Organic film-forming composition, method for forming organic film, patterning method, and polymer

Abstract

To provide: an organic film-forming composition that is excellent in film formability (in-plane uniformity) on a substrate (a wafer) and in filling properties and has excellent hump-reducing properties in an EBR process, and that can form an organic film having excellent process margin when used as an organic film for a multilayer resist; a method for forming an organic film and a patterning method that use the composition; and a polymer for use in the organic film-forming composition.SOLUTION: The polymer has a repeating unit represented by the formula (B1) in the figure. In the formula, R1 represents a single bond or a divalent organic group having 1 to 6 carbon atoms, R2 represents a divalent organic group having 1 to 6 carbon atoms, R3 represents a divalent organic group having 1 to 30 carbon atoms and optionally having an oxygen atom, and W1 represents a fluorine-containing group.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a composition for forming an organic film, a method for forming an organic film and a method for forming a pattern using the composition, and a polymer. [Background technology]

[0002] In recent years, with the increasing integration and speed of semiconductor devices, there has been a demand for finer pattern rules. In light of this, in lithography, which is currently used as a general-purpose technology using optical exposure, various technological developments have been carried out to enable finer and more accurate pattern processing using the light source used.

[0003] As a light source for lithography used in forming resist patterns, light exposure using mercury lamp g-line (436 nm) or i-line (365 nm) light sources is widely used in areas with low integration. On the other hand, in areas with high integration and requiring finer detail, lithography using shorter wavelength KrF excimer lasers (248 nm) and ArF excimer lasers (193 nm) has also been put to practical use, and for the most advanced generation requiring even finer detail, extreme ultraviolet (EUV, 13.5 nm) lithography is approaching practical use.

[0004] As resist patterns become thinner, the ratio of pattern height to pattern linewidth (aspect ratio) increases in the single-layer resist method, a typical method for forming resist patterns. It is well known that this increases the surface tension of the developer during development, causing pattern collapse. Therefore, multilayer resist methods, in which layers of films with different dry etching properties are stacked, are known to be superior for forming high-aspect-ratio patterns on uneven substrates. Two-layer resist methods (Patent Document 1) have been developed, combining a photoresist layer (resist top layer) made of a silicon-containing photosensitive polymer with a resist bottom layer made of an organic polymer primarily composed of carbon, hydrogen, and oxygen, such as a novolac polymer. Another three-layer resist method (Patent Document 2) combines a photoresist layer made of an organic photosensitive polymer used in the single-layer resist method with a resist middle layer made of a silicon-based polymer or silicon-based CVD film and a resist bottom layer made of an organic polymer.

[0005] In this three-layer resist method, for example, an organic film such as novolac is uniformly formed on a substrate to be processed as a resist underlayer, a silicon-containing resist intermediate film is formed on top of that as a resist intermediate film, and a conventional organic photoresist film is formed on top of that as a resist upper layer. Because the organic resist upper layer has a favorable etching selectivity relative to the silicon-containing resist intermediate film when dry-etched with a fluorine-based gas plasma, the resist pattern can be transferred to the silicon-containing resist intermediate film by dry-etching with a fluorine-based gas plasma. This method allows for pattern transfer to the silicon-containing resist intermediate 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 pattern in an organic film (e.g., a novolac film or other resist underlayer) with sufficient dry-etching resistance for processing.

[0006] Although many technologies for the organic film (organic underlayer film) described above are already known (for example, Patent Document 3), with the recent advances in miniaturization, there is an increasing need for excellent filling properties in addition to dry etching properties. There is a need for organic film materials that can be uniformly formed on the underlying substrate to be processed, even on substrates or materials with complex shapes, and that have filling properties that enable them to fill the required pattern without voids.

[0007] The organic films described above are 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, for example, a mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30% by mass:70% by mass). This remover is widely used in the EBR process of resist top layers and resist bottom layers (silicon-containing resist intermediate layers, organic films).

[0008] The remover used in the EBR process can cause a thick humps on the periphery of the organic film. Because humps can cause defects in the dry etching process used in substrate processing, there is a demand for organic films that suppress humps.

[0009] Furthermore, after forming a spin-coated organic film, it is baked to form a hardened film for use in a multilayer resist process. This must be an insoluble and infusible organic film so that a silicon-containing resist interlayer can be applied as an upper layer. The surface of the organic film formed by the bake process has a hydrophobic surface due to the surfactant contained in the organic film-forming composition, which can cause coating abnormalities in the silicon-containing resist interlayer. Control of the contact angle on the organic film surface is required to improve the coatability of the silicon-containing resist interlayer and expand the process tolerance. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 6-118651 [Patent Document 2] Japanese Patent Application Laid-Open No. 2005-128509 [Patent Document 3] Japanese Patent Application Laid-Open No. 2004-205685 Summary of the Invention [Problem to be solved by the invention]

[0011] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition for forming an organic film that is excellent in film-forming properties (in-plane uniformity) and filling properties on a substrate (wafer), excellent in suppressing humps during an EBR process, and capable of forming an organic film that has excellent process tolerance when used as an organic film for a multilayer resist; an organic film-forming method and a pattern-forming method that use the composition; and a polymer for use in the composition for forming an organic film. [Means for solving the problem]

[0012] In order to solve the above problems, the present invention provides a polymer having a repeating unit represented by the following formula (B1). [ka] (In the formula, R1 is a single bond or a divalent organic group having 1 to 6 carbon atoms, R2 is a divalent organic group having 1 to 6 carbon atoms, R3 is a divalent organic group having 1 to 30 carbon atoms which may contain an oxygen atom, and W1 is a fluorine-containing group represented by the following formula (B2).) [ka] (In the formula, the dashed line indicates a bond to R1 in the above formula (B1), and may have one or more of the structures represented by the above formula (B2).)

[0013] By combining such a polymer with a fluorine substituent such as that represented by the above formula (B2), the polymer becomes suitable for forming an organic film that has excellent in-plane uniformity and embedding properties and that is suppressed from forming humps due to the influence of the remover in the EBR process.

[0014] In the present invention, R3 in (B1) is preferably a group represented by the following formula (B3). [ka] (In the formula, the dashed line represents a bond to the sulfur atom in the above formula (B1), n=1 to 6, and the compound may have one or more of the structures represented by the above formula (B3).)

[0015] An organic film-forming composition containing such a polymer can further improve film-forming properties during application by having an appropriate fluorine content.

[0016] The polymer (B) is preferably a polymer represented by any one of the following general formulas (B4) to (B6). [ka] (In the formula, R1, R2, and R3 are the same as above, R4 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, and R5 is a divalent organic group having 1 to 6 carbon atoms. m represents the average number of repeating units and is 3 to 2,000.)

[0017] A composition for forming an organic film containing such a polymer is preferable because it allows the formation of an organic film with better in-plane uniformity.

[0018] The weight average molecular weight of the polymer is preferably 1,000 to 30,000.

[0019] Within this range of weight-average molecular weight, it is possible to form an organic film that is excellent in film-forming property and filling property. The weight-average molecular weight can be determined by the method described below.

[0020] Further, the present invention provides a composition for forming an organic film, comprising: (A) an organic film-forming material; (B) a polymer having a repeating unit represented by the following formula (B1): (C) Solvent The present invention provides a composition for forming an organic film, which comprises: [ka] (In the formula, R1 is a single bond or a divalent organic group having 1 to 6 carbon atoms, R2 is a divalent organic group having 1 to 6 carbon atoms, R3 is a divalent organic group having 1 to 30 carbon atoms which may contain an oxygen atom, and W1 is a fluorine-containing group represented by the following formula (B2).) [ka] (In the formula, the dashed line indicates a bond to R1 in the above formula (B1), and may have one or more of the structures represented by the above formula (B2).)

[0021] Such a composition for forming an organic film makes it possible to form an organic film that has excellent in-plane uniformity and filling properties, and that can suppress the formation of humps due to the influence of the remover in the EBR process.

[0022] In the present invention, R3 in (B1) is preferably a group represented by the following formula (B3). [ka] (In the formula, the dashed line represents a bond to the sulfur atom in the above formula (B1), n=1 to 6, and the compound may have one or more of the structures represented by the above formula (B3).)

[0023] Such an organic film-forming composition has an appropriate fluorine content, which enables improved film-forming properties during application, and also prevents decomposition products generated during baking from impairing the in-plane uniformity of the film, and also prevents the formation of insoluble matters due to reactions between decomposition products, etc. Therefore, when used for forming an organic film, the process tolerance is not narrowed, and no equipment contamination or other inconveniences occur.

[0024] In the present invention, the polymer (B) preferably contains one or more polymers represented by any one of the following general formulas (B4) to (B6). [ka] (In the formula, R1, R2, and R3 are the same as above, R4 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, and R5 is a divalent organic group having 1 to 6 carbon atoms. m represents the average number of repeating units and is 3 to 2,000.)

[0025] A composition for forming an organic film containing such a polymer is preferable because it allows the formation of an organic film with better in-plane uniformity.

[0026] The weight average molecular weight of the component (B) is preferably 1,000 to 30,000.

[0027] Within this range of weight average molecular weight, it is possible to form an organic film with excellent film-forming and filling properties.

[0028] Furthermore, it is preferable that the content of the component (B) is 0.01 to 5 parts by mass relative to 100 parts by mass of the material (A) for forming an organic film.

[0029] A composition for forming an organic film containing the component (B) in such an amount is preferred because the organic film formed will have better in-plane uniformity.

[0030] The present invention also provides a method for forming an organic film used in a manufacturing process of a semiconductor device, comprising: The composition for forming an organic film of the present invention is spin-coated on a substrate to be processed to obtain a coating film; The coating film is heat-treated at a temperature of 100° C. or higher and 600° C. or lower for 10 to 600 seconds to harden it, thereby forming an organic film.

[0031] The organic film-forming composition of the present invention is particularly useful for filling patterns of complex shapes on a workpiece substrate by spin coating, forming an organic film with excellent in-plane uniformity, and removing the organic film from the edges while suppressing humps in the EBR process. Therefore, the organic film-forming method of the present invention can form an organic film that exhibits excellent film-forming properties, excellent filling characteristics, and excellent hump suppression during the EBR process, and further has excellent process tolerance when used as an organic film for a multilayer resist.

[0032] Further, the present invention provides a pattern forming method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition of the present invention; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming a resist upper layer film on the silicon-containing resist intermediate film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist top layer film, and transferring the pattern to the silicon-containing resist intermediate film by etching using the resist top layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which a pattern is formed on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0033] Further, the present invention provides a pattern forming method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition of the present invention; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, and forming an organic anti-reflective film or an adhesion film on the silicon-containing 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, and 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 adhesive film and the silicon-containing resist intermediate film by etching; transferring the pattern to the organic film by etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which a pattern is formed on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0034] Further, the present invention provides a pattern forming method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition of the present invention; forming an inorganic hard mask intermediate film selected from the group consisting of 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 intermediate 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 inorganic hard mask 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 inorganic hard mask intermediate film to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which a pattern is formed on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0035] Further, the present invention provides a pattern forming method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition of the present invention; forming an inorganic hard mask intermediate film selected from the group consisting of 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 intermediate film, and forming a resist upper layer film 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; a resist upper layer film on which the circuit pattern is formed is used as a mask to transfer the pattern to the organic anti-reflective film or adhesion film and the inorganic hard mask intermediate film by etching; transferring the pattern to the organic film by etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which a pattern is formed on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0036] As described above, 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 intermediate film, and a four-layer resist process using an organic antireflective film or an adhesive film in addition to these. 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.

[0037] The inorganic hard mask intermediate film is preferably formed by a CVD method or an ALD method.

[0038] In the pattern formation method of the present invention, for example, an inorganic hard mask intermediate film can be formed by such a method.

[0039] 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.

[0040] In forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0041] In the pattern forming method of the present invention, such circuit pattern forming means and developing means can be suitably used.

[0042] Furthermore, it is preferable that 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.

[0043] In this case, it is preferable to use a workpiece whose metal is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0044] The pattern forming method of the present invention makes it possible to form a pattern by processing the above-mentioned workpiece. [Effects of the Invention]

[0045] As described above, the present invention provides an organic film-forming composition and a polymer contained therein that exhibit excellent film-forming properties (in-plane uniformity) and filling properties on a substrate (wafer), excellent film-forming properties for an intermediate film on the organic film when used as an organic film, and excellent suppression of humps during the EBR process. The organic film-forming composition of the present invention exhibits excellent film-forming properties, filling properties, and suppression of humps during the EBR process, making it 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 intermediate film or an inorganic hard mask intermediate film, or a four-layer resist process using a silicon-containing resist intermediate film or an inorganic hard mask intermediate film and an organic anti-reflective film or adhesive film, or as an organic film-forming material for semiconductor device manufacturing. Furthermore, the organic film-forming method of the present invention enables the formation of an organic film with suppressed humps, thereby enabling the efficient production of semiconductor devices and the like. Furthermore, by incorporating the polymer of the present invention into a PEG structure and a specific fluorine substituent, the above properties are exhibited, making it particularly useful in organic film-forming compositions. [Brief explanation of the drawings]

[0046] [Figure 1] 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 2] 10 is an example of a graph showing the height of a hump measured using a contact profiler in Example 2. [Figure 3] 10 is an example of a graph showing the height of a hump measured using a contact profiler in Comparative Example 2. [Figure 4] FIG. 1 is an explanatory diagram of a method for evaluating filling characteristics in an example. DETAILED DESCRIPTION OF THE INVENTION

[0047] As described above, there has been a need for the development of an organic film-forming composition that is excellent in film-forming properties (in-plane uniformity) and filling properties on a substrate (wafer) and that can form an organic film that suppresses humps during the EBR process, an organic film-forming method and a pattern-forming method that use this composition, and a polymer that can be used in the organic film-forming composition.

[0048] Typically, 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 then applied to a substrate on which structures, wiring, etc. are formed using a coater and developer.The composition is spread as the substrate rotates, and the composition at the edges is removed in an EBR process, followed by baking to form the organic film.

[0049] If the fluidity of the above composition is insufficient, voids will occur when filling holes or trenches with very high aspect ratios, and if the resin or additives used to form the organic film have poor solubility in the remover used in the EBR process, humps will occur on the periphery of the organic film.

[0050] As a result of further intensive research into the above-mentioned problems, the inventors have discovered that by incorporating a thermally decomposable polymer having a specific repeating unit into a composition for forming an organic film, it is possible to obtain a composition for forming an organic film that has both excellent film-forming properties and high-level filling properties, and is also excellent in suppressing hump formation during the EBR process, and have completed the present invention.

[0051] That is, the present invention is a polymer having a repeating unit represented by the following formula (B1). [ka] (In the formula, R1 is a single bond or a divalent organic group having 1 to 6 carbon atoms, R2 is a divalent organic group having 1 to 6 carbon atoms, R3 is a divalent organic group having 1 to 30 carbon atoms which may contain an oxygen atom, and W1 is a fluorine-containing group represented by the following formula (B2).) [ka] (In the formula, the dashed line indicates a bond to R1 in the above formula (B1), and may have one or more of the structures represented by the above formula (B2).)

[0052] The present invention also provides a composition for forming an organic film, (A) Material for organic film formation (B) a polymer having a repeating unit represented by the following formula (B1): (C) Solvent The organic film-forming composition comprises: [ka] (In the formula, R1 is a single bond or a divalent organic group having 1 to 6 carbon atoms, R2 is a divalent organic group having 1 to 6 carbon atoms, R3 is a divalent organic group having 1 to 30 carbon atoms which may contain an oxygen atom, and W1 is a fluorine-containing group represented by the following formula (B2).) [ka] (In the formula, the dashed line indicates a bond to R1 in the above formula (B1), and may have one or more of the structures represented by the above formula (B2).)

[0053] The present invention will be described in detail below, but the present invention is not limited thereto.

[0054] [Composition for organic film formation] The organic film-forming composition of the present invention contains (A) an organic film-forming material, (B) a polymer having a repeating unit represented by the following formula (B1), and (C) a solvent. [ka] (In the formula, R1 is a single bond or a divalent organic group having 1 to 6 carbon atoms, R2 is a divalent organic group having 1 to 6 carbon atoms, R3 is a divalent organic group having 1 to 30 carbon atoms which may contain an oxygen atom, and W1 is a fluorine-containing group represented by the following formula (B2).) [ka] (In the formula, the dashed line indicates a bond to R1 in the above formula (B1), and may have one or more of the structures represented by the above formula (B2).)

[0055] In the organic film-forming composition of the present invention, the (B) polymer, the (A) organic film-forming material, and the (C) solvent may each be used alone or in combination of two or more.

[0056] Among the components of the organic film-forming composition, the (B) polymer, which is a feature of the present invention, will be first described below, followed by a description of the (A) organic film-forming material, (C) solvent, and other components.

[0057] [(B) Polymer] The component (B) in the composition for forming an organic film of the present invention is a polymer having a repeating unit represented by the above general formula (B1). When blended into the composition for forming an organic film, this polymer becomes useful for forming an organic film.

[0058] The (B) polymer of the present invention is a compound containing a fluorine-containing tertiary amine and a thioether structure. Coating films formed using the (A) organic film-forming material and the (B) polymer-containing organic film-forming composition described below are less likely to develop humps during the EBR process. Furthermore, by introducing an appropriate fluorine-containing substituent, such as that represented by formula (B2), it is possible to impart surfactant functionality, which reduces surface tension and provides excellent uniform coating (leveling) properties for organic films. Therefore, when the (B) polymer 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. Thus, the (B) polymer of the present invention is characterized by its ability to function as a surfactant.

[0059] That is, the organic film-forming composition of the present invention, which contains (A) an organic film-forming material and (B) a polymer, can form an organic film that has excellent film-forming properties and filling properties on a substrate, excellent hump suppression properties during an EBR process, and excellent process tolerance when used as an organic film for a multilayer resist. For example, the organic film-forming composition of the present invention can form an organic film that is excellent for use as a multilayer resist for microfabrication in the manufacture of semiconductor devices, etc., or an organic film that is excellent for planarization in the manufacture of semiconductor devices, etc.

[0060] In the above general formula (B1), R1 is a single bond or a divalent organic group having 1 to 6 carbon atoms. When R1 is a divalent organic group having 1 to 6 carbon atoms, examples of the divalent organic group include a methylene group, an ethanediyl group, a propanediyl group, a butanediyl group, a pentanediyl group, and a hexanediyl group.

[0061] From the viewpoint of raw material availability, the organic group represented by R1 is preferably a single bond or a methylene group.

[0062] In the above general formula (B1), examples of the divalent organic group having 1 to 6 carbon atoms represented by R2 include a methylene group, an ethanediyl group, a propanediyl group, a butanediyl group, a pentanediyl group, and a hexanediyl group.

[0063] As the organic group represented by R2, a propanediyl group is preferred from the viewpoint of raw material availability.

[0064] In the above general formula (B1), examples of the divalent organic group having 1 to 30 carbon atoms which may contain an oxygen atom and is represented by R3 include groups represented by the following formulas. [ka]

[0065] In particular, it is preferable that R3 in the polymer (B) is a group represented by the following formula (B3). [ka] (In the formula, the dashed line represents a bond to the sulfur atom in the above formula (B1), n=1 to 6, and the compound may have one or more of the structures represented by the above formula (B3).)

[0066] An organic film-forming composition containing such a polymer has an appropriate fluorine content, which improves film-forming properties during application, and also prevents decomposition products generated during baking from impairing the in-plane uniformity of the film, and also prevents the formation of insoluble matters due to reactions between decomposition products, etc. Therefore, when used as an organic film, the process tolerance is not narrowed, and no equipment contamination or other inconveniences occur.

[0067] Furthermore, the polymer (B) is preferably one or more of the following general formulae (B4) to (B6). [ka] (In the formula, R1, R2, and R3 are the same as above, R4 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, and R5 is a divalent organic group having 1 to 6 carbon atoms. m represents the average number of repeating units and is 3 to 2,000.)

[0068] A composition for forming an organic film containing such a polymer is preferable because it allows the formation of an organic film with better in-plane uniformity.

[0069] In the general formula (B5), examples of the saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms represented by R4 include a methyl group, an ethyl group, a vinyl group, a 2,2,2-trifluoroethyl group, a propyl group, an isopropyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a butyl group, a s-butyl group, a t-butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a cyclohexenyl group, a decyl group, a dodecyl group, an icosanyl group, a norbornyl group, Examples of such an alkyl group include an adamantyl group, a phenyl group, a toluyl group, a xylyl group, a naphthyl group, a phenanthrenyl group, an anthracenyl group, a benzyl group, a fluorenyl group, a naphthylmethyl group, a norbornenyl group, an icosanyl group, a triacontyl group, a 2-furanyl group, a 2-tetrahydrofuranyl group, a phenyl group, a toluyl group, a xylyl group, a naphthyl group, a phenanthrenyl group, an anthracenyl group, a 2-furanyl group, an anisyl group, an acryloyl group, a methacryloyl group, and an acetyl group. When R4 has an aromatic ring, the aromatic ring may have a substituent, such as a halogen group such as fluorine, chlorine, bromine, or iodine, an alkyloxy group such as a methoxy group or an ethoxy group, an alkynyloxy group such as an allyloxy group, or an alkenyloxy group such as a propargyloxy group. The hydrogen atom on the methylene constituting these alkylene groups may be substituted with a fluorine atom.

[0070] As the organic group represented by R4, an allyl group can be preferably mentioned from the viewpoint of availability of raw materials.

[0071] In the general formula (B6), examples of the divalent organic group having 1 to 6 carbon atoms represented by R5 include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an s-butylene group, a t-butylene group, an isobutylene group, a pentylene group, a cyclopentylene group, a hexylene group, a cyclohexylene group, etc. A hydrogen atom on a methylene constituting these alkylene groups may be substituted with a fluorine atom.

[0072] As the organic group represented by R5, a propylene group can be preferably mentioned from the viewpoint of availability of raw materials.

[0073] m represents the average number of repeating units, and is 3 to 2,000, preferably 3 to 500, and more preferably 3 to 300.

[0074] The polymer (B) may have only one repeating unit represented by the general formula (B1) above, or may have a combination of two or more repeating units.

[0075] Specific examples of the repeating unit represented by the above general formula (B1) include, but are not limited to, the following: In the examples below, R1 is a single bond or one or more divalent organic groups having 1 to 6 carbon atoms, and W1 is one or more fluorine-containing groups represented by the above formula (B2). [ka]

[0076] Specific examples of the repeating unit represented by the above general formula (B4) include, but are not limited to, the following: In the examples below, R1 is a single bond or one or more divalent organic groups having 1 to 6 carbon atoms, and W1 is one or more fluorine-containing groups represented by the above formula (B2). [ka]

[0077] Specific examples of the repeating unit represented by the above general formula (B5) include, but are not limited to, the following: In the examples below, R1 is a single bond or one or more divalent organic groups having 1 to 6 carbon atoms, and W1 is one or more fluorine-containing groups represented by the above formula (B2). [ka]

[0078] Specific examples of the repeating unit represented by the above general formula (B6) include, but are not limited to, the following: In the examples below, R1 is a single bond or one or more divalent organic groups having 1 to 6 carbon atoms, and W1 is one or more fluorine-containing groups represented by the above formula (B2). [ka]

[0079] With the above structure, the thermal decomposition property, surface activity effect, and polymer flowability can be adjusted, and the compound can more reliably achieve both film-forming property and embedding property.

[0080] The weight-average molecular weight of the (B) polymer is preferably 1,000 to 30,000, more preferably 1,500 to 25,000. When the weight-average molecular weight is 1,000 or more, a decrease in the blending effect due to evaporation or the like can be suppressed, and a sufficient blending effect can be obtained. Furthermore, when the weight-average molecular weight is 30,000 or less, there is no deterioration in flowability, and excellent embedding properties can be obtained.

[0081] 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) at a measurement temperature of 40°C, and the dispersity (Mw / Mn) is calculated from Mw and Mn.

[0082] [(B) Method for producing polymer] The method for obtaining the polymer (B) of the present invention is not limited, but can be synthesized by, for example, the thiol-ene reaction of a dithiol compound and a diallyl compound, as shown below. The dithiol compound and diallyl compound used in the synthesis can be used alone or in combination of two or more. These can be selected and combined appropriately depending on the required properties. In the following example, a diallyl compound is used, but other compounds having a vinyl group, a butenyl group, or a compound having multiple types of these groups can also be used. R1, R3, and W1 in the following formula are the same as above.

[0083] [ka]

[0084] Examples of the radical initiator used in this case include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, lauroyl peroxide, etc. These may be used alone or in combination of two or more. The amount of these radical initiators added is preferably 0.01 to 25 mol% based on the total amount of monomers to be reacted.

[0085] The solvent used in this reaction is not particularly limited as long as it is inert to the reaction, but examples thereof include ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; aromatic solvents such as benzene, toluene, and xylene; and esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate. These solvents can be used in an amount of 0 to 2,000 parts by mass per 100 parts by mass of the reaction raw materials, and the reaction temperature is preferably 50 to 150°C, more preferably 60 to 100°C. The reaction time is appropriately selected from the range of 0.1 to 100 hours.

[0086] Reaction methods include a method in which the dithiol compound and the diallyl compound are charged in a solvent all at once, a method in which the dithiol compound and the diallyl compound are each dispersed or dissolved in a different solvent and then charged dropwise, and a method in which one of the dithiol compound and the diallyl compound is dispersed or dissolved in a solvent and then the other dispersed or dissolved in a solvent is added dropwise to the resulting mixture.In addition, when multiple dithiol compounds and multiple diallyl compounds are charged, they may be mixed and reacted in advance, or they may be reacted individually and sequentially.When a radical initiator is used, examples include a method in which the dithiol compound and the diallyl compound are charged in a single batch, a method in which the dithiol compound and the diallyl compound are dispersed or dissolved in a solvent and then the radical initiator is added or dropped, and a method in which the radical initiator is dispersed or dissolved in advance and then the dithiol compound and the diallyl compound are added dropwise.

[0087] In order to remove unreacted raw materials, catalysts, and the like present in the system, the reaction solution obtained by the method described above may be diluted with an organic solvent, followed by separation and washing to recover the polymer (B).

[0088] 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. 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. The number of washes may be one or more times, but washing 10 or more times does not necessarily provide the desired effect, so washing is preferably performed 1 to 5 times.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] After the separation washing with the basic aqueous solution or acidic aqueous solution, washing with neutral water may be performed. As the neutral water, deionized water or ultrapure water as described above may be used. The number of washings may be one or more, but if the number of washings is too small, the basic and acidic components may not be removed. Washing ten or more times may not necessarily provide the desired effect, so washing is preferably performed about one to five times.

[0093] 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.

[0094] 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.

[0095] In the above reaction, dithiol compounds and diallyl compounds can be combined according to the required performance. For example, fluorine-containing substituents can be optionally combined to change the surfactant properties by controlling the surface tension. Therefore, when an organic film-forming composition using these compounds is used to form an organic film, it is possible to achieve high levels of performance, such as film-forming ability and embedding ability.

[0096] The polymers represented by the above general formulas (B4) and (B5) can be easily produced by adjusting the ratio of the dithiolic compound and the diallyl compound during charging. Specifically, when the number of moles of the dithiolic compound charged is x and the number of moles of the diallyl compound charged is y, in the case of (B4), the charging ratio of the dithiolic compound to the diallyl compound should be increased, that is, the charging ratio should be such that x > y. In this case, by making the dithiolic component excessive, unreacted thiol can be left at the ends. Similarly, in the case of (B5), the charging ratio of the diallyl compound to the dithiolic compound should be increased, that is, the charging ratio should be such that x < y. In this case, the ends are sealed with the diallyl compound.

[0097] [Production method of (B4): When the charging ratio is x > y]

Chemical formula

[0098] [Production method of (B5): When the charging ratio is x < y]

Chemical formula

[0099] Furthermore, in the case of the above general formula (B6), there are methods of further sealing the ends with a monoallyl compound using the polymer represented by the above general formula (B4), or reacting the dithiolic compound, the diallyl compound, and the monoallyl compound together at once. When charging them together at once, it is necessary to strictly control the charging ratio. Industrially, the method of sealing the ends with a monoallyl compound after producing the polymer represented by (B4) is preferred. [[ID=**28**]]

[0100] [[ID=**29**]] [End-capping of the polymer of (B4)]

Chemical formula

[0101] [Bulk input] [ka] (wherein R1, R3, and W1 are the same as above.)

[0102] The production methods for (B4) and (B5) can be carried out by the method described in the production method for (B1) above, by simply adjusting the ratio of the dithiol compound and the diallyl compound when charging them to match the structure to be obtained. The reaction method and the polymer recovery method can be carried out by the method described in the production method for the polymer of general formula (B1) above.

[0103] Furthermore, when the production method for (B6) is carried out in a lump, it can be carried out in accordance with the production method, reaction method, and polymer recovery method for (B1) by simply using a dithiol compound, a diallyl compound, and a monoallyl compound simultaneously. When end-capping the polymer (B4), there are two methods: first, recovering the polymer (B4) once and then reacting it again with a monoallyl compound, as in the production method for the polymer (B1); or, after the reaction between the dithiol compound and the diallyl compound is completed during the reaction to produce the polymer (B4), adding the monoallyl compound used for end-capping and carrying out the reaction in one pot. In either case, the reaction method can be carried out in accordance with the production method, reaction method, and polymer recovery method for (B1), with the only difference being the substrate.

[0104] [(A) Organic film forming material] The organic film-forming material (A) (resin or compound) 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, from the viewpoints of etching resistance, optical properties, heat resistance, etc., a resin or compound (different from the polymer (B)) containing an aromatic skeleton is more preferred.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] [ka] (In formula (1), the ring structures Ar1 and Ar2 each independently 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 definitions of the symbols in the formula apply only to this formula.)

[0109] [ka] (In formula (2), the ring structures Ar1 and Ar2 each independently represent a benzene ring or a naphthalene ring. n represents any natural number such that the weight average molecular weight, as measured by gel permeation chromatography in terms of polystyrene, is 100,000 or less. The definitions of the symbols in the formula apply only to this formula.)

[0110] 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.

[0111] [ka] (In formula (3) and formula (4), R 1 and R 2 each independently 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 definitions of the symbols in the formula apply only to this formula.

[0112] [ka] (In formula (5), R1 is a monovalent atom or group other than a hydrogen atom, and n is an integer of 0 to 4. However, when n is 2 to 4, multiple R1s may be the same or different. R2 and R3 are each independently a monovalent atom or group. X is a divalent group. Note that the definitions of the symbols in the formula apply only to this formula.)

[0113] [ka] In formula (6), R1 is a hydrogen atom or a methyl group. R2 is a single bond, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 10 carbon atoms, and may have an ether, ester, lactone, or amide group. R 3 and R 4are each independently 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 and R 6 R are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 7 is any one of a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a hydroxy group, and 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. The definitions of the symbols in the formula apply only to this formula.

[0114] [ka] (In formula (7), 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. The definitions of the symbols in the formula apply only to this formula.)

[0115] Further 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.

[0116] [ka] (In formula (8) and formula (9), R 1 ~R 8are, independently of each other, a hydrogen atom, a hydroxyl group, a substitutable alkyl group having 1 to 6 carbon atoms, a substitutable alkoxy group having 1 to 6 carbon atoms, a substitutable alkoxycarbonyl group having 2 to 6 carbon atoms, a substitutable aryl group having 6 to 10 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, an isocyanate group, or a glycidyl group. m and n are positive integers. The definitions of the symbols in the formula are applicable only within this formula.)

[0117]

Chemical formula

[0118]

Chemical formula

[0119] Examples of the resin represented by formula (11) include the following resins.

[0120] [ka]

[0121] [ka]

[0122] 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. 2007-199653, 2008-274250, and 2010-122656.

[0123] [ka] (In formula (12), R 1 and R 2are each independently the same or different hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, 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 definitions of the symbols in the formula apply only to this formula.

[0124] [ka] (In formula (13), R 1 and R 2 are each independently the same or different and represent 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, or an alkenyl group having 2 to 10 carbon atoms; 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 definitions of the symbols in the formula apply only to this formula.

[0125] [ka] (In formula (14), ring Z 1 and ring Z 2 is a fused polycyclic aromatic hydrocarbon ring, and R 1a , R 1b , R 2a , and R 2brepresents a substituent which may be the same or different. k1 and k2 may be the same or different and each represents 0 or an integer of 1 to 4, m1 and m2 each represents 0 or an integer of 1 or more, and n1 and n2 each represents 0 or an integer of 1 or more. However, n1 + n2 ≧ 1. Note that the definitions of the symbols in the formula apply only within this formula.)

[0126] [Chemical formula] (In formula (15), R 1 and R 2 are the same or different and are 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, or an alkenyl group having 2 to 10 carbon atoms. R 3 and R 4 are each independently a hydrogen atom or a glycidyl group, R 5 is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, R 6 and R 7 are each independently a benzene ring or a naphthalene ring. p and q are each 1 or 2. n is 0 < n ≦ 1. Note that the definitions of the symbols in the formula apply only within this formula.)

[0127] Examples of the resin represented by formula (15) include the following resins.

[0128] [Chemical formula]

[0129] [Chemical formula]

[0130] [Chemical formula]

[0131] [Chemical formula]

[0132] Further 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.

[0133] [ka] (In formula (16), the ring structures Ar1 and Ar2 each independently represent a benzene ring or a naphthalene ring. x and z each independently represent 0 or 1. The definitions of the symbols in the formula apply only within this formula.)

[0134] Further examples of the organic film-forming material (A) used in the present invention include resins described in JP-A-2014-29435.

[0135] [ka] (In formula (17), A represents a structure having carbazole, B represents a structure having an aromatic ring, 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 has 1 to 4 carboxyl groups or salts thereof, or carboxylate ester groups. Note that the definitions of the symbols in the formula apply only to this formula.)

[0136] Further examples of the organic film-forming material (A) used in the present invention include polymers described in WO 2012 / 077640, which contain a unit structure represented by the following formula (18) and a unit structure represented by the following formula (19), and in which the molar ratio of the unit structure represented by formula (18) to the unit structure represented by formula (19) is 3 to 97:97 to 3.

[0137] [ka] In formula (18), 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. 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 definitions of the symbols in the formula apply only to this formula.

[0138] [ka] In formula (19), 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 carbon atom which may be substituted with a halogen atom, 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 atoms which may be substituted on the aromatic ring group Ar. The definitions of the symbols in the formula apply only to this formula.

[0139] Further examples of the organic film-forming material (A) used in the present invention include polymers containing a unit structure represented by the following formula (20) described in WO 2010 / 147155.

[0140] [ka] In formula (20), R1 and R2 are each independently 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 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, or the aryl group may contain an ether bond, a ketone bond, or an ester bond; The group or 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 definitions of the symbols in the formula apply only to this formula.

[0141] Further 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 (21), which are described in WO 2012 / 176767.

[0142] [ka] (In formula (21), 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 definitions of the symbols in the formula apply only to this formula.)

[0143] Further examples of the organic film-forming material (A) used in the present invention include novolak resins having a fluorene or tetrahydrospirobiindene structure, as 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 (22-1) or (22-2):

[0144] [ka] (In formula (22-1) and formula (22-2), R 1 , R 2 , R 6 and R 7 are each 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 and R 9 are each 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; R 5 and R 14 are each 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 13are each 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. The definitions of the symbols in the formula apply only to this formula.)

[0145] Further examples of the organic film-forming material (A) used in the present invention include reaction products obtained by the method described in JP 2012-145897 A. More specifically, examples include polymers obtained by condensing one or more compounds represented by the following general formula (23-1) and / or (23-2) with one or more compounds represented by the following general formula (24-1) and / or (24-2) and / or equivalents thereof.

[0146] [ka] (In the general formula (23-1) and the general formula (23-2), 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 definitions of the symbols in the formula apply only to this formula.)

[0147] [ka] (In general formula (24-1) and general formula (24-2), 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 number of each substituent, and n1 to n6 are 0, 1, or 2, and in formula (24-1), hydroxybenzaldehyde is excluded. In addition, in formula (24-2), the relationships 0≦n3+n5≦3, 0≦n4+n6≦4, and 1≦n3+n4≦4 are satisfied. Note that the definitions of the symbols in the formulas apply only within this formula.)

[0148] Further, examples of the polymers include those obtained by condensing one or more compounds represented by the above general formula (23-1) and / or (23-2), one or more compounds represented by the above general formula (24-1) and / or (24-2) and / or equivalents thereof, and one or more compounds represented by the following general formula (25) and / or equivalents thereof.

[0149] [ka] (In formula (25), Y is a hydrogen atom or a monovalent organic group having 30 or less carbon atoms which may have a substituent, and formula (25) is different from general formula (24-1) and general formula (24-2). Note that the definitions of the symbols in the formula apply only to this formula.)

[0150] Further 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.

[0151] [ka] (In formula (26-1), R is a single bond or an organic group having 1 to 50 carbon atoms, X is a group represented by the following general formula (26-2), and m1 is an integer satisfying 2≦m1≦10. Note that the definitions of the symbols in the formula apply only within this formula.)

[0152] [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 (26-3), and n5 is 0, 1, or 2. The definitions of the symbols in the formula apply only to this formula.

[0153] [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. The definitions of the symbols in the formula apply only to this formula.

[0154] Examples of compounds containing the above structure include the following compounds.

[0155] [ka]

[0156] Further 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 (27-1), which are described in JP-A-2019-044022.

[0157] [ka] In formula (27-1), AR1 and AR2 are benzene rings or naphthalene rings which may have a substituent, and R 1 and R 2 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R 1 and R 2 When and are organic groups, R 1 and R 2may 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 a group represented by the following formula (27-2). Y is a group represented by the following formula (27-3). Note that the definitions of the symbols in the formula apply only within this formula.

[0158] [ka] (In formula (27-3), 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. The definitions of the symbols in the formula apply only to this formula.

[0159] Examples of polymers having a repeating unit represented by the above general formula (27-1) include the following polymers.

[0160] [ka]

[0161] [ka]

[0162] (A) The organic film-forming material may be synthesized by a known method, or a commercially available product may be used.

[0163] 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.

[0164] 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.

[0165] [(C) Solvent] 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 organic film-forming material (A) and the polymer (B), and is preferably one that can also dissolve the acid generator, crosslinking agent, and additional surfactant, 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.

[0166] The content of the (C) solvent is 200 to 10,000 parts by mass, more preferably 300 to 5,000 parts by mass, per 100 parts by mass of the (A) organic film-forming material. By setting the content within this range, the concentration can be adjusted according to the film thickness to be consumed.

[0167] Furthermore, in the organic film-forming material of the present invention, as the organic solvent (C), 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 (A) the organic film-forming material and (B) the polymer, and may be any of hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc. Specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-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.

[0168] The boiling point of the high-boiling solvent may be appropriately selected according to the temperature at which (A) 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.

[0169] Furthermore, when using the above-mentioned high-boiling point solvent, the blending amount of the high-boiling point solvent is preferably 1 to 30 parts by mass per 100 parts by mass of the solvent having a boiling point of less than 180° C. Such a blending amount is appropriate, can impart sufficient thermal fluidity during baking, and does not remain in the film, leading to deterioration of film properties such as etching resistance.

[0170] In the case of such an organic film-forming composition, the addition of a high-boiling point solvent to the above-mentioned (A) organic film-forming material gives it thermal fluidity, thereby making it an organic film-forming composition that has both high embedding properties and excellent planarization properties.

[0171] [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 (A) the organic film-forming material. This amount promotes the crosslinking reaction and enables the formation of a dense film.

[0172] 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) the organic film-forming material. This amount enhances curability and further suppresses intermixing with the overlying film.

[0173] Furthermore, to further improve the in-plane uniformity in spin coating, an additional surfactant other than the polymer (B) of the present invention can be added to the organic film-forming composition of the present invention. Specific examples of such additional surfactants include those described in paragraphs

[0142] to

[0147] of JP 2009-269953 A. The aforementioned additional surfactants can be used alone or in combination of two or more. When an additional 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 organic film-forming material. This amount enables the formation of an organic film with excellent in-plane uniformity.

[0174] 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 (A) the organic film-forming material. This amount can improve the storage stability of the organic film-forming composition.

[0175] As described above, the organic film-forming composition of the present invention is an organic film-forming composition that is excellent in suppressing humps during the EBR process. Therefore, the organic film-forming composition of the present invention is extremely useful as a resist underlayer 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 interlayer or a silicon-containing inorganic hard mask interlayer, and a four-layer resist process using a silicon-containing resist interlayer or a silicon-containing inorganic hard mask interlayer and an organic antireflective film or adhesive film.

[0176] [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 to obtain a coating film, and then curing the coating film by heat-treating it at a temperature of 100° C. to 600° C. for 10 to 600 seconds. For example, an organic film is formed by curing a substrate coated with the organic film-forming composition by heat-treating it within the above-mentioned temperature and time ranges.

[0177] 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.

[0178] Baking is preferably carried out at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, more preferably at a temperature of 200°C or higher and 500°C or lower for 10 to 300 seconds. Considering the effects on device damage and wafer deformation, the upper limit of the heating temperature in the lithography wafer process is preferably 600°C or lower, more preferably 500°C or lower. 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.

[0179] [Pattern formation method] A pattern forming method using the organic film-forming composition of the present invention will be described below.

[0180] [Trilayer resist process using silicon-containing resist interlayer] The present invention provides a pattern formation method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition of the present invention; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming a resist upper layer film on the silicon-containing resist intermediate film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist top layer film, and transferring the pattern to the silicon-containing resist intermediate film by etching using the resist top layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which a pattern is formed on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0181] The workpiece is preferably, for example, a semiconductor device substrate, or the 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 carbide oxide film, and a metal oxynitride film is formed. More specifically, although not limited to, substrates such as Si, α-Si, p-Si, SiO, SiN, SiON, W, TiN, and Al, or the substrate on which any of the above metal films is formed as a workpiece layer, may be used.

[0182] 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.

[0183] It is preferable to use a metal constituting the workpiece that includes silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0184] When forming an organic film on a workpiece using the organic film-forming composition of the present invention, for example, but not limited to, the above-described organic film-forming method of the present invention may be applied.

[0185] 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 absorption that results in an appropriate k value, reflection can be reduced, and substrate reflection can be reduced to 0.5% or less. For silicon-containing resist interlayers with anti-reflective properties, preferred are polysiloxanes that have anthryl groups in their pendant structures for 248 nm or 157 nm exposure, and phenyl groups or light-absorbing groups with silicon-silicon bonds for 193 nm exposure, and that are crosslinked by acid or heat.

[0186] 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.

[0187] Next, a circuit pattern (resist upper layer film pattern) is formed on the resist upper layer film, preferably by lithography using light with a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0188] 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, and X-rays.

[0189] In forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0190] Next, the resist top layer film on which the circuit pattern has been formed is used as a mask to etch the silicon-containing resist intermediate film, and the pattern is transferred to the silicon-containing resist intermediate film. The etching of the silicon-containing resist intermediate film using the resist top layer film pattern as a mask is preferably carried out using a fluorocarbon gas. This allows the pattern (silicon-containing resist intermediate film pattern) to be transferred to the silicon-containing resist intermediate film.

[0191] Next, the pattern is transferred to the organic film by etching using the silicon-containing resist intermediate film (silicon-containing resist intermediate film 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 pattern (organic film pattern) to be transferred to the organic film.

[0192] Next, the organic film onto which the pattern has been transferred (organic film pattern) is used as a mask to form a pattern on the workpiece by etching.

[0193] The next etching of the workpiece (processing layer) can be performed using conventional methods. For example, if the workpiece is SiO2, SiN, or a silica-based low-dielectric-constant insulating film, etching is performed primarily with fluorocarbon-based gases; if it is p-Si, Al, or W, etching is performed primarily with chlorine- or bromine-based gases. When substrate processing is performed using etching with fluorocarbon-based gases, the silicon-containing resist intermediate film pattern is stripped simultaneously with processing of the workpiece. On the other hand, when processing of the workpiece is performed using etching with chlorine- or bromine-based gases, a separate dry etching stripping process using fluorocarbon-based gases must be performed after processing of the workpiece in order to strip the silicon-containing resist intermediate film pattern.

[0194] 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.

[0195] [Four-layer resist process using silicon-containing resist interlayer and organic anti-reflective or adhesive coating] Further, the present invention provides a pattern forming method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition of the present invention; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, and forming an organic anti-reflective film or an adhesion film on the silicon-containing 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, and 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 adhesive film and the silicon-containing resist intermediate film by etching; transferring the pattern to the organic film by etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which a pattern is formed on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0196] 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.

[0197] The organic anti-reflection film and the adhesive film can be formed by spin coating using known organic anti-reflection film materials.

[0198] [Trilayer resist process using inorganic hard mask intermediate film] Further, the present invention provides a pattern forming method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition of the present invention; forming an inorganic hard mask intermediate film selected from the group consisting of 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 intermediate 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 inorganic hard mask 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 inorganic hard mask intermediate film to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which a pattern is formed on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0199] 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.

[0200] The inorganic hard mask intermediate film selected from the group consisting of silicon oxide film, silicon nitride film, and silicon oxynitride film (SiON film) can be formed by, for example, CVD or ALD. Methods for forming silicon nitride film are described, for example, in JP 2002-334869 A and WO 2004 / 066377 A. 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.

[0201] [Four-layer resist process using inorganic hard mask intermediate film and organic anti-reflective or adhesive film] Further, the present invention provides a pattern forming method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition of the present invention; forming an inorganic hard mask intermediate film selected from the group consisting of 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 intermediate film, and forming a resist upper layer film 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; a resist upper layer film on which the circuit pattern is formed is used as a mask to transfer the pattern to the organic anti-reflective film or adhesion film and the inorganic hard mask intermediate film by etching; transferring the pattern to the organic film by etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which a pattern is formed on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0202] 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.

[0203] 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.

[0204] An example of a pattern formation method using the three-layer resist process of the present invention is shown in Figures 1(A) to 1(F). In the three-layer resist process, as shown in Figure 1(A), an organic film 3 is formed on a workpiece (workpiece) 2 formed on a substrate 1 using the organic film-forming composition of the present invention. Next, a silicon-containing resist intermediate film 4 is formed on the organic film 3, and a resist upper layer film 5 is formed thereon. Next, as shown in Figure 1(B), the exposed portion 6 of the resist upper layer film 5 is exposed, followed by PEB (post-exposure bake). Next, as shown in Figure 1(C), development is performed to form a resist upper layer film pattern 5a. Next, as shown in Figure 1(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, the resist upper layer film pattern 5a is removed, and then, as shown in Figure 1(E), 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. Furthermore, as shown in Figure 1(F), the silicon-containing resist intermediate film pattern 4a is removed, and then, using the organic film pattern 3a as a mask, the processable layer 2 is etched to form a pattern 2a.

[0205] In the pattern formation method of this example, humps are suppressed during the formation of the organic film 3, which makes it possible to reduce defects caused by humps in the organic film during the dry etching process of Figures 1(D), (E), and (F).

[0206] 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.

[0207] 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]

[0208] The present invention will be explained in more detail below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. The molecular weight was measured specifically 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) at 40°C using tetrahydrofuran as an eluent (solvent), and the polydispersity (Mw / Mn) was also determined.

[0209] [Synthesis of polymers (B-1) to (B-12)] The compounds (B-1) to (B-12) used in preparing the organic film-forming compositions (UDL-1 to 77) of the examples were synthesized using the following dithiol compounds (a1) to (a3) ​​and diallyl compounds (b1) to (b8).

[0210] (Dithiol compounds) [ka]

[0211] (Diallyl compounds, monoallyl compounds) [ka]

[0212] [Synthesis Example 1] Synthesis of polymer (B-1) [ka]

[0213] 2.76 g of dithiol compound (a1) and 3.51 g of diallyl compound (b1) were added with 30.0 g of PGMEA (propylene glycol monoethyl ether acetate), stirred to form a homogeneous solution, and then nitrogen bubbling was performed for 15 minutes. 0.22 g of AIBN (azobisisobutyronitrile) was then added to the homogeneous solution, and the temperature was raised to 85°C under a nitrogen atmosphere, and the reaction was carried out at an internal temperature of 85°C for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 41.8 g of a PGMEA solution of polymer (B-1) (compound concentration 15%).

[0214] The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (B-1): Mw = 1710, Mw / Mn = 2.09

[0215] [Synthesis Example 2] Synthesis of polymer (B-2) [ka]

[0216] 2.76 g of dithiol compound (a1) and 3.43 g of diallyl compound (b2) were added with 30.0 g of PGMEA (propylene glycol monoethyl ether acetate), stirred to form a homogeneous solution, and then nitrogen bubbling was performed for 15 minutes. 0.22 g of AIBN (azobisisobutyronitrile) was then added to the homogeneous solution, and the temperature was raised to 85°C under a nitrogen atmosphere, and the reaction was carried out at an internal temperature of 85°C for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 41.3 g of a PGMEA solution of polymer (B-2) (compound concentration 15%).

[0217] The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (B-2): Mw = 1650, Mw / Mn = 2.14

[0218] [Synthesis Example 3] Synthesis of polymer (B-3) [ka]

[0219] 2.76 g of dithiol compound (a1) and 3.99 g of diallyl compound (b3) were added with 30.0 g of PGMEA (propylene glycol monoethyl ether acetate), stirred to form a homogeneous solution, and then nitrogen bubbling was performed for 15 minutes. 0.22 g of AIBN (azobisisobutyronitrile) was then added to the homogeneous solution, and the temperature was raised to 85 ° C under a nitrogen atmosphere, and the reaction was carried out at an internal temperature of 85 ° C for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 45.0 g of a PGMEA solution of polymer (B-3) (compound concentration 15%).

[0220] The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (B-3): Mw = 1750, Mw / Mn = 2.15

[0221] [Synthesis Example 4] Synthesis of polymer (B-4) [ka]

[0222] 2.43 g of dithiol compound (a2) and 5.26 g of diallyl compound (b1) were added with 30.0 g of PGMEA (propylene glycol monoethyl ether acetate), stirred to form a homogeneous solution, and then nitrogen bubbling was performed for 15 minutes. 0.22 g of AIBN (azobisisobutyronitrile) was then added to the homogeneous solution, and the temperature was raised to 85 ° C under a nitrogen atmosphere, and the reaction was carried out at an internal temperature of 85 ° C for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 51.3 g of a PGMEA solution of polymer (B-4) (compound concentration 15%).

[0223] The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (B-4): Mw = 1920, Mw / Mn = 2.39

[0224] [Synthesis Example 5] Synthesis of polymer (B-5) [ka]

[0225] 2.43 g of dithiol compound (a2) and 5.14 g of diallyl compound (b4) were added with 30.0 g of PGMEA (propylene glycol monoethyl ether acetate), stirred to form a homogeneous solution, and then nitrogen bubbling was performed for 15 minutes. 0.22 g of AIBN (azobisisobutyronitrile) was then added to the homogeneous solution, and the temperature was raised to 85 ° C under a nitrogen atmosphere, and the reaction was carried out at an internal temperature of 85 ° C for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 50.5 g of a PGMEA solution of polymer (B-5) (compound concentration 15%).

[0226] The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (B-5): Mw = 1870, Mw / Mn = 2.21

[0227] [Synthesis Example 6] Synthesis of polymer (B-6) [ka]

[0228] 2.43 g of dithiol compound (a2) and 5.99 g of diallyl compound (b3) were added with 30.0 g of PGMEA (propylene glycol monoethyl ether acetate), stirred to form a homogeneous solution, and then nitrogen bubbling was performed for 15 minutes. 0.22 g of AIBN (azobisisobutyronitrile) was then added to the homogeneous solution, and the temperature was raised to 85 ° C under a nitrogen atmosphere, and the reaction was carried out at an internal temperature of 85 ° C for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 56.1 g of a PGMEA solution of polymer (B-6) (compound concentration 15%).

[0229] The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (B-6): Mw = 1970, Mw / Mn = 2.41

[0230] [Synthesis Example 7] Synthesis of polymer (B-7) [ka]

[0231] 6.29 g of dithiol compound (a3), 3.51 g of diallyl compound (b1), and 2.99 g of monoallyl compound (b5) were added with 30.0 g of PGMEA (propylene glycol monoethyl ether acetate), stirred to form a homogeneous solution, and then nitrogen bubbling was performed for 15 minutes. 0.22 g of AIBN (azobisisobutyronitrile) was then added to the homogeneous solution, and the temperature was raised to 85 ° C under a nitrogen atmosphere, and the reaction was carried out at an internal temperature of 85 ° C for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 61.7 g of a PGMEA solution of polymer (B-7) (compound concentration 15%).

[0232] The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (B-7): Mw = 2420, Mw / Mn = 2.74

[0233] [Synthesis Example 8] Synthesis of polymer (B-8) [ka]

[0234] 6.29 g of dithiol compound (a3), 3.43 g of diallyl compound (b4), and 2.91 g of diallyl compound (b6) were mixed with 30.0 g of PGMEA (propylene glycol monoethyl ether acetate), stirred to form a homogeneous solution, and then nitrogen bubbling was performed for 15 minutes. 0.22 g of AIBN (azobisisobutyronitrile) was then added to the homogeneous solution, and the mixture was heated to 85°C under a nitrogen atmosphere and reacted at an internal temperature of 85°C for 24 hours. The reaction solution was cooled to room temperature and diluted with PGMEA to obtain 60.7 g of a PGMEA solution of polymer (B-8) (compound concentration 15%).

[0235] The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (B-8): Mw = 2390, Mw / Mn = 2.78

[0236] [Synthesis Example 9] Synthesis of polymer (B-9) [ka]

[0237] 3.65 g of dithiol compound (a2), 3.51 g of diallyl compound (b1), and 2.99 g of diallyl compound (b5) were added with 30.0 g of PGMEA (propylene glycol monoethyl ether acetate), stirred to form a homogeneous solution, and then nitrogen bubbling was performed for 15 minutes. 0.22 g of AIBN (azobisisobutyronitrile) was then added to the homogeneous solution, and the temperature was raised to 85 ° C under a nitrogen atmosphere, and the reaction was carried out at an internal temperature of 85 ° C for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 67.7 g of a PGMEA solution of polymer (B-9) (compound concentration 15%).

[0238] The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (B-9): Mw = 1470, Mw / Mn = 2.44

[0239] [Synthesis Example 10] Synthesis of polymer (B-10) [ka]

[0240] 3.65 g of dithiol compound (a2), 3.43 g of diallyl compound (b4), and 2.91 g of monoallyl compound (b6) were added with 30.0 g of PGMEA (propylene glycol monoethyl ether acetate), stirred to form a homogeneous solution, and then nitrogen bubbling was performed for 15 minutes. 0.22 g of AIBN (azobisisobutyronitrile) was then added to the homogeneous solution, and the temperature was raised to 85 ° C under a nitrogen atmosphere, and the reaction was carried out at an internal temperature of 85 ° C for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 66.6 g of a PGMEA solution of polymer (B-10) (compound concentration 15%).

[0241] The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (B-10): Mw = 1520, Mw / Mn = 2.39

[0242] [Synthesis Example 11] Synthesis of polymer (B-11) [ka]

[0243] 3.65 g of dithiol compound (a1) and 3.70 g of diallyl compound (b7) were added with 30.0 g of PGMEA (propylene glycol monoethyl ether acetate), stirred to form a homogeneous solution, and then nitrogen bubbling was performed for 15 minutes. 0.22 g of AIBN (azobisisobutyronitrile) was then added to the homogeneous solution, and the temperature was raised to 85 ° C under a nitrogen atmosphere, and the reaction was carried out at an internal temperature of 85 ° C for 24 hours. After cooling the reaction solution to room temperature, it was diluted with PGMEA to obtain 49.0 g of a PGMEA solution of polymer (B-11) (compound concentration 15%).

[0244] The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (B-11): Mw = 1730, Mw / Mn = 2.11

[0245] [Synthesis Example 12] Synthesis of polymer (B-12) [ka]

[0246] 30.0 g of PGMEA (propylene glycol monoethyl ether acetate) was added to 3.65 g of dithiol compound (a1) and 3.62 g of diallyl compound (b8), and the mixture was stirred to form a homogeneous solution. Nitrogen bubbling was then performed for 15 minutes. 0.22 g of AIBN (azobisisobutyronitrile) was then added to the homogeneous solution, and the mixture was heated to 85°C under a nitrogen atmosphere. The reaction mixture was then cooled to room temperature and diluted with PGMEA to obtain 48.5 g of a PGMEA solution of polymer (B-12) (compound concentration 15%).

[0247] The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (B-12): Mw = 1670, Mw / Mn = 2.16

[0248] [Synthesis of comparative polymers (R1) to (R5)] The comparative polymers (R1) to (R5) used in preparing the organic film-forming compositions were synthesized using the following monomers (r1) to (r6). [ka]

[0249] [Comparative Synthesis Example 1] Synthesis of Comparative Polymer (R1) [ka] Under a nitrogen atmosphere, 6.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80°C. To this was added dropwise a mixture of 3.44 g (0.011 mol) of monomer (r1), 7.46 g (0.034 mol) of monomer (r3), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target comparative polymer (R1). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R1): Mw = 9,500, Mw / Mn = 1.20

[0250] [Comparative Synthesis Example 2] Synthesis of Comparative Polymer (R2) [ka] Under a nitrogen atmosphere, 6.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80°C. To this was added dropwise a mixture of 1.43 g (0.005 mol) of monomer (r1), 5.76 g (0.041 mol) of monomer (r4), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target comparative polymer (R2). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R2): Mw = 5,800, Mw / Mn = 1.42

[0251] [Comparative Synthesis Example 3] Synthesis of Comparative Polymer (R3) [ka] Under a nitrogen atmosphere, 6.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80°C. To this was added dropwise a mixture of 7.00 g (0.032 mol) of monomer (r2), 1.92 g (0.014 mol) of monomer (r4), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target comparative polymer (R3). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R3): Mw = 6,200, Mw / Mn = 1.33

[0252] [Comparative Synthesis Example 4] Synthesis of Comparative Polymer (R4) [ka] Under a nitrogen atmosphere, 6.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80°C. To this was added dropwise a mixture of 5.00 g (0.023 mol) of monomer (r2), 3.20 g (0.023 mol) of monomer (r5), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target comparative polymer (R4). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R4): Mw = 8,300, Mw / Mn = 1.33

[0253] [Comparative Synthesis Example 5] Synthesis of Comparative Polymer (R5) [ka] Under a nitrogen atmosphere, 6.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80°C. To this was added dropwise a mixture of 2.00 g (0.009 mol) of monomer (r2), 5.41 g (0.036 mol) of monomer (r6), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target comparative polymer (R5). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R5): Mw = 3,800, Mw / Mn = 1.44

[0254] [(A) Organic film-forming material (resin or compound)] In preparing the organic film-forming compositions of Examples and Comparative Examples (UDL-1 to 77 and Comparative UDL-1 to 16), the following resins or compounds were used as the organic film-forming material (A). 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)

[0255] [ka]

[0256] [(C) Solvent] In preparing the organic film-forming compositions of Examples and Comparative Examples (UDL-1 to 77 and Comparative UDL-1 to 16), the following solvents were used as the solvent (C). (S1): Propylene glycol monomethyl ether acetate (S2): Propylene glycol monoethyl ether

[0257] [Preparation of Organic Film-Forming Compositions (UDL-1 to 77, Comparative UDL-1 to 16)] One of the compounds (B-1) to (B-12) and (R1) to (R5) was dissolved as the polymer, one of the organic film-forming materials (M1) to (M6) was dissolved as the organic film-forming resin, and one or both of the solvents (C) were dissolved in the proportions shown in Tables 1 to 5. The resulting mixture was filtered through a 0.1 μm fluororesin filter to prepare organic film materials (resist underlayer film materials: UDL-1 to 77, comparative UDL-1 to 10). Furthermore, one of the organic film-forming materials (M1) to (M6) was dissolved in the solvent (S1) in the proportions shown in Table 5 to prepare the organic film-forming composition (resist underlayer film materials: comparative UDL-11 to 16). The resulting mixture was filtered through a 0.1 μm fluororesin filter to prepare the organic film-forming composition. The results are shown in Tables 1 to 5.

[0258] [Table 1]

[0259] [Table 2]

[0260] [Table 3]

[0261] [Table 4]

[0262] [Table 5]

[0263] [Preparation of Silicon Wafers with Organic Cured Films Formed Using Organic Film-Forming Compositions (UDL-1 to 77, Comparative UDL-1 to 16)] 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 77, Comparative UDL-1 to 16) was dispensed onto the center of a silicon wafer, which was then rotated at a rotation speed corresponding to the average film thickness shown in Tables 6 to 10. The wafer was then baked at 350°C to form a coating of the organic film-forming composition. While the silicon wafer was being rotated at 1000 rpm, a remover discharge 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 and propylene glycol monomethyl ether (30:70, mass ratio)) at a rate of 2 mL / s. The remover was then discharged at this position for 5 seconds at a rate of 2 mL / s. Thereafter, the discharge of the discharge liquid was stopped, and the silicon wafer was further rotated at a speed of 1000 rpm for 30 seconds, and then heated at 350°C for 60 seconds to obtain a silicon wafer on which an organic film (cured organic film) of each example was formed.

[0264] [Solvent Resistance Evaluation: Examples 1-1 to 1-77, Comparative Examples 1-1 to 1-16] Using the above method, organic films were formed on silicon wafers using each organic film-forming composition (UDL-1 to 77, Comparative UDL-1 to 16), and their thicknesses were measured. Next, PGMEA solvent was dispensed onto each organic film, 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 to determine the film thickness change rate (%). A film thickness change rate of less than 0.5% was considered good, and a film thickness change rate of 0.5% or greater was considered poor. The results are shown in Tables 6 to 10 below.

[0265] [In-plane uniformity evaluation: Examples 1-1 to 1-77, Comparative Examples 1-1 to 1-16] Using the above method, an organic film was formed on a silicon wafer using each organic film-forming composition (UDL-1 to 77, Comparative UDL-1 to 16), and the film thickness within a radius of 145 mm from the center of the 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 calculated by multiplying the square root of the square root by 100 was taken as the in-plane uniformity (%). When the in-plane uniformity was less than 2%, it was rated A (good), when it was 2% or more but less than 3%, it was rated B, and when it was 3% or more, it was rated C (poor). The results are shown in Tables 6 to 10.

[0266] [Table 6]

[0267] [Table 7]

[0268] [Table 8]

[0269] [Table 9]

[0270] [Table 10]

[0271] As shown in Tables 6 to 10, in Examples 1-1 to 1-77, which used the organic film-forming composition of the present invention, organic films with both good solvent resistance and in-plane uniformity were obtained, but in Comparative Examples 1-11 to 1-16 (Comparative UDL-11 to 1-16), which were made using compositions that did not contain the polymer contained in the organic film-forming composition of the present invention, the in-plane uniformity was poor. Therefore, in the following evaluation, UDL-1 to 77 and Comparative UDL-1 to 10, which had good solvent resistance and in-plane uniformity, were examined.

[0272] [Hump suppression evaluation: Examples 2-1 to 2-77, Comparative Examples 2-1 to 2-10] Organic films were formed on silicon wafers using the organic film-forming compositions (UDL-1 to 77, Comparative UDL-1 to 10) 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, a maximum height of less than 110% of the film thickness, as shown in Figure 2, was evaluated as A (good); a maximum height of 110% or more but less than 150% was evaluated as B; and a region with a height of 150% or more was evaluated as C (poor), as shown in Figure 3. The results are shown in Tables 11 to 15.

[0273] [Embedding Evaluation: Examples 2-1 to 2-77, Comparative Examples 2-1 to 2-10] As shown in Figure 4, organic film-forming compositions (UDL-1 to 77, comparative UDL-1 to 10) were deposited 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 above method, resulting in an organic film 8 as shown in Figure 4(I) (cross-sectional view). 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-forming composition with poor filling properties was used, voids were generated within the holes. When an organic film-forming composition with good filling properties was used, the organic film filled the holes without any voids, as shown in Figure 4(I). The case where no voids were generated was evaluated as good, and the case where voids were generated was evaluated as poor. The results are shown in Tables 11 to 15.

[0274] [Table 11]

[0275] [Table 12]

[0276] [Table 13]

[0277] [Table 14]

[0278] [Table 15]

[0279] As shown in Tables 11 to 15, it was confirmed that Examples 2-1 to 2-77, which used the organic film-forming compositions of the present invention (UDL-1 to 77), were excellent in solvent resistance, in-plane uniformity, hump suppression, and filling properties. On the other hand, in Comparative Examples 2-1 to 2-9, the hump suppression evaluation was C (poor) and the embedding characteristics evaluation was also poor. In Comparative Example 2-10, the hump characteristics evaluation was A (good), but the embedding characteristics evaluation was C (poor).

[0280] [Pattern formation test: Examples 3-1 to 3-77] Using the above method (baked at 350°C), an organic film was formed on a SiO2 wafer substrate using each organic film-forming composition (UDL-1 to 77). The following silicon-containing resist intermediate film material (SOG1) was then applied on top of the organic 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 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.

[0281] A 2% solution of the following polymer in propylene glycol ethyl ether was prepared as a silicon-containing resist interlayer material (SOG1).

[0282] [ka]

[0283] The resist top layer film material (ArF single-layer resist) was prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) in a solvent (PGMEA) containing 0.1 mass% of FC-430 (Sumitomo 3M Limited) in the proportions shown in Table 16, and filtering the solution through a 0.1 μm fluororesin filter.

[0284] [Table 16]

[0285] The polymer (RP1), acid generator (PAG1), and basic compound (Amine1) are shown below.

[0286] [ka]

[0287] The immersion protective film material (TC-1) was prepared by dissolving the polymer (PP1) in an organic solvent in the ratio shown in Table 17 and filtering the solution through a 0.1 μm fluororesin filter.

[0288] [Table 17]

[0289] The polymer (PP1) is shown below. [ka]

[0290] 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).

[0291] Next, using a Tokyo Electron etching device Telius, the resist upper layer film pattern was used as a mask to dry etch (pattern transfer) the silicon-containing resist intermediate film to obtain a silicon-containing resist intermediate film pattern, and the resulting silicon-containing resist intermediate film pattern was used as a mask to dry etch (pattern transfer) the organic film to obtain an organic film pattern, and the resulting organic film pattern was used as a mask to dry etch (pattern transfer) the SiO2 wafer substrate (SiO2 film). The etching conditions are as shown below.

[0292] (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

[0293] (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

[0294] (Conditions for transferring organic film patterns onto SiO2 wafer substrates) Chamber pressure 2.0Pa RF power 2,200W C5F12 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

[0295] The cross section of the obtained pattern was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Tables 18 to 22.

[0296] [Table 18]

[0297] [Table 19]

[0298] [Table 20]

[0299] [Table 21]

[0300] [Table 22]

[0301] As shown in Tables 18 to 22, in Examples 3-1 to 3-77, in which the organic film-forming compositions (UDL-1 to 77) of the examples of the present invention were used, the resist upper layer film pattern was ultimately transferred successfully to the SiO2 wafer substrate, confirming that the organic film-forming compositions of the examples of the present invention are suitable for use in microfabrication using the multilayer resist method.

[0302] From the above, it can be seen that the organic film-forming composition of the present invention has excellent film-forming properties, high-level filling properties, and excellent hump suppression properties, and is therefore extremely useful as an organic film material used in multilayer resist processes. Furthermore, the pattern formation method of the present invention using the organic film-forming composition of the present invention is capable of filling holes and trenches with very high aspect ratios without voids, forming fine patterns with high precision, and forming an organic film with suppressed humps, thereby enabling the efficient manufacture of semiconductor devices, etc.

[0303] The present specification includes the following aspects. [1] A polymer having a repeating unit represented by the following formula (B1): [ka] (In the formula, R1 is a single bond or a divalent organic group having 1 to 6 carbon atoms, R2 is a divalent organic group having 1 to 6 carbon atoms, R3 is a divalent organic group having 1 to 30 carbon atoms which may contain an oxygen atom, and W1 is a fluorine-containing group represented by the following formula (B2).) [ka] (In the formula, the dashed line indicates a bond to R1 in the above formula (B1), and may have one or more of the structures represented by the above formula (B2).) [2] The polymer according to [1], wherein R3 in (B1) is a group represented by the following formula (B3): [ka] (In the formula, the dashed line represents a bond to the sulfur atom in the above formula (B1), n=1 to 6, and the compound may have one or two of the structures represented by the above formula (B3).) [3] The polymer according to [1] or [2], wherein the polymer (B) is represented by any one of the following general formulae (B4) to (B6): [ka] (In the formula, R1, R2, and R3 are the same as above, R4 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, and R5 is a divalent organic group having 1 to 6 carbon atoms. m represents the average number of repeating units and is 3 to 2,000.) [4] The polymer according to any one of [1] to [3], wherein the polymer has a weight average molecular weight of 1,000 to 30,000. [5] A composition for forming an organic film, comprising: (A) an organic film-forming material; (B) a polymer having a repeating unit represented by the following formula (B1); and (C) a solvent. [ka] (In the formula, R1 is a single bond or a divalent organic group having 1 to 6 carbon atoms, R2 is a divalent organic group having 1 to 6 carbon atoms, R3 is a divalent organic group having 1 to 30 carbon atoms which may contain an oxygen atom, and W1 is a fluorine-containing group represented by the following formula (B2).) [ka] (In the formula, the dashed line indicates a bond to R1 in the above formula (B1), and may have one or more of the structures represented by the above formula (B2).) [6] The composition for forming an organic film according to [5], wherein R3 in the formula (B1) is a group represented by the following formula (B3): [ka] (In the formula, the dashed line represents a bond to the sulfur atom in the above formula (B1), n=1 to 6, and the compound may have one or more of the structures represented by the above formula (B3).) [7] The composition for forming an organic film according to [5] or [6], wherein the polymer (B) contains one or more compounds represented by any one of the following general formulas (B4) to (B6): [ka] (In the formula, R1, R2, and R3 are the same as above, R4 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, and R5 is a divalent organic group having 1 to 6 carbon atoms. m represents the average number of repeating units and is 3 to 2,000.) [8] The composition for forming an organic film according to any one of [5] to [7], wherein the weight average molecular weight of the component (B) is 1,000 to 30,000. [9] The composition for forming an organic film according to any one of [5] to [8], characterized in that the content of the component (B) is 0.01 to 5 parts by mass relative to 100 parts by mass of the material for forming an organic film (A).

[10] A method for forming an organic film used in a manufacturing process of a semiconductor device, comprising:

[0033] The composition for forming an organic film according to any one of [5] to [9] is spin-coated on a substrate to be processed to obtain a coating film; The organic film forming method is characterized in that the coating film is cured by heat treating it at a temperature of 100° C. or higher and 600° C. or lower for 10 to 600 seconds to form an organic film.

[11] A pattern forming method, forming an organic film on a workpiece using the organic film-forming composition according to any one of [5] to [9]; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming a resist upper layer film on the silicon-containing resist intermediate film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist top layer film, and transferring the pattern to the silicon-containing resist intermediate film by etching using the resist top layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; Furthermore, the pattern forming method is characterized in that a pattern is formed on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[12] A pattern forming method, forming an organic film on a workpiece using the organic film-forming composition according to any one of [5] to [9]; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, and forming an organic anti-reflective film or an adhesion film on the silicon-containing 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, and 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 adhesive film and the silicon-containing resist intermediate film by etching; transferring the pattern to the organic film by etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; Furthermore, the pattern forming method is characterized in that a pattern is formed on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[13] A pattern forming method, forming an organic film on a workpiece using the organic film-forming composition according to any one of [5] to [9]; forming an inorganic hard mask intermediate film selected from the group consisting of 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 intermediate 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 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 intermediate film to which the pattern has been transferred as a mask; Furthermore, the pattern forming method is characterized in that a pattern is formed on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[14] A pattern forming method, forming an organic film on a workpiece using the organic film-forming composition according to any one of [5] to [9]; forming an inorganic hard mask intermediate film selected from the group consisting of 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 intermediate film, and forming a resist upper layer film 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; a resist upper layer film on which the circuit pattern is formed is used as a mask to transfer the pattern to the organic anti-reflective film or adhesion film and the inorganic hard mask intermediate film by etching; transferring the pattern to the organic film by etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; Furthermore, the pattern forming method is characterized in that a pattern is formed on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[15] The pattern forming method according to

[13] or

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

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

[11] to

[15] , 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.

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

[11] to

[16] , wherein the circuit pattern is developed using an alkaline developer or an organic solvent.

[18] The pattern forming method according to any one of

[11] to

[17] , 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.

[19] The pattern formation method according to

[18] , characterized in that the workpiece is made of a metal selected from the group consisting of silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, and alloys thereof.

[0304] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention. [Explanation of symbols]

[0305] 1...substrate, 2...processed layer, 2a...pattern (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 polymer having a repeating unit represented by the following formula (B1): 【Chemistry 1】 (In the formula, R １ represents a single bond or a divalent organic group having 1 to 6 carbon atoms, R ２ is a divalent organic group having 1 to 6 carbon atoms, R ３ represents a divalent organic group having 1 to 30 carbon atoms which may contain an oxygen atom; W １ is a fluorine-containing group represented by the following formula (B2): 【Chemistry 2】 (In the formula, the dashed line represents R in the above formula (B1) １ and may have one or more of the structures represented by the above formula (B2).

2. R in (B1) ３ The polymer according to claim 1, wherein is a group represented by the following formula (B3): 【Transformation 3】 (In the formula, the dashed line represents a bond to the sulfur atom in the above formula (B1), n=1 to 6, and the compound may have one or more of the structures represented by the above formula (B3).)

3. 2. The polymer according to claim 1, wherein the polymer (B) is represented by any one of the following general formulas (B4) to (B6): 【Chemistry 4】 (In the formula, R １ , R ２ and R ３ is the same as above, and R ４ is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, and R ５ is a divalent organic group having 1 to 6 carbon atoms; m represents the average number of repeating units and is 3 to 2,000.

4. 4. The polymer according to claim 1, wherein the weight average molecular weight of the polymer is 1,000 to 30,000.

5. A composition for forming an organic film, comprising: (A) an organic film-forming material; (B) a polymer having a repeating unit represented by the following formula (B1); and (C) a solvent: 【Transformation 5】 (In the formula, R １ represents a single bond or a divalent organic group having 1 to 6 carbon atoms, R ２ is a divalent organic group having 1 to 6 carbon atoms, R ３ represents a divalent organic group having 1 to 30 carbon atoms which may contain an oxygen atom; W １ is a fluorine-containing group represented by the following formula (B2): 【Transformation 6】 (In the formula, the dashed line represents R in the above formula (B1) １ and may have one or more of the structures represented by the above formula (B2).

6. R in the above formula (B1) ３ The composition for forming an organic film according to claim 5, wherein is a group represented by the following formula (B3): 【Transformation 7】 (In the formula, the dashed line represents a bond to the sulfur atom in the above formula (B1), n=1 to 6, and the compound may have one or more of the structures represented by the above formula (B3).)

7. The composition for forming an organic film according to claim 5, wherein the polymer (B) contains one or more compounds represented by any one of the following general formulas (B4) to (B6): 【Transformation 8】 (In the formula, R １ , R ２ and R ３ is the same as above, and R ４ is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, and R ５ is a divalent organic group having 1 to 6 carbon atoms; m represents the average number of repeating units and is 3 to 2,000.

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

9. 6. The organic film-forming composition according to claim 5, wherein the content of the component (B) is 0.01 to 5 parts by mass relative to 100 parts by mass of the material (A) for forming an organic film.

10. A method for forming an organic film used in a manufacturing process of a semiconductor device, comprising: A coating film is obtained by spin-coating the organic film-forming composition according to any one of claims 5 to 9 on a substrate to be processed, The method for forming an organic film is characterized in that the coating film is cured by heat treating it at a temperature of 100° C. or higher and 600° C. or lower for 10 to 600 seconds, thereby forming an organic film.

11. A pattern formation method, comprising: forming an organic film on a workpiece using the organic film-forming composition according to any one of claims 5 to 9; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming a resist upper layer film on the silicon-containing resist intermediate film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist top layer film, and transferring the pattern to the silicon-containing resist intermediate film by etching using the resist top layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; Furthermore, the pattern forming method is characterized in that a pattern is formed on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

12. A pattern formation method, comprising: forming an organic film on a workpiece using the organic film-forming composition according to any one of claims 5 to 9; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, and forming an organic anti-reflective film or an adhesion film on the silicon-containing 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, and 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 adhesive film and the silicon-containing resist intermediate film by etching; transferring the pattern to the organic film by etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; Furthermore, the pattern forming method is characterized in that a pattern is formed on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

13. A pattern formation method, comprising: forming an organic film on a workpiece using the organic film-forming composition according to any one of claims 5 to 9; forming an inorganic hard mask intermediate film selected from the group consisting of 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 intermediate 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 inorganic hard mask 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 inorganic hard mask intermediate film to which the pattern has been transferred as a mask; Furthermore, the pattern forming method is characterized in that a pattern is formed on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

14. A pattern formation method, comprising: forming an organic film on a workpiece using the organic film-forming composition according to any one of claims 5 to 9; forming an inorganic hard mask intermediate film selected from the group consisting of 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 intermediate film, and forming a resist upper layer film 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; a resist upper layer film on which the circuit pattern is formed is used as a mask to transfer the pattern to the organic anti-reflective film or adhesion film and the inorganic hard mask intermediate film by etching; transferring the pattern to the organic film by etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; Furthermore, the pattern forming method is characterized in that a pattern is formed on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

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

16. 12. The pattern forming method according to claim 11, 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.

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

18. 12. The pattern forming method according to claim 11, 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.

19. 19. The pattern formation method according to claim 18, wherein the workpiece is made of a metal selected from the group consisting of silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, and alloys thereof.

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