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

Abstract

To provide: a composition capable of forming an organic film which is excellent in film formability on a substrate, filling properties and hump suppression and has an excellent process margin when used as an organic film for a multilayer resist.SOLUTION: A composition for forming an organic film contains: (A) a material for forming an organic film; (B) an aryl benzyl ether compound containing a partial structure represented by the general formula (B1) in the figure; and (C) a solvent. In the formula, R1 represents a benzyl substituent having a specific structure containing a fluorine atom or a trifluoromethoxy group on a benzene ring.SELECTED DRAWING: Figure 2

Description

Technical Field

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

Background Art

[0002] In recent years, with the high integration and high speed of semiconductor elements, miniaturization of pattern rules has been demanded. Among them, in lithography using optical exposure, which is currently a general-purpose technology, various technical developments have been carried out on how to perform finer and more accurate pattern processing with respect to the light source used.

[0003] As a light source for lithography used in forming a resist pattern, in parts with low integration, optical exposure using the g-line (436 nm) or i-line (365 nm) of a mercury lamp as a light source is widely used. On the other hand, in parts where high integration and miniaturization are required, lithography using a KrF excimer laser (248 nm) or an ArF excimer laser (193 nm) with a shorter wavelength has also been put into practical use, and in the most advanced generation where further miniaturization is required, lithography using extreme ultraviolet light (EUV, 13.5 nm) is also approaching practical use.

[0004] As the line width of the resist pattern is reduced in this way, in the single-layer resist method, which is a typical resist pattern formation method, the ratio of the pattern height to the pattern line width (aspect ratio) increases, and it is well known that pattern collapse occurs due to the surface tension of the developer during development. Therefore, in order to form a pattern with a high aspect ratio on a stepped substrate, it is known that a multilayer resist method in which films with different dry etching characteristics are laminated to form a pattern is excellent. A two-layer resist method (Patent Document 1) that combines a photoresist layer (resist upper layer film) made of a silicon-containing photosensitive polymer and a resist lower layer film made of an organic polymer mainly composed of carbon, hydrogen, and oxygen, such as a novolak-based polymer, or a three-layer resist method (Patent Document 2) that combines a photoresist layer made of an organic photosensitive polymer used in the single-layer resist method, a resist intermediate film made of a silicon-based polymer or a silicon-based CVD film, and a resist lower layer film made of an organic polymer have been developed.

[0005] In this three-layer resist method, for example, an organic film such as novolak is uniformly formed as a resist lower layer film on a substrate to be processed, a silicon-containing resist intermediate film is formed as a resist intermediate film thereon, and a normal organic photoresist film is formed as a resist upper layer film thereon. For dry etching with a fluorine-based gas plasma, the organic resist upper layer film has a good etching selectivity with respect to the silicon-containing resist intermediate film, so the resist pattern is transferred to the silicon-containing resist intermediate film by using dry etching with a fluorine-based gas plasma. According to this method, even if a resist composition that is difficult to form a pattern with a sufficient film thickness for directly processing the substrate to be processed or a resist composition that does not have sufficient dry etching resistance for processing the substrate is used, the pattern can be transferred to the silicon-containing resist intermediate film. Subsequently, if pattern transfer using dry etching with an oxygen-based gas plasma is performed, a pattern of an organic film (for example, a resist lower layer film such as a novolak film) having sufficient dry etching resistance for processing can be obtained.

[0006] Although a number of techniques for such an organic film (organic underlayer film) are already known (for example, Patent Document 3), with the recent progress in miniaturization, in addition to dry etching characteristics, the need for excellent embedding characteristics has been increasing. There is a need for an organic film material that can form a uniform film even on a substrate to be processed with a complex shape or material and has an embedding property that can fill the inside of a required pattern without voids.

[0007] An organic film as described above is formed using a coater / developer capable of performing processes such as a spin coating process, an EBR process, and a baking process when manufacturing a semiconductor substrate or the like. The EBR (Edge Bead Removal) process is a process of removing the coating film at the edge of a substrate with a removal liquid for the purpose of preventing contamination of the substrate transfer arm of the coater / developer after forming a coating film on the substrate (wafer) by spin coating. As the removal liquid used in the EBR process, for example, there is a mixed liquid of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30% by mass: 70% by mass), and such a removal liquid is widely used in the EBR process of a resist upper layer film and a resist lower layer film (silicon-containing resist intermediate film, organic film).

[0008] Due to the influence of the remover in the EBR process, a state where the outer peripheral portion of the organic film has a thick film thickness (hump) may be formed. In the dry etching process during the above-mentioned substrate processing, since the hump causes defects, an organic film with suppressed hump is required.

[0009] Furthermore, after forming a spin-coated film, the organic film is baked to form a cured film for use in a multilayer resist process. This is because it is necessary to form an insoluble and infusible organic film for applying a silicon-containing resist intermediate film on the upper layer. The surface of the organic film formed by the baking process has a hydrophobic surface caused by the surfactant contained in the organic film-forming composition, which may induce abnormal coating of the silicon-containing resist intermediate film. Control of the contact angle of the surface of the organic film is required to improve the coatability of the silicon-containing resist intermediate film and widen the process margin.

Prior Art Documents

Patent Document

[0010]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0011] The present invention has been made in view of the above circumstances, and is excellent in film-forming properties (in-plane uniformity) and embedding characteristics on a substrate (wafer), and is excellent in hump suppression during the EBR process. Furthermore, an object of the present invention is to provide an organic film-forming composition capable of forming an organic film excellent in process margin when used as an organic film for a multilayer resist, and an organic film-forming method and a pattern-forming method using this composition.

Means for Solving the Problems

[0012] In order to solve the above problems, the present invention provides an organic film-forming composition comprising: (A) a material for forming an organic film; (B) an aryl benzyl ether compound containing a partial structure represented by the following general formula (B1) but not containing a partial structure represented by the following general formula (B0); (C) a solvent and is characterized by providing an organic film-forming composition.

Chemical Formula

[0013] For such a composition for forming an organic film, it is possible to form an organic film that is excellent in in-plane uniformity and embedding characteristics and in which the formation of humps due to the influence of the remover in the EBR process is suppressed. Further, since the phenolic hydroxyl group is modified with a structure as represented by the above formula (B2), the hydrophobic components unevenly distributed on the surface of the organic film are thermally decomposed at the benzyl position by baking during the formation of the cured film, and phenolic hydroxyl groups are generated. As a result, since the contact angle of the surface of the organic film can be lowered, it becomes a composition for forming an organic film on which an intermediate film, for example, a silicon-containing intermediate film, can be formed with excellent coatability. That is, according to the composition for forming an organic film of the present invention, it is possible to form an organic film that is excellent in film-forming properties and embedding characteristics on a substrate, excellent in hump suppression during the EBR process, and further excellent in process margin when used as an organic film for a multilayer resist.

[0014] In the present invention, it is preferable that the (B) aryl benzyl ether compound is a compound represented by the following general formulas (B3), (B4), (B6), (B8), (B10), or (B11). [Chemical formula] (In the formula, R1 is one or two kinds of fluorine-containing groups represented by the formula (B2), R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R3 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a1 is 0 or 1, when a1 is 0, b1 is 1 to 5, c1 is 0 to 4, when a1 is 1, b1 is 1 to 7, and c1 is 0 to 6.) [Chemical formula] (In the formula, R1 is one or two kinds of fluorine-containing groups represented by the formula (B2), R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R4 is a single bond or any one of the groups represented by the following formula (B5), R5 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a2 is 0 or 1, when a2 is 0, b2 is 1 to 5, c2 is 0 to 4, when a2 is 1, b2 is 1 to 7, and c2 is 0 to 6.) [Chemical formula] [Chemical formula] (In the formula, R1 is one or two kinds of fluorine-containing groups represented by the formula (B2), R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R6 is a group represented by the following formula (B7), R7 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a3 is 0 or 1, when a3 is 0, b3 is 1 to 5, c3 is 0 to 4, when a3 is 1, b3 is 1 to 7, and c3 is 0 to 6.) [Chemical formula] [Chemical formula] (In the formula, R1 is one or two kinds of fluorine-containing groups represented by the formula (B2), W1 is a group represented by the following formula (B9), a4 is 0 or 1, b4 is 1 or 2, and d4 is 1 to 4.)

Chemical formula

Chemical formula

Chemical formula

[0015] For an organic film-forming composition containing such an (B) aryl benzyl ether compound, by having an appropriate fluorine content, the film-forming property during coating can be improved, and the decomposition products generated during baking do not impair the in-plane uniformity of the film, and insoluble components are not formed due to the reaction between the decomposition products. Therefore, when used for forming an organic film, the process margin is not narrowed, and device contamination and inconveniences do not occur either.

[0016] Also, it is preferable that the weight average molecular weight of the (B) aryl benzyl ether compound is 1000 to 30000.

[0017] Within such a range of the weight average molecular weight, it is possible to form an organic film with excellent film-forming property and embedding characteristics.

[0018] Further, with respect to 100 parts by mass of the content of the material for forming the organic film (A), the content of the aryl benzyl ether compound (B) is preferably from 0.01 part by mass to 5 parts by mass.

[0019] An organic film-forming composition containing the aryl benzyl ether compound (B) having such a content is preferable because the in-plane uniformity of the formed organic film is more excellent.

[0020] Further, the present invention provides a method for forming an organic film used in a manufacturing process of a semiconductor device, spin-coating the organic film-forming composition of the present invention on a substrate to be processed to obtain a coating film, and heat-treating the coating film at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to cure it, thereby forming an organic film.

[0021] The organic film-forming composition of the present invention can fill a complex-shaped pattern on a substrate to be processed by spin-coating and form an organic film having excellent in-plane uniformity, and is particularly useful when removing the organic film at the edge while suppressing humps in the EBR process. Therefore, according to the organic film-forming method of the present invention, excellent film-forming properties, excellent embedding properties, excellent hump suppression properties during the EBR process, and further, an organic film having excellent process margin when used as an organic film for a multilayer resist can be formed.

[0022] Further, the present invention provides a patterning method, forming an organic film on a workpiece using the organic film-forming composition of the present invention, forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, forming a resist upper layer film on the silicon-containing resist intermediate film using a resist upper layer film material composed of a photoresist composition, forming a circuit pattern on the resist upper layer film, and transferring the pattern to the silicon-containing resist intermediate film by etching using the resist upper layer film on which the circuit pattern is formed as a mask, Using the silicon-containing resist intermediate film onto which the pattern has been transferred as a mask, transfer the pattern to the organic film by etching, Furthermore, provided is a pattern formation method characterized by forming a pattern on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0023] Also, in the present invention, there is provided a pattern formation method, Form an organic film on the workpiece using the composition for forming an organic film of the present invention, Form a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, and form an organic antireflection film or an adhesion film on the silicon-containing resist intermediate film, Form a resist upper layer film on the organic antireflection film or the adhesion film using a resist upper layer film material composed of a photoresist composition, and form a circuit pattern on the resist upper layer film, Using the resist upper layer film on which the circuit pattern has been formed as a mask, transfer the pattern to the organic antireflection film or the adhesion film and the silicon-containing resist intermediate film by etching, Using the silicon-containing resist intermediate film onto which the pattern has been transferred as a mask, transfer the pattern to the organic film by etching, Furthermore, provided is a pattern formation method characterized by forming a pattern on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0024] Also, in the present invention, there is provided a pattern formation method, Form an organic film on the workpiece using the composition for forming an organic film of the present invention, Form an inorganic hard mask selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, Form a resist upper layer film on the inorganic hard mask using a resist upper layer film material composed of a photoresist composition, Form a circuit pattern on the resist upper layer film, Using the resist upper layer film on which the circuit pattern has been formed as a mask, transfer the pattern to the inorganic hard mask by etching, Using the inorganic hard mask onto which the pattern has been transferred as a mask, transfer the pattern to the organic film by etching, Furthermore, provided is a pattern formation method characterized by forming a pattern on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0025] Also, in the present invention, there is provided a pattern formation method, Form an organic film on the workpiece using the composition for forming an organic film of the present invention, Form an inorganic hard mask selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, Form an organic antireflection film or an adhesion film on the inorganic hard mask, and form a resist upper layer film on the organic antireflection film or the adhesion film using a resist upper layer film material composed of a photoresist composition, Form a circuit pattern on the resist upper layer film, Using the resist upper layer film on which the circuit pattern has been formed as a mask, transfer the pattern to the organic antireflection film or the adhesion film and the inorganic hard mask by etching, Using the inorganic hard mask onto which the pattern has been transferred as a mask, transfer the pattern to the organic film by etching, Furthermore, provided is a pattern formation method characterized by forming a pattern on the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0026] Thus, the composition for forming an organic film of the present invention can be suitably used in various pattern formation methods such as a three-layer resist process using a silicon-containing resist intermediate film or an inorganic hard mask, and a four-layer resist process using an organic antireflection film or an adhesion film in addition to these. With such a pattern formation method of the present invention, the circuit pattern of the resist upper layer film can be transferred and formed on the workpiece with high precision.

[0027] Also, it is preferable to form the inorganic hard mask by a CVD method or an ALD method.

[0028] In the pattern formation method of the present invention, an inorganic hard mask can be formed by such a method, for example.

[0029] In addition, in the formation of the circuit pattern, it is preferable to form the circuit pattern by lithography using light with a wavelength of 10 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination thereof.

[0030] In addition, in the formation of the circuit pattern, it is preferable to develop the circuit pattern with an alkali developer or an organic solvent.

[0031] In the pattern formation method of the present invention, such means for forming a circuit pattern and means for development can be preferably used.

[0032] In addition, it is preferable that the workpiece is a semiconductor device substrate or a substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film is formed on the semiconductor device substrate.

[0033] In this case, as the workpiece, it is preferable to use one in which the metal constituting the workpiece is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0034] In the pattern formation method of the present invention, a pattern can be formed by processing the workpiece as described above.

Advantages of the Invention

[0035] As described above, according to the present invention, there can be provided a composition for forming an organic film which is excellent in film-forming properties (in-plane uniformity) and embedding properties on a substrate (wafer), and is excellent in film-forming properties of an intermediate film on the organic film and in hump suppression properties during the EBR process when used as an organic film. Further, since the composition for forming an organic film of the present invention is excellent in film-forming properties, embedding properties, and hump suppression properties generated during the EBR process, for example, it is extremely useful as an organic film material used 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 an inorganic hard mask, or a four-layer resist process using a silicon-containing resist intermediate film or an inorganic hard mask and an organic antireflection film or an adhesion film, or as a material for forming an organic film for manufacturing a semiconductor device. Further, according to the method for forming an organic film of the present invention, since an organic film with humps suppressed can be formed, semiconductor elements and the like can be efficiently manufactured. Further, the aryl benzyl ether compound contained in the composition for forming an organic film of the present invention has a thermally decomposable aryl benzyl ether structure and exhibits the above characteristics by having a specific fluorine substituent, and thus is useful for the composition for forming an organic film.

Brief Description of the Drawings

[0036]

Figure 1

Figure 2

Figure 3

Figure 4

Embodiments for Carrying Out the Invention

[0037] As described above, there has been a demand for the development of a composition for forming an organic film that is excellent in film-forming properties (in-plane uniformity) and embedding characteristics on a substrate (wafer) and suppresses humps during the EBR process.

[0038] Generally, when forming an organic film, a resin for forming an organic film and additives are dissolved in an organic solvent to form a composition, which is applied onto a substrate on which a structure, wiring, etc. are formed using a coater and a developer. The composition is spread by rotating the substrate, the composition at the end is removed in the EBR process, and then an organic film is formed by firing.

[0039] When the fluidity of the above composition is insufficient, voids are generated when filling holes or trenches with a very high aspect ratio, and when the resin for forming an organic film and additives are inferior in solubility to the remover used in the EBR process, humps are considered to occur on the outer periphery of the organic film.

[0040] As a result of further intensive studies on the above problems, the present inventors have found that by blending a thermally decomposable compound having a specific repeating unit into a composition for forming an organic film, excellent film-forming properties and high embedding characteristics can be achieved simultaneously, and a composition for forming an organic film excellent in hump suppression during the EBR process can be provided, thus completing the present invention.

[0041] That is, the present invention is a composition for forming an organic film, (A) a material for forming an organic film, (B) an arylbenzyl ether compound containing a partial structure represented by the following general formula (B1) but not containing a partial structure represented by the following general formula (B0), (C) a solvent and is characterized by comprising the same.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0042] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0043] [Composition for forming organic film] The composition for forming an organic film of the present invention is (A) a material for forming an organic film, (B) an aryl benzyl ether compound containing a partial structure represented by the following general formula (B1) but not containing a partial structure represented by the following general formula (B0), (C) a solvent and contains them.

Chemical formula

[0044] In the composition for forming an organic film of the present invention, as the (B) aryl benzyl ether compound, the (A) material for forming an organic film, and the (C) solvent, each may be used alone or in combination of two or more.

[0045] Hereinafter, among the constituent components of the above composition for forming an organic film, first, the (B) aryl benzyl ether compound which is a feature of the present invention will be described, and then the above material for forming an organic film, solvent, and other components will be described.

[0046] [(B) Aryl benzyl ether compound] Component (B) in the composition for forming an organic film of the present invention is a compound that contains a partial structure represented by the above general formula (B1) but does not contain a partial structure represented by the above general formula (B0). By blending this compound into the composition for forming an organic film, it becomes useful for forming an organic film.

[0047] The (B) aryl benzyl ether compound of the present invention is a compound containing an aryl benzyl ether structure containing a fluorine atom. In the coating film formed by the (A) material for forming an organic film described later and the composition for forming an organic film containing such a (B) aryl benzyl ether compound, it is difficult for hamping to occur during the EBR process. Further, by introducing a substituent containing an appropriate fluorine atom such as the above formula (B2), it is possible to impart a function as a surfactant having the ability to lower the surface tension and providing excellent uniform coatability (leveling property) of the organic film. Therefore, when the (B) aryl benzyl ether compound of the present invention is used as a surfactant, it can be used not only for organic films but also for coating materials for photolithography in general. Specifically, photosensitive resist materials, materials for forming a top coat formed on a resist film, etc. can be exemplified. Further, the aryl benzyl ether structure incorporated in the (B) aryl benzyl ether compound is decomposed at the benzyl position by heat or the like. Since the phenolic hydroxyl group generated at this time can lower the contact angle of the organic film surface, it becomes a composition for forming an organic film capable of improving the coatability when an intermediate film, for example, a silicon-containing intermediate film is coated thereon. That is, as described above, the (B) aryl benzyl ether compound of the present invention has the characteristics of having thermal decomposability and being able to function as a surfactant.

[0048] That is, according to the composition for forming an organic film of the present invention containing (A) a material for forming an organic film and (B) an aryl benzyl ether compound, it is excellent in film-forming properties and embedding characteristics on a substrate, excellent in suppressing humps during the EBR process, and further, an organic film excellent in process margin when used as an organic film for a multilayer resist can be formed. For example, by using the composition for forming an organic film of the present invention, an organic film excellent for a multilayer resist for fine processing in the manufacture of semiconductor devices and the like or an organic film excellent for planarization in the manufacture of semiconductor devices and the like can be formed.

[0049] It is preferable that the (B) aryl benzyl ether compound is a compound represented by the following general formulas (B3), (B4), (B6), (B8), (B10), or (B11).

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0050] For an organic film-forming composition containing such a compound, by having an appropriate fluorine content, the film-forming property during coating can be improved, and the decomposition products generated during baking do not impair the in-plane uniformity of the film, nor are insoluble components formed due to reactions between the decomposition products. Therefore, without narrowing the process margin when used as an organic film, there will be no equipment contamination or inconvenience.

[0051] In the above general formulas (B1), (B3), (B4), and (B6), examples of the saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms represented by R2 include monovalent saturated hydrocarbon groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, sec-pentyl group, and tert-pentyl group; monovalent unsaturated chain hydrocarbon groups such as ethenyl group, propenyl group, butenyl group, pentenyl group, ethynyl group, and propynyl group; monocyclic saturated cyclic hydrocarbon groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group; monovalent monocyclic unsaturated cyclic hydrocarbon groups such as cyclobutenyl group, cyclopentenyl group, and cyclohexenyl group; monovalent polycyclic cyclic hydrocarbon groups such as norbornyl group and adamantyl group; and monovalent aromatic hydrocarbon groups such as phenyl group, methylphenyl group, naphthyl group, methylnaphthyl group, anthryl group, and methylanthryl group.

[0052] Other examples of the organic group represented by R2 include alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, and n-hexyloxy group; and alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, and n-hexyloxycarbonyl group.

[0053] Some or all of the hydrogen atoms of the organic groups such as the above-mentioned saturated hydrocarbon group, unsaturated chain hydrocarbon group, monocyclic saturated cyclic hydrocarbon group, monocyclic unsaturated cyclic hydrocarbon group, polycyclic cyclic hydrocarbon group, aromatic hydrocarbon group, alkoxy group, and alkoxycarbonyl group may be substituted. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, hydroxyl group, cyano group, carboxy group, nitro group, amino group, alkoxy group, alkoxycarbonyl group, acyl group, alkoxycarbonyloxy group, aryl group, aliphatic heterocyclic group such as lactone group, and aromatic heterocyclic group such as furyl group and pyridyl group.

[0054] From the viewpoint of raw material availability, the organic group represented by the above R2 preferably includes a methyl group.

[0055] In the above general formulas (B3), (B4) and (B6), examples of the saturated or unsaturated divalent organic group having 1 to 30 carbon atoms represented by R3, R5 or R7 include alkane diyl groups such as methylene group, ethanediyl group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, octanediyl group, and decanediyl group, monocyclic cycloalkane diyl groups such as cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cycloheptanediyl group, cyclooctanediyl group, cyclodecanediyl group, methylcyclohexanediyl group, and ethylcyclohexanediyl group, polycyclic cycloalkane diyl groups such as bicyclo[2.2.1]heptane diyl group, bicyclo[2.2.2]octane diyl group, tricyclo[5.2.1.0 2,6 decane diyl group (dicyclopentylene group), tricyclo[3.3.1.1 3,7 decane diyl group, tetracyclo[6.2.1.1 3,6 .0 2,7 dodecane diyl group, and adamantane diyl group, and arene diyl groups such as phenylene group and naphthylene group.

[0056] Examples of the alkanediyl-oxy group represented by R3, R5 or R7 include a group formed by combining the above alkanediyl group and an oxygen atom. Examples of the cycloalkanediyl-oxy group represented by R3, R5 or R7 include a group formed by combining the above cycloalkanediyl group and an oxygen atom.

[0057] Some or all of the hydrogen atoms of the above alkanediyl group, cycloalkanediyl group, alkanediyl-oxy group, cycloalkanediyl-oxy group and arenediyl group may be substituted, and examples of the substituent include the same groups as the examples of the substituent that the organic group represented by R2 may have.

[0058] Examples of the organic group represented by R3, R5 or R7 include a group represented by the following formula.

Chemical formula

[0059] From the viewpoint of raw material availability, R3, R5, and R7 preferably include a methylene group.

[0060] W2 is a single bond or an organic group having 1 to 50 carbon atoms, and examples thereof include a group represented by the following formula.

Chemical formula

[0061] Specific examples of the compound represented by the general formula (B3) include, but are not limited to, the following. In the following examples, R1 is one or two of the fluorine-containing groups represented by the above formula (B2).

[0062]

Chemical formula

[0063] Examples of the compound represented by the general formula (B4) include, but are not limited to, the following. In the following examples, R1 is one or two kinds of fluorine-containing groups represented by the above formula (B2).

[0064]

Chemical formula

[0065] Examples of the compound represented by the general formula (B6) include, but are not limited to, the following. In the following examples, R1 is one or two kinds of fluorine-containing groups represented by the above formula (B2).

[0066]

Chemical formula

[0067] Examples of the compound represented by the general formula (B8) include, but are not limited to, the following. In the following examples, R1 is one or two kinds of fluorine-containing groups represented by the above formula (B2).

[0068]

Chemical formula

[0069]

Chemical formula

[0070]

Chemical formula

[0071] Examples of the compound represented by the general formula (B10) include, but are not limited to, the following. In the following examples, R1 is one or two kinds of fluorine-containing groups represented by the above formula (B2).

[0072] [Chemical formula]

[0073] As the compound represented by the general formula (B11), specifically, the following can be exemplified, but are not limited thereto. In the following exemplification, R1 is one or two kinds of fluorine-containing groups represented by the above formula (B2).

[0074] [Chemical formula]

[0075] If it has the above structure, the thermal decomposability, surface activity effect, and fluidity of the polymer can be adjusted, and it becomes a compound that can more surely achieve both film-forming properties and embedding properties.

[0076] The weight average molecular weight of the (B) aryl benzyl ether compound is preferably 1,000 to 30,000, and more preferably 1,500 to 25,000. If the weight average molecular weight is 1,000 or more, a decrease in the compounding effect due to volatilization or the like can be suppressed, and a sufficient compounding effect can be obtained. Further, if the weight average molecular weight is 30,000 or less, the fluidity does not deteriorate, etc., and the embedding characteristics are excellent.

[0077] In the present invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) are polystyrene conversion values by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent (solvent), and the dispersity (Mw / Mn) is obtained from Mw and Mn.

[0078] [Manufacturing method of (B) aryl benzyl ether compound] As a means for obtaining the (B) aryl benzyl ether compound of the present invention, although not limited, for example, the synthesis by a substitution reaction of b-valent phenols or naphthols with pentafluorobenzyl halide, 2-(trifluoromethoxy)benzyl halide, 3-(trifluoromethoxy)benzyl halide, or 4-(trifluoromethoxy)benzyl halide using a base catalyst as shown below can be mentioned. The b-valent phenols or naphthols, and pentafluorobenzyl halide, 2-(trifluoromethoxy)benzyl halide, 3-(trifluoromethoxy)benzyl halide, or 4-(trifluoromethoxy)benzyl halide used in this synthesis can be used alone or in combination of two or more. These can be appropriately selected and combined according to the required properties. R1, R2, a, b, and c in the following formula are the same as above, and X is a CI atom, a Br atom, or an I atom.

[0079] [Chemical formula]

[0080] Examples of the base catalyst used at this time include inorganic base compounds such as sodium hydrogen carbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, and potassium phosphate, and organic amine compounds such as triethylamine, pyridine, and N-methylmorpholine. These may be used alone or in combination of two or more. The usage amount of these catalysts is preferably in the range of 0.1 to 20 moles, more preferably 0.2 to 10 moles, per 1 mole of the hydroxyl group of the b-valent phenols or naphthols as the raw material.

[0081] The solvent used at this time is not particularly limited as long as it is inert to the above reaction. For example, ether solvents such as diethyl ether, tetrahydrofuran, and dioxane, aromatic solvents such as benzene, toluene, and xylene, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, water, etc. These can be used alone or in combination. These solvents can be used, for example, in the range of 0 to 2000 parts by mass relative to 100 parts by mass of the reaction raw material. The reaction temperature is preferably from -50°C to about the boiling point of the solvent, and more preferably from room temperature to 150°C. The reaction time is appropriately selected from 0.1 to 100 hours.

[0082] As reaction methods, there are methods such as charging phenols or naphthols and pentafluorobenzyl halide, 2-(trifluoromethoxy)benzyl halide, 3-(trifluoromethoxy)benzyl halide, or 4-(trifluoromethoxy)benzyl halide all at once in a solvent; dispersing or dissolving each of phenols or naphthols and pentafluorobenzyl halide, 2-(trifluoromethoxy)benzyl halide, 3-(trifluoromethoxy)benzyl halide, or 4-(trifluoromethoxy)benzyl halide in separate solvents and charging them dropwise; dispersing or dissolving either one of phenols or naphthols and pentafluorobenzyl halide, 2-(trifluoromethoxy)benzyl halide, 3-(trifluoromethoxy)benzyl halide, or 4-(trifluoromethoxy)benzyl halide in a solvent and then dropping and charging the other one dispersed or dissolved in a solvent. Also, when charging a plurality of types of phenols or naphthols and pentafluorobenzyl halide, 2-(trifluoromethoxy)benzyl halide, 3-(trifluoromethoxy)benzyl halide, or 4-(trifluoromethoxy)benzyl halide respectively, they may be mixed and reacted in advance, or can be reacted sequentially individually. When using a base catalyst, there are methods such as charging phenols or naphthols and pentafluorobenzyl halide, 2-(trifluoromethoxy)benzyl halide, 3-(trifluoromethoxy)benzyl halide, or 4-(trifluoromethoxy)benzyl halide all at once; dropping after previously dispersing or dissolving the base catalyst.

[0083] In order to remove unreacted raw materials, catalysts, etc. present in the system, the reaction solution obtained by the methods described with examples above can be diluted with an organic solvent, and then liquid separation washing is performed to recover (B) the aryl benzyl ether compound.

[0084] As the organic solvent used for liquid separation washing, there is no particular limitation as long as it can dissolve the compound and separate into two layers when mixed with water. Examples include hydrocarbons such as hexane, heptane, benzene, toluene, and xylene; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and methyl isobutyl ketone; ethers such as diethyl ether, diisopropyl ether, methyl-tert-butyl ether, and ethyl cyclopentyl methyl ether; chlorinated solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene; and mixtures thereof. As the washing water used at this time, usually, what is called deionized water or ultrapure water may be used. The number of washing times may be 1 or more, but even if washed 10 or more times, the effect of just washing may not be obtained. Therefore, it is preferably about 1 to 5 times.

[0085] During liquid separation washing, in order to remove unreacted raw materials or acidic components in the system, washing with a basic aqueous solution may be performed. Specific examples of the base include hydroxides of alkali metals, carbonates of alkali metals, hydroxides of alkaline earth metals, carbonates of alkaline earth metals, ammonia, and organic ammonium.

[0086] Furthermore, during liquid separation washing, in order to remove unreacted raw materials, metal impurities, or basic components in the system, washing with an acidic aqueous solution may be performed. Specific examples of the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropolyacid; and organic acids such as oxalic acid, fumaric acid, maleic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

[0087] The liquid separation washing with the above basic aqueous solution or acidic aqueous solution may be performed only with either one, but it can also be performed in combination. From the viewpoint of removing metal impurities, it is preferable to perform the liquid separation washing in the order of the basic aqueous solution and then the acidic aqueous solution.

[0088] After liquid separation and washing with the above basic aqueous solution and acidic aqueous solution, subsequent washing with neutral water may be performed. As the neutral water, deionized water, ultrapure water, etc. described above may be used. The number of washing times may be 1 or more, but if the number is small, the basic component and acidic component may not be removed. Even if washing is performed 10 or more times, the effect of just washing may not always be obtained, so preferably it is about 1 to 5 times.

[0089] Furthermore, the reaction product after the liquid separation operation can be recovered as a powder by concentrating and drying or crystallizing the solvent under reduced pressure or normal pressure, but for improving the operability when preparing the material for forming an organic film, it is also possible to keep it in a solution state with an appropriate concentration. The concentration at this time is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass. With such a concentration, the viscosity is less likely to increase, so it is possible to prevent the impairment of operability, and also, since the amount of the solvent does not become excessive, it is economical.

[0090] The solvent at this time is not particularly limited as long as it can dissolve the compound. Specific examples include ketones such as cyclohexanone and methyl-2-amyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; and ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate. These can be used alone or in a mixture of two or more.

[0091] For the above reaction, phenols or naphthols can be combined with pentafluorobenzyl halide, 2-(trifluoromethoxy)benzyl halide, 3-(trifluoromethoxy)benzyl halide, or 4-(trifluoromethoxy)benzyl halide according to the required performance. For example, fluorine-containing substituents such as those for controlling surface tension and changing interfacial activity performance can be arbitrarily combined. Therefore, when an organic film-forming composition using these compounds is used for an organic film, various performances such as film-forming property and embedding property can be achieved simultaneously at a high level.

[0092] [(A) Material for forming organic film] As the (A) material for forming an organic film (resin or compound) used in the organic film-forming composition of the present invention, there is no particular limitation as long as it is a resin or compound that satisfies the film-forming property and curability of spin coating. However, from the viewpoints of etching resistance, optical properties, heat resistance, etc., a resin or compound containing an aromatic skeleton (different from the (B) arylbenzyl ether compound) is more preferable.

[0093] Examples of the above aromatic skeleton include benzene, naphthalene, anthracene, pyrene, indene, fluorene, furan, pyrrole, thiophene, phosphole, pyrazole, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, and carbazole. Among these, benzene, naphthalene, fluorene, and carbazole are particularly preferable.

[0094] Hereinafter, specific examples of the above (A) material for forming an organic film will be given and described, but these are merely examples and are not limited thereto. Also, the formula numbers shown in the following examples are applicable only for the explanation of the following formulas.

[0095] Examples of the (A) material for forming an organic film (resin or compound) used in the present invention include resins containing the following structures described in JP-A-2012-001687 and JP-A-2012-077295.

[0096]

Chem.

[0097]

Chem.

[0098] Examples of the material (A) for forming an organic film used in the present invention include resins containing the following structures described in JP-A-2004-264710, JP-A-2005-043471, JP-A-2005-250434, JP-A-2007-293294, and JP-A-2008-065303.

[0099]

Chem.

[0100]

Chem.

[0101]

Chemical formula

[0102]

Chemical formula

[0103] As the material for forming the organic film (A) used in the present invention, specifically, resins containing the following structures described in JP-A-2004-205685, JP-A-2007-171895, and JP-A-2009-014816 can be further exemplified.

[0104]

Chemical formula

[0105]

Chemical formula

[0106]

Chemical formula

[0107] Examples of the resin represented by formula (11) include the following resins.

[0108]

Chemical formula

[0109]

Chemical formula

[0110] Examples of the material (A) for forming an organic film used in the present invention further include resins containing the following structures described in JP-A-2007-199653, JP-A-2008-274250, and JP-A-2010-122656.

[0111]

Chemical formula

[0112]

Chemical formula

[0113] [Chemical formula] (In formula (14), ring Z 1 and ring Z 2 are fused polycyclic aromatic hydrocarbon rings, and R 1a , R 1b , R 2a , and R 2b represent substituents which may be the same or different. k1 and k2 may be the same or different and represent 0 or an integer from 1 to 4, m1 and m2 each represent 0 or an integer of 1 or more, and n1 and n2 each represent 0 or an integer of 1 or more. However, n1 + n2 ≥ 1. Note that the definitions of the symbols in the formula apply only within this formula.)

[0114] [Chemical formula] (In formula (15), R 1 and R 2 are the same or different and are a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. R 3 and R 4 are each independently a hydrogen atom or a glycidyl group, R 5 is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, and R 6 and R 7 are each independently a benzene ring or a naphthalene ring. p and q are each 1 or 2. 0 < n ≤ 1. Note that the definitions of the symbols in the formula apply only within this formula.)

[0115] Examples of the resin represented by formula (15) include the following resins.

[0116] [Chemical formula]

[0117] [Chemical formula]

[0118]

Chem.

[0119]

Chem.

[0120] Examples of the material (A) for forming an organic film used in the present invention further include resins containing the following structures described in JP-A-2012-214720.

[0121]

Chem.

[0122] Examples of the material (A) for forming an organic film used in the present invention further include resins described in JP-A-2014-29435.

[0123]

Chem.

[0124] In addition, as the material for forming the organic film (A) used in the present invention, a polymer containing a unit structure represented by the following formula (18) and a unit structure represented by the following formula (19) described in International Publication No. 2012 / 077640 can be further exemplified, and the ratio of the unit structure represented by formula (18) to the unit structure represented by formula (19) is 3 to 97:97 to 3 in molar ratio.

[0125]

Chemical formula

[0126]

Chemical formula

[0127] As the material (A) for forming an organic film used in the present invention, a polymer containing a unit structure represented by the following formula (20) described in International Publication No. 2010 / 147155 can be further exemplified.

[0128] [Chemical formula] (In formula (20), R1 and R2 are each independently selected from the group consisting of a hydrogen atom, a halogen group, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and 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 or the aryl group represents a group which may contain an ether bond, a ketone bond or an ester bond; R4 represents an aryl group having 6 to 40 carbon atoms or a heterocyclic group 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 having 6 to 40 carbon atoms or a heterocyclic group which may be substituted with a halogen group, a nitro group, an amino group or a hydroxy group, and R4 and R5 may together form a ring with the carbon atom to which they are attached; n1 and n2 are each an integer from 1 to 3. Note that the definitions of the symbols in the formula are applicable only within this formula.)

[0129] Examples of the (A) organic film-forming material used in the present invention further include novolak resins obtained by reacting one or more of phenols such as phenol, cresol, xylenol, catechol, resorcinol, hydroquinone, pyrogallol, hydroxyquinol, phloroglucinol with one or more of aldehyde sources such as formaldehyde, paraformaldehyde, and trioxane using an acidic catalyst, resins containing a repeating unit structure represented by the following formula (21) described in International Publication No. 2012 / 176767, and the like.

[0130] [Chemical formula] (In formula (21), A represents a hydroxy group-substituted phenylene group derived from polyhydroxybenzene, and B represents a monovalent condensed aromatic hydrocarbon ring group in which 2 to 6 benzene rings are condensed. Note that the definitions of the symbols in the formula are applicable only within this formula.)

[0131] Examples of the (A) organic film-forming material used in the present invention further include novolak resins having a fluorene or tetrahydrospirobiindene structure described in JP-A-2005-128509, JP-A-2006-259249, JP-A-2006-259482, JP-A-2006-293298, and JP-A-2007-316282, and resins containing a repeating unit structure represented by the following formula (22-1) or (22-2).

[0132] [Chemical formula] (In formula (22-1) and formula (22-2), R 1 , R 2 , R 6 and R 7 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an allyl group or a halogen atom, and R 3 , R 4 , R 8 and R 9 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms or a glycidyl group, and R 5 and R 14 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. n, m, p and q are integers from 1 to 3. R 10 ~R 13Each independently represents 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 definitions of the symbols in the formula are applicable only within this formula.)

[0133] Examples of the material (A) for forming an organic film used in the present invention include a reaction product obtained by the method described in JP-A-2012-145897. More specifically, examples include polymers obtained by condensing one or more compounds represented by the following general formula (23-1) and / or (23-2) with one or more compounds represented by the following general formula (24-1) and / or (24-2) and / or their equivalents.)

[0134] [Chemical formula] (In general formula (23-1) and general formula (23-2), R 1 ~R 8 each independently represents 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. Further, two substituents each arbitrarily selected from R 1 ~R 4 or R 5 ~R 8 may be bonded to form a cyclic substituent. Note that the definitions of the symbols in the formula are applicable only within this formula.)

[0135] [Chemical formula] (In general formulas (24-1) and (24-2), Q is an optionally substituted organic group having 1 to 30 carbon atoms, and further, two Q's arbitrarily selected within the molecule may be bonded to form a cyclic substituent. n1 to n6 are the numbers of each substituent, n1 to n6 are 0, 1, or 2, and in formula (24-1), hydroxybenzaldehyde is excluded. In formula (24-2), the relationships of 0≦n3 + n5≦3, 0≦n4 + n6≦4, and 1≦n3 + n4≦4 are satisfied. Note that the definitions of the symbols in the formula are applicable only within this formula.)

[0136] In addition, examples of the polymer obtained by condensing one or more compounds represented by the above general formula (23-1) and / or (23-2), one or more compounds represented by the above general formula (24-1) and / or (24-2) and / or their equivalents, and one or more compounds represented by the following general formula (25) and / or their equivalents can be given.

[0137]

Chemical formula

[0138] Examples of the material (A) for forming an organic film used in the present invention further include compounds containing the following structure described in JP-A-2017-119671.

[0139]

Chemical formula

[0140]

Chemical formula

[0141]

Chemical formula

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

[0143]

Chemical formula

[0144] Examples of the material (A) for forming an organic film used in the present invention further include a polymer having a repeating unit represented by the following general formula (27-1) described in JP-A-2019-044022.

[0145]

Chemical formula

[0146] [Chemical formula] (In formula (27-3), R 3 is either a single bond or a divalent organic group having 1 to 20 carbon atoms, R 4 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and the dashed line indicates a bond. The definitions of the symbols in the formula are applicable only within this formula.)

[0147] Examples of the polymer having the repeating unit represented by the above general formula (27-1) include the following polymers.

[0148] [Chemical formula]

[0149] [Chemical formula]

[0150] (A) The material for forming the organic film may be synthesized by a known method or a commercially available product may be used.

[0151] The blending amount of the above-mentioned (A) organic film-forming material is not particularly limited as long as the film-forming property of the spin coating of the organic film-forming composition is satisfied. However, taking the organic film-forming composition as 100 parts by mass, the content of the (A) organic film-forming material is preferably 10 to 40 parts by mass, more preferably 10 to 30 parts by mass, and still more preferably 10 to 25 parts by mass. For example, when filling holes or trenches with a very high aspect ratio in a 3D NAND memory architecture with the organic film-forming composition, it is necessary to increase the blending amount of the organic film-forming material. On the other hand, such organic film-forming compositions have a high viscosity, and the in-plane uniformity and embedding characteristics after spin coating deteriorate. Even with the above blending ratio of the (A) organic film-forming material, the organic film-forming composition of the present invention can preferably be applied because it can form an organic film excellent in in-plane uniformity and embedding characteristics.

[0152] Further, with respect to 100 parts by mass of the above-mentioned (A) organic film-forming material, the content of the (B) aryl benzyl ether compound is preferably from 0.01 part by mass to 5 parts by mass. If it is an organic film-forming composition containing the (B) aryl benzyl ether compound with such a content, the in-plane uniformity of the formed organic film is more excellent.

[0153] [(C) Solvent] As the (C) solvent that can be used in the organic film-forming material of the present invention, there is no particular limitation as long as it can dissolve the above-mentioned (A) organic film-forming material and the above-mentioned (B) aryl benzyl ether compound, and it is preferable that it can also dissolve an acid generator, a crosslinking agent, a further surfactant, etc. described later. Specifically, solvents with a boiling point of less than 180°C such as the solvents described in paragraphs (0091) to (0092) of JP-A No. 2007-199653 can be used. Among them, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and mixtures of two or more of these are preferably used.

[0154] (C) The content of the solvent is preferably 200 to 10,000 parts by mass, more preferably 300 to 5,000 parts by mass, with respect to 100 parts by mass of the organic film-forming material (A). By setting it within such a range, the concentration can be adjusted according to the thickness of the film that is consumed.

[0155] Furthermore, as the organic solvent which is the solvent (C) in the material for forming an organic film of the present invention, it is also possible to add a high-boiling solvent having a boiling point of 180°C or higher to the solvent having a boiling point of less than 180°C (a mixture of a solvent having a boiling point of less than 180°C and a solvent having a boiling point of 180°C or higher). As the high-boiling organic solvent, there are no particular restrictions as long as it can dissolve the (A) material for forming an organic film and the (B) aryl benzyl ether compound, and specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3 - hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, n - nonyl acetate, ethylene glycol monohexyl ether, ethylene glycol mono - 2 - ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono - n - butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol - n - butyl ether, triethylene glycol butyl methyl ether, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono - n - propyl ether, dipropylene glycol mono - n - butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono - n - propyl ether, tripropylene glycol mono - n - butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl - n - propyl ether, dipropylene glycol methyl ether acetate, 1,4 - butanediol diacetate, 1,3 - butylene glycol diacetate, 1,Examples thereof include 6 - hexanediol diacetate, triethylene glycol diacetate, γ - butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, etc., and these may be used alone or in combination.

[0156] Regarding the above, the boiling point of the high - boiling solvent may be appropriately selected according to the temperature for heat - treating the material for forming the organic film. The boiling point of the added high - boiling solvent is preferably 180°C to 300°C, and more preferably 200°C to 300°C. With such a boiling point, there is no fear that the volatilization during baking (heat - treatment) is too fast due to the boiling point being too low, so sufficient heat fluidity can be obtained. Also, with such a boiling point, since the boiling point is high, it will not remain in the film without volatilizing after baking, so there is no fear of adversely affecting the film physical properties such as etching resistance.

[0157] Also, when using the above high - boiling solvent, the blending amount of the high - boiling solvent is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the solvent having a boiling point of less than 180°C. With such a blending amount, sufficient heat fluidity can be imparted during baking, and there is no fear of remaining in the film and leading to deterioration of film physical properties such as etching resistance.

[0158] For such a composition for forming an organic film, by adding a high - boiling solvent to the above - mentioned (A) material for forming an organic film, heat fluidity is imparted, resulting in a composition for forming an organic film having both high - level embedding and excellent planarization characteristics.

[0159] [Other Components] In addition, an acid generator or a cross - linking agent for further promoting the cross - linking reaction can be added to the composition for forming an organic film of the present invention.

[0160] As the acid generator, there are those that generate acid by thermal decomposition and those that generate acid by light irradiation, and any of them can be added. Specifically, examples of the acid generator include those described in paragraphs

[0061] to

[0085] of JP-A-2007-199653. The above acid generator can be used alone or in combination of two or more. When adding the acid generator, the addition amount is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the organic film-forming material (A). With such an amount, it becomes possible to promote the crosslinking reaction and form a dense film.

[0161] Also, as the crosslinking agent, specifically, examples include those described in paragraphs

[0055] to

[0060] of JP-A-2007-199653. The crosslinking agent can be used alone or in combination of two or more. The addition amount of the crosslinking agent is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the organic film-forming material (A). With such an amount, it becomes possible to enhance the curability and further suppress the intermixing with the upper layer film.

[0162] In addition, in the organic film-forming composition of the present invention, in order to further improve the in-plane uniformity in spin coating, a further surfactant other than the (B) aryl benzyl ether compound of the present invention can be added. Specifically, examples of the further surfactant include those described in paragraphs

[0142] to

[0147] of JP-A-2009-269953. The above further surfactant can be used alone or in combination of two or more. When adding the further surfactant, the addition amount is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the organic film-forming material. With such an amount, it becomes possible to form an organic film with excellent in-plane uniformity.

[0163] Furthermore, a basic compound for improving storage stability can be added to the composition for forming an organic film of the present invention. The basic compound serves as a quencher for an acid to prevent the acid generated in a trace amount from the acid generator from promoting the crosslinking reaction. Specific examples of such a basic compound include those described in paragraphs

[0086] to

[0090] of JP-A-2007-199653. The above basic compound can be used alone or in combination of two or more. When adding an acid generator, the addition amount is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the material for forming an organic film (A). With such an amount, it becomes possible to improve the storage stability of the composition for forming an organic film.

[0164] As described above, the composition for forming an organic film of the present invention becomes a composition for forming an organic film excellent in hump suppression property during the EBR process. Therefore, the composition for forming an organic film of the present invention is extremely useful as a resist underlayer film material (organic film material) for 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 silicon-containing inorganic hard mask intermediate film, or a four-layer resist process using a silicon-containing resist intermediate film or a silicon-containing inorganic hard mask intermediate film and an organic antireflection film or an adhesion film.

[0165] [Method for forming an organic film] In the present invention, there is provided a method for forming an organic film used in a manufacturing process of a semiconductor device, comprising spin-coating the composition for forming an organic film of the present invention on a substrate to be processed to obtain a coating film, and heat-treating the coating film at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to cure it, thereby forming an organic film. For example, an organic film is formed by heat-treating a substrate coated with the above composition for forming an organic film within the above temperature and time ranges to cure it.

[0166] In this method for forming an organic film, first, the above-described composition for forming an organic film of the present invention is spin-coated onto a substrate to be processed. By using the spin-coating method, good embedding characteristics can be obtained. After removing the film at the edge in the EBR process, baking (heat treatment) is performed to promote the crosslinking reaction. Note that since the solvent in the composition can be evaporated by this baking, mixing can be prevented even when forming a resist upper layer film or a silicon-containing resist intermediate film on the organic film.

[0167] The baking is performed in the range of a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, preferably in the range of a temperature of 200°C or higher and 500°C or lower for 10 to 300 seconds, and particularly preferably in the range of a temperature of 300°C or higher and 500°C or lower for 10 to 300 seconds. Considering the influence on device damage and wafer deformation, the upper limit of the heating temperature in the wafer process of lithography is preferably 600°C or lower, more preferably 500°C or lower. By performing heat treatment under such conditions, the crosslinking reaction can be promoted, and an organic film without mixing with the film formed on the upper layer can be formed.

[0168] [Pattern Formation Method] Hereinafter, a pattern formation method using the composition for forming an organic film of the present invention will be described.

[0169] [Three-Layer Resist Process Using a Silicon-Containing Resist Intermediate Film] In the present invention, a pattern formation method is an organic film is formed on a workpiece using the composition for forming an organic film of the present invention, a silicon-containing resist intermediate film is formed on the organic film using a silicon-containing resist intermediate film material, a resist upper layer film is formed on the silicon-containing resist intermediate film using a resist upper layer film material composed of a photoresist composition, a circuit pattern is formed on the resist upper layer film, and the pattern is transferred to the silicon-containing resist intermediate film by etching using the resist upper layer film on which the circuit pattern is formed as a mask, Using the silicon-containing resist intermediate film onto which the pattern has been transferred as a mask, transfer the pattern to the organic film by etching, Furthermore, provided is a pattern forming method characterized by forming a pattern by etching on the workpiece using the organic film onto which the pattern has been transferred as a mask.

[0170] As the workpiece, for example, a semiconductor device substrate, or a substrate having a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxynitride film, or a metal carbonitride film formed thereon is preferably used. More specifically, although not particularly limited, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., and those having the above metal films or the like formed as a processing layer on the substrate are used.

[0171] As the processing layer, for example, various Low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, etc. and their stopper films are used, and they can usually be formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm. When forming the processing layer, the substrate and the processing layer are made of different materials.

[0172] Note that as the metal constituting the workpiece, those containing silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or alloys thereof are preferably used.

[0173] When forming an organic film on the workpiece using the composition for forming an organic film of the present invention, for example, although not limited, the above-described organic film forming method of the present invention may be applied.

[0174] Next, a resist intermediate film (silicon-containing resist intermediate film) is formed on the organic film using a resist intermediate film material containing silicon atoms. As the resist intermediate film material containing silicon atoms, a polysiloxane-based intermediate film material is preferred. By imparting an antireflection effect to the silicon-containing resist intermediate film, reflection can be suppressed. Particularly for 193 nm exposure, when a material with a high etching selectivity with respect to the substrate and containing many aromatic groups is used as the composition for forming the organic film, the k value increases and the substrate reflection increases. However, by providing absorption such that the k value becomes appropriate for the silicon-containing resist intermediate film, it becomes possible to suppress reflection and reduce the substrate reflection to 0.5% or less. As the silicon-containing resist intermediate film having an antireflection effect, for 248 nm or 157 nm exposure, a polysiloxane having an anthryl group, and for 193 nm exposure, a phenyl group or an absorptive group having a silicon-silicon bond in a pendant structure and crosslinkable by an acid or heat is preferably used.

[0175] Next, a resist upper layer film is formed on the silicon-containing resist intermediate film using a resist upper layer film material composed of a photoresist composition. The resist upper layer film material can be either positive or negative, and the same photoresist composition as that commonly used can be used. After spin-coating the resist upper layer film material, it is preferably prebaked at 60 to 180 °C for 10 to 300 seconds. Thereafter, exposure is performed according to a conventional method, and further, post-exposure bake (PEB) and development are performed to obtain a resist upper layer film pattern. The thickness of the resist upper layer film is not particularly limited, but is preferably 30 to 500 nm, and particularly preferably 50 to 400 nm.

[0176] Next, a circuit pattern (resist upper layer film pattern) is formed on the resist upper layer film. In forming the circuit pattern, it is preferable to form the circuit pattern by lithography using light with a wavelength of 10 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination thereof.

[0177] As the exposure light, high-energy rays with a wavelength of 300 nm or less can be mentioned. Specifically, deep ultraviolet rays, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F2 laser light (157 nm), Kr2 laser light (146 nm), Ar2 laser light (126 nm), soft X-rays (EUV) of 3 to 20 nm, electron beam (EB), ion beam, and X-rays, etc. can be given.

[0178] In addition, in the formation of the circuit pattern, it is preferable to develop the circuit pattern with alkali development or an organic solvent.

[0179] Next, using the resist upper layer film on which the circuit pattern is formed as a mask, the pattern is transferred to the silicon-containing resist intermediate film by etching. The etching of the silicon-containing resist intermediate film performed using the resist upper layer film pattern as a mask is preferably performed using a fluorocarbon-based gas. Thereby, the pattern (silicon-containing resist intermediate film pattern) is transferred to the silicon-containing resist intermediate film.

[0180] Next, using the silicon-containing resist intermediate film (silicon-containing resist intermediate film pattern) on which the pattern is transferred as a mask, the pattern is transferred to the organic film by etching. Since the silicon-containing resist intermediate film exhibits etching resistance to oxygen gas or hydrogen gas, the etching of the organic film performed using the silicon-containing resist intermediate film pattern as a mask is preferably performed using an etching gas mainly composed of oxygen gas or hydrogen gas. Thereby, the pattern (organic film pattern) is transferred to the organic film.

[0181] Next, using the organic film (organic film pattern) on which the pattern is transferred as a mask, a pattern is formed on the workpiece by etching.

[0182] Etching of the following workpiece (work layer) can be performed by a conventional method. For example, if the workpiece is SiO2, SiN, or a silica-based low dielectric constant insulating film, etching mainly using a fluorocarbon gas is performed. If it is p-Si, Al, or W, etching mainly using a chlorine-based or bromine-based gas is performed. When substrate processing is performed by etching with a fluorocarbon gas, the silicon-containing resist intermediate film pattern is peeled off simultaneously with the processing of the workpiece. On the other hand, when the processing of the workpiece is performed by etching with a chlorine-based or bromine-based gas, in order to peel off the silicon-containing resist intermediate film pattern, it is necessary to separately perform dry etching peeling with a fluorocarbon gas after the processing of the workpiece.

[0183] The organic film obtained by using the composition for forming an organic film of the present invention can be excellent in etching resistance during etching of the workpiece as described above.

[0184] [Four-layer resist process using a silicon-containing resist intermediate film and an organic antireflection film or adhesion film] Further, in the present invention, a pattern forming method is provided, forming an organic film on a workpiece using the composition for forming an organic film of the present invention, forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, forming an organic antireflection film or adhesion film on the silicon-containing resist intermediate film, forming a resist upper layer film on the organic antireflection film or adhesion film using a resist upper layer film material composed of a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring a pattern by etching to the organic antireflection film or adhesion film and the silicon-containing resist intermediate film using the resist upper layer film on which the circuit pattern is formed as a mask, transferring a pattern by etching to the organic film using the silicon-containing resist intermediate film on which the pattern is transferred as a mask, Furthermore, a pattern forming method is provided, which is characterized by forming a pattern by etching on the workpiece using the organic film on which the pattern is transferred as a mask.

[0185] Note that this method can be carried out in the same manner as the three-layer resist process using the above-mentioned silicon-containing resist intermediate film, except that an organic anti-reflection film (BARC) or an adhesion film is formed between the silicon-containing resist intermediate film and the resist upper layer film.

[0186] The organic anti-reflection film and the adhesion film can be formed by spin coating using known organic anti-reflection film materials.

[0187] [Three-Layer Resist Process Using Inorganic Hard Mask Intermediate Film] Further, in the present invention, there is provided a patterning method comprising: forming an organic film on a workpiece using the composition for forming an organic film of the present invention; forming an inorganic hard mask selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming a resist upper layer film on the inorganic hard mask using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern is formed as a mask; transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern is transferred as a mask; and further, providing a patterning method characterized by forming a pattern on the workpiece by etching using the organic film on which the pattern is transferred as a mask.

[0188] Note that this method can be carried out in the same manner as the three-layer resist process using the above-mentioned silicon-containing resist intermediate film, except that an inorganic hard mask intermediate film is formed on the organic film instead of the silicon-containing resist intermediate film.

[0189] The inorganic hard mask intermediate film selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) can be formed, for example, by a CVD method, an ALD method, or the like. As a method for forming the silicon nitride film, for example, it is described in JP-A-2002-334869, WO 2004 / 066377, and the like. The film thickness of the inorganic hard mask intermediate film is preferably 5 to 200 nm, more preferably 10 to 100 nm. As the inorganic hard mask intermediate film, a SiON film having a high antireflection effect is most preferably used.

[0190] [Four-layer resist process using an inorganic hard mask intermediate film and an organic antireflection film or adhesion film] Further, in the present invention, there is provided a patterning method comprising: forming an organic film on a workpiece using the composition for forming an organic film of the present invention; forming an inorganic hard mask selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming an organic antireflection film or adhesion film on the inorganic hard mask, and forming a resist upper layer film on the organic antireflection film or adhesion film using a resist upper layer film material composed of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the organic antireflection film or adhesion film and the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern is formed as a mask; transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern is transferred as a mask; and further providing a patterning method characterized by forming a pattern on the workpiece by etching using the organic film on which the pattern is transferred as a mask.

[0191] This method can be carried out in the same manner as the three-layer resist process using the above inorganic hard mask intermediate film, except that an organic antireflection film (BARC) or adhesion film is formed between the inorganic hard mask intermediate film and the resist upper layer film.

[0192] In particular, when a SiON film is used as the inorganic hard mask intermediate film, it becomes possible to suppress reflection even in immersion lithography with a high NA exceeding 1.0 by the two-layer antireflection films of the SiON film and the BARC. Another merit of forming the BARC is that it has the effect of reducing the pulling of the resist upper layer film pattern directly on the SiON film.

[0193] Here, an example of a pattern formation method by the three-layer resist process of the present invention is shown in FIGS. 1(A) to (F). In the case of the three-layer resist process, as shown in FIG. 1(A), an organic film 3 is formed on a processed layer (object to be processed) 2 formed on a substrate 1 using the composition for forming an organic film of the present invention. Next, a silicon-containing resist intermediate film 4 is formed on the organic film 3, and a resist upper layer film 5 is formed thereon. Next, as shown in FIG. 1(B), the exposed portion 6 of the resist upper layer film 5 is exposed, and then PEB (post-exposure bake) is performed. Next, as shown in FIG. 1(C), development is performed to form a resist upper layer film pattern 5a. Next, as shown in FIG. 1(D), using the resist upper layer film pattern 5a as a mask, the silicon-containing resist intermediate film 4 is dry-etched using a fluorocarbon gas to form a silicon-containing resist intermediate film pattern 4a. Next, the resist upper layer film pattern 5a is removed, and then, as shown in FIG. 1(E), using the silicon-containing resist intermediate film pattern 4a as a mask, the organic film 3 is etched with oxygen plasma to form an organic film pattern 3a. Further, as shown in FIG. 1(F), the silicon-containing resist intermediate film pattern 4a is removed, and then, using the organic film pattern 3a as a mask, the processed layer 2 is etched to form a pattern 2a.

[0194] In the pattern formation method of this example, by suppressing the hump during the formation of the organic film 3, it becomes possible to reduce the defects generated due to the hump of the organic film during the dry etching processes of FIGS. 1(D), (E), and (F).

[0195] When forming an inorganic hard mask intermediate film, the silicon-containing resist intermediate film 4 may be changed to an inorganic hard mask intermediate film. When forming a BARC or an adhesion film, a BARC or an adhesion film may be formed between the silicon-containing resist intermediate film 4 and the resist upper layer film 5. The etching of the BARC or the adhesion film may be continuously performed prior to the etching of the silicon-containing resist intermediate film 4, or the etching of only the BARC or the adhesion film may be performed and then the etching of the silicon-containing resist intermediate film 4 may be performed after changing the etching apparatus or the like.

[0196] As described above, according to the pattern forming method of the present invention, by a multilayer resist process, a fine pattern can be formed on a workpiece with high precision, and by suppressing the formation of humps in the organic film, defects derived from the humps in the organic film can be reduced.

Example

[0197] Hereinafter, the present invention will be described more specifically by showing synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited thereto. The method for measuring the molecular weight was specifically carried out by the following method. The weight average molecular weight (Mw), number average molecular weight (Mn) in terms of polystyrene were determined by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent (solvent), and the dispersity (Mw / Mn) was determined.

[0198] [Synthesis of aryl benzyl ether compounds (B-1) to (B-14)] For the synthesis of aryl benzyl ether compounds (B-1) to (B-14) used in the preparation of the organic film forming compositions (UDL-1 to 89) of the examples, the following phenolic compounds (a1) to (a14) and bromo compounds (b1) to (b4) were used.

[0199] (Phenolic compound)

Chem.

[0200] (Bromo compound) [Chemical]

[0201] [Synthesis Example 1] Synthesis of Aryl Benzyl Ether Compound (B-1) [Chemical]

[0202] 60.0 g of DMF (N,N-dimethylformamide) was added to 2.12 g of a phenolic compound (a1) and 2.76 g of potassium carbonate, and the mixture was stirred at an internal temperature of 60 °C under a nitrogen atmosphere to form a homogeneous solution. Then, 5.22 g of a bromo compound (b1) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Further, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-1).

[0203] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-1): Mw = 4030, Mw / Mn = 2.64

[0204] [Synthesis Example 2] Synthesis of Aryl Benzyl Ether Compound (B-2) [Chemical]

[0205] 2.67 g of a phenolic compound (a2) and 2.76 g of potassium carbonate were added to 60.0 g of DMF (N,N-dimethylformamide), and the mixture was stirred at an internal temperature of 60 °C under a nitrogen atmosphere to form a homogeneous solution. Then, 5.10 g of a bromo compound (b2) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Further, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-2).

[0206] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-2): Mw = 7780, Mw / Mn = 5.15

[0207] [Synthesis Example 3] Synthesis of aryl benzyl ether compound (B-3) [Chemical formula]

[0208] 2.90 g of a phenolic compound (a3) and 2.76 g of potassium carbonate were added to 60.0 g of DMF (N,N-dimethylformamide), and the mixture was stirred at an internal temperature of 60 °C under a nitrogen atmosphere to form a homogeneous solution. Then, 5.22 g of a bromo compound (b1) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Further, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-3).

[0209] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-3): Mw = 5180, Mw / Mn = 2.78

[0210] [Synthesis Example 4] Synthesis of Aryl Benzyl Ether Compound (B-4)

Chemical Structure

[0211] 6.30 g of phenolic compound (a4) and 5.53 g of potassium carbonate were added to 60.0 g of DMF (N,N-dimethylformamide), and the mixture was stirred at an internal temperature of 60 °C under a nitrogen atmosphere to form a homogeneous solution. Then, 10.20 g of bromo compound (b2) was added dropwise to the homogeneous solution over 10 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to make it homogeneous, and then the separated aqueous layer was removed. Furthermore, the organic layer was washed twice with 100 ml of 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain aryl benzyl ether compound (B-4).

[0212] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-4): Mw = 4745, Mw / Mn = 2.42

[0213] [Synthesis Example 5] Synthesis of Aryl Benzyl Ether Compound (B-5)

Chemical Structure

[0214] 5.70 g of a phenolic compound (a5) and 5.53 g of potassium carbonate were added to 60.0 g of DMF (N,N-dimethylformamide), and the mixture was stirred at an internal temperature of 60 °C under a nitrogen atmosphere to form a homogeneous solution. Then, 10.44 g of a bromo compound (b1) was added dropwise to the homogeneous solution over 10 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Further, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-5).

[0215] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-5): Mw = 3790, Mw / Mn = 2.81

[0216] [Synthesis Example 6] Synthesis of aryl benzyl ether compound (B-6) [Chemical formula]

[0217] 7.52 g of a phenolic compound (a6) and 5.53 g of potassium carbonate were added to 60.0 g of DMF (N,N-dimethylformamide), and the mixture was stirred at an internal temperature of 60 °C under a nitrogen atmosphere to form a homogeneous solution. Then, 10.20 g of a bromo compound (b3) was added dropwise to the homogeneous solution over 10 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Further, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-6).

[0218] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-6): Mw = 4120, Mw / Mn = 3.24

[0219] [Synthesis Example 7] Synthesis of Aryl Benzyl Ether Compound (B-7) [Chemical Formula]

[0220] 6.35 g of phenolic compound (a7) and 8.29 g of potassium carbonate were added to 60.0 g of DMF (N,N-dimethylformamide), and the mixture was stirred at an internal temperature of 60 °C under a nitrogen atmosphere to form a homogeneous solution. Then, 15.66 g of bromo compound (b1) was added dropwise to the homogeneous solution over 20 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Furthermore, the organic layer was washed twice with 100 ml of 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain aryl benzyl ether compound (B-7).

[0221] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-7): Mw = 12830, Mw / Mn = 6.47

[0222] [Synthesis Example 8] Synthesis of Aryl Benzyl Ether Compound (B-8) [Chemical Formula]

[0223] 9.63 g of a phenolic compound (a8) and 8.29 g of potassium carbonate were added to 60.0 g of DMF (N,N-dimethylformamide), and the mixture was stirred at an internal temperature of 60°C under a nitrogen atmosphere to form a homogeneous solution. Then, 15.30 g of a bromo compound (b2) was added dropwise to the homogeneous solution over 20 minutes, and the reaction was carried out at an internal temperature of 60°C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Further, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-8).

[0224] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-8): Mw = 2780, Mw / Mn = 1.62

[0225] [Synthesis Example 9] Synthesis of aryl benzyl ether compound (B-9) [Chemical formula]

[0226] 11.69 g of a phenolic compound (a9) and 16.58 g of potassium carbonate were added to 60.0 g of DMF (N,N-dimethylformamide), and the mixture was stirred at an internal temperature of 60°C under a nitrogen atmosphere to form a homogeneous solution. Then, 31.32 g of a bromo compound (b1) was added dropwise to the homogeneous solution over 30 minutes, and the reaction was carried out at an internal temperature of 60°C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Further, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-9).

[0227] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-9): Mw = 2040, Mw / Mn = 1.24

[0228] [Synthesis Example 10] Synthesis of Aryl Benzyl Ether Compound (B-10) [Chemical Formula]

[0229] 60.0 g of DMF (N,N-dimethylformamide) was added to 11.69 g of phenolic compound (a10) and 16.58 g of potassium carbonate, and the mixture was stirred at an internal temperature of 60 °C under a nitrogen atmosphere to form a homogeneous solution. Then, 30.60 g of bromo compound (b2) was added dropwise to the homogeneous solution over 30 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to make it homogeneous, and then the separated aqueous layer was removed. Further, the organic layer was washed twice with 100 ml of 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain aryl benzyl ether compound (B-10).

[0230] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-10): Mw = 2240, Mw / Mn = 1.18

[0231] [Synthesis Example 11] Synthesis of Aryl Benzyl Ether Compound (B-11) [Chemical Formula]

[0232] 17.50 g of a phenolic compound (a11) and 16.58 g of potassium carbonate were added with 60.0 g of DMF (N,N-dimethylformamide), and the mixture was stirred at an internal temperature of 60 °C under a nitrogen atmosphere to form a homogeneous solution. Then, 31.32 g of a bromo compound (b1) was added dropwise to the homogeneous solution over 30 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Further, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-11).

[0233] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-11): Mw = 3750, Mw / Mn = 1.49

[0234] [Synthesis Example 12] Synthesis of aryl benzyl ether compound (B-12) [Chemical formula]

[0235] 15.50 g of a phenolic compound (a12) and 16.58 g of potassium carbonate were added with 60.0 g of DMF (N,N-dimethylformamide), and the mixture was stirred at an internal temperature of 60 °C under a nitrogen atmosphere to form a homogeneous solution. Then, 30.60 g of a bromo compound (b4) was added dropwise to the homogeneous solution over 30 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Further, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-12).

[0236] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-12): Mw = 3120, Mw / Mn = 2.33

[0237] [Synthesis Example 13] Synthesis of Aryl Benzyl Ether Compound (B-13) [Chemical Formula]

[0238] 60.0 g of DMF (N,N-dimethylformamide) was added to 2.40 g of a phenolic compound (a13) and 2.76 g of potassium carbonate, and the mixture was stirred at an internal temperature of 60°C under a nitrogen atmosphere to form a homogeneous solution. Then, 5.22 g of a bromo compound (b1) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60°C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to make it homogeneous, and then the separated aqueous layer was removed. Further, the organic layer was washed twice with 100 ml of 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-13).

[0239] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-13): Mw = 23560, Mw / Mn = 1.13

[0240] [Synthesis Example 14] Synthesis of Aryl Benzyl Ether Compound (B-14) [Chemical Formula]

[0241] 2.40 g of a phenolic compound (a14) and 2.76 g of potassium carbonate were added to 60.0 g of DMF (N,N-dimethylformamide), and the mixture was stirred at an internal temperature of 60 °C under a nitrogen atmosphere to form a homogeneous solution. Then, 5.10 g of a bromo compound (b2) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Further, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-14).

[0242] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-14): Mw = 20726, Mw / Mn = 1.10

[0243] [Synthesis of Comparative Compounds (R1) to (R8)] The following monomers (r1) to (r12) were used for the synthesis of comparative compounds (R1) to (R8) used in the preparation of the organic film-forming compositions (Comparative UDL-1 to 13) of the comparative examples.

[0244] [Chemical Formula]

[0245] [Comparative Synthesis Example 1] Synthesis of Comparative Compound (R1) [Chemical Formula]

[0246] In a nitrogen atmosphere, 6.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80 °C. To this, a mixture of 3.44 g (0.011 mol) of monomer (r1), 7.46 g (0.034 mol) of monomer (r3), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA was added dropwise over 4 hours. After further heating and stirring for 16 hours, it was cooled to room temperature to obtain a PGMEA solution of the target compound (R1).

[0247] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (R1): Mw = 9500, Mw / Mn = 1.20

[0248] [Comparative Synthesis Example 2] Synthesis of Comparative Compound (R2) [Chemical formula]

[0249] In a nitrogen atmosphere, 6.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80 °C. To this, a mixture of 1.43 g (0.005 mol) of monomer (r1), 5.76 g (0.041 mol) of monomer (r4), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA was added dropwise over 4 hours. After further heating and stirring for 16 hours, it was cooled to room temperature to obtain a PGMEA solution of the target compound (R2).

[0250] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (R2): Mw = 5800, Mw / Mn = 1.42

[0251] [Comparative Synthesis Example 3] Synthesis of Comparative Compound (R3) [Chemical formula]

[0252] In a nitrogen atmosphere, 6.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80 °C. To this, a mixture of 7.00 g (0.032 mol) of monomer (r2), 1.92 g (0.014 mol) of monomer (r4), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA was added dropwise over 4 hours. After further heating and stirring for 16 hours, it was cooled to room temperature to obtain a PGMEA solution of the target compound (R3).

[0253] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (R3): Mw = 6200, Mw / Mn = 1.33

[0254] [Comparative Synthesis Example 4] Synthesis of Comparative Compound (R4)

Chemical Structure

[0255] In a nitrogen atmosphere, 6.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80 °C. To this, a mixture of 5.00 g (0.023 mol) of monomer (r2), 3.20 g (0.023 mol) of monomer (r5), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA was added dropwise over 4 hours. After further heating and stirring for 16 hours, it was cooled to room temperature to obtain a PGMEA solution of the target compound (R4).

[0256] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (R4): Mw = 8300, Mw / Mn = 1.33

[0257] [Comparative Synthesis Example 5] Synthesis of Comparative Compound (R5)

Chemical Structure

[0258] In a nitrogen atmosphere, 6.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80 °C. To this, a mixture of 2.00 g (0.009 mol) of monomer (r2), 5.41 g (0.036 mol) of monomer (r6), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA was added dropwise over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target compound (R5).

[0259] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (R5): Mw = 3800, Mw / Mn = 1.44

[0260] [Comparative Synthesis Example 6] Synthesis of Comparative Compound (R6) [Chemical formula]

[0261] In a nitrogen atmosphere, 40.0 g of PGME (propylene glycol monomethyl ether) was added to 2.16 g of monomer (r7) and 0.54 g of monomer (r8), and the mixture was stirred at an internal temperature of 110 °C to form a homogeneous solution. Then, 0.38 g of p-toluenesulfonic acid was added to the homogeneous solution, and the reaction was carried out at an internal temperature of 110 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. After further washing 5 times with 100 ml of pure water, the organic layer was dried under reduced pressure to obtain the target compound (R6).

[0262] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (R6): Mw = 5700, Mw / Mn = 3.55

[0263] [Comparative Synthesis Example 7] Synthesis of Comparative Compound (R7) [Chemical formula]

[0264] Under a nitrogen atmosphere, 40.0 g of 1,2-dichloroethane was added to 3.20 g of monomer (r9) and 3.42 g of monomer (r10), and the mixture was stirred at an internal temperature of 50 °C to form a homogeneous solution. Then, 1.92 g of methanesulfonic acid was added to the homogeneous solution, and the reaction was carried out at an internal temperature of 70 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. After further washing 5 times with 100 ml of pure water, the organic layer was dried under reduced pressure to obtain the target compound (R7).

[0265] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (R7): Mw = 3250, Mw / Mn = 2.12

[0266] [Comparative Synthesis Example 8] Synthesis of Comparative Compound (R8)

Chemical Structure

[0267] Under a nitrogen atmosphere, 40.0 g of 1,2-dichloroethane was added to 6.13 g of monomer (r11) and 3.53 g of monomer (r12), and the mixture was stirred at an internal temperature of 50 °C to form a homogeneous solution. Then, 1.92 g of methanesulfonic acid was added, and the reaction was carried out at an internal temperature of 70 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. After further washing 5 times with 100 ml of pure water, the organic layer was dried under reduced pressure to obtain the target compound (R8).

[0268] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (R8): Mw = 1660, Mw / Mn = 1.92

[0269] [(A) Material for forming organic film (resin or compound)] In the preparation of the organic film-forming compositions (UDL-1 to 89 and Comparative UDL-1 to 19) of the examples and comparative examples, the following resins or compounds were used as the (A) organic film-forming materials. M1: Resin represented by the following formula (M1) M2: Resin represented by the following formula (M2) M3: Compound represented by the following formula (M3) M4: Compound represented by the following formula (M4) M5: Resin represented by the following formula (M5) M6: Resin represented by the following formula (M6)

[0270] [Chemical formula]

[0271] [(C) Solvent] In the preparation of the organic film-forming compositions (UDL-1 to 89 and Comparative UDL-1 to 19) of the examples and comparative examples, the following solvents were used as the (C) solvents, respectively. (S1): Propylene glycol monomethyl ether acetate (S2): Propylene glycol monoethyl ether

[0272] [Preparation of organic film-forming compositions (UDL-1 to 89, Comparative UDL-1 to 19)] Any one of the above compounds (B-1) to (B-14) and (R1) to (R8) was dissolved with any one of the above organic film-forming materials (M1) to (M6) and one or both of the above solvents at the ratios shown in Tables 1 to 3. The thus-obtained mixture was filtered through a 0.1-μm fluororesin filter to prepare organic film-forming compositions (resist underlayer film materials: UDL-1 to 89, Comparative UDL-1 to 13), respectively. Further, any one of the above organic film-forming materials (M1) to (M6) was dissolved with the above solvent (S1) at the ratio shown in Table 3. The thus-obtained mixture was filtered through a 0.1-μm fluororesin filter to prepare organic film-forming compositions (resist underlayer film materials: Comparative UDL-14 to 19), respectively.

[0273]

Table 1

[0274]

Table 2

[0275]

Table 3

[0276] [Fabrication of Silicon Wafers with Organic Films Formed Using Organic Film-Forming Compositions (UDL-1 to 89, Comparative UDL-1 to 19)] Using the coater / developer "CLEAN TRACK LITHIUS Pro AP" of Tokyo Electron Limited, 2 mL of each of the above-prepared organic film-forming compositions (UDL-1 to 89, Comparative UDL-1 to 19) was discharged onto the center of a silicon wafer and rotated at a rotational speed to achieve the average film thicknesses described in Tables 4 to 6, spread, and then baked at 350 °C to form a coating film of the organic film-forming composition. While rotating the silicon wafer at a speed of 1000 rpm, a removal liquid discharge nozzle was moved from the outer peripheral portion to a position 3 mm from the center of the silicon wafer at a speed of 5 mm / s while discharging a removal liquid (a mixed solution of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30:70, mass ratio)) at a discharge rate of 2 mL / s, and the removal liquid was discharged at the same discharge rate of 2 mL / s for 5 seconds at that position. Then, the discharge of the discharge liquid was stopped, and the silicon wafer was further rotated at a speed of 1000 rpm for 30 seconds. Next, the silicon wafer was heated at 350 °C for 60 seconds to obtain silicon wafers with organic films (organic cured films) formed in each example.

[0277] [Solvent Resistance Evaluation: Examples 1-1 to 1-89, Comparative Examples 1-1 to 1-19] Using each composition for forming an organic film (UDL-1 to 89, Comparative UDL-1 to 19), an organic film was formed on a silicon wafer by the above method, and the film thickness was measured. Next, PGMEA solvent was dispensed onto each organic film, left for 30 seconds, spin-dried, baked at 100 °C for 60 seconds to evaporate PGMEA, and the film thickness was measured. Let the film thickness before dispensing the PGMEA solvent be X and the film thickness after dispensing the PGMEA solvent be X1. The absolute value of the value obtained by (X1 - X) / X × 100 was defined as the film thickness change rate (%). When the film thickness change rate was less than 0.5%, it was considered good; when it was 0.5% or more, it was considered bad. The results are shown in Tables 4 to 6 below.

[0278] [In-plane uniformity evaluation: Examples 1-1 to 1-89, Comparative Examples 1-1 to 1-19] Using each composition for forming an organic film (UDL-1 to 89, Comparative UDL-1 to 19), an organic film was formed on a silicon wafer by the above method, and the film thickness within a radius of 145 mm from the center of the organic film was measured, and the maximum film thickness Xmax, the minimum film thickness Xmin, and the average film thickness X average were taken. The value obtained by (X max - X min ) / X average was defined as the in-plane uniformity (%). When the in-plane uniformity was less than 2%, it was rated as A (good); when it was 2% or more and less than 3%, it was rated as B; when it was 3% or more, it was rated as C (bad). The results are shown in Tables 4 to 6.

[0279]

Table 4

[0280]

Table 5

[0281]

Table 6

[0282] As shown in Tables 4 to 6, in Examples 1-1 to 1-89 using the composition for forming an organic film of the present invention, an organic film having good solvent resistance and in-plane uniformity was obtained. However, among Comparative Examples 1-1 to 1-19 using a composition not containing the aryl benzyl ether compound contained in the composition for forming an organic film of the present invention, in Comparative Examples 1-11 to 1-19, the in-plane uniformity was poor. Therefore, in the following evaluation, UDL-1 to 89 and Comparative UDL-1 to 10, which had good solvent resistance and in-plane uniformity, were examined.

[0283] [Hump suppression evaluation: Examples 2-1 to 2-89, Comparative Examples 2-1 to 2-10] An organic film was formed on a silicon wafer using each composition for forming an organic film (UDL-1 to 89, Comparative UDL-1 to 10) by the above method, and the height change at positions up to 1000 μm from the outer peripheral end of the organic film toward the center of the silicon wafer was measured using an Alpha-Step D-600 (contact profiler) manufactured by KLA-TENCOR. When the height of the silicon wafer was set to 0, as shown in FIG. 2, when the maximum height was less than 110% of the film thickness, it was evaluated as A (good), when the maximum height was 110% or more and less than 150%, it was evaluated as B, and when a region where the height was 150% or more occurred as shown in FIG. 3, it was evaluated as C (bad). The results are shown in Tables 7 to 9.

[0284] [Embedding evaluation: Examples 2-1 to 2-89, Comparative Examples 2-1 to 2-10] As shown in Fig. 4, on a SiO2 wafer substrate having a dense hole pattern (hole diameter 0.2 μm, hole depth 1.0 μm, distance between the centers of two adjacent holes 0.4 μm), each organic film-forming composition (UDL-1 to 89, Comparative UDL-1 to 10) was used to form a film by the above method, and an organic film 8 was formed. The substrate used was a base substrate (SiO2 wafer substrate) 7 having a dense hole pattern as shown in Figs. 4(G) (plan view) and (H) (cross-sectional view). The cross-sectional shape of each obtained wafer substrate was observed using a scanning electron microscope (SEM) to confirm whether the holes were filled with the organic film without voids. When an organic film-forming composition with poor embedding characteristics was used, voids occurred inside the holes. When an organic film-forming composition with good embedding characteristics was used, in this evaluation, as shown in Fig. 4(I), the holes were filled with the organic film without voids. When no voids occurred, it was evaluated as good, and when voids occurred, it was evaluated as bad. The results are shown in Tables 7 to 9.

[0285] [Evaluation of the coating property of the silicon-containing resist intermediate film: Examples 2-1 to 2-89, Comparative Examples 2-1 to 2-10] An organic film was formed on a silicon wafer substrate using each organic film-forming composition (UDL-1 to 89, Comparative UDL-1 to 10) by the above method, and the following silicon-containing resist intermediate film material (SOG1) was applied thereon and baked at 200 °C for 60 seconds to form a silicon-containing resist intermediate film. Then, the state of the coating film of the silicon-containing resist intermediate film was visually observed and evaluated.

[0286] When the state of the coating film of the silicon-containing resist intermediate film was good, it was evaluated as good, and when dewetting occurred, it was evaluated as bad.

[0287] In addition, in this evaluation, in order to evaluate the superiority or inferiority of the coating property of the silicon-containing resist intermediate film, strict evaluation conditions were set with the film thickness of the silicon-containing resist intermediate film being 10 nm. The results are shown in Tables 7 to 9.

[0288] As a silicon-containing resist intermediate film material (SOG1), a propylene glycol ethyl ether solution of the following polymer was prepared. The polymer solution used for evaluating the coating property of the silicon-containing resist intermediate film was 0.5% by weight.

[0289] [Chemical formula]

[0290] [Contact angle evaluation: Examples 2-1 to 2-89, Comparative Examples 2-1 to 2-10] Using the above method, organic films were formed on a silicon wafer substrate using each organic film-forming composition (UDL-1 to 89, Comparative UDL-1 to 10), and the contact angles with pure water were measured. The results are shown in Tables 7 to 9.

[0291] [Table 7]

[0292] [Table 8]

[0293] [Table 9]

[0294] As shown in Tables 7 to 9, the organic film-forming compositions (UDL-1 to 89) of the examples of the present invention were confirmed to be excellent in solvent resistance, in-plane uniformity, hump suppression property, embedding property, and coating property of the silicon-containing resist intermediate film. Also, the contact angles were between 55 and 66 degrees.

[0295] [Pattern formation test: Examples 3-1 to 3-89] An organic film was formed on a SiO2 wafer substrate using each composition for forming an organic film (UDL-1 to 89) by the above method (baking at 350 °C). The following silicon-containing resist intermediate film material (SOG1) was applied thereon and baked at 200 °C for 60 seconds to form a silicon-containing resist intermediate film with a film thickness of 35 nm. The following single-layer resist for ArF was applied thereon as a resist upper-layer film material and baked at 105 °C for 60 seconds to form a photoresist film with a film thickness of 100 nm. The following immersion protective film material (TC-1) was applied on the photoresist film and baked at 90 °C for 60 seconds to form a protective film with a film thickness of 50 nm.

[0296] As the silicon-containing resist intermediate film material (SOG1), a 2% solution of the following polymer in propylene glycol ethyl ether was prepared.

[0297] [Chemical formula]

[0298] The resist upper-layer film material (single-layer resist for ArF) was prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) in a solvent (PGMEA) containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M Limited) at the ratios shown in Table 10 and filtering through a 0.1-μm fluororesin filter.

[0299] [Table 10]

[0300] The polymer (RP1), the acid generator (PAG1), and the basic compound (Amine1) are shown below. [Chemical formula]

[0301] The immersion protective film material (TC-1) was prepared by dissolving a polymer (PP1) in an organic solvent at the ratios shown in Table 11 and filtering through a 0.1-μm fluororesin filter.

[0302]

Table 11

[0303] The polymer (PP1) is shown below.

Chemical formula

[0304] Next, it was exposed using an ArF immersion exposure apparatus (manufactured by Nikon Corporation; NSR-S610C, NA1.30, σ0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% halftone phase shift mask), baked at 100 °C for 60 seconds (PEB), developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds, and a 55 nm 1:1 positive line-and-space pattern (resist upper layer film pattern) was obtained.

[0305] Next, using an etching apparatus Telius manufactured by Tokyo Electron, the resist upper layer film pattern was used as a mask to dry-etch (pattern transfer) the silicon-containing resist intermediate film to obtain a silicon-containing resist intermediate film pattern. Using the obtained silicon-containing resist intermediate film pattern as a mask, the organic film was dry-etched (pattern transfer) to obtain an organic film pattern. Using the obtained organic film pattern as a mask, the SiO2 wafer substrate (SiO2 film) was dry-etched (pattern transfer). The etching conditions are as shown below.

[0306] (Transfer conditions of the resist upper layer film pattern to the silicon-containing resist intermediate film) Chamber pressure 10.0 Pa RF power 1,500 W CF4 gas flow rate 75 mL / min O2 gas flow rate 15 mL / min Time 15 sec

[0307] (Transfer conditions of the silicon-containing resist intermediate film pattern to the organic film) Chamber pressure: 2.0 Pa RF power: 500 W Ar gas flow rate: 75 mL / min O2 gas flow rate: 45 mL / min Time: 120 sec

[0308] (Transfer conditions of the organic film pattern to the SiO2 wafer substrate) Chamber pressure: 2.0 Pa RF power: 2,200 W C5F 12 Gas flow rate: 20 mL / min C2F6 gas flow rate: 10 mL / min Ar gas flow rate: 300 mL / min O2 gas flow rate: 60 mL / min Time: 90 sec

[0309] The cross-sections of the obtained patterns were observed with an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the results are shown in Tables 12 to 14.

[0310] [Table 12]

[0311] [Table 13]

[0312] [Table 14]

[0313] As shown in Tables 12 to 14, in Examples 3-1 to 3-89 using the composition for forming an organic film (UDL-1 to 89) which is an example of the present invention, the resist upper layer film patterns were all successfully transferred to the SiO2 wafer substrate in the end, and it was confirmed that the composition for forming an organic film of the examples of the present invention is suitably used for microfabrication by the multilayer resist method.

[0314] From the above, it can be seen that the composition for forming an organic film of the present invention has excellent film-forming properties, high embedding characteristics, and excellent hump suppression properties, and is excellent in the coatability of an intermediate film such as a silicon-containing resist intermediate film. Therefore, it is extremely useful as an organic film material used in a multilayer resist process. Further, from the above, in the pattern forming method of the present invention using the composition for forming an organic film of the present invention, it is possible to embed holes and trenches having a very high aspect ratio without gaps, and to form fine patterns with high precision. Moreover, since an organic film with suppressed humps can be formed, it can be seen that semiconductor elements and the like can be efficiently manufactured.

[0315] This specification includes the following aspects. [1] (A) A material for forming an organic film, (B) An aryl benzyl ether compound containing a partial structure represented by the following general formula (B1) but not containing a partial structure represented by the following general formula (B0), (C) A solvent and is characterized by containing the same. A composition for forming an organic film.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[10] The pattern formation method according to [8] or [9], wherein the formation of the inorganic hard mask is performed by a CVD method or an ALD method.

[11] In the formation of the circuit pattern, the circuit pattern is formed by lithography using light having a wavelength of 10 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination thereof. The pattern formation method according to any one of [6] to

[10] .

[12] In the formation of the circuit pattern, the circuit pattern is developed by alkali development or an organic solvent. The pattern formation method according to any one of [6] to

[11] .

[13] The workpiece is a semiconductor device substrate or a substrate obtained by forming any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film on the semiconductor device substrate. The pattern formation method according to any one of [6] to

[12] .

[14] As the workpiece, the metal constituting the workpiece is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof, and the pattern forming method according to

[13] is characterized by using such a workpiece.

[0316] Note that the present invention is not limited to the above-described embodiment. The above-described embodiment is an example, and any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same operational effects is included in the technical scope of the present invention.

Explanation of Reference Numerals

[0317] 1... substrate, 2... processed layer, 2a... pattern (pattern formed on the processed layer), 3... organic film, 3a... organic film pattern, 4... silicon-containing resist intermediate film, 4a... silicon-containing resist intermediate film pattern, 5... resist upper layer film, 5a... resist upper layer film pattern, 6... exposed portion, 7... underlying substrate, 8... organic film.

Claims

1. A composition for forming an organic film, comprising: (A) a material for forming an organic film; (B) an aryl benzyl ether compound that contains a partial structure represented by the following general formula (B1) but does not contain a partial structure represented by the following general formula (B0); and (C) a solvent. The composition for forming an organic film is characterized by containing the above components. 【Chemical 1】 (wherein, R １ is any one of the fluorine-containing groups represented by the following formula (B2), R ２ is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, a is 0 or 1, when a is 0, b is 1 to 5, c is 0 to 4, when a is 1, b is 1 to 7, c is 0 to 6, and * indicates a bond to another atom.) [Chemical Formula 2] (In the formula, the dashed line indicates a bond with the oxygen atom in the above formula (B1), and it may have one or two of the structures represented by the above formula (B2).) [Chemical Formula 3] (In the formula, R' １ is a hydrogen atom or a group represented by the following formula (B0-1), R ２ is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, a is 0 or 1, when a is 0, b is 1 to 5, c is 0 to 4, when a is 1, b is 1 to 7, c is 0 to 6, and * represents a bond with another atom.) [Chemical Formula 4] (In the formula, the dashed line indicates a bond with the oxygen atom in the above formula (B0), and n is 1 to 6.)

2. The composition for forming an organic film according to claim 1, wherein the (B) aryl benzyl ether compound is a compound represented by the following general formula (B3), (B4), (B6), (B8), (B10), or (B11). 【Chemical Formula 5】 (wherein, R １ is one or two kinds of fluorine-containing groups represented by the formula (B2), and R ２ is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, and R ３ is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a1 is 0 or 1, b1 is 1 to 5 when a1 is 0, c1 is 0 to 4, and when a1 is 1, b1 is 1 to 7 and c1 is 0 to 6.) 【Chemical Formula 6】 (wherein, R １ is one or two kinds of fluorine-containing groups represented by the above formula (B2), R ２ is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R ４ is a single bond or any one of the groups represented by the following formula (B5), R ５ is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a2 is 0 or 1, when a2 is 0, b2 is 1 to 5, c2 is 0 to 4, when a2 is 1, b2 is 1 to 7, c2 is 0 to 6).) [Chemical Formula 7] [Chemical Formula 6] (wherein, R １ is one or two kinds of fluorine-containing groups represented by the above formula (B2), R ２ is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R ６ is a group represented by the following formula (B7), R ７ is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a3 is 0 or 1, when a3 is 0, b3 is 1 to 5, c3 is 0 to 4, when a3 is 1, b3 is 1 to 7, c3 is 0 to 6.) 【Chemical Formula 9】 【Chemical 10】 (wherein R １ is one or two kinds of fluorine-containing groups represented by the above formula (B2), W １ is a group represented by the following formula (B9), a4 is 0 or 1, b4 is 1 or 2, and d4 is 1 to 4.) 【Chemical 11】 (wherein R １ is any of the fluorine-containing groups represented by the above formula (B2).) 【Chemical Formula 12】 (wherein, R １ is one or two kinds of fluorine-containing groups represented by the above formula (B2), W １ is a group represented by the above formula (B9), W ２ is a single bond or an organic group having 1 to 50 carbon atoms, m is an integer satisfying 1 ≦ m ≦ 5, a5 is 0 or 1, b5 is 1 or 2, and d5 is 1 to 4).) 【Chemical 13】 (wherein R １ is one or two kinds of fluorine-containing groups represented by the above formula (B2), R ８ is a hydrogen atom or a methyl group, and b6 is 1 to 5.)

3. The composition for forming an organic film according to claim 1, wherein the weight average molecular weight of the (B) aryl benzyl ether compound is 1,000 to 30,000.

4. The composition for forming an organic film according to claim 1, wherein the content of the (B) aryl benzyl ether compound is 0.01 part by mass to 5 parts by mass with respect to 100 parts by mass of the content of the (A) material for forming an organic film.

5. A method for forming an organic film used in the manufacturing process of a semiconductor device, comprising: spin-coating the composition for forming an organic film according to any one of claims 1 to 4 on a substrate to be processed to obtain a coating film; and heat-treating the coating film at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to cure it, thereby forming an organic film.

6. A patterning method, comprising: forming an organic film on a workpiece using the composition for forming an organic film according to any one of claims 1 to 4; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming a resist upper layer film on the silicon-containing resist intermediate film using a resist upper layer film material composed of a photoresist composition; forming a circuit pattern on the resist upper layer film, transferring the pattern to the silicon-containing resist intermediate film by etching using the resist upper layer film on which the circuit pattern is formed as a mask; and transferring the pattern to the organic film by etching using the silicon-containing resist intermediate film on which the pattern is transferred as a mask. Furthermore, a pattern forming method is characterized in that a pattern is formed on the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

7. A pattern forming method comprising: forming an organic film on a workpiece using the composition for forming an organic film according to any one of claims 1 to 4; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, and forming an organic antireflection film or an adhesion film on the silicon-containing resist intermediate film; forming a resist upper layer film on the organic antireflection film or the adhesion film using a resist upper layer film material composed of a photoresist composition, and forming a circuit pattern on the resist upper layer film; transferring the pattern by etching to the organic antireflection film or the adhesion film and the silicon-containing resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching to the organic film using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; Furthermore, a pattern forming method is characterized in that a pattern is formed on the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

8. A pattern forming method comprising: forming an organic film on a workpiece using the composition for forming an organic film according to any one of claims 1 to 4; forming an inorganic hard mask selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming a resist upper layer film on the inorganic hard mask using a resist upper layer film material composed of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern by etching to the inorganic hard mask using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching to the organic film using the inorganic hard mask on which the pattern has been transferred as a mask; Furthermore, a pattern forming method is characterized in that a pattern is formed on the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

9. A pattern forming method comprising: forming an organic film on a workpiece using the composition for forming an organic film according to any one of claims 1 to 4; forming an inorganic hard mask selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; An organic antireflection film or an adhesion film is formed on the inorganic hard mask, and a resist upper layer film is formed on the organic antireflection film or the adhesion film using a resist upper layer film material composed of a photoresist composition. A circuit pattern is formed on the resist upper layer film. Using the resist upper layer film on which the circuit pattern is formed as a mask, a pattern is transferred by etching to the organic antireflection film or the adhesion film and the inorganic hard mask. Using the inorganic hard mask on which the pattern is transferred as a mask, a pattern is transferred by etching to the organic film. Furthermore, a pattern is formed by etching on the workpiece using the organic film on which the pattern is transferred as a mask. A pattern forming method characterized by this.

10. The pattern forming method according to claim 8, wherein the inorganic hard mask is formed by a CVD method or an ALD method.

11. In the formation of the circuit pattern, the circuit pattern is formed by lithography using light having a wavelength of 10 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination thereof. The pattern forming method according to claim 6, characterized by this.

12. In the formation of the circuit pattern, the circuit pattern is developed by alkali development or an organic solvent. The pattern forming method according to claim 6, characterized by this.

13. The workpiece is a semiconductor device substrate, or a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxynitride film, or a metal oxynitride film is formed on the semiconductor device substrate. The pattern forming method according to claim 6, characterized by this.

14. As the workpiece, the metal constituting the workpiece is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof. The pattern forming method according to claim 13, characterized by using such a material.

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