketone structure. By appropriately selecting the structure represented by L1 in the polymer backbone, fluidity can be imparted, filling the uneven pattern after spin coating. Furthermore, the flow is promoted by heat, so it flows further during high-temperature baking, thereby improving the flatness of the uneven surface. Conventional polyethylene and polyethylene glycol have concerns about solvent solubility, poor compatibility with the main resin, and poor film formation due to sublimation. However, by containing a β-diketone structure, poor solubility and compatibility are eliminated, and due to the interaction of the main polymer, sublimation is less likely. Moreover, the β-diketone structure and L1 are less prone to thermal decomposition, and the sublimation of low-molecular-weight components caused by thermal decomposition is also suppressed. Therefore, an organic film-forming composition with excellent film-forming properties can be provided.

[0025] The resin containing an aromatic ring in (A) above preferably contains hydrogen at the diarylmethylene position or hydrogen at the triphenylmethyl position.

[0026] If the resin containing an aromatic ring in (A) above contains hydrogen at the diarylmethylene position or hydrogen at the triphenylmethyl position, then by containing them as part of the structure, an oxidative coupling reaction accompanied by dehydrogenation will occur due to heat, and the film can be hardened by the cross-linking reaction.

[0027] Furthermore, in the resin containing an aromatic ring described above (A), it is preferable that the aromatic ring contains a hydroxyl group as a substituent.

[0028] If the aromatic ring substituents in the resin containing the aromatic ring in (A) above contain hydroxyl groups, they will not only promote oxidative coupling more effectively, but also undergo dehydration reactions between the hydroxyl groups. Therefore, they will undergo thermosetting more efficiently and become a composition capable of forming films with high crosslinking group density and high processing resistance. Furthermore, if hydroxyl groups are present, the interaction between the resin and the β-diketone structure in (B) will be stronger, making it less prone to sublimation during baking and resulting in a composition capable of forming films with excellent film-forming properties.

[0029] The resin containing an aromatic ring in (A) above preferably contains polymers selected from repeating units having the following formulas (P-1) and (P-2), and compounds having the following formulas (P-3) to (P-6).

[0030] [Chemistry 2]

[0031]

[0032] In equations (P-1) and (P-2) above, R represents a hydrogen atom or a substituted or unsubstituted benzene ring or naphthalene ring. In equations (P-1) to (P-6), R1 represents a hydrogen atom or a saturated or unsaturated hydrocarbon group with 1 to 20 carbon atoms. In equations (P-1), (P-3), (P-4), and (P-5), m1 represents an integer of 0 or 1. In equations (P-1), (P-3), (P-4), and (P-6), n1 represents an integer of 1 to 4. In equations (P-2) and (P-5), n2 represents an integer of 1 or 2. In equations (P-3) and (P-5), n3 represents an integer of 0 to 2. In equations (P-3) to (P-6), l represents an integer of 5 to 20. However, l represents the feed ratio.

[0033] If the resin containing an aromatic ring in (A) above has the structure represented by formulas (P-1) to (P-6), then the structure contains hydrogen at the diarylmethylene position or hydrogen at the triphenylmethyl position, so it has excellent thermosetting properties. Furthermore, since R1 is hydrogen and contains hydroxyl groups, it can be densely cross-linked, and thus the interaction with the β-diketone structure in (B) is stronger, so it becomes a component that can form a film with excellent film-forming properties.

[0034] In equation (1) above, R A and R B The preferred compounds are hydrogen atoms, substituted or unsubstituted straight-chain alkyl groups with 1 to 20 carbon atoms, substituted or unsubstituted branched or cyclic alkyl groups with 3 to 20 carbon atoms, or substituted or unsubstituted aliphatic unsaturated hydrocarbon groups with 2 to 20 carbon atoms containing one or more double or triple bonds.

[0035] In equation (1) above, R A and R B Those with hydrogen atoms are preferred.

[0036] In equation (1) above, if R A and R B Hydrogen atoms, substituted or unsubstituted straight-chain alkyl groups with 1 to 20 carbon atoms, substituted or unsubstituted branched or cyclic alkyl groups with 3 to 20 carbon atoms, or substituted or unsubstituted aliphatic unsaturated hydrocarbon groups with 2 to 20 carbon atoms containing one or more double or triple bonds will result in a more flowable structure, which will further enhance the flatness improvement caused by thermal flow during the filling of uneven substrates and high-temperature baking. Furthermore, if R... A and R B If it is hydrogen atoms, raw material management becomes easier, making it more ideal.

[0037] In the above formula (1), it is preferable that L1 is a saturated or unsaturated straight-chain or branched hydrocarbon group with 2 to 20 carbon atoms that does not contain heteroatoms.

[0038] In formula (1) above, if L1 is a saturated or unsaturated straight-chain or branched hydrocarbon group with 2 to 20 carbon atoms that does not contain heteroatoms, it is less likely to undergo bond separation due to heat, and can suppress sublimation, thus resulting in a film with better film-forming properties. Furthermore, from the viewpoint of obtaining raw materials, it is preferable for L1 to be a straight-chain hydrocarbon group with 2 to 20 carbon atoms.

[0039] The content of the polymer containing a β-diketone structure in the repeating unit of the above-mentioned (B) is preferably 0.5 to 30 parts by mass relative to 100 parts by mass of the resin containing an aromatic ring in (A) above-mentioned.

[0040] If the amount of (B) is 0.5 to 30 parts by mass relative to 100 parts by mass of the resin containing aromatic rings in (A), then the processing resistance and etching resistance of the resin containing aromatic rings in (A) can be improved without affecting the planarization characteristics, and more preferably it is 0.5 to 15 parts by mass.

[0041] The solvent (C) of the aforementioned organic film forming composition is preferably a mixture of high-boiling-point and low-boiling-point solvents.

[0042] If it is a mixture of such solvents, there is no risk that the evaporation during baking (heat treatment) will become too rapid, so sufficient thermal fluidity can be obtained during film formation, and an organic film with excellent packing / planarization properties can be formed.

[0043] It is preferable that the aforementioned organic film forming composition contains one or more of (D) a crosslinking agent and (E) a surfactant.

[0044] An organic film forming method is provided, which is an organic film forming method used as a manufacturing step of a semiconductor device, and is an organic planarization film forming method. The organic film forming composition described above is spin-coated on a substrate to be processed, and the substrate coated with the organic film forming composition is heat-treated at a temperature of 100°C to 600°C for 10 to 600 seconds to form a hardened film.

[0045] By performing heat treatment under such conditions, planarization and cross-linking reactions can be promoted using heat flow, resulting in an organic membrane that does not mix with the membrane formed on the upper layer.

[0046] Furthermore, the present invention provides an organic film forming method, which is an organic film forming method used as a manufacturing step of a semiconductor device, wherein the above-mentioned organic film forming composition is spin-coated on a substrate to be processed, and the substrate coated with the organic film forming composition is heat-treated in a gas environment with an oxygen concentration of 0.1% to 21% to form a hardened film.

[0047] By firing in an oxygen-rich environment in this way, a fully hardened organic film can be formed.

[0048] Furthermore, it is preferable to use a substrate with a height of 30 nm or more or a substrate with a height difference for the aforementioned processed substrate.

[0049] The composition for forming organic films of the present invention is particularly useful for situations where a planar organic film needs to be formed on a substrate being processed due to its excellent packing / planarization properties.

[0050] Furthermore, the present invention provides a pattern forming method, which involves forming an organic film on a workpiece using the organic film forming composition described above, forming a photoresist intermediate film on the organic film using a photoresist intermediate film material containing silicon atoms, forming a photoresist upper film on the photoresist intermediate film using a photoresist upper film material composed of a photoresist composition, forming a circuit pattern on the photoresist upper film, using the photoresist upper film with the formed circuit pattern as a mask to etch and transfer the pattern onto the aforementioned photoresist intermediate film, using the photoresist intermediate film with the transferred pattern as a mask to etch and transfer the pattern onto the aforementioned organic film, and then using the organic film with the transferred pattern as a mask to etch and transfer the pattern onto the aforementioned workpiece.

[0051] Furthermore, the present invention provides a pattern forming method, which involves forming an organic film on a workpiece using the aforementioned composition for forming an organic film, forming a photoresist intermediate film on the organic film using a photoresist intermediate film material containing silicon atoms, forming an organic antireflective film on the photoresist intermediate film, forming a photoresist upper film on the organic antireflective film using a photoresist upper film material composed of a photoresist composition, forming a circuit pattern on the photoresist upper film, using the photoresist upper film with the formed circuit pattern as a mask to etch and transfer the pattern onto the aforementioned organic antireflective film and the aforementioned photoresist intermediate film, using the photoresist intermediate film with the transferred pattern as a mask to etch and transfer the pattern onto the aforementioned organic film, and then using the organic film with the transferred pattern as a mask to etch and transfer the pattern onto the aforementioned workpiece.

[0052] Furthermore, the present invention provides a pattern forming method, which involves forming an organic film on a workpiece using the aforementioned composition for forming an organic film, forming an inorganic hard mask selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film on the organic film, forming a photoresist upper layer film on the inorganic hard mask using a photoresist upper layer film material composed of a photoresist composition, forming a circuit pattern on the photoresist upper layer film, using the photoresist upper layer film with the formed circuit pattern as a mask to etch and transfer the pattern onto the aforementioned inorganic hard mask, using the inorganic hard mask with the transferred pattern as a mask to etch and transfer the pattern onto the aforementioned organic film, and then using the organic film with the transferred pattern as a mask to etch and transfer the pattern onto the aforementioned workpiece.

[0053] Furthermore, the present invention provides a pattern forming method, which involves forming an organic film on a workpiece using the aforementioned composition for forming an organic film, forming an inorganic hard mask selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film on the organic film, forming an organic antireflective film on the inorganic hard mask, forming an upper resist film on the organic antireflective film using an upper resist film material composed of a photoresist composition, forming a circuit pattern on the upper resist film, using the upper resist film with the formed circuit pattern as a mask to etch and transfer the pattern onto the aforementioned organic antireflective film and the aforementioned inorganic hard mask, using the inorganic hard mask with the transferred pattern as a mask to etch and transfer the pattern onto the aforementioned organic film, and then using the organic film with the transferred pattern as a mask to etch and transfer the pattern onto the aforementioned workpiece.

[0054] Thus, the composition for forming organic films of the present invention can be ideally applied to various pattern forming methods, such as three-layer resist treatment using a resist intermediate film containing silicon atoms or an inorganic hard mask, and four-layer resist treatment using an organic anti-reflective film. In such a pattern forming method of the present invention, circuit patterns of resist upper film can be transferred to the workpiece with high precision.

[0055] Furthermore, the formation of the aforementioned inorganic hard mask is preferably carried out using CVD or ALD methods.

[0056] The pattern forming method of the present invention can, for example, form an inorganic hard mask in such a way.

[0057] [The effects of the invention]

[0058] As explained above, the present invention provides an organic film forming composition with a high degree of embedding / planarization characteristics. Furthermore, this organic film forming composition of the present invention possesses excellent embedding / planarization characteristics, as well as excellent heat resistance, etching resistance, and other properties. Therefore, it is extremely useful, for example, as an organic film material used in two-layer resist processing, three-layer resist processing using a silicon-containing resist interlayer or an inorganic hard mask, or four-layer resist processing using a silicon-containing resist interlayer or an inorganic hard mask and an organic antireflective film, or as a planarization material for semiconductor device manufacturing. Furthermore, the organic film forming method of the present invention allows the formation of a very flat organic film with sufficient organic solvent resistance on a processed substrate. Furthermore, the pattern forming method of the present invention allows the formation of fine patterns on a processed body with high precision using multilayer resist processing. Attached Figure Description

[0059] Figure 1 Figures (A) to (F) are explanatory diagrams of an example of the pattern forming method of the present invention using a three-layer resist treatment.

[0060] Figure 2 (A) and (B) are explanatory diagrams of the evaluation methods for landfill characteristics and leveling characteristics. Detailed Implementation

[0061] As mentioned above, the aim is to develop organic membrane forming compositions with high landfill / planarization properties, and organic membrane forming compounds useful for such compositions.

[0062] Typically, when forming an organic film, an organic film-forming compound is dissolved in an organic solvent to prepare a composition, which is then coated onto a substrate on which the structure and wiring of a semiconductor device have already been formed, and fired to form an organic film. When the composition is first coated, it forms a coating film that follows the shape of the structure on the substrate. However, if this coating film is fired, most of the organic solvent evaporates until it hardens, and an organic film is formed due to the organic film-forming compound remaining on the substrate. The inventors of this application conceived that if the organic film-forming compound remaining on the substrate at this time has sufficient thermal fluidity, the uneven shape initially formed during coating can be planarized by thermal fluidity, resulting in a flat film.

[0063] The inventors of this application have made further efforts to explore the possibility that if a polymer with a specific structure having a β-diketone structure in the repeating unit is added to the general composition of (A) a resin containing an aromatic ring and (C) a solvent, the β-diketone structure is easily retained in the film due to the interaction between the resin containing the aromatic ring in (A). Furthermore, if the repeating unit contains a hydrocarbon group, it will become a structure that is easily thermally fluid. Therefore, a film with excellent planarization characteristics can be formed, and the present invention has been completed.

[0064] Furthermore, the polymer of the present invention containing repeating units with a β-diketone structure is a polyester in which the β-diketone structure constitutes the polymer backbone. Previously, there were no known examples of using polyesters with such a structure in compositions for organic films used in photolithography, etc.

[0065] That is, the present invention is a composition for forming organic films, characterized by containing:

[0066] (A) Resins containing aromatic rings

[0067] (B) Polymers containing repeating units with a β-diketone structure as represented by formula (1)

[0068] (C) Solvent.

[0069] [Chemistry 3]

[0070]

[0071] In equation (1) above, L1 is a saturated or unsaturated straight-chain or branched divalent hydrocarbon group with 2 to 20 carbon atoms, which may be interrupted once or multiple times by atoms selected from oxygen, nitrogen, and sulfur. RA and R B They may be the same or different from each other, and may be hydrogen atoms, substituted or unsubstituted straight-chain alkyl groups with 1 to 20 carbon atoms, substituted or unsubstituted branched or cyclic alkyl groups with 3 to 20 carbon atoms, substituted or unsubstituted aliphatic unsaturated hydrocarbon groups with 2 to 20 carbon atoms containing one or more double or triple bonds, substituted or unsubstituted heteroalkyl groups with 1 to 30 carbon atoms, or substituted or unsubstituted aryl, thiol, hydroxyl, amino, carboxyl, or halogen groups with 6 to 30 carbon atoms.

[0072] The present invention will be described in detail below, but the present invention is not limited thereto.

[0073] Hereinafter, the necessary components of the organic film forming composition of the present invention will be described in sequence: (B) a polymer containing a β-diketone structure in repeating units, (A) a resin containing an aromatic ring, and (C) a solvent.

[0074] [(B) Polymers with repeating units containing β-diketone structures]

[0075] The polymer containing a β-diketone structure in the repeating unit (B) of the present invention is a polymer represented by the following formula (1).

[0076] [Chemistry 4]

[0077]

[0078] In equation (1) above, L1 is a saturated or unsaturated straight-chain or branched divalent hydrocarbon group with 2 to 20 carbon atoms, which may be interrupted once or multiple times by atoms selected from oxygen, nitrogen, and sulfur. R A and R B They may be the same or different from each other, and may be hydrogen atoms, substituted or unsubstituted straight-chain alkyl groups with 1 to 20 carbon atoms, substituted or unsubstituted branched or cyclic alkyl groups with 3 to 20 carbon atoms, substituted or unsubstituted aliphatic unsaturated hydrocarbon groups with 2 to 20 carbon atoms containing one or more double or triple bonds, substituted or unsubstituted heteroalkyl groups with 1 to 30 carbon atoms, or substituted or unsubstituted aryl, thiol, hydroxyl, amino, carboxyl, or halogen groups with 6 to 30 carbon atoms.

[0079] In the above formula (1), L1 is a saturated or unsaturated straight-chain or branched divalent hydrocarbon group with 2 to 20 carbon atoms, which may be interrupted once or multiple times by atoms selected from oxygen, nitrogen and sulfur.

[0080] Specific examples of L1 can be listed below, but are not limited to these.

[0081] [Chemistry 5]

[0082]

[0083] * represents the bonding portion with the oxygen atom, and n is an integer from 1 to 10.

[0084] Considering thermal stability, L1 is preferably a pure hydrocarbon group that is not interrupted by heteroatoms; furthermore, from the viewpoint of thermal fluidity, a straight-chain form is preferred. From the viewpoint of raw material sourcing, L1 is preferably a straight-chain hydrocarbon group with 2 to 20 carbon atoms.

[0085] In equation (1) above, R A and R B They may be the same or different from each other, and may be hydrogen atoms, substituted or unsubstituted straight-chain alkyl groups with 1 to 20 carbon atoms, substituted or unsubstituted branched or cyclic alkyl groups with 3 to 20 carbon atoms, substituted or unsubstituted aliphatic unsaturated hydrocarbon groups with 2 to 20 carbon atoms containing one or more double or triple bonds, substituted or unsubstituted heteroalkyl groups with 1 to 30 carbon atoms, or substituted or unsubstituted aryl, thiol, hydroxyl, amino, carboxyl, or halogen groups with 6 to 30 carbon atoms.

[0086] R A and R B Examples of substituted or unsubstituted straight-chain alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, octyl, etc. Examples of substituted or unsubstituted branched alkyl groups having 3 to 20 carbon atoms include isopropyl, isobutyl, isopentyl, etc. Examples of cyclic alkyl groups having 3 to 20 carbon atoms include cyclohexane, cyclopentyl, methylcyclohexyl, etc. Examples of substituted or unsubstituted aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms containing one or more double or triple bonds include allyl, propargyl, etc. Examples of substituted or unsubstituted heteroalkyl groups having 1 to 30 carbon atoms include alkyl groups whose atoms can be interrupted one or more times by atoms selected from oxygen, nitrogen, and sulfur. Examples of substituted or unsubstituted aryl groups having 6 to 30 carbon atoms include phenyl, tolyl, etc. R A and R B The substituents represented are not limited to these specific examples.

[0087] R A and R B The following structures can be cited as specific examples.

[0088] [Chemistry 6]

[0089]

[0090] If thermal fluidity is taken into account, then R A and R B It is preferred to have hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, or substituted or unsubstituted branched or cyclic alkyl groups having 3 to 20 carbon atoms. From the viewpoint of obtaining raw materials, hydrogen atoms are more preferred.

[0091] For the polymers with β-diketone structures in the aforementioned repeating unit (B), it is preferable that the weight-average molecular weight (Mw) of the polystyrene obtained by gel permeation chromatography is between 1,000 and 20,000. If the weight-average molecular weight (Mw) is in such a range, it is less likely to sublimate at high temperatures, will not cause poor film formation, and will help improve flatness by utilizing thermal flow, thus becoming a polymer with good solvent solubility.

[0092] Compared to the aforementioned (A) resin containing an aromatic ring, 100 parts by weight of the aforementioned (B) repeating unit containing a polymer having a β-diketone structure contains 0.5 to 50 parts by weight of the polymer, which has a β-diketone structure, is more ideal from the viewpoint of processing resistance and etching resistance, and more preferably 0.5 to 30 parts by weight.

[0093] [Method for manufacturing polymer (B)]

[0094] Polymer (B) having repeating units represented by formula (1) is called polyester. Using diols containing the L1 structure and those having R in some structural respects... A R B Polymers can be obtained through dehydration condensation of dicarboxylic acids, reaction of diols containing an L1 structure with the corresponding acyl halide or anhydride of dicarboxylic acids, and transesterification of dicarboxylic acid esters. Examples of reaction formulas for dehydration condensation, acyl halide, and transesterification are given below. These can be appropriately selected considering factors such as the stability of the raw materials used. Furthermore, in these cases, the amount of diol used is preferably 0.8 to 1.2 equivalents relative to the dicarboxylic acid and its derivatives; from the viewpoint of reducing the molecular weight of the obtained polymer and minimizing unreacted raw materials, 0.9 to 1.1 equivalents is more preferable.

[0095] R in the following formula A R B As mentioned above, L1 represents a halogen atom, and R" represents an alkyl group with 1 to 5 carbon atoms.

[0096] [Chemistry 7]

[0097] [Dehydration condensation]

[0098]

[0099] [Ester exchange]

[0100]

[0101] [Acylhalides]

[0102]

[0103] When polymer (B) is manufactured using dehydration condensation or transesterification as described above, diols and dicarboxylic acids or their corresponding ester compounds can be used to remove the generated water or alcohol during the reaction in the absence of a catalyst or in the presence of a catalyst.

[0104] Even if the reaction proceeds without a catalyst, there is no problem as long as the reaction will continue. However, when using a catalyst, examples include metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; amines such as imidazoles and benzotriazoles; phosphine compounds such as triphenylphosphine; quaternary ammonium salts such as tetraethylammonium chloride and tetraethylammonium bromide, benzyltrimethylammonium chloride and benzyltriethylammonium chloride; quaternary phosphonium salts such as benzyltriphenylphosphonium chloride; aluminum compounds such as trialkylaluminum; tin compounds such as tin chloride and tin carboxylates; and titanium compounds such as titanium alkyl oxides. The amount of catalyst used can be selected from 0.001 to 1.0 mol relative to the total amount of diol and dicarboxylic acid (1.0 mol), with 0.003 to 0.3 mol being ideal, and 0.005 to 0.1 mol being even better.

[0105] The reaction can be carried out in solvent-free conditions, but a solvent may be used to reduce the viscosity of the resulting polymer. There are no particular restrictions on solvents that are inert to the above reaction, such as aromatic solvents like benzene, toluene, and xylene, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, diphenyl sulfone, diphenyl ether, trichlorobiphenyl, trichlorobenzene, and dichlorobenzene. These solvents can be used alone or in combination. The range of these solvents is 0 to 2000 parts by mass relative to 100 parts by mass of the reactants. A reaction temperature of -50°C to approximately the boiling point of the solvent is preferred, with 100°C to 150°C being more ideal. The reaction time can be appropriately selected from 0.1 to 100 hours. It is preferable to remove the water or alcohol generated during the reaction from the system while carrying out the reaction.

[0106] When manufacturing polymer (B) using acyl halides, acyl halides corresponding to dicarboxylic acids, such as acyl chlorides, can be used to react in the presence of a base catalyst to obtain the polymer.

[0107] The base catalysts used here include, for example: amines, specifically, tertiary amines such as trimethylamine, triethylamine, tripropylamine, diisopropylethylamine, tributylamine, tripentylamine, and trihexylamine; aliphatic amines with aromatic rings such as N,N-dimethylaniline, phenyldimethylamine, diphenylmethylamine, and triphenylamine; cyclic aliphatic amines such as 1-methylpyrrolidine, 1-methylpiperidine, and 4-methylmorpholine; and 1,8-diazabicyclo[5.4.0]- The catalysts used include amidines such as 7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonene; guanidines such as guanidine, 1,1,3,3-tetramethylguanidine, and 1,2,3-triphenylguanidine; aromatic amines such as 1-methylpyrrole, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-dimethylpyridine, and N,N-dimethyl-5-aminopyridine; and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. One or more of these catalysts may be used individually or in combination, and the amount of these catalysts used relative to the molar amount of the acyl halide of the feedstock is in the range of 0.1 to 20 moles, preferably 0.2 to 10 moles.

[0108] The solvents used at this stage are not particularly restricted as long as they are inert to the above reaction. Examples include ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; aromatic solvents such as benzene, toluene, and xylene; acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and water. These solvents can be used alone or in combination. The range of these solvents is 0 to 2000 parts by mass relative to 100 parts by mass of the reactants. A reaction temperature of -50°C to approximately the boiling point of the solvent is preferred, with room temperature to 150°C being even more ideal. The reaction time can be appropriately selected from 0.1 to 100 hours.

[0109] After the above-mentioned dehydration condensation, transesterification, and acyl halide reactions are completed, in order to remove unreacted raw materials, catalysts, etc., present in the system, methods such as raising the temperature of the reactor to 130-230°C and removing volatile components at approximately 1-50 mmHg, adding appropriate unsuitable solvents or water to precipitate the polymer, and fractionation methods can be implemented, depending on the properties of the raw materials used and the reaction products obtained. Finally, the obtained polymer can be recovered by diluting it in an organic solvent and then performing a liquid-liquid separation wash.

[0110] The organic solvent used at this stage is not particularly restricted as long as it can dissolve the compound and separates into two layers when mixed with water. Examples include hydrocarbons such as hexane, heptane, benzene, toluene, and xylene; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; ketones such as methyl ethyl ketone, methyl pentanone, cyclohexanone, and methyl isobutyl ketone; ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, and ethyl cyclopentyl methyl ether; chlorinated solvents such as dichloromethane, chloroform, dichloroethane, and trichloroethylene; and mixtures thereof. The rinsing water used at this stage is usually deionized water or ultrapure water. A rinsing frequency of more than one time results in good purification and is considered optimal. A frequency of less than 10 times is economical. The optimal frequency is approximately 1 to 5 times.

[0111] In separation and washing, alkaline aqueous solutions can also be used to remove unreacted raw materials or acidic components from the system. Specifically, alkalis include, for example, alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, ammonia, and organic ammonium compounds.

[0112] Furthermore, during separation and washing, acidic aqueous solutions can be used to remove unreacted raw materials, metallic impurities, or alkaline components from the system. Specifically, acids include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acids, as well as organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

[0113] The separation and washing process using the aforementioned alkaline and acidic aqueous solutions can be performed using only one or a combination of both. Ideally, separation and washing should be carried out sequentially using alkaline and acidic aqueous solutions to remove metallic impurities.

[0114] After the above-mentioned separation and washing with alkaline and acidic aqueous solutions, a subsequent wash with neutral water can be performed. Washing should be performed at least once, preferably 1 to 5 times. Deionized water or ultrapure water can be used as described above. Washing more than once results in good purification, which is preferred. Washing less than 10 times is economical. Preferably, 1 to 5 times.

[0115] Furthermore, the reaction products after the liquid-liquid separation operation can be concentrated and dried or crystallized under reduced pressure or normal pressure to recover them in powder form. However, to improve the operability when preparing organic membrane materials, a solution of appropriate concentration can also be prepared beforehand. An ideal concentration is 0.1–50% by mass, and more preferably 0.5–30% by weight. At such a concentration, the viscosity is less likely to become excessively high, resulting in good operability. Also, the amount of solvent will not become excessive, making it economical.

[0116] At this point, there are no special restrictions on the solvent as long as it can dissolve the compound. For specific examples, ketones such as cyclohexanone and methyl-2-pentanone; 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, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate can be used alone or in combination of two or more.

[0117] It is preferable to filter the aforementioned polymer solution. By filtering, foreign matter and gel that may cause poor film formation can be removed, which is effective in stabilizing the quality.

[0118] The materials used in the aforementioned filters, such as fluorocarbon, cellulose, nylon, polyester, and hydrocarbon-based materials, are preferred for filtration steps involving chemically amplified resist compositions. Filters made of fluorocarbon (such as Teflon, a registered trademark), polyethylene, polypropylene, or nylon are also preferable. The filter pore size can be appropriately selected to match the target cleanliness level, preferably below 100 nm, and more preferably below 20 nm. Furthermore, these filters can be used individually or in combination. The filtration method can involve passing the solution through only once, but multiple filtrations with solution circulation are preferable. The filtration steps can be performed in any order and number of times during the polymer solution manufacturing process; however, filtering the reaction solution after polymerization, the polymer solution, or both is preferred.

[0119] [Other methods for manufacturing polymer (B)]

[0120] Furthermore, other methods for manufacturing the aforementioned polymer (B), such as changing the raw materials used to obtain the aforementioned polymer (B), namely dicarboxylic acid, dicarboxylic acid ester, and halide of dicarboxylic acid, to malonic acid derivatives to obtain the polymer [STEP1], and then subjecting the obtained polymer to an alkaline catalyst, using a reaction with R A R B Methods such as the addition reaction [STEP2] of partially structured halides, methanesulfonates, or toluenesulfonates, etc., to obtain them. At this time, R... A R B When all molecules are hydrogen, the reaction can be stopped at [STEP1]. (In the following formula, X represents a halide or methanesulfonate, toluenesulfonate, R...) A R B (L1 is as described above.)

[0121] [Chemistry 8]

[0122] [STEP1]

[0123]

[0124] [STEP2]

[0125]

[0126] When using the above reaction method, due to the relationship of reaction selectivity, there are two reaction sites for the repeating unit of the polymer. Therefore, a reaction rate of 100% is R A , R B completely introduced as a substituent, R A ≠R B When, the following three types are obtained, R A =R B =R' one type is obtained when. Also, when the reaction rate < 100%, a polymer with a repeating unit having various combinations as follows can be obtained. R A ≠R B When, the following six types are obtained, R A =R B =R' two types are obtained when. They can control the reaction rate for all reaction sites by adjusting the overall feed ratio, and multiple or single substituents corresponding to R A , R B can be used in combination according to the required properties. For example: when the substitution rate in the repeating unit of the polymer is set to 100, when the proportion substituted by R A , R B is a and the proportion present as an unmodified hydrogen atom is b, 0 ≤ a + b ≤ 100, 0.5 < b ≤ 1.0 is preferable, and 0.7 ≤ b ≤ 1.0 is more preferable. At this time, it becomes a polymer containing the repeating units shown below according to the relationship between R A and R B .

[0127] [Chemical formula 9]

[0128] [Case of reaction rate = 100%]

[0129] R A ≠R B

[0130]

[0131] R A =R B =R‘

[0132]

[0133] [Case of reaction rate < 100%]

[0134] R A ≠R B

[0135]

[0136] R A =R B =R'

[0137]

[0138] As a method for obtaining the above-mentioned polymer, for the polymerization of STEP1, only the dicarboxylic acid of the aforementioned (B) raw material is changed to the corresponding malonic acid, and it can be obtained by the method described in [Method for Manufacturing Polymer (B)] above. The polymer obtained by STEP1 can be used in the addition reaction of STEP2.

[0139] The base catalysts used in the substitution reaction of STEP2, such as inorganic base compounds like sodium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, and potassium phosphate, as well as organic amine compounds like triethylamine, pyridine, and N-methylmorpholine, can be used alone or in combination of two or more. The amount of these catalysts used relative to the molar amount of α-hydrogen in the starting material is 0.1 to 2.5 moles, preferably 0.2 to 2.0 moles.

[0140] The solvents used at this stage are not particularly restricted as long as they are inert to the above reaction. Examples include ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; aromatic solvents such as benzene, toluene, and xylene; acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and water. These solvents can be used alone or in combination. The range of these solvents is 0 to 2000 parts by mass relative to 100 parts by mass of the reactants. A reaction temperature of -50°C to approximately the boiling point of the solvent is preferred, with room temperature to 150°C being even more ideal. The reaction time can be appropriately selected from 0.1 to 100 hours.

[0141] As a reaction method, for example: the polymer obtained from STEP1 and having R A R B A batch feeding method using halides, methanesulfonates, or toluenesulfonates as part of the structure, and a catalyst, to produce the polymer obtained from STEP1 and having R A R B After dispersing or dissolving a partially structured halide, methanesulfonate, or toluenesulfonate, the catalyst is added in batches or diluted with a solvent and added dropwise; or after dispersing or dissolving the catalyst, it is added in batches or diluted with a solvent and added dropwise. This process is repeated with the addition of the polymer obtained from STEP1, where the substituents contain R... A R BMethods for the preparation of halides, methanesulfonates, or toluenesulfonates.

[0142] After the reaction is complete, the separation, washing, and filtration steps described above in the [Method for Manufacturing Polymer (B)] can be added.

[0143] The polymers used in the organic film forming compositions obtained by these methods are combined according to the required performance during the manufacturing process. A R B By adjusting the structure, proportions, and manufacturing methods of the polymer, polymers can be obtained to meet specific performance requirements. For example, polymers can be arbitrarily combined with side chain structures that improve planarization properties, or with fluorinated substituents that alter interfacial activity by controlling surface tension.

[0144] [(A) Resins containing aromatic rings]

[0145] (A) Resins containing aromatic rings are not specifically limited to any polymer containing aromatic rings, such as phenolic varnish resins, polyether resins, polyester resins, polystyrene resins, and polymethyl methacrylate resins. Here, phenolic varnish resin refers to a resin that can be synthesized by condensing compounds containing aromatic rings, aldehyde compounds, and compounds having benzyl alcohol units under acidic or alkaline conditions. Polyether resins and polyester resins refer to resins containing ethers or esters in repeating units. Polystyrene resins and polymethyl methacrylate resins are resins polymerized by free radical polymerization of styrene and monomers having methacrylic (acrylic) groups.

[0146] Furthermore, the resin containing aromatic rings in (A) of the present invention comprises, in addition to polymers with repeating units having specific structures as described above, compounds having structures having multiple aromatic compounds bonded together. The polymers having repeating units and the compounds having structures having multiple aromatic compounds bonded together are described below.

[0147] Aromatic rings not only contain structures formed by the condensation of benzene rings, such as benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, pyrene rings, benzo[a]phenanthrene rings, benzo[a]pyrene rings, and crown ene rings, but can also contain heterocycles such as pyrrole, pyridine, furan, and thiophene. Furthermore, they can be linked through hydrocarbon, ether, ester, and other bonds to form multiple aromatic rings such as biphenyl, diaryl ether, and fluorene.

[0148] The resin containing an aromatic ring (A) used in this invention includes, for example, the resins containing the following structures described in Japanese Patent Application Publication No. 2012-001687 and Japanese Patent Application Publication No. 2012-077295.

[0149] [Chemistry 10]

[0150]

[0151] In formula (1), the ring structures Ar1 and Ar2 represent benzene rings or naphthalene rings. X represents a single bond or an alkylene group having 1 to 20 carbon atoms. m represents 0 or 1. n represents any natural number with a molecular weight of less than 100,000. Furthermore, the notations in the formula apply only to this specific formula.

[0152] [Chemistry 11]

[0153]

[0154] In equation (2), the ring structures Ar1 and Ar2 represent benzene rings or naphthalene rings. n represents any natural number that makes the equivalent weight-average molecular weight of the polystyrene obtained by gel permeation chromatography less than 100,000. Furthermore, the notations in the equation apply only to this specific equation.

[0155] As the resin containing an aromatic ring used in this invention, further examples include resins containing the following structures as described in Japanese Patent Application Publication Nos. 2004-264710, 2005-043471, 2005-250434, 2007-293294, and 2008-065303.

[0156] [Chemistry 12]

[0157]

[0158] In equations (3) and (4), R 1 and R 2 R represents hydrogen atoms or alkyl and aryl groups having 1 to 3 carbon atoms. 3 The symbols represent alkyl, vinyl, allyl, or substituted aryl groups having 1 to 3 carbon atoms; n represents 0 or 1; and m represents 0, 1, or 2. Furthermore, the notations in the formula apply only to this formula.

[0159] [Chemistry 13]

[0160]

[0161] In equation (5), R1 is a monovalent atom or group other than hydrogen, and n is an integer from 0 to 4. However, when n is 2 to 4, multiple R1s may be the same or different. R2 and R3 are independently monovalent atoms or groups. X is a divalent group. Also, the notation in the equation applies only to this equation.

[0162] [Chemistry 14]

[0163]

[0164] 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 alkylene group with 1 to 20 carbon atoms, or an aryl group with 6 to 10 carbon atoms; it may also be any one of an ether, ester, lactone, or amide. 3 R 4 Each is a hydrogen atom or an epoxypropyl group. X represents any polymer of hydrocarbons containing an indene skeleton, cycloalkenes with 3 to 10 carbon atoms, or maleimides, and may also be any of ethers, esters, lactones, or carboxylic anhydrides. R 5 R 6 Each can be any one of hydrogen atom, fluorine atom, methyl group, or trifluoromethyl group. R 7 The carbon atom is any of the following: a linear, branched, or cyclic alkyl, hydroxyl, or alkoxycarbonyl group consisting of hydrogen atoms and carbon atoms numbering 1 to 6. p and q are integers from 1 to 4. r is an integer from 0 to 4. a, b, and c are each within 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. Furthermore, the notation in the formula applies only to this specific formula.

[0165] [Chemistry 15]

[0166]

[0167] In equation (7), R1 represents a hydrogen atom or a monovalent organic group, and R2 and R3 independently represent monovalent atoms or monovalent organic groups. Furthermore, the notations in the equation apply only to this specific equation.

[0168] The resin containing an aromatic ring (A) used in this invention can specifically include resins containing the following structures 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.

[0169] [Chemistry 16]

[0170]

[0171] In equations (8) and (9), R 1 ~R 8 Each group is independently composed of a hydrogen atom, a hydroxyl group, a substituted alkyl group with 1 to 6 carbon atoms, a substituted alkoxy group with 1 to 6 carbon atoms, a substituted alkoxycarboxyl group with 2 to 6 carbon atoms, a substituted aryl group with 6 to 10 carbon atoms, a hydroxyalkyl group with 1 to 6 carbon atoms, an isocyanate group, or an epoxypropyl group. m and n are positive integers. Furthermore, the notations in the formula apply only to this formula.

[0172] [Chemistry 17]

[0173]

[0174] In formula (10), R 1 and R 6 are a hydrogen atom or a methyl group. R 2 , R 3 , R 4 are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a hydroxyl group, an acetoxy group or an alkoxycarbonyl group, or an aryl group having 6 to 10 carbon atoms. R 5 is a condensed polycyclic hydrocarbon group having 13 to 30 carbon atoms, -O-R 7 , -C(=O)-O-R 7 , -O-C(=O)-R 7 , or -C(=O)-NR 8 -R 7 . m is 1 or 2, n is an integer from 0 to 4, and p is an integer from 0 to 6. R 7 is an organic group having 7 to 30 carbon atoms, R 8 is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms. Z is any one of a methylene group, -O-, -S-, -NH-. a, b, c, d, e are each in the range 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. Also, the notations in the formula are only applicable in this formula.

[0175] [Chemical formula 18]

[0176]

[0177] In formula (11), n represents 0 or 1. R 1 represents an optionally substituted methylene group, an optionally substituted alkylene group having 2 to 20 carbon atoms, or an optionally substituted arylene group having 6 to 20 carbon atoms. R 2 represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. R 3 to R 7 represent a hydroxyl group, an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted alkoxy group having 1 to 6 carbon atoms, an optionally substituted alkoxycarbonyl group having 2 to 10 carbon atoms, an optionally substituted aryl group having 6 to 14 carbon atoms, or an optionally substituted glycidyl ether group having 2 to 6 carbon atoms. R 9 represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Also, the notations in the formula are only applicable in this formula.

[0178] Formula (11), for example: the following resins.

[0179] [Chemical formula 19]

[0180]

[0181] [Chemistry 20]

[0182]

[0183] The resin containing an aromatic ring (A) used in this invention includes, for example, the resins containing the following structures described in Japanese Patent Application Publication No. 2007-199653, Japanese Patent Application Publication No. 2008-274250, and Japanese Patent Application Publication No. 2010-122656.

[0184] [Chemistry 21]

[0185]

[0186] In equation (12), R 1 With R 2 Independently composed of the same or different hydrogen atoms, a straight-chain, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, R 3 It is a single bond, or a straight-chain alkylene group with 1 to 30 carbon atoms, having a branched or cyclic structure; it may also have a bridged cyclic hydrocarbon group, a double bond, a heteroatom, or an aromatic group with 6 to 30 carbon atoms. R 4 With R 5 Each atom is independently a hydrogen atom or an epoxypropyl group, and n is an integer from 1 to 4. Furthermore, the notation in the formula applies only to this formula.

[0187] [Chemistry 22]

[0188]

[0189] In equation (13), R 1 With R 2 Independently composed of the same or different hydrogen atoms, a straight-chain, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, R 3 It is a single bond, or a straight-chain alkylene group with 1 to 30 carbon atoms, having a branched or cyclic structure; it may also have a bridged cyclic hydrocarbon group, a double bond, a heteroatom, or an aromatic group with 6 to 30 carbon atoms. R 4 With R 5 Each is independently a hydrogen atom or an epoxypropyl group, R 6 It is a single bond, or a straight-chain or branched alkylene group having 1 to 10 carbon atoms. Furthermore, the notations in the formula apply only to this formula.

[0190] [Chemistry 23]

[0191]

[0192] In equation (14), ring Z 1 and ring Z2 represents a condensed polycyclic aromatic hydrocarbon ring, R 1a , R 1b , R 2a , and R 2b are the same or different and represent substituents. k1 and k2 are the same or different and represent an integer of 0 or 1 to 4, m1 and m2 each represent an integer of 0 or 1 or more, and n1 and n2 each represent an integer of 0 or 1 or more. However, n1 + n2 ≥ 1. Also, the notations in the formula are only applicable in this formula.

[0193] [Chemical formula 24]

[0194]

[0195] 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. R 3 , R 4 are each a hydrogen atom or glycidyl, and R 5 is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, and R 6 , R 7 are benzene rings or naphthalene rings. p and q are each 1 or 2. n is 0 < n ≤ 1. Also, the notations in the formula are only applicable in this formula.

[0196] Formula (15), for example: the following resins.

[0197] [Chemical formula 25]

[0198]

[0199] [Chemical formula 26]

[0200]

[0201] [Chemical formula 27]

[0202]

[0203] [Chemical formula 28]

[0204]

[0205] The resin (A) containing an aromatic ring used in the present invention, for example, resins having the following structures described in Japanese Patent Laid-Open No. 2012-214720 etc.

[0206] [Chemical formula 29]

[0207]

[0208] In equation (16), the ring structures Ar1 and Ar2 represent benzene rings or naphthalene rings. x and z each independently represent 0 or 1. Furthermore, the notation in the equation applies only to this equation.

[0209] The resin containing an aromatic ring (A) used in this invention is, for example, the resin described in Japanese Patent Application Publication No. 2014-29435.

[0210] [Chemistry 30]

[0211]

[0212] In formula (17), A represents a structure having carbazole, B represents a structure having an aromatic ring, and C represents a hydrogen atom, an alkyl group, or a structure having an aromatic ring. B and C can form a ring with each other. The combined structure of A, B, and C has 1 to 4 carboxyl groups or their salts, or carboxylic acid ester groups. Furthermore, the notations in the formula are only applicable to this formula.

[0213] Furthermore, the resin containing aromatic rings (A) used in this invention is, for example, the polymer disclosed in International Publication No. 2012 / 077640, which contains a unit structure represented by formula (18) and a unit structure represented by formula (19), and the ratio of the unit structure represented by formula (18) to the unit structure represented by formula (19) is 3 to 97: 97 to 3 in molar ratio.

[0214] [Chemistry 31]

[0215]

[0216] In formula (18), R1 and R2 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a hydroxyl group, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an aryl group with 6 to 40 carbon atoms, or a combination of these groups that may contain ether bonds, ketone bonds, or ester bonds. R3 represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an aryl group with 6 to 40 carbon atoms, or a combination of these groups that may contain ether bonds, ketone bonds, or ester bonds. R4 represents a hydrogen atom, or an aryl group with 6 to 40 carbon atoms that may be substituted with a halogen atom, a nitro group, an amino group, or a hydroxyl group. R5 represents a hydrogen atom, or an alkyl group with 1 to 10 carbon atoms, an aryl group with 6 to 40 carbon atoms that may be substituted with a halogen atom, a nitro group, an amino group, or a hydroxyl group. R4 and R5 may also form a ring with each other. n1 and n2 each represent an integer from 1 to 3. Furthermore, the notation in the formula applies only to this formula.

[0217] [Chemistry 32]

[0218]

[0219] In formula (19), Ar represents an aromatic ring 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 groups that may contain 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 a ring with each other. n6 represents an integer from 1 to p, and n7 represents an integer from p to n6. Here, p represents the maximum number of Ar groups that can be substituted into an aromatic ring group. Also, the notation in the formula applies only to this formula.

[0220] The resin containing aromatic rings (A) used in this invention is, for example, the polymer containing the unit structure represented by the following formula (20) as described in International Publication No. 2010 / 147155.

[0221] [Chemistry 33]

[0222]

[0223] In formula (20), R1 and R2 are each selected from the group consisting of hydrogen atoms, halogen groups, nitro groups, amino groups, hydroxyl groups, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 40 carbon atoms, and combinations thereof, and the alkyl, alkenyl, or aryl group may also contain ether bonds, ketone bonds, or ester bonds. R3 is selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 40 carbon atoms, and combinations thereof. The group consisting of alkyl, alkenyl, or aryl groups, where R4 represents an aryl or heterocyclic group with 6 to 40 carbon atoms that may also be substituted with a halogen, nitro, amino, or hydroxyl group, and R5 represents a hydrogen atom, or an alkyl, aryl, or heterocyclic group with 1 to 10 carbon atoms that may also be substituted with a halogen, nitro, amino, or hydroxyl group. R4 and R5 may also form a ring with the carbon atoms to which they are bonded, and n1 and n2 are integers from 1 to 3. Furthermore, the notations in the formula apply only to this formula.

[0224] The resin containing an aromatic ring used in this invention (A) includes, for example, phenolic varnish resin obtained by reacting one or more of the following phenols, such as phenol, cresol, xylenol, catechol, resorcinol, hydroquinone, gallol, pyrogallol, and resorcinol, with one or more of the following aldehyde sources, such as formaldehyde, trioxymethylene, and trioxane, using an acidic catalyst; and resin containing a repeating unit structure represented by the following formula (21), as described in International Publication No. 2012 / 176767.

[0225] [Chemistry 34]

[0226]

[0227] In formula (21), A represents a hydroxylated phenylene derived from polyhydroxybenzene, and B represents a monovalent condensed aromatic hydrocarbon cyclogroup formed by the condensation of 2 to 6 benzene rings. Furthermore, the notations in the formula apply only to this specific formula.

[0228] The resin containing aromatic rings (A) used in this invention includes, for example, phenolic varnish resins having fluorene or tetrahydrospiroindene structures as described in Japanese Patent Application Publication Nos. 2005-128509, 2006-259249, 2006-259482, 2006-293298, and 2007-316282, as well as resins containing repeating unit structures represented by formula (22-1) or (22-2).

[0229] [Chemistry 35]

[0230]

[0231] In equations (22-1) and (22-2), R 1 R 2 R 6 R 7 Independently comprising a hydrogen atom, a straight-chain, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an allyl group, or a halogen atom, R 3 R 4 R 8 R 9 Independently comprising a hydrogen atom, a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a straight-chain, branched, or cyclic alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an epoxypropyl group, R 5 R 14 Independently, it consists of a hydrogen atom, a straight-chain, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. n, m, p, and q are integers from 1 to 3. R 10 ~R 13Independently, it consists of 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 notations in the formula apply only to this formula.

[0232] The resin containing an aromatic ring used in this invention (A) is, for example, a reaction product obtained by the method described in Japanese Patent Application Publication No. 2012-145897. More specifically, it is, for example, a polymer obtained by condensing one or more compounds of the following formula (23-1) and / or (23-2) with one or more compounds of the following formula (24-1) and / or (24-2) and / or their equivalents.

[0233] [Chemistry 36]

[0234]

[0235] In equations (23-1) and (23-2), R 1 ~R 8 Independently, these can be hydrogen atoms, halogen atoms, hydroxyl groups, isocyanates, epoxypropoxy groups, carboxyl groups, amino groups, alkoxy groups with 1 to 30 carbon atoms, alkoxycarbonyl groups with 1 to 30 carbon atoms, alkanoyloxy groups with 1 to 30 carbon atoms, or substituted organic groups with 1 to 30 carbon atoms, whether saturated or unsaturated. Furthermore, they can also be intramolecularly derived from R... 1 ~R 4 Or R 5 ~R 8 Two randomly selected substituents are bonded together and further form cyclic substituents. Also, the notation in the formula applies only to this formula.

[0236] [Chemistry 37]

[0237]

[0238] In formulas (24-1) and (24-2), Q is an organic group with 1 to 30 carbon atoms that can also be substituted, and two Q groups can be arbitrarily selected within the molecule to form a cyclic substituent. n1 to n6 are the numbers of each substituent, n1 to n6 = 0, 1, and 2, except for hydroxybenzaldehyde in formula (24-1). Furthermore, formula (24-2) conforms to the relationships 0 ≤ n3 + n5 ≤ 3, 0 ≤ n4 + n6 ≤ 4, and 1 ≤ n3 + n4 ≤ 4. Also, the notation in the formula applies only to this specific formula.

[0239] Furthermore, examples include one or more compounds represented by formula (23-1) and / or (23-2), one or more compounds and / or their equivalents represented by formula (24-1) and / or (24-2), and polymers obtained by condensation of one or more compounds and / or their equivalents represented by formula (25).

[0240] [Chemistry 38]

[0241] Y-CHO (25)

[0242] In formula (25), Y is a hydrogen atom or a monovalent organic group with 30 or fewer carbon atoms that may also have substituents. Formula (25) is different from formulas (24-1) and (24-2). Furthermore, the notations in the formulas are only applicable to this formula.

[0243] The resin containing an aromatic ring (A) used in this invention includes, for example, the compound containing the following structure disclosed in Japanese Patent Application Publication No. 2017-119671.

[0244] [Chemistry 39]

[0245]

[0246] In formula (26-1), R is a single bond or an organic group with 1 to 50 carbon atoms, X is the group represented by formula (26-2), and m1 is an integer satisfying 2 ≤ m1 ≤ 10. Furthermore, the notation in the formula applies only to this specific formula.

[0247] [Chemistry 40]

[0248]

[0249] In the formula, X 2 It is a divalent organic group with 1 to 10 carbon atoms, where n1 is 0 or 1, n2 is 1 or 2, and X 3 For the group represented by the following formula (26-3), n5 is 0, 1, or 2. Also, the notation in the formula applies only to this formula.

[0250] [Chemistry 41]

[0251]

[0252] In the formula, R 10 The group consisting of a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms may also be replaced by a methyl or methoxy group. Furthermore, the notations in the formula apply only to this specific formula.

[0253] Compounds containing the above structure, for example: the following compounds.

[0254] [Chemistry 42]

[0255]

[0256] The resin containing an aromatic ring (A) used in this invention can be exemplified by polymers having repeating units represented by the following formula (27-1) as described in Japanese Patent Application Publication No. 2019-044022.

[0257] [Chemistry 43]

[0258]

[0259] In formula (27-1), AR1 and AR2 are benzene rings or naphthalene rings that may also have substituents, R 1 R 2 Each is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, R 1 With R 2 When R is an organic group, 1 With R 2 Cyclic organic groups can also be formed through intramolecular bonding. n is 0 or 1. When n = 0, AR1 and AR2 do not form a bridge between their aromatic rings via Z. When n = 1, AR1 and AR2 form a bridge between their aromatic rings via Z. Z is a single bond or any of the following formula (27-2). Y is a group represented by the following formula (27-3). Furthermore, the notations in the formula apply only to this formula.

[0260] [Chemistry 44]

[0261]

[0262] [Chemistry 45]

[0263]

[0264] In the formula, R 3 R is a single bond or a divalent organic group having 1 to 20 carbon atoms. 4 A hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms is represented by a dashed line, indicating an atomic bond. Furthermore, the notation in the formula applies only to this specific formula.

[0265] Polymers having repeating units represented by the above formula (27-1), for example: the following polymers.

[0266] [Chemistry 46]

[0267]

[0268] [Chemistry 47]

[0269]

[0270] Furthermore, only one type of resin containing aromatic rings can be used, or multiple resins with different structures can be combined. By combining multiple resins containing aromatic rings, crystallization can be suppressed more effectively than when using a single resin, thereby improving thermal fluidity and flatness.

[0271] From the viewpoint of thermosetting properties, the resin containing an aromatic ring in (A) above is preferably one containing hydrogen at the diarylmethylene position or hydrogen at the triphenylmethyl position.

[0272] The hydrogen atom at the diarylmethylene position, as shown in the following formula, is the hydrogen atom remaining in the structure where two hydrogen atoms of methane are substituted to form an aryl group. The hydrogen atom at the triphenylmethyl position is the hydrogen atom remaining in the structure where three hydrogen atoms of methane are substituted to form an aryl group. By including these as part of the structure, an oxidative coupling reaction accompanied by thermal dehydrogenation can occur, and the film can be hardened by a cross-linking reaction. In the following formula, phenyl is given as a specific example for aryl groups, but it is not limited to this.

[0273] [Chemistry 48]

[0274]

[0275] The aromatic ring substituents in the resin containing the aromatic ring in (A) above, such as hydroxyl, ether, carboxyl, ketone, amino, alkylamino, halogen, alkyl, alkenyl, alkynyl and other substituents, are not particularly limited in terms of the substituents that can be used.

[0276] The resin containing an aromatic ring in (A) mentioned above, if it contains hydroxyl groups as substituents, not only is the aforementioned oxidative coupling easier to occur, but the dehydration reaction caused by the hydroxyl groups also occurs, thus forming a film with a high density of crosslinked groups, providing a film with excellent processing resistance. Furthermore, due to the presence of hydroxyl groups and their strong interaction with the β-diketone structure of (B), the sublimation of the polymer containing the β-diketone structure in (B) can be inhibited, also providing a film with excellent film-forming properties.

[0277] The resin containing an aromatic ring in (A) above is preferably a polymer containing a repeating unit selected from those having the following formulas (P-1) and (P-2), and compounds represented by formulas (P-3) to (P-6).

[0278] [Chemistry 49]

[0279]

[0280] In equations (P-1) and (P-2) above, R represents a hydrogen atom or a substituted or unsubstituted benzene ring or naphthalene ring. In equations (P-1) to (P-6), R1 represents a hydrogen atom or a saturated or unsaturated hydrocarbon group with 1 to 20 carbon atoms. In equations (P-1), (P-3), (P-4), and (P-5), m1 represents an integer of 0 or 1. In equations (P-1), (P-3), (P-4), and (P-6), n1 represents an integer of 1 to 4. In equations (P-2) and (P-5), n2 represents an integer of 1 or 2. In equations (P-3) and (P-5), n3 represents an integer of 0 to 2. In equations (P-3) to (P-6), l represents an integer of 5 to 20. However, l represents the feed ratio.

[0281] In formulas (P-1) to (P-2) above, R is a hydrogen atom or a substituted or unsubstituted benzene ring or naphthalene ring. From the viewpoint of obtaining raw materials, it is preferable to have a hydrogen atom or a substituted or unsubstituted benzene ring. Furthermore, when it is a benzene ring, considering the thermosetting properties, the following structure is preferable.

[0282] [Transformation 50]

[0283]

[0284] In the above formula, * represents the bonding portion with the methylene part, and R1 is the same as R1 in formulas (P-1) to (P-6) above.

[0285] In (P-1) to (P-6), R1 is a hydrogen atom or a saturated or unsaturated hydrocarbon group with 1 to 20 carbon atoms. However, considering the sublimation inhibition caused by the interaction with polymers containing β-diketone structures in the repeating unit (B), a hydrogen atom is preferred. Considering the curability of the resin alone, a hydrogen atom or a hydrocarbon group containing unsaturated bonds is preferred. Considering the thermal fluidity of the resin alone, a long-chain saturated hydrocarbon group is preferred.

[0286] Specific examples of R1 other than hydrogen atoms in (P-1) to (P-6) can be listed below, but are not limited to these structures.

[0287] [Chemistry 51]

[0288]

[0289] In the above formula, * represents the bond portion with the oxygen atom.

[0290] [Method for manufacturing resins (P-1) to (P-2) containing aromatic rings]

[0291] Formulas (P-1) to (P-2) above involve a condensation reaction (STEP1) using a compound (X) containing an aromatic ring with a hydroxyl group as a substituent, formaldehyde or a benzene ring or naphthalene ring containing an aldehyde group as a substituent, and a catalyst. Subsequently, when R1 is partially etherified with respect to the hydrocarbon group, the resulting condensate can be etherified using a haloalkane, toluenesulfonate alkyl ester, or methanesulfonate alkyl ester (Z) and a catalyst (STEP2). However, the STEP2 reaction can also be omitted, and the final resin can be obtained entirely in the form of hydroxyl groups. When carrying out the STEP2 reaction, the input ratio of (Z) is 0.1 to 0.9 equivalents when the hydroxyl group is set to 1 equivalent, preferably 0.3 to 0.7 equivalents. (R, R1, n1, m1 are as described above; X represents a halogen group, methanesulfonyl group, or toluenesulfonyl group. For simplicity, (P-1) is used as an example in the reaction formula.)

[0292] [Chemistry 52]

[0293] (STEP1)

[0294]

[0295] [Chemistry 53]

[0296] (STEP2)

[0297]

[0298] The condensation reaction described above, which uses catalysts (X) and (Y), can typically be carried out in solvent-free conditions or in solvents using acid or base as catalysts, at room temperature or under cooling or heating conditions as needed. Solvents that can be used include methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether and other alcohols, diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane and other ethers, dichloromethane, chloroform, dichloroethane, trichloroethylene and other chlorinated solvents, hexane, heptane, benzene, toluene, xylene, cumene and other hydrocarbons, acetonitrile and other nitriles, acetone, ethyl methyl ketone, isobutyl methyl ketone and other ketones, ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate and other esters, γ-butyrolactone and other lactones, dimethyl sulfoxide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamine and other nonprotic polar solvents, which can be used alone or in combination of two or more. These solvents can be used in the range of 0 to 3000 parts by mass relative to 100 parts by mass of the reactants.

[0299] The acid catalysts that can be used include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acids; organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxyl, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyldimethoxytin, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium methoxide (IV), titanium ethoxide (IV), titanium isopropoxide (IV), and titanium oxide (IV). Suitable alkaline catalysts include inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, lithium hydride, sodium hydride, potassium hydride, and calcium hydride; alkyl metals such as methyllithium, n-butyllithium, methylmagnesium chloride, and ethylmagnesium bromide; alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide; and organic bases such as triethylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, and 4-dimethylaminopyridine. The amount used relative to the raw materials is 0.001–100% by weight, preferably 0.005–50% by weight. The reaction temperature is preferably around -50°C to the boiling point of the solvent, and room temperature to 130°C is even more ideal.

[0300] The condensation reaction can be carried out by the following methods: feeding (X), (Y), and catalyst in batches; adding (Y) and a solution of (Y) dissolved in a reaction solvent dropwise in the presence of (X) and the catalyst; or adding (X) and a solution of (X) dissolved in a reaction solvent dropwise in the presence of (Y) and the catalyst. In this case, when synthesizing the resins represented by formulas (P-1) and (P-2) above, the amount of (Y) used relative to (X) is preferably 0.7 to 1.2 equivalents, more preferably 0.8 to 1.05 equivalents. When synthesizing the resins represented by formulas (P-3) to (P-6) above, the amount of (Y) relative to (X) is preferably 5.0 to 20 equivalents, more preferably 6.0 to 15.0 equivalents. After the condensation reaction is completed, in order to remove unreacted raw materials, catalysts, etc., present in the system, methods may be used depending on the nature of the raw materials used and the reaction products obtained. These methods include raising the temperature of the reactor to 130–230°C and removing volatile components at approximately 1–50 mmHg; adding a suitable unsuitable solvent or water to redefine the polymer; or fractionating the polymer. Alternatively, a step may be added to dissolve the obtained condensate in methyl isobutyl ketone, ethyl acetate, etc., and then washing with water.

[0301] For subsequent etherification, it can usually be carried out in solvent-free or solvent-based environments using a base as a catalyst, at room temperature or under cooling or heating as needed. The solvents that can be used include, for example, methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether and other alcohols, diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane and other ethers, dichloromethane, chloroform, dichloroethane, trichloroethylene and other chlorinated solvents, hexane, heptane, benzene, toluene, xylene, cumene and other hydrocarbons, acetonitrile and other nitriles, acetone, ethyl methyl ketone, isobutyl methyl ketone and other ketones, ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate and other esters, γ-butyrolactone and other lactones, dimethyl sulfoxide, N,N-dimethylformamide, hexamethylphosphoryltriamine, N-methylpyrrolidone and other nonprotic polar solvents. They can be used alone or in combination of two or more. These solvents can be used in the range of 0 to 2,000 parts by mass relative to 100 parts by mass of the reactants.

[0302] Suitable alkaline catalysts include inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, lithium hydride, sodium hydride, potassium hydride, and calcium hydride; alkyl metals such as methyllithium, n-butyllithium, methylmagnesium chloride, and ethylmagnesium bromide; alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide; and organic bases such as triethylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, and 4-dimethylaminopyridine. The optimal amount of catalyst used relative to the hydroxyl groups in the starting materials for the condensation reaction is 0.5–1.5 equivalents, more preferably 1.0–1.2 equivalents. The optimal reaction temperature is -50°C to approximately the boiling point of the solvent, with room temperature to 130°C being more ideal.

[0303] Regarding the reaction method, the following methods are available: batch feeding of the above condensate with R2-X(Z) and the catalyst; dropwise addition of (Z) or a solution of (Z) dissolved in a reaction solvent in the presence of the above condensate and the catalyst; and dropwise addition of the above condensate dissolved in a reaction solvent in the presence of (Z) and the catalyst. In this case, the amount of (Z) used is preferably 0.1 to 0.9 equivalents relative to the amount of hydroxyl groups in the above condensate, more preferably 0.3 to 0.7 equivalents.

[0304] After etherification, the same separation, washing, and filtration steps described above in the [Method for Manufacturing Polymer (B)] can be added to polymer (B).

[0305] [Manufacturing method of resins (P-3) to (P-6) containing aromatic rings]

[0306] The compounds represented by formulas (P-3) to (P-6) above are synthesized by condensation reaction of an aromatic ring containing a hydroxyl group (X), a benzene ring containing hydroxymethyl or methoxymethyl, a naphthyl ring, a diphenyl ether, etc. (W) using a catalyst (STEP1). Then, an etherification reaction is used to introduce R1. The condensate obtained from the reaction of STEP1 is then etherified with a haloalkane, toluenesulfonate alkyl ester, or methanesulfonate alkyl ester (Z) using a catalyst to synthesize (STEP2). However, the STEP2 reaction may be omitted, and the final resin is obtained entirely in the hydroxyl form. When carrying out the STEP2 reaction, the feed ratio of (Z) is 0.1 to 0.9 equivalents, more preferably 0.3 to 0.7 equivalents, when 1 equivalent of hydroxyl group is assumed. (R, R1, n1, n3, m1, l are as described above; X represents a halogen group, methanesulfonyl group, or toluenesulfonyl group. For simplicity, the reaction formula is described using (P-3) as an example.)

[0307] [Chemistry 54]

[0308] (STEP1)

[0309]

[0310] [Chemistry 55]

[0311] (STEP2)

[0312]

[0313] The notation of resins containing aromatic rings in formulas (P-3) to (P-6) in this specification is explained.

[0314] The products in the condensation reactions of (X) and (W) above are described as having condensed an aromatic ring containing hydroxymethyl or methoxymethyl relative to one parent nucleus. However, in this specification, 1 represents the feed ratio of the synthetic raw materials in the synthesis reaction of resins (P-3) to (P-6) containing aromatic rings. For example, when 1 equivalent of 2,3-dihydroxynaphthalene is used for (X) and 12 equivalents of 4-hydroxybenzyl alcohol is used for (W), it is recorded as 12.

[0315] In the synthesis reaction of this compound, in the reaction of condensation of 2,3-dihydroxynaphthalene (X) with 4-hydroxybenzyl alcohol (W) (reaction (a)), the most reactive position of 2,3-dihydroxynaphthalene (X) has 6 hydrogen atoms in its aromatic ring, so it will react with a maximum of only 6 equivalents of 4-hydroxybenzyl alcohol. On the other hand, a condensation reaction of 4-hydroxybenzyl alcohol (W) with itself also occurs simultaneously with this reaction (reaction (b)). As a result, the product of this reaction is a complex mixture of the two reactions (a) and (b) above. Therefore, for the product of this reaction, the amount of 4-hydroxybenzyl alcohol reacted is equal to the feed equivalent, let the feed amount be 1, and the product is represented by the following formula (c).

[0316] In this synthetic reaction, 2,3-dihydroxynaphthalene acts as a sealant in the condensation reaction between it and 4-hydroxybenzyl alcohol, and is believed to have the function of adjusting the molecular weight (Mw) of the product, preventing the increase in molecular weight and the decrease in resin fluidity.

[0317] As mentioned above, 2,3-dihydroxynaphthalene does not possess reactive functional groups. Therefore, the reaction occurs when 0.5 equivalents of propargyl bromide, as a haloalkane, are reacted relative to 1 equivalent of the total hydroxyl groups in the condensed resin, resulting in the following formula. In this case, since the hydroxyl groups of the resin are randomly introduced, it becomes a mixture with different hydroxyl equivalents, and the ratio of the total hydroxyl groups of the resin to propargyl ether is 0.5:0.5, meaning that 50% is propargylated.

[0318] [Chemistry 56]

[0319] (STEP1)

[0320]

[0321] [Chemistry 57]

[0322] (STEP2)

[0323]

[0324] The condensation reaction described above, which uses (X), (W), and catalysts, can be prepared by simply changing (Y) to (W) using the method described in (STEP1) above.

[0325] For resins containing aromatic rings (A) obtained in this manner, the weight-average molecular weight (Mw) of polystyrene obtained by gel permeation chromatography is preferably between 1,000 and 20,000. If the weight-average molecular weight (Mw) is within this range, it is less likely to sublimate at high temperatures, thus avoiding poor film formation. It can also suppress the deterioration of flatness caused by poor packing and poor thermal flowability due to excessively large molecular weight.

[0326] The following describes the components that may be contained in the organic film-forming composition of the present invention, other than the resin containing an aromatic ring in (A) and the polymer having a β-diketone structure in the repeating unit in (B).

[0327] <(C) Solvent>

[0328] The solvent (C) that can be used in the organic film forming composition of the present invention is not particularly limited as long as it is a solvent that can be dissolved by one or more of the polymers containing aromatic rings (A), polymers having a β-diketone structure in the repeating unit (B), crosslinking agents, surfactants, or other additives.

[0329] Specifically, the organic solvent described in paragraphs

[0091] to

[0092] of Japanese Patent Application Publication No. 2007-199653 may be added. Furthermore, it is preferable to use propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, 2-heptanone, cyclopentanone, cyclohexanone and γ-butyrolactone, or a mixture containing one or more of these.

[0330] The amount of organic solvent incorporated is preferably 200 to 10,000 parts by weight relative to 100 parts by weight of the resin containing aromatic rings (A), and more preferably 250 to 5,000 parts by weight.

[0331] High-boiling-point solvents

[0332] In the organic film forming composition of the present invention, the solvent mentioned in (C) can be a mixture of one or more solvents with a boiling point of less than 180°C and one or more solvents with a boiling point of 180°C or higher (high boiling point solvents).

[0333] High-boiling-point solvents are acceptable as long as they can dissolve the components of the resin containing aromatic rings of this invention. There are no particular limitations on hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc. Specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, and 2-ethyl-1,3-hexanediol. Alkanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, n-nonyl acetate, monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, tri... Ethylene glycol n-butyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, di... Propylene 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, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, etc., can be used alone or in combination.

[0334] The high-boiling-point solvent, in conjunction with the heat treatment temperature of the composition for forming the organic film of the present invention, can be appropriately selected from the above, for example. A boiling point of 180°C to 300°C is preferred, and 200°C to 300°C is more ideal. With such a boiling point, there is no risk of excessively rapid evaporation during baking (heat treatment), thus sufficient thermal fluidity can be obtained during film formation, which is believed to enable the formation of an organic film with excellent embedding / planarization characteristics. Furthermore, with such a boiling point, it will not remain in the film after baking without evaporation, thus not adversely affecting film properties such as etching resistance.

[0335] Furthermore, when using high-boiling-point solvents, the mixing amount is preferably 1 to 30 parts by mass relative to 100 parts by mass of organic solvents with a boiling point not reaching 180°C. With such a mixing amount, sufficient thermal fluidity can be imparted during baking, and no residue will remain in the film, thus preventing degradation of film properties such as etching resistance.

[0336] The aforementioned composition is an organic film that can be used in the multilayer resist method, and may contain one or more of (D) crosslinking agent and (E) surfactant.

[0337] The following describes (D) the crosslinking agent and (E) the surfactant mentioned above.

[0338] [(D) Crosslinking agent]

[0339] In the organic film-forming composition of the present invention, in order to improve film density and further suppress cross-mixing with the upper layer of the resist film, it may contain more (D) crosslinking agent. There are no particular limitations on the crosslinking agent, and various known crosslinking agents can be widely used. Examples include melamine-based crosslinking agents, acrylate-based crosslinking agents, glycourea-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, phenol-based crosslinking agents (e.g., hydroxymethyl or alkoxymethyl type crosslinking agents of polynuclear phenols), epoxy-based crosslinking agents, and oxetane-based crosslinking agents. The content of the aforementioned (D) crosslinking agent is preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight, relative to 100 parts by weight of one or more polymers containing aromatic rings as described in (A).

[0340] Melamine is a crosslinking agent, specifically including hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy and / or hydroxy substituted forms of these, and some of their self-condensing forms.

[0341] Acrylic ester crosslinking agents, specifically dinepentyl tert-hexaacrylate, can be listed as an example.

[0342] Glycourea is a crosslinking agent, specifically including tetramethoxymethylated glycourea, tetrabutoxymethylated glycourea, their alkoxy and / or hydroxy substituted forms, and their partial self-condensing forms.

[0343] Benzoguanidine is a crosslinking agent. Specifically, examples include tetramethoxymethylated benzoguanidine, tetrabutoxymethylated benzoguanidine, their alkoxy and / or hydroxy substituted forms, and their partial self-condensation forms.

[0344] Urea crosslinking agents, specifically, include dimethoxymethylated dimethoxyethylurea, its alkoxy and / or hydroxy substituted forms, and some of these self-condensing forms.

[0345] β-hydroxyalkylamide crosslinking agents, specifically N,N,N',N'-tetra(2-hydroxyethyl)hexamethylenediamide, can be listed.

[0346] Isocyanurate is a crosslinking agent; specifically, examples include trichloropropyl isocyanurate and triallyl isocyanurate.

[0347] Aziridine is a crosslinking agent, specifically, examples include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-dihydroxymethylbutanol-tris[3-(1-aziridine)propionate].

[0348] Oxazoline crosslinking agents, specifically, include 2,2'-isopropylidene bis(4-benzyl-2-oxazoline), 2,2'-isopropylidene bis(4-phenyl-2-oxazoline), 2,2'-isopropylidene bis(4-phenyl-2-oxazoline), 2,2'-methylene bis-4,5-diphenyl-2-oxazoline, 2,2'-methylene bis-4-phenyl-2-oxazoline, 2,2'-methylene bis-4-tert-butyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylene bis(2-oxazoline), 1,4-phenylene bis(2-oxazoline), and 2-isopropylidene oxazoline copolymers.

[0349] Polynuclear phenolic crosslinking agents, specifically, can be listed as compounds represented by the following formula (XL-1).

[0350] [Chem.58]

[0351]

[0352] In the formula, S is a single bond or an s-valent hydrocarbon group with 1 to 20 carbon atoms. R6 is a hydrogen atom or an alkyl group with 1 to 20 carbon atoms. s is an integer from 1 to 5. The definition of R6 here refers to R6 in formula (XL-1).

[0353] S is a single bond or an s-valent hydrocarbon group having 1 to 20 carbon atoms. s is an integer from 1 to 5, preferably 2 or 3. Specifically, S is, for example, a group from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, or eicosane in which q hydrogen atoms have been removed. R6 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Alkyl groups having 1 to 20 carbon atoms, specifically, are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, or eicosyl, with hydrogen atoms or methyl being preferred.

[0354] Examples of compounds represented by formula (XL-1) are specifically listed below. Among them, considering the curability of organic films and the improvement of film thickness uniformity, triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and the hexamethoxymethylated form of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred. R6 is as described above.

[0355] [Chemistry 59]

[0356]

[0357] [Transformation 60]

[0358]

[0359] Epoxy-based crosslinking agents and oxetane-based crosslinking agents, such as monomeric and polymeric types, are examples of which are listed below, but are not limited to these.

[0360] [Chemistry 61]

[0361]

[0362] The aforementioned compounds are also commercially available, but epoxy-based crosslinking agents and oxetane-based crosslinking agents can also be obtained by reacting hydroxyl groups with epibromool, 3-bromomethyloxetane, etc., according to the following formula. In the following formula, R is a substituted or unsubstituted monovalent organic group with 1 to 20 carbon atoms (saturated or unsaturated with 2 to 20 carbon atoms), a substituted or unsubstituted aryl group with 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group with 7 to 31 carbon atoms. Alternatively, the hydroxyl groups can be left unreacted. In this case, it is preferable that the number of epoxy + oxetane groups > the number of hydroxyl groups, and more preferably, the number of epoxy + oxetane groups > the number of hydroxyl groups * 2. Furthermore, it is ideal that the content of these compounds is 5 to 50 parts by mass relative to 100 parts by mass of the resin containing the aromatic ring described in (a) above, and more preferably 10 to 40 parts by mass.

[0363] [Chemistry 62]

[0364]

[0365] The above reactions can utilize compounds with hydroxyl groups, specifically listed below, but are not limited to these.

[0366] [Chemistry 63]

[0367]

[0368] Furthermore, in terms of polymer types, specifically, polymers in which the mole fraction of repeating units represented by the following formulas (XL-2) and (XL-3) is 20% or more can be listed. When the total mole fraction of the structural units represented by formulas (XL-2) and (XL-3) is not 100%, then for other structural units, any combination of structural units from other acrylates, other methacrylates, other acrylamides, other methacrylamides, crotonates, maleates, itaconic acid, etc., α,β-unsaturated carboxylic acids; methacrylic acid, acrylic acid, maleic acid, itaconic acid, etc., α,β-unsaturated lactones; methacrylonitrile; 5,5-dimethyl-3-methylene-2-oxotetrahydrofuran, etc., α,β-unsaturated lactones; norundenene derivatives, tetracyclic [4.4.0.12,5.17,10]dodecene derivatives, etc., cyclic alkenes; maleic anhydride, itaconic anhydride, etc., α,β-unsaturated carboxylic anhydrides; allyl ethers; vinyl ethers; vinyl esters; vinyl silanes can be used. Furthermore, it is preferable that these polymers have a weight-average molecular weight of 1,000 to 20,000 and a GPC dispersion of 2.0 or less. Also, it is preferable that the content of these compounds is 5 to 50 parts by mass relative to 100 parts by mass of the aforementioned resin containing aromatic rings (A), and more preferably 10 to 40 parts by mass.

[0369] [Chemistry 64]

[0370]

[0371] In the formula, R7 is a hydrogen atom or a methyl group, R8 is a hydrogen atom or a group selected from formulas (2-1) to (2-3) below, and L1 represents a single bond, a divalent organic group containing -C(=O)O- or C(=O)NH- or C(=O)NCH3-.

[0372] In the above formula (XL-2), from the viewpoint of hardening, it is better for the number of groups in (2-1) to (2-3) to be greater than the number of hydrogen atoms, and more preferably the number of groups in (2-1) to (2-3) to be greater than the number of hydrogen atoms * 2.

[0373] [Chemistry 65]

[0374]

[0375] In the formula, R7 is a hydrogen atom or a methyl group, and R9 is a group selected from formulas (2-1) to (2-3).

[0376] [Chemistry 66]

[0377]

[0378] In the above formula, the dashed lines represent atomic bonds.

[0379] <(E) Surfactants>

[0380] In the organic film forming composition of the present invention, a surfactant (E) may be added to improve the coatability of spin coating. The surfactant, for example, may be one described in

[0142] to

[0147] of Japanese Patent Application Publication No. 2009-269953. The amount of surfactant added is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts, relative to 100 parts by weight of one or more polymers containing an aromatic ring as described in (A).

[0381] <Methods for forming organic films>

[0382] The present invention provides an organic film forming method, which is an organic film forming method used as a manufacturing step of a semiconductor device, wherein the above-mentioned organic film forming composition is spin-coated on a substrate to be processed, and the substrate coated with the organic film forming composition is heat-treated at a temperature of 100°C to 600°C for 10 to 600 seconds to form a hardened film.

[0383] Furthermore, an organic film forming method is provided, which is an organic film forming method used as a manufacturing step of a semiconductor device, wherein the above-mentioned organic film forming composition is spin-coated on a substrate to be processed, and the substrate coated with the organic film forming composition is heat-treated in a gas environment with an oxygen concentration of 0.1% to 21% to form a hardened film.

[0384] Furthermore, it is preferable to use a substrate with a height of 30 nm or more or a height difference for the substrate being processed.

[0385] <Pattern Formation Methods>

[0386] [A three-layer resist treatment using a silicon-containing resist interlayer]

[0387] This invention provides a pattern forming method, which involves forming an organic film using the aforementioned composition for forming an organic film, forming a photoresist intermediate film on the organic film using a photoresist intermediate film material containing silicon atoms, forming a photoresist upper film on the photoresist intermediate film using a photoresist upper film material composed of a photoresist composition, forming a circuit pattern on the photoresist upper film, using the photoresist upper film with the formed circuit pattern as a mask to etch and transfer the pattern onto the aforementioned photoresist intermediate film, using the photoresist intermediate film with the transferred pattern as a mask to etch and transfer the pattern onto the aforementioned organic film, and then using the organic film with the transferred pattern as a mask to etch and transfer the pattern onto the aforementioned workpiece.

[0388] It is preferable to use a semiconductor device substrate, or a semiconductor device substrate on which any of the following films, such as metal film, metal carbide film, metal oxide film, metal nitride film, metal oxide carbide film, and metal oxide nitride film, has been formed. More specifically, without particular limitation, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, and Al, on which the aforementioned metal films have been formed, can be used as the layer to be processed.

[0389] 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, and can typically be formed with a thickness of 50–10,000 nm, especially 100–5,000 nm. Furthermore, the substrate and the processed layer can be made of different materials when forming the film.

[0390] Furthermore, the metal constituting the workpiece is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or alloys thereof.

[0391] 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.

[0392] Then, a photoresist interlayer (silicon-containing photoresist interlayer) is formed on top of the organic film using a photoresist interlayer material containing silicon atoms. A polysiloxane-based lower film material is preferred for the silicon-containing photoresist interlayer. By giving the silicon-containing photoresist interlayer an anti-reflective effect, reflection can be suppressed. Especially for 193nm exposure applications, if a material containing many aromatic groups and with high etch selectivity to the substrate is used as the composition for forming the organic film, the k-value increases, and the substrate reflection increases. However, by giving it an absorption value appropriate for a silicon-containing photoresist interlayer as a whole, reflection can be suppressed, and the substrate reflection can be reduced to 0.5% or less. As a silicon-containing photoresist interlayer with anti-reflective effect, anthracene is preferred for 248nm and 157nm exposure, and a polysiloxane with phenyl or silicon-silicon bond-containing light-absorbing groups in the side group structure and crosslinked by acid or heat is preferred for 193nm exposure.

[0393] Then, a top resist film is formed on top of the intermediate resist film 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 at 60–180°C for 10–300 seconds is preferable. Afterwards, exposure is performed as usual, 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 30–500 nm is ideal, especially 50–400 nm.

[0394] Then, a circuit pattern (resist overlayer pattern) is formed on the resist film. The circuit pattern is preferably formed using photolithography with light wavelengths of 10 nm to 300 nm, direct drawing using an electron beam, nanoimprinting, or a combination thereof.

[0395] Furthermore, exposure light can include high-energy rays with wavelengths below 300nm, specifically far-ultraviolet light, KrF excimer laser (248nm), ArF excimer laser (193nm), F2 laser (157nm), Kr2 laser (146nm), Ar2 laser (126nm), soft X-rays (EUV) with wavelengths of 3-20nm, electron beams (EB), ion beams, X-rays, etc.

[0396] Furthermore, in the formation of circuit patterns, it is better to use alkaline development or organic solvents to develop the circuit patterns.

[0397] Then, using the upper resist film with the circuit pattern already formed as a mask, the pattern is etched onto the intermediate resist film. Etching of the intermediate resist film using the upper resist film pattern as a mask is preferably performed using a fluorocarbon-based gas. This forms a silicon-containing intermediate resist film pattern.

[0398] Then, using the transferred patterned resist interlayer as a mask, the transferred pattern is etched onto the organic film. Since the silicon-containing resist interlayer exhibits resistance to etching by oxygen or hydrogen, it is preferable to use an etching gas primarily composed of oxygen or hydrogen for etching the organic film using the silicon-containing resist interlayer pattern as a mask. This forms the organic film pattern.

[0399] Then, the organic film with the transferred pattern is used as a mask to etch the transferred pattern onto the substrate. The subsequent etching of the substrate (processed layer) can be performed using conventional methods. For example, if the substrate is a low-dielectric-constant insulating film based on SiO2, SiN, or silicon dioxide, etching is performed primarily using chlorofluorocarbon (CFC) gases; if it is p-Si, Al, or W, etching is performed primarily using chlorine or bromine gases. When etching with CFC gases during substrate processing, the silicon-containing resist interlayer pattern is stripped away simultaneously with substrate processing. On the other hand, when etching with chlorine or bromine gases during substrate processing, dry etching with CFC gases is required after substrate processing to strip the silicon-containing resist interlayer pattern.

[0400] Organic films obtained using the composition for forming organic films of the present invention, as described above, exhibit excellent etch resistance when the workpiece is etched.

[0401] [A four-layer resist treatment was used, consisting of a silicon-containing resist interlayer and an organic anti-reflective film.]

[0402] Furthermore, the present invention provides a pattern forming method, characterized by:

[0403] An organic film is formed on a workpiece using the aforementioned composition for forming an organic film. A photoresist intermediate film is formed on the organic film using a photoresist intermediate film material containing silicon atoms. An organic antireflective film is formed on the photoresist intermediate film. A photoresist upper film is formed on the organic antireflective film using a photoresist upper film material composed of a photoresist composition. A circuit pattern is formed on the photoresist upper film. The photoresist upper film with the circuit pattern is used as a mask to etch and transfer the pattern onto the aforementioned organic antireflective film and the aforementioned photoresist intermediate film. The photoresist intermediate film with the transferred pattern is used as a mask to etch and transfer the pattern onto the aforementioned organic film. The organic film with the transferred pattern is then used as a mask to etch and transfer the pattern onto the aforementioned workpiece.

[0404] Furthermore, this method, except for forming an organic antireflective film (BARC) between the resist intermediate film and the resist upper film, can be performed in the same way as the three-layer resist treatment using a silicon-containing resist intermediate film described above.

[0405] Organic antireflective films can be formed by spin coating using known organic antireflective film materials.

[0406] [Three layers of resist were applied using an inorganic hard mask]

[0407] Furthermore, the present invention provides a pattern forming method, which is a pattern forming method using a three-layer resist treatment with an organic film forming composition, characterized in that:

[0408] An organic film is formed on a workpiece using the aforementioned composition for forming an organic film. An inorganic hard mask selected from silicon oxide film, silicon nitride film, and silicon oxide nitride 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 to transfer the pattern onto the aforementioned inorganic hard mask by etching. The inorganic hard mask with the transferred pattern is used as a mask to transfer the pattern onto the aforementioned organic film by etching. The organic film with the transferred pattern is then used as a mask to transfer the pattern onto the aforementioned workpiece by etching.

[0409] Furthermore, this method, except that instead of forming an inorganic hard mask on top of the organic film, can form an inorganic hard mask, can be performed in the same way as the three-layer resist treatment using a silicon-containing resist interlayer film mentioned above.

[0410] Inorganic hard masks selected from silicon oxide films, silicon nitride films, and silicon oxide nitride films (SiON films) can be formed using CVD methods, ALD methods, etc. 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 mask is preferably 5–200 nm, more preferably 10–100 nm. SiON films, which are highly effective as anti-reflective films, are preferred as inorganic hard masks. Since the substrate temperature during SiON film formation is 300–500°C, the underlying film must be able to withstand temperatures of 300–500°C. Organic films formed using the composition for organic film formation of the present invention have high heat resistance and can withstand high temperatures of 300°C–500°C; therefore, a combination of an inorganic hard mask formed by CVD or ALD and an organic film formed by spin coating can be used.

[0411] [A four-layer photoresist treatment using an inorganic hard mask and an organic anti-reflective film]

[0412] Furthermore, the present invention provides a pattern forming method, which is a pattern forming method using an organic film forming composition for four-layer resist treatment, characterized by:

[0413] An organic film is formed on a workpiece using the aforementioned composition for forming an organic film. An inorganic hard mask selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film is formed on the organic film. An organic antireflective film is formed on the inorganic hard mask. An upper resist film is formed on the organic antireflective film 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 formed circuit pattern is used as a mask to etch and transfer the pattern onto the aforementioned organic antireflective film and the aforementioned inorganic hard mask. The inorganic hard mask with the transferred pattern is used as a mask to etch and transfer the pattern onto the aforementioned organic film. The organic film with the transferred pattern is then used as a mask to etch and transfer the pattern onto the aforementioned workpiece.

[0414] Furthermore, this method, except for forming an organic antireflective film (BARC) between the inorganic hard mask and the upper resist film, can be performed in the same way as the three-layer resist treatment using the inorganic hard mask described above.

[0415] In particular, when using a SiON film as an inorganic hard mask, the two-layer anti-reflection film of SiON film and BARC can suppress reflection even at immersion exposure with a high NA exceeding 1.0. Another advantage of forming BARC is that it can reduce the trailing of the resist pattern on the SiON film.

[0416] Here, an example of the pattern forming method of the present invention using a three-layer resist treatment is given. Figure 1 As shown in (A) to (F). When treating with 3 layers of resist, as... Figure 1 As shown in (A), after forming an organic film 3 using the organic film forming composition of the present invention on the processed layer 2 formed on the substrate 1, a silicon-containing photoresist intermediate film 4 is formed, and a photoresist upper film 5 is formed thereon. Next, as... Figure 1 As shown in (B), the exposed portion 6 of the upper resist film 5 is exposed and subjected to PEB (post-exposure baking). Then, as... Figure 1 As shown in (C), development is performed to form the resist upper film pattern 5a. Next, as... Figure 1 As shown in (D), using the upper resist film pattern 5a as a mask, the silicon-containing resist intermediate film 4 is dry-etched using a chlorofluorocarbon gas to form the silicon-containing resist intermediate film pattern 4a. Next, as... Figure 1 As shown in (E), after removing the upper resist film pattern 5a, the silicon-containing resist intermediate film pattern 4a is used as a mask to perform oxygen plasma etching on the organic film 3, forming the organic film pattern 3a. For example... Figure 1 As shown in (F), after removing the silicon-containing photoresist intermediate film pattern 4a, the organic film pattern 3a is used as a mask to etch the processed layer 2 to form pattern 2a.

[0417] When forming an inorganic hard mask, the silicon-containing photoresist intermediate film 4 can be replaced with an inorganic hard mask. When forming a BARC, a BARC can be formed between the silicon-containing photoresist intermediate film 4 and the upper photoresist film 5. The etching of the BARC can be performed continuously before etching the silicon-containing photoresist intermediate film 4, or the etching of the silicon-containing photoresist intermediate film 4 can be performed after etching only the BARC, by changing the etching equipment, etc.

[0418] As described above, if it is the pattern forming method of the present invention, then a fine pattern can be formed on the workpiece with high precision by using a multilayer resist treatment.

[0419] Example

[0420] The following synthetic examples, embodiments, and comparative examples illustrate the present invention in more detail, but the present invention is not limited thereto. Furthermore, molecular weight and dispersity are weight-average molecular weights (Mw) derived from polystyrene obtained by gel permeation chromatography (GPC) using tetrahydrofuran as the dissolving agent.

[0421] [Synthetic Example 1] Synthesis of a resin compound (A-1) containing an aromatic ring

[0422] Under nitrogen atmosphere, 1.0 g of 2,3-dihydroxynaphthalene, 9.0 g of methanesulfonic acid, and 30 g of 1,2-dichloroethane were added to a flask and stirred at an internal temperature of 60 °C. After preparing a homogeneous solution, 18.8 g of 3-phenoxybenzyl alcohol was slowly added dropwise, and the reaction was carried out at an internal temperature of 70 °C for 5 hours. After cooling to room temperature, the solution was diluted with 200 g of methyl isobutyl ketone (MIBK) and washed five times with 50 g of ultrapure water. The organic layer was then recovered, and methyl isobutyl ketone was removed under reduced pressure. 150 g of PGMEA was added and a homogeneous solution was prepared. Water and low-boiling-point solvents were distilled off, and the concentration was adjusted to recover a 20% PGMEA solution containing an aromatic ring resin compound (A-1).

[0423] (A-1): Mw=2080, Mw / Mn=2.2

[0424] [Chemistry 67]

[0425]

[0426] [Synthetic Example 2] Synthesis of a resin compound (A-2) containing an aromatic ring

[0427] Under nitrogen atmosphere, 1.0 g of 2,3-dihydroxynaphthalene, 9.0 g of methanesulfonic acid, and 30 g of 1,2-dichloroethane were added to a flask and stirred at an internal temperature of 60 °C. After forming a homogeneous solution, 11.6 g of 4-hydroxybenzyl alcohol was slowly added dropwise, and the reaction was carried out at an internal temperature of 70 °C for 5 hours. After cooling to room temperature, the solution was diluted with 200 g of methyl isobutyl ketone (MIBK) and washed five times with 50 g of ultrapure water. The organic layer was then recovered, and the methyl isobutyl ketone was removed under reduced pressure. 150 g of PGMEA was added to form a homogeneous solution, and the water and low-boiling solvent were distilled off. The concentration was then adjusted to recover the solution as a 20% PGMEA solution containing the aromatic ring resin compound (A-2).

[0428] (A-2): Mw=1900, Mw / Mn=2.3

[0429] [Chemistry 68]

[0430]

[0431] [Synthetic Example 3] Synthesis of a resin compound (A-3) containing an aromatic ring

[0432] Under nitrogen atmosphere, 1.0 g of 4,4'-dihydroxydiphenyl ether, 5.9 g of methanesulfonic acid, and 30 g of 1,2-dichloroethane were added to a flask and stirred at an internal temperature of 60 °C. After preparing a homogeneous solution, 11.8 g of 3-phenoxybenzyl alcohol was slowly added dropwise, and the reaction was carried out at an internal temperature of 70 °C for 5 hours. After cooling to room temperature, the solution was diluted with 200 g of methyl isobutyl ketone (MIBK) and washed five times with 50 g of ultrapure water. The organic layer was then recovered, and the methyl isobutyl ketone was removed under reduced pressure. 150 g of PGMEA was added to prepare a homogeneous solution. Water and low-boiling-point solvents were distilled off, and the concentration was adjusted to recover a 20% PGMEA solution containing an aromatic ring resin compound (A-3).

[0433] (A-3): Mw=1880, Mw / Mn=2.1

[0434] [Chemistry 69]

[0435]

[0436] [Synthetic Example 4] Synthesis of a resin compound (A-4) containing an aromatic ring

[0437] Under nitrogen atmosphere, 1.0 g of 4,4'-dihydroxydiphenyl ether, 5.9 g of methanesulfonic acid, and 30 g of 1,2-dichloroethane were added to a flask and stirred at an internal temperature of 60 °C. After preparing a homogeneous solution, a solution pre-homogenized with 9.4 g of 2-naphthalenemethanol and 30 g of 1,2-dichloroethane was slowly added dropwise, and the reaction was carried out at an internal temperature of 70 °C for 5 hours. After cooling to room temperature, the solution was diluted with 200 g of methyl isobutyl ketone (MIBK) and washed five times with 50 g of ultrapure water. The organic layer was then recovered, and methyl isobutyl ketone was removed under reduced pressure. 150 g of PGMEA was added to prepare a homogeneous solution, and water and low-boiling-point solvents were distilled off. The concentration was then adjusted to recover the solution as a 20% PGMEA solution containing an aromatic ring resin compound (A-4).

[0438] (A-4): Mw=1760, Mw / Mn=2.4

[0439] [Chemistry 70]

[0440]

[0441] [Synthetic Example 5] Synthesis of a resin polymer containing an aromatic ring (A-5)

[0442] Under nitrogen atmosphere, 20.0 g of 4,4'-dihydroxydiphenyl ether, 0.4 g of p-toluenesulfonic acid, and 60 g of propylene glycol monomethyl ether were added to a flask and stirred at an internal temperature of 90 °C. After preparing a homogeneous solution, 17.8 g of a 37% aqueous solution of formaldehyde was slowly added dropwise, and the reaction was carried out at an internal temperature of 105 °C for 20 hours. After cooling to room temperature, 150 g of hexane was added while stirring, causing a rice cake-like precipitate to form. After standing for a period of time, the upper layer was decanted. 30 g of PGME was added to the residue and stirred to prepare a homogeneous solution. This solution was then diluted with 150 g of MIBK and washed five times with 50 g of ultrapure water. The organic layer was then recovered, methyl isobutyl ketone was removed under reduced pressure, 150g of PGMEA was added to make a homogeneous solution, water and low-boiling-point solvent were distilled off, and the concentration was adjusted to recover a PGMEA solution with a concentration of 20% containing an aromatic ring resin compound (A-5).

[0443] (A-5)Mw=6030,Mw / Mn=1.7

[0444] [Chemistry 71]

[0445]

[0446] [Synthetic Example 6] Synthesis of a resin polymer containing an aromatic ring (A-6)

[0447] Under nitrogen atmosphere, 10.0 g of polymer (A-5), 6.5 g of potassium carbonate, and 40 g of N,N-dimethylformamide were added to a flask and stirred at 50°C to form a suspension. 7.0 g of 80% toluene solution of propargyl bromide was added dropwise to the dispersion, and the reaction was carried out at 50°C for 15 hours. After the reaction, 150 g of ultrapure water and 150 g of MIBK were added to form a homogeneous solution, and the reaction was stopped. The solution was transferred to a separatory funnel, and after removing the separated aqueous layer, it was washed twice with 100 g of 3% nitric acid aqueous solution and five times with 150 g of ultrapure water. The organic layer was recovered, and methyl isobutyl ketone was removed under reduced pressure. 150 g of PGMEA was added to form a homogeneous solution, and water and low-boiling solvents were distilled off. The concentration was then adjusted to recover the solution as a 20% PGMEA solution containing the aromatic ring resin compound (A-6).

[0448] (A-6)Mw=7400, Mw / Mn=1.9

[0449] [Chemistry 72]

[0450]

[0451] [Synthetic Example 7] Synthesis of a resin polymer containing an aromatic ring (A-7)

[0452] Under nitrogen atmosphere, 20.0 g of catechol, 0.4 g of p-toluenesulfonic acid, and 60 g of propylene glycol monomethyl ether were added to a flask and stirred at an internal temperature of 90 °C. After preparing a homogeneous solution, 11.8 g of a 37% aqueous solution of formaldehyde was slowly added dropwise, and the reaction was carried out at an internal temperature of 105 °C for 20 hours. After cooling to room temperature, 150 g of ultrapure water was added while stirring to precipitate a rice cake-like precipitate. After standing for a period of time, the upper layer was decanted. 30 g of PGME was added to the residue and stirred to prepare a homogeneous solution. This solution was then diluted with 150 g of MIBK and washed five times with 50 g of ultrapure water. The organic layer was then recovered, and methyl isobutyl ketone was removed under reduced pressure. 150 g of PGMEA was added to prepare a homogeneous solution, and water and low-boiling solvents were distilled off. The concentration was then adjusted to recover a 20% PGMEA solution containing an aromatic ring resin compound (A-7).

[0453] (A-7)Mw=3900, Mw / Mn=1.6

[0454] [Chemistry 73]

[0455]

[0456] [Synthetic Example 8] Synthesis of a resin polymer containing an aromatic ring (A-8)

[0457] Under nitrogen atmosphere, 10.0 g of polymer (A-7), 11.4 g of potassium carbonate, and 40 g of N,N-dimethylformamide were added to a flask and stirred at 50°C to form a suspension. 12.2 g of 80% toluene solution of propargyl bromide was added dropwise to the dispersion, and the reaction was carried out at 50°C for 15 hours. After the reaction, 150 g of ultrapure water and 150 g of MIBK were added to form a homogeneous solution, and the reaction was stopped. The solution was transferred to a separatory funnel, and the separated aqueous layer was removed. The solution was then washed twice with 100 g of 3% nitric acid aqueous solution and five times with 150 g of ultrapure water. The organic layer was recovered, and methyl isobutyl ketone was removed under reduced pressure. 150 g of PGMEA was added to form a homogeneous solution, and the water and low-boiling solvent were distilled off. The concentration was then adjusted to recover the solution as a 20% PGMEA solution containing the aromatic ring resin compound (A-8).

[0458] (A-8)Mw=4120、Mw / Mn=1.7

[0459] [Chemistry 74]

[0460]

[0461] [Synthetic Example 9] Synthesis of a resin polymer containing an aromatic ring (A-9)

[0462] Under nitrogen atmosphere, 10.0 g of p-cresol, 0.2 g of p-toluenesulfonic acid, and 40 g of propylene glycol monomethyl ether were added to a flask and stirred at an internal temperature of 90 °C. After preparing a homogeneous solution, 6.0 g of a 37% aqueous solution of formaldehyde was slowly added dropwise, and the reaction was carried out at an internal temperature of 105 °C for 20 hours. After cooling to room temperature, 100 g of ultrapure water was added while stirring to precipitate a rice cake-like precipitate. After standing for a period of time, the upper layer was decanted. 20 g of PGME was added to the residue and stirred to prepare a homogeneous solution. This solution was then diluted with 100 g of MIBK and washed five times with 50 g of ultrapure water. The organic layer was then recovered, and methyl isobutyl ketone was removed under reduced pressure. 150 g of PGMEA was added to prepare a homogeneous solution, and water and low-boiling solvents were distilled off. The concentration was then adjusted to recover a 20% PGMEA solution containing an aromatic ring resin compound (A-9).

[0463] (A-9)Mw=3400,Mw / Mn=1.6

[0464] [Chemistry 75]

[0465]

[0466] [Synthetic Example 10] Synthesis of a resin polymer containing an aromatic ring (A-10)

[0467] Under nitrogen atmosphere, 10.0 g of 1,3,5-trihydroxybenzene, 10.0 g of 3,4-dihydroxybenzaldehyde, 0.2 g of p-toluenesulfonic acid, and 40 g of propylene glycol monomethyl ether were added to a flask and stirred at an internal temperature of 90°C. After preparing a homogeneous solution, the reaction was carried out at an internal temperature of 105°C for 5 hours. After cooling to room temperature, the solution was diluted with 100 g of MIBK and washed five times with 50 g of ultrapure water. The organic layer was then recovered, and methyl isobutyl ketone was removed under reduced pressure. 150 g of PGMEA was added to prepare a homogeneous solution, and water and low-boiling solvents were distilled off. The concentration was then adjusted to recover a 20% PGMEA solution containing an aromatic ring resin compound (A-10).

[0468] (A-10)Mw=1125,Mw / Mn=1.4

[0469] [Chemistry 76]

[0470]

[0471] [Synthetic Example 11] Synthesis of a resin compound (A-11) containing an aromatic ring

[0472] Under nitrogen atmosphere, 1.0 g of catechol, 21.0 g of methanesulfonic acid, and 30 g of 1,2-dichloroethane were added to a flask and stirred at an internal temperature of 60 °C. After preparing a homogeneous solution, 21.9 g of 3-phenoxybenzyl alcohol was slowly added dropwise, and the reaction was carried out at an internal temperature of 70 °C for 5 hours. After cooling to room temperature, the solution was diluted with 200 g of methyl isobutyl ketone (MIBK) and washed five times with 50 g of ultrapure water. The organic layer was then recovered, and methyl isobutyl ketone was removed under reduced pressure. 150 g of PGMEA was added to prepare a homogeneous solution, and water and low-boiling solvents were distilled off. The concentration was then adjusted to recover a 20% PGMEA solution containing an aromatic ring resin compound (A-11).

[0473] (A-11): Mw=1680, Mw / Mn=2.0

[0474] [Chemistry 77]

[0475]

[0476] [Synthetic Example 12] Synthesis of a polymer (B-1) containing a β-diketone structure in a repeating unit.

[0477] Under nitrogen atmosphere, 10.0 g of di-tert-butyl malonate, 3.7 g of 1,4-butanediol, and 50 g of xylene were added to a flask. The reaction was carried out for 2 hours at an internal temperature of 140°C while removing tert-butanol generated during the transesterification reaction. Then, the internal temperature was raised to 160°C while removing tert-butanol and o-xylene, and the reaction was carried out for 6 hours at 160°C. After cooling to an internal temperature of 50°C, 200 g of hexane was added, causing the polymer to precipitate as a gel. The mixture was directly cooled to room temperature and allowed to stand for 1 hour. The supernatant was then decanted. 100 g of PGMEA (propylene glycol monomethyl ether acetate) was added to the residue to prepare a homogeneous solution. Water and low-boiling-point solvents were distilled off, and the concentration was adjusted to recover the polymer (B-1) as a 50% PGMEA solution.

[0478] (B-1): Mw=11500, Mw / Mn=1.7

[0479] [Chemistry 78]

[0480]

[0481] [Synthetic Example 13] Synthesis of a polymer (B-2) containing a β-diketone structure in a repeating unit.

[0482] Under nitrogen atmosphere, 10.0 g of di-tert-butyl malonate, 8.4 g of 1,12-dodecanediol, and 50 g of xylene were added to a flask. The reaction was carried out for 2 hours at an internal temperature of 140°C while removing tert-butanol generated during the transesterification reaction. Then, the internal temperature was raised to 160°C while removing tert-butanol and o-xylene, and the reaction was carried out for 6 hours at 160°C. After cooling to an internal temperature of 50°C, 200 g of hexane was added, causing the polymer to precipitate as a gel. The mixture was directly cooled to room temperature and allowed to stand for 1 hour. The supernatant was then decanted. 100 g of PGMEA (propylene glycol monomethyl ether acetate) was added to the residue to prepare a homogeneous solution. Water and low-boiling-point solvents were distilled off, and the concentration was adjusted to recover the polymer (B-2) as a 50% PGMEA solution.

[0483] (B-2): Mw=17500, Mw / Mn=2.2

[0484] [Chemistry 79]

[0485]

[0486] [Synthetic Example 14] Synthesis of a polymer (B-3) containing a β-diketone structure in a repeating unit.

[0487] Under nitrogen atmosphere, 10.0 g of di-tert-butyl malonate, 11.7 g of hexaethylene glycol, and 50 g of xylene were added to a flask. The reaction was carried out for 2 hours at an internal temperature of 140°C while removing tert-butanol generated during the transesterification reaction. Then, the internal temperature was raised to 160°C while removing tert-butanol and o-xylene, and the reaction was carried out for 6 hours at 160°C. After cooling to an internal temperature of 50°C, 200 g of hexane was added, causing the polymer to precipitate as a gel. The mixture was directly cooled to room temperature and allowed to stand for 1 hour. The supernatant was then decanted. 100 g of PGMEA (propylene glycol monomethyl ether acetate) was added to the residue to prepare a homogeneous solution. Water and low-boiling-point solvents were distilled off, and the concentration was adjusted to recover the polymer (B-3) as a 50% PGMEA solution.

[0488] (B-3): Mw=14800, Mw / Mn=2.1

[0489] [Chemistry 80]

[0490]

[0491] [Synthetic Example 15] Synthesis of a polymer (B-4) containing a β-diketone structure in a repeating unit.

[0492] Under nitrogen atmosphere, 10.0 g of di-tert-butyl malonate, 14.1 g of potassium carbonate, and 50 g of DMF were added to a flask, followed by the dropwise addition of 12.5 g of 1-bromopropane. The mixture was then heated to an internal temperature of 60 °C and reacted for 15 hours. After cooling to room temperature, 200 g of methyl isobutyl ketone was added, and the mixture was washed twice with 150 g of ultrapure water. The organic layer was recovered, and the methyl isobutyl ketone was removed under reduced pressure. After removing the methyl isobutyl ketone, the mixture was dissolved in 50 g of xylene, and 8.4 g of 1,12-dodecanediol was added. The reaction was carried out at an internal temperature of 140 °C for 2 hours while removing the tert-butanol generated by the transesterification reaction. Then, the mixture was heated to an internal temperature of 160 °C for 6 hours while removing the tert-butanol and o-xylene. After cooling to an internal temperature of 50 °C, 200 g of hexane was added, causing the polymer to precipitate as a gel. The solution was cooled directly to room temperature and allowed to stand for 1 hour. The supernatant was then decanted. The residue was dissolved in 150 g of methyl isobutyl ketone and washed with 100 g of 3% nitric acid, followed by washing five times with ultrapure water. The methyl isobutyl ketone was removed under reduced pressure. 150 g of PGMEA (propylene glycol monomethyl ether acetate) was added to prepare a homogeneous solution. Water and low-boiling-point solvents were distilled off, and the concentration was adjusted to recover the solution as a 50% PGMEA solution containing polymer (B-4).

[0493] (B-4): Mw=19250, Mw / Mn=2.2

[0494] [Chemistry 81]

[0495]

[0496] [Organic film formation composition UDL-1]

[0497] The polymer containing an aromatic ring (A-1) and the polymer containing a β-diketone structure in repeating units (B-1) were dissolved in propylene glycol monomethyl ether acetate (PGMEA) containing 0.5% by mass of surfactant FC-4430 (manufactured by Sumitomo 3M Ltd.) in the proportions shown in Table 1, and filtered through a 0.02 μm membrane filter to prepare an organic membrane forming composition (UDL-1).

[0498] [Preparation of organic film forming compositions (UDL-2 to 21) and comparative examples of organic film forming compositions (Comparative Examples UDL-1 to 12)]

[0499] The types and contents of each component are shown in Table 1. Otherwise, the preparation of each solution is the same as UDL-1. Also, in Table 1, "-" indicates that the component was not used. The crosslinking agent used is formula (D-1), the high-boiling solvent (F-1) is 1,6-diacetoxyhexane (boiling point 260°C), the thermally decomposable resin used is formula (G-1), (P-1) is polyethylene glycol methyl ether 10000 (PEGME10000), and (M-1) is dimethyl malonate.

[0500] [Cross-linking agent]

[0501] The crosslinking agent (D-1) used in the composition for organic film formation is shown below.

[0502] [Chemistry 82]

[0503]

[0504] [Thermolytic resin]

[0505] The thermally decomposable resin (G-1) used in the composition for organic film formation is shown below.

[0506] [Chemistry 83]

[0507]

[0508] Mw = 6,400 Mw / Mn = 2.5 [Table 1]

[0509]

[0510] [Solvent Resistance Evaluation]

[0511] The organic film forming compositions (UDL-1 to 21, Comparative Examples UDL-1 to 12) prepared above were coated on a silicon substrate and fired at 180°C for 60 seconds, followed by firing at 350°C for 60 seconds. The film thickness (a [nm]) was then measured. Furthermore, the film thickness from the center of the substrate to the outer periphery was measured, and the thickness difference and range (b [nm]) between the maximum and minimum film thicknesses were calculated. The in-plane uniformity ((b / a) × 100) was then determined.

[0512] Then, PGMEA was applied onto the film, left to stand for 30 seconds, and then spun dry. The film was then baked at 100°C for 60 seconds to evaporate the PGMEA, and the film thickness (c [nm]) was measured. The difference in film thickness before and after PGMEA treatment was calculated (residual film rate: (c / a) × 100). The results are shown in Table 2 below.

[0513] [Table 2]

[0514]

[0515]

[0516] As shown in Table 2, the organic film-forming compositions of the present invention (Examples 1-1 to 1-21) were confirmed to have a residual film yield ((c / a)×100) of 98.5% or higher after firing, exhibiting sufficient thermosetting properties for the resist underlayer film. In-plane uniformity was also good, thus confirming that the compositions are not prone to sublimation, poor compatibility, or poor film formation / coating. Comparative Examples 1-1 to 1-3, which are compositions of polymers containing a β-diketone structure in the main chain of polymer (B) of the present invention, also showed the same results, thus confirming that the addition of component (B) does not adversely affect film curing and film formation properties. On the other hand, Comparative Examples 1-4 to 1-6, which contain only polyethylene glycol (P-1) without a β-diketone structure, Comparative Examples 1-7 to 1-9, which contain a thermally decomposable resin (G-1), and Comparative Examples 1-10 to 1-12, which contain a monomolecular compound (M-1) with a β-diketone structure, showed significantly deteriorated in-plane uniformity. The reason is believed to be the poor compatibility between (P-1) and the main resin, leading to uneven coating. Furthermore, when (G-1) is present, it contains sublimation products of low molecular weight components generated by thermal decomposition; when (M-1) is present, it is believed that the low molecular weight of (M-1) itself causes sublimation, resulting in unevenness in the film.

[0517] [Landfill Characteristics / Leveling Evaluation]

[0518] The organic film forming compositions (UDL-1 to 21 and Comparative Examples UDL-1 to 9) prepared above were respectively coated on SiO2 wafer substrates having a dense line and spacing pattern (line width 60 nm, line depth 100 nm, distance between the centers of two adjacent lines 120 nm). The substrates were heated at 350°C for 60 seconds using a heating plate to form an organic film with a thickness of approximately 150 nm. The substrates used were as follows... Figure 2 The substrate 8 (SiO2 wafer substrate) with a dense line and spacing pattern is shown. The cross-sectional shape of each wafer substrate was observed using a Hitachi, Ltd. electron microscope (S-4700) to confirm whether there was substrate filling with unevenness. The results are shown in Table 3. When an organic film forming composition with poor filling characteristics was used, unevenness substrates could not be successfully filled in this evaluation. When an organic film forming composition with good filling characteristics was used, in this evaluation, if... Figure 2 As shown, it can fill the spaces between lines with dense line and spacing patterns without gaps. A is able to fill without large pores, B has visible pores, and C cannot be filled. Furthermore, the cross-sectional shape of each wafer substrate obtained from the above-mentioned filling characteristic evaluation was observed using a scanning electron microscope (SEM), and the height difference of the filling film (coating film) 9 between the densely patterned areas and the non-line patterned areas was observed using a Hitachi, Ltd. S-4700 electron microscope. Figure 2 (Delta10 in (B)). The results are shown in Table 3. In this evaluation, the smaller the height difference, the better the flattening characteristics.

[0519] [Table 3]

[0520]

[0521]

[0522] As shown in Table 3, Examples 2-1 to 2-21, which used the organic film-forming composition (UDL-1 to 21) of the present invention, and Comparative Examples 2-1 to 2-3, which used comparative examples UDL-1 to 3 without additives, were able to fill the dense line and spacing patterns without pores, demonstrating good filling characteristics. However, Comparative Examples 2-4 to 2-6, which contained only polyethylene glycol (P-1), could not fill the patterns or had pores, failing to fill the dense line and spacing patterns. This is believed to be due to poor compatibility, which, like poor film-forming properties, prevented successful filling of the spacing during spin coating. Furthermore, Comparative Examples 2-7 to 2-9, which contained a thermally decomposable resin (G-1), and Comparative Examples 2-10 to 2-12, which contained a β-diketone compound (M-1), were able to fill the patterns but pores occurred. This is believed to be because the thermally decomposable resin decomposed and sublimated, and the β-diketone compound itself sublimated, resulting in gaps in the filled spacing.

[0523] Regarding flatness, comparing Examples 2-1 to 2-21 (using organic film forming compositions (UDL-1 to 21) employing a polymer containing a β-diketone structure in the repeating unit of the present invention) with Comparative Examples 2-1 to 2-3 (using Comparative Examples UDL-1 to 3 that do not contain the polymer of the present invention), Examples 2-1 to 2-21 containing the polymer of the present invention showed an improvement of more than 10 nm compared to Comparative Examples 2-1 to 2-3. This is believed to be because the addition of a polymer containing a β-diketone structure in the repeating unit ensures thermal fluidity, and good results were also obtained for other organic film forming compositions of the present invention.

[0524] [Etching Resistance Evaluation]

[0525] Organic film forming compositions of the present invention (UDL-1, 5, 7) containing (A) resins containing aromatic rings (A-1, (A-5, (A-7)) and (B) polymers containing repeating units with β-diketone structures, and comparative examples UDL-1 to 3 without the polymer (B) of the present invention, were coated on a silicon substrate. The substrate was heated at 350°C for 60 seconds using a heating plate and treated under the plasma treatment conditions described below to form an organic film, and the film thickness a was measured. Then, etching using CF4 gas was performed under the following conditions using the Telius etching apparatus manufactured by Tokyo Powertech, and the film thickness b was measured. The film thickness etched in 1 minute (film thickness a - film thickness b) during a specified time period using CF4 gas was calculated and defined as the etching rate B (nm / min). A smaller etching rate indicates better etching resistance to CF4 gas.

[0526] Dry etching conditions with CF4 gas

[0527] Chamber pressure: 100mT

[0528] RF power (top): 500W

[0529] RF power (bottom): 400W

[0530] CF4 gas flow rate: 300 sccm

[0531] Time: 30 seconds

[0532] [Table 4]

[0533]

[0534] As shown in Table 4, Examples 3-1 to 3-3, which used the resist underlayer film forming composition (UDL-1, 5, 7) of the present invention, and Comparative Examples 3-1 to 3-3, which used polymers without β-diketone structures, showed the same etching resistance for each gas type, confirming that there was no adverse effect on etching resistance due to polymers containing β-diketone structures.

[0535] As described above, the composition for forming organic films of the present invention can take into account both thermal fluidity and thermosetting properties to a high degree, and can form an organic film with high film-forming properties, filling properties and planarization properties without compromising the etching resistance of the original main resin. It is extremely useful as a resist lower layer film material used in multilayer resist methods and as a reverse agent used in tone-reverse etching methods.

[0536] This specification includes the following inventions.

[0537] [1]: An organic film forming composition characterized by containing:

[0538] (A) Resins containing aromatic rings

[0539] (B) Polymers containing repeating units with a β-diketone structure as represented by formula (1)

[0540] (C) Solvent,

[0541] [Chemistry 84]

[0542]

[0543] In equation (1) above, L1 is a saturated or unsaturated straight-chain or branched divalent hydrocarbon group with 2 to 20 carbon atoms. This hydrocarbon group can be interrupted once or multiple times by atoms selected from oxygen, nitrogen, and sulfur. A and R B They may be the same or different from each other, and may be hydrogen atoms, substituted or unsubstituted straight-chain alkyl groups with 1 to 20 carbon atoms, substituted or unsubstituted branched or cyclic alkyl groups with 3 to 20 carbon atoms, substituted or unsubstituted aliphatic unsaturated hydrocarbon groups with 2 to 20 carbon atoms containing one or more double or triple bonds, substituted or unsubstituted heteroalkyl groups with 1 to 30 carbon atoms, or substituted or unsubstituted aryl, thiol, hydroxyl, amino, carboxyl, or halogen groups with 6 to 30 carbon atoms.

[0544] [2]: Organic film forming composition such as [1], wherein the resin containing an aromatic ring in (A) above contains hydrogen at the diarylmethylene position or hydrogen at the triphenylmethyl position.

[0545] [3]: The composition for forming organic films, such as [2], wherein the aromatic ring in the resin containing the aromatic ring of (A) contains hydroxyl groups as substituents.

[0546] [4]: An organic film-forming composition as described in any one of [1] to [3], wherein the resin containing an aromatic ring in (A) comprises a polymer selected from repeating units having the following formulas (P-1) and (P-2), and compounds having the following formulas (P-3) to (P-6).

[0547] [Chemistry 85]

[0548]

[0549] In formulas (P-1) and (P-2) above, R is a hydrogen atom or a substituted or unsubstituted benzene ring or naphthalene ring; in formulas (P-1) to (P-6), R1 is a hydrogen atom or a saturated or unsaturated hydrocarbon group with 1 to 20 carbon atoms; in formulas (P-1), (P-3), (P-4) and (P-5), m1 is an integer of 0 or 1; in formulas (P-1), (P-3), (P-4) and (P-6), n1 is an integer of 1 to 4; in formulas (P-2) and (P-5), n2 is an integer of 1 or 2; in formulas (P-3) and (P-5), n3 is an integer of 0 to 2; in formulas (P-3) to (P-6), l is an integer of 5 to 20, but l represents the feed ratio.

[0550] [5]: Organic film-forming composition as described in any of [1] to [4], wherein, in formula (1) above, R A and R B It consists of a hydrogen atom, a straight-chain alkyl group with 1 to 20 carbon atoms (substituted or unsubstituted), a branched or cyclic alkyl group with 3 to 20 carbon atoms (substituted or unsubstituted), or an aliphatic unsaturated hydrocarbon group with 2 to 20 carbon atoms (substituted or unsubstituted) containing one or more double or triple bonds.

[0551] [6]: Organic film-forming composition as described in any of [1] to [5], wherein, in formula (1) above, R A and R B It is a hydrogen atom.

[0552] [7]: An organic film-forming composition such as any one of [1] to [6], wherein in the above formula (1), L1 is a saturated or unsaturated straight-chain or branched hydrocarbon group with 2 to 20 carbon atoms that does not contain heteroatoms.

[0553] [8]: An organic film-forming composition of any one of [1] to [7], wherein, relative to 100 parts by mass of the resin containing an aromatic ring in (A), there are 0.5 to 30 parts by mass of a polymer having a β-diketone structure in the repeating unit of (B).

[0554] [9]: An organic film forming composition of any one of [1] to [8], wherein the solvent (C) of the organic film forming composition is a mixture of high-boiling-point and low-boiling-point solvents.

[0555]

[10] : An organic film forming composition of any one of [1] to [9], wherein the organic film forming composition further contains one or more of (D) a crosslinking agent and (E) a surfactant.

[0556]

[11] : An organic film formation method, which is a method for forming an organic film acting as an organic planarization film used as a manufacturing step of a semiconductor device, characterized in that:

[0557] An organic film forming composition, such as any one of [1] to

[10] , is spin-coated onto a substrate to be processed, and the substrate coated with the organic film forming composition is heat-treated at a temperature of 100°C to 600°C for 10 to 600 seconds to form a hardened film.

[0558]

[12] : An organic film formation method, which is a method for forming an organic film acting as an organic planarization film used as a manufacturing step of a semiconductor device, characterized in that:

[0559] An organic film forming composition of any one of [1] to

[10] is spin-coated onto a substrate to be processed, and the substrate coated with the organic film forming composition is heat-treated in a gas environment with an oxygen concentration of 0.1% to 21% to form a hardened film.

[0560]

[13] : Organic film formation methods such as

[11] or

[12] , wherein a substrate with a structure or height difference of 30 nm or more is used as the substrate.

[0561]

[14] : A method for forming a pattern, characterized by:

[0562] An organic film is formed on a workpiece using an organic film forming composition of any one of [1] to

[10] . An intermediate resist film is formed on the organic film using a resist intermediate film material containing silicon atoms. An upper resist film is formed on the intermediate resist film 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 to etch and transfer the pattern to the intermediate resist film. The intermediate resist film with the transferred pattern is used as a mask to etch and transfer the pattern to the organic film. The organic film with the transferred pattern is used as a mask to etch and transfer the pattern to the workpiece.

[0563]

[15] : A method for forming a pattern, characterized by:

[0564] An organic film is formed on a workpiece using an organic film forming composition of any one of [1] to

[10] . An intermediate resist film is formed on the organic film using a resist intermediate film material containing silicon atoms. An organic antireflective film is formed on the intermediate resist film. An upper resist film is formed on the organic antireflective film 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 to etch and transfer the pattern to the organic antireflective film and the intermediate resist film. The intermediate resist film with the transferred pattern is used as a mask to etch and transfer the pattern to the organic film. The organic film with the transferred pattern is used as a mask to etch and transfer the pattern to the workpiece.

[0565]

[16] : A method for forming a pattern, characterized by:

[0566] An organic film is formed on a workpiece using an organic film forming composition of any one of [1] to

[10] . An inorganic hard mask selected from silicon oxide film, silicon nitride film and silicon oxide nitride 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 to transfer the pattern to the inorganic hard mask by etching. The inorganic hard mask with the transferred pattern is used as a mask to transfer the pattern to the organic film by etching. The organic film with the transferred pattern is used as a mask to transfer the pattern to the workpiece by etching.

[0567]

[17] : A method for forming a pattern, characterized by:

[0568] An organic film is formed on a workpiece using an organic film forming composition of any one of [1] to

[10] . An inorganic hard mask selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film is formed on the organic film. An organic antireflective film is formed on the inorganic hard mask. An upper resist film is formed on the organic antireflective film 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 to etch and transfer the pattern to the organic antireflective film and the inorganic hard mask. The inorganic hard mask with the transferred pattern is used as a mask to etch and transfer the pattern to the organic film. The organic film with the transferred pattern is used as a mask to etch and transfer the pattern to the workpiece.

[0569]

[18] : A pattern forming method as described in any of

[16] and

[17] , wherein the inorganic hard mask is formed using CVD or ALD.

[0570] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and those that have substantially the same structure and perform the same function as the technical concept described in the claims of the present invention are all included within the technical scope of the present invention.

[0571] Explanation of reference numerals in the attached figures

[0572] 1:Substrate

[0573] 2: Processed layer

[0574] 2a: Pattern formed by the processed layer

[0575] 3: Organic membrane

[0576] 3a: Organic film pattern

[0577] 4: Silicon-containing photoresist interlayer

[0578] 4a: Pattern of silicon-containing photoresist interlayer

[0579] 5: Top layer of resist film

[0580] 5a: Pattern of the upper layer of the resist film

[0581] 6: Exposure section

[0582] 8: Patterned substrate

[0583] 9: Coated film

[0584] Delta10: The height difference of the coating film 9 between the patterned and non-patterned areas.

Claims

1. A composition for forming an organic film, characterized in that: contain: (A) Resins containing aromatic rings (B) Polymers containing repeating units with a β-diketone structure as represented by formula (1) (C) Solvent, In equation (1) above, L1 is a saturated or unsaturated straight-chain or branched divalent hydrocarbon group with 2 to 20 carbon atoms. This hydrocarbon group can be interrupted once or multiple times by atoms selected from oxygen, nitrogen, and sulfur. A and R B They may be the same or different from each other, and may be hydrogen atoms, substituted or unsubstituted straight-chain alkyl groups with 1 to 20 carbon atoms, substituted or unsubstituted branched or cyclic alkyl groups with 3 to 20 carbon atoms, substituted or unsubstituted aliphatic unsaturated hydrocarbon groups with 2 to 20 carbon atoms containing one or more double or triple bonds, substituted or unsubstituted heteroalkyl groups with 1 to 30 carbon atoms, or substituted or unsubstituted aryl, thiol, hydroxyl, amino, carboxyl, or halogen groups with 6 to 30 carbon atoms.

2. The composition for forming organic films according to claim 1, wherein, The resin containing an aromatic ring in (A) above contains hydrogen at the diarylmethylene position or hydrogen at the triphenylmethyl position.

3. The composition for forming organic films according to claim 2, wherein, The aromatic ring in the resin containing the aromatic ring of (A) contains hydroxyl groups as substituents.

4. The composition for forming organic films according to claim 1, wherein, The resin containing an aromatic ring in (A) comprises polymers selected from repeating units having the following formulas (P-1) and (P-2), and compounds having the following formulas (P-3) to (P-6). In formulas (P-1) and (P-2) above, R is a hydrogen atom or a substituted or unsubstituted benzene ring or naphthalene ring; in formulas (P-1) to (P-6), R1 is a hydrogen atom or a saturated or unsaturated hydrocarbon group with 1 to 20 carbon atoms; in formulas (P-1), (P-3), (P-4) and (P-5), m1 is an integer of 0 or 1; in formulas (P-1), (P-3), (P-4) and (P-6), n1 is an integer of 1 to 4; in formulas (P-2) and (P-5), n2 is an integer of 1 or 2; in formulas (P-3) and (P-5), n3 is an integer of 0 to 2; in formulas (P-3) to (P-6), l is an integer of 5 to 20, but l represents the feed ratio.

5. The composition for forming organic films according to claim 1, wherein, In equation (1) above, R A and R B It consists of a hydrogen atom, a straight-chain alkyl group with 1 to 20 carbon atoms (substituted or unsubstituted), a branched or cyclic alkyl group with 3 to 20 carbon atoms (substituted or unsubstituted), or an aliphatic unsaturated hydrocarbon group with 2 to 20 carbon atoms (substituted or unsubstituted) containing one or more double or triple bonds.

6. The composition for forming organic films according to claim 1, wherein, In equation (1) above, R A and R B It is a hydrogen atom.

7. The composition for forming organic films according to claim 1, wherein, In the above formula (1), L1 is a saturated or unsaturated straight-chain or branched hydrocarbon group with 2 to 20 carbon atoms that does not contain heteroatoms.

8. The composition for forming organic films according to claim 1, wherein, Relative to 100 parts by mass of the resin containing an aromatic ring (A), there are 0.5 to 30 parts by mass of the polymer having a β-diketone structure in the repeating unit (B).

9. The composition for forming an organic film according to claim 1, wherein, The solvent (C) of the organic film forming composition is a mixture of high-boiling-point and low-boiling-point solvents.

10. The composition for forming an organic film according to claim 1, wherein, The composition for forming organic films contains one or more of (D) crosslinking agents and (E) surfactants.

11. A method for forming an organic film, which is a method for forming an organic film acting as an organic planarization film used as a manufacturing step of a semiconductor device, characterized in that: An organic film forming composition according to any one of claims 1 to 10 is spin-coated onto a substrate to be processed, and the substrate coated with the organic film forming composition is heat-treated at a temperature of 100°C to 600°C for 10 to 600 seconds to form a hardened film.

12. An organic film formation method, which is a method for forming an organic film acting as an organic planarization film used as a manufacturing step of a semiconductor device, characterized in that: An organic film forming composition according to any one of claims 1 to 10 is spin-coated onto a substrate to be processed, and the substrate coated with the organic film forming composition is heat-treated in a gaseous environment with an oxygen concentration of 0.1% to 21% to form a hardened film.

13. The method for forming an organic film according to claim 11, wherein, The substrate to be processed is a structure with a height of 30 nm or more or a height difference.

14. A method for forming a pattern, characterized by: An organic film is formed on a workpiece using an organic film forming composition according to any one of claims 1 to 10. A photoresist intermediate film is formed on the organic film using a photoresist intermediate film material containing silicon atoms. A photoresist upper film is formed on the photoresist intermediate film using a photoresist upper film material composed of a photoresist composition. A circuit pattern is formed on the photoresist upper film. The photoresist upper film with the circuit pattern is used as a mask to etch and transfer the pattern to the photoresist intermediate film. The photoresist intermediate film with the transferred pattern is used as a mask to etch and transfer the pattern to the organic film. The organic film with the transferred pattern is then used as a mask to etch and transfer the pattern to the workpiece.

15. A method for forming a pattern, characterized by: An organic film is formed on a workpiece using an organic film forming composition according to any one of claims 1 to 10. A photoresist intermediate film is formed on the organic film using a photoresist intermediate film material containing silicon atoms. An organic antireflective film is formed on the photoresist intermediate film. A photoresist upper film is formed on the organic antireflective film using a photoresist upper film material composed of a photoresist composition. A circuit pattern is formed on the photoresist upper film. The photoresist upper film with the circuit pattern is used as a mask to etch and transfer the pattern to the organic antireflective film and the photoresist intermediate film. The photoresist intermediate film with the transferred pattern is used as a mask to etch and transfer the pattern to the organic film. The organic film with the transferred pattern is then used as a mask to etch and transfer the pattern to the workpiece.

16. A method for forming a pattern, characterized by: An organic film is formed on a workpiece using an organic film forming composition according to any one of claims 1 to 10. An inorganic hard mask selected from silicon oxide film, silicon nitride film, and silicon oxide nitride 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 to etch and transfer the pattern to the inorganic hard mask. The inorganic hard mask with the transferred pattern is used as a mask to etch and transfer the pattern to the organic film. The organic film with the transferred pattern is then used as a mask to etch and transfer the pattern to the workpiece.

17. A method for forming a pattern, characterized by: An organic film is formed on a workpiece using an organic film forming composition according to any one of claims 1 to 10. An inorganic hard mask selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film is formed on the organic film. An organic antireflective film is formed on the inorganic hard mask. A photoresist top layer film is formed on the organic antireflective film using a photoresist top layer film material composed of a photoresist composition. A circuit pattern is formed on the photoresist top layer film. The photoresist top layer film with the circuit pattern is used as a mask to etch and transfer the pattern to the organic antireflective film and the inorganic hard mask. The inorganic hard mask with the transferred pattern is used as a mask to etch and transfer the pattern to the organic film. The organic film with the transferred pattern is then used as a mask to etch and transfer the pattern to the workpiece.

18. The pattern forming method according to claim 16, wherein, The inorganic hard mask is formed using CVD or ALD methods.

Images