Polymer for organic film-forming composition and method for producing the same, and organic film-forming composition using the polymer, and method for forming organic film and patterning process using the composition

Abstract

To provide an organic film material composition containing a specific polymer containing no fluorine atom, capable of forming a film excellent in coating defects such as pinholes on a substrate (wafer) and coating properties such as film-forming properties (in-plane uniformity) and embedding properties. The present invention further provides a method for forming an organic film and a patterning process using the composition for forming an organic film, and the polymer.SOLUTION: A composition for forming an organic film, comprising a resin and / or compound (A) for forming an organic film, a polymer (B) containing no halogen atom and containing a repeating unit shown by the following formula (1) and a repeating unit shown by the following formula (1 '), and a solvent (C).SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention relates to a polymer for an organic film-forming composition and a method for producing the same, a composition for an organic film using the polymer, and a method for forming an organic film and a method for forming a pattern using the composition. The present invention also relates to a composition for forming an organic film, which can form an organic film for a multilayer resist for microfabrication in the production of semiconductor devices and the like, or an organic film for planarization in the production of semiconductor devices and the like; a method for forming an organic film using the composition; a method for forming a pattern using the composition; and a polymer for use in the composition. [Background technology]

[0002] As LSIs become more highly integrated and faster, pattern rules are becoming increasingly miniaturized. This is due to the increasing popularity of 5G high-speed communications and artificial intelligence (AI), which require high-performance devices to process these. The most advanced miniaturization technology is extreme ultraviolet (EUV) lithography with a wavelength of 13.5 nm, which is currently used to mass-produce 5 nm node devices. Furthermore, the use of EUV lithography is being considered for next-generation 3 nm node devices and the next-generation 2 nm node devices.

[0003] As resist patterns become thinner in this way, it becomes difficult to form patterns using the single-layer resist method, which is a typical method for forming resist patterns.As a method for processing fine patterns, it is known that a multi-layer resist method, in which patterns are formed by stacking films with different dry etching properties in order to form high aspect ratio patterns on uneven substrates, is superior.A three-layer resist method (Patent Document 1) has been developed and put into practical use, which combines a photoresist layer made of an organic photosensitive polymer used in the single-layer resist method, an intermediate layer made of a silicon-based polymer or a silicon-based CVD film, and a lower layer made of an organic polymer.

[0004] In this three-layer resist method, for example, an organic film such as novolak is uniformly deposited on a substrate to be processed as a resist middle layer, a silicon-containing resist middle layer is deposited on top of that, and a conventional organic photoresist film is deposited on top of that as a resist top layer. Because the organic resist top layer has a favorable etching selectivity relative to the silicon-containing resist middle layer when dry-etched with a fluorine-based gas plasma, the resist pattern is transferred to the silicon-containing resist middle layer by dry-etching with a fluorine-based gas plasma. This method allows for pattern transfer to the silicon-containing film even when using a resist composition that is difficult to form a pattern with a thickness sufficient for direct processing of the substrate to be processed or a resist composition that does not have sufficient dry-etching resistance for substrate processing. Subsequent pattern transfer using dry-etching with an oxygen-based gas plasma allows for the formation of a novolak film (resist middle layer) pattern with sufficient dry-etching resistance for processing.

[0005] Although many technologies for the organic underlayer film described above are already known (e.g., Patent Documents 2 and 3), the recent advances in miniaturization have led to an increasing need for excellent filling properties in addition to dry etching properties. There is a need for organic underlayer film materials that can be uniformly deposited on the underlying substrate to be processed, even on substrates or materials with complex shapes, and that have filling properties that enable the necessary patterns to be filled without voids.

[0006] The organic underlayer film described above is formed using a coater / developer capable of spin coating, EBR, baking, and other processes when manufacturing semiconductor substrates, etc. The EBR (Edge Bead Removal) process is a process in which, after a coating is formed on a substrate (wafer) by spin coating, the coating on the edge of the substrate is removed with a remover to prevent contamination of the coater / developer's substrate transfer arm. The remover used in the EBR process is a mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30% by mass:70% by mass), which is widely used in the EBR process of resist films and resist intermediate layers (silicon-containing intermediate layers, organic underlayer films).

[0007] The remover used in the EBR process can cause a thick film thickness (hump) on the outer periphery of the organic underlayer film. Because humps can cause defects in the dry etching process used in substrate processing, there is a demand for organic underlayer films that suppress hump formation.

[0008] Resist materials used in photolithography using organic photosensitive polymers, as well as organic underlayer films, are applied in solution by spin coating or other methods, and then baked to evaporate the solvent, forming a film. As with organic underlayer films, the film thickness after baking must be uniform and flat, and the requirements for uniformity and flatness are becoming stricter every year.

[0009] In recent years, thicker resist films are required for 3D-NAND memory applications, and even greater flatness is required. As the film thickness increases, it becomes more difficult to achieve flatness within the film. Meanwhile, as miniaturization progresses, thinner films are being made, which increases the risk of pinhole defects and other defects.

[0010] The above describes examples of film materials using organic substances that are used in semiconductor processing materials, but even in film-forming materials that do not use organic substances, it would be a great industrial advantage to obtain a material that can form a film with uniform in-plane film thickness and without pinholes.

[0011] In recent years, the health effects of perfluoroalkyl substances (PFAS) have been pointed out, and there are moves to impose restrictions on the manufacture and sale of PFAS compounds under the European REACH. Perfluoroalkyl compounds have a wide range of uses, and due to their structural properties such as repelling water and oil, being resistant to heat and chemicals, and not absorbing light, they are used in a wide range of applications such as water repellents, surface treatment agents, emulsifiers, fire extinguishing agents, and coating agents, so there is an urgent need to develop alternative materials that do not contain the PFAS structure.

[0012] As an example of the above-mentioned material using a perfluoroalkyl compound, a surfactant having a fluoroalkyl group or a silicone chain is highly effective in reducing surface tension, and fluoroalkyl group surfactants are widely used, as they have a low risk of generating silicon-derived particles after dry ashing of the resist film (Patent Documents 3 and 4). Fluorine-based surfactants are also used not only in resist materials, but also in top coats formed on top of resists and in anti-reflective coatings formed on bottom layers of resists (Patent Document 5).

[0013] In light of future tightening of regulations, it is necessary to use materials that do not fall under PFAS regulations. For example, surfactants having trifluoromethoxy groups or pentafluorosulfanyl groups and their use have been proposed as surfactants mentioned above (Patent Document 6). In addition, in the field of resist materials, resist materials using photoacid generators have also been proposed (Patent Document 7). Furthermore, surfactants that do not contain fluorine have been proposed (Patent Document 8). [Prior art documents] [Patent documents]

[0014] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-205685 [Patent Document 2] Patent No. 4355943 etc. [Patent Document 3] Japanese Patent Application Publication No. 6-186735 [Patent Document 4] Japanese Patent Application Publication No. 6-214380 [Patent Document 5] Japanese Patent Application Laid-Open No. 2010-139822 [Patent Document 6] Special Publication No. 2008-526792 [Patent Document 7] International Publication No. 2023-223624 [Patent Document 8] International Publication No. 2022-073921 Summary of the Invention [Problem to be solved by the invention]

[0015] The present invention has been made in consideration of the above circumstances and provides a polymer that does not contain fluorine atoms. Use of an organic film material composition containing this polymer enables the formation of a film that has excellent coating properties, such as reduced pinholes and other coating defects on a substrate (wafer), film-forming properties (in-plane uniformity), and embedding properties. Furthermore, use of this organic film-forming composition as an organic underlayer film material makes it possible to provide an organic film that has excellent process latitude and suppresses humps when used as an organic underlayer film for a multilayer resist. The present invention also aims to provide an organic film-forming method and a pattern-forming method using this organic film-forming composition. Furthermore, the present invention aims to provide a film-forming material that does not fall under the category of perfluoroalkyl compounds (PFAS), thereby reducing the environmental impact. [Means for solving the problem]

[0016] In order to solve the above problems, the present invention provides the following.

[0017] The present invention provides a composition for forming an organic film, which comprises an organic film-forming resin and / or compound (A), a polymer (B) that is a halogen-free polymer and includes a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (1'), and a solvent (C). [ka] (In the formula, R2 and R3 each independently represent a saturated or unsaturated organic group having 1 to 20 carbon atoms which may have a substituent. y and z are each independently in the range of 0 < y < 1 and 0 < z < 1. However, y + z = 1.)

[0018] With such a composition for forming an organic film, it is possible to form an organic film that is excellent in in-plane uniformity and embedding characteristics and in which the formation of humps due to the influence of the remover in the EBR process is suppressed. Further, the structure of the alkyl groups of R2 and R3 in the above formula (1) provides an appropriate contact angle on the surface of the organic film, and the composition for forming an organic film is excellent in the coatability of the silicon-containing intermediate film.

[0019] It is preferable that the polymer (B) is the one of formula (2).

Chemical formula

[0020] With such a polymer that extends in both directions, the uniformity of the polymer can be enhanced. Therefore, by using it in a composition for forming an organic film, it is possible to form an organic film that is excellent in in-plane uniformity and embedding characteristics and in which the formation of humps due to the influence of the remover in the EBR process is suppressed.

[0021] It is preferable that the polymer represented by the above formula (2) is a polymer in which x, y, and z in the above formula are each independently in the range of 0 < x < 1, 0 < y < 1, and 0 < z < 1, and x + y + z = 1.

[0022] Further, it is preferable that the polymer (B) is the one of formula (3).

Chemical formula

[0023] For an organic film-forming composition containing such a compound, by having an alkyl group and a hydroxyl group, the film-forming property during coating can be improved. Moreover, the decomposition products generated during baking do not impair the in-plane uniformity of the film, and no insoluble matter is formed due to the reaction between the decomposition products. Therefore, without narrowing the process margin when used as an organic film, no equipment contamination or inconvenience occurs either.)

[0024] In the general formula (2), it is preferable that x, y, and z satisfy x + y + z = 1, z < x < y, and z + x < y.)

[0025] It is preferable that the weight average molecular weight of the polymer (B) is 1000 to 30000.)

[0026] Within such a range of the weight average molecular weight, it is possible to form an organic film excellent in film-forming property and embedding characteristics.)

[0027] When the organic film-forming resin and / or the compound (A) is 100 parts by mass, it is preferable that the content of the polymer (B) is 0.01 to 5 parts by mass.)

[0028] For an organic film-forming composition containing such a polymer with such a content, the in-plane uniformity of the formed organic film is more excellent.)

[0029] The present invention provides a method for producing a polymer containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (1') without containing a halogen atom, which comprises ring-opening polymerization of a Lewis acid cationic polymerization catalyst, tetrahydrofuran, and an oxetane ring-containing compound represented by the following formula (4).) [Chemical formula] (In the formula, R2 and R3 each independently represent a saturated or unsaturated organic group having 1 to 20 carbon atoms which may have a substituent. y and z are each independently in the range of 0 < y < 1 and 0 < z < 1. However, y + z = 1.) [Chemical formula] (In the formula, R2 and R3 have the same meanings as those in the above formula (1).)

[0030] With such a production method, the polymer for the composition for forming an organic film of the present invention can be preferably produced.

[0031] In the present invention, there is provided a method for forming an organic film used in the manufacturing process of a semiconductor device, comprising spin-coating the above-described composition for forming an organic film on a substrate to be processed, and heat-treating the substrate coated with the composition for forming an organic film at a temperature of 100°C or higher and 600°C or lower for 10 to 60o seconds to form a cured film.

[0032] With such a method for forming an organic film, it is particularly suitable for embedding a pattern with a complex shape on a substrate to be processed by spin-coating, forming an organic film with excellent in-plane uniformity, and removing the organic film at the edge while suppressing humps in the EBR process.

[0033] The present invention also provides a pattern formation method, comprising: forming an organic film on a workpiece using the organic film-forming composition described above; forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms; forming a resist upper layer film on the resist intermediate film using a resist upper layer film material consisting of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0034] The present invention also provides a pattern formation method, comprising: forming an organic film on a workpiece using the organic film-forming composition described above; forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms; forming an organic antireflective film or an adhesive film on the resist intermediate film; forming a resist upper layer film on the organic antireflective film or adhesive film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern by etching onto the organic antireflective film or adhesive film and the resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching onto the organic film using the resist intermediate film on which the pattern has been transferred as a mask; and further transferring the pattern onto the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0035] The present invention also provides a pattern formation method, comprising: forming an organic film on a workpiece using the organic film-forming composition described above; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming a resist upper layer film on the inorganic hard mask using a resist upper layer film material consisting of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0036] The present invention also provides a pattern formation method, comprising: forming an organic film on a workpiece using the organic film-forming composition described above; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming an organic antireflective film or an adhesive film on the inorganic hard mask; forming a resist upper layer film on the organic antireflective film or adhesive film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern by etching onto the organic antireflective film or adhesive film and the inorganic hard mask using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching onto the organic film using the inorganic hard mask on which the pattern has been transferred as a mask; and further transferring the pattern onto the workpiece by etching using the organic film on which the pattern has been transferred as a mask. .

[0037] Thus, the organic film-forming composition of the present invention can be suitably used in various pattern formation methods, such as a three-layer resist process using a silicon-containing resist intermediate film or an inorganic hard mask, or a four-layer resist process using an organic antireflective film or an adhesive film in addition to these. Furthermore, such a pattern formation method of the present invention makes it possible to transfer and form the circuit pattern of the resist upper layer film onto the workpiece with high precision.

[0038] The inorganic hard mask is preferably formed by a CVD method or an ALD method.

[0039] By such a patterning method, an inorganic hard mask can be formed.

[0040] In forming the circuit pattern, it is preferable to form the circuit pattern by lithography using light having a wavelength of 10 nm or more and 300 nm or less, direct drawing with an electron beam, nanoimprinting, or a combination thereof.

[0041] In forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0042] Such a pattern forming method can be suitably used as a circuit pattern forming means and a development means.

[0043] In the pattern formation method, the workpiece is preferably a semiconductor device substrate, or a semiconductor device substrate having 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 formed thereon.

[0044] In the pattern formation method described above, the metal constituting the workpiece is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0045] The pattern forming method of the present invention can form a pattern by processing the above-mentioned workpiece.

[0046] The present invention provides a polymer for an organic film-forming composition, which is a polymer that does not contain halogen atoms and contains a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (1'): [Chemical formula] (In the formula, R2 and R3 each independently represent a saturated or unsaturated organic group having 1 to 20 carbon atoms which may have a substituent. y and z are each independently in the range of 0 < y < 1 and 0 < z < 1. However, y + z = 1.)

[0047] <000​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​represents a saturated or unsaturated divalent organic group having 1 to 16 carbon atoms which may each have a substituent. x1, y, and z are each independently in the range of 0 < x1 < 1, 0 < y < 1, and 0 < z < 1. However, x1 + y + z = 1.)

[0051] For such a polymer for an organic film-forming composition, it is possible to provide an organic film-forming composition with improved film-forming properties during coating, no decrease in the in-plane uniformity of the film due to decomposition products generated during baking, and no formation of insoluble components due to reactions between decomposition products.)

[0052] In the general formula (2), it is preferable that x, y, and z satisfy x + y + z = 1, z < x < y, and z + x < y.)

[0053] Within such a range, it is more preferably applicable to an organic film-forming composition used as a semiconductor processing material.)

[0054] It is preferable that the weight average molecular weight of the polymer is 1000 to 30000.)

[0055] Within such a range of the weight average molecular weight, it is possible to form an organic film excellent in film-forming properties and embedding characteristics.)

Advantages of the Invention

[0056] As described above, the present invention can provide an organic film-forming composition that exhibits excellent film-forming properties (in-plane uniformity) and filling characteristics on a substrate (wafer), excellent film-forming properties on the organic film when used as an organic film, and suppresses hump formation during the EBR process. Because the organic film-forming composition of the present invention exhibits excellent film-forming properties, filling characteristics, and suppresses hump formation during the EBR process, it is extremely useful as an organic film material for use in multilayer resist processes, such as a two-layer resist process, a three-layer resist process using a silicon-containing resist interlayer or an inorganic hard mask, or a four-layer resist process using a silicon-containing resist interlayer or an inorganic hard mask and an organic anti-reflective coating or adhesive coating, or as an organic film-forming material for semiconductor device manufacturing. Furthermore, the organic film-forming method of the present invention can form an organic film with suppressed hump formation, thereby enabling the efficient manufacture of semiconductor devices and the like. [Brief explanation of the drawings]

[0057] [Figure 1] 1 is an example of a graph showing the height of humps measured using a contact profiler in a composition for forming an organic film in which humps are suppressed. [Figure 2] 1 is an example of a graph showing the height of humps measured using a contact profiler in an organic film-forming composition in which humps are not suppressed. [Figure 3] 1A to 1C are explanatory diagrams illustrating an example of a pattern formation method using a three-layer resist process according to the present invention. [Figure 4] FIG. 1 is an explanatory diagram of a method for evaluating filling characteristics in an example. DETAILED DESCRIPTION OF THE INVENTION

[0058] As described above, there has been a demand for the development of a composition for forming an organic film that has excellent film-forming properties (in-plane uniformity) and filling properties on a substrate (wafer) and that suppresses humps during the EBR process.

[0059] Generally, when forming an organic film, a resin for forming the organic film and additives are dissolved in an organic solvent to form a composition, which is applied onto a substrate on which structures, wirings, etc. are formed by a coater / developer. The composition is spread by rotating the substrate, the composition at the edge is removed in an EBR process, and then the organic film is formed by baking. When the fluidity of the above composition is insufficient, voids are generated when filling holes or trenches with a very high aspect ratio, and it is considered that humps are generated on the outer periphery of the organic film when the resin for forming the organic film and additives are inferior in solubility to the remover used in the EBR process. The inventors of the present invention have further intensively studied and found that by blending a thermally decomposable compound having a specific repeating unit into the composition for forming an organic film, it is possible to provide a composition for forming an organic film excellent in film-forming properties, high embedding properties, and suppression of humps during the EBR process, and thus completed the present invention.

[0060] That is, the present invention is a composition for forming an organic film, which comprises a resin for forming an organic film and / or compound (A), a polymer containing no halogen atom, a polymer (B) containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (1'), and a solvent (C).

Chemical formula

[0061] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0062] [Composition for forming an organic film] The composition for forming an organic film of the present invention contains constituent components (A), (B), and (C). First, component (B) will be described, and then components (A), component (C), and other components will be described.

[0063] [Component (B)] Component (B) is a polymer that does not contain halogen atoms and contains a repeating unit represented by the above formula (1) and a repeating unit represented by the above formula (1').

[0064] Component (B) can be synthesized by ring-opening polymerization using a cationic polymerization catalyst, tetrahydrofuran, and an oxetane ring-containing compound represented by the following formula (4). [ka] (In the formula, R2 and R3 each independently represent a saturated or unsaturated organic group having 1 to 20 carbon atoms which may have a substituent.)

[0065] Component (B) of the present invention functions as a surfactant that imparts excellent film-forming properties and high leveling performance. Furthermore, it can be applied not only to organic film-forming materials but also to silicon-containing resist intermediate films, and can be used as a surfactant suitable for achieving highly versatile film-forming properties that can be applied to a variety of film-forming materials.

[0066] Component (B) of the present invention functions as a surfactant that provides uniform coating properties (leveling properties) of organic films by making R2 and R3 organic groups. Therefore, when the compound of the present invention is used as a surfactant, it can be used not only for organic films but also for general photolithography coating materials. Specific examples include photosensitive resist materials and materials for forming top coats on resist films. Furthermore, those in which R3 is a branched alkyl group are more effective as surfactants that provide an appropriate contact angle.

[0067] The repeating unit of formula (1) is derived from the synthetic raw material, an oxetane compound of formula (4). R2 and R3 are R2 and R3 of the oxetane compound.

[0068] In formula (1), R2 is a saturated or unsaturated organic group having 1 to 20 carbon atoms which may have a substituent. As the organic group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms is preferable. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group. From the viewpoint of raw material availability, a methyl group or an ethyl group is preferable.

[0069] As the organic group represented by R3 above, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms and a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms are preferable. Specific examples thereof include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group, and alkoxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, an i-butoxycarbonyl group, a sec-butoxycarbonyl group, a t-butoxycarbonyl group, an n-pentyloxycarbonyl group, and an n-hexyloxycarbonyl group. A branched alkyl group is preferable, and branched alkyl groups having 3 to 20 carbon atoms such as an i-propyl group, an i-butyl group, a sec-butyl group, and a tert-butyl group are included.

[0070] Formula (1') is a repeating unit derived from tetrahydrofuran as a raw material.

[0071] The polymer of the component (B) is preferably the one represented by formula (2).

Chemical formula

[0072] The polymer represented by the formula (2) can be synthesized by ring-opening polymerization using a cationic polymerization catalyst, tetrahydrofuran, an oxetane ring-containing compound represented by the following formula (4), and a diol represented by the following formula (5). [ka] (In the formula, R8 represents a saturated or unsaturated organic group having 1 to 20 carbon atoms which may have a substituent.)

[0073] The compound represented by formula (5) is a diol compound used as a raw material when synthesizing the polymer of formula (2). R8 in formula (2) is R8 of the compound represented by formula (5) used as a raw material. R8 is a divalent saturated chain hydrocarbon group such as methylene, ethylene, n-propylene, i-propylene, n-butylene, i-butylene, sec-butylene, tert-butylene, n-pentylene, iso-pentylene, sec-pentylene, or tert-pentylene; a divalent unsaturated chain hydrocarbon group such as ethenylene, propenylene, butenylene, pentenylene, ethynylene, or propynylene; a cyclobutylene group, cyclopentene, or cyclopentylene; divalent monocyclic saturated cyclic hydrocarbon groups such as ethylene group, cyclohexylene group, cycloheptylene group, and cyclooctylene group; monocyclic unsaturated cyclic hydrocarbon groups such as cyclobutenylene group, cyclopentenylene group, and cyclohexenylene group; divalent polycyclic cyclic hydrocarbon groups such as norbornylene group and adamantylene group; and divalent aromatic hydrocarbon groups such as phenylene group, methylphenylene group, naphthylene group, methylnaphthylene group, anthrylene group, and methylanthrylene group. These substituents may be further substituted with a substituent. R8 is preferably an unsubstituted or alkylene group substituted with an alkyl group.

[0074] For an organic film-forming composition containing such a compound, the film-forming property during coating can be improved without containing fluorine, and the decomposition products generated during baking do not impair the in-plane uniformity of the film, and insoluble matter is not formed due to the reaction between the decomposition products. Therefore, it does not cause equipment contamination or inconvenience without narrowing the process margin when used as an organic film.

[0075] In the polymer represented by the above formula (2), it is preferable that x, y, and z in the above formula are each independently in the range of 0 < x < 1, 0 < y < 1, and 0 < z < 1, and x + y + z = 1.

[0076] It is preferable that x, y, and z in the above formula (2) satisfy x + y + z = 1, z < x < y, and z + x < y.

[0077] A polymer having such a structure can provide an organic film-forming composition having an appropriate contact angle.

[0078] Furthermore, it is preferable that the polymer of the component (B) is the one of the formula (3). [Chemical formula] (In the formula, R2 and R3 have the same meanings as those in the above formula (2). R 12 , R 13 each represent a saturated or unsaturated divalent organic group having 1 to 16 carbon atoms which may have a substituent. x1, y, and z are each independently in the range of 0 < x1 < 1, 0 < y < 1, and 0 < z < 1. However, x1 + y + z = 1.)

[0079] In the formula (3), the unit repeated x1 times is derived from the diol compound represented by the formula (5) which is a raw material. The unit repeated y times is derived from the oxetane compound represented by the formula (4) which is another raw material. The unit repeated z times is derived from tetrahydrofuran which is another raw material.

[0080] The above R 12 , R13 The divalent organic group represented by the formula (I) is preferably a divalent saturated hydrocarbon group having 1 to 16 carbon atoms, a divalent unsaturated chain hydrocarbon group having 2 to 16 carbon atoms, a divalent monocyclic saturated cyclic hydrocarbon group having 6 to 16 carbon atoms, a divalent monocyclic unsaturated cyclic hydrocarbon group having 6 to 16 carbon atoms, a divalent polycyclic cyclic hydrocarbon group having 6 to 16 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 16 carbon atoms. 12 , R 13 Specific examples of R include those described above for R8. 12 , R 13 are each independently preferably an unsubstituted or alkylene group substituted with an alkyl group.

[0081] When they are substituted, examples of the substituent include alkoxy groups such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, sec-butoxy, t-butoxy, n-pentyloxy, and n-hexyloxy; and alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, i-butoxycarbonyl, sec-butoxycarbonyl, t-butoxycarbonyl, n-pentyloxycarbonyl, and n-hexyloxycarbonyl.

[0082] The structure represented by formula (3) makes it easy to adjust the molecular weight from the viewpoint of polymer synthesis, and allows the production of a uniform polymer.

[0083] Specific examples of the oxetane compound represented by formula (4), which is a raw material for synthesizing the polymer of formula (2), include, but are not limited to, the following: [ka]

[0084] Specific examples of the diol-derived structure of the polymer represented by the above formula (2) include, but are not limited to, the following. [ka]

[0085] The compound of formula (5) used as a raw material for synthesizing the polymer of formula (2) is preferably the following. [ka]

[0086] With the above structure, the thermal decomposition property, surface activity effect, and polymer flowability can be adjusted, and the compound can be made to have both film-forming property and embedding property.

[0087] The weight average molecular weight of the polymer (B) is preferably 1,000 to 30,000.

[0088] Such a polymer can prevent a decrease in the blending effect due to volatilization or the like, and can provide a composition for forming an organic film that can obtain a sufficient blending effect. The weight-average molecular weight of the polymer (B) is more preferably 1,500 to 25,000. If the weight-average molecular weight is 1,000 or more, there are no problems due to volatility, and if the weight-average molecular weight is 30,000 or less, there is no deterioration in fluidity and the composition has excellent embedding properties.

[0089] In the present invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) are polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent (solvent), and the dispersity (Mw / Mn) is calculated from Mw and Mn.

[0090] [Method for synthesizing polymer (B)] The synthesis method of the polymer (B) of the present invention will be explained below. As a means for obtaining the compound for forming an organic film of the present invention, it is synthesized by cationic polymerization of an oxetane compound in the presence of a cationic polymerization catalyst (Lewis acid catalyst) and tetrahydrofuran. As the cationic polymerization catalyst, those having an action of initiating cationic polymerization can be appropriately selected and used. As the cationic polymerization catalyst, a Lewis acid catalyst is preferable. Specific examples of the Lewis acid catalyst include metal halides (BF3, AlCl3, TiCl4, SnCl4, FeCl3), organometallic compounds (EtAlCl2, Et2AlCl, Et3Al). Preferably, it is boron trifluoride (BF3).

[0091] Tetrahydrofuran may be coexisted in the reaction system. As one method, a tetrahydrofuran complex of boron trifluoride can be used as the Lewis acid catalyst. From the viewpoint of industrial availability, it is preferable to use a tetrahydrofuran complex of boron trifluoride or the like.

[0092] In the ring-opening polymerization reaction of oxetane, a divalent alcohol represented by the formula (5) can be coexisted. In that case, the polymer contains a repeating unit derived from the alcohol. The divalent alcohol and oxetanes used in the synthesis can be used alone or in combination of two or more. These can be appropriately selected and combined according to the required properties.

[0093] This reaction is represented by the following reaction formula.

Chemical formula

[0094] R2, R3, and R8 in the following formula have the same meanings as those in the formula (2). x, y, and z are each independently in the range of 0 ≦ x < 1, 0 < y < 1, and 0 < z < 1. However, x + y + z = 1.)

[0095] The amount of the Lewis acid catalyst used at this time is preferably in the range of 0.01 to 1 mol, more preferably 0.02 to 0.2 mol, per 1 mol of the raw material oxetanes.

[0096] The solvent used in this reaction is not particularly limited as long as it is inert to the reaction, and examples thereof include halogenated solvents such as 1,2-dichloromethane and chloroform, aromatic solvents such as benzene, toluene, and xylene, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, and N-methylpyrrolidone, which can be used alone or in combination. These solvents can be used in an amount of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials, and the reaction temperature is preferably from -50°C to the boiling point of the solvent, more preferably from room temperature to 150°C. The reaction time is appropriately selected from the range of 0.1 to 100 hours.

[0097] Reaction methods include charging boron trifluoride tetrahydrofuran, dihydric alcohols, or oxetanes all at once into a solvent, charging boron trifluoride tetrahydrofuran, dihydric alcohols, or oxetanes individually or mixed together and dispersed or dissolved, and charging dropwise, and dissolving either boron trifluoride tetrahydrofuran, dihydric alcohols, or oxetanes in a solvent, and then charging dropwise the other dispersed or dissolved in a solvent, etc. When charging multiple dihydric alcohols or oxetanes, they may be mixed and reacted in advance, or they may be reacted individually and sequentially.

[0098] The reaction mixture obtained by the production method of the present invention can be diluted with an organic solvent to remove unreacted raw materials, catalysts, etc. present in the system, and then recovered by separation and washing.

[0099] The organic solvent used for separation washing is not particularly limited as long as it can dissolve the compound and separate into two layers when mixed with water. Specific examples include hydrocarbons such as hexane, heptane, benzene, toluene, and xylene; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and methyl isobutyl ketone; ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, and ethyl cyclopentyl methyl ether; chlorinated solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene; and mixtures thereof. The washing water used in this process is typically what is known as deionized water or ultrapure water. While washing may be performed at least once, washing 10 or more times does not necessarily provide the desired effect, so washing 1 to 5 times is preferred.

[0100] In order to remove unreacted raw materials or acidic components from the system during separation and washing, washing may be performed with a basic aqueous solution. Specific examples of the base include alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, ammonia, and organic ammonium.

[0101] Furthermore, in order to remove unreacted raw materials, metal impurities, or basic components from the system during separation and washing, washing with an acidic aqueous solution may be performed. Specific examples of the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropolyacids, and organic acids such as oxalic acid, fumaric acid, maleic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

[0102] The separation washing with the basic aqueous solution and the acidic aqueous solution may be carried out either alone or in combination. From the viewpoint of removing metal impurities, the separation washing is preferably carried out in the order of the basic aqueous solution and the acidic aqueous solution.

[0103] After the separation washing with the basic aqueous solution or acidic aqueous solution, washing with neutral water may be carried out subsequently. As the neutral water, deionized water or ultrapure water as described above may be used. The number of washings is preferably from 1 to 10 times, and more preferably about 1 to 5 times. Washing can remove basic and acidic components, and washing within 10 times is economically advantageous.

[0104] Furthermore, the reaction product after the separation operation can be recovered as a powder by concentrating the solvent to dryness or crystallizing it under reduced or normal pressure, but it can also be left in a solution state with a moderate concentration to improve operability when preparing an organic film-forming material. The concentration in this case is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass. At such a concentration, the viscosity is unlikely to increase, preventing a loss of operability, and the amount of solvent is not excessive, making it economical.

[0105] The solvent used in this case is not particularly limited as long as it can dissolve the compound, and specific examples include ketones such as cyclohexanone and methyl 2-amyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono tert-butyl ether acetate, and these can be used alone or in combination of two or more.

[0106] This polymer is useful for forming organic films. The polymer may have two types of structures represented by the above formula (2).

[0107] In the organic film-forming composition of the present invention, the (B) polymer, the (A) organic film-forming resin or compound, and the (C) solvent can each be used alone or in combination of two or more.

[0108] [(A) Organic film-forming resin and / or compound] The organic film-forming resin and / or compound (A) contained in the organic film-forming composition will be explained.

[0109] The organic film-forming resin and / or compound (A) used in the organic film-forming composition of the present invention is not particularly limited as long as it is a resin or compound that satisfies the film-forming properties and curing properties of spin coating. However, when used as an organic underlayer film material, a resin or compound containing an aromatic skeleton is more preferred from the viewpoints of etching resistance, optical properties, heat resistance, etc.

[0110] Examples of the aromatic skeleton include benzene, naphthalene, anthracene, pyrene, indene, fluorene, furan, pyrrole, thiophene, phosphole, pyrazole, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, carbazole, etc. Among these, benzene, naphthalene, fluorene, and carbazole are particularly preferred.

[0111] Hereinafter, the organic film-forming material (A) will be described with specific examples, but these are merely examples and are not intended to limit the scope of the invention. Furthermore, the numbers in the formulae shown in the following examples are used only for the purpose of explaining the formulae.

[0112] Examples of the organic film-forming material (resin or compound) (A) used in the present invention include resins containing the following structures described in JP-A Nos. 2012-001687 and 2012-077295. [ka] (In formula (6), 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 such that the molecular weight is 100,000 or less. Note that the symbols in the formula apply only within this formula.)

[0113] [ka] (In formula (7), the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. n represents any natural number such that the weight average molecular weight, as calculated using polystyrene standards by gel permeation chromatography, is 100,000 or less. Note that the symbols in the formula are used only within this formula.)

[0114] Further examples of the organic film-forming material (A) used in the present invention include resins containing the following structures described in JP-A Nos. 2004-264710, 2005-043471, 2005-250434, 2007-293294, and 2008-065303. [ka] (In formula (8) and formula (9), R 1 and R 2 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group; R 3 represents an alkyl group having 1 to 3 carbon atoms, a vinyl group, an allyl group, or an aryl group which may be substituted, n represents 0 or 1, and m represents 0, 1, or 2. The symbols in the formulae apply only within the formulae.

[0115] [ka] (In formula (10), 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 a monovalent atom or group. X is a divalent group. Note that the symbols in the formula apply only within this formula.)

[0116] [ka] In formula (11), 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 have any of ether, ester, lactone, and amide. R 3 , R 4 are each a hydrogen atom or a glycidyl group. X represents a polymer of any one of hydrocarbons containing an indene skeleton, cycloolefins having 3 to 10 carbon atoms, and maleimide, and may have any one of ethers, esters, lactones, and carboxylic acid anhydrides. R 5 , R 6 R is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 7 is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a hydroxy group, or an alkoxycarbonyl group. p and q are each an integer of 1 to 4. 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. Note that the symbols in the formulae apply only within this formula.)

[0117] [ka] (In formula (12), R1 represents a hydrogen atom or a monovalent organic group, and R2 and R3 each independently represent a monovalent atom or a monovalent organic group. Note that the symbols in the formula apply only within this formula.)

[0118] Specific examples of the organic film-forming material (A) used in the present invention include resins containing the following structures described in JP-A Nos. 2004-205685, 2007-171895, and 2009-014816. [ka] (In formula (13) and formula (14), R 1 ~R 8 are each independently a hydrogen atom, 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 alkoxycarboxyl group having 2 to 6 carbon atoms, an optionally 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. Note that the symbols in the formula apply only within this formula.

[0119] [ka] (In formula (15), 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 hydroxy group, an acetoxy group, or an alkoxycarbonyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and 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 where m is 1 or 2, n is an integer of 0 to 4, and p is an integer of 0 to 6. 7 is an organic group with 7 to 30 carbon atoms, R 8is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Z is any one of a methylene group, -O-, -S-, -NH-. a, b, c, d, e are respectively in the ranges of 0 < a < 1.0, 0 ≤ b ≤ 0.8, 0 ≤ c ≤ 0.8, 0 ≤ d ≤ 0.8, 0 ≤ e ≤ 0.8, and 0 < b + c + d + e < 1.0. Note that the symbols in the formula are applicable only within this formula.)

[0120]

Chemical formula

[0121] Examples of formula (16) include the following resins.

Chemical formula

[0122]

Chemical formula

[0123] Examples of the organic film-forming material (A) used in the present invention include resins containing the following structures described in JP-A Nos. 2007-199653, 2008-274250, and 2010-122656. [ka] (In formula (17), 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 an alkylene group having a linear, branched or cyclic structure and having 1 to 30 carbon atoms, which may have a bridged cyclic hydrocarbon group, a double bond, a heteroatom or an aromatic group having 6 to 30 carbon atoms; R 4 and R 5 are each independently a hydrogen atom or a glycidyl group, and n is an integer of 1 to 4. The symbols in the formula are applicable only within this formula.

[0124] [ka] (In formula (18), 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 an alkylene group having a linear, branched or cyclic structure and having 1 to 30 carbon atoms, which may have a bridged cyclic hydrocarbon group, a double bond, a heteroatom or an aromatic group having 6 to 30 carbon atoms; R 4 and R 5 are each independently a hydrogen atom or a glycidyl group, and R 6 is a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms. The symbols in the formula are only applicable within this formula.

[0125] [ka] (In formula (19), ring Z 1 and ring Z 2 are fused polycyclic aromatic hydrocarbon rings, R 1a , R 1b , R 2a , and R 2b represent substituents that are the same or different. k1 and k2 are the same or different and represent 0 or an integer from 1 to 4, m1 and m2 are each 0 or an integer of 1 or more, and n1 and n2 are each 0 or an integer of 1 or more. However, n1 + n2 ≥ 1. Note that the symbols in the formula are applicable only within this formula.)

[0126]

Chemical formula

[0127] Examples of formula (20) include, for example, the following resins.

Chemical formula

[0128]

Chemical formula

[0129]

Chemical formula

[0130] [ka]

[0131] Examples of the organic film-forming material (A) used in the present invention include resins containing the following structure described in JP-A No. 2012-214720. [ka] (In formula (21), the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. x and z each independently represent 0 or 1. Note that the symbols in the formula apply only within this formula.)

[0132] Examples of the organic film-forming material (A) used in the present invention include resins described in JP-A-2014-29435. [ka] (In formula (22), A represents a structure having carbazole, B represents a structure having an aromatic ring, and C represents a structure having a hydrogen atom, an alkyl group, or an aromatic ring, and B and C may form a ring together. The combined structure of A, B, and C contains 1 to 4 carboxyl groups or salts thereof, or carboxylate ester groups. Note that the symbols in the formula apply only within this formula.)

[0133] Furthermore, examples of the organic film-forming material (A) used in the present invention include polymers containing a unit structure represented by the following formula (23) and a unit structure represented by the following formula (24) described in WO 2012 / 077640, in which the molar ratio of the unit structure represented by formula (23) to the unit structure represented by formula (24) is 3 to 97:97 to 3. [ka] In formula (23), R1 and R2 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a hydroxy 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 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 contain an ether bond, a ketone bond, or an ester bond. represents a combination of these groups. 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 hydroxy group, or a heterocyclic group; R5 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, a nitro group, an amino group, or a hydroxy group, or an aryl group having 6 to 40 carbon atoms, or a heterocyclic group; R4 and R5 may together form a ring; n1 and n2 each represent an integer of 1 to 3; and the symbols in the formula are applicable only within this formula.

[0134] [ka] In formula (24), Ar represents an aromatic ring group having 6 to 20 carbon atoms, R6 represents a hydroxy 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 contain an ether bond, a ketone bond, or an ester bond, and R8 represents a hydrogen atom, or a halogen atom which may be substituted with a nitro group, an amino group, or a hydroxy group. R8 represents an aryl group or heterocyclic group having 6 to 40 carbon atoms, R9 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, a nitro group, an amino group, or a hydroxy group, or an aryl group or heterocyclic group having 6 to 40 carbon atoms, and R8 and R9 may together form a ring. n6 represents an integer of 1 to p, and n7 represents an integer of p-n6, where p represents the maximum number of substituents that can be substituted on the aromatic ring group Ar. The symbols in the formula are only applicable within this formula.

[0135] An example of the organic film-forming material (A) used in the present invention is a polymer containing a unit structure represented by the following formula (25) described in WO 2010 / 147155. [ka] In formula (25), R1 and R2 are each selected from the group consisting of a hydrogen atom, a halogen group, a nitro group, an amino group, a hydroxy 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 which may contain an ether bond, a ketone bond, or an ester bond; 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, and the alkyl group, the alkenyl group Alternatively, the aryl group represents a group which may contain an ether bond, a ketone bond, or an ester bond; R4 represents an aryl group or heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; R5 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 with a halogen group, a nitro group, an amino group, or a hydroxy group; R4 and R5 may form a ring together with the carbon atoms to which they are bonded; and n1 and n2 are each an integer of 1 to 3. Note that the symbols in the formula apply only within this formula.

[0136] Examples of the organic film-forming material (A) used in the present invention include novolak resins obtained by reacting one or more phenols, such as phenol, cresol, xylenol, catechol, resorcinol, hydroquinone, pyrogallol, hydroxyquinol, and phloroglucinol, 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 (26), which are described in WO 2012 / 176767. [ka] (In formula (26), A represents a hydroxy-substituted phenylene group derived from polyhydroxybenzene, and B represents a monovalent fused aromatic hydrocarbon ring group in which 2 to 6 benzene rings are fused. Note that the symbols in the formula apply only within this formula.)

[0137] Examples of the organic film-forming material (A) used in the present invention include novolak resins having a fluorene or tetrahydrospirobiindene structure described in JP-A Nos. 2005-128509, 2006-259249, 2006-259482, 2006-293298, and 2007-316282, which contain a repeating unit structure represented by the following formula (27-1) or (27-2): [ka] (In formula (27-1) and formula (27-2), 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; 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 are 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. R 10 ~R 13 are independently a hydrogen atom, a halogen atom, a hydroxy 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. Note that the symbols in the formula apply only within this formula.)

[0138] An example of the organic film-forming material (A) used in the present invention is a reaction product obtained by the method described in JP-A-2012-145897. More specifically, an example is a polymer obtained by condensing one or more compounds represented by the following general formula (28-1) and / or (28-2) with one or more compounds represented by the following general formula (29-1) and / or (29-2) and / or their equivalents: [ka] (In the general formula (28-1) and the general formula (28-2), R 1 ~R 8 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an isocyanato group, a glycidyloxy 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 alkanoyloxy 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 Two substituents arbitrarily selected from the following may be bonded to form a cyclic substituent. The symbols in the formula are applicable only within this formula.)

[0139] [ka] (In general formula (29-1) and general formula (29-2), Q is an organic group having 1 to 30 carbon atoms which may be substituted, and two Qs arbitrarily selected in the molecule may be bonded to form a cyclic substituent. n1 to n6 are the numbers of each substituent, and n1 to n6 = 0, 1, 2, and in formula (29-1), hydroxybenzaldehyde is excluded. In addition, in formula (29-2), the relationships 0 ≦ n3 + n5 ≦ 3, 0 ≦ n4 + n6 ≦ 4, 1 ≦ n3 + n4 ≦ 4 are satisfied. Note that the symbols in the formulas apply only within this formula.)

[0140] Further, examples of the polymers include those obtained by condensing one or more compounds represented by the above general formula (28-1) and / or (28-2), one or more compounds represented by the above general formula (29-1) and / or (29-2) and / or equivalents thereof, and one or more compounds represented by the following general formula (30) and / or equivalents thereof. [ka] (In formula (30), Y is a hydrogen atom or a monovalent organic group having 30 or less carbon atoms which may have a substituent, and formula (30) is different from general formula (29-1) and general formula (29-2). Note that the symbols in the formula apply only within this formula.)

[0141] Examples of the organic film-forming material (A) used in the present invention include compounds containing the following structure described in JP-A-2017-119671. [ka] (In formula (31-1), 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 (31-2), and m1 is an integer satisfying 2≦m1≦10. Note that the symbols in the formula apply only within this formula.) [ka] (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, and X 3 is a group represented by the following general formula (31-3), and n5 is 0, 1, or 2. The symbols in the formula apply only within this formula. [ka] (In the formula, R 10 is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom on the benzene ring in the formula may be substituted with a methyl group or a methoxy group. Note that the symbols in the formula apply only within this formula.

[0142] Examples of compounds containing the above structure include the following compounds. [ka]

[0143] Examples of the organic film-forming material (A) used in the present invention include polymers having a repeating unit represented by the following general formula (32-1), which are described in JP-A-2019-044022. [ka] In formula (32-1), AR1 and AR2 are benzene rings or naphthalene rings which may have a substituent, and R 1 , R 2 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R 1 and R 2 If is an organic group, R 1 and R 2 may form a cyclic organic group by bonding intramolecularly. n is 0 or 1, and when n=0, AR1 and AR2 do not form a bridged structure between the aromatic rings of AR1 and AR2 via Z, and when n=1, AR1 and AR2 form a bridged structure between the aromatic rings of AR1 and AR2 via Z, and Z is either a single bond or the following formula (32-2). Y is a group represented by the following formula (32-3). Note that the symbols in the formulas apply only within this formula. [ka] [ka] (In the formula, R 3 is a single bond or a divalent organic group having 1 to 20 carbon atoms, and R 4 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and the dashed line represents a bond. Note that the symbols in the formula apply only within this formula.)

[0144] Examples of polymers having a repeating unit represented by the above general formula (32-1) include the following polymers. [ka]

[0145] [ka]

[0146] (A) The organic film-forming material may be synthesized by a known method, or a commercially available product may be used.

[0147] The amount of the (A) organic film-forming material is not particularly limited as long as the organic film-forming composition satisfies the film-forming properties of spin coating. Preferably, the amount of the (A) organic film-forming material is 10 to 40 parts by weight, more preferably 10 to 30 parts by weight, and even more preferably 10 to 25 parts by weight, per 100 parts by weight of the organic film-forming composition. For example, when filling holes or trenches with extremely high aspect ratios in 3D NAND memory architecture with the organic film-forming composition, a large amount of the organic film-forming material is required. However, such organic film-forming compositions have high viscosity, which can degrade the in-plane uniformity and filling characteristics after spin coating. Even with the above-mentioned ratio of the (A) organic film-forming material, the organic film-forming composition of the present invention can be suitably applied because it can form organic films with excellent in-plane uniformity and filling characteristics.

[0148] Furthermore, the content of the polymer (B) is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the material (A) for forming an organic film. When the composition for forming an organic film contains the polymer in such a content, the formed organic film has better in-plane uniformity.

[0149] [Solvent (C)] The solvent (C) that can be used in the organic film-forming material of the present invention is not particularly limited as long as it can dissolve the (A) organic film-forming resin and / or compound and the (B) polymer, and is preferably one that can also dissolve the acid generator, crosslinking agent, surfactant, etc., which will be described later. Specifically, solvents with a boiling point of less than 180°C, such as those described in paragraphs (0091) and (0092) of JP-A No. 2007-199653, can be used. Among these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and mixtures of two or more of these are preferably used.

[0150] The content of the (C) solvent is 200 to 10,000 parts by mass, and more preferably 300 to 5,000 parts by mass, relative to 100 parts by mass of the (A) organic film-forming material. By adjusting the content within this range, the concentration can be adjusted to match the desired film thickness.

[0151] Furthermore, in the organic film-forming material of the present invention, a high-boiling solvent having a boiling point of 180° C. or higher can be added to the above-mentioned solvent having a boiling point of less than 180° C. (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). The high-boiling organic solvent is not particularly limited as long as it can dissolve the organic film-forming compound, and may be any of hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc., but specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-Hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, n-nonyl acetate, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol-n-butyl ether, triethylene glycol butyl methyl ether, triethylene Glycol diacetate, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, 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-butylene glycol diacetate, 1,Examples of the diester include 6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, and dibutyl adipate, and these may be used alone or in combination.

[0152] The boiling point of the high-boiling solvent may be appropriately selected according to the temperature at which the organic film-forming material is heat-treated, and the boiling point of the high-boiling solvent to be added is preferably 180°C to 300°C, and more preferably 200°C to 300°C. Such a boiling point prevents the solvent from volatilizing too quickly during baking (heat treatment) due to a boiling point that is too low, thereby ensuring sufficient thermal fluidity. Furthermore, such a boiling point is so high that the solvent does not remain in the film after baking without volatilizing, and therefore does not adversely affect film properties such as etching resistance.

[0153] Furthermore, when a high-boiling point solvent is used, the blending amount of the high-boiling point solvent is preferably 1 to 30 parts by mass per 100 parts by mass of a solvent having a boiling point of less than 180° C. If the blending amount is within this range, there is no risk that the blending amount is too small to impart sufficient thermal fluidity during baking, or that the blending amount is too large to remain in the film and lead to deterioration of film properties such as etching resistance.

[0154] In the case of such an organic film-forming composition, the addition of a high-boiling point solvent to the above-mentioned organic film-forming material gives it thermal fluidity, thereby making it an organic film-forming composition that also has high-level filling / planarizing properties.

[0155] [Other ingredients] In addition, an acid generator or crosslinking agent can be added to the organic film-forming composition of the present invention to further promote the crosslinking reaction. Acid generators include those that generate acid upon thermal decomposition and those that generate acid upon light irradiation, and either can be added. Specific examples of acid generators include those described in paragraphs

[0061] to

[0085] of JP 2007-199653 A. The above acid generators can be used alone or in combination of two or more. When an acid generator is added, the amount added is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the (A) organic film-forming resin and / or compound. This amount promotes the crosslinking reaction and enables the formation of a dense film.

[0156] Specific examples of crosslinking agents include those described in paragraphs

[0055] to

[0060] of JP 2007-199653 A. Crosslinking agents can be used singly or in combination of two or more. The amount of crosslinking agent added is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, per 100 parts by mass of (A) organic film-forming resin and / or compound. This amount enhances curability and further suppresses intermixing with the overlying film.

[0157] Furthermore, a surfactant other than the polymer (B) of the present invention can be added to the organic film-forming composition of the present invention to further improve in-plane uniformity during spin coating. Specific examples of surfactants include those described in paragraphs

[0142] to

[0147] of JP 2009-269953 A. The above surfactants can be used alone or in combination of two or more. When a surfactant is added, the amount added is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the resin and / or compound for forming the organic film. This amount enables the formation of an organic film with excellent in-plane uniformity.

[0158] Furthermore, a basic compound can be added to the organic film-forming composition of the present invention to improve storage stability. The basic compound acts as an acid quencher to prevent a small amount of acid generated by the acid generator from promoting a crosslinking reaction. Specific examples of such basic compounds include those described in paragraphs

[0086] to

[0090] of JP 2007-199653 A. The basic compounds can be used alone or in combination of two or more. When an acid generator is added, the amount added is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the (A) organic film-forming resin and / or compound. This amount can improve the storage stability of the organic film-forming composition.

[0159] As described above, the organic film-forming composition of the present invention is an organic film-forming composition that is excellent at suppressing humps during the EBR process. Therefore, the organic film-forming composition of the present invention is extremely useful as a resist intermediate film material (organic film material) for multilayer resist processes such as a two-layer resist process, a three-layer resist process using a silicon-containing resist intermediate film or a silicon-containing inorganic hard mask intermediate film, and a four-layer resist process using a silicon-containing resist intermediate film or a silicon-containing inorganic hard mask intermediate film and an organic antireflective film or adhesive film.

[0160] [Organic film formation method] The present invention provides a method for forming an organic film used in the manufacturing process of a semiconductor device, which comprises spin-coating the organic film-forming composition of the present invention onto a substrate to be processed and heat-treating the substrate coated with the organic film-forming composition for 10 to 600 seconds at a temperature of 100° C. to 600° C. For example, an organic film is formed by heat-treating the substrate coated with the organic film-forming composition within the above-mentioned temperature and time ranges to harden it.

[0161] In this organic film formation method, the organic film-forming composition of the present invention is first spin-coated onto a substrate to be processed. By using the spin-coating method, excellent embedding properties can be obtained. After removing the coating from the edges in the EBR process, baking (heat treatment) is performed to promote the crosslinking reaction. This baking process also evaporates the solvent in the composition, preventing mixing even when forming a resist top layer or a silicon-containing resist intermediate layer on the organic film.

[0162] 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 effect on device damage and wafer deformation, the upper limit of the heating temperature in the lithography wafer process is preferably 600°C or less, more preferably 500°C or less. Heat treatment under these conditions promotes the crosslinking reaction, making it possible to form an organic film that does not mix with the film formed on top.

[0163] [Pattern formation method] A pattern forming method using the organic film-forming composition of the present invention will be described below.

[0164] [Trilayer resist process using silicon-containing resist interlayer] In the present invention, there is provided a pattern forming method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition described above; forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms; forming a resist upper layer film on the resist intermediate film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; the resist upper layer film on which the circuit pattern has been formed is used as a mask to transfer the pattern to the resist intermediate film by etching; the resist intermediate film onto which the pattern has been transferred is used as a mask to transfer the pattern to the organic film by etching; Furthermore, the present invention provides a pattern forming method in which the pattern is transferred onto the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0165] The workpiece is preferably a semiconductor device substrate, or the semiconductor device substrate on which any of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal carbide oxide film, and a metal oxynitride film is formed. More specifically, although not particularly limited, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, and Al, or the substrate on which the above-mentioned metal film or the like is formed as a workpiece layer, can be used.

[0166] The work layer may be a low-k film or a stopper film thereof, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, or Al-Si, and may be formed to a thickness of typically 50 to 10,000 nm, particularly 100 to 5,000 nm. When forming the work layer, the substrate and the work layer are made of different materials.

[0167] The metal constituting the workpiece is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0168] When forming an organic film on a workpiece using the organic film-forming composition of the present invention, the above-described organic film-forming method of the present invention may be applied.

[0169] Next, a resist interlayer (silicon-containing resist interlayer) is formed on the organic film using a resist interlayer material containing silicon atoms. A polysiloxane-based interlayer material is preferred as the silicon-containing resist interlayer material. By imparting anti-reflective properties to the silicon-containing resist interlayer, reflection can be reduced. For 193 nm exposure, in particular, using a material containing many aromatic groups as the organic film-forming composition and exhibiting high etching selectivity with the substrate increases the k value and increases substrate reflection. However, by providing the silicon-containing resist interlayer with an appropriate k value, reflection can be reduced, reducing substrate reflection to 0.5% or less. Preferred silicon-containing resist interlayers with anti-reflective properties are polysiloxanes that have anthryl groups in their pendant structures for 248 nm and 157 nm exposure, and phenyl groups or silicon-silicon bond-containing light-absorbing groups in their pendant structures for 193 nm exposure, and that are crosslinked by acid or heat.

[0170] Next, a resist top layer film is formed on the silicon-containing resist intermediate film using a resist top layer film material composed of a photoresist composition. The resist top layer film material may be either positive or negative, and the same materials as commonly used photoresist compositions can be used. After spin-coating the resist top layer film material, it is preferable to prebake at 60 to 180°C for 10 to 300 seconds. Thereafter, exposure is performed according to a conventional method, followed by post-exposure baking (PEB) and development to obtain a resist top layer film pattern. The thickness of the resist top layer film is not particularly limited, but is preferably 30 to 500 nm, and particularly preferably 50 to 400 nm.

[0171] Next, a circuit pattern (resist upper layer film pattern) is formed on the resist upper layer film, preferably by lithography using light having a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0172] Examples of exposure light include high-energy rays with a wavelength of 300 nm or less, specifically far ultraviolet rays, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F2 laser light (157 nm), Kr2 laser light (146 nm), Ar2 laser light (126 nm), soft X-rays (EUV) of 3 to 20 nm, electron beams (EB), ion beams, X-rays, and the like.

[0173] In forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0174] Next, the circuit pattern is formed on the resist upper layer film 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 layer film pattern as a mask is preferably carried out using a fluorocarbon gas. This allows the silicon-containing resist intermediate film pattern to be transferred.

[0175] Next, the pattern is transferred to the organic film by etching using the silicon-containing resist intermediate film with the transferred pattern as a mask. Because the silicon-containing resist intermediate film exhibits etching resistance to oxygen gas or hydrogen gas, the etching of the organic film using the silicon-containing resist intermediate film pattern as a mask is preferably carried out using an etching gas mainly composed of oxygen gas or hydrogen gas. This allows the organic film pattern to be transferred.

[0176] Next, the pattern is transferred to the workpiece by etching using the organic film with the transferred pattern as a mask. The subsequent etching of the workpiece (layer to be processed) can be performed using standard methods. For example, if the workpiece is made of SiO2, SiN, or a silica-based low-k dielectric insulating film, etching is performed primarily with fluorocarbon-based gases; if the workpiece is made of p-Si, Al, or W, etching is performed primarily with chlorine- or bromine-based gases. If the substrate is processed using fluorocarbon-based etching, the silicon-containing resist intermediate film pattern is stripped simultaneously with the substrate processing. On the other hand, if the substrate is processed using chlorine- or bromine-based etching, a separate dry etching stripping process using fluorocarbon-based gases is required after substrate processing to strip the silicon-containing resist intermediate film pattern.

[0177] An organic film obtained by using the organic film-forming composition of the present invention can have excellent etching resistance when etching the workpiece as described above.

[0178] [Four-layer resist process using silicon-containing resist interlayer and organic anti-reflective or adhesive coating] The present invention provides the following pattern formation method. forming an organic film on a workpiece using the organic film-forming composition described above; forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms; forming an organic anti-reflective film or an adhesion film on the resist intermediate film; forming a resist upper layer film on the organic antireflective film or the adhesion film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; the resist upper layer film on which the circuit pattern has been formed is used as a mask to transfer the pattern to the organic anti-reflective film or adhesive film and the resist intermediate film by etching; the resist intermediate film onto which the pattern has been transferred is used as a mask to transfer the pattern to the organic film by etching; Furthermore, a pattern forming method is provided in which the pattern is transferred onto the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0179] This method can be performed in the same manner as the three-layer resist process using the silicon-containing resist intermediate film described above, except that an organic antireflective coating (BARC) or an adhesion film is formed between the silicon-containing resist intermediate film and the resist top layer film.

[0180] The organic anti-reflection film and the adhesive film can be formed by spin coating using known organic anti-reflection film materials.

[0181] [Trilayer resist process using inorganic hard mask intermediate film] The present invention provides the following pattern formation method. forming an organic film on a workpiece using the organic film-forming composition described above; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming a resist upper layer film on the inorganic hard mask using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; the resist upper layer film on which the circuit pattern has been formed is used as a mask to transfer the pattern to the inorganic hard mask by etching; the pattern is transferred to the organic film by etching using the inorganic hard mask to which the pattern has been transferred as a mask; Furthermore, a pattern forming method is provided in which the pattern is transferred onto the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0182] This method can be performed in the same manner as the three-layer resist process using the silicon-containing resist interlayer described above, except that an inorganic hard mask interlayer is formed on the organic film instead of the silicon-containing resist interlayer.

[0183] The inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) can be formed by a CVD method or an ALD method. Methods for forming silicon nitride films are described, for example, in JP-A No. 2002-334869 and WO 2004 / 066377. The thickness of the inorganic hard mask intermediate film is preferably 5 to 200 nm, more preferably 10 to 100 nm. As the inorganic hard mask intermediate film, a SiON film is most preferably used because of its high anti-reflection effect.

[0184] [Four-layer resist process using inorganic hard mask intermediate film and organic anti-reflective or adhesive film] The present invention provides the following pattern formation method. forming an organic film on a workpiece using the organic film-forming composition described above; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming an organic anti-reflective film or an adhesion film on the inorganic hard mask; forming a resist upper layer film on the organic antireflective film or the adhesion film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; using the resist upper layer film on which the circuit pattern has been formed as a mask, to transfer the pattern to the organic anti-reflective film or adhesion film and the inorganic hard mask by etching; the pattern is transferred to the organic film by etching using the inorganic hard mask to which the pattern has been transferred as a mask; Furthermore, a pattern forming method is provided in which the pattern is transferred onto the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0185] This method can be performed in the same manner as the above-mentioned three-layer resist process using an inorganic hard mask intermediate film, except that an organic antireflective coating (BARC) or an adhesion film is formed between the inorganic hard mask intermediate film and the resist top layer film.

[0186] In particular, when a SiON film is used as the inorganic hard mask intermediate film, the two-layer anti-reflection coating of the SiON film and BARC makes it possible to suppress reflection even in immersion lithography with a high NA exceeding 1.0. Another benefit of forming a BARC is that it reduces the footing of the resist top layer pattern directly above the SiON film.

[0187] An example of a pattern formation method using the three-layer resist process of the present invention is shown in Figures 3(A) to 3(F). In the three-layer resist process, as shown in Figure 3(A), an organic film 3 is formed on a processable layer 2 formed on a substrate 1 using the organic film-forming composition of the present invention, followed by the formation of a silicon-containing resist intermediate film 4, and then a resist upper layer film 5 is formed thereon. Next, as shown in Figure 3(B), the exposed portion 6 of the resist upper layer film 5 is exposed and subjected to PEB (post-exposure bake). Next, as shown in Figure 3(C), development is performed to form a resist upper layer film pattern 5a. Next, as shown in Figure 3(D), using the resist upper layer film pattern 5a as a mask, the silicon-containing resist intermediate film 4 is dry-etched using a fluorocarbon-based gas to form a silicon-containing resist intermediate film pattern 4a. Next, as shown in Figure 3(E), after removing the resist upper layer film pattern 5a, the organic film 3 is oxygen-plasma etched using the silicon-containing resist intermediate film pattern 4a as a mask to form an organic film pattern 3a. 3(F), after removing the silicon-containing resist intermediate film pattern 4a, the workpiece layer 2 is etched using the organic film pattern 3a as a mask to form a pattern 2a. By suppressing the formation of humps during the formation of the organic film, it is possible to reduce defects caused by humps in the organic film during the dry etching process shown in Figures (D), (E), and (F).

[0188] When an inorganic hard mask intermediate film is formed, the silicon-containing resist intermediate film 4 can be replaced with an inorganic hard mask intermediate film, and when a BARC or adhesion film is formed, the BARC or adhesion film can be formed between the silicon-containing resist intermediate film 4 and the resist upper layer film 5. Etching of the BARC or adhesion film can be performed consecutively prior to etching of the silicon-containing resist intermediate film 4, or etching of the silicon-containing resist intermediate film 4 can be performed after etching of the BARC or adhesion film alone, by changing the etching apparatus, for example.

[0189] As described above, the pattern formation method of the present invention makes it possible to form a fine pattern on a workpiece with high precision by a multilayer resist process, and also to reduce defects resulting from humps in the organic film by suppressing hump formation in the organic film. [Example]

[0190] The present invention will be explained in more detail below by showing synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited to these.

[0191] The molecular weight was measured as follows: The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene were determined by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent (solvent), and the polydispersity (Mw / Mn) was then calculated.

[0192] [Synthesis of polymers (A1) to (A14)] The compounds (A1) to (A14) used in preparing the organic film-forming composition were synthesized using the following diol compounds (B1) to (B2) and oxetane compounds (B4) to (B14).

[0193] (Diol compounds and alcohol compounds) [ka]

[0194] (Oxetane compounds) [ka]

[0195] [Synthesis Example 1] Synthesis of ether compound (A1) [ka] 10.0 g of methylene chloride was added to 0.30 g of diol compound (B1) and 0.24 g of boron trifluoride tetrahydrofuran, and the mixture was stirred under a nitrogen atmosphere at room temperature (25°C) for 30 minutes to form a homogeneous solution. Then, 10.0 g of oxetane compound (B4) was added dropwise over 5 minutes, and the mixture was allowed to react at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was then washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, and then evaporated to dryness under reduced pressure to obtain ether compound (A1). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A1): Mw = 3500, Mw / Mn = 1.58

[0196] [Synthesis Example 2] Synthesis of ether compound (A2) [ka] 10.0 g of methylene chloride was added to 0.30 g of diol compound (B1) and 0.23 g of boron trifluoride tetrahydrofuran, and the mixture was stirred under a nitrogen atmosphere at room temperature (25°C) for 30 minutes to form a homogeneous solution. Then, 10.0 g of oxetane compound (B5) was added dropwise over 5 minutes, and the mixture was allowed to react at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was then washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, and then evaporated to dryness under reduced pressure to obtain ether compound (A2). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A2): Mw = 3800, Mw / Mn = 1.81

[0197] [Synthesis Example 3] Synthesis of ether compound (A3) [ka] 10.0 g of methylene chloride was added to 0.87 g of diol compound (B1) and 0.21 g of boron trifluoride tetrahydrofuran, and the mixture was stirred under a nitrogen atmosphere at room temperature (25°C) for 30 minutes to form a homogeneous solution. Then, 10.0 g of oxetane compound (B6) was added dropwise over 5 minutes, and the mixture was allowed to react at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was then washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, and then evaporated to dryness under reduced pressure to obtain ether compound (A3). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A3): Mw = 2100, Mw / Mn = 1.62

[0198] [Synthesis Example 4] Synthesis of ether compound (A4) [ka] 10.0 g of methylene chloride was added to 0.40 g of diol compound (B1) and 0.21 g of boron trifluoride tetrahydrofuran, and the mixture was stirred under a nitrogen atmosphere at room temperature (25°C) for 30 minutes to form a homogeneous solution. Then, 10.0 g of oxetane compound (B6) was added dropwise over 5 minutes, and the mixture was allowed to react at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was then washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, and then evaporated to dryness under reduced pressure to obtain ether compound (A4). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A4): Mw = 2900, Mw / Mn = 1.67

[0199] [Synthesis Example 5] Synthesis of ether compound (A5) [ka] 10.0 g of methylene chloride was added to 0.26 g of diol compound (B1) and 0.21 g of boron trifluoride tetrahydrofuran, and the mixture was stirred under a nitrogen atmosphere at room temperature (25°C) for 30 minutes to form a homogeneous solution. Then, 10.0 g of oxetane compound (B6) was added dropwise over 5 minutes, and the mixture was allowed to react at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was then washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, and then evaporated to dryness under reduced pressure to obtain ether compound (A5). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A5): Mw = 3700, Mw / Mn = 1.75

[0200] [Synthesis Example 6] Synthesis of ether compound (A6) [ka] 10.0 g of methylene chloride was added to 0.23 g of diol compound (B1) and 0.18 g of boron trifluoride tetrahydrofuran, and the mixture was stirred under a nitrogen atmosphere at room temperature (25°C) for 30 minutes to form a homogeneous solution. Then, 10.0 g of oxetane compound (B7) was added dropwise over 5 minutes, and the mixture was allowed to react at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was then washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, and then evaporated to dryness under reduced pressure to obtain ether compound (A6). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A6): Mw = 3900, Mw / Mn = 1.64

[0201] [Synthesis Example 7] Synthesis of ether compound (A7) [ka] 10.0 g of methylene chloride was added to 0.18 g of diol compound (B1) and 0.15 g of boron trifluoride tetrahydrofuran, and the mixture was stirred under a nitrogen atmosphere at room temperature (25°C) for 30 minutes to form a homogeneous solution. Then, 10.0 g of oxetane compound (B8) was added dropwise over 5 minutes, and the mixture was allowed to react at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was then washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, and then evaporated to dryness under reduced pressure to obtain ether compound (A7). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A7): Mw = 4200, Mw / Mn = 1.85

[0202] [Synthesis Example 8] Synthesis of ether compound (A8) [ka] 10.0 g of methylene chloride was added to 0.28 g of diol compound (B1) and 0.23 g of boron trifluoride tetrahydrofuran, and the mixture was stirred under a nitrogen atmosphere at room temperature (25°C) for 30 minutes to form a homogeneous solution. Then, 10.0 g of oxetane compound (B9) was added dropwise over 5 minutes, and the mixture was allowed to react at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was then washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, and then evaporated to dryness under reduced pressure to obtain ether compound (A8). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A8): Mw = 3600, Mw / Mn = 1.67

[0203] [Synthesis Example 9] Synthesis of ether compound (A9) [ka] 10.0 g of methylene chloride was added to 0.24 g of diol compound (B1) and 0.20 g of boron trifluoride tetrahydrofuran, and the mixture was stirred under a nitrogen atmosphere at room temperature (25°C) for 30 minutes to form a homogeneous solution. Then, 10.0 g of oxetane compound (B10) was added dropwise over 5 minutes, and the mixture was allowed to react at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was then washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, and then evaporated to dryness under reduced pressure to obtain ether compound (A9). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A9): Mw = 3800, Mw / Mn = 1.83

[0204] [Synthesis Example 10] Synthesis of ether compound (A10) [ka] 10.0 g of methylene chloride was added to 0.19 g of diol compound (B2) and 0.21 g of boron trifluoride tetrahydrofuran, and the mixture was stirred under a nitrogen atmosphere at room temperature (25°C) for 30 minutes to form a homogeneous solution. Then, 10.0 g of oxetane compound (B6) was added dropwise over 5 minutes, and the mixture was allowed to react at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was then washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, and then evaporated to dryness under reduced pressure to obtain ether compound (A10). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A10): Mw = 3700, Mw / Mn = 1.78

[0205] [Synthesis Example 11] Synthesis of ether compound (A11) [ka] 10.0 g of methylene chloride was added to 0.40 g of diol compound (B1) and 0.32 g of boron trifluoride tetrahydrofuran, and the mixture was stirred under a nitrogen atmosphere at room temperature (25°C) for 30 minutes to form a homogeneous solution. Then, 10.0 g of oxetane compound (B11) was added dropwise over 5 minutes, and the mixture was allowed to react at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was then washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, and then evaporated to dryness under reduced pressure to obtain ether compound (A11). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A11): Mw = 3400, Mw / Mn = 1.82

[0206] [Synthesis Example 12] Synthesis of ether compound (A12) [ka] 10.0 g of methylene chloride was added to 0.36 g of diol compound (B1) and 0.29 g of boron trifluoride tetrahydrofuran, and the mixture was stirred under a nitrogen atmosphere at room temperature (25°C) for 30 minutes to form a homogeneous solution. Then, 10.0 g of oxetane compound (B12) was added dropwise over 5 minutes, and the mixture was allowed to react at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was then washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, and then evaporated to dryness under reduced pressure to obtain ether compound (A12). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A12): Mw = 3600, Mw / Mn = 1.63

[0207] [Synthesis Example 13] Synthesis of ether compound (A13) [ka] 10.0 g of methylene chloride was added to 0.30 g of diol compound (B1) and 0.24 g of boron trifluoride tetrahydrofuran, and the mixture was stirred under a nitrogen atmosphere at room temperature (25°C) for 30 minutes to form a homogeneous solution. Then, 10.0 g of oxetane compound (B13) was added dropwise over 5 minutes, and the mixture was allowed to react at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was then washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, and then evaporated to dryness under reduced pressure to obtain ether compound (A13). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A13): Mw = 3500, Mw / Mn = 1.59

[0208] [Synthesis Example 14] Synthesis of ether compound (A14) [ka] 10.0 g of methylene chloride was added to 0.23 g of diol compound (B1) and 0.18 g of boron trifluoride tetrahydrofuran, and the mixture was stirred under a nitrogen atmosphere at room temperature (25°C) for 30 minutes to form a homogeneous solution. Then, 10.0 g of oxetane compound (B14) was added dropwise over 5 minutes, and the mixture was allowed to react at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was then washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, and then evaporated to dryness under reduced pressure to obtain ether compound (A14). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A14): Mw = 3900, Mw / Mn = 1.75

[0209] [Synthesis of comparative compounds (R1) to (R3)] The comparative compounds (R1) to (R3) used in preparing the organic film-forming composition were synthesized using the following monomers (B1), (B3), (B6), and (B11). [ka]

[0210] [Comparative Synthesis Example 1] Synthesis of comparative compound (R1) [ka] 10.0 g of methylene chloride was added to 0.26 g of diol compound (B1) and 0.21 g of boron trifluoride diethyl ether, and the mixture was stirred under a nitrogen atmosphere at room temperature (25°C) for 30 minutes to form a homogeneous solution. Then, 10.0 g of oxetane compound (B6) was added dropwise over 5 minutes, and the mixture was allowed to react at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was then washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, after which the organic layer was evaporated to dryness under reduced pressure to obtain comparative compound (R1). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R1): Mw = 4100, Mw / Mn = 1.82

[0211] [Comparative Synthesis Example 2] Synthesis of comparative compound (R2) [ka] 10.0 g of methylene chloride was added to 0.33 g of boron trifluoride diethyl etherate and stirred at room temperature (25°C) under a nitrogen atmosphere to form a homogeneous solution. Then, 10.0 g of oxetane compound (B11) was added dropwise over 5 minutes, and the reaction was carried out at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was further washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, and then evaporated to dryness under reduced pressure to obtain comparative compound (R2). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R2): Mw = 61200, Mw / Mn = 2.71

[0212] [Comparative Synthesis Example 3] Synthesis of comparative compound (R3) [ka] 10.0 g of methylene chloride was added to 0.71 g of alcohol compound (B3) and 0.33 g of boron trifluoride diethyl ether, and the mixture was stirred under a nitrogen atmosphere at room temperature (25°C) to form a homogeneous solution. Then, 10.0 g of oxetane compound (B11) was added dropwise over 5 minutes, and the mixture was allowed to react at room temperature (25°C) for 3 hours. After the reaction, 50 ml of methylene chloride and 50 ml of pure water were added to the reaction solution to homogenize it, and the separated aqueous layer was removed. The organic layer was then washed twice with 50 ml of saturated sodium bicarbonate solution and five times with 50 ml of pure water, after which the organic layer was evaporated to dryness under reduced pressure to obtain comparative compound (R3). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R3): Mw = 7600, Mw / Mn = 3.32

[0213] [Organic film forming materials (resins or compounds)] M1: a resin represented by the following formula (M1): M2: a resin represented by the following formula (M2) M3: a compound represented by the following formula (M3): M4: a compound represented by the following formula (M4): M5: Resin represented by the following formula (M5) M6: Resin represented by the following formula (M6)

[0214] [ka]

[0215] [solvent] (S1): Propylene glycol monomethyl ether acetate (PGMEA) (S2): Propylene glycol monoethyl ether

[0216] [Preparation of Organic Film-Forming Compositions (UDL-1 to 46, Comparative UDL-1 to 14)] The above compounds (A1) to (A14), (R1) to (R3), organic film-forming materials (M1) to (M6), and solvents were dissolved in the proportions shown in Tables 1 and 2, and the resulting solution was filtered through a 0.1 μm fluorine resin filter to prepare organic film materials (resist intermediate film materials: UDL-1 to 46, comparative UDL-1 to 14).

[0217] [Table 1]

[0218] [Table 2]

[0219] [Preparation of Silicon Wafers with Organic Cured Films Formed Using Organic Film-Forming Compositions (UDL-1 to 46, Comparative UDL-1 to 14)] Using a Tokyo Electron Limited coater / developer "CLEAN TRACK LITHIUS Pro AP," 2 mL of each of the organic film-forming compositions (UDL-1 to 46, comparative UDL-1 to 14) was dispensed onto the center of a silicon wafer. After baking, the wafer was rotated at a rotation speed sufficient to achieve the average film thickness shown in Tables 3 and 4. While the silicon wafer was rotated at 1000 rpm, the remover nozzle was moved at a speed of 5 mm / s from the outer periphery of the silicon wafer to a position 3 mm toward the center, discharging the remover (a mixture of propylene glycol monomethyl ether acetate (S1) and propylene glycol monomethyl ether (S2) (30:70, mass ratio)) at a rate of 2 mL / s. At this position, the remover was further dispensed at a rate of 2 mL / s for 5 seconds. Dispensing of the dispensed solution was then stopped, and the wafer was rotated at 1000 rpm for an additional 30 seconds. Next, the silicon wafer on which the organic film-forming composition was formed was heated at 350° C. for 60 seconds to obtain a silicon wafer on which a cured organic film was formed.

[0220] [Solvent Resistance Evaluation: Examples 1-1 to 1-46, Comparative Examples 1-1 to 1-14] Using the method described above, organic film-forming compositions (UDL-1 to 46, Comparative UDL-1 to 14) were deposited on silicon wafers, the film thickness was measured, and PGMEA solvent was dispensed onto the film. The film was left for 30 seconds, spin-dried, and baked at 100°C for 60 seconds to evaporate the PGMEA, and the film thickness was measured. The film thickness before dispensing the PGMEA solvent was defined as X, and the film thickness after dispensing the PGMEA solvent was defined as X1. The absolute value of the value calculated by (X1 - X) / X x 100 was used as the film thickness change rate (%). A film thickness change rate of less than 0.5% was considered good, and a film thickness change of 0.5% or greater was considered poor. The results are shown in Tables 3 and 4.

[0221] [In-plane uniformity evaluation: Examples 1-1 to 1-46, Comparative Examples 1-1 to 1-14] The organic film-forming compositions (UDL-1 to 46, Comparative UDL-1 to 14) were formed on silicon wafers using the above method, and the film thickness within a radius of 145 mm from the center of the cured organic film was measured. The maximum film thickness Xmax, minimum film thickness Xmin, and average film thickness X average As, (X max -X min ) / X average The value obtained by the above was taken as the in-plane uniformity (%). When the in-plane uniformity was less than 2%, it was rated as A (good), when it was 2% or more but less than 3%, it was rated as B, and when it was 3% or more, it was rated as C (poor). The results are shown in Tables 3 and 4.

[0222] [Table 3]

[0223] [Table 4]

[0224] As shown in Tables 3 and 4, Examples 1-1 to 1-46, which used organic film-forming compositions containing a polymer of the present invention containing a repeating unit represented by formula (1) and a repeating unit represented by formula (1') as component (B), and Comparative Example 1-8, which used a polymer similar to the polymer of the present invention, yielded organic films with good solvent resistance and in-plane uniformity (Evaluation A to Evaluation B). On the other hand, Comparative Examples 1-9 to 1-14, which used compositions not containing such a polymer as component (B), yielded poor in-plane uniformity (Evaluation C).

[0225] In the above-mentioned in-plane uniformity evaluation, comparative UDL-1 to 8, which had good solvent resistance and in-plane uniformity, and examples 2-1 to 2-46 of the present invention were evaluated for hump suppression, embedding, and silicon intermediate film applicability in order to clarify the difference in performance.

[0226] [Hump suppression evaluation: Examples 2-1 to 2-46, Comparative Examples 2-1 to 2-8] Organic film-forming compositions (UDL-1 to 46, comparative UDL-1 to 8) were deposited on silicon wafers using the method described above, and the height change from the outer periphery of the organic film to 1000 μm toward the center of the silicon wafer was measured using a KLA-Tencor Alpha-Step D-600 (contact profiler). Assuming the height of the silicon wafer was 0, the maximum height was rated A (good) if it was less than 110% of the film thickness, as shown in Figure 1; B if it was 110% or more but less than 150%; and C (poor) if there was a region where the height was 150% or more, as shown in Figure 2. The results are shown in Tables 5 and 6.

[0227] [Embedding Evaluation: Examples 2-1 to 2-46, Comparative Examples 2-1 to 2-8] As shown in Figure 4, organic film 8 was formed by depositing organic film-forming compositions (UDL-1 to 46, Comparative UDL-1 to 8) on a SiO2 wafer substrate with a dense hole pattern (hole diameter 0.2 μm, hole depth 1.0 μm, center-to-center distance between adjacent holes 0.4 μm) using the method described above. The substrate used was a base substrate (SiO2 wafer substrate) 7 with a dense hole pattern as shown in Figure 4(G) (overhead view) and (H) (cross-sectional view). The cross-sectional shape of each wafer substrate was observed using a scanning electron microscope (SEM) to confirm whether the holes were filled with the organic film without any voids. When an organic film material with poor filling properties was used, voids were generated within the holes. When an organic film material with good filling properties was used, the holes were filled with the organic film without any voids, as shown in Figure 4(I). A good result was obtained when no voids were generated, and a poor result was obtained when voids were generated. The results are shown in Tables 5 and 6.

[0228] [Silicon Interlayer Coating Evaluation: Examples 2-1 to 2-46, Comparative Examples 2-1 to 2-8] Using the above method, an organic cured film was formed on a silicon wafer substrate using the organic film-forming compositions (UDL-1 to 46, comparative UDL-1 to 8), and the silicon-containing resist interlayer material (SOG1) described below was applied thereon and baked at 200°C for 60 seconds to form a silicon-containing resist interlayer. The state of the silicon interlayer coating was then visually observed and evaluated. If the coating film was in good condition, it was rated as good, and if dewetting occurred, it was rated as poor. In this evaluation, in order to evaluate the superiority or inferiority of the coating properties of the silicon interlayer, the thickness of the silicon interlayer was set to 10 nm, which was a strict evaluation condition. The results are shown in Tables 5 and 6.

[0229] A propylene glycol ethyl ether solution of the following polymer was prepared as a silicon-containing resist interlayer material (SOG1). The polymer solution used for evaluating the silicon interlayer coatability was 0.5 wt %. [ka]

[0230] [Contact Angle Evaluation: Examples 2-1 to 2-46, Comparative Examples 2-1 to 2-8] The organic cured films were formed on silicon wafer substrates using the organic film-forming compositions (UDL-1 to 46, Comparative UDL-1 to 8) by the above method, and the contact angles with pure water were measured. The results are shown in Tables 5 and 6.

[0231] [Table 5]

[0232] [Table 6]

[0233] As shown in Tables 5 and 6, the organic film-forming compositions of the present invention (UDL-1 to 46) were confirmed to be excellent in hump suppression, filling properties, and coating properties of silicon intermediate films. In addition, the contact angle was between 65 and 68 degrees.

[0234] [Pattern formation test: Examples 3-1 to 3-42] Using the above method, an organic cured film was formed on a SiO2 wafer substrate using an organic film-forming composition (UDL-1 to 42). The following silicon-containing resist intermediate film material (SOG1) was then applied on top of the organic cured film and baked at 200°C for 60 seconds to form a 35 nm thick silicon-containing resist intermediate film. The following ArF single-layer resist was then applied on top of the organic cured film as a resist top layer material and baked at 105°C for 60 seconds to form a 100 nm thick photoresist film. The following immersion protective film material (TC-1) was then applied on top of the photoresist film and baked at 90°C for 60 seconds to form a 50 nm thick protective film.

[0235] As a silicon-containing resist intermediate film material (SOG1), a 2% solution of the following polymer in propylene glycol ethyl ether was prepared. [ka]

[0236] The resist top layer material (ArF single-layer resist) was prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) in a propylene glycol monomethyl ether acetate (PGMEA) solvent containing 0.1 mass% FC-430 (manufactured by Sumitomo 3M Limited) in the proportions shown in Table 7, and filtering the solution through a 0.1 μm fluororesin filter. [Table 7]

[0237] The polymer (RP1), acid generator (PAG1), and basic compound (Amine1) are shown below. [ka]

[0238] The immersion protective film material (TC-1) was prepared by dissolving the polymer (PP1) in an organic solvent in the ratio shown in Table 8 and filtering the solution through a 0.1 μm fluorine resin filter. [Table 8]

[0239] The polymer (PP1) is shown below. [ka]

[0240] The resist was then exposed using an ArF immersion exposure system (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% halftone phase-shift mask), baked at 100°C for 60 seconds (PEB), and developed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds to obtain a 55 nm 1:1 positive line-and-space pattern (resist upper layer film pattern).

[0241] Next, using the resist upper layer film pattern as a mask, the silicon-containing resist intermediate film was dry-etched (pattern transferred) using a Tokyo Electron etching system Telius, and using the resulting silicon-containing resist intermediate film pattern as a mask, the organic film was dry-etched (pattern transferred), and using the resulting organic film pattern as a mask, the SiO2 wafer substrate (SiO2 film) was dry-etched (pattern transferred). The etching conditions are as shown below.

[0242] (Conditions for transferring the resist top layer pattern to the silicon-containing resist intermediate film) Chamber pressure 10.0Pa RF power 1,500W CF4 gas flow rate: 75mL / min O2 gas flow rate: 15mL / min Time 15sec

[0243] (Conditions for transferring silicon-containing resist intermediate film patterns to organic films) Chamber pressure 2.0Pa RF power 500W Ar gas flow rate: 75 mL / min O2 gas flow rate: 45mL / min Time 120sec

[0244] (Conditions for transferring organic film patterns onto SiO2 wafer substrates) Chamber pressure 2.0Pa RF power 2,200W C5F 12 Gas flow rate: 20 mL / min C2F6 gas flow rate 10mL / min Ar gas flow rate: 300 mL / min O2 gas flow rate 60mL / min Time 90sec

[0245] The cross section of the obtained pattern was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Table 9.

[0246] [Table 9]

[0247] As shown in Table 9, in Examples 3-1 to 3-42 in which the organic film-forming compositions (UDL-1 to 42) of the present invention were used, the resist upper layer film pattern was successfully transferred to the SiO2 wafer substrate in all cases, confirming that the organic film-forming compositions of the present invention are suitable for use in microfabrication using the multilayer resist method.

[0248] [Preparation of resist top layer materials (ArFPR1-14, comparative ArFPR)] Polymer (RP1), acid generator (PAG1), basic compound (Amine1), and compound were dissolved in a solvent in the proportions shown in Table 10, and the resulting solution was filtered through a 0.1 μm fluororesin filter to prepare resist top layer film materials (ArFPR1 to 14, comparative ArFPR). [Table 10]

[0249] [Preparation of silicon wafers with resist top layer films formed using resist top layer film materials (ArFPR1-14, comparative ArFPR)] Using a Tokyo Electron Co., Ltd. coater / developer "CLEAN TRACK LITHIUS Pro AP," 2 ml of the resist top layer material (ArFPR1-14, comparative ArFPR) prepared above was dispensed onto the center of a silicon wafer and spread by rotating it at a rotation speed that would result in an average film thickness of 100 nm after baking. Next, the silicon wafer coated with the resist top layer film was heated at 105°C for 60 seconds to obtain a silicon wafer with a resist top layer film formed thereon.

[0250] [Evaluation of In-Plane Uniformity of Resist Top Layer Film: Examples 4-1 to 4-14, Comparative Example 4-1] The thickness of the resist top layer (ArFPR1-14, comparative ArFPR) formed on the silicon wafer by the above method was measured within a radius of 145 mm from the center, and the maximum thickness Xmax, minimum thickness Xmin, and average thickness X average As, (X max -X min ) / X average The value obtained by the above formula was taken as the in-plane uniformity (%). In-plane uniformity of less than 3% was considered good, and 3% or more was considered poor. [Table 11]

[0251] As shown in Table 11, the resist top layer film materials of the present invention (ArFPR1 to 14) have excellent in-plane uniformity, which indicates that the (B) polymer of the present invention functions as a surfactant that imparts excellent leveling performance and can be used in various organic film-forming compositions regardless of the type of resin combined with it.

[0252] [Preparation of silicon-containing resist intermediate film materials (SOG3-16)] Silicon-containing resist interlayer materials (SOG3-16) were prepared by dissolving the polymer (SP1), crosslinking catalyst (TMPANO3), and maleic acid in an organic solvent (PGEE) and water in the proportions shown in Table 12, and then filtering the mixture through a 0.1 μm fluororesin filter.

[0253] The polymer (SP1) is shown below. [ka]

[0254] TMPANO3: Trimethylphenylammonium nitrate PGEE: Propylene glycol ethyl ether [Table 12]

[0255] [Evaluation of Coatability of Silicon-Containing Resist Interlayer: Examples 5-1 to 5-14, Comparative Example 5-1] Using the above method, an organic cured film was formed on a silicon wafer substrate using an organic film-forming composition (Comparative UDL-1), and the following silicon-containing resist interlayer film materials (SOG1, 3-16) were applied thereon and baked at 200°C for 60 seconds to form silicon-containing resist interlayer films. The state of the silicon-containing resist interlayer film coating was then visually observed and evaluated. If the coating film was in good condition, it was rated as good, and if dewetting occurred, it was rated as poor. In this evaluation, in order to evaluate the superiority or inferiority of the coating properties of the silicon-containing resist interlayer, the thickness of the silicon-containing resist interlayer was set to 5 nm, which was a special and strict evaluation condition. [Table 13]

[0256] As shown in Table 13, the silicon-containing resist intermediate film materials (SOG3 to 16) exhibit no dewetting and have excellent film-forming properties. This indicates that the polymer (B) of the present invention can be used as a surfactant to impart high film-forming properties to various film-forming compositions.

[0257] From the above, the organic film-forming composition of the present invention has excellent film-forming properties, high-level filling properties, and hump-suppressing properties, and also has excellent coatability for silicon intermediate films, making it extremely useful as an organic film material for use in multilayer resist processes.Furthermore, the pattern formation method of the present invention using this composition is capable of filling holes and trenches with very high aspect ratios without voids, and is also capable of forming fine patterns with high precision.In addition, it is possible to form an organic film in which humps are suppressed, making it possible to efficiently manufacture semiconductor elements and the like. This specification includes the following inventions.

[0258] [1]: A composition for forming an organic film, comprising a resin and / or compound (A) for forming an organic film, a polymer containing no halogen atom, the polymer (B) containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (1'), and a solvent (C). [Chemical formula] (In the formula, R2 and R3 each independently represent a saturated or unsaturated organic group having 1 to 20 carbon atoms which may have a substituent. y and z are each independently in the range of 0 < y < 1 and 0 < z < 1. However, y + z = 1.) [2]: The composition for forming an organic film according to [1], wherein the polymer (B) is the one represented by formula (2). [Chemical formula] (In the formula, R2 and R3 have the same meanings as those in the above formula (1). R8 represents a saturated or unsaturated organic group having 1 to 20 carbon atoms which may have a substituent. x, y, and z are each independently in the range of 0 ≦ x < 1, 0 < y < 1, and 0 < z < 1. However, x + y + z = 1.) [3]: The composition for forming an organic film according to [2], wherein the polymer represented by the formula (2) is a polymer in which x, y, and z in the above formula are each independently in the range of 0 < x < 1, 0 < y < 1, and 0 < z < 1, and x + y + z = 1. [4]: The composition for forming an organic film according to [1], wherein the polymer (B) is the one represented by formula (3). [Chemical formula] (In the formula, R2 and R3 have the same meanings as those in the above formula (2). R 12 , R 13 each represent a saturated or unsaturated divalent organic group having 1 to 16 carbon atoms which may have a substituent. x1, y, and z are each independently in the range of 0 < x1 < 1, 0 < y < 1, and 0 < z < 1. However, x1 + y + z = 1.) [5]: The organic film-forming composition according to [2], wherein in the general formula (2), x, y, and z satisfy x + y + z = 1, z < x < y, and z + x < y. [6]: The organic film-forming composition according to any one of [1] to [5], wherein the weight-average molecular weight of the polymer (B) is 1,000 to 30,000. [7]: The organic film-forming composition according to any one of [1] to [6], wherein when the organic film-forming resin and / or the compound (A) is 100 parts by mass, the content of the polymer (B) is 0.01 to 5 parts by mass. [8]: A method for producing a polymer containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (1') without halogen atoms, which comprises ring-opening polymerization of a Lewis acid cationic polymerization catalyst, tetrahydrofuran, and an oxetane ring-containing compound represented by the following formula (4).

Chemical formula

Chemical formula

[10] : A pattern forming method comprising the steps of forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to [7], forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming a resist upper layer film on the resist intermediate film using a resist upper layer film material consisting of a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[11] : A pattern forming method comprising the steps of forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to [7], forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming an organic antireflective film or an adhesive film on the resist intermediate film, forming a resist upper layer film on the organic antireflective film or adhesive film using a resist upper layer film material consisting of a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the organic antireflective film or adhesive film and the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[12] : A pattern formation method comprising the steps of forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to [7], forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[13] : A pattern formation method comprising the steps of forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to [7], forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming an organic antireflective film or an adhesive film on the inorganic hard mask, forming a resist upper layer film on the organic antireflective film or adhesive film using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the organic antireflective film or adhesive film and the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[14] : The pattern forming method according to

[12] or

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

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

[10] to

[14] , characterized in that in forming the circuit pattern, the circuit pattern is formed by lithography using light having a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

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

[10] to

[15] , wherein in forming the circuit pattern, the circuit pattern is developed with an alkali developer or an organic solvent.

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

[10] to

[16] , wherein the workpiece is 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 oxynitride film, and a metal oxynitride film is formed.

[18] : The pattern forming method according to

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

[19] : A polymer containing no halogen atom, which is a polymer for an organic film forming composition containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (1').

Chemical formula

[20] : The polymer for an organic film forming composition according to

[19] , wherein the polymer is represented by the formula (2).

Chemical formula

[21] : The polymer for an organic film forming composition according to

[19] , wherein the polymer is represented by the formula (3).

Chemical formula

[22] : The polymer for an organic film-forming composition according to

[20] , wherein in the general formula (2), x, y, and z satisfy x + y + z = 1, z < x < y, and z + x < y.

[23] : The polymer for an organic film-forming composition according to any one of

[19] to

[21] , wherein the weight-average molecular weight of the polymer is 1000 to 30000.

[0259] Note that the present invention is not limited to the above-described embodiments. The above-described embodiments are examples, and any structure that has substantially the same structure as the technical idea described in the claims of the present invention and exhibits the same operational effects is included in the technical scope of the present invention.

Explanation of Reference Numerals

[0260] 1... Substrate, 2... Processed layer, 2a... Pattern formed on the processed layer 3... Organic film, 3a... Organic film pattern 4... Silicon-containing resist intermediate film, 4a... Silicon-containing resist intermediate film pattern 5... Resist upper layer film, 5a... Resist upper layer film pattern, 6... Exposed portion 7... Underlying substrate, 8... Organic film

Claims

1. A composition for forming an organic film, comprising: an organic film-forming resin and / or compound (A); a polymer (B) that is a polymer not containing halogen atoms and that includes a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (1'); and a solvent (C). 【Chemistry 1】 (In the formula, R ２ , R ３ each independently represents a saturated or unsaturated organic group having 1 to 20 carbon atoms, which may have a substituent; y and z independently fall within the ranges of 0<y<1 and 0<z<1, respectively, provided that y+z=1.

2. 2. The organic film-forming composition according to claim 1, wherein the polymer (B) is represented by formula (2). 【Chemistry 2】 (In the formula, R ２ , R ３ has the same meaning as in the above formula (1). ８ represents a saturated or unsaturated organic group having 1 to 20 carbon atoms which may have a substituent; x, y, and z are independently in the ranges of 0≦x<1, 0<y<1, and 0<z<1, with the proviso that x+y+z=1.)

3. The composition for forming an organic film according to claim 2, characterized in that the polymer represented by formula (2) is a polymer in which x, y, and z in the formula are independently in the ranges of 0<x<1, 0<y<1, and 0<z<1, respectively, and x+y+z=1.

4. 2. The organic film-forming composition according to claim 1, wherein the polymer (B) is represented by formula (3). 【Transformation 3】 (In the formula, R ２ , R ３ has the same meaning as above. １２ , R １３ represents a saturated or unsaturated divalent organic group having 1 to 16 carbon atoms, each of which may have a substituent; x1, y, and z are independently in the ranges of 0<x1<1, 0<y<1, and 0<z<1, provided that x1+y+z=1.)

5. 3. The organic film-forming composition according to claim 2, wherein x, y, and z in the general formula (2) satisfy x+y+z=1, z<x<y, and z+x<y.

6. 2. 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.

7. The composition for forming an organic film according to claim 1, characterized in that the content of the polymer (B) is 0.01 parts by mass to 5 parts by mass when the resin for forming an organic film and / or the compound (A) is 100 parts by mass.

8. A method for producing a polymer containing no halogen atoms and including a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (1'), the method comprising ring-opening polymerization of a Lewis acid cationic polymerization catalyst, tetrahydrofuran, and an oxetane ring-containing compound represented by the following formula (4): 【Chemistry 4】 (In the formula, R ２ , R ３ each independently represents a saturated or unsaturated organic group having 1 to 20 carbon atoms, which may have a substituent; y and z independently fall within the ranges of 0<y<1 and 0<z<1, respectively, provided that y+z=1. 【Transformation 5】 (In the formula, R ２ , R ３ has the same meaning as in the above formula (1).

9. A method for forming an organic film used in a manufacturing process of a semiconductor device, comprising spin-coating the composition for forming an organic film according to any one of claims 1 to 7 onto a substrate to be processed, and heat-treating the substrate coated with the composition for forming an organic film at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, thereby forming a cured film.

10. 8. A pattern formation method comprising: forming an organic film on a workpiece using the organic film-forming composition according to claim 1; forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms; forming a resist upper layer film on the resist intermediate film using a resist upper layer film material consisting of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

11. a resist intermediate film material containing silicon atoms formed on the organic film; an organic antireflective film or an adhesive film formed on the resist intermediate film; a resist upper layer film formed on the organic antireflective film or the adhesive film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the organic antireflective film or the adhesive film and the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

12. 8. A pattern formation method comprising: forming an organic film on a workpiece using the organic film-forming composition according to claim 1; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming a resist upper layer film on the inorganic hard mask using a resist upper layer film material comprising the photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern onto the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern onto the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask; and further transferring the pattern onto the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

13. a resist upper layer film formed on the organic antireflective film or the adhesive film using a resist upper layer film material comprising a photoresist composition; a circuit pattern formed on the resist upper layer film; transferring the pattern by etching the organic antireflective film or the adhesive film and the inorganic hard mask using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching the organic antireflective film or the adhesive film and the inorganic hard mask using the inorganic hard mask on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

14. 13. The pattern formation method according to claim 12, wherein the inorganic hard mask is formed by a CVD method or an ALD method.

15. 11. The pattern forming method according to claim 10, wherein the circuit pattern is formed by lithography using light having a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

16. 11. The pattern forming method according to claim 10, wherein the circuit pattern is developed using an alkali developer or an organic solvent.

17. 11. The pattern forming method according to claim 10, wherein the workpiece is a semiconductor device substrate, or a semiconductor device 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.

18. 18. The pattern formation method according to claim 17, wherein the metal constituting the workpiece is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

19. A polymer for an organic film-forming composition, which is a polymer containing no halogen atoms and contains a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (1'): 【Transformation 6】 (In the formula, R ２ , R ３ each independently represents a saturated or unsaturated organic group having 1 to 20 carbon atoms, which may have a substituent; y and z independently fall within the ranges of 0<y<1 and 0<z<1, respectively, provided that y+z=1.

20. 20. The polymer for an organic film-forming composition according to claim 19, wherein the polymer is represented by formula (2). 【Transformation 7】 (In the formula, R ２ , R ３ has the same meaning as in the above formula (1). ８ represents a saturated or unsaturated organic group having 1 to 20 carbon atoms which may have a substituent; x, y, and z are independently in the ranges of 0≦x<1, 0<y≦1, and 0<z≦1, provided that x+y+z=1.

21. 20. The polymer for an organic film-forming composition according to claim 19, wherein the polymer is represented by formula (3). 【Transformation 8】 (In the formula, R ２ , R ３ has the same meaning as above. １２ , R １３ represents a saturated or unsaturated divalent organic group having 1 to 16 carbon atoms, each of which may have a substituent; x1, y, and z are independently in the ranges of 0<x1<1, 0<y<1, and 0<z<1, provided that x1+y+z=1.)

22. The polymer for an organic film-forming composition according to claim 20, characterized in that x, y, and z in the general formula (2) satisfy x + y + z = 1, z < x < y, and z + x < y.

23. 20. The polymer for an organic film-forming composition according to claim 19, wherein the weight average molecular weight of the polymer is 1,000 to 30,000.

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