Method for forming organic film and method for manufacturing substrate for semiconductor device

Abstract

To provide a method for forming an organic film capable of filling a concave-convex pattern on a substrate and highly planarizing the substrate at low cost in a process of manufacturing a semiconductor device or the like.SOLUTION: A method for forming an organic film on a substrate having a concave-convex pattern, the method comprising: a step of forming a coating film on the substrate by spin-coating with a composition for forming an organic film; a step of spin-coating the coating film with a coating solvent having a normal boiling point of 160°C or higher and lower than 500°C and capable of dissolving the coating film; and a step of forming the organic film by subjecting the coating film to an insolubilization treatment against the coating solvent.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a method for forming a flat organic film that can be used in the microfabrication process of semiconductor devices and the like, and a method for manufacturing a substrate for a semiconductor device using the organic film forming method. [Background technology]

[0002] The advancement of semiconductor device processing performance has been driven by the miniaturization of pattern dimensions due to the shortening of light source wavelengths in lithography technology. However, the rate of wavelength shortening has slowed since the advent of ArF light sources, necessitating the need for performance enhancement instead of miniaturization. Accordingly, development is underway to improve semiconductor device performance by implementing three-dimensional semiconductor structures and arranging transistors at higher densities. Substrates for semiconductor devices with such three-dimensional structures require deeper and thinner circuit patterns than conventional substrates. Therefore, lithography techniques optimized for the formation of planar structures cannot provide practical process tolerances. Therefore, it is necessary to create a flat surface using a material capable of planarizing the substrate on which the three-dimensional structure is formed, and then pattern the resulting surface using lithography to ensure process tolerances.

[0003] Many techniques for forming planarized films using spin-coated organic films are already known to produce such flat surfaces (Patent Documents 1-5). However, organic films formed from such materials are not suitable for all patterns on substrates used in semiconductor device manufacturing. Furthermore, the addition of liquid additives such as polyether polyols and polyacetals has also been proposed (Patent Documents 6-7). However, these additives typically have poor dry-etching resistance. If these additives remain in the coated film, they may result in insufficient dry-etching resistance during substrate processing, potentially resulting in insufficient dry-etching resistance performance for the organic film used in substrate processing. Another practical method for planarization is to fill in the irregularities on the substrate and then planarize it using a chemical-mechanical polishing (CMP) process (Patent Document 8). However, CMP is a costly process. Given these circumstances, a low-cost method for achieving high-level planarization of substrates for semiconductor device manufacturing using organic films is needed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-292528 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-65081 [Patent Document 3] Japanese Patent Application Laid-Open No. 2008-242492 [Patent Document 4] Japanese Patent Application Laid-Open No. 2014-24831 [Patent Document 5] Japanese Patent Application Laid-Open No. 2014-219559 [Patent Document 6] International Publication No. 2008 / 026468 [Patent Document 7] Japanese Patent Application Laid-Open No. 2013-253227 [Patent Document 8] Japanese Patent Application Laid-Open No. 2004-335873 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for forming an organic film that can fill an uneven pattern on a substrate and highly planarize the substrate at low cost in a manufacturing process for a semiconductor device or the like. [Means for solving the problem]

[0006] In order to achieve the above object, the present invention provides a method for forming an organic film on a substrate having a concave-convex pattern, the method comprising the steps of: a step of spin-coating a composition for forming an organic film on the substrate to form a coating film; A step of spin-coating a coating solvent having a normal boiling point of 160°C or higher and lower than 500°C, which can dissolve the coating film, onto the coating film; The present invention provides a method for forming an organic film, comprising the step of forming an organic film by subjecting the coating film to an insolubilization treatment in the coating solvent.

[0007] This method makes it possible to form an organic film that fills the uneven pattern on a substrate and highly flattens the substrate at low cost in the manufacturing process of a semiconductor device or the like.

[0008] The insolubilization treatment is preferably any one of heat treatment at 100° C. to 600° C., ultraviolet irradiation treatment with a wavelength of 400 nm or less, electron beam irradiation treatment, and plasma irradiation treatment, or a combination thereof.

[0009] By carrying out the insolubilization treatment in this manner, it is possible to form an organic film that maintains a flat state.

[0010] The coating solvent is preferably an alcohol, an ester, a ketone, a carbonate, an ether, or a combination thereof.

[0011] By using such a coating solvent, an organic film that highly flattens the substrate can be formed.

[0012] As the coating solvent, it is preferable to use an aromatic compound having a benzyl group or a benzoyl group.

[0013] Use of such an aromatic compound provides favorable solubility and wettability to the organic film, enabling the organic film to be planarized to a higher degree.

[0014] Furthermore, it is preferable to use a composition containing a resin containing one or more aromatic rings as the organic film-forming composition.

[0015] In the method for forming an organic film of the present invention, from the viewpoints of etching resistance, optical properties, and heat resistance, a composition for forming an organic film containing a resin having an aromatic ring can be suitably used.

[0016] The present invention also provides a method for manufacturing a substrate for a semiconductor device, which includes forming an organic film on a substrate having a concave-convex pattern by the above-mentioned method, forming a silicon-containing resist intermediate film on the organic film using a silicon-containing composition for forming a resist intermediate film, forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask, transferring the pattern to the organic film by dry etching using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern to the substrate by dry etching using the organic film on which the pattern has been transferred as a mask.

[0017] The present invention also provides a method for manufacturing a substrate for a semiconductor device, which includes forming an organic film on a substrate having a concave-convex pattern by the above-mentioned method, forming a silicon-containing resist intermediate film on the organic film using a silicon-containing composition for forming a resist intermediate film, forming an organic antireflective film on the silicon-containing resist intermediate film, forming a resist upper layer film on the organic antireflective film using a photoresist composition to form a four-layer resist film, forming a circuit pattern on the resist upper layer film, transferring the pattern to the organic antireflective film and the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask, transferring the pattern to the organic film by dry etching using the organic antireflective film and the silicon-containing resist intermediate film to which the pattern has been transferred as masks, and further transferring the pattern to the substrate by dry etching using the organic film to which the pattern has been transferred as a mask.

[0018] The present invention also provides a method for manufacturing a substrate for a semiconductor device, which includes forming an organic film on a substrate having a concave-convex pattern by the above-described method, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, an amorphous silicon film, and a titanium nitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the inorganic hard mask by dry etching using the resist upper layer film on which the pattern has been formed as a mask, transferring the pattern to an organic film by dry etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the substrate by dry etching using the organic film on which the pattern has been transferred as a mask.

[0019] The present invention also provides a method for manufacturing a substrate for a semiconductor device, comprising: forming an organic film on a substrate having a concave-convex pattern by the method described above; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, an amorphous silicon film, and a titanium nitride film on the organic film; forming a multilayer resist film or an organic antireflective film consisting of an organic film and a silicon-containing resist intermediate film on the inorganic hard mask; forming a resist upper layer film on the multilayer resist film or the organic antireflective film using a photoresist composition; forming a circuit pattern on the resist upper layer film; using the resist upper layer film on which the pattern has been formed as a mask, transferring the pattern to the multilayer resist film or the organic antireflective film, and then transferring the pattern to the inorganic hard mask by dry etching; using the inorganic hard mask on which the pattern has been transferred as a mask, transferring the pattern to an organic film formed on the substrate by dry etching; and further transferring the pattern to the substrate by dry etching using the organic film on which the pattern has been transferred as a mask.

[0020] As described above, the organic film formed by the method of the present invention has excellent planarization properties, and therefore, by using this organic film in combination with various film materials in a multilayer resist process, such as a two-layer resist process, a three-layer resist process using a silicon-containing resist intermediate film, or a four-layer resist process using a silicon-containing resist intermediate film and an organic anti-reflective film, the pattern of the upper-layer photoresist (resist upper-layer film) can be transferred to the substrate with high precision, thereby forming a pattern on the substrate. In other words, the method of manufacturing a substrate for a semiconductor device of the present invention makes it possible to manufacture a substrate for a semiconductor device with high precision.

[0021] In this case, the inorganic hard mask is preferably formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

[0022] In the method for manufacturing a substrate for a semiconductor device of the present invention, an inorganic hard mask can be formed by such a method, for example.

[0023] In forming the circuit pattern, it is preferable to form the circuit pattern by any one of lithography using high-energy rays with a wavelength of 10 nm or more and 300 nm or less, direct writing using an electron beam, and nanoimprinting, or a combination of these.

[0024] In forming the circuit pattern, it is preferable to develop the circuit pattern by alkaline development or organic solvent development.

[0025] In the method of manufacturing a substrate for a semiconductor device of the present invention, such circuit pattern forming means and developing means can be suitably used. [Effects of the Invention]

[0026] As described above, the present invention makes it possible to form an organic film that can fill the uneven pattern on a substrate and highly planarize the substrate. Furthermore, since the substrate can be highly planarized without using the costly CMP process, substrate planarization can be achieved at low cost. Furthermore, the organic film formed by the method of the present invention has excellent planarization properties, making it extremely useful for semiconductor device manufacturing. By using this organic film in combination with various film materials in a multilayer resist process, such as a two-layer resist process, a three-layer resist process using a silicon-containing resist interlayer, or a four-layer resist process using a silicon-containing resist interlayer and an organic anti-reflective coating, the pattern of the upper photoresist (resist upper layer) can be transferred to the substrate with high precision, forming a pattern on the substrate. In other words, the method of manufacturing a substrate for a semiconductor device of the present invention makes it possible to manufacture a substrate for a semiconductor device with high precision. [Brief explanation of the drawings]

[0027] [Figure 1] 1 is a flow chart of an example of forming an organic film on a substrate having a trench pattern by the organic film forming method of the present invention. [Figure 2] 1 is a flow chart of an example of forming an organic film on a substrate having a line pattern by the organic film forming method of the present invention. [Figure 3] FIG. 2 is an explanatory diagram of a method for flattening the trench pattern (pattern A) of the present invention. [Figure 4] FIG. 10 is an explanatory diagram of a method for flattening the line pattern (pattern B) of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0028] As described above, there has been a demand for a method of forming an organic film that can fill in the uneven patterns on a substrate and highly planarize the substrate at low cost in the manufacturing process of a semiconductor device or the like.

[0029] Conventionally, a method for flattening a substrate having an uneven pattern, such as a substrate on which a part or all of a semiconductor circuit is formed, involves spin-coating an organic film-forming composition onto the substrate, followed by baking to fill the uneven pattern on the substrate surface with an organic film and form a flat surface. However, while this method can fill in minute unevenness on the surface, it is difficult to form a uniformly flat surface across the entire substrate surface, between areas with high pattern density and areas with low pattern density that need to be filled. Generally, the applied composition forms an uneven coating film that follows the uneven pattern formed on the substrate. Typically, in the process of forming semiconductor circuits, such a coating film is insolubilized before proceeding to the next film formation step. As a result of extensive research into the flattening of substrates, the present inventors discovered that an extremely flat organic film can be formed by applying an organic film-forming composition, spin-coating a coating solvent with a normal boiling point of 160°C or higher but lower than 500°C onto the coating film before the insolubilization treatment, and causing the coating film to flow, thereby completing the present invention. In this specification, the term "normal boiling point" refers to the boiling point at 1 atmosphere (1013.25 hPa). Hereinafter, this may be simply referred to as "boiling point."

[0030] That is, the present invention provides a method for forming an organic film on a substrate having a concave-convex pattern, comprising the steps of: a step of spin-coating a composition for forming an organic film on the substrate to form a coating film; A step of spin-coating a coating solvent having a normal boiling point of 160°C or higher and lower than 500°C, which can dissolve the coating film, onto the coating film; The organic film forming method is characterized by including a step of forming an organic film by subjecting the coating film to an insolubilization treatment in the coating solvent.

[0031] The present invention will be described in detail below, but the present invention is not limited thereto.

[0032] The present invention relates to a method for forming an extremely flat organic film that can be used in the microfabrication process of semiconductor devices and the like, and a method for manufacturing a substrate for a semiconductor device using the organic film forming method. The method for forming an organic film of the present invention and the method for manufacturing a substrate for a semiconductor device using the method for forming an organic film will be described below.

[0033] <Method for forming organic film> The present invention relates to a method for forming an organic film on a substrate having a concave-convex pattern, a step of spin-coating the organic film-forming composition on the substrate to form a coating film (coating film forming step); A step of spin-coating a coating solvent having a normal boiling point of 160°C or more and less than 500°C, which can dissolve the coating film, onto the coating film (coating solvent application step); The method is characterized by including a step of forming an organic film by subjecting the coating film to an insolubilization treatment in the coating solvent (organic film forming step). In the present invention, the coating solvent refers to an organic solvent to be applied onto the coating film formed on the substrate, which is capable of dissolving the coating film and has a normal boiling point of 160° C. or more and less than 500° C. The coating solvent may be different from or the same as the organic solvent contained in the coating film (derived from the organic solvent contained in the organic film-forming composition), but it is preferable that the coating solvent has a normal boiling point higher than that of the organic solvent contained in the coating film.

[0034] The standard boiling point can be determined from values ​​such as those listed in Chemistry Handbook (Basic Edition) (Revised 6th Edition, edited by the Chemical Society of Japan, Maruzen Publishing, January 2021) and Solvent Handbook (edited by Teruzo Asahara et al., Kodansha, 1976), and can also be determined from the boiling point under reduced pressure of less than 1 atmosphere using the method described in the literature (Science of Petroleum, Vol. II, p. 1281, (1938)). The spin coating method includes a static dispensing method in which a solution (fluid) is dripped onto a stationary substrate, and then the substrate is rotated to coat the solution, and a dynamic dispensing method in which a solution is dripped onto a rotating substrate to coat the solution. Either static dispensing or dynamic dispensing can be used in the present invention.

[0035] The present invention will now be described with reference to the drawings. FIG. 1 is a flow diagram of an example of the organic film formation method of the present invention for forming an organic film on a substrate having a trench pattern. In the method of FIG. 1, an organic film-forming composition is first spin-coated onto substrate 1 to form coating film 2. During this process, the uneven pattern on substrate 1 causes coating film 2 to conform to the shape of the substrate (FIG. 1(A)). A coating solvent 3 with a normal boiling point of 160°C or higher but lower than 500°C is then spin-coated onto this coating film 2. When coating solvent 3 is applied to uncured coating film 2, coating film 2 (mainly the resin in coating film 2) flows (FIG. 1(B)). As a result, the unevenness is eliminated, and a flat coating film 2 is formed (FIG. 1(C)). Finally, this flat coating film 2 is insolubilized by treatment with heat, light, plasma, or any combination thereof to form a flat organic film 4 (FIG. 1(D)). A coating film can then be formed on this insolubilized organic film 4 by spin-coating a coating film-forming composition, such as a silicon-containing resist intermediate film-forming composition described below. In the method of Fig. 1, after coating film 2 is formed, the organic solvent contained in coating film 2 may be removed by treatment with heat, light, plasma, or any combination thereof, to the extent that coating film 2 does not completely harden.

[0036] Figure 2 is a flow diagram of an example of the organic film forming method of the present invention for forming an organic film on a portion having a fine pattern over a wide area on a substrate having a line pattern (line and space pattern). In the method of Figure 2, a composition for forming an organic film is first spin-coated onto substrate 1 to form coating film 2. When the pattern pitch is large, as shown in Figure 1, coating film 2 is formed with irregularities that follow the shape of the substrate due to the influence of the irregularities on the substrate. However, with fine patterns, such as patterns with a half pitch of less than 200 nm, coating film 2 does not follow the individual patterns, but rather has an average concave shape at the center of the pattern (the entire area having the pattern has a gently concave shape) (Figure 2(A)). A coating solvent 3 having a normal boiling point of 160°C or higher but lower than 500°C is spin-coated onto the coating film 2. When the coating solvent 3 is applied to the uncured coating film 2, the coating film 2 (mainly the resin in the coating film 2) flows (FIG. 2(B)). As a result, the unevenness is eliminated, and a flat coating film 2 is formed (FIG. 2(C)). Finally, this flat coating film 2 can be insolubilized by treatment with heat, light, plasma, or any combination thereof to form a flat organic film 4 (FIG. 2(D)). Then, a coating film-forming composition, such as a silicon-containing resist interlayer film-forming composition described below, can be spin-coated onto this insolubilized organic film 4 to form a coating film. In the method of FIG. 2, after the coating film 2 is formed, the organic solvent contained in the coating film 2 may be removed by treatment with heat, light, plasma, or any combination thereof, as long as the coating film 2 does not completely harden.

[0037] Each step of the organic film forming method of the present invention will be described in more detail below.

[0038] [Coating film formation process] In the organic film forming method of the present invention, a coating film is first formed by spin-coating an organic film-forming composition on a substrate having a concave-convex pattern. The substrate having the concave-convex pattern is not particularly limited, and for example, a substrate having a trench pattern, a space pattern, or a line pattern can be used. Furthermore, the organic film-forming composition used in the present invention is not particularly limited, but it is preferable to use an organic film-forming composition containing a resin having one or more aromatic rings. The spin-coating method is not particularly limited, and may be performed by a known method using a spin coater or the like.

[0039] In the present invention, after forming the coating film, the organic solvent contained in the coating film may be removed by treatment with heat, light, plasma or any combination thereof, as long as the coating film does not completely harden.

[0040] The heat, light, and plasma irradiation methods can be the same as the insolubilization treatment methods described below, but from the perspective of process simplicity, it is preferable to use heat treatment, with heat treatment at 50°C or higher and 450°C or lower being more preferable, heat treatment at 80°C or higher and 400°C or lower being even more preferable, and heat treatment at 100°C or higher and 350°C or lower being particularly preferable.

[0041] The organic film-forming resin that can be used in the organic film-forming composition used in the present invention is not particularly limited as long as it is a resin that satisfies the film-forming properties and curing properties of spin coating. However, from the viewpoints of etching resistance, optical properties, heat resistance, etc., compounds that contain an aromatic skeleton are more preferred.

[0042] 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, and fluorene are particularly preferred.

[0043] Examples of the organic film-forming resin applicable to the present invention include resins containing the following structures described in JP-A Nos. 2012-1687 and 2012-77295. [ka] (In formula (1), the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. X represents a single bond or an alkylene group having 1 to 20 carbon atoms. m represents 0 or 1. n represents any natural number such that the molecular weight is 100,000 or less. Note that the symbols in the formula apply only within this formula.)

[0044] [ka] (In formula (2), the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. n represents any natural number such that the weight average molecular weight (as measured by gel permeation chromatography using THF as an eluent) in terms of polystyrene is 100,000 or less. The symbols in the formula are used only within this formula.)

[0045] Further examples of organic film-forming resins applicable to the present invention include resins containing the following structures described in JP-A Nos. 2004-264710, 2005-043471, 2005-250434, 2007-293294, and 2008-65303. [ka] (In formula (3) and formula (4), R 1 and R 2 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group; R 3 represents an alkyl group having 1 to 3 carbon atoms, a vinyl group, an allyl group, or an aryl group which may be substituted, n represents 0 or 1, and m represents 0, 1, or 2. The symbols in the formulae apply only within the formulae.

[0046] [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 independently a monovalent atom or group. X is a divalent group. Note that the symbols in the formula apply only within this formula.)

[0047] [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 any of ether, ester, lactone, and amide. R 3 , R 4 are each a hydrogen atom or a glycidyl group. X represents a polymer of any one of hydrocarbons containing an indene skeleton, cycloolefins having 3 to 10 carbon atoms, and maleimide, and may have any one of ethers, esters, lactones, and carboxylic acid anhydrides. R 5 , R 6 R is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 7 is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a hydroxy group, or an alkoxycarbonyl group. p and q are each an integer of 1 to 4. r is an integer of 0 to 4. a, b, and c are in the ranges of 0.5≦a+b+c≦1, 0≦a≦0.8, 0≦b≦0.8, 0.1≦a+b≦0.8, and 0.1≦c≦0.8, respectively. Note that the symbols in the formula apply only within this formula.

[0048] [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. Note that the symbols in the formula apply only within this formula.)

[0049] As the resin for forming an organic film applied to the present invention, specifically, resins including the following structures described in JP-A-2004-205685, JP-A-2007-171895, and JP-A-2009-14816 can be exemplified.

Chemical formula

[0050]

Chemical formula

[0051] [ka] (In formula (11), n ​​represents 0 or 1. R 1 represents an optionally substituted methylene group, an optionally substituted alkylene group having 2 to 20 carbon atoms, or an optionally substituted arylene group having 6 to 20 carbon atoms. 2 represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. 3 ~R 7 represents a hydroxyl group, an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted alkoxy group having 1 to 6 carbon atoms, an optionally substituted alkoxycarbonyl group having 2 to 10 carbon atoms, an optionally substituted aryl group having 6 to 14 carbon atoms, or an optionally substituted glycidyl ether group having 2 to 6 carbon atoms. 9 represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic alkyl ether group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Note that the symbols in the formulae apply only within this formula.)

[0052] For example, the following compounds are exemplified. [ka]

[0053] Examples of organic film-forming resins applicable to the present invention include resins containing the following structures described in JP-A Nos. 2007-199653, 2008-274250, and 2010-122656. [ka] (In formula (12), R 1 and R 2 are independently the same or different hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms, and R 3is a single bond or an alkylene group having a linear, branched or cyclic structure and having 1 to 30 carbon atoms, which may have a bridged cyclic hydrocarbon group, a double bond, a heteroatom or an aromatic group having 6 to 30 carbon atoms; R 4 and R 5 are each independently a hydrogen atom or a glycidyl group, and n is an integer of 1 to 4. The symbols in the formula are applicable only within this formula.

[0054] [ka] (In formula (13), R 1 and R 2 are independently the same or different hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms, and R 3 is a single bond or an alkylene group having a linear, branched or cyclic structure and having 1 to 30 carbon atoms, which may have a bridged cyclic hydrocarbon group, a double bond, a heteroatom or an aromatic group having 6 to 30 carbon atoms; R 4 and R 5 are each independently a hydrogen atom or a glycidyl group, and R 6 is a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms. The symbols in the formula are only applicable within this formula.

[0055] [ka] (In formula (14), ring Z 1 and ring Z 2 is a fused polycyclic aromatic hydrocarbon ring, R 1a , R 1b , R 2a , and R 2b are the same or different and represent a substituent. k1 and k2 are the same or different and represent an integer of 0 or 1 to 4, m1 and m2 are each an integer of 0 or 1 or more, and n1 and n2 are each an integer of 0 or 1 or more, provided that n1+n2≧1. The symbols in the formulae are only applicable within this formula.

[0056] [Chemical formula] (In formula (15), R 1 , R 2 are the same or different hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms. R 3 , R 4 are each a hydrogen atom or a glycidyl group, and R 5 is a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, and R 6 , R 7 are a benzene ring and a naphthalene ring. p and q are each 1 or 2. n is 0 < n ≤ 1. Note that the symbols in the formula are applicable only within this formula.)

[0057] For example, the following compounds are exemplified. [Chemical formula]

[0058] [Chemical formula]

[0059] [Chemical formula]

[0060] [Chemical formula]

[0061] Examples of the resin for forming an organic film applied to the present invention include resins containing the following structures described in JP-A-No. 2012-214720. [Chemical formula] (In formula (16), the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. x and z each independently represent 0 or 1. Note that the symbols in the formula apply only within this formula.)

[0062] Examples of organic film-forming resins applicable to the present invention include resins described in JP-A-2014-29435, WO2012 / 077640, and WO2010 / 147155. [ka] (In formula (17), A represents a structure having carbazole, B represents a structure having an aromatic ring, and C represents a structure having a hydrogen atom, an alkyl group, or an aromatic ring, and B and C may form a ring together. The combined structure of A, B, and C contains 1 to 4 carboxyl groups or salts thereof, or carboxylate ester groups. Note that the symbols in the formula apply only within this formula.)

[0063] Another example is a polymer that contains a unit structure represented by the following formula (18) and a unit structure represented by the following formula (19), which are described in International Publication WO2012 / 077640, 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. [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. represents a combination of these groups. R4 represents a hydrogen atom, or an aryl group having 6 to 40 carbon atoms which may be substituted with a halogen atom, a nitro group, an amino group, or a hydroxy group, or a heterocyclic group; R5 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, a nitro group, an amino group, or a hydroxy group, or an aryl group having 6 to 40 carbon atoms, or a heterocyclic group; R4 and R5 may together form a ring; n1 and n2 each represent an integer of 1 to 3; and the symbols in the formula are applicable only within this formula.

[0064] [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 may be substituted with a hydrogen atom, 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 substituents that can be substituted on the aromatic ring group Ar. The symbols in the formula are only applicable within this formula.

[0065] An example of the organic film-forming resin applicable to the present invention is a polymer containing a unit structure represented by the following formula (20) described in International Publication WO2010 / 147155. [ka] (In formula (20), R1 and R2 are each selected from the group consisting of a hydrogen atom, a halogen group, a nitro group, an amino group, a 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 combinations thereof, and the alkyl group, the alkenyl group, or the aryl group represents a group which may contain an ether bond, a ketone bond, or an ester bond; R3 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group Alternatively, the aryl group represents a group which may contain an ether bond, a ketone bond, or an ester bond; R4 represents an aryl group or heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; R5 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group or a heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; R4 and R5 may form a ring together with the carbon atoms to which they are bonded; and n1 and n2 are each an integer of 1 to 3. Note that the symbols in the formula apply only within this formula.

[0066] Examples of organic film-forming resins applicable to 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 International Publication WO2012 / 176767. [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 symbols in the formula apply only within this formula.)

[0067] Examples of organic film-forming resins applicable to the present invention include novolak resins having a fluorene or tetrahydrospirobiindene structure described in JP-A Nos. 2005-128509, 2006-259249, 2006-259482, 2006-293298, and 2007-316282, and include resins containing a repeating unit structure represented by the following formula (22-1) or (22-2): [ka] (In formula (22-1) and formula (22-2), R 1 , R 2 , R 6 , R 7 are independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an allyl group, or a halogen atom; R 3 , R 4 , R 8 , R 9 are independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms or a glycidyl group, and R 5 , R 14 are independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. n, m, p and q are integers of 1 to 3. R 10 ~R 13 are independently a hydrogen atom, a halogen atom, a hydroxy group, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms. Note that the symbols in the formula apply only within this formula.)

[0068] An example of the organic film-forming resin that can be used in the present invention is a reaction product obtained by the method described in JP-A-2012-145897. More specifically, examples of the polymers include those obtained by condensing one or more compounds represented by the following general formula (23-1) and / or (23-2) with one or more compounds represented by the following general formula (24-1) and / or (24-2) and / or their equivalents. [ka] (In formula (23-1) and 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 symbols in the formula are applicable only within this formula.) [ka] (In formula (24-1) and 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 numbers of each substituent, and n1 to n6 = 0, 1, 2, and hydroxybenzaldehyde is excluded in formula (24-1). In formula (24-2), the relationships 0≦n3+n5≦3, 0≦n4+n6≦4, 1≦n3+n4≦4 are satisfied. Note that the symbols in the formulas apply only within this formula.)

[0069] 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. [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 formula (24-1) and formula (24-2). Note that the symbols in the formula apply only within this formula.)

[0070] Examples of the organic film-forming resin applicable to the present invention include resins containing the following structure described in JP-A-2017-119671. [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 symbols in the formula apply only within this formula.) [ka] (In the formula, X 2 is a divalent organic group having 1 to 10 carbon atoms, n1 is 0 or 1, n2 is 1 or 2, and X 3 is a group represented by the following general formula (26-3), and n5 is 0, 1, or 2. The symbols in the formula apply only within this formula. [ka] (In the formula, R 10 is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom on the benzene ring in the formula may be substituted with a methyl group or a methoxy group. Note that the symbols in the formula apply only within this formula.

[0071] For example, the following compounds are exemplified. [ka]

[0072] Examples of the organic film-forming resin applicable to the present invention include polymers having a repeating unit represented by the following general formula (27-1), which are described in JP-A-2019-44022. [ka] In formula (27-1), AR1 and AR2 are benzene rings or naphthalene rings which may have a substituent, and R 1 , R 2 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R 1 and R 2 If is an organic group, R 1 and R 2 may form a cyclic organic group by bonding intramolecularly. n is 0 or 1, and when n=0, AR1 and AR2 do not form a bridged structure between the aromatic rings of AR1 and AR2 via Z, and when n=1, AR1 and AR2 form a bridged structure between the aromatic rings of AR1 and AR2 via Z, and Z is either a single bond or the following formula (27-2). Y is a group represented by the following formula (27-3). Note that the symbols in the formula apply only within this formula. [ka] [ka] (In the formula, R 3 is a single bond or a divalent organic group having 1 to 20 carbon atoms, and R 4 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and the dashed line represents a bond. Note that the symbols in the formula are only applicable within this formula.

[0073] For example, the following polymers are exemplified. [ka]

[0074] [ka]

[0075] The organic film-forming resin may be synthesized by a known method, or a commercially available product may be used.

[0076] The amount of the organic film-forming resin to be added is, for example, preferably 0.2 to 50 parts by mass, more preferably 1 to 33.3 parts by mass, relative to 100 parts by mass of the organic film-forming composition.

[0077] The organic film-forming composition may contain an organic film-forming resin and a solvent, and may also contain other additives such as a crosslinking agent, an acid generator, and a surfactant.

[0078] The solvent that can be used in the organic film-forming composition is not particularly limited as long as it can dissolve the organic film-forming resin, and it is preferable that it can also dissolve the acid generator, crosslinking agent, surfactant, etc., which will be described later. Specific examples include ketones such as 2-heptanone, cyclopentanone, and cyclohexanone; 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, γ-butyrolactone, and propylene glycol mono-tert-butyl ether acetate. These may be used alone or in combination of two or more, but are not limited thereto.

[0079] Among these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, γ-butyrolactone, and mixtures of two or more of these are preferably used.

[0080] Usable solvents include those having a normal boiling point of 80°C or higher and lower than 160°C.

[0081] The amount of the solvent to be added is preferably 100 to 50,000 parts by mass, and more preferably 200 to 10,000 parts by mass, relative to 100 parts by mass of the resin for forming an organic film.

[0082] [Other ingredients] Furthermore, an acid generator, a crosslinking agent, or the like may be added to the organic film-forming composition in order to further promote the crosslinking reaction.

[0083] The acid generator may be one that generates an acid by thermal decomposition or one that generates an acid by light irradiation, and either one may be added. Specific examples of the acid generator include those described in paragraphs (0061) to (0085) of JP-A No. 2007-199653. The amount of the acid generator to be added is not particularly limited, but can be, for example, 0.05 to 50 parts by mass per 100 parts by mass of the resin for forming an organic film.

[0084] Specific examples of the crosslinking agent include those described in paragraphs (0055) to (0060) of JP-A No. 2007-199653. The amount of the crosslinking agent to be added is not particularly limited, but can be, for example, 1 to 50 parts by mass per 100 parts by mass of the resin for forming an organic film.

[0085] A surfactant may also be added to the organic film-forming composition to improve the coating properties during spin coating. Specific examples of surfactants include those described in paragraphs (0142) to (0147) of JP 2009-269953 A. The amount of surfactant to be added is not particularly limited, but can be, for example, 0.001 to 20 parts by mass per 100 parts by mass of the resin for forming an organic film.

[0086] Furthermore, a basic compound can be added to the organic film-forming composition to improve storage stability. The basic compound acts as an acid quencher to prevent a small amount of acid generated from 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.

[0087] [Coating solvent application process] In the organic film forming method of the present invention, after forming a coating film, a coating solvent having a normal boiling point of 160°C or more but less than 500°C is spin-coated onto the coating film before the insolubilization treatment. The method for applying the coating solvent is not particularly limited, and may be a known method using a spin coater or the like. Note that either static dispensing or dynamic dispensing can be used as the spin-coating method.

[0088] In the organic film-forming method of the present invention, the coating film before the insolubilization treatment dissolves in the coating solvent, allowing the resin component in the uncured coating film to acquire sufficient thermal fluidity, thereby forming a resist underlayer film with excellent filling and planarization properties. Therefore, it is necessary for the coating film before the insolubilization treatment to dissolve in the coating solvent. Specifically, assuming that the thickness of a coating film before the insolubilization treatment formed on a substrate without a patterned surface by spin-coating the organic film-forming composition is a, and the thickness of an organic film formed by spin-coating the coating film with the coating solvent and then heat-treating it at 100°C for 60 seconds is b, the upper limit of the ratio b / a is preferably 99.5% or less, more preferably 99% or less, and even more preferably 98% or less. The lower limit of the ratio b / a is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.

[0089] By dissolving the coating film before the insolubilization treatment in the coating solvent within the above range, the resin component contained in the coating film can obtain sufficient thermal fluidity. If the upper limit of the ratio b / a is 99.5% or less, the resin component contained in the coating film can obtain sufficient thermal fluidity, and if the lower limit of the ratio b / a is 30% or more, excessive thinning of the film can be suppressed, which is preferable from the viewpoint of saving resist.

[0090] The coating solvent is an organic solvent having a normal boiling point of 160° C. or higher and lower than 500° C., and is only required to be liquid when used in the coating solvent application step, and is preferably liquid at room temperature (25° C.). There are no particular restrictions on the alcohols, esters, ketones, carbonates, ethers, amides, chlorine-based solvents, etc., but from the viewpoint of compatibility with the coating film, alcohols, esters, ketones, carbonates, ethers, or combinations thereof are preferred. Specific examples of alcohols 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, and glycerin; and ethers include 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, and diethylene glycol monoisopropyl ether. isobutyl 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, 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;Esters include n-nonyl acetate, 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 methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol di Examples of suitable ketones include acetate, 1,6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, and dibutyl adipate; examples of suitable ketones include ethyl amyl ketone, dibutyl ketone, and diamyl ketone; and examples of suitable carbonates include ethylene carbonate and propylene carbonate. These may be used alone or in combination.

[0091] The normal boiling point of the coating solvent must be 160°C or higher but lower than 500°C, and may be 180°C or higher, preferably 200°C or higher but lower than 400°C. If the boiling point is outside this range, the resin component in the uncured coating film will not be able to obtain sufficient thermal fluidity, making it impossible to form a resist underlayer film with excellent filling / planarization properties. Furthermore, if the boiling point is within this range, the solvent will not volatilize and remain in the film after the insolubilization treatment, which will not adversely affect film properties such as etching resistance.

[0092] The coating solvent may be the same as or different from the organic solvent contained in the coating film (derived from the organic solvent contained in the organic film-forming composition), but preferably has a higher standard boiling point than the standard boiling point of the organic solvent contained in the coating film. Such a coating solvent is less likely to volatilize than the organic solvent contained in the coating film, so that the resin component in the uncured coating film exhibits favorable thermal fluidity during the insolubilization treatment, allowing the formation of a film with better filling / planarization properties.

[0093] In consideration of solubility and wettability in the organic film, aromatic compounds having a benzyl group or a benzoyl group are preferred.

[0094] In particular, the following aromatic compounds are preferred: (i) (Poly)ethylene glycol dibenzoate (ii) (Poly)ethylene glycol dibenzyl ether (iii) (Poly)propylene glycol dibenzyl ether (iv) (Poly)butylene glycol dibenzyl ether (v) Dibenzyl linear aliphatic dicarboxylate (vi) (Poly)ethylene glycol monobenzyl ether (vii) (Poly)phenyl ethers (viii) alkylbenzyl phthalate

[0095] [ka] In the above formula, n is an integer that gives a molecular weight in the range of 150 to 500, and is applied only within this formula.

[0096] There are no particular restrictions on the amount of coating solvent to be applied when coating the coating film, but it is preferably 0.5 ml to 20 ml, more preferably 1 ml to 15 ml, and even more preferably 1.5 ml to 10 ml.

[0097] [Organic film formation process] The organic film forming step is a step of forming an organic film by subjecting the coating film to an insolubilization treatment in the coating solvent following the coating solvent application step. In the organic film forming method of the present invention, the coating film before the insolubilization treatment is in an uncured or incompletely cured state, and the resin components in the coating film dissolve in the coating solvent, allowing the resin components in the uncured or incompletely cured coating film to acquire sufficient thermal fluidity. In contrast, the coating film after the insolubilization treatment is in a cured state, and the resin components in the coating film do not dissolve in the coating solvent and do not have thermal fluidity. In this way, the organic film is formed. As mentioned above, the method for applying the coating solvent is not particularly limited, and both static dispensing and dynamic dispensing can be used.

[0098] [Insolubilization treatment] In the organic film forming method of the present invention, after forming a coating film, the coating film is subjected to an insolubilization treatment in a coating solvent. The insolubilization treatment is not particularly limited as long as the resin component in the coating film is insoluble in the coating solvent. However, it is preferable to use any one of heat treatment at 100°C to 600°C, ultraviolet irradiation treatment (light treatment) with a wavelength of 400 nm or less, electron beam irradiation treatment (electron beam treatment), plasma irradiation treatment (plasma treatment), or a combination thereof. By performing the insolubilization treatment using such a means, an organic film that maintains a flat state can be formed.

[0099] [Heat treatment] The heat treatment is carried out at a temperature range of 100°C to 600°C, preferably 150°C to 550°C, and more preferably 180°C to 500°C, for 10 to 600 seconds, preferably 10 to 300 seconds. By appropriately adjusting the baking temperature and time within the above ranges, it is possible to obtain curing properties such as planarization and filling characteristics suitable for the application, as well as dry etching resistance and heat resistance. At a baking temperature of 100°C or higher, curing proceeds sufficiently and mixing with the resist top layer film or resist intermediate film does not occur. At a baking temperature of 600°C or lower, thermal decomposition of the base resin can be suppressed, the film thickness does not decrease, and the film surface becomes uniform.

[0100] The atmosphere during baking can be selected as needed, either an oxygen-containing atmosphere such as air (oxygen concentration 1% to 21%) or an oxygen-free atmosphere such as nitrogen. For example, if the substrate to be processed is susceptible to air oxidation, substrate damage can be suppressed by forming a hardened film by heat treatment in an atmosphere with an oxygen concentration of less than 1%. The unit is volume %.

[0101] [Light Processing] The exposure light used in the phototreatment is actinic radiation such as near ultraviolet, far ultraviolet, or extreme ultraviolet (e.g., EUV, wavelength 13.5 nm), and light with wavelengths of, for example, 248 nm (KrF laser light), 193 nm (ArF laser light), 172 nm (xenon excimer light), 157 nm (F2 laser light), etc. The exposure wavelength can be 400 nm or less, particularly ultraviolet light of 10 nm to 380 nm, with wavelengths of 10 to 200 nm being preferred.

[0102] This exposure causes crosslinking of the resin contained in the coating film. The exposure dose is 10 mJ / cm 2 ~10,000mJ / cm 2 The exposure amount within this range causes a photoreaction, crosslinking, and resistance to organic solvents.

[0103] [Electron beam processing] The electron beam irradiation can be carried out by a known method. For example, the method described in "Electron Beam Irradiation Device Technology and Its Use" (SEI Technical Review, July 2012, No. 181, pp. 50-57, non-patent document) can be mentioned. The acceleration voltage can be selected from 2 to 200 kV. The irradiation dose can be selected from 100 to 5,000 kGy. Electron beam irradiation is preferably performed while heating. In this case, the temperature can be selected from 80 to 800°C (preferably 200 to 700°C, more preferably 300 to 600°C). Ion irradiation can be performed by known methods. For example, the method described in "Raman spectroscopy and microhardness of ion-implanted aC:H-films" (Ceramics Int. 26(1), 2000, pp. 29-32, non-patent document) can be mentioned. One preferred embodiment of ion irradiation in the present invention is ion implantation. The elemental species of the ions to be irradiated include hydrogen, boron, carbon, nitrogen, and rare gases; preferably, boron, carbon, nitrogen, neon, argon, etc.; more preferably, carbon, nitrogen, etc. These gases may be used in combination of two or more. The acceleration voltage can be selected from 3 to 1000 kV. The acceleration voltage is more preferably 5 to 750 kV, and even more preferably 10 to 500 kV. The irradiation dose is 10 13 ~10 18 ion / cm 2 The irradiation dose can be selected from the following: 13 ~5×10 17 ion / cm 2 and more preferably 10 14 ~10 17 ion / cm 2 The ion irradiation can also be carried out while heating the inside of the chamber of the apparatus. In this case, a temperature of 500°C or less can be selected. When heating is carried out after plasma irradiation and electron beam irradiation, the heating conditions are appropriately selected from the ranges of a heating temperature of 80 to 800°C (preferably 200 to 700°C, more preferably 300 to 600°C) and a heating time of 30 to 180 seconds (preferably 30 to 120 seconds). Without being bound by theory, it is believed that high-temperature heating after plasma and electron beam irradiation can bond dangling bonds, contributing to the densification of the cured film.

[0104] As the irradiation device, Tactras Vigus, EB-ENGINE (Hamamatsu Photonics), and EXCEED2300AH (Nissin Ion Equipment) can be used. It is possible to select the device and set the conditions so as to achieve the effects of the present invention.

[0105] [Plasma treatment] The plasma irradiation can be performed by a known method, such as the method described in Japanese Patent No. 5746670, "Improvement of the wiggling profile of spin-on carbon hard mask by H2 plasma treatment" (J. Vac. Sci. Technol. B26 (1), January / February 2008, pp. 67-71).

[0106] The RF discharge power is preferably 100 to 10,000 W, and more preferably 500 to 5,000 W.

[0107] Examples of suitable gas atmospheres include rare gases such as N2, NF3, H2, and He, and fluorocarbons; more preferably, He, Ar, N2, Ne, NF3, H2, CF4, CHF3, CH2F2, CH3F, C4F6, and C4F8. Two or more of these gases may be mixed for use. An advantage of the present invention is that the effects of the present invention can be expected even when a gas atmosphere that does not contain O2 is used.

[0108] The plasma irradiation time can be selected from the range of, for example, 10 to 240 seconds, and the pressure can be selected appropriately.

[0109] The plasma irradiation is preferably carried out in an atmosphere of N2, NF3, H2, fluorocarbon, a rare gas such as He, or a mixture of any of these.

[0110] From the viewpoint of productivity, particularly preferred gas atmospheres include He, Ar, N2, and H2.

[0111] Heat treatment may be performed before or after plasma irradiation. When heating is performed before plasma irradiation, the heating conditions can be appropriately selected from the ranges of 80 to 400°C (preferably 100 to 350°C, more preferably 150 to 300°C) and 30 to 180 seconds (preferably 30 to 120 seconds). Heating before plasma irradiation can remove the coating solvent contained in the coating film. When heating is performed after plasma irradiation, the heating conditions can be appropriately selected from the ranges of 80 to 800°C (preferably 100 to 700°C, more preferably 200 to 600°C) and 30 to 180 seconds (preferably 30 to 120 seconds). Without being bound by theory, it is believed that high-temperature heating after plasma irradiation can bond dangling bonds and contribute to densifying the cured film (resist underlayer film).

[0112] The atmosphere in which the substrate is heated after plasma irradiation can be selected as needed from either an oxygen-containing atmosphere such as air (oxygen concentration 1% by volume to 21% by volume) or an oxygen-free atmosphere such as nitrogen (oxygen concentration less than 1% by volume). For example, if the substrate is susceptible to air oxidation, substrate damage can be suppressed by forming a cured film by heat treatment in an atmosphere with an oxygen concentration less than 1% by volume.

[0113] The irradiation device is not particularly limited as long as it is capable of irradiating plasma, and for example, Telius SP and Tactras Vigus manufactured by Tokyo Electron Ltd. can be used. The device can be selected and the conditions can be set so that the effects of the present invention can be more pronounced.

[0114] Through the above-described steps, an insolubilized organic film can be formed on a substrate having a pattern of protrusions and recesses. The thickness of the organic film is appropriately selected depending on the depth of the pattern, but is preferably 10 to 20,000 nm, and more preferably 20 to 15,000 nm.

[0115] When the organic film thus formed is applied to a multilayer resist process, an inorganic hard mask such as a silicon-containing resist intermediate film, a silicon-free resist top layer (single-layer resist film), a silicon oxide film, a silicon nitride film, a silicon oxynitride film, an amorphous silicon film, or a titanium nitride film can be formed thereon. Furthermore, since the substrate can be highly planarized without using CMP, which is a costly process, the substrate can be planarized at low cost.

[0116] <Method of manufacturing a substrate for a semiconductor device> The present invention provides a method for manufacturing a substrate for a semiconductor device, which includes forming an organic film on a substrate having a concave-convex pattern by the above-mentioned method for forming an organic film of the present invention, forming a silicon-containing resist intermediate film on the organic film using a silicon-containing composition for forming a resist intermediate film, forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask, transferring the pattern to the organic film by dry etching using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern to the substrate by dry etching using the organic film on which the pattern has been transferred as a mask.

[0117] The substrate used in the method for manufacturing a substrate for a semiconductor device of the present invention preferably includes a metal film, a metal carbide film, a metal oxide film, a metal nitride film, or a metal oxynitride film.

[0118] The metal constituting the substrate is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0119] In the method for manufacturing a substrate for a semiconductor device, the organic film can also be used as a sacrificial film.

[0120] The substrate having the concave-convex pattern preferably has an open area (non-pattern area) and DENSE and ISO pattern areas, and the aspect ratio of the pattern is preferably 0.1 to 10. In addition, the bias (coating step) between the open area and the pattern area is preferably 1 to 100 nm.

[0121] As for the organic film-forming composition, it is preferable to use a composition containing a resin containing an aromatic ring, as described above. For 193 nm exposure, using a material containing many aromatic groups and having high substrate etching resistance can result in a high k value and high substrate reflection, but by suppressing reflection with a silicon-containing resist intermediate film, substrate reflection can be reduced to 0.5% or less. Furthermore, for extreme ultraviolet (EUV) exposure, using an organic film material containing many aromatic groups and having high substrate etching resistance makes it possible to form fine patterns.

[0122] As the silicon-containing resist intermediate film, a polysiloxane-based coating film is preferably used. By providing this silicon-containing resist intermediate film with the effect of an anti-reflection film, reflection can be suppressed. Specifically, silicon-containing resist intermediate films obtained from compositions disclosed in JP-A Nos. 2004-310019, 2007-302873, and 2009-126940 can be mentioned.

[0123] The photoresist composition for forming the resist upper layer film may be either positive or negative, and the same photoresist composition as commonly used can be used. When forming the resist upper layer film using the photoresist composition, a spin coating method is preferably used, as in the case of forming the organic film. After spin coating the photoresist composition, pre-baking is performed, preferably at 60 to 180°C for 10 to 300 seconds. Thereafter, exposure, post-exposure baking (PEB), and development are performed according to a conventional method to obtain a resist pattern (circuit pattern). The thickness of the resist upper layer film is not particularly limited, but is preferably 30 to 500 nm, more preferably 50 to 400 nm.

[0124] In forming the circuit pattern, it is preferable to form the circuit pattern by any one of lithography using high-energy rays with a wavelength of 10 nm or more and 300 nm or less, direct writing using an electron beam, and nanoimprinting, or a combination of these.

[0125] Examples of exposure light include high-energy rays with wavelengths of 300 nm or less, specifically excimer lasers of 248 nm, 193 nm, and 157 nm, soft X-rays of 3 to 20 nm, so-called EUV light, electron beams, and X-rays.

[0126] In forming the circuit pattern, it is preferable to develop the circuit pattern by alkaline development or development using an organic solvent.

[0127] Next, etching is performed using the obtained resist pattern as a mask. Dry etching of the silicon-containing resist intermediate film can be performed using, for example, a chlorofluorocarbon-based gas, with the resist pattern as a mask. Next, dry etching of the organic film can be performed using, for example, oxygen gas or hydrogen gas, with the silicon-containing resist intermediate film pattern (the silicon-containing resist intermediate film with the pattern transferred thereto) as a mask.

[0128] The next step, etching of the substrate, can also be carried out using standard methods. For example, if the substrate is made of SiO2, SiN, or a silica-based low-dielectric-constant insulating film, etching can be carried out using primarily fluorocarbon-based gases, and if the substrate is p-Si, Al, or W, etching can be carried out using primarily chlorine- or bromine-based gases, thereby transferring the pattern to the substrate.

[0129] An organic antireflective coating (BARC) may be formed on the silicon-containing resist intermediate film, and a resist upper layer film may be formed thereon. That is, the present invention provides a method for manufacturing a substrate for a semiconductor device, which includes forming an organic film on a substrate having a concave-convex pattern by the organic film forming method of the present invention, forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film forming composition, forming an organic antireflective film on the silicon-containing resist intermediate film, and forming a resist upper layer film on the organic antireflective film using a photoresist composition to form a four-layer resist film, forming a circuit pattern on the resist upper layer film, using the resist upper layer film on which the pattern has been formed as a mask to transfer the pattern to the organic antireflective film and the silicon-containing resist intermediate film by dry etching, using the organic antireflective film and the silicon-containing resist intermediate film on which the pattern has been transferred as a mask to transfer the pattern to the organic film by dry etching, and further using the organic film on which the pattern has been transferred as a mask to transfer the pattern to the substrate by dry etching.

[0130] This method can be carried out in the same manner as the method for manufacturing a substrate for a semiconductor device using the above-mentioned silicon-containing resist interlayer film, except that an organic antireflective film is formed on the silicon-containing resist interlayer film. The organic antireflective film is not particularly limited, and any known organic antireflective film can be used, and can be formed by a known method such as spin coating.

[0131] Furthermore, an inorganic hard mask such as a silicon oxide film, a silicon nitride film, a silicon oxynitride film, an amorphous silicon film, or a titanium nitride film can be formed on the organic film. That is, the present invention provides a method for manufacturing a substrate for a semiconductor device, which includes forming an organic film on a substrate having a concave-convex pattern by the above-mentioned organic film forming method of the present invention, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, an amorphous silicon film, and a titanium nitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the inorganic hard mask by dry etching using the resist upper layer film on which the pattern has been formed as a mask, transferring the pattern to an organic film by dry etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the substrate by dry etching using the organic film on which the pattern has been transferred as a mask.

[0132] The inorganic hard mask is preferably formed by a CVD method or an ALD method.

[0133] Etching of the inorganic hard mask can be carried out using, for example, a chlorofluorocarbon-based gas, with the resist pattern as a mask. Then, dry etching of the organic film can be carried out using oxygen gas or hydrogen gas, with the inorganic hard mask pattern as a mask. This can be carried out in the same manner as in the method for producing a substrate for a semiconductor device using the silicon-containing resist interlayer, except that an inorganic hard mask is formed on the organic film instead of the silicon-containing resist interlayer.

[0134] Alternatively, a multilayer resist film or an organic antireflective film consisting of an organic film and a silicon-containing resist intermediate film may be formed on the inorganic hard mask. That is, the present invention provides a method for manufacturing a substrate for a semiconductor device, comprising: forming an organic film on a substrate having a concave-convex pattern by the organic film-forming method of the present invention; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, an amorphous silicon film, and a titanium nitride film on the organic film; forming a multilayer resist film or an organic antireflective film consisting of an organic film and a silicon-containing resist intermediate film on the inorganic hard mask; forming a resist upper layer film on the multilayer resist film or the organic antireflective film using a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the multilayer resist film or the organic antireflective film using the resist upper layer film having the pattern formed as a mask; transferring the pattern to the inorganic hard mask by dry etching using the pattern-transferred inorganic hard mask as a mask; transferring the pattern to an organic film formed on the substrate by dry etching using the pattern-transferred inorganic hard mask as a mask; and further transferring the pattern to the substrate by dry etching using the pattern-transferred organic film as a mask.

[0135] When an inorganic hard mask such as a silicon oxide film, silicon nitride film, silicon oxynitride film, amorphous silicon film, or titanium nitride film is used, the combination of the inorganic hard mask and BARC makes it possible to suppress reflection even in immersion lithography with a high NA exceeding 1.0. Another advantage of forming a BARC is that it widens the process margin directly above the inorganic hard mask.

[0136] This method can be performed in the same manner as the method for manufacturing a substrate for a semiconductor device using the inorganic hard mask, except that a multilayer resist film or an organic anti-reflective film composed of an organic film and a silicon-containing resist intermediate film is formed on the inorganic hard mask.

[0137] As described above, the organic film formed by the method of the present invention has excellent planarization properties, and therefore, by using this organic film in combination with various film materials in a multilayer resist process, such as a two-layer resist process, a three-layer resist process using a silicon-containing resist intermediate film, or a four-layer resist process using a silicon-containing resist intermediate film and an organic anti-reflective film, the pattern of the upper-layer photoresist (resist upper-layer film) can be transferred to the substrate with high precision, thereby forming a pattern on the substrate. In other words, the method of manufacturing a substrate for a semiconductor device of the present invention makes it possible to manufacture a substrate for a semiconductor device with high precision. [Example]

[0138] The present invention will be explained in more detail below by showing synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited to these.

[0139] [Preparation of Organic Film-Forming Compositions (UDL-1 to UDL-6)] The organic film-forming resins (B1) to (B6) and the solvent (C-1) used in the preparation of the organic film-forming composition are shown below.

[0140] [Organic film forming resin] B1: Resin represented by the following formula (B-1) B2: Resin represented by the following formula (B-2) B3: Resin represented by the following formula (B-3) B4: Resin represented by the following formula (B-4) B5: Resin represented by the following formula (B-5) B6: Resin represented by the following formula (B-6)

[0141] [ka]

[0142] [solvent] C-1: Propylene glycol monomethyl ether acetate (boiling point: 146°C)

[0143] The organic film-forming resins (B1) to (B6) were dissolved in a solvent (C-1) containing 0.5% by mass of FC-4430 (manufactured by Sumitomo 3M Limited) in the proportions shown in Table 1, and the resulting solution was filtered through a 0.1 μm fluororesin filter to prepare organic film materials (organic film-forming compositions: UDL-1 to 6). The numbers in the table indicate parts by mass.

[0144] [Table 1]

[0145] (A) Coating solvents (A-1) to (A-5) and comparative organic solvent (R-1) are shown below. [Table 2]

[0146] [Evaluation of Solubility in Organic Solvents: Examples 1-1 to 1-9, Comparative Examples 1-1 to 1-2] The organic film-forming compositions (UDL-1 to 6) were applied to silicon substrates without a concave-convex pattern and baked under the baking conditions listed in Table 3. The film thickness was then measured from the center to the periphery of the substrate, and the average film thickness (a [nm]) was calculated. Next, the coating solvent (A) listed in Table 3 was dispensed onto the substrate, left for 30 seconds, spin-dried, and baked at 100°C for 60 seconds to evaporate the coating solvent, and the film thickness (b [nm]) was measured. The difference in film thickness before and after the coating solvent treatment (residual film ratio: (b / a) × 100) was calculated. [Table 3]

[0147] As shown in Table 3, in Examples 1-1 to 1-9, after forming a coating film, a coating solvent having a normal boiling point of 160°C or more and less than 500°C was spin-coated onto the coating film before the insolubilization treatment. As a result, the film thickness was reduced after the insolubilization treatment, and it was observed that a portion of the coating film was dissolved in each coating solvent. On the other hand, in Comparative Example 1-2, almost no change in film thickness was observed before and after application of the coating solvent. This indicates that the resin in the coating film (organic polymer (B-1) in UDL-1) is insoluble in the coating solvent (A-5). In this Comparative Example, the film thickness after application of the coating solvent is slightly thicker than the film thickness before application of the coating solvent. This is presumably because the coating solvent remained in the coating film and thickened it because the film was not baked at a temperature sufficiently high relative to the boiling point of the coating solvent.

[0148] [Planarization Property Evaluation: Examples 2-1 to 2-10, Comparative Examples 2-1 to 2-8] [Pattern A] Each of the organic film-forming compositions (UDL-1 to UDL-6) was applied to a base substrate 5 (SiO2 wafer substrate) having a large isolated trench pattern (Figure 3(A), trench width 10 μm, trench depth 0.10 μm) and baked under the conditions listed in Table 4. After that, each coating solvent was applied to the organic film by spin coating and treated with the insolubilization treatment method listed in Table 4. The step (delta 7 in Figure 3(B)) between the trench and non-trench portions of the insolubilized coating film (organic film) 6 was observed using a Park Systems NX10 atomic force microscope (AFM). The results are shown in Table 4. In this evaluation (flatness A), the smaller the step, the better the planarization characteristics. In this evaluation, a 0.10 μm-deep trench pattern was planarized by forming an organic film with a typical thickness of approximately 0.2 μm using the organic film-forming composition. This required special, strict evaluation conditions to evaluate the superiority or inferiority of the planarization characteristics.

[0149] [Pattern B] Each of the organic film-forming compositions (UDL-1 to UDL-6) was applied to a base substrate 8 (SiO2 wafer substrate) having a dense line and space pattern (Figure 4(A), line width 60 nm, line depth 100 nm, distance between the centers of adjacent two lines 120 nm). The substrate was baked under the conditions listed in Table 4. Each coating solvent was then applied to the organic film by spin coating and treated with the insolubilization treatment method listed in Table 4. The cross-sectional shape of each wafer substrate was observed using a scanning electron microscope (SEM). The step Delta 10 between the dense line pattern area and the non-line pattern area of ​​the insolubilized coating film (filler film) 9 was observed using a Hitachi electron microscope (S-4700). The results are shown in Table 4. In this evaluation (flatness B), the smaller the step, the better the flatness.

[0150] Additional processing conditions (plasma processing) Plasma treatment was carried out using a Telius etching system manufactured by Tokyo Electron under the following conditions. Plasma treatment conditions Chamber pressure: 100mT RF power (top): 100W RF power (bottom): 3500W H2 gas flow rate: 200sccm Time: 20sec

[0151] [Table 4]

[0152] As shown in Table 4, it was confirmed that Examples 2-1 to 2-10, which used the organic film forming method of the present invention, exhibited superior planarization properties in both Pattern A and Pattern B compared to Comparative Examples 2-1 and 2-4 to 2-8, which used the conventional organic film forming method (which did not include a step of spin-coating a coating solvent having a normal boiling point of 160°C or higher and lower than 500°C onto the coating film before the insolubilization treatment). Among them, Examples 2-4, 2-5, and 2-7 to 2-9, which used aromatic-containing compounds (A-4) and (A-5) having a benzyl group or a benzoyl group as the coating solvent, showed excellent planarization properties. On the other hand, the organic film formation method (Comparative Example 2-2) including the step of spin-coating an organic solvent having a boiling point of less than 160°C onto the coating film did not provide sufficient improvement in flatness compared to the conventional organic film formation method. Also, in the organic film formation method (Comparative Example 2-3) in which no change in film thickness was observed before and after the coating solvent treatment in the solvent resistance evaluation of Example 1, the coating solvent was unable to dissolve the coating film and provide sufficient thermal fluidity to the resin component in the uncured coating film, so no improvement in flatness compared to the conventional organic film formation method was observed.

[0153] In the organic film-forming method of the present invention, the coating film before the insolubilization treatment dissolves in the coating solvent, and the resin component in the uncured coating film can acquire sufficient thermal fluidity, which is thought to enable the formation of a resist underlayer film with excellent filling / planarization properties. For this reason, it is preferable that the coating film before the insolubilization treatment dissolves in the coating solvent. From the results of Examples 1 and 2, it can be said that, when the thickness of the coating film before the insolubilization treatment formed by spin-coating using an organic film-forming composition is a, and the thickness of the organic film formed by spin-coating the coating solvent onto the coating film and then heat-treating it at 100°C for 60 seconds is b, the ratio of b / a is preferably 99.5% or less.

[0154] The present specification includes the following aspects. [1]: A method for forming an organic film on a substrate having a concave-convex pattern, a step of spin-coating a composition for forming an organic film on the substrate to form a coating film; A step of spin-coating a coating solvent having a normal boiling point of 160°C or higher and lower than 500°C, which can dissolve the coating film, onto the coating film; The organic film forming method includes a step of forming an organic film by subjecting the coating film to an insolubilization treatment in the coating solvent. [2]: The method for forming an organic film according to [1], characterized in that the insolubilization treatment is one of a heat treatment at 100°C or higher and 600°C or lower, an ultraviolet irradiation treatment having a wavelength of 400 nm or less, an electron beam irradiation treatment, and a plasma irradiation treatment, or a combination thereof. [3]: The organic film forming method according to [1] or [2], wherein the coating solvent is an alcohol, an ester, a ketone, a carbonate, an ether, or a combination thereof. [4]: The organic film forming method according to any one of [1] to [3], wherein the coating solvent is an aromatic-containing compound having a benzyl group or a benzoyl group. [5]: The method for forming an organic film according to any one of [1] to [4], wherein a composition containing a resin containing one or more aromatic rings is used as the composition for forming an organic film. [6]: A method for manufacturing a substrate for a semiconductor device, comprising: forming an organic film on a substrate having a concave-convex pattern by any one of methods [1] to [5]; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing composition for forming a resist intermediate film; forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; transferring the pattern to the organic film by dry etching using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; and further transferring the pattern to the substrate by dry etching using the organic film on which the pattern has been transferred as a mask. [7]: A method for manufacturing a substrate for a semiconductor device, comprising: forming an organic film on a substrate having a concave-convex pattern by any one of methods [1] to [5]; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing composition for forming a resist intermediate film; forming an organic antireflective film on the silicon-containing resist intermediate film; forming a resist upper layer film on the organic antireflective film using a photoresist composition to form a four-layer resist film; forming a circuit pattern on the resist upper layer film; transferring the pattern to the organic antireflective film and the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; transferring the pattern to the organic film by dry etching using the organic antireflective film and the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; and further transferring the pattern to the substrate by dry etching using the organic film on which the pattern has been transferred as a mask. [8]: A method for manufacturing a substrate for a semiconductor device, comprising: forming an organic film on a substrate having a pattern of protrusions and recesses by any one of methods [1] to [5]; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, an amorphous silicon film, and a titanium nitride film on the organic film; forming a resist upper layer film on the inorganic hard mask using a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the inorganic hard mask by dry etching using the resist upper layer film on which the pattern has been formed as a mask; transferring the pattern to an organic film by dry etching using the inorganic hard mask on which the pattern has been transferred as a mask; and further transferring the pattern to the substrate by dry etching using the organic film on which the pattern has been transferred as a mask. [9]: A method for manufacturing a substrate for a semiconductor device, comprising: forming an organic film on a substrate having a pattern of protrusions and recesses by any one of methods [1] to [5]; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, an amorphous silicon film, and a titanium nitride film on the organic film; forming a multilayer resist film or an organic antireflective film consisting of an organic film and a silicon-containing resist intermediate film on the inorganic hard mask; forming a resist upper layer film on the multilayer resist film or the organic antireflective film using a photoresist composition; forming a circuit pattern on the resist upper layer film; using the resist upper layer film on which the pattern has been formed as a mask to transfer the pattern to the multilayer resist film or the organic antireflective film, and then transferring the pattern to the inorganic hard mask by dry etching; using the inorganic hard mask on which the pattern has been transferred as a mask to transfer the pattern to an organic film formed on the substrate by dry etching; and further using the organic film on which the pattern has been transferred as a mask to transfer the pattern to the substrate by dry etching.

[10] : The method for manufacturing a substrate for a semiconductor device according to [8] or [9], wherein the inorganic hard mask is formed by a CVD method or an ALD method.

[11] : The method for manufacturing a substrate for a semiconductor device according to any one of [6] to

[10] , characterized in that in forming the circuit pattern, the circuit pattern is formed by one of lithography using high-energy rays having a wavelength of 10 nm or more and 300 nm or less, direct writing using an electron beam, and nanoimprinting, or a combination of these.

[12] : The method for manufacturing a substrate for a semiconductor device according to any one of [6] to

[11] , wherein in forming the circuit pattern, the circuit pattern is developed by alkaline development or development using an organic solvent.

[0155] 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]

[0156] 1...substrate, 2...coating film, 3...coating solvent, 4...coating film after insolubilization treatment, 5...substrate having pattern A, 6...insolubilized coating film, Delta7: Step between the patterned portion and the non-patterned portion of the insolubilized coating film 6 8...substrate having pattern B, 9...insolubilized coating film, Delta 10: Step difference between the patterned portion and the non-patterned portion of the insolubilized coating film 9.

Claims

1. A method for forming an organic film on a substrate having a relief pattern, comprising: a step of spin-coating a composition for forming an organic film on the substrate to form a coating film; A step of spin-coating a coating solvent having a normal boiling point of 160°C or higher and lower than 500°C, which can dissolve the coating film, onto the coating film; The organic film forming method includes a step of forming an organic film by subjecting the coating film to an insolubilization treatment in the coating solvent.

2. 2. The method for forming an organic film according to claim 1, wherein the insolubilization treatment is one of a heat treatment at 100°C or higher and 600°C or lower, an ultraviolet irradiation treatment having a wavelength of 400 nm or less, an electron beam irradiation treatment, and a plasma irradiation treatment, or a combination thereof.

3. 2. The method for forming an organic film according to claim 1, wherein the coating solvent is selected from the group consisting of alcohols, esters, ketones, carbonates, ethers, and combinations thereof.

4. 2. The method for forming an organic film according to claim 1, wherein the coating solvent is an aromatic compound having a benzyl group or a benzoyl group.

5. 2. The method for forming an organic film according to claim 1, wherein the composition for forming an organic film includes a resin containing one or more aromatic rings.

6. 10. A method for manufacturing a substrate for a semiconductor device, comprising: forming an organic film on a substrate having a concave-convex pattern by the method of claim 1; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing composition for forming a resist intermediate film; forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; transferring the pattern to the organic film by dry etching using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; and further transferring the pattern to the substrate by dry etching using the organic film on which the pattern has been transferred as a mask.

7. 10. A method for manufacturing a substrate for a semiconductor device, comprising: forming an organic film on a substrate having a concave-convex pattern by the method of claim 1; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing composition for forming a resist intermediate film; forming an organic antireflective film on the silicon-containing resist intermediate film; forming a resist upper layer film on the organic antireflective film using a photoresist composition to form a four-layer resist film; forming a circuit pattern on the resist upper layer film; transferring the pattern to the organic antireflective film and the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; transferring the pattern to the organic film by dry etching using the organic antireflective film and the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; and further transferring the pattern to the substrate by dry etching using the organic film on which the pattern has been transferred as a mask.

8. 10. A method for manufacturing a substrate for a semiconductor device, comprising: forming an organic film on a substrate having a pattern of protrusions and recesses by the method of claim 1; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, an amorphous silicon film, and a titanium nitride film on the organic film; forming a resist upper layer film on the inorganic hard mask using a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the inorganic hard mask by dry etching using the resist upper layer film on which the pattern has been formed as a mask; transferring the pattern to an organic film by dry etching using the inorganic hard mask on which the pattern has been transferred as a mask; and further transferring the pattern to the substrate by dry etching using the organic film on which the pattern has been transferred as a mask.

9. 10. A method for manufacturing a substrate for a semiconductor device, comprising: forming an organic film on a substrate having a pattern of protrusions and recesses by the method of claim 1; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film, an amorphous silicon film, and a titanium nitride film on the organic film; forming a multilayer resist film or an organic antireflective film consisting of an organic film and a silicon-containing resist intermediate film on the inorganic hard mask; forming a resist upper layer film on the multilayer resist film or the organic antireflective film using a photoresist composition; forming a circuit pattern on the resist upper layer film; using the resist upper layer film on which the pattern has been formed as a mask to transfer the pattern to the multilayer resist film or the organic antireflective film, and then transferring the pattern to the inorganic hard mask by dry etching; using the inorganic hard mask on which the pattern has been transferred as a mask to transfer the pattern to an organic film formed on the substrate by dry etching; and further using the organic film on which the pattern has been transferred as a mask to transfer the pattern to the substrate by dry etching.

10. 10. The method for manufacturing a substrate for a semiconductor device according to claim 8, wherein the inorganic hard mask is formed by a CVD method or an ALD method.

11. 10. The method for manufacturing a substrate for a semiconductor device according to claim 6, wherein the circuit pattern is formed by one of lithography using a high-energy beam having a wavelength of 10 nm or more and 300 nm or less, direct writing using an electron beam, and nanoimprinting, or a combination thereof.

12. 10. The method for manufacturing a substrate for a semiconductor device according to claim 6, wherein the circuit pattern is developed by alkaline development or organic solvent development in forming the circuit pattern.

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