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

Abstract

The invention relates to a composition for forming an organic film, an organic film forming method, a pattern forming method, and a polymer. The present invention addresses the problem of providing: a substrate which has excellent film-forming properties and landfill characteristics on the substrate, and which suppresses upheaval during an EBR step; the present invention relates to a composition for forming an organic film, which has excellent processing tolerance when used as an organic film for a multilayer resist, an organic film forming method using the composition, a pattern forming method, and a polymer used in the composition for forming an organic film. The solution of the present invention is a composition for forming an organic film, which is characterized by containing (A) a material for forming an organic film, (B) a polymer having a repeating unit represented by general formula (1), and (C) a solvent (in the formula, W1 represents a C2-50 saturated or unsaturated divalent organic group having one or more fluorine-containing structures represented by general formula (2), W2 represents a C2-50 saturated or unsaturated divalent organic group having one or more fluorine-containing structures represented by general formula (3), and W3 represents a C2-50 saturated or unsaturated divalent organic group having one or more fluorine-containing structures represented by general formula (4). And W2 represents a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms. [2] # imgabs1 #

Description

Technical Field

[0001] The present invention relates to an organic film for a multilayer resist used for microfabrication in the manufacture of semiconductor devices, etc., an organic film forming composition capable of forming an organic film for flattening in the manufacture of semiconductor devices, etc., an organic film forming method using the composition, and a pattern forming method using the aforementioned composition. Background Art

[0002] In recent years, with the high integration and high speed of semiconductor devices, the pattern rules are being sought to be miniaturized. In photolithography using light exposure, which is currently a widely used technology, various technical developments are being carried out on how to perform fine and high-precision pattern processing with respect to the light source used.

[0003] As for the light source for lithography used in resist pattern formation, light exposure using g-rays (436nm) or i-rays (365nm) of mercury lamps is widely used as the light source for low integration. On the other hand, for parts with high integration and requiring miniaturization, lithography using shorter wavelengths of KrF excimer lasers (248nm) and ArF excimer lasers (193nm) has also been put into practical use, and for the most advanced generation that requires even more miniaturization, lithography using extreme ultraviolet rays (EUV, 13.5nm) is also close to being put into practical use.

[0004] If the thinning of the resist pattern is carried out in this way, the ratio of the pattern height to the pattern line width (aspect ratio) will become larger in the single-layer resist method used in the typical resist pattern forming method, and it is well known that the pattern collapses due to the surface tension of the developer during development. Therefore, in order to form a pattern with a high aspect ratio on a high-height substrate, it is known that a multilayer resist method in which films with different dry etching characteristics are stacked to form a pattern is excellent, and a two-layer resist method (Patent Document 1) combining a photoresist layer (resist upper film) obtained from a silicon-containing photosensitive polymer and a resist lower film obtained from an organic polymer such as a novolac polymer having carbon, hydrogen and oxygen as main constituent elements has been developed, and a three-layer resist method (Patent Document 2) combining a photoresist layer obtained from an organic photosensitive polymer used in the single-layer resist method, a resist intermediate film obtained from a silicon polymer or a silicon CVD film, and a resist lower film obtained from an organic polymer has been developed.

[0005] In the three-layer resist method, for example, an organic film obtained by novolac or the like is uniformly formed on a substrate to be processed as a resist lower layer film, a silicon-containing resist intermediate film is formed thereon as a resist intermediate film, and a general organic photoresist film is formed thereon as a resist upper layer film. In dry etching by fluorine-based gas plasma, the organic resist upper layer film can obtain a good etching selectivity ratio to the silicon-containing resist intermediate film, so the resist pattern is transferred to the silicon-containing resist intermediate film by dry etching using fluorine-based gas plasma. By this method, even if a resist composition is used that is difficult to form a pattern with a sufficient film thickness for directly processing a processed substrate or a resist composition that has insufficient dry etching resistance for processing a substrate, the pattern can still be transferred to a silicon-containing resist intermediate film. If the pattern transfer is then performed by dry etching using oxygen-based gas plasma, a pattern of a phenolic varnish film (resist lower layer film) with sufficient dry etching resistance during processing can be obtained.

[0006] As for the organic film (organic lower layer film) mentioned above, there are many technologies known (e.g., Patent Document 3), but in recent years, with the progress of miniaturization, in addition to dry etching characteristics, the need for excellent embedding characteristics has gradually increased. It is necessary to have an organic film material that can form a film uniformly on the base, i.e., the processed substrate, even if the substrate has a complex shape and material, and has embedding characteristics that can be embedded in the required pattern in a void-free manner.

[0007] When manufacturing semiconductor substrates, etc., organic films such as those described above are formed using a coater / developer that can perform processes such as spin coating, EBR, and firing. The so-called EBR (Edge Bead Removal) step is a step in which, after forming a film on a substrate (wafer) by spin coating, a removal liquid is used to remove the film at the end of the substrate in order to prevent contamination of the substrate transport arm of the coater / developer. As for the removal liquid used in the EBR step, there is a mixed solution of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30% by mass: 70% by mass), which is widely used in the EBR step of resist upper films and resist lower films (silicon-containing resist intermediate films, organic films).

[0008] The removal agent in the EBR step may cause the outer periphery of the organic film to be thick (protrusion). In the dry etching step during substrate processing, the protrusion may cause defects, so an organic film with suppressed protrusion is required.

[0009] After the organic film forms a spin-coated film, a baking treatment is performed to form a hardened film in order to be used for multilayer resist processing. This is because an insoluble and infusible organic film is required to coat the silicon-containing resist intermediate film on the upper layer. The surface of the organic film formed by the baking treatment forms a hydrophobic surface due to the surfactant contained in the organic film forming composition, which sometimes causes abnormal coating of the silicon-containing resist intermediate film. In order to improve the coating properties of the silicon-containing resist intermediate film and expand the processing tolerance, it is necessary to control the contact angle of the surface of the organic film.

[0010] Prior art literature

[0011] Patent Literature

[0012] [Patent Document 1] Japanese Patent Application Laid-Open No. 6-118651

[0013] [Patent Document 2] Japanese Patent No. 4355943

[0014] [Patent Document 3] Japanese Patent Application Publication No. 2004-205685 Summary of the invention

[0015] [Problems to be solved by the invention]

[0016] The present invention is made in view of the above situation, and its object is to provide an organic film forming composition which has excellent film forming properties (in-plane uniformity) and filling characteristics on a substrate (wafer), suppresses protrusions during the EBR step, and has excellent processing tolerance when used as an organic film for a multilayer resist, an organic film forming method using the composition, a pattern forming method, and a polymer used in the aforementioned organic film forming composition.

[0017] [Methods to solve the problem]

[0018] In order to solve the above problems, the present invention provides an organic film-forming composition, characterized in that it comprises (A) an organic film-forming material, (B) a polymer having a repeating unit represented by the following general formula (1), and (C) a solvent.

[0019] [Chemistry 1]

[0020]

[0021] In the formula, W1 is a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms, which is a divalent organic group having one or more fluorine-containing structures represented by the following formula (2) in the organic group, and W2 is a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms,

[0022] [Chemistry 2]

[0023]

[0024] In the formula, * represents an atomic bond in the organic group represented by W1, and the organic group may have any two or more structures represented by the above formula (2) or two or more identical structures.

[0025] Such an organic film-forming composition can form an organic film having excellent in-plane uniformity and filling characteristics, and suppressing the formation of protrusions due to the influence of the remover in the EBR step. In addition, since the repeating unit has an acetal structure, when used as an organic film, the hydrophobic component unevenly distributed on the surface of the organic film is removed by thermal decomposition by baking during the formation of a hardened film, so it is an organic film-forming composition with excellent coating properties for a silicon-containing interlayer.

[0026] In the present invention, W1 in the above-mentioned general formula (1) is preferably a divalent organic group represented by the following general formula (3).

[0027] [Chemistry 3]

[0028]

[0029] In the formula, * represents an atomic bond to an oxygen atom, L is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, and R1 is a substituent having one or more structures represented by the formula (2).

[0030] If the organic film-forming composition includes such a polymer, the film-forming property during coating can be improved due to the appropriate fluorine content, and the thermal decomposition temperature of the polymer can be controlled within an appropriate range, and the decomposition products can be removed from the film without forming residues on the surface and inside the cured film after baking the organic film.

[0031] Furthermore, in the present invention, R1 in the above-mentioned general formula (3) is more preferably a group represented by the following general formula (4).

[0032] [Chemistry 4]

[0033]

[0034] In the formula, * represents an atomic bond to an oxygen atom, and n1, n2, and n3 represent integers of 1 to 10.

[0035] The organic film-forming composition containing such a polymer has an appropriate fluorine content, and thus can improve film-forming properties during coating.

[0036] Furthermore, W2 in the above general formula (1) may be the following general formula (5).

[0037] [Chemistry 5]

[0038]

[0039] In the formula, * represents an atomic bond to an oxygen atom, and n4 and n5 represent integers of 1 to 10.

[0040] If the composition for forming an organic film includes such a polymer, the decomposition products generated during baking will not damage the uniformity of the film surface, and insoluble components will not be formed due to the reaction between the decomposition products. Therefore, the handling tolerance when used as an organic film will not be narrowed, and equipment contamination and inconvenience will not occur.

[0041] The weight average molecular weight of the polymer (B) is preferably 1,000 to 30,000.

[0042] When the weight average molecular weight is within such a range, an organic film having excellent film-forming properties and filling characteristics can be formed.

[0043] The content of the polymer (B) is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the organic film-forming material (A).

[0044] It is preferred that the organic film-forming composition contains the polymer in such a content because the in-plane uniformity of the formed organic film is further improved.

[0045] Furthermore, the present invention provides an organic film forming method, which is used in the manufacturing process of a semiconductor device, characterized in that:

[0046] The organic film-forming composition is spin-coated on a substrate to be processed to form a coating film, and the coating film is heat-treated at a temperature ranging from 100° C. to 600° C. for 10 to 600 seconds to cure the coating film and form an organic film.

[0047] The organic film forming composition of the present invention is particularly useful for filling a complex pattern on a substrate to be processed by spin coating and forming an organic film with excellent in-plane uniformity, and for removing the organic film at the edge while suppressing bulges in the EBR step.

[0048] Furthermore, the present invention provides a pattern forming method, characterized in that:

[0049] An organic film is formed on a workpiece using the above-mentioned organic film forming composition, a silicon-containing resist intermediate film is formed on the organic film using a silicon-containing resist intermediate film material, a resist upper film material composed of a photoresist composition is used on the silicon-containing resist intermediate film to form a resist upper film, a circuit pattern is formed on the resist upper film, the resist upper film on which the circuit pattern is formed is used as a mask and the pattern is transferred to the silicon-containing resist intermediate film by etching, the silicon-containing resist intermediate film to which the pattern is transferred is used as a mask and the pattern is transferred to the organic film by etching, and the organic film to which the pattern is transferred is used as a mask and the pattern is transferred to the workpiece by etching.

[0050] Furthermore, the present invention provides a pattern forming method, characterized in that:

[0051] An organic film is formed on a workpiece using the above-mentioned organic film forming composition, a silicon-containing resist intermediate film is formed on the organic film using a silicon-containing resist intermediate film material, an organic anti-reflective film or a bonding film is formed on the silicon-containing resist intermediate film, a resist upper film material composed of a photoresist composition is used on the organic anti-reflective film or the bonding film to form a resist upper film, a circuit pattern is formed on the resist upper film, the resist upper film on which the circuit pattern is formed is used as a mask and the pattern is transferred to the organic anti-reflective film or the bonding film and the silicon-containing resist intermediate film by etching, the silicon-containing resist intermediate film to which the pattern is transferred is used as a mask and the pattern is transferred to the organic film by etching, and the organic film to which the pattern is transferred is used as a mask and the pattern is transferred to the workpiece by etching.

[0052] Furthermore, the present invention provides a pattern forming method, characterized in that:

[0053] An organic film is formed on a workpiece using the organic film forming composition, an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film is formed on the organic film, a resist upper film material composed of a photoresist composition is used on the inorganic hard mask to form a resist upper film, a circuit pattern is formed on the resist upper film, the resist upper film on which the circuit pattern is formed is used as a mask and the pattern is transferred to the inorganic hard mask by etching, the inorganic hard mask to which the pattern is transferred is used as a mask and the pattern is transferred to the organic film by etching, and the organic film to which the pattern is transferred is used as a mask and the pattern is transferred to the workpiece by etching.

[0054] Furthermore, the present invention provides a pattern forming method, characterized in that:

[0055] An organic film is formed on a workpiece using the above-mentioned organic film forming composition, 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 or a bonding film is formed on the inorganic hard mask, a resist upper film material composed of a photoresist composition is used on the organic antireflective film or the bonding film to form a resist upper film, a circuit pattern is formed on the resist upper film, the resist upper film on which the circuit pattern is formed is used as a mask and the pattern is transferred to the organic antireflective film or the bonding film and the inorganic hard mask by etching, the inorganic hard mask to which the pattern is transferred is used as a mask and the pattern is transferred to the organic film by etching, and the organic film to which the pattern is transferred is used as a mask and the pattern is transferred to the workpiece by etching.

[0056] Thus, the organic film forming composition of the present invention is suitable for various pattern forming methods such as three-layer resist processing using a silicon-containing resist intermediate film or an inorganic hard mask, and four-layer resist processing using an organic anti-reflective film or a bonding film in addition to these. If it is such a pattern forming method of the present invention, the circuit pattern of the resist upper layer film can be transferred to the processed body with high precision to form.

[0057] Furthermore, the inorganic hard mask is preferably formed by a CVD method or an ALD method.

[0058] The pattern forming method of the present invention can form an inorganic hard mask by using such a method, for example.

[0059] In the formation of the circuit pattern, it is preferred that the circuit pattern be formed by photolithography using light with a wavelength of 10 nm to 300 nm, direct drawing with an electron beam, nanoimprinting, or a combination thereof.

[0060] Furthermore, in the formation of the aforementioned circuit pattern, it is preferred that the circuit pattern be developed by alkaline development or organic solvent.

[0061] The pattern forming method of the present invention is suitable for use in such a circuit pattern forming means and developing means.

[0062] Furthermore, the aforementioned object to be processed is preferably a semiconductor device substrate, or a substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film is formed.

[0063] In this case, the metal constituting the processed material is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0064] According to the pattern forming method of the present invention, the above-mentioned object to be processed can be processed to form a pattern.

[0065] The present invention further provides a polymer having a repeating unit represented by the following general formula (1):

[0066] [Chemistry 6]

[0067]

[0068] In the formula, W1 is a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms, which is a divalent organic group having one or more fluorine-containing structures represented by the following formula (2) in the organic group, and W2 is a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms,

[0069] [Chemistry 7]

[0070]

[0071] In the formula, * represents an atomic bond in the organic group represented by W1, and the organic group may have any two or more structures represented by the above formula (2) or two or more identical structures.

[0072] Such a polymer is an ideal polymer because it has excellent in-plane uniformity and filling characteristics and suppresses the formation of ridges due to the influence of the remover in the EBR step by combining specific fluorine substituents. In addition, since the polymer has an acetal structure in the repeating unit, when the polymer of the present invention is used as an organic film-forming composition for forming an organic film, the hydrophobic components unevenly distributed on the surface of the organic film are removed by thermal decomposition by baking during the formation of the cured film, so that the coating property of the silicon-containing intermediate film is excellent and an organic film with a good surface can be formed.

[0073] In this case, W1 in the general formula (1) is preferably a divalent organic group represented by the following formula (3).

[0074] [Chemistry 8]

[0075]

[0076] In the formula, * represents an atomic bond to an oxygen atom, L is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, and R1 is a substituent having one or more structures represented by the formula (2).

[0077] Since the repeating unit of such a polymer has a structure in which a secondary alcohol is acetalized, the polymer can be completely decomposed by setting the thermal decomposition temperature of the polymer to the range of the baking temperature for curing the film during the formation of the organic film. Therefore, when an organic film is formed using the organic film-forming composition, the decomposition product does not remain as residue on the surface of the cured film and in the film after baking.

[0078] In this case, R1 in the above general formula (3) is preferably a group represented by the following general formula (4).

[0079] [Chemistry 9]

[0080]

[0081] In the formula, * represents an atomic bond to an oxygen atom, and n1, n2, and n3 represent integers of 1 to 10.

[0082] By introducing a structure having an appropriate fluorine substituent as described above into a polymer, the film-forming property when applying the organic film-forming composition can be improved.

[0083] W2 in the above general formula (1) is preferably the following formula (5).

[0084] [Chemistry 10]

[0085]

[0086] In the formula, * represents an atomic bond to an oxygen atom, and n4 and n5 represent integers of 1 to 10.

[0087] By introducing such a partial structure, the generated decomposition products do not impair the in-plane uniformity of the film, and insoluble components are not formed due to reactions between the decomposition products.

[0088] The weight average molecular weight of the aforementioned polymer is preferably 1,000 to 30,000.

[0089] When the weight average molecular weight is within such a range, an organic film having excellent film-forming properties and filling properties can be formed. The weight average molecular weight can be obtained by the method described below.

[0090] [Effects of the Invention]

[0091] As described above, the present invention can provide an organic film forming composition having excellent film forming properties (uniformity in the plane) and embedding properties on a substrate (wafer), excellent film forming properties on an organic film when used as an organic film, and suppressed ridges during an EBR step. The organic film forming composition of the present invention is excellent in film forming properties, embedding properties, and suppression of ridges generated during an EBR step, and is therefore very useful, for example, for organic film materials used in multilayer resist processes such as two-layer resist processes, three-layer resist processes using a silicon-containing resist intermediate film or an inorganic hard mask, or four-layer resist processes using a silicon-containing resist intermediate film or an inorganic hard mask and an organic antireflective film or a bonding film, or for the formation of organic films for semiconductor device manufacturing. Furthermore, the organic film forming method of the present invention can form an organic film with suppressed ridges, so that semiconductor elements and the like can be efficiently manufactured. Furthermore, the polymer of the present invention has a thermally decomposable acetal structure and has a specific fluorine substituent, thereby exhibiting the above-mentioned characteristics and is useful for an organic film-forming composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0092] [ Figure 1 ] is an example of a graph showing the height of ridges of an organic film-forming composition in which ridges are suppressed, measured using a contact profiler.

[0093] [ Figure 2 ] is an example of a graph showing the height of ridges of an organic film-forming composition in which ridges are not suppressed, measured using a contact profiler.

[0094] [ Figure 3 ] (A) to (F) are explanatory diagrams of an example of a pattern forming method by a three-layer resist process of the present invention.

[0095] [ Figure 4 ](G) to (I) are explanatory diagrams of the landfill characteristic evaluation method in the example. DETAILED DESCRIPTION

[0096] As described above, there is a need to develop an organic film-forming composition that has excellent film-forming properties (in-plane uniformity) and filling properties on a substrate (wafer) and that has suppressed protrusions during an EBR step.

[0097] Typically, when forming an organic film, an organic film-forming resin and additives are dissolved in an organic solvent to form a composition, which is then applied to a substrate having a structure, wiring, etc. formed thereon by a coater / developer. The substrate is rotated to unfold the composition, and the composition at the end is removed in an EBR step, followed by firing to form an organic film.

[0098] If the composition has insufficient fluidity, voids may be generated when filling holes or trenches with very high aspect ratios. If the organic film-forming resin or additives have poor solubility in the remover used in the EBR step, bulges may be generated on the periphery of the organic film.

[0099] The inventors of the present application have further conducted in-depth studies and found that by blending a thermally decomposable polymer having a specific repeating unit into an organic film-forming composition, an organic film-forming composition having excellent film-forming properties, high-level filling characteristics, and swelling suppression during the EBR step can be provided, thereby completing the present invention.

[0100] That is, the present invention is an organic film-forming composition characterized by comprising (A) an organic film-forming material, (B) a polymer having a repeating unit represented by the following general formula (1), and (C) a solvent.

[0101] [Chemistry 11]

[0102]

[0103] In the formula, W1 is a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms, which is a divalent organic group having one or more fluorine-containing structures represented by the following formula (2) in the organic group, and W2 is a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms,

[0104] [Chemistry 12]

[0105]

[0106] In the formula, * represents an atomic bond in the organic group represented by W1, and the organic group may have any two or more structures represented by the above formula (2) or two or more identical structures.

[0107] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0108] [Organic film forming composition]

[0109] The organic film-forming composition of the present invention comprises (A) an organic film-forming material, (B) a polymer having a repeating unit represented by the following general formula (1), and (C) a solvent.

[0110] [Chemistry 13]

[0111]

[0112] In the formula, W1 is a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms, which is a divalent organic group having one or more fluorine-containing structures represented by the following formula (2) in the organic group, and W2 is a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms.

[0113] [Chemistry 14]

[0114]

[0115] In the formula, * represents a site in the divalent organic group W1 to which the fluorine-containing structure is bonded (an atomic bond in the organic group represented by W1), and the organic group may have any two or more structures represented by the above formula (2) or two or more identical structures.

[0116] In the organic film-forming composition of the present invention, the (B) polymer, the (A) organic film-forming material, and the (C) solvent may be used alone or in combination of two or more.

[0117] Hereinafter, among the constituent components of the organic film-forming composition, the polymer that is a characteristic of the present invention will be described first, and then the organic film-forming material, solvent, and other components will be described.

[0118] [polymer]

[0119] The polymer (B) of the present invention is a polymer having a repeating unit represented by the above general formula (1). This polymer is useful for forming an organic film.

[0120] The polymer (polymer for forming organic film) of the present invention is a polymer containing an acetal structure in the repeating unit. The acetal structure added to the polymer will decompose due to heat, etc. If the decomposition product generated at this time remains in the film or on the film surface, when used as an organic film, it will affect the coating property of the silicon-containing intermediate film formed on the organic film, etc. . Therefore, by appropriately designing the W1 and W2 of the main structure of the repeating unit of the polymer of the present invention, a polymer with a suitable structure and decomposition temperature that will not remain on the film surface or in the film due to thermal decomposition is designed. In addition, by introducing a suitable fluorine-containing substituent or linking group into the main skeleton of the polymer, the surface tension will be reduced, and the effect of a surfactant that brings uniform coating (leveling) of an excellent organic film can be provided. Therefore, when the polymer of the present invention is used as a surfactant, it is not limited to organic films, and can also be used in all coating materials for optical lithography. Specifically, it can be exemplified as a photosensitive resist material, a surface coating forming material formed on a resist film, etc. In this way, the polymer of the present invention has thermal decomposition and has the characteristics of being able to function as a surfactant.

[0121] W1 in the above general formula (1) is preferably the following general formula (3).

[0122] [Chemistry 15]

[0123]

[0124] In the formula, * represents an atomic bond to an oxygen atom, L is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, and R1 is a substituent having one or more structures represented by the formula (2).

[0125] By introducing W1 as described above into the main chain structure to form an acetal structure derived from a secondary alcohol, an appropriate thermal decomposition temperature can be designed. When the organic film-forming composition is formed into a film and then hardened by heat treatment, the polymer will decompose due to heat and will not remain in the film (yes, inside).

[0126] L is a linking group, and may be a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, and is not particularly limited. Examples thereof include a linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms, a linear, branched, or cyclic alkylene group having 2 to 30 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an arylene group having 6 to 30 carbon atoms, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylene group having 7 to 15 carbon atoms, a fluorenediyl group, and the like, and these may be combined in the range of 1 to 30 carbon atoms. In addition, L may have a halogen atom such as fluorine or chlorine, an ether bond, a carbonyl group, an ester group, an amide group, or an amino group in its structure, and may form a heterocyclic structure via an amide group, an ester group, or the like.

[0127] Furthermore, considering the availability of raw materials and the ease of synthesis, the two ends of the linking group L are not oxygen atoms (ether bonds), and may be methylene groups, for example (CH2) a Straight chain alkylene, CH2(OCH2CH2) b (OCH2) represents an ethylene glycol dimethyl ether chain with methylene groups at both ends, CH2(CF2) c CH2 represents a divalent group having methylene groups at both ends and a linear perfluoroalkylene group between them (here, a is an integer of 1 to 12, b is an integer of 1 to 5, and c is an integer of 1 to 10).

[0128] More specifically, there can be exemplified an ethylene group, a propylene group, a butylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a decamethylene group, a dodecamethylene group, an eicosamethylene group, a triacontamethylene group, a cyclopentanediyl group, a cyclohexanediyl group, a dimethylcyclohexanediyl group, a 2-butene-1,4-diyl group, a 2,4-hexadiene-1,6-diyl group, a 3-oxypentane-1,5-diyl group, a 3,6-dioxyoctane-1,8-diyl group, a 3,6,9-trioxyundecane-1,11-diyl group, a phenylene group, a dimethylphenyl group, a naphthalenediyl group, a dimethylnaphthalenediyl group, and an adamantanediyl group.

[0129] These groups may constitute L alone or in combination of two or more.

[0130] As W1 mentioned above, the following can be exemplified. R1 is a substituent having one or more structures represented by the above formula (2), and * represents an atomic bond to an oxygen atom.

[0131] [Chemistry 16]

[0132]

[0133] [Chemistry 17]

[0134]

[0135] [Chemistry 18]

[0136]

[0137] Among the above, from the viewpoint of improving thermal decomposition properties, a structure without an aromatic ring is preferred, and from the viewpoint of surface activity, a structure without nitrogen is preferred. For examples satisfying these requirements, the following linking group preferably has a structure connected via an ethylene glycol dimethyl ether chain or a linear alkylene group.

[0138] [Chemistry 19]

[0139]

[0140] In the formula, * represents an atomic bond to an oxygen atom.

[0141] R1 in the above general formula (3) is a substituent having at least one structure represented by general formula (2), and specific examples thereof include the following. (In the formula, n1, n2, and n3 represent integers of 1 to 10. n6 to n9 represent integers of 1 to 10. * represents an atomic bond.)

[0142] [Chemistry 20]

[0143]

[0144] [Chemistry 21]

[0145]

[0146] [Chemistry 22]

[0147]

[0148] Among the above, the viewpoints of considering the surface activity are preferably as follows. If these are the above, the film forming property can be expected to be improved due to the introduction of appropriate fluorine content and fluorine structure. (n1, n2, and n3 are the same as above.)

[0149] [Chemistry 23]

[0150]

[0151] Examples of W2 in the general formula (1) include the following. (n4 and n5 represent integers of 1 to 10.)

[0152] [Chemistry 24]

[0153]

[0154] Among the above, from the perspective of improving thermal decomposition properties, structures without aromatic rings are preferred. For examples that meet these requirements, the connecting group has a structure represented by the following formula (5) connected via an ethylene glycol dimethyl ether chain, or a linear alkylene group. (n4 and n5 are the same as above)

[0155] [Chemistry 25]

[0156]

[0157] With the above-mentioned structure, the thermal decomposition property, the surface active effect, and the fluidity of the polymer can be adjusted, thereby achieving a polymer having both film-forming property and embedding property.

[0158] The weight average molecular weight of the polymer (B) is preferably 1,000 to 30,000, more preferably 1,500 to 25,000. If the weight average molecular weight is 1,000 or more, the decrease in the blending effect due to volatilization can be suppressed, and a sufficient blending effect can be obtained. If the weight average molecular weight is 30,000 or less, there is no deterioration in fluidity, and the landfill property is excellent.

[0159] In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene-equivalent values ​​obtained by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent (solvent), and the dispersion degree (Mw / Mn) is calculated from Mw and Mn.

[0160] [Method for producing polymer]

[0161] The above-mentioned polymer having a structure represented by the general formula (1) can be produced by selecting the best method according to the structure, and an example thereof is a polyaddition reaction of a diol compound having W1 as a partial structure (connecting group) and a divinyl ether compound having W2 as a partial structure (connecting group) using an acid catalyst.

[0162] [Chemistry 26]

[0163]

[0164] Where W1 and W2 are the same as above.

[0165] The above reaction is a general acetal formation reaction using an acid catalyst as a basic reaction. This basic reaction is repeated to eventually obtain a polymer. In the above reaction, the optimal amount of the divinyl ether compound having W2 as a partial structure relative to the diol compound having W1 as a partial structure is preferably 0.5 mol to 2 mol, and more preferably 0.8 mol to 1.2 mol, relative to 1 mol of the diol compound.

[0166] The acetalization reaction can be carried out by mixing the raw materials with an acid catalyst in a solvent or in a solvent-free state, and cooling or heating. When a solvent is used in the reaction, the solvent is selected from aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene, xylene, trimethylbenzene, methylnaphthalene; ethers such as diethyl ether, butyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran; ketones such as acetone and 2-butanone; alcohols such as tert-butyl alcohol and tert-amyl alcohol; esters such as ethyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone; nitriles such as acetonitrile; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; halogenated hydrocarbons such as o-dichlorobenzene, dichloromethane, 1,2-dichloroethane, etc., and can be used alone or in combination of two or more.

[0167] As the acid catalyst used in the reaction, various inorganic acids, organic acids, and solid acids can be used. Specifically, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, camphorsulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, cation exchange resin, sodium hydrogen sulfate, pyridinium p-toluenesulfonate and the like can be mentioned. The amount of these acid catalysts used is preferably 1×10 -5 ~5×10 -1 Moore.

[0168] The reaction temperature is preferably -20°C to 100°C, more preferably 0°C to 80°C. When a solvent is used, it is better to set the upper limit to about the boiling point of the solvent. If the reaction temperature is above -20°C, the reaction will proceed smoothly. If it is below 100°C, side reactions such as decomposition reactions of the product can be suppressed. In order to improve the yield, the reaction time of the above reaction is preferably determined by tracking the progress of the reaction by thin layer chromatography, liquid chromatography, colloid filtration chromatography, etc., and is usually about 0.5 to 200 hours. After the reaction is completed, the aforementioned thermally decomposable polymer, which is the target, can be obtained by general aqueous work-up and / or filtration of the insoluble components.

[0169] The obtained polymer having the structure (repeating unit) represented by the general formula (1) can be purified by conventional methods such as liquid separation, crystallization, vacuum concentration, dialysis, ultrafiltration, etc., depending on its properties, if necessary. In addition, the metal content can be reduced by passing through a commercially available metal removal filter, if necessary.

[0170] Furthermore, the polymer having the structure represented by the above general formula (1) after purification can also be concentrated to dryness or crystallized by reduced pressure or normal pressure as described above, and recovered as a powder depending on the properties of the polymer. In order to improve the operability when preparing the organic film-forming composition, it can also be adjusted in advance to a solution state of appropriate concentration. As for the concentration at this time, it is preferably 0.1 to 50% by mass, and more preferably 0.5 to 30% by mass. If it is such a concentration, the viscosity is not easy to become too high, so it can prevent damage to the operability, and the amount of the solvent will not become too large, so it is economical.

[0171] The solvent at this time is not particularly limited as long as it can dissolve the compound. Specific examples include ketones such as cyclohexanone and methyl-2-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono-tert-butyl ether acetate. These can be used alone or in combination of two or more.

[0172] As for the reaction method, for example, a method of adding each raw material, an acid catalyst, and a solvent as required, a method of dropping each raw material or raw material solution alone or mixed in the presence of a catalyst, or a method of passing a mixed raw material or mixed raw material solution through a column filled with a solid acid catalyst, etc. The molecular weight can be adjusted, for example, by controlling the reaction time, the amount of the acid catalyst, the addition / content adjustment of a polymerization terminator such as water / alcohol / alkaline compound, the raw material input ratio when two raw materials are used, or a combination of these.

[0173] The diol compound having W1 as a partial structure and the divinyl ether compound having W2 as a partial structure may be used alone or in combination of two or more. The divinyl ether compound having W2 as a partial structure may be unstable to oxygen, light, moisture, etc. In such a case, the reaction is preferably carried out in an inert environment such as nitrogen or under light shielding.

[0174] [Another method for producing a polymer]

[0175] When producing a polymer having a structure represented by the above general formula (1), when a diol compound having W1 as a partial structure and a divinyl ether compound having W2 as a partial structure are subjected to a polyaddition reaction using an acid catalyst, the number of moles of the diol component is A and the number of moles of the divinyl ether component is B, and the input ratio A and B can produce a polymer having the following terminal structure. (W1 and W2 are the same as above)

[0176] [Chemistry 27]

[0177]

[0178] In the case of the above method 2, since the vinyl ether group that can react with alcohol remains at the end, a block copolymer (I) can be obtained by further using a diol component, and the end can be sealed (II) by using a monool component. For block polymers, when multiple diol components are used in the reaction shown in the above method 2, they are randomly incorporated into the polymer. Different repeating units can be incorporated into the two ends of the polymer in two steps, and different diol components can be further multi-blocked by reacting in multiple stages. Furthermore, after the block polymer is synthesized, if the input ratio of the diol component to the divinyl ether component is further adjusted in advance, the end can also be modified using a monool (III).

[0179] (W3 is a monovalent organic group having 1 to 30 carbon atoms, and W1' is a group having a different structure from W1 used in Embodiment 1 and a similar partial structure)

[0180] (I) Block polymer

[0181] [Chemistry 28]

[0182]

[0183] (II) Polymer terminal modification

[0184] [Chemistry 29]

[0185]

[0186] (III) Block polymer + terminal modification

[0187] [Chemistry 30]

[0188]

[0189] The above reaction is carried out by simply adding the diol component and the monool component in multiple stages. The reaction method and the polymer recovery method can be carried out by the above-described method for producing the polymer having a structure represented by the general formula (1).

[0190] Examples of the monohydric alcohol component using W3 as a partial structure in the above reaction formula include the following. Among these, since thermal decomposition improves the landfilling property during decomposition, it is preferred to use a monohydric alcohol component with a boiling point of 180°C or higher. (n10 to n15 represent integers of 1 to 10.)

[0191] [Chemistry 31]

[0192]

[0193] In the preparation of the polymer used in the organic film-forming composition obtained by this method, various diol components and monool components can be used and the manufacturing method of the polymer can be appropriately selected in combination with the required performance. For example, the side chain structure and surface tension that contribute to the improvement of the planarization characteristics can be controlled and fluorine-containing substituents and the like that are used to change the surface activity can be arbitrarily combined. Therefore, when the organic film-forming composition using these polymers is used for the organic film, various properties such as film forming properties and embedding properties can be taken into consideration at high standards.

[0194] [Organic film forming materials]

[0195] As for the (A) organic film-forming material (resin or compound) used in the organic film-forming composition of the present invention, there is no particular limitation on the resin or compound that satisfies the film-forming and curing properties of spin coating. Considering the etching resistance, optical properties, heat resistance, etc., resins or compounds containing an aromatic skeleton are preferred.

[0196] Examples of the aromatic skeleton include benzene, naphthalene, anthracene, pyrene, indene, fluorene, furan, pyrrole, thiophene, oxazole, pyrazole, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, and carbazole. Among these, benzene, naphthalene, fluorene, and carbazole are particularly preferred.

[0197] Hereinafter, specific examples of the above-mentioned (A) organic film-forming material will be described, but these are merely illustrative and the present invention is not limited thereto. In addition, the numbers of the chemical formulas shown in the following examples are only applicable to the description of the following formulas.

[0198] Examples of the (A) organic film-forming material (resin or compound) used in the present invention include resins having the following structures and the like described in JP-A-2012-001687 and JP-A-2012-077295.

[0199] [Chemistry 32]

[0200]

[0201] In formula (1), the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. 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 that makes the molecular weight 100,000 or less. The symbols in the formula apply only to the formula.

[0202] [Chemistry 33]

[0203]

[0204] In formula (2), the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. n represents an arbitrary natural number that makes the polystyrene-equivalent weight average molecular weight for gel permeation chromatography 100,000 or less. The symbols in the formula apply only to the formula.

[0205] Examples of the (A) organic film-forming material used in the present invention include resins having the following structures and the like described in Japanese Patent Application Laid-Open Nos. 2004-264710, 2005-043471, 2005-250434, 2007-293294, and 2008-065303.

[0206] [Chemistry 34]

[0207]

[0208] In formula (3) and formula (4), R 1 and R 2 represents a hydrogen atom or an alkyl or aryl group having 1 to 3 carbon atoms, and R 3 represents an alkyl group having 1 to 3 carbon atoms, a vinyl group, an allyl group, or an optionally substituted aryl group, n represents 0 or 1, and m represents 0, 1 or 2. The symbols in the formula apply only to the formula.

[0209] [Chemistry 35]

[0210]

[0211] In formula (5), R1 is a monovalent atom or group other than a hydrogen atom, and n is an integer of 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. In addition, the symbols in the formula apply only to the formula.

[0212] [Chemistry 36]

[0213]

[0214] In formula (6), R1 is a hydrogen atom or a methyl group. R2 is a single bond, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 10 carbon atoms, and may be an ether, an ester, a lactone, or an amide. 3 , R 4 X represents a polymer of any of an indene skeleton-containing hydrocarbon, a cycloolefin having 3 to 10 carbon atoms, and maleimide, and may have any of ether, ester, lactone, and carboxylic anhydride. 5 , R 6 R is any of a hydrogen atom, a fluorine atom, a methyl group, and a trifluoromethyl group. 7It is any of a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a hydroxyl group, and an alkoxycarbonyl group. p and q are integers of 1 to 4, respectively. r is an integer of 0 to 4. a, b, and c are in the ranges of 0.5≤a+b+c≤1, 0≤a≤0.8, 0≤b≤0.8, 0.1≤a+b≤0.8, and 0.1≤c≤0.8, respectively. The symbols in the formula apply only to the formula.

[0215] [Chemistry 37]

[0216]

[0217] In formula (7), R1 represents a hydrogen atom or a monovalent organic group, and R2 and R3 independently represent a monovalent atom or a monovalent organic group. The symbols in the formula apply only to the formula.

[0218] Specific examples of the (A) organic film-forming material used in the present invention include resins having the following structures and described in Japanese Patent Application Laid-Open Nos. 2004-205685, 2007-171895, and 2009-014816.

[0219] [Chemistry 38]

[0220]

[0221] In formula (8) and formula (9), R 1 ~R 8 Each of the above is independently a hydrogen atom, a hydroxyl group, a substituted alkyl group having 1 to 6 carbon atoms, a substituted alkoxy group having 1 to 6 carbon atoms, a substituted alkoxycarboxyl group having 2 to 6 carbon atoms, a substituted aryl group having 6 to 10 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, an isocyanate group, or a glycidyl group. m and n are positive integers. The symbols in the formula apply only to the formula.

[0222] [Chemistry 39]

[0223]

[0224] In formula (10), R 1 , R 6 is a hydrogen atom or a methyl group. 2 , R 3 , R 4 is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, an acetoxy group or an alkoxycarbonyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, R 5 is a condensed polycyclic hydrocarbon group having 13 to 30 carbon atoms, -OR 7 、-C(=O)-OR 7 、-OC(=O)-R 7、 or -C(=O)-NR 8 -R 7 wherein 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, and R 8 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Z is any one of methylene, -O-, -S-, -NH-. a, b, c, d, e respectively satisfy the ranges of 0 < a < 1.0, 0 ≤ b ≤ 0.8, 0 ≤ c ≤ 0.8, 0 ≤ d ≤ 0.8, 0 ≤ e ≤ 0.8, and 0 < b + c + d + e < 1.0. And, the notations in the formula are only applicable to this formula.

[0225] [Chemical formula 40]

[0226]

[0227] 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 alkyl ether group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. And, the notations in the formula are only applicable to this formula.

[0228] Regarding formula (11), for example, the following resins can be exemplified.

[0229] [Chemical formula 41]

[0230]

[0231] [Chemical formula 42]

[0232]

[0233] Regarding the material (A) for forming an organic film used in the present invention, resins having the following structures described in JP-A-2007-199653, JP-A-2008-274250, and JP-A-2010-122656 can be exemplified.

[0234] [Chemical formula 43]

[0235]

[0236] In formula (12), R 1 and R 2 are independently 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, and R 3 is a single bond, or a linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms, and may also have a bridged hydrocarbon group, a double bond, a heteroatom, or an aromatic group having 6 to 30 carbon atoms, R 4 and R 5 Each is independently a hydrogen atom or a glycidyl group, and n is an integer of 1 to 4. In addition, the symbols in the formula apply only to the formula.

[0237] [Chemistry 44]

[0238]

[0239] In formula (13), R 1 and R 2 are independently 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, and R 3 is a single bond, or a linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms, and may also have a bridged hydrocarbon group, a double bond, a heteroatom, or an aromatic group having 6 to 30 carbon atoms, R 4 and R 5 are independently a hydrogen atom or a glycidyl group, R 6 It is a single bond, or a linear or branched alkylene group having 1 to 10 carbon atoms. The symbols in the formula apply only to the formula.

[0240] [Chemistry 45]

[0241]

[0242] In formula (14), ring Z 1 and Ring Z 2 is a condensed polycyclic aromatic hydrocarbon ring, R 1a , R 1b , R 2a , and R 2b are the same or different and represent a substituent. k1 and k2 are the same or different and represent an integer of 0 or 1 to 4, m1 and m2 are integers of 0 or 1 or more, and n1 and n2 are integers of 0 or 1 or more. However, n1+n2≥1. In addition, the symbols in the formula apply only to the formula.

[0243] [Chemistry 46]

[0244]

[0245] In formula (15), R 1 , R 2 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 an epoxypropyl group, and R 5 is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, R 6 , R 7 are a benzene ring or a naphthalene ring. p and q are each 1 or 2. n satisfies 0 < n ≤ 1. And the notations in the formula are only applicable to that formula.

[0246] Regarding formula (15), for example, the following resins can be exemplified.

[0247] [Chemical formula 47]

[0248]

[0249] [Chemical formula 48]

[0250]

[0251] [Chemical formula 49]

[0252]

[0253] [Chemical formula 50]

[0254]

[0255] Regarding the (A) organic film-forming material used in the present invention, resins described in Japanese Patent Application Laid-Open No. 2012-214720 and having the following structure can be exemplified.

[0256] [Chemical formula 51]

[0257]

[0258] In formula (16), the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. x and z each independently represent 0 or 1. And the notations in the formula are only applicable to that formula.

[0259] Regarding the (A) organic film-forming material used in the present invention, resins described in Japanese Patent Application Laid-Open No. 2014-29435 can be exemplified.

[0260] [Chemical formula 52]

[0261]

[0262] In formula (17), A represents a carbazole structure, 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 may form a ring with each other. The structure in which A, B, and C are combined has 1 to 4 carboxyl groups or salts thereof, or carboxylate groups. In addition, the symbols in the formula apply only to the formula.

[0263] In addition, as for the (A) organic film forming material used in the present invention, an example is a polymer described in International Publication No. 2012 / 077640, which contains a unit structure represented by the following formula (18) and a unit structure represented by the following 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 terms of molar ratio.

[0264] [Chemistry 53]

[0265]

[0266] 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 having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination of these groups which may also contain an ether bond, a ketone bond, or an ester bond. R3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination of these groups which may also contain an ether bond, a ketone bond, or an ester bond. R4 represents a hydrogen atom, or an aryl group having 6 to 40 carbon atoms which may be substituted with a halogen atom, a nitro group, an amino group, or a hydroxyl group, or a heterocyclic group. R5 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group which may also be substituted with a halogen atom, a nitro group, an amino group, or a hydroxyl group. R4 and R5 may form a ring with each other. n1 and n2 each represent an integer of 1 to 3. In addition, the symbols in the formula apply only to the formula.

[0267] [Chemistry 54]

[0268]

[0269] In formula (19), Ar represents an aromatic ring group having 6 to 20 carbon atoms, R6 represents a hydroxyl group, R7 represents a hydrogen atom, a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination of these groups which may also contain an ether bond, a ketone bond, or an ester bond. R8 represents a hydrogen atom, or an aryl group or a heterocyclic group having 6 to 40 carbon atoms which may be substituted by a halogen atom, a nitro group, an amino group, or a hydroxyl group, R9 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group or a heterocyclic group having 6 to 40 carbon atoms which may be substituted by a halogen atom, a nitro group, an amino group, or a hydroxyl group, and R8 and R9 may 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 substituents on the aromatic ring group Ar. In addition, the symbols in the formula apply only to the formula.

[0270] Examples of the (A) organic film-forming material used in the present invention include polymers having a unit structure represented by the following formula (20) described in International Publication No. 2010 / 147155.

[0271] [Chemistry 55]

[0272]

[0273] In formula (20), R1 and R2 are each selected from the group consisting of a hydrogen atom, a halogen group, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof, and the alkyl group, the alkenyl group, or the aryl group represents a group that may also contain an ether bond, a ketone bond, or an ester bond, and R3 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof. The alkyl, alkenyl or aryl group is a group that may contain an ether bond, a ketone bond or an ester bond, R4 is an aryl or heterocyclic group with 6 to 40 carbon atoms that may be substituted by a halogen group, a nitro group, an amino group or a hydroxyl group, R5 is a hydrogen atom, or an alkyl group with 1 to 10 carbon atoms, an aryl or heterocyclic group with 6 to 40 carbon atoms that may be substituted by a halogen group, a nitro group, an amino group or a hydroxyl group, and R4 and R5 may form a ring together with these bonded carbon atoms, and n1 and n2 are integers of 1 to 3. In addition, the symbols in the formula apply only to the formula.

[0274] As for the (A) organic film-forming material used in the present invention, examples include novolac resins obtained by reacting one or more phenols such as phenol, cresol, xylenol, catechol, resorcinol, hydroquinone, pyrogallol, trimerol, and pyrogallol with one or more aldehyde sources such as formaldehyde, paraformaldehyde, and trioxane using an acidic catalyst, and resins containing a repeating unit structure represented by the following formula (21) described in International Publication No. 2012 / 176767.

[0275] [Chemistry 56]

[0276]

[0277] In formula (21), A represents a hydroxy-substituted phenylene group derived from polyhydroxybenzene, and B represents a monovalent condensed aromatic hydrocarbon ring group in which 2 to 6 benzene rings are condensed. The symbols in the formula apply only to the formula itself.

[0278] As for the (A) organic film-forming material used in the present invention, examples include novolac resins having a fluorene or tetrahydrospirobiindene structure described in JP-A-2005-128509, JP-A-2006-259249, JP-A-2006-259482, JP-A-2006-293298, and JP-A-2007-316282, and resins having a repeating unit structure represented by the following formula (22-1) or (22-2).

[0279] [Chemistry 57]

[0280]

[0281] In formula (22-1) and formula (22-2), R 1 , R 2 , R 6 , R 7 are independently a hydrogen atom, a linear, 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, and R 3 , R 4 , R 8 , R 9 are independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms or a glycidyl group, and R 5 , R 14 R is independently a hydrogen atom, a linear, 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 of 1 to 3. 10 ~R 13are independently a hydrogen atom, a halogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms. The symbols in the formula apply only to the formula.

[0282] As for the (A) organic film-forming material used in the present invention, a reaction product obtained by the method described in Japanese Patent Application Publication No. 2012-145897 can be exemplified. More specifically, a polymer obtained by condensing one or more compounds represented by the following general formula (23-1) and / or (23-2) with one or more compounds represented by the following general formula (24-1) and / or (24-2) and / or their equivalents can be exemplified.

[0283] [Chemistry 58]

[0284]

[0285] In the general formula (23-1) and the general formula (23-2), R 1 ~R 8 are independently a hydrogen atom, a halogen atom, a hydroxyl group, an isocyano group, a glycidyl group, a carboxyl group, an amino group, an alkoxy group having 1 to 30 carbon atoms, an alkoxycarbonyl group having 1 to 30 carbon atoms, an alkylacyloxy group having 1 to 30 carbon atoms, or an optionally substituted saturated or unsaturated organic group having 1 to 30 carbon atoms. 1 ~R 4 or R 5 ~R 8 The two substituents in the formula may also be bonded to further form a cyclic substituent. Also, the symbols in the formula apply only to the formula.

[0286] [Chemistry 59]

[0287]

[0288] In the general formula (24-1) and the general formula (24-2), Q is an organic group having 1 to 30 carbon atoms which may be substituted, and two Qs selected arbitrarily in the molecule may be bonded to form a cyclic substituent. n1 to n6 are the number of each substituent, n1 to n6 = 0, 1, 2, and the formula (24-1) excludes hydroxybenzaldehyde. In addition, the formula (24-2) satisfies the relationship of 0≤n3+n5≤3, 0≤n4+n6≤4, 1≤n3+n4≤4. Moreover, the symbols in the formula apply only to the formula.

[0289] In addition, examples include polymers obtained by condensing one or more compounds represented by the above general formula (23-1) and / or (23-2), one or more compounds represented by the above general formula (24-1) and / or (24-2) and / or their equivalents, and one or more compounds represented by the following general formula (25) and / or their equivalents.

[0290] [Chemistry 60]

[0291] Y-CHO (25)

[0292] In formula (25), Y is a hydrogen atom or a monovalent organic group having 30 or less carbon atoms which may have a substituent, and formula (25) is different from general formula (24-1) and general formula (24-2). In addition, the symbols in the formula apply only to the formula.

[0293] Examples of the (A) organic film-forming material used in the present invention include compounds having the following structure and the like described in JP-A-2017-119671.

[0294] [Chemistry 61]

[0295]

[0296] In formula (26-1), R is a single bond or an organic group having 1 to 50 carbon atoms, X is a group represented by the following general formula (26-2), and m1 is an integer satisfying 2≤m1≤10. The symbols in the formula apply only to the formula.

[0297] [Chemistry 62]

[0298]

[0299] In the formula, X 2 is a divalent organic group having 1 to 10 carbon atoms, n1 is 0 or 1, n2 is 1 or 2, X 3 It is a group represented by the following general formula (26-3), and n5 is 0, 1 or 2. In addition, the symbols in the formula apply only to the formula.

[0300] [Chemistry 63]

[0301]

[0302] In the formula, R 10 It is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atoms on the benzene ring in the formula may be substituted by a methyl group or a methoxy group. The symbols in the formula apply only to the formula.

[0303] As the compound having the above structure, for example, the following compounds can be exemplified.

[0304] [Chemistry 64]

[0305]

[0306] Examples of the (A) organic film-forming material used in the present invention include polymers described in JP-A-2019-044022 and having a repeating unit represented by the following general formula (27-1).

[0307] [Chemistry 65]

[0308]

[0309] In formula (27-1), AR1 and AR2 are benzene rings or naphthalene rings which may have substituents, and R 1 , R 2 Each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, R 1 and R 2 When it is an organic group, R 1 With R 2 A cyclic organic group can also be formed by bonding in the molecule. n is 0 or 1. When n=0, AR1 and AR2 are not connected via Z, but the aromatic rings of AR1 and AR2 form a bridged structure. When n=1, AR1 and AR2 are connected via Z, but the aromatic rings of AR1 and AR2 form a bridged structure. Z is a single bond or any of the following formula (27-2). Y is a group represented by the following formula (27-3). In addition, the symbols in the formula apply only to the formula.

[0310] [Chemistry 66]

[0311]

[0312] [Chemistry 67]

[0313] ----R3-C==CR 4 (27-3)

[0314] In the formula, R 3 is a single bond or a divalent organic group having 1 to 20 carbon atoms, R 4 It is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and the dotted line represents an atomic bond. The symbols in the formula apply only to the formula.

[0315] Examples of the polymer having a repeating unit represented by the general formula (27-1) include the following polymers.

[0316] [Chemistry 68]

[0317]

[0318] [Chemistry 69]

[0319]

[0320] (A) The organic film-forming material may be synthesized by a known method, or a commercially available product may be used.

[0321] The amount of the aforementioned (A) organic film-forming material blended is not particularly limited if it satisfies the film-forming property of the organic film-forming composition by spin coating. Suppose that the aforementioned organic film-forming composition is 100 parts by mass, the content of the aforementioned (A) organic film-forming material is preferably 10 to 40 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 10 to 25 parts by mass. For example, when using the organic film-forming composition to fill extremely high aspect ratio holes and trenches of the 3D NAND memory structure, it is necessary to increase the amount of the organic film-forming material blended, but on the other hand, the viscosity of such an organic film-forming composition is high, and the in-plane uniformity and filling characteristics after spin coating will be deteriorated. Even with the blending ratio of the aforementioned (A) organic film-forming material, the organic film-forming composition of the present invention can still form an organic film with excellent in-plane uniformity and filling characteristics, so it can be ideally used.

[0322] The content of the polymer (B) is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the organic film-forming material (A). The organic film-forming composition containing such a polymer content has better in-plane uniformity of the formed organic film.

[0323] [Solvent]

[0324] 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 can dissolve the aforementioned (A) organic film-forming material and the aforementioned (B) polymer, and can be a solvent that can also dissolve the acid generator, crosslinking agent, surfactant, etc. described below. Specifically, a solvent having a boiling point of less than 180° C. such as the solvents described in paragraphs (0091) to (0092) of Japanese Patent Application Laid-Open No. 2007-199653 can be used. Among them, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and a mixture of two or more thereof are preferably used.

[0325] The content of the solvent (C) is 200 to 10,000 parts by mass, more preferably 300 to 5,000 parts by mass, based on 100 parts by mass of the organic film-forming material (A). By setting the content within such a range, the concentration can be adjusted according to the desired film thickness.

[0326] Furthermore, in the composition for forming an organic film of the present invention, as for the organic solvent, a high boiling point solvent having a boiling point of 180°C or higher (a mixture of a solvent having a boiling point of less than 180°C and a solvent having a boiling point of 180°C or higher) may be added to the solvent having a boiling point of less than 180°C. As for the high boiling point organic solvent, there is no particular limitation on hydrocarbons, alcohols, ketones, esters, ethers, chlorine-based solvents, etc., as long as the organic film-forming compound can be dissolved. Specific examples thereof include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, Alcohol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, n-nonyl acetate, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol ethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol Ethylene glycol monomethyl ether, triethylene glycol n-butyl ether, triethylene glycol butyl methyl ether, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin Ester, propylene glycol diacetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, etc., can also be used alone or in combination.

[0327] As mentioned above, the boiling point of the high boiling point solvent can be appropriately selected in accordance with the temperature at which the organic film forming composition is heat treated. The boiling point of the added high boiling point solvent is preferably 180°C to 300°C, and more preferably 200°C to 300°C. If it is such a boiling point, there is no concern that the solvent volatilizes too quickly during baking (heat treatment) due to a too low boiling point, so sufficient thermal fluidity can be obtained. In addition, if it is such a boiling point, there is no situation where the solvent remains in the film after baking without volatilization due to a high boiling point, so there is no concern that it will adversely affect the film properties such as etching resistance.

[0328] When a high boiling point solvent is used, the amount of the high boiling point solvent blended is preferably 1 to 30 parts by mass relative to 100 parts by mass of the solvent having a boiling point of less than 180° C. If the blended amount is such, there is no concern that the blended amount is too small and sufficient thermal fluidity cannot be provided during baking, or that the blended amount is too large and remains in the film, thereby deteriorating the film properties such as etching resistance.

[0329] Such an organic film forming composition can provide thermal fluidity by adding a high boiling point solvent to the organic film forming composition, thereby achieving an organic film forming composition having both high-level filling and planarizing properties.

[0330] [Other ingredients]

[0331] In addition, an acid generator and a crosslinking agent for further promoting the crosslinking reaction may be added to the organic film forming composition of the present invention. As for the acid generator, those that generate acid due to thermal decomposition and those that generate acid due to light exposure can all be added. As for the acid generator, specifically, those recorded in paragraphs

[0061] to

[0085] of Japanese Patent Gazette No. 2007-199653 can be cited. The above-mentioned acid generator can be used alone or in combination of two or more. The amount of the acid generator added is preferably 0.05 to 50 parts by mass, and more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the organic film forming material (A). If it is such an amount, the crosslinking reaction will be promoted and a dense film can be formed.

[0332] In addition, as for the crosslinking agent, specifically, those described in paragraphs

[0055] to

[0060] of Japanese Patent Publication No. 2007-199653 can be cited. The crosslinking agent can be used alone or in combination of two or more. The amount of the crosslinking agent added is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the organic film-forming material (A). If it is such an amount, the hardening property will be improved, and mixing with the upper film can be further suppressed.

[0333] In addition, in the organic film forming composition of the present invention, in order to further improve the in-plane uniformity during spin coating, a surfactant other than the (B) polymer of the present invention may also be added. As for the surfactant, specifically, those recorded in paragraphs

[0142] to

[0147] of Japanese Patent Publication No. 2009-269953 can be cited. The above-mentioned surfactant can be used alone or in combination of two or more. The amount added when adding the surfactant is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the organic film forming material. If it is such an amount, an organic film with excellent in-plane uniformity can be formed.

[0334] Furthermore, in the organic film forming composition of the present invention, a basic compound for improving storage stability can be added. The basic compound will play the role of a quencher for the acid used to prevent the acid generated in trace amounts by the acid generator from causing the crosslinking reaction to proceed. As for such basic compounds, specifically, those described in paragraphs

[0086] to

[0090] of Japanese Patent Publication No. 2007-199653 can be cited. The above-mentioned basic compounds can be used alone or in combination of two or more. The amount of addition when adding the basic compound is preferably 0.05 to 50 parts by mass, and more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the organic film forming material (A). If it is such an amount, the storage stability of the organic film forming composition can be improved.

[0335] As described above, the organic film forming composition of the present invention is an organic film forming composition that is excellent in suppressing ridges during the EBR step. Therefore, the organic film forming composition of the present invention is very useful as a resist underlayer film material (organic film material) for multilayer resist processing such as a two-layer resist processing, a three-layer resist processing using a silicon-containing resist interlayer or a silicon-containing inorganic hard mask interlayer, and a four-layer resist processing using a silicon-containing resist interlayer or a silicon-containing inorganic hard mask interlayer and an organic antireflective film or a bonding film.

[0336] [Organic film formation method]

[0337] The present invention provides an organic film forming method, which is used in the manufacturing process of a semiconductor device, wherein the organic film forming composition of the present invention is spin-coated on a substrate to be processed to form a coating film, and the coating film is heat-treated at a temperature in the range of 100° C. to 600° C. for 10 to 600 seconds to harden the coating film and form an organic film. For example, the organic film is formed by hardening the substrate coated with the organic film forming composition by heat-treating the substrate at the temperature and time range.

[0338] With respect to the organic film forming method, first, the organic film forming composition of the present invention is spin-coated (spin-coated) on the substrate to be processed. By using the spin coating method, good filling characteristics can be obtained. After removing the film at the end in the EBR step, baking (heat treatment) is performed to promote the cross-linking reaction. In addition, by this baking, the solvent in the composition can be evaporated, so when forming the resist upper film and the silicon-containing resist intermediate film on the organic film, mixing can also be prevented.

[0339] The baking is performed at a temperature of 100°C to 600°C for 10 to 600 seconds, preferably at a temperature of 200°C to 500°C for 10 to 300 seconds. Considering the impact on device damage and wafer deformation, the upper limit of the heating temperature in wafer processing such as photolithography is preferably 600°C or less, more preferably 500°C or less. By performing heat treatment under such conditions, the cross-linking reaction is promoted, and an organic film that does not mix with the film formed on the upper layer can be formed.

[0340] [Pattern Formation Method]

[0341] Hereinafter, a pattern forming method using the organic film-forming composition of the present invention will be described.

[0342] [Three-layer resist processing using a silicon-containing resist interlayer]

[0343] The present invention provides a pattern forming method:

[0344] The organic film is formed on a workpiece using the organic film-forming composition described above.

[0345] A silicon-containing resist interlayer film material is used on the organic film to form a silicon-containing resist interlayer film.

[0346] A resist upper film is formed on the silicon-containing resist intermediate film using a resist upper film material composed of a photoresist composition.

[0347] forming a circuit pattern on the resist upper film,

[0348] The resist upper layer film having the circuit pattern formed thereon is used as a mask and the pattern is transferred to the silicon-containing resist intermediate film by etching.

[0349] The pattern is transferred to the organic film by etching using the silicon-containing resist intermediate film to which the pattern is transferred as a mask.

[0350] The pattern is transferred to the object to be processed by etching using the organic film to which the pattern is transferred as a mask.

[0351] As for the processed body, it is preferred to use a semiconductor device substrate, or to form a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film on the aforementioned semiconductor device substrate. More specifically, without particular limitation, a substrate such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., or to form a film of the above-mentioned metal film as a processed layer on the aforementioned substrate, etc. can be used.

[0352] As for the processed layer, various low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si and their barrier films are used, and the thickness can usually be formed to 50 to 10,000 nm, especially 100 to 5,000 nm. In addition, when forming the processed layer, the substrate and the processed layer are made of different materials.

[0353] Furthermore, as for the metal constituting the workpiece, it is preferred to use silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0354] When an organic film is formed on a workpiece using the organic film-forming composition of the present invention, the organic film-forming method of the present invention described above may be used.

[0355] Then, a resist interlayer film material containing silicon atoms is used on the organic film to form a resist interlayer film (silicon-containing resist interlayer film). As for the resist interlayer film material containing silicon atoms, a polysiloxane-based interlayer film material is preferred. By making the silicon-containing resist interlayer film have an anti-reflection effect, reflection can be suppressed. Especially for 193nm exposure, if a material containing a large amount of aromatic groups and having a high etching selectivity with the substrate is used as an organic film forming composition, the k value will become higher and the substrate reflection will become higher. As for the silicon-containing resist interlayer film, by having absorption that makes it an appropriate k value, it becomes possible to suppress reflection, and the substrate reflection can be set to less than 0.5%. As for the silicon-containing resist intermediate film with anti-reflective effect, for 248nm and 157nm exposure, it is preferable to use a polysiloxane whose pendant structure has an anthracene-based light-absorbing group and can be cross-linked by acid or heat. For 193nm exposure, it is preferable to use a polysiloxane whose pendant structure has a phenyl or silicon-silicon bond-based light-absorbing group and can be cross-linked by acid or heat.

[0356] Then, a resist upper film is formed on the silicon-containing resist intermediate film using a resist upper film material composed of a photoresist composition. As for the resist upper film material, either positive or negative type can be used, and the same photoresist composition as generally used can be used. After spin coating the resist upper film material, it is preferably pre-baked in the range of 60 to 180°C and 10 to 300 seconds. Thereafter, exposure is performed according to the conventional method, and post-exposure baking (PEB) and development are performed to obtain a resist upper film pattern. In addition, the thickness of the resist upper film is not particularly limited, and 30 to 500 nm is preferred, and 50 to 400 nm is particularly preferred.

[0357] Then, a circuit pattern (resist upper film pattern) is formed on the resist upper film. The circuit pattern is preferably formed by photolithography using light with a wavelength of 10 nm to 300 nm, direct drawing with an electron beam, nanoimprinting, or a combination thereof.

[0358] Moreover, the exposure light is high-energy radiation with a wavelength of less than 300nm, specifically, far ultraviolet rays, KrF excimer laser (248nm), ArF excimer laser (193nm), F2 laser (157nm), Kr2 laser (146nm), Ar2 laser (126nm), 3 to 20nm soft X-rays (EUV), electron beams (EB), ion beams, X-rays, etc.

[0359] In the formation of the circuit pattern, it is preferred to develop the circuit pattern by alkaline development or organic solvent.

[0360] Then, the resist upper film with the circuit pattern formed thereon is used as a mask and the pattern is transferred to the silicon-containing resist intermediate film by etching. The etching of the silicon-containing resist intermediate film using the resist upper film pattern as a mask is preferably performed using a fluorocarbon-based gas. In this way, the silicon-containing resist intermediate film pattern is transferred.

[0361] Then, the silicon-containing resist intermediate film to which the pattern is transferred is used as a mask and the pattern is transferred to the organic film by etching. Since the silicon-containing resist intermediate film exhibits resistance to etching by oxygen or hydrogen, it is preferable to use an etching gas mainly composed of oxygen or hydrogen to etch the organic film using the silicon-containing resist intermediate film pattern as a mask. In this way, the organic film pattern is transferred.

[0362] Then, the organic film to which the pattern has been transferred is used as a mask and the pattern is transferred to the workpiece by etching. The subsequent etching of the workpiece (the layer to be processed) can be carried out by conventional methods. For example, if the workpiece is a SiO2, SiN, or silicon dioxide-based low dielectric constant insulating film, etching using fluorochlorocarbon-based gases is performed. If it is p-Si, Al, or W, etching using chlorine-based or bromine-based gases is performed. When the substrate processing is carried out by etching using fluorochlorocarbon-based gases, the silicon-containing resist intermediate film pattern will be stripped off simultaneously with the substrate processing. On the other hand, when the substrate processing is carried out by etching using chlorine-based or bromine-based gases, in order to strip off the silicon-containing resist intermediate film pattern, it is necessary to perform dry etching stripping using fluorochlorocarbon-based gases after the substrate processing.

[0363] The organic film obtained by using the organic film-forming composition of the present invention can be excellent in etching resistance when etching the object to be processed as described above.

[0364] [Four-layer resist process using silicon-containing resist interlayer and organic antireflection film or adhesion film]

[0365] Furthermore, the present invention provides a pattern forming method:

[0366] The organic film is formed on a workpiece using the organic film-forming composition described above.

[0367] A silicon-containing resist interlayer film material is used on the organic film to form a silicon-containing resist interlayer film.

[0368] forming an organic anti-reflection film or a close-fitting film on the aforementioned silicon-containing resist intermediate film,

[0369] A resist upper layer film is formed on the organic antireflection film or the adhesion film using a resist upper layer film material composed of a photoresist composition.

[0370] forming a circuit pattern on the resist upper film,

[0371] The resist upper layer film having the circuit pattern formed thereon is used as a mask to transfer the pattern to the organic antireflection film or the adhesion film and the silicon-containing resist intermediate film by etching.

[0372] The pattern is transferred to the organic film by etching using the silicon-containing resist intermediate film to which the pattern is transferred as a mask.

[0373] Then, the pattern is transferred to the object to be processed by etching using the organic film to which the pattern has been transferred as a mask.

[0374] This method can be performed in the same manner as the above-mentioned three-layer resist process using the silicon-containing resist interlayer film, except that an organic antireflection film (BARC) or an adhesion film is formed between the silicon-containing resist interlayer film and the resist upper film.

[0375] The organic antireflection film and the adhesion film can be formed by spin coating using a known organic antireflection film material.

[0376] [Three-layer resist processing using an inorganic hard mask interlayer]

[0377] Furthermore, the present invention provides a pattern forming method:

[0378] The organic film is formed on a workpiece using the organic film-forming composition described above.

[0379] forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the organic film;

[0380] A resist upper layer film is formed on the inorganic hard mask intermediate film using a resist upper layer film material composed of a photoresist composition.

[0381] forming a circuit pattern on the resist upper film,

[0382] The resist upper layer film having the circuit pattern formed thereon is used as a mask and the pattern is transferred to the inorganic hard mask intermediate film by etching.

[0383] The inorganic hard mask intermediate film to which the pattern is transferred is used as a mask and the pattern is transferred to the organic film by etching.

[0384] The pattern is transferred to the object to be processed by etching using the organic film to which the pattern is transferred as a mask.

[0385] This method can be performed in the same manner as the above-mentioned three-layer resist process using the silicon-containing resist interlayer film, except that an inorganic hard mask interlayer film is formed on the organic film instead of the silicon-containing resist interlayer film.

[0386] The inorganic hard mask intermediate film selected from silicon oxide film, silicon nitride film, and silicon oxide nitride film (SiON film) can be formed by CVD method, ALD method, etc. As for the formation method of silicon nitride film, for example, Japanese Patent Publication No. 2002-334869 and International Publication No. 2004 / 066377 are described. The film thickness of the inorganic hard mask intermediate film is preferably 5 to 200 nm, more preferably 10 to 100 nm. As for the inorganic hard mask intermediate film, it is best to use SiON film which has a high effect as an anti-reflection film.

[0387] [Four-layer resist processing using an inorganic hard mask interlayer and an organic anti-reflection film or a bonding film]

[0388] Furthermore, the present invention provides a pattern forming method:

[0389] The organic film is formed on a workpiece using the organic film-forming composition described above.

[0390] forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film on the organic film;

[0391] An organic anti-reflection film or a sealing film is formed on the inorganic hard mask intermediate film.

[0392] A resist upper layer film is formed on the organic antireflection film or the adhesion film using a resist upper layer film material composed of a photoresist composition.

[0393] forming a circuit pattern on the resist upper film,

[0394] The resist upper layer film having the circuit pattern formed thereon is used as a mask and the pattern is transferred to the organic antireflection film or the adhesion film and the inorganic hard mask intermediate film by etching.

[0395] The inorganic hard mask intermediate film to which the pattern is transferred is used as a mask and the pattern is transferred to the organic film by etching.

[0396] The pattern is transferred to the object to be processed by etching using the organic film to which the pattern is transferred as a mask.

[0397] This method can be performed in the same manner as the above-mentioned three-layer resist process using an inorganic hard mask interlayer film, except that an organic antireflection film (BARC) or a bonding film is formed between the inorganic hard mask interlayer film and the resist upper layer film.

[0398] In particular, when a SiON film is used as an inorganic hard mask intermediate film, the two-layer antireflection film of the SiON film and the BARC can suppress reflection even in a high NA immersion exposure exceeding 1.0. Another advantage of forming a BARC is that it has the effect of reducing the tailing of the resist upper film pattern directly on the SiON film.

[0399] Here, an example of a pattern forming method by a three-layer resist process of the present invention is shown in Figure 3 (A) to (F). In the case of 3-layer resist processing, Figure 3 As shown in (A), an organic film 3 is formed on a workpiece layer 2 formed on a substrate 1 using the composition for forming an organic film of the present invention, and then a silicon-containing resist intermediate film 4 is formed, and a resist upper film 5 is formed thereon. Then, as Figure 3 As shown in (B), the exposed portion 6 of the resist upper film 5 is exposed and PEB (post-exposure baking) is performed. Figure 3 As shown in (C), development is performed to form a resist upper film pattern 5a. Then, as Figure 3 As shown in (D), the resist upper film pattern 5a is used as a mask, and the silicon-containing resist intermediate film 4 is dry-etched using a chlorofluorocarbon gas to form a silicon-containing resist intermediate film pattern 4a. Then, as shown in FIG. Figure 3 As shown in (E), after removing the resist upper film pattern 5a, the silicon-containing resist intermediate film pattern 4a is used as a mask to etch the organic film 3 with oxygen plasma to form an organic film pattern 3a. Figure 3 As shown in (F), after removing the silicon-containing resist intermediate film pattern 4a, the processed layer 2 is etched using the organic film pattern 3a as a mask to form a pattern 2a. Since the bulge is suppressed when the organic film is formed, the defects caused by the bulge of the organic film during the dry etching process of Figures (D), (E), and (F) can be reduced.

[0400] When forming an inorganic hard mask intermediate film, the silicon-containing resist intermediate film 4 may be replaced with an inorganic hard mask intermediate film, and when forming a BARC or a bonding film, the BARC or the bonding film may be formed between the silicon-containing resist intermediate film 4 and the resist upper film 5. The etching of the BARC or the bonding film may be performed continuously before the etching of the silicon-containing resist intermediate film 4, or the etching of the silicon-containing resist intermediate film 4 may be performed by changing the etching device after only etching the BARC or the bonding film.

[0401] As described above, according to the pattern forming method of the present invention, a fine pattern can be formed on a workpiece with high precision by multilayer resist processing, and the formation of ridges of an organic film can be suppressed to reduce defects caused by the ridges of the organic film.

[0402] [Example]

[0403] The present invention is described in more detail below by citing synthesis examples, comparative synthesis examples, embodiments, and comparative examples, but the present invention is not limited thereto. Furthermore, the molecular weight is specifically determined by the following method. The polystyrene-converted weight average molecular weight (Mw) and number average molecular weight (Mn) of gel permeation chromatography (GPC) using tetrahydrofuran as an eluent (solvent) are obtained to obtain the dispersion degree (Mw / Mn).

[0404] [Synthesis of polymers (A1) to (A25)]

[0405] The following diol compounds (B1) to (B22), divinyl ether compounds (C1) to (C4), and alcohol compounds (D1) to (D3) were used to synthesize the polymers (A1) to (A25) used in the preparation of the organic film-forming composition.

[0406] (Diol Compound)

[0407] [Chemistry 70]

[0408]

[0409] (Divinyl ether compound)

[0410] [Chemistry 71]

[0411]

[0412] (Alcohol Compound)

[0413] [Chemistry 72]

[0414]

[0415] The synthesis of diol compounds (B2) to (B22) is performed using the epoxy compounds (E1) to (E6), fluorine-containing alcohol compounds and carboxylic acid compounds (F1) to (F13) shown below. The diol compounds (B2) to (B3), (B5) to (B14), (B16), (B17), (B19), (B21) containing ether structures and (B4), (B15), (B18), (B20), (B22) containing ester structures are different in the synthesis method. They are shown below. In addition, the diol compound (B1) uses commercially available 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol.

[0416] (Epoxides)

[0417] [Chemistry 73]

[0418]

[0419] (Fluorinated alcohol or carboxylic acid compound)

[0420] [Chemistry 74]

[0421]

[0422] [Synthesis Example 1] Synthesis of Ether Structure-Containing Diol Compound (B2)

[0423] [Chemistry 75]

[0424]

[0425] Under nitrogen atmosphere, 100.0 g of THF (tetrahydrofuran) and 32.1 g (190.9 mmol) of the alcohol compound (F1) were added and stirred in an ice bath to form a uniform solution, and then 21.4 g (190.9 mmol) of potassium tert-butoxide was added and stirred to form a uniform solution. Thereafter, a mixed solution of 20.0 g (63.6 mmol) of the epoxy compound (E1) and 20.0 g of THF was added dropwise over 30 minutes, and the reaction was carried out at an internal temperature of 60°C for 24 hours. After the reaction solution was cooled to room temperature, the reaction was terminated with 100 ml of ultrapure water, and the separated lower layer was removed after dilution with 300 ml of toluene. After washing with 100 g of a 5% potassium hydroxide aqueous solution twice, 100 ml of ultrapure water, 100 ml of a 3.0% nitric acid aqueous solution twice, and 100 g of ultrapure water five times in this order, the organic layer was dried under reduced pressure to obtain a diol compound (B2).

[0426] [Synthesis Example 2] Synthesis of Ester-containing Diol Compound (B4)

[0427] [Chemistry 76]

[0428]

[0429] Under nitrogen atmosphere, 20.0 g (63.6 mmol) of epoxy compound (E1), 28.6 g (133.6 mmol) of carboxylic acid compound (F3), 1.5 g (6.4 mmol) of benzyltriethylammonium chloride and 100 g of 2-methoxy-1-propanol were added and a uniform solution was obtained at an internal temperature of 80°C, and then stirred at an internal temperature of 100°C for 24 hours. After cooling to room temperature, 200 ml of toluene was added, and the mixture was washed in the order of 100 g of 3% NaHCO3 aqueous solution twice, 100 g of ultrapure water, 100 g of 3% nitric acid aqueous solution twice, and 100 g of ultrapure water five times, and the organic layer was dried under reduced pressure to obtain diol compound (B4).

[0430] Diol compounds (B2) to (B22) were obtained as products under the same reaction conditions as in Synthesis Example 1 or Synthesis Example 2, except that the epoxy compound, alcohol compound or carboxylic acid compound shown in Table 1 was used. The synthesis method (Synthesis Example 1 or 2) used in the synthesis of the diol is shown together in the table.

[0431] [Table 1]

[0432]

[0433]

[0434] [Synthesis Example 3] Synthesis of polymer (A1)

[0435] [Chemistry 77]

[0436]

[0437] In a nitrogen atmosphere, 10.0 g (38.2 mmol) of the diol compound (B1) was stirred at room temperature and uniformly dispersed in a mixture of 0.81 g of a cation exchange resin (AMBERLYST (registered trademark) 15DRY) and 30 g of ethyl acetate. 5.2 g (36.3 mmol) of the divinyl ether compound (C1) was added dropwise over 20 minutes, and after the addition, the mixture was stirred at room temperature for 5 hours. After the reaction was stopped by adding 0.8 g (7.6 mmol) of triethylamine, the cation exchange resin was removed by filtration. The filtrate was concentrated under reduced pressure to obtain a polymer (A1) as a highly viscous liquid. Mw = 5200, Mw / Mn = 2.73.

[0438] [Synthesis Examples 4 to 24] Synthesis of Polymers (A2) to (A22)

[0439] Except for using the diol compound and divinyl ether compound shown in Table 2, the same reaction conditions as in Synthesis Example 3 were used to obtain polymers (A2) to (A22) shown in Table 2 as products.

[0440] Table 2 summarizes the raw materials used in Synthesis Examples 3 to 24.

[0441] [Table 2]

[0442] Synthesis example polymer Diol Compounds Input amount (g) Divinyl ether compounds Input amount (g) 3 A1 B1 10.0 C1 5.2 4 A2 B2 24.8 C1 5.2 5 A3 B3 19.6 C2 5.7 6 A4 B4 28.3 C3 7.3 7 A5 B5 12.0 C1 5.2 8 A6 B6 16.9 C2 5.7 9 A7 B7 17.9 C3 7.3 10 A8 B8 19.0 C1 5.2 11 A9 B9 19.5 C4 7.1 12 A10 B10 15.4 C1 5.2 13 A11 B11 19.2 C2 5.7 14 A12 B12 21.8 C3 7.3 15 A13 B13 21.6 C1 5.2 16 A14 B14 28.9 C2 5.7 17 A15 B15 25.0 C3 7.3 18 A16 B16 18.1 C1 5.2 19 A17 B17 20.2 C2 5.7 20 A18 B18 22.4 C3 7.3 21 A19 B19 23.0 C4 7.1 22 A20 B20 24.1 C1 5.2 23 A21 B21 23.4 C2 5.7 24 A22 B22 24.5 C3 7.3

[0443] [Synthesis Example 25] Synthesis of polymer (A23)

[0444] [Chemistry 78]

[0445]

[0446] In a nitrogen atmosphere, 16.9 g (38.2 mmol) of the diol compound (B6) was stirred and uniformly dispersed at room temperature in a mixture of 0.81 g of a cation exchange resin (AMBERLYST (registered trademark) 15DRY) and 30 g of ethyl acetate. 6.0 g (42.0 mmol) of the divinyl ether compound (C1) was added dropwise over 20 minutes, and after stirring at room temperature for 3 hours, 0.9 g of the alcohol compound (D1) was added dropwise over 10 minutes, and further stirred at room temperature for 3 hours. After adding 0.8 g (7.6 mmol) of triethylamine to stop the reaction, the cation exchange resin was removed by filtration. The filtrate was concentrated under reduced pressure to obtain a polymer (A23) as a highly viscous liquid. Mw = 8800, Mw / Mn = 2.53.

[0447] [Synthesis Example 26] Synthesis of polymer (A24)

[0448] [Chemistry 79]

[0449]

[0450] In a nitrogen atmosphere, 15.4 g (38.2 mmol) of the diol compound (B10) was stirred and uniformly dispersed at room temperature in a mixture of 0.81 g of a cation exchange resin (AMBERLYST (registered trademark) 15DRY) and 30 g of ethyl acetate. 6.6 g (42.0 mmol) of the divinyl ether compound (C2) was added dropwise over 20 minutes, and after stirring at room temperature for 3 hours, 1.3 g of the alcohol compound (D2) was added dropwise over 10 minutes, and further stirred at room temperature for 3 hours. After adding 0.8 g (7.6 mmol) of triethylamine to stop the reaction, the cation exchange resin was removed by filtration. The filtrate was concentrated under reduced pressure to obtain a polymer (A24) as a highly viscous liquid. Mw = 8000, Mw / Mn = 2.19.

[0451] [Synthesis Example 27] Synthesis of polymer (A25)

[0452] [Chemistry 80]

[0453]

[0454] In a nitrogen atmosphere, 20.2 g (38.2 mmol) of the diol compound (B17) was stirred at room temperature and uniformly dispersed in a mixture of 0.81 g of a cation exchange resin (AMBERLYST (registered trademark) 15DRY) and 30 g of ethyl acetate. 8.5 g (42.0 mmol) of the divinyl ether compound (C3) was added dropwise over 20 minutes, and after stirring at room temperature for 3 hours, 1.6 g of the alcohol compound (D3) was added dropwise over 10 minutes, and further stirred at room temperature for 3 hours. After adding 0.8 g (7.6 mmol) of triethylamine to stop the reaction, the cation exchange resin was removed by filtration. The filtrate was concentrated under reduced pressure to obtain a polymer (A25) as a highly viscous liquid. Mw = 10500, Mw / Mn = 1.93.

[0455] The structural formula, weight average molecular weight (Mw), and dispersity (Mw / Mn) of the polymers obtained in Synthesis Examples 3 to 27 were determined and are shown in Tables 3 to 8.

[0456] [Table 3]

[0457]

[0458]

[0459] [Table 4]

[0460]

[0461]

[0462] [Table 5]

[0463]

[0464]

[0465] [Table 6]

[0466]

[0467]

[0468] [Table 7]

[0469]

[0470]

[0471] [Table 8]

[0472]

[0473]

[0474] [Synthesis of Comparative Polymers (R1) to (R6)]

[0475] The following monomers (b1) to (b7) and the above-described divinyl ether (C1) were used to synthesize the comparative polymers (R1) to (R6) used in the preparation of the organic film-forming composition.

[0476] [Chemistry 81]

[0477]

[0478] [Comparative Synthesis Example 1] Synthesis of Comparative Polymer (R1)

[0479] [Chemistry 82]

[0480]

[0481] In a nitrogen atmosphere, 6.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80°C. A mixture of 3.44 g (0.011 mol) of (b1), 7.46 g (0.034 mol) of (b3), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate) and 34 g of PGMEA was added dropwise over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R1).

[0482] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC. The results are as follows.

[0483] (R1): Mw=9500, Mw / Mn=1.20

[0484] [Comparative Synthesis Example 2] Synthesis of Comparative Polymer (R2)

[0485] [Chemistry 83]

[0486]

[0487] In a nitrogen atmosphere, 6.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80°C. A mixture of 1.43 g (0.005 mol) of (b1), 5.76 g (0.041 mol) of (b4), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate) and 34 g of PGMEA was added dropwise over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R2).

[0488] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC. The results are as follows.

[0489] (R2): Mw=5800, Mw / Mn=1.42

[0490] [Comparative Synthesis Example 3] Synthesis of Comparative Polymer (R3)

[0491] [Chemistry 84]

[0492]

[0493] In a nitrogen atmosphere, 6.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80°C. A mixture of 7.00 g (0.032 mol) of (b2), 1.92 g (0.014 mol) of (b4), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate) and 34 g of PGMEA was added dropwise over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R3).

[0494] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC. The results are as follows.

[0495] (R3): Mw=6200, Mw / Mn=1.33

[0496] [Comparative Synthesis Example 4] Synthesis of Comparative Polymer (R4)

[0497] [Chemistry 85]

[0498]

[0499] In a nitrogen atmosphere, 6.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80°C. A mixture of 5.00 g (0.023 mol) of (b2), 3.20 g (0.023 mol) of (b5), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate) and 34 g of PGMEA was added dropwise over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R4).

[0500] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC. The results are as follows.

[0501] (R4): Mw=8300, Mw / Mn=1.33

[0502] [Comparative Synthesis Example 5] Synthesis of Comparative Polymer (R5)

[0503] [Chemistry 86]

[0504]

[0505] In a nitrogen atmosphere, 6.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80°C. A mixture of 2.00 g (0.009 mol) of (b2), 5.41 g (0.036 mol) of (b6), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate) and 34 g of PGMEA was added dropwise over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R5).

[0506] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) were determined by GPC. The results are as follows.

[0507] (R5): Mw=3800, Mw / Mn=1.44

[0508] [Comparative Synthesis Example 6] Synthesis of Comparative Polymer (R6)

[0509] [Chemistry 87]

[0510]

[0511] In a nitrogen atmosphere, 7.4 g (38.2 mmol) of compound (b7) was stirred at room temperature and uniformly dispersed in a mixture of 0.81 g of cation exchange resin (AMBERLYST (registered trademark) 15DRY) and 30 g of ethyl acetate. 5.3 g (37.4 mmol) of divinyl ether compound (C1) was added dropwise over 20 minutes, and the mixture was stirred at room temperature for 5 hours. After adding 0.8 g (7.6 mmol) of triethylamine to stop the reaction, the cation exchange resin was removed by filtration. The filtrate was concentrated under reduced pressure to obtain a polymer (R6) as a highly viscous liquid.

[0512] (R6) Mw=8200, Mw / Mn=2.77.

[0513] [Organic film forming material (resin or compound)]

[0514] M1: Resin represented by the following formula (M1)

[0515] M2: Resin represented by the following formula (M2)

[0516] M3: A compound represented by the following formula (M3)

[0517] M4: Compound represented by the following formula (M4): M5: Resin represented by the following formula (M5): M6: Resin represented by the following formula (M6):

[0518]

[0519] [Solvent]

[0520] (S1): Propylene glycol monomethyl ether acetate

[0521] (S2): Propylene glycol monoethyl ether

[0522] [Preparation of organic film-forming compositions (UDL-1 to 155, comparative UDL-1 to 17)]

[0523] The above-mentioned polymers (A1) to (A25), (R1) to (R6), organic film-forming materials (M1) to (M6), and solvents were dissolved in the proportions shown in Tables 9 to 13, and filtered using a 0.1 μm fluororesin filter to prepare organic film-forming compositions (resist underlayer film materials: UDL-1 to 155, comparative examples UDL-1 to 17).

[0524] [Table 9]

[0525]

[0526]

[0527] [Table 10]

[0528]

[0529]

[0530] [Table 11]

[0531]

[0532]

[0533] [Table 12]

[0534]

[0535]

[0536] [Table 13]

[0537]

[0538]

[0539] [Preparation of Silicon Wafer Having Organic Cured Film Formed Using Organic Film Forming Compositions (UDL-1 to 155, Comparative UDL-1 to 17)]

[0540] Using a coater / developer "CLEAN TRACK LITHIUS Pro AP" manufactured by Tokyo Electron Co., Ltd., 2 ml of the organic film-forming composition (UDL-1 to 155, comparative UDL-1 to 17) prepared above was sprayed onto the center of a silicon wafer, and after baking, the wafer was rotated at a rotation speed that gave an average film thickness as shown in Tables 14 to 18, and a film was formed by coating and spreading. While the silicon wafer was rotated at a speed of 1000 rpm, a removal liquid (a mixed solution of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30:70, mass ratio)) was sprayed from the removal liquid nozzle at a spray rate of 2 mL / s, while the wafer was moved from the outer periphery of the silicon wafer to a position 3 mm from the center at a speed of 5 mm / s, and the removal liquid was further sprayed at a spray rate of 2 mL / s at the position for 5 seconds. Thereafter, the spraying of the spray liquid was stopped, and the wafer was rotated at a speed of 1000 rpm for 30 seconds. Then, the silicon wafer on which the organic film-forming composition was formed was heated at 350 degrees for 60 seconds to obtain a silicon wafer on which an organic cured film was formed.

[0541] [Evaluation of Solvent Resistance: Examples 1-1 to 1-155, Comparative Examples 1-1 to 1-17]

[0542] The organic film-forming composition (UDL-1 to 155, comparative UDL-1 to 17) was formed on a silicon wafer using the above method, and the film thickness was measured. PGMEA solvent was dispensed thereon, left for 30 seconds, spin dried, baked at 100°C for 60 seconds to evaporate PGMEA, and the film thickness was measured. The film thickness before dispensing the PGMEA solvent is X, and the film thickness after dispensing the PGMEA solvent is X1. The absolute value of the value obtained by (X1-X) / X×100 is defined as the film thickness change rate (%). The case where the film thickness change rate is less than 0.5% is rated as good, and the case where it is more than 0.5% is rated as poor. The results are shown in Tables 14 to 18.

[0543] [Evaluation of In-Plane Uniformity: Examples 1-1 to 1-155, Comparative Examples 1-1 to 1-17]

[0544] The organic film forming composition (UDL-1 to 155, comparative UDL-1 to 17) was formed on a silicon wafer by the above method, and the film thickness within a radius of 145 mm from the center of the organic cured film was measured, and the maximum film thickness was Xmax, the minimum film thickness was Xmin, and the average film thickness was X. average , will be (X max -X min ) / X average The obtained value is defined as the in-plane uniformity (%). The case where the in-plane uniformity is less than 2% is rated as A (good), the case where it is 2% or more but less than 3% is rated as B, and the case where it is 3% or more is rated as C (poor). The results are shown in Tables 14 to 18.

[0545] [Table 14]

[0546]

[0547]

[0548] [Table 15]

[0549]

[0550]

[0551] [Table 16]

[0552]

[0553]

[0554] [Table 17]

[0555]

[0556]

[0557] [Table 18]

[0558]

[0559]

[0560] As shown in Tables 14 to 18, Examples 1-1 to 1-155 using the organic film-forming composition of the present invention can obtain organic films with good solvent resistance and in-plane uniformity, but Comparative Examples 1-11 to 1-17 using the composition not containing the polymer of the present invention have poor in-plane uniformity. Therefore, the following evaluation will focus on Comparative Examples UDL-1 to 10 having good solvent resistance and in-plane uniformity.

[0561] [Evaluation of bulging suppression property: Examples 2-1 to 2-155, Comparative Examples 2-1 to 2-10]

[0562] The organic film-forming composition (UDL-1 to 155, comparative UDL-1 to 10) was formed on a silicon wafer by the above method, and the height change from the outer peripheral end of the organic film to the position of 1000 μm in the direction of the center of the silicon wafer was measured using Alpha-Step D-600 (contact profiler) manufactured by KLA-TENCOR. When the height of the silicon wafer is set to 0, Figure 1 When the maximum height shown is less than 110% of the film thickness, it is rated A (good), and when the maximum height is more than 110% but less than 150%, it is rated B. Figure 2 When the generation height was 150% or more, it was rated as C (bad). The results are shown in Tables 19 to 23.

[0563] [Landfill evaluation: Examples 2-1 to 2-155, Comparative Examples 2-1 to 2-10]

[0564] like Figure 4 On a SiO2 wafer substrate having a dense hole pattern (hole diameter 0.2μm, hole depth 1.0μm, distance between the centers of two adjacent holes 0.4μm), an organic film forming composition (UDL-1 to 155, comparative UDL-1 to 10) was formed using the above method to form an organic film 8. The substrate used was as follows Figure 4 The base substrate (SiO2 wafer substrate) 7 with a dense hole pattern shown in (G) (bird's-eye view) and (H) (cross-sectional view). The cross-sectional shape of each wafer substrate obtained was observed using a scanning electron microscope (SEM) to confirm whether there were no voids inside the holes and they were filled with organic films. When an organic film material with poor filling characteristics is used, voids will appear inside the holes. When an organic film material with good filling characteristics is used, in this evaluation, if Figure 4As shown in (I), there was no void inside the pores and the pores were filled with the organic film. The evaluation was good when no voids were generated, and poor when voids were generated. The results are shown in Tables 19 to 23.

[0565] [Evaluation of coating properties of silicon interlayer films-1: Examples 2-1 to 2-155, Comparative Examples 2-1 to 2-10]

[0566] An organic cured film was formed on a silicon wafer substrate using the organic film-forming composition (UDL-1 to 155, comparative UDL-1 to 10) by the above method, and the silicon-containing resist interlayer material (SOG1) was applied thereon, and baked at 200° C. for 60 seconds to form a silicon-containing resist interlayer. The coating state of the silicon interlayer was visually observed and evaluated.

[0567] When the state of the coating film was good, it was rated as good, and when dewetting occurred, it was rated as bad.

[0568] In addition, in order to evaluate the coating quality of the silicon interlayer film in this evaluation, strict evaluation conditions were adopted in which the film thickness of the silicon interlayer film was set to 10 nm. The results are shown in Tables 19 to 23.

[0569] [Evaluation of coating properties of silicon interlayer films-2: Examples 2-1 to 2-155, Comparative Examples 2-1 to 2-10]

[0570] An organic cured film was formed on a silicon wafer substrate using the organic film-forming composition (UDL-1 to 155, comparative UDL-1 to 10) by the above method, and the silicon-containing resist interlayer material (SOG1) was applied thereon, and baked at 200° C. for 60 seconds to form a silicon-containing resist interlayer. The coating state of the silicon interlayer was visually observed and evaluated.

[0571] When the state of the coating film was good, it was rated as good, and when dewetting occurred, it was rated as poor.

[0572] In addition, in order to evaluate the coating quality of the silicon interlayer film in this evaluation, particularly strict evaluation conditions were adopted in which the film thickness of the silicon interlayer film was set to 5 nm. The results are shown in Tables 19 to 23.

[0573] The following polymer propylene glycol ethyl ether solutions were prepared as silicon-containing resist interlayer film materials (SOG1). The polymer solution used in silicon interlayer film coating evaluation-1 was 0.5 wt %, and the polymer solution used in silicon interlayer film coating evaluation-2 was 0.2 wt %.

[0574] [Chemistry 89]

[0575]

[0576] [Table 19]

[0577]

[0578]

[0579] [Table 20]

[0580]

[0581]

[0582] [Table 21]

[0583]

[0584]

[0585] [Table 22]

[0586]

[0587]

[0588] [Table 23]

[0589]

[0590]

[0591] As shown in Tables 19 to 23, it was confirmed that the organic film-forming composition of the present invention (UDL-1 to 155) was excellent in solvent resistance, in-plane uniformity, swelling suppression, filling characteristics, and coating properties of a silicon interlayer.

[0592] [Pattern Formation Test: Examples 3-1 to 3-155]

[0593] An organic cured film was formed on a SiO2 wafer substrate using an organic film forming composition (UDL-1 to 155) by the above method, and the following silicon-containing resist intermediate film material (SOG1) was coated thereon, and baked at 200°C for 60 seconds to form a silicon-containing resist intermediate film with a film thickness of 35nm. The following ArF single-layer resist as a resist upper film material was coated thereon, and baked at 105°C for 60 seconds to form a photoresist film with a film thickness of 100nm. The following wet protection film material (TC-1) was coated on the photoresist film, and baked at 90°C for 60 seconds to form a protective film with a film thickness of 50nm.

[0594] As for the silicon-containing resist interlayer material (SOG1), a 2% solution of the following polymer in propylene glycol ethyl ether was prepared.

[0595] [Chemistry 90]

[0596]

[0597] As for the resist upper layer film material (single-layer resist for ArF), it is prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) in a solvent containing 0.1 mass% of FC-430 (manufactured by Sumitomo 3M Co., Ltd.) in the proportions shown in Table 24, and filtering using a 0.1 μm fluororesin filter.

[0598] [Table 24]

[0599]

[0600] The polymer (RP1), the acid generator (PAG1), and the basic compound (Amine1) are shown below.

[0601] [Chemistry 91]

[0602]

[0603] The wet protective film material (TC-1) was prepared by dissolving the polymer (PP1) in an organic solvent at the ratio shown in Table 25 and filtering the solution through a 0.1 μm fluororesin filter.

[0604] [Table 25]

[0605]

[0606] Polymer (PP1) is shown below.

[0607] [Chemistry 92]

[0608]

[0609] Then, exposure was performed using an ArF immersion exposure device (manufactured by Nikon Co., Ltd.; NSR-S610C, NA1.30, σ0.98 / 0.65, 35 degree dipole s-polarized illumination, 6% half-step phase shift mask), baked (PEB) at 100°C for 60 seconds, and developed using a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a 55nm 1:1 positive line and space pattern (resist upper film pattern).

[0610] Then, the resist upper film pattern was used as a mask and the etching device Telius manufactured by Tokyo Electron was used to dry-etch the silicon-containing resist intermediate film (pattern transfer), the obtained silicon-containing resist intermediate film pattern was used as a mask and the organic film was dry-etched (pattern transfer), and the obtained organic film pattern was used as a mask and the SiO2 wafer substrate (SiO2 film) was dry-etched (pattern transfer). The etching conditions are as follows.

[0611] (Transfer Conditions of Resist Upper Layer Film Pattern to Silicon-Containing Resist Interlayer Film)

[0612]

[0613]

[0614] (Transfer Conditions of Silicon-Containing Resist Interlayer Pattern to Organic Film)

[0615]

[0616] (Transfer conditions of organic film pattern to SiO2 wafer substrate)

[0617]

[0618] The cross sections of the obtained patterns were observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the results are shown in Tables 26 to 30.

[0619] [Table 26]

[0620]

[0621]

[0622] [Table 27]

[0623]

[0624]

[0625] [Table 28]

[0626]

[0627]

[0628] [Table 29]

[0629]

[0630]

[0631] [Table 30]

[0632]

[0633]

[0634] As shown in Tables 26 to 30, for Examples 3-1 to 3-155 using the organic film forming composition (UDL-1 to 155) of the present invention, the resist upper film pattern is finally well transferred to the SiO2 wafer substrate, confirming that the organic film forming composition of the present invention is suitable for micro-processing by the multilayer resist method.

[0635] According to the above, if it is the composition for forming an organic film of the present invention, it has excellent film-forming properties and high-level filling characteristics and ridge suppression properties, and the coating properties of the silicon intermediate film are excellent, so it is very useful as an organic film material used in multi-layer anti-etching processing. If it is the pattern forming method of the present invention using it, it can fill holes and trenches with very high aspect ratios without gaps and can form fine patterns with high precision, and can form an organic film with suppressed ridges, so semiconductor elements can be efficiently manufactured.

[0636] This manual contains the following aspects.

[0637] [1]: A composition for forming an organic film, comprising (A) an organic film-forming material, (B) a polymer having a repeating unit represented by the following general formula (1), and (C) a solvent.

[0638] [Chemistry 93]

[0639]

[0640] In the formula, W1 is a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms, which is a divalent organic group having one or more fluorine-containing structures represented by the following formula (2) in the organic group, and W2 is a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms,

[0641] [Chemistry 94]

[0642]

[0643] In the formula, * represents an atomic bond in the organic group represented by W1, and the organic group may have any two or more structures represented by the above formula (2) or two or more identical structures.

[0644] [2]: The organic film-forming composition according to [1], wherein W1 in the general formula (1) is a divalent organic group represented by the following general formula (3),

[0645] [Chemistry 95]

[0646]

[0647] In the formula, * represents an atomic bond to an oxygen atom, L is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, and R1 is a substituent having one or more structures represented by the formula (2).

[0648] [3]: The organic film-forming composition according to [2], wherein R1 in the general formula (3) is a group represented by the following general formula (4),

[0649] [Chemistry 96]

[0650]

[0651] In the formula, * represents an atomic bond to an oxygen atom, and n1, n2, and n3 represent integers of 1 to 10.

[0652] [4]: The organic film-forming composition according to any one of [1] to [3], wherein W2 in the general formula (1) is the following general formula (5),

[0653] [Chemistry 97]

[0654]

[0655] In the formula, * represents an atomic bond to an oxygen atom, and n4 and n5 represent integers of 1 to 10.

[0656] [5]: The organic film-forming composition according to any one of [1] to [4], wherein the weight average molecular weight of the polymer (B) is 1,000 to 30,000.

[0657] [6]: The organic film-forming composition according to any one of [1] to [5], wherein the content of the (B) polymer is 0.01 to 5 parts by mass based on 100 parts by mass of the (A) organic film-forming material.

[0658] [7]: An organic film forming method is used in the manufacturing process of a semiconductor device, characterized in that:

[0659] The organic film is formed by spin-coating the organic film forming composition as described in any one of [1] to [6] on the substrate to be processed, and the coating is heat-treated at a temperature in the range of 100°C to 600°C for 10 to 600 seconds to harden the coating and form an organic film.

[0660] [8]: A pattern forming method, characterized in that:

[0661] An organic film is formed on a workpiece using an organic film forming composition as described in any one of [1] to [6], a silicon-containing resist intermediate film is formed on the organic film using a silicon-containing resist intermediate film material, a resist upper film material composed of a photoresist composition is used on the silicon-containing resist intermediate film to form a resist upper film, a circuit pattern is formed on the resist upper film, the resist upper film on which the circuit pattern is formed is used as a mask and the pattern is transferred to the silicon-containing resist intermediate film by etching, the silicon-containing resist intermediate film to which the pattern is transferred is used as a mask and the pattern is transferred to the organic film by etching, and the organic film to which the pattern is transferred is used as a mask and the pattern is transferred to the workpiece by etching.

[0662] [9]: A pattern forming method, characterized in that:

[0663] An organic film is formed on a workpiece using an organic film forming composition as described in any one of [1] to [6], a silicon-containing resist intermediate film is formed on the organic film using a silicon-containing resist intermediate film material, an organic anti-reflective film or a bonding film is formed on the silicon-containing resist intermediate film, a resist upper film material composed of a photoresist composition is used on the organic anti-reflective film or the bonding film to form a resist upper film, a circuit pattern is formed on the resist upper film, the resist upper film on which the circuit pattern is formed is used as a mask and the pattern is transferred to the organic anti-reflective film or the bonding film and the silicon-containing resist intermediate film by etching, the silicon-containing resist intermediate film to which the pattern is transferred is used as a mask and the pattern is transferred to the organic film by etching, and the organic film to which the pattern is transferred is used as a mask and the pattern is transferred to the workpiece by etching.

[0664]

[10] : A pattern forming method, characterized in that:

[0665] An organic film is formed on a workpiece using an organic film forming composition as described in any one of [1] to [6], an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film is formed on the organic film, a resist upper film is formed on the inorganic hard mask using a resist upper film material composed of a photoresist composition, a circuit pattern is formed on the resist upper film, the resist upper film on which the circuit pattern is formed is used as a mask and the pattern is transferred to the inorganic hard mask by etching, the inorganic hard mask to which the pattern is transferred is used as a mask and the pattern is transferred to the organic film by etching, and the organic film to which the pattern is transferred is used as a mask and the pattern is transferred to the workpiece by etching.

[0666]

[11] : A pattern forming method, characterized in that:

[0667] An organic film is formed on a workpiece using an organic film forming composition as described in any one of [1] to [6], an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film is formed on the organic film, an organic antireflective film or a bonding film is formed on the inorganic hard mask, a resist upper film material composed of a photoresist composition is used on the organic antireflective film or the bonding film to form a resist upper film, a circuit pattern is formed on the resist upper film, the resist upper film on which the circuit pattern is formed is used as a mask and the pattern is transferred to the organic antireflective film or the bonding film and the inorganic hard mask by etching, the inorganic hard mask to which the pattern is transferred is used as a mask and the pattern is transferred to the organic film by etching, and the organic film to which the pattern is transferred is used as a mask and the pattern is transferred to the workpiece by etching.

[0668]

[12] : The pattern forming method of

[10] or

[11] , wherein the inorganic hard mask is formed by a CVD method or an ALD method.

[0669]

[13] : A pattern forming method as described in any one of [8] to

[12] , wherein the circuit pattern is formed by photolithography using light with a wavelength of not less than 10 nm and not more than 300 nm, direct drawing using an electron beam, nanoimprinting, or a combination thereof.

[0670]

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

[13] , wherein the circuit pattern is developed by alkaline development or an organic solvent during the formation of the circuit pattern.

[0671]

[15] : A pattern forming method as described in any one of [8] to

[14] , wherein the processed body is a semiconductor device substrate, or a substrate on which a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film is formed.

[0672]

[16] : A pattern forming method as described in

[15] , wherein the metal to be processed is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0673]

[17] : A polymer having a repeating unit represented by the following general formula (1),

[0674] [Chemistry 98]

[0675]

[0676] In the formula, W1 is a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms, which is a divalent organic group having one or more fluorine-containing structures represented by the following formula (2) in the organic group, and W2 is a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms,

[0677] [Chemistry 99]

[0678]

[0679] In the formula, * represents an atomic bond in the organic group represented by W1, and the organic group may have any two or more structures represented by the above formula (2) or two or more identical structures.

[0680]

[18] : The polymer according to

[17] , wherein W1 in the general formula (1) is a divalent organic group represented by the following formula (3),

[0681] [Chemical 100]

[0682]

[0683] In the formula, * represents an atomic bond to an oxygen atom, L is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, and R1 is a substituent having one or more structures represented by the formula (2).

[0684]

[19] : The polymer according to

[18] , wherein R1 in the general formula (3) is a group represented by the following general formula (4),

[0685] [Chemistry 101]

[0686]

[0687] In the formula, * represents an atomic bond to an oxygen atom, and n1, n2, and n3 represent integers of 1 to 10.

[0688]

[20] : The polymer according to any one of

[17] to

[19] , wherein W2 in the general formula (1) is the following formula (5),

[0689] [Chemistry 102]

[0690]

[0691] In the formula, * represents an atomic bond to an oxygen atom, and n4 and n5 represent integers of 1 to 10.

[0692]

[21] : The polymer according to any one of

[17] to

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

[0693] The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are illustrative, and those having substantially the same configuration as the technical concept described in the claims of the present invention and having the same functions and effects are all within the technical scope of the present invention.

[0694]

Explanation of symbols

[0695] 1:Substrate

[0696] 2: Processing layer

[0697] 2a: Pattern formed on the processed layer

[0698] 3: Organic film

[0699] 3a: Organic film pattern

[0700] 4: Silicon-containing resist interlayer

[0701] 4a: Silicon-containing resist interlayer pattern

[0702] 5: Resist upper film

[0703] 5a: Resist upper film pattern

[0704] 6: Exposure part

[0705] 7: Base substrate

[0706] 8: Organic film

Claims

1. A composition for forming an organic film, characterized in that The invention comprises (A) an organic film-forming material, (B) a polymer having a repeating unit represented by the following general formula (1), and (C) a solvent. In the formula, W1 is a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms, which is a divalent organic group having one or more fluorine-containing structures represented by the following formula (2) in the organic group, and W2 is a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms, In the formula, * represents an atomic bond in the organic group represented by W1, and the organic group may have any two or more structures represented by the above formula (2) or two or more identical structures.

2. The organic film-forming composition according to claim 1, wherein W1 in the general formula (1) is a divalent organic group represented by the following general formula (3), In the formula, * represents an atomic bond to an oxygen atom, L is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, and R1 is a substituent having one or more structures represented by the formula (2).

3. The organic film-forming composition according to claim 2, wherein R1 in the general formula (3) is a group represented by the following general formula (4): In the formula, * represents an atomic bond to an oxygen atom, and n1, n2, and n3 represent integers of 1 to 10.

4. The organic film-forming composition according to claim 1, wherein W2 in the general formula (1) is the following general formula (5), In the formula, * represents an atomic bond to an oxygen atom, and n4 and n5 represent integers of 1 to 10.

5. The organic film-forming composition according to claim 1, wherein The weight average molecular weight of the polymer (B) is 1,000 to 30,000.

6. The organic film-forming composition according to claim 1, wherein The content of the (B) polymer is 0.01 to 5 parts by mass based on 100 parts by mass of the (A) organic film-forming material.

7. An organic film forming method, which is used in the manufacturing process of a semiconductor device, characterized in that: The organic film is formed by spin-coating the organic film-forming composition according to any one of claims 1 to 6 on a substrate to be processed to form a coating film, and the coating film is heat-treated at a temperature ranging from 100° C. to 600° C. for 10 to 600 seconds to cure the coating film to form an organic film.

8. A pattern forming method, characterized in that: An organic film is formed on a workpiece using an organic film-forming composition according to any one of claims 1 to 6, a silicon-containing resist intermediate film is formed on the organic film using a silicon-containing resist intermediate film material, a resist upper film is formed on the silicon-containing resist intermediate film using a resist upper film material composed of a photoresist composition, a circuit pattern is formed on the resist upper film, the resist upper film on which the circuit pattern is formed is used as a mask and the pattern is transferred to the silicon-containing resist intermediate film by etching, the silicon-containing resist intermediate film to which the pattern is transferred is used as a mask and the pattern is transferred to the organic film by etching, and the organic film to which the pattern is transferred is used as a mask and the pattern is transferred to the workpiece by etching.

9. A pattern forming method, characterized in that: An organic film is formed on a workpiece using an organic film-forming composition according to any one of claims 1 to 6, a silicon-containing resist intermediate film is formed on the organic film using a silicon-containing resist intermediate film material, an organic anti-reflective film or a bonding film is formed on the silicon-containing resist intermediate film, a resist upper film material composed of a photoresist composition is used on the organic anti-reflective film or the bonding film to form a resist upper film, a circuit pattern is formed on the resist upper film, the resist upper film on which the circuit pattern is formed is used as a mask to transfer the pattern to the organic anti-reflective film or the bonding film and the silicon-containing resist intermediate film by etching, the silicon-containing resist intermediate film to which the pattern is transferred is used as a mask to transfer the pattern to the organic film by etching, and the organic film to which the pattern is transferred is used as a mask to transfer the pattern to the workpiece by etching.

10. A pattern forming method, characterized in that: An organic film is formed on a workpiece using the organic film forming composition according to any one of claims 1 to 6, an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film is formed on the organic film, a resist upper film is formed on the inorganic hard mask using a resist upper film material composed of a photoresist composition, a circuit pattern is formed on the resist upper film, the resist upper film on which the circuit pattern is formed is used as a mask and the pattern is transferred to the inorganic hard mask by etching, the inorganic hard mask to which the pattern is transferred is used as a mask and the pattern is transferred to the organic film by etching, and the organic film to which the pattern is transferred is used as a mask and the pattern is transferred to the workpiece by etching.

11. A pattern forming method, characterized in that: An organic film is formed on a workpiece using the organic film forming composition according to any one of claims 1 to 6, an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film is formed on the organic film, an organic antireflective film or a bonding film is formed on the inorganic hard mask, a resist upper film material composed of a photoresist composition is used on the organic antireflective film or the bonding film to form a resist upper film, a circuit pattern is formed on the resist upper film, the resist upper film on which the circuit pattern is formed is used as a mask to transfer the pattern to the organic antireflective film or the bonding film and the inorganic hard mask by etching, the inorganic hard mask to which the pattern is transferred is used as a mask to transfer the pattern to the organic film by etching, and the organic film to which the pattern is transferred is used as a mask to transfer the pattern to the workpiece by etching.

12. The pattern forming method according to claim 10, wherein: The inorganic hard mask is formed by a CVD method or an ALD method.

13. The pattern forming method according to claim 8, wherein: In forming the circuit pattern, the circuit pattern is formed by photolithography using light with a wavelength of 10 nm to 300 nm, direct drawing with an electron beam, nanoimprinting, or a combination thereof.

14. The pattern forming method according to claim 8, wherein: In the formation of the circuit pattern, the circuit pattern is developed by alkaline development or an organic solvent.

15. The pattern forming method according to claim 8, wherein: The object to be processed is a semiconductor device substrate, or a substrate on which a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film are formed.

16. The pattern forming method according to claim 15, wherein: The metal to be processed is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

17. A polymer having a repeating unit represented by the following general formula (1): In the formula, W1 is a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms, which is a divalent organic group having one or more fluorine-containing structures represented by the following formula (2) in the organic group, and W2 is a saturated or unsaturated divalent organic group having 2 to 50 carbon atoms, In the formula, * represents an atomic bond in the organic group represented by W1, and the organic group may have any two or more structures represented by the above formula (2) or two or more identical structures.

18. The polymer according to claim 17, wherein W1 in the general formula (1) is a divalent organic group represented by the following formula (3): In the formula, * represents an atomic bond to an oxygen atom, L is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, and R1 is a substituent having one or more structures represented by the formula (2).

19. The polymer according to claim 18, wherein R1 in the general formula (3) is a group represented by the following general formula (4): In the formula, * represents an atomic bond to an oxygen atom, and n1, n2, and n3 represent integers of 1 to 10.

20. The polymer according to claim 17, wherein W2 in the general formula (1) is the following formula (5), In the formula, * represents an atomic bond to an oxygen atom, and n4 and n5 represent integers of 1 to 10.

21. The polymer according to any one of claims 17 to 20, wherein The weight average molecular weight of the polymer is 1,000 to 30,000.

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