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

Abstract

To provide: a composition for forming an organic film capable of forming an organic film which is excellent in film formability, 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 having a specific structure; and (C) a solvent.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In recent years, with the high integration and high speed of semiconductor devices, miniaturization of pattern rules has been required. Among them, in lithography using optical exposure, which is currently a general-purpose technology, various technological 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 a part with a low integration degree, 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 a part where high integration and miniaturization are required, lithography using a shorter wavelength KrF excimer laser (248 nm) or ArF excimer laser (193 nm) has also been put into practical use. 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, it is known that the multilayer resist method, in which films with different dry etching characteristics are laminated to form a pattern, is excellent for forming a pattern with a high aspect ratio on a stepped substrate. 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 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 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 film thickness is thick (hump) may be formed at the outer peripheral portion of the organic film. 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 Documents

[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, an organic film-forming method and a pattern-forming method using this composition, and a surfactant which is a compound used in the organic film-forming 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 having a partial structure represented by the following general formula (B1), and (C) a solvent.

Chemical Formula

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[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 bumps 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 (B2-2), the hydrophobic components unevenly distributed on the surface of the organic film are thermally decomposed at the benzyl position during baking for forming 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 capable of forming, with excellent coatability thereon, an intermediate film, for example, a silicon-containing intermediate film. Further, by adjusting the ratios α and β of the structure within the above ranges, even in a low-temperature region where thermal decomposition does not occur at the benzyl position, due to the presence of a PEG (polyethylene glycol) chain as represented by the above formula (B2-1), the contact angle can be adjusted, so that it becomes a composition for forming an organic film capable of forming, with excellent coatability thereon, an intermediate film, for example, a silicon-containing intermediate film. 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 bump suppression properties 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

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[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 no insoluble matter is formed due to the reaction between the decomposition products. Therefore, when used for forming an organic film, the process margin is not narrowed, and no device contamination or inconvenience occurs.

[0016] Further, 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 having excellent film-forming properties and embedding characteristics.

[0018] Further, with respect to 100 parts by mass of the content of the (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.

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

[0020] Further, the present invention is 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 providing an organic film-forming method characterized by curing the coating film by heat treatment at a temperature of 100°C or higher and 600°C or lower for a range of 10 to 600 seconds to form an organic film.

[0021] The organic film-forming composition of the present invention fills a pattern with a complex shape on a substrate to be processed by spin coating, and forms an organic film having excellent in-plane uniformity, and is particularly useful when removing the organic film at the end 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 characteristics, 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, in the present invention, a patterning method is provided, 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 forming 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 forming method, Form an organic film on a 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 forming 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 forming 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 forming 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 circuit pattern forming means and developing means can be suitably 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 oxynitride 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.

[0035] Furthermore, the present invention provides a surfactant comprising an aryl benzyl ether compound having a partial structure represented by the following general formula (B1). [Chemical formula] (In the formula, R1 is a group represented by the following formula (B2-1) or any fluorine-containing group represented by the following formula (B2-2). Among the structures constituting R1, when the ratio of the group represented by the following formula (B2-1) is α and the ratio of the fluorine-containing group represented by the following formula (B2-2) is β, the relationship α + β = 1, 0.1 ≦ α ≦ 0.5, and 0.5 ≦ β ≦ 0.9 is satisfied. R2 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 and c is 0 to 4. When a is 1, b is 1 to 7 and c is 0 to 6. * represents a bond to another atom.) [Chemical formula] (In the formula, the dashed line represents a bond to the oxygen atom in the above formula (B1), n is 1 to 6, and it may have one or two of the structures represented by the above formula (B2-1).) [Chemical formula] (In the formula, the dashed line represents a bond to the oxygen atom in the above formula (B1), and it may have one or two of the structures represented by the above formula (B2-2).)

[0036] Such a surfactant is suitable for forming 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 by combining fluorine substituents such as the structure represented by the above formula (B2-2). Further, since it is a surfactant in which the ratio α of the PEG chain such as the structure represented by the above formula (B2-1) and the ratio β of the fluorine substituent such as the structure represented by the above formula (B2-2) are adjusted within the above range, when the surfactant of the present invention is used for forming an organic film as an organic film-forming composition, even in a low-temperature region where thermal decomposition does not occur at the benzyl position, due to the sufficient presence of the PEG chain such as the structure represented by the above formula (B2-1), the contact angle can be adjusted. Therefore, an organic film-forming composition capable of forming an organic film with excellent coatability on an intermediate film, for example, a silicon-containing intermediate film, can be realized.)

[0037] Moreover, the surfactant of the present invention is not limited to the composition for forming an organic film, and can be usefully used in all coating materials for photolithography. Furthermore, the surfactant of the present invention is useful in any composition as long as it is a composition containing a surfactant, and its applications can extend not only to industrial applications but also to daily necessities applications such as cosmetics.

[0038] In the present invention, the aryl benzyl ether compound is preferably a compound represented by the following general formulas (B3), (B4), (B6), (B8), (B10), or (B11).

Chemical formula

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[0039] For an organic film-forming composition containing such a surfactant, by having an appropriate fluorine content, the film-forming property during coating can be further improved.

[0040] The weight average molecular weight of the aryl benzyl ether compound is preferably from 1000 to 30000.

[0041] If it is in such a range of the weight average molecular weight, it becomes a surfactant capable of forming an organic film excellent in film-forming property and embedding characteristics. The weight average molecular weight can be determined by the method described later.

Effects of the Invention

[0042] As described above, according to the present invention, it is possible to provide a composition for forming an organic film that is excellent in film-forming properties (in-plane uniformity) and embedding properties on a substrate (wafer), has excellent film-forming properties of an intermediate film on the organic film when used as an organic film, and is excellent in suppressing humps during the EBR process. Since the composition for forming an organic film of the present invention is excellent in film-forming properties, embedding properties, and hump suppression during the EBR process, for example, it is used in a multi-layer 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. It is extremely useful as an organic film material or as an organic film-forming material for manufacturing semiconductor devices. Further, according to the organic film-forming method of the present invention, since an organic film with suppressed humps 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, so it is useful for the composition for forming an organic film. Furthermore, by adjusting the ratio α of the PEG chain such as the structure represented by the above formula (B2-1) and the ratio β of the fluorine substituent such as the structure represented by the above formula (B2-2) within the above range, even in a low-temperature region where thermal decomposition does not occur at the benzyl position, due to the sufficient presence of the PEG chain, the contact angle can be adjusted, resulting in a composition for forming an organic film with excellent coatability for a silicon-containing intermediate film.

[0043] Further, the surfactant of the present invention is excellent in in-plane uniformity and embedding properties, and is a suitable surfactant for forming an organic film in which the formation of humps due to the influence of the remover in the EBR process is suppressed. Further, the surfactant of the present invention can be usefully used not only in all coating materials for photolithography such as for forming an organic film, but also in various industrial applications and daily commodity applications.

Brief Description of the Drawings

[0044]

Figure 1

Figure 2

Figure 3

Figure 4

Mode for Carrying Out the Invention

[0045] 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 properties on a substrate (wafer), and that suppresses humps during the EBR process.

[0046] Usually, 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, and 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 baking.

[0047] 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.

[0048] 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 properties 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.

[0049] That is, the present invention is a composition for forming an organic film, (A) Material for forming an organic film, (B) An aryl benzyl ether compound having a partial structure represented by the following general formula (B1), and (C) A composition for forming an organic film, characterized by containing a solvent. [Chemical formula] (In the formula, R1 is a group represented by the following formula (B2-1) or any fluorine-containing group represented by the following formula (B2-2). Among the structures constituting R1, when the ratio of the group represented by the following formula (B2-1) is α and the ratio of the fluorine-containing group represented by the following formula (B2-2) is β, α + β = 1, and the relationship 0.1 ≦ α ≦ 0.5, 0.5 ≦ β ≦ 0.9 is satisfied. R2 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 and c is 0 to 4. When a is 1, b is 1 to 7 and c is 0 to 6. * represents a bond to another atom.) [Chemical formula] (In the formula, the dashed line represents a bond to the oxygen atom in the above formula (B1), n is 1 to 6, and it may have one or two of the structures represented by the above formula (B2-1).) [Chemical formula] (In the formula, the dashed line represents a bond to the oxygen atom in the above formula (B1), and it may have one or two of the structures represented by the above formula (B2-2).)

[0050] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0051] [Composition for forming an organic film] The composition for forming an organic film of the present invention is (A) Material for forming an organic film, (B) An aryl benzyl ether compound having a partial structure represented by the following general formula (B1), and (C) It contains a solvent. [Chemical formula] (In the formula, R1 is a group represented by the following formula (B2-1) or any fluorine-containing group represented by the following formula (B2-2). Among the structures constituting R1, when the ratio of the group represented by the following formula (B2-1) is α and the ratio of the fluorine-containing group represented by the following formula (B2-2) is β, it satisfies the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9. R2 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 and c is 0 to 4. When a is 1, b is 1 to 7 and c is 0 to 6. * represents a bond to another atom.) [Chemical formula] (In the formula, the dashed line represents a bond to the oxygen atom in the above formula (B1), n is 1 to 6, and it may have one or two of the structures represented by the above formula (B2-1).) [Chemical formula] (In the formula, the dashed line represents a bond to the oxygen atom in the above formula (B1), and it may have one or two of the structures represented by the above formula (B2-2).)

[0052] 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 can be used alone or in combination of two or more.

[0053] 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.

[0054] [(B) Aryl benzyl ether compound] Component (B) in the composition for forming an organic film of the present invention is a compound having a partial structure represented by the above general formula (B1). By blending this compound into the composition for forming an organic film, it becomes useful for forming an organic film.

[0055] The (B) aryl benzyl ether compound of the present invention is a compound containing an aryl benzyl ether structure containing a fluorine atom. In a coating film formed by the (A) material for forming an organic film described later and a composition for forming an organic film containing such a (B) aryl benzyl ether compound, occurrence of humps is less likely to occur during the EBR process. Further, by introducing a substituent containing an appropriate fluorine atom such as the above formula (B2-2), it has the ability to lower the surface tension and can function as a surfactant that brings 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. Furthermore, by adjusting the ratio α of the PEG chain such as the structure represented by the above formula (B2-1) and the ratio β of the fluorine substituent such as the structure represented by the above formula (B2-2) within the above range, even in a low temperature region where it is not thermally decomposed at the benzyl position, due to the sufficient presence of the PEG chain, the contact angle can be adjusted, so 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. Thus, the (B) aryl benzyl ether compound of the present invention has the characteristic of being able to function as a surfactant.

[0056] 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 properties on a substrate, and excellent in hump suppression properties during the EBR process. Furthermore, 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, and an organic film excellent for planarization in the manufacture of semiconductor devices and the like can be formed.

[0057] 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).

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[0058] 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. In addition, 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, it does not cause equipment contamination or inconvenience without narrowing the process margin when used as an organic film.

[0059] 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, etc.

[0060] Examples of the other organic groups 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.

[0061] Some or all of the hydrogen atoms of the organic groups such as the 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 substituents 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 groups such as lactone group, and aromatic heterocyclic groups such as furyl group and pyridyl group.

[0062] From the perspective of raw material availability, the organic group represented by R2 preferably includes a methyl group.

[0063] In the above general formulas (B3), (B4), and (B6), examples of the saturated or unsaturated divalent organic group represented by R3, R5, or R7 having 1 to 30 carbon atoms 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.

[0064] Examples of the alkanediyl oxy group represented by the above 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 the above R3, R5, or R7 include a group formed by combining the above cycloalkanediyl group and an oxygen atom.

[0065] Some or all of the hydrogen atoms of the above alkanediyl group, cycloalkanediyl group, alkanediyl oxy group, cycloalkanediyl oxy group, and arene diyl 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 the above R2 may have.

[0066] Examples of the organic group represented by the above R3, R5, or R7 include a group represented by the following formula.

Chemical formula

[0067] As the above R3, R5, or R7, from the viewpoint of raw material availability, a methylene group can preferably be mentioned.

[0068] The above 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, etc. [Chemical formula] (In the above formula, * represents a bond.)

[0069] As the compound represented by the above general formula (B3), specifically, the following can be exemplified, but it is not limited thereto. In the following exemplification, R1 is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2). Among the structures constituting R1, when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationship of α + β = 1, 0.1 ≦ α ≦ 0.5, and 0.5 ≦ β ≦ 0.9.

[0070] [Chemical formula]

[0071] As the compound represented by the above general formula (B4), specifically, the following can be exemplified, but it is not limited thereto. In the following exemplification, R1 is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2). Among the structures constituting R1, when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationship of α + β = 1, 0.1 ≦ α ≦ 0.5, and 0.5 ≦ β ≦ 0.9. [Chemical formula]

[0072] As the compound represented by the general formula (B6) above, specifically, the following can be exemplified, but it is not limited thereto. In the following exemplification, R1 is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2). Among the structures constituting R1, when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationships of α + β = 1, 0.1 ≦ α ≦ 0.5, and 0.5 ≦ β ≦ 0.9.

[0073]

Chemical formula

[0074] As the compound represented by the general formula (B8) above, specifically, the following can be exemplified, but it is not limited thereto. In the following exemplification, R1 is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2). Among the structures constituting R1, when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationships of α + β = 1, 0.1 ≦ α ≦ 0.5, and 0.5 ≦ β ≦ 0.9.

[0075]

Chemical formula

[0076]

Chemical formula

[0077]

Chemical formula

[0078] As the compound represented by the general formula (B10), specifically, the following can be exemplified, but it is not limited thereto. In the following examples, R1 is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2). Among the structures constituting R1, when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationships of α + β = 1, 0.1 ≦ α ≦ 0.5, and 0.5 ≦ β ≦ 0.9.

[0079]

Chemical formula

[0080] As the compound represented by the general formula (B11), specifically, the following can be exemplified, but it is not limited thereto. In the following examples, R1 is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2). Among the structures constituting R1, when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationships of α + β = 1, 0.1 ≦ α ≦ 0.5, and 0.5 ≦ β ≦ 0.9.

[0081]

Chemical formula

[0082] With the above structure, the thermal decomposability, surface activity effect, and fluidity of the polymer can be adjusted, resulting in a compound that more surely achieves both film-forming properties and embedding properties.

[0083] Furthermore, in the general formulas (B3), (B4), (B6), (B8), (B10), or (B11), among the structures constituting R1, when the ratio of the group represented by the above formula (B2-1), that is, the PEG chain, is α, and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, α and β satisfy the relationship of α + β = 1, 0.1 ≦ α ≦ 0.5, and 0.5 ≦ β ≦ 0.9. As the relationship between α and β, preferably, α + β = 1, 0.15 ≦ α ≦ 0.4, and 0.6 ≦ β ≦ 0.85. When the ratio of the structure is within the above range, it can have a more sufficient ability to lower the surface tension to impart a surfactant effect, and can achieve better coatability. Also, even in a low-temperature region where thermal decomposition does not occur at the benzyl position, an appropriate contact angle can be obtained, and an organic film capable of forming an intermediate film such as a silicon-containing intermediate film thereon with excellent coatability can be formed.

[0084] (B) Among the structures constituting R1 in the aryl benzyl ether compound, the ratio α of the PEG chain and the ratio β of the fluorine-containing group represented by the above formula (B2-2) can be confirmed by nuclear magnetic resonance (NMR) spectroscopy or high performance liquid chromatography (HPLC).

[0085] The weight average molecular weight of the (B) aryl benzyl ether compound is preferably 1,000 to 30,000, more preferably 1,500 to 25,000. If the weight average molecular weight is 1,000 or more, a decrease in the compounding effect due to volatilization or the like can be suppressed, and a sufficient compounding effect can be obtained. Also, if the weight average molecular weight is 30,000 or less, the fluidity does not deteriorate, and the embedding characteristics are excellent.

[0086] In the present invention, the weight average molecular weight (Mw) and the 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 determined from Mw and Mn.

[0087] [Production method of (B) aryl benzyl ether compound] As a means for obtaining the (B) aryl benzyl ether compound of the present invention, for example, but not limited to, dibasic phenols or naphthols using a base catalyst as shown below, a halogen compound represented by the following formula (2b-1), and pentafluorobenzyl halide, 2-(trifluoromethoxy)benzyl halide, 3-(trifluoromethoxy)benzyl halide, or 4-(trifluoromethoxy)benzyl halide can be synthesized by a substitution reaction or the like. The dibasic phenols or naphthols used in the synthesis, the halogen compound represented by the following formula (2b-1), and pentafluorobenzyl halide, 2-(trifluoromethoxy)benzyl halide, 3-(trifluoromethoxy)benzyl halide, or 4-(trifluoromethoxy)benzyl halide can each 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, c, and n in the following formula are the same as above, and X is a Cl atom, a Br atom, or an I atom.

[0088]

Chemical formula

[0089] 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 amount of these catalysts used is preferably in the range of 0.1 to 20 moles, more preferably 0.2 to 10 moles, per mole of the hydroxyl group of the dibasic phenols or naphthols as the raw material.

[0090] The solvent used at this time is not particularly limited as long as it is a solvent 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., can be used alone or in combination. These solvents can be used, for example, in the range of 0 to 2000 parts by mass based on 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, more preferably from room temperature to 150°C. The reaction time is appropriately selected from 0.1 to 100 hours.

[0091] As the reaction method, there are methods such as charging phenols or naphthols, the halogen compound represented by the above formula (2b-1), and pentafluorobenzyl halide, 2-(trifluoromethoxy)benzyl halide, 3-(trifluoromethoxy)benzyl halide, or 4-(trifluoromethoxy)benzyl halide all at once in a solvent; a method of separately or mixing phenols or naphthols, the halogen compound represented by the above formula (2b-1), and pentafluorobenzyl halide, 2-(trifluoromethoxy)benzyl halide, 3-(trifluoromethoxy)benzyl halide, or 4-(trifluoromethoxy)benzyl halide, and then dropping and charging the dispersed or dissolved ones; a method of dispersing or dissolving a part of phenols or naphthols, the halogen compound represented by the above formula (2b-1), 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 remaining raw materials dispersed or dissolved in the solvent. Further, when a plurality of phenols or naphthols, the halogen compound represented by the above formula (2b-1), and pentafluorobenzyl halide, 2-(trifluoromethoxy)benzyl halide, 3-(trifluoromethoxy)benzyl halide, or 4-(trifluoromethoxy)benzyl halide are charged, they may be mixed and reacted in advance or reacted sequentially individually. When using a base catalyst, there are methods such as charging phenols or naphthols, the halogen compound represented by the above formula (2b-1), and pentafluorobenzyl halide, 2-(trifluoromethoxy)benzyl halide, 3-(trifluoromethoxy)benzyl halide, or 4-(trifluoromethoxy)benzyl halide all at once; a method of dropping after previously dispersing or dissolving the base catalyst.

[0092] 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.

[0093] As the organic solvent used for liquid-liquid washing, there is no particular limitation as long as it can dissolve the compound and separates 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, what is usually 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.

[0094] In order to remove unreacted raw materials or acidic components in the system during liquid-liquid washing, washing may be performed with a basic aqueous solution. 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.

[0095] Furthermore, in order to remove unreacted raw materials, metal impurities, or basic components in the system during liquid-liquid washing, washing may be performed with an acidic aqueous solution. 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.

[0096] The liquid-liquid washing with the above basic aqueous solution or acidic aqueous solution may be performed with only one of them, but they can also be combined. From the viewpoint of removing metal impurities, it is preferable to perform the liquid-liquid washing in the order of the basic aqueous solution and the acidic aqueous solution.

[0097] After liquid separation and washing with the above-mentioned basic aqueous solution and acidic aqueous solution, subsequent washing with neutral water may be carried out. 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 of times is small, the basic component and acidic component may not be removed. Since washing more than 10 times does not necessarily result in the obtained washing effect, it is preferably about 1 to 5 times.

[0098] Furthermore, the reaction product after the liquid separation operation can be recovered as a powder by concentrating and drying the solvent under reduced pressure or normal pressure or performing a crystallization operation, but for improving the operability when preparing the material for forming the 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.

[0099] 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; 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 combination of two or more.

[0100] In the above reaction, phenols or naphthols can be combined with the halogen compound represented by the following formula (2b-1) and 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 for controlling surface tension and the like to change the interfacial activity performance can be arbitrarily combined. Therefore, when the composition for forming an organic film using these compounds is used for an organic film, various performances such as film-forming property and embedding property can be achieved in a high dimension.

[0101] [(A) Material for forming organic film] The (A) material for forming an organic film (resin or compound) used in the composition for forming an organic film of the present invention is not particularly limited 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.

[0102] 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, carbazole, and the like. Among these, benzene, naphthalene, fluorene, and carbazole are particularly preferable.

[0103] 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.

[0104] 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 No. 2012-001687 and JP-A No. 2012-077295.

[0105]

Chem.

[0106]

Chem.

[0107] As the material (A) for forming an organic film used in the present invention, resins including 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 can be further exemplified.

[0108]

Chem.

[0109]

Chem.

[0110]

Chemical formula

[0111]

Chemical formula

[0112] Specific 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-2004-205685, JP-A-2007-171895, and JP-A-2009-014816, and the like can be further exemplified.

[0113]

Chemical formula

[0114]

Chemical formula

[0115]

Chemical formula

[0116] Examples of the resin represented by formula (11) include the following resins.

[0117]

Chemical formula

[0118]

Chemical formula

[0119] 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-2007-199653, JP-A-2008-274250, and JP-A-2010-122656.

[0120]

Chemical formula

[0121]

Chemical formula

[0122] [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.)

[0123] [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.)

[0124] Examples of the resin represented by formula (15) include the following resins.

[0125] [Chemical formula]

[0126] [Chemical formula]

[0127]

Chem.

[0128]

Chem.

[0129] 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.

[0130]

Chem.

[0131] Examples of the material (A) for forming an organic film used in the present invention further include resins described in JP-A-2014-29435.

Chem.

[0132] 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.

[0133]

Chemical formula

[0134]

Chemical formula

[0135] 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.

[0136] [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 of 1 to 3. Note that the definitions of the symbols in the formula are applicable only within this formula.)

[0137] Examples of the material (A) for forming an organic film 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.

[0138]

Chemical formula

[0139] Examples of the material (A) for forming an organic film used in the present invention further include a novolak resin having a fluorene or tetrahydrospirobiindene structure described in JP-A No. 2005-128509, JP-A No. 2006-259249, JP-A No. 2006-259482, JP-A No. 2006-293298, and JP-A No. 2007-316282, and a resin containing a repeating unit structure represented by the following formula (22-1) or (22-2).

[0140]

Chemical formula

[0141] As the (A) organic film-forming material used in the present invention, a reaction product obtained by the method described in JP-A-2012-145897 can be further exemplified. More specifically, a polymer obtained by condensing one or more compounds represented by the following general formula (23-1) and / or (23-2) with one or more compounds represented by the following general formula (24-1) and / or (24-2) and / or their equivalents can be exemplified.)

[0142] [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 arbitrarily selected from R 1 ~R 4 or R 5 ~R 8 in the molecule may combine with each other to further form a cyclic substituent. Note that the definitions of the symbols in the formula are applicable only within this formula.)

[0143] [Chemical formula] (In general formula (24-1) and general formula (24-2), Q is an optionally substituted organic group having 1 to 30 carbon atoms, and further, two Qs arbitrarily selected in 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. Further, 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.)

[0144] In addition, examples thereof include polymers obtained by condensing one or more compounds represented by the above general formula (23-1) and / or (23-2), one or more compounds represented by the above general formula (24-1) and / or (24-2) and / or their equivalents, and one or more compounds represented by the following general formula (25) and / or their equivalents.

[0145]

Chemical formula

[0146] Examples of the material (A) for forming an organic film used in the present invention further include compounds containing the following structures described in JP-A-2017-119671.

[0147]

Chemical formula

[0148]

Chemical formula

[0149]

Chemical formula

[0150] Examples of the compound containing the above structure include the following compounds.

Chemical formula

[0151] 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.

Chemical formula

[0152] Examples of the polymer having the repeating unit represented by the above general formula (27-1) include the following polymers.

[0153] [Chemical formula]

[0154] [Chemical formula]

[0155] (A) The material for forming the organic film may be synthesized by a known method or a commercially available product may be used.

[0156] The blending amount of the above-mentioned (A) material for forming an organic film is not particularly limited as long as the film-forming property of the spin coating of the composition for forming an organic film is satisfied. However, when the composition for forming an organic film is 100 parts by mass, the content of the above-mentioned (A) material for forming an organic film 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 composition for forming an organic film, it is necessary to increase the blending amount of the material for forming an organic film. On the other hand, such a composition for forming an organic film has a high viscosity, and the in-plane uniformity and embedding characteristics after spin coating deteriorate. Even with the above blending ratio of the above-mentioned (A) material for forming an organic film, the composition for forming an organic film of the present invention can preferably be applied because it can form an organic film excellent in in-plane uniformity and embedding characteristics.

[0157] Further, with respect to 100 parts by mass of the above-mentioned (A) material for forming an organic film, the content of the above-mentioned (B) aryl benzyl ether compound is preferably 0.01 part by mass to 5 parts by mass. If it is a composition for forming an organic film containing an aryl benzyl ether compound with such a content, the in-plane uniformity of the formed organic film is more excellent.

[0158] [(C) Solvent] As the (C) solvent that can be used in the material for forming an organic film of the present invention, there is no particular limitation as long as it can dissolve the above-mentioned (A) material for forming an organic film and the above-mentioned (B) aryl benzyl ether compound, and it is preferably one that can also dissolve an acid generator, a crosslinking agent, a further surfactant, etc. described later. Specifically, for example, a solvent having 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 a mixture of two or more of these are preferably used.

[0159] (C) The content of the solvent is preferably 200 to 10,000 parts by mass, more preferably 300 to 5,000 parts by mass, relative 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 to be consumed. 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. Examples include hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc. Specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-Hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, n-nonyl acetate, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol-n-butyl ether, triethylene glycol butyl methyl ether, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,Examples 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.

[0160] 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 high-boiling solvent to be added 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.

[0161] 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, if the blending amount is too small, sufficient heat fluidity cannot be imparted during baking, and there is no fear that it will remain in the film and lead to deterioration of film physical properties such as etching resistance.

[0162] For such a composition for forming an organic film, by imparting heat fluidity to the above (A) material for forming an organic film by adding a high-boiling solvent, it becomes a composition for forming an organic film having both high embedding and excellent planarization characteristics.

[0163] [Other Components] In addition, an acid generator or a crosslinking agent for further promoting the crosslinking reaction can be added to the composition for forming an organic film of the present invention. As the acid generator, there are those that generate an acid by thermal decomposition and those that generate an 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 material for forming the organic film (A). With such an amount, it is possible to promote the crosslinking reaction and form a dense film.

[0164] In addition, as the crosslinking agent, specifically, those described in paragraphs

[0055] to

[0060] of JP-A-2007-199653 can be mentioned. 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 material for forming the organic film (A). With such an amount, it is possible to enhance the curability and further suppress the intermixing with the upper layer film.

[0165] In addition, a further surfactant other than the (B) aryl benzyl ether compound of the present invention can be added to the composition for forming an organic film of the present invention in order to further improve the in-plane uniformity in spin coating. 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 material for forming the organic film. With such an amount, it is possible to form an organic film having excellent in-plane uniformity.

[0166] 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 acid to prevent the acid generated in a trace amount from the acid generator from promoting the crosslinking reaction. Specifically, examples of such basic compounds 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.

[0167] 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 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 multilayer resist processes such as a two-layer resist process, a three-layer resist process using a silicon-containing resist intermediate film or a silicon-containing inorganic hard mask intermediate film, and a four-layer resist process using a silicon-containing resist intermediate film or a silicon-containing inorganic hard mask intermediate film and an organic antireflection film or an adhesion film.

[0168] [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.

[0169] In this method for forming an organic film, first, the composition for forming an organic film of the present invention described above is spin-coated on 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.

[0170] The baking is performed in the range of 100°C or higher and 600°C or lower for 10 to 600 seconds, preferably in the range of 200°C or higher and 500°C or lower for 10 to 300 seconds, and particularly preferably in the range of 250°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.

[0171] [Pattern formation method] Hereinafter, a pattern formation method using the composition for forming an organic film of the present invention will be described.

[0172] [Three-layer resist process using a silicon-containing resist intermediate film] In the present invention, a pattern formation 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 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 forming 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.

[0173] As the workpiece, for example, it is preferable to use a semiconductor device substrate or a substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxynitride film, and a metal oxynitride film is formed on the semiconductor device substrate. More specifically, although not particularly limited, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., and those in which the above metal films and the like are formed as a processed layer on the substrate are used.

[0174] As the processed 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 can usually be formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm. When forming the processed layer, substrates and processed layers made of different materials are used.

[0175] In addition, as the metal constituting the workpiece, it is preferable to use those containing silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or alloys thereof.

[0176] 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.

[0177] 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 preferable. By imparting an antireflection effect to the silicon-containing resist intermediate film, reflection can be suppressed. Particularly for 193 nm exposure, when a material containing a large number of aromatic groups and having a high etching selectivity with respect to the substrate is used as the composition for forming the organic film, the k value becomes high and the substrate reflection becomes high. 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 the substrate reflection can be reduced 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 polysiloxane having a phenyl group or an absorptive group having a silicon-silicon bond in a pendant structure and crosslinking with an acid or heat is preferably used.

[0178] 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 usually 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.

[0179] 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 having a wavelength of 10 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination thereof.

[0180] Note that as the exposure light, high-energy rays with a wavelength of 300 nm or less can be mentioned, specifically, far ultraviolet rays, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F2 laser light (157 nm), Kr2 laser light (146 nm), Ar2 laser light (126 nm), soft X-rays (EUV) of 3 to 20 nm, electron beam (EB), ion beam, and X-rays, etc.

[0181] In addition, in the formation of the circuit pattern, it is preferable to develop the circuit pattern with alkali development or an organic solvent.

[0182] 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.

[0183] 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.

[0184] 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.

[0185] Etching of the following workpiece (work layer) can be carried out 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 carried out. 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 carried out 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.

[0186] The organic film obtained by using the composition for forming an organic film of the present invention can be made excellent in etching resistance during etching of the workpiece as described above.

[0187] [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.

[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 organic anti-reflection film (BARC) or an adhesion film is formed between the silicon-containing resist intermediate film and the resist upper layer film.

[0189] The organic anti-reflection film and the adhesion film can be formed by spin coating using a known organic anti-reflection film material.

[0190] [Three-Layer Resist Process Using Inorganic Hard Mask Intermediate Film] Further, in the present invention, a patterning method includes: 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 composed of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern 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; Furthermore, there is provided 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] 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.

[0192] 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 Japanese Patent Application Laid-Open No. 2002-334869, International Publication No. 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 effect as an antireflection film is most preferably used.

[0193] [Four-layer resist process using an inorganic hard mask intermediate film and an organic antireflection film or adhesion film] Further, in the present invention, a patterning method is provided, an organic film is formed on a workpiece using the composition for forming an organic film of the present invention, an inorganic hard mask selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film, an organic antireflection film or adhesion film is formed on the inorganic hard mask, and a resist upper layer film is formed on the organic antireflection film or 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 to the organic antireflection film or adhesion film and the inorganic hard mask by etching, using the inorganic hard mask on which the pattern is transferred as a mask, a pattern is transferred to the organic film by etching, Furthermore, a patterning method is provided, characterized in that a pattern is formed on the workpiece by etching using the organic film on which the pattern is transferred as a mask.

[0194] 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.

[0195] 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 footing of the resist upper layer film pattern directly on the SiON film.

[0196] 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 (workpiece) 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.

[0197] 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 from the hump of the organic film during the dry etching processes of FIGS. 1(D), (E), and (F).

[0198] When forming the inorganic hard mask intermediate film, the silicon-containing resist intermediate film 4 may be changed to the inorganic hard mask intermediate film. When forming the BARC or the adhesion film, the BARC or the 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.

[0199] As described above, in the pattern forming method of the present invention, by the multilayer resist process, a fine pattern can be formed on the 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.

[0200] [Surfactant] The surfactant of the present invention is a surfactant composed of the (B) aryl benzyl ether compound contained in the composition for forming an organic film of the present invention described above.

[0201] The surfactant of the present invention combines fluorine substituents such as the structure represented by the formula (B2-2) described above, and is excellent in in-plane uniformity and embedding characteristics, and is suitable for forming an organic film in which the formation of humps due to the influence of the remover in the EBR process is suppressed. Further, by adjusting the ratio α of the PEG chain such as the structure represented by the formula (B2-1) and the ratio β of the fluorine substituent such as the structure represented by the formula (B2-2) to the above range, even in a low temperature region where thermal decomposition does not occur at the benzyl position, due to the sufficient presence of the PEG chain, the contact angle can be adjusted, so that it is possible to realize a composition for forming an organic film capable of improving the coatability when applying an intermediate film, for example, a silicon-containing intermediate film thereon.

[0202] In the present invention, the aryl benzyl ether compound is preferably a compound represented by the general formulas (B3), (B4), (B6), (B8), (B10), or (B11) described above.

[0203] For an organic film-forming composition containing such a surfactant, by having an appropriate fluorine content, the film-forming property during coating can be further improved.

[0204] The weight-average molecular weight of the aryl benzyl ether compound is preferably from 1000 to 30000.

[0205] If it is within such a range of the weight-average molecular weight, it becomes possible to form an organic film excellent in film-forming property and embedding characteristics. The weight-average molecular weight can be determined by the method described above.

[0206] The surfactant of the present invention is not limited to the use for forming an organic film, and can also be used, for example, in the following applications.

[0207] The surfactant of the present invention can be used for all coating materials for photolithography. Specifically, photosensitive resist materials, materials for forming a top coat formed on a resist film, etc. can be exemplified.

[0208] Also, unexpectedly, the surfactant of the present invention functions as a wetting agent, a flow agent, or a leveling agent in various aqueous or non-aqueous coatings. Examples of aqueous coatings include latex paints and floor polishes applied to glass, wood, metal, ceramic, and polymer substrates. Examples of non-aqueous or solvent-based coatings typically include enamels and varnishes applied to the same substrates as above. Furthermore, various of the above fluorinated polar polymers are useful wetting agents, flow agents, or leveling agents in various powders and radiation-curable coatings. The above fluorinated polar polymers exert their function by lowering the surface tension of the coating compared to the surface tension of the substrate to which they are applied.

[0209] Furthermore, various fluorinated polar polymers can be used as additives for various consumer products, such as cleaners, shampoos, and cosmetics, as well as furniture and glass cleaners, automotive polishers, and the like.

[0210] Furthermore, the fluorinated polar polymers of the present invention can be utilized in coatings on various substrates to form laminates.

[0211] Further end uses can be classified, although not limited to, for example, as follows. (1) For paints and coatings, as a flow modifier, for improved wetting, improved leveling and gloss, for improved stain resistance, and as a Teflon® wetting aid. (2) For waxes and polishers, for improved leveling and gloss, for improved wetting, and as a Teflon® wetting aid. (3) For aqueous adhesives, as a semi - peeling adhesive for improved wetting and leveling. The same also applies to non - aqueous adhesives. (4) For various graphic art applications, for improved leveling, reduced ink wicking, for wetting of photographic emulsions, and for improved cylinder life. (5) For various polymer technology applications, such as release agent sprays, emulsion polymerization, anti - fogging agents, external lubricants, internal lubricants, coupling agents, Teflon® wetting aids, wetting agents for olefins and acrylates, and CaSO4 scale removers. (6) For electronic applications, for example, as a zinc battery scale inhibitor and as a plating bath aid. (7) For caulking materials having improved leveling and stain resistance. (8) For metal technology applications, for example, for corrosion resistance, wetting of etching baths, cleaning and scale removal, and for degreasing. (9) For various cleaning applications, for example for hair conditioning and rinsing, alkaline cleaners, glass cleaners and anti-fog agents, for shampoos, and for solvent degreasing.

[0212] Further applications include floor polish emulsion; electrolytic conversion coating; photographic process; fluoropolymer emulsion; specialty ink; aqueous coating; solvent-based coating; electro-etching bath; corrosion inhibitor; solder system; alkaline system; pre-plating etchant for plastics.

[0213] That is, the surfactant of the present invention is useful not only for industrial applications but also for daily necessities applications.

Examples

[0214] Hereinafter, synthesis examples, comparative synthesis examples, examples, and comparative examples are shown to more specifically explain the present invention, 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.

[0215] [Synthesis of aryl benzyl ether compounds (B-1) to (B-18)] For the synthesis of aryl benzyl ether compounds (B-1) to (B-18) used in the preparation of the organic film-forming compositions (UDL-1 to 113) of the examples, the following phenolic compounds (a1) to (a14) and bromo compounds (b1) to (b4) were used.

[0216] (Phenolic compounds)

Chemical formula

[0217] (Bromo compounds)

Chemical formula

[0218] [Synthesis Example 1] Synthesis of aryl benzyl ether compound (B-1) [Chemical Formula] 60.0 g of DMF (N,N-dimethylformamide) was added to 2.12 g of 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, 1.63 g of triethylene glycol 2-bromoethyl methyl ether and 3.65 g of bromo compound (b1) were 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 cooling the reaction solution 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-1).

[0219] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-1): Mw = 3990, Mw / Mn = 2.81

[0220] [Synthesis Example 2] Synthesis of aryl benzyl ether compound (B-2) [Chemical Formula] 2.12 g of a phenolic compound (a1) 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, 2.71 g of triethylene glycol 2-bromoethyl methyl ether and 2.61 g of a bromo compound (b1) were 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).

[0221] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-2): Mw = 3850, Mw / Mn = 2.84

[0222] [Synthesis Example 3] Synthesis of aryl benzyl ether compound (B-3)

Chemical formula

[0223] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-3): Mw = 4100, Mw / Mn = 2.77

[0224] [Synthesis Example 4] Synthesis of Aryl Benzyl Ether Compound (B-4)

Chemical Structure

[0225] [Synthesis Example 5] Synthesis of Aryl Benzyl Ether Compound (B-5)

Chemical Structure

[0226] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-5): Mw = 7340, Mw / Mn = 5.53

[0227] [Synthesis Example 6] Synthesis of aryl benzyl ether compound (B-6) [Chemical formula] 2.67 g of the 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, 0.45 g of diethylene glycol 2-bromoethyl methyl ether and 4.59 g of the bromo compound (b2) were 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 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 the aryl benzyl ether compound (B-6).

[0228] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-6): Mw = 7780, Mw / Mn = 5.29

[0229] [Synthesis Example 7] Synthesis of Aryl Benzyl Ether Compound (B-7)

Chemical Structure

[0230] To 2.90 g of a phenolic compound (a3) and 2.76 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred at an internal temperature of 60°C under a nitrogen atmosphere to form a homogeneous solution. Then, 1.82 g of diethylene glycol 2-bromoethyl methyl ether and 3.13 g of bromo compound (b1) were 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 cooling the reaction solution 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-7).

[0231] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-7): Mw = 5160, Mw / Mn = 2.88

[0232] [Synthesis Example 8] Synthesis of Aryl Benzyl Ether Compound (B-8)

Chemical Structure

[0233] 6.30 g of a 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, 2.17 g of triethylene glycol 2-bromoethyl methyl ether and 8.16 g of a bromo compound (b2) were 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-8).

[0234] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-8): Mw = 4720, Mw / Mn = 2.52

[0235] [Synthesis Example 9] Synthesis of aryl benzyl ether compound (B-9) [Chemical formula]

[0236] 5.07 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, 3.25 g of triethylene glycol 2-bromoethyl methyl ether and 7.31 g of a bromo compound (b1) were 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-9).

[0237] When the weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-9): Mw = 3800, Mw / Mn = 2.93

[0238] [Synthesis Example 10] Synthesis of aryl benzyl ether compound (B-10) [Chemical Formula] 60.0 g of DMF (N,N-dimethylformamide) was added to 7.52 g of a phenolic compound (a6) and 5.53 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, 2.72 g of diethylene glycol 2-bromoethyl methyl ether and 7.14 g of bromo compound (b3) were 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 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-10).

[0239] When the weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-10): Mw = 4120, Mw / Mn = 3.39

[0240] [Synthesis Example 11] Synthesis of aryl benzyl ether compound (B-11) [Chemical Formula]

[0241] 6.35 g of a 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, 3.25 g of triethylene glycol 2-bromoethyl methyl ether and 12.53 g of a bromo compound (b1) were 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 make it homogeneous, 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).

[0242] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-11): Mw = 11900, Mw / Mn = 6.59

[0243] [Synthesis Example 12] Synthesis of aryl benzyl ether compound (B-12)

Chemical formula

[0244] 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, 5.45 g of diethylene glycol 2-bromoethyl methyl ether and 9.18 g of a bromo compound (b2) were 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 make it homogeneous, 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).

[0245] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-12): Mw = 2680, Mw / Mn = 1.88

[0246] [Synthesis Example 13] Synthesis of aryl benzyl ether compound (B-13) [Chemical formula]

[0247] 60.0 g of DMF (N,N-dimethylformamide) was added to 11.69 g of a phenolic compound (a9) 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, 8.18 g of diethylene glycol 2-bromoethyl methyl ether and 21.92 g of bromo compound (b1) were 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 an aryl benzyl ether compound (B-13).

[0248] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-13): Mw = 2020, Mw / Mn = 1.36

[0249] [Synthesis Example 14] Synthesis of aryl benzyl ether compound (B-14) [Chemical formula]

[0250] 11.69 g of a phenolic compound (a10) 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, 9.76 g of triethylene glycol 2-bromoethyl methyl ether and 21.42 g of a bromo compound (b2) were 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-14).

[0251] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-14): Mw = 2230, Mw / Mn = 1.29

[0252] [Synthesis Example 15] Synthesis of aryl benzyl ether compound (B-15) [Chemical formula]

[0253] 17.50 g of a phenolic compound (a11) 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, 8.18 g of diethylene glycol 2-bromoethyl methyl ether and 21.92 g of a bromo compound (b1) were 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-15).

[0254] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-15): Mw = 3730, Mw / Mn = 1.63

[0255] [Synthesis Example 16] Synthesis of aryl benzyl ether compound (B-16)

Chemical formula

[0256] 60.0 g of DMF (N,N-dimethylformamide) was added to 15.50 g of a phenolic compound (a12) 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, 9.76 g of triethylene glycol 2-bromoethyl methyl ether and 21.42 g of bromo compound (b4) were 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 an aryl benzyl ether compound (B-16).

[0257] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-16): Mw = 3150, Mw / Mn = 2.46

[0258] [Synthesis Example 17] Synthesis of aryl benzyl ether compound (B-17)

Chemical formula

[0259] 2.40 g of the phenolic compound (a13) 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, 1.63 g of triethylene glycol 2-bromoethyl methyl ether and 3.65 g of bromo compound (b1) were 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 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-17).

[0260] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-17): Mw = 23350, Mw / Mn = 1.21

[0261] [Synthesis Example 18] Synthesis of aryl benzyl ether compound (B-18) [Chemical formula]

[0262] 2.40 g of the 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, 1.36 g of diethylene glycol 2-bromoethyl methyl ether and 3.57 g of bromo compound (b2) were 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 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-18).

[0263] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (B-18): Mw = 20490, Mw / Mn = 1.14

[0264] [Synthesis of Comparative Compounds (R1) to (R6)] For the synthesis of the comparative compounds (R1) to (R6) used in the preparation of the organic film-forming compositions (Comparative UDL-7 to 17) of the comparative examples, the following monomers (r1) to (r3) and the bromo compounds (r4) and (r5) were used.

[0265] [Chemical Formula]

[0266] [Comparative Synthesis Example 1] Synthesis of Comparative Compound (R1) [Chemical Formula]

[0267] Under a nitrogen atmosphere, 40.0 g of PGME (propylene glycol monomethyl ether) was added to 7.45 g of the monomer (r1), and the mixture was stirred at an internal temperature of 110 °C to form a homogeneous solution. Then, 1.14 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 (R1).

[0268] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (R1): Mw = 5020, Mw / Mn = 3.11

[0269] [Comparative Synthesis Example 2] Synthesis of Comparative Compound (R2) [Chemical Formula]

[0270] Under a nitrogen atmosphere, 40.0 g of PGME (propylene glycol monomethyl ether) was added to 2.16 g of monomer (r2) and 0.54 g of monomer (r3), 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 (R2).

[0271] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (R2): Mw = 5700, Mw / Mn = 3.55

[0272] [Comparative Synthesis Example 3] Synthesis of Comparative Compound (R3)

Chemical Formula

[0273] 60.0 g of DMF (N,N-dimethylformamide) was added to 2.12 g of phenolic compound (R1) 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, 2.98 g of triethylene glycol 2-bromoethyl methyl ether and 2.35 g of bromo compound (r4) were 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 2 times with 100 ml of 3% aqueous nitric acid solution and 5 times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain the aryl benzyl ether compound (R3).

[0274] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (R3): Mw = 3790, Mw / Mn = 2.88

[0275] [Comparative Synthesis Example 4] Synthesis of Comparative Compound (R4)

Chemical Structure

[0276] To 2.67 g of phenolic compound (R2) and 2.76 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred at an internal temperature of 60 °C under a nitrogen atmosphere to form a homogeneous solution. Then, 2.50 g of diethylene glycol 2-bromoethyl methyl ether and 2.30 g of bromo compound (r5) were 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 cooling the reaction solution 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 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 (R4).

[0277] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (R4): Mw = 7330, Mw / Mn = 5.55

[0278] [Comparative Synthesis Example 5] Synthesis of Comparative Compound (R5)

Chemical Structure

[0279] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (R5): Mw = 4050, Mw / Mn = 2.75

[0280] [Comparative Synthesis Example 6] Synthesis of Comparative Compound (R6) [Chemical Formula]

[0281] 2.67 g of a phenolic compound (R2) 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, 0.23 g of diethylene glycol 2-bromoethyl methyl ether and 4.84 g of a bromo compound (r5) were 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 (R6).

[0282] When the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained. (R6): Mw = 7810, Mw / Mn = 5.29

[0283] [(A) Material for forming organic film (resin or compound)] In the preparation of the organic film-forming compositions (UDL-1 to 113, and Comparative UDL-1 to 17) of the Examples and Comparative Examples, the following resins or compounds were used as the (A) material for forming the organic film. 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)

[0284] [Chemical formula]

[0285] [(C) Solvent] In the preparation of the organic film-forming compositions (UDL-1 to 113 and Comparative UDL-1 to 17) of the Examples and Comparative Examples, the following solvents were used as the (C) solvent, respectively. (S1): Propylene glycol monomethyl ether acetate (S2): Propylene glycol monoethyl ether

[0286] [Preparation of organic film-forming compositions (UDL-1 to 113, Comparative UDL-1 to 17)] Either one or both of the above compounds (B-1) to (B-18) and (R1) to (R6), and either one or both of the above organic film-forming materials (M1) to (M6) were dissolved at the ratios shown in Tables 1 to 4. The thus-obtained mixtures were filtered through a 0.1-μm fluororesin filter to prepare organic film materials (resist underlayer film materials: UDL-1 to 113, Comparative UDL-7 to 17), respectively. Further, either one of the above organic film-forming materials (M1) to (M6) and the above solvent (S1) were dissolved at the ratio shown in Table 4. The thus-obtained mixtures were filtered through a 0.1-μm fluororesin filter to prepare organic film-forming compositions (resist underlayer film materials: Comparative UDL-1 to 6), respectively.

[0287]

Table 1

[0288]

Table 2

[0289]

Table 3

[0290]

Table 4

[0291] [Fabrication of a silicon wafer on which an organic cured film was formed using the organic film-forming composition (UDL-1 to 113, Comparative UDL-1 to 17)] Using the coater / developer "CLEAN TRACK LITHIUS Pro AP" of Tokyo Electron Limited, 2 ml of each of the organic film-forming compositions (UDL-1 to 113, Comparative UDL-1 to 17) prepared above was discharged at the center of a silicon wafer, and rotated at a rotational speed to obtain the average film thickness described in Tables 5 to 8 to spread it, 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, the removal liquid discharge nozzle was moved from the outer peripheral portion to the center portion of the silicon wafer at a speed of 5 mm / s while discharging the removal liquid (a mixed liquid of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30:70, mass ratio)) at a discharge rate of 2 mL / s to a position 3 mm from the center, and at that position, the removal liquid was discharged for 5 seconds at a discharge rate of 2 mL / s. 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 a silicon wafer on which an organic film (organic cured film) of each example was formed.

[0292] [Solvent Resistance Evaluation: Examples 1-1 to 1-113, Comparative Examples 1-1 to 1-17] An organic film was formed on a silicon wafer using each of the organic film-forming compositions (UDL-1 to 113, Comparative UDL-1 to 17) 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, and 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, and when it was 0.5% or more, it was considered bad. The results are shown in Tables 5 to 8 below.

[0293] [In-plane Uniformity Evaluation: Examples 1-1 to 1-113, Comparative Examples 1-1 to 1-17] Using the above method, an organic film was formed on a silicon wafer using each organic film-forming composition (UDL-1 to 113, Comparative UDL-1 to 17). 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 defined as (X max - X min ) / X average , and the value obtained was defined as the in-plane uniformity (%). When the in-plane uniformity was less than 2%, it was rated A (good); when it was 2% or more and less than 3%, it was rated B; when it was 3% or more, it was rated C (poor). The results are shown in Tables 5 to 8.

[0294]

Table 5

[0295]

Table 6

[0296]

Table 7

[0297]

Table 8

[0298] As shown in Tables 5 to 8, in Examples 1-1 to 1-113 using the organic film-forming composition of the present invention, an organic film with good solvent resistance and in-plane uniformity was obtained. However, among Comparative Examples 1-1 to 1-17 (Comparative UDL-1 to 15) using a composition that does not contain the aryl benzyl ether compound contained in the organic film-forming composition of the present invention, the in-plane uniformity was poor. Therefore, in the following evaluation, UDL-1 to 113 and Comparative UDL-16 to 17, which had good solvent resistance and in-plane uniformity, were examined.

[0299] [Hump Suppression Evaluation: Examples 2-1 to 2-113, Comparative Examples 2-1 to 2-2] Using the above method, an organic film was formed on a silicon wafer using each organic film-forming composition (UDL-1 to 113, Comparative UDL-16 to 17), 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 profilometer) manufactured by KLA-TENCOR. When the height of the silicon wafer was set to 0, as shown in Figure 2, if the maximum height was less than 110% of the film thickness, it was evaluated as A (good); if the maximum height was 110% or more and less than 150%, it was B; and as shown in Figure 3, if a region with a height of 150% or more occurred, it was evaluated as C (bad). The results are shown in Tables 9 to 12.

[0300] [Embedding evaluation: Examples 2-1 to 2-113, Comparative Examples 2-1 to 2-2] As shown in Figure 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 113, Comparative UDL-16 to 17) was used to form an organic film 8 by the above method. The substrate used was a base substrate (SiO2 wafer substrate) 7 having a dense hole pattern as shown in Figures 4(G) (top 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 Figure 4(I), the holes were filled with the organic film without voids. If no voids occurred, it was evaluated as good; if voids occurred, it was evaluated as bad. The results are shown in Tables 9 to 12.

[0301] [Evaluation of coating property of silicon-containing resist intermediate film: Examples 2-1 to 2-113, Comparative Examples 2-1 to 2-2] Using each composition for forming an organic film (UDL-1 to 113, Comparative UDL-16 to 17), an organic film was formed on a silicon wafer substrate by the above method. Then, 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.

[0302] When the state of the coating film of the silicon-containing resist intermediate film was good, it was rated as good; when dewetting occurred, it was rated as bad.

[0303] In this evaluation, in order to evaluate the superiority or inferiority of the coatability of the silicon-containing resist intermediate film, severe evaluation conditions were set with the film thickness of the silicon-containing resist intermediate film being 10 nm. The results are shown in Tables 9 to 12.

[0304] As the silicon-containing resist intermediate film material (SOG1), a propylene glycol ethyl ether solution of the following polymer was prepared. The polymer solution used for the evaluation of the coatability of the silicon intermediate film was 0.5% by weight.

[0305]

Chemical formula

[0306] [Contact angle evaluation: Examples 2-1 to 2-113, Comparative Examples 2-1 to 2-2] Using each composition for forming an organic film (UDL-1 to 113, Comparative UDL-16 to 17), an organic film was formed on a silicon wafer substrate by the above method, and the contact angle with pure water was measured. The results are shown in Tables 9 to 12.

[0307]

Table 9

[0308]

Table 10

[0309]

Table 11

[0310]

Table 12

[0311] As shown in Tables 9 to 12, it was confirmed that the composition for forming an organic film (UDL-1 to 113) of the present invention is excellent in solvent resistance, in-plane uniformity, hump suppression property, embedding property, and coatability of the silicon-containing resist intermediate film. Also, the contact angle was between 52 and 64 degrees.

[0312] [Comparison of contact angle evaluation between 250 °C bake and 350 °C bake: Examples 3-1 to 3-54 and Comparative Examples 3-1 to 3-2] An organic film was formed on a silicon wafer substrate using each composition for forming an organic film (UDL-24 to 77 and Comparative UDL-16 to 17) in the same manner as the above method except that the silicon wafer coated with the composition for forming an organic film was heated at 250 °C for 60 seconds, and the contact angle with pure water was measured. The results are shown in Tables 13 to 14.

[0313] Note that, as the composition for forming an organic film, a resin for forming an organic film with good results in solvent resistance evaluation was selected in the same manner as the above method by baking at 250 °C. The results are shown in Tables 13 to 14.

[0314] Also, each result of the contact angle evaluation at 350 °C bake was obtained in Example 2.

[0315] [Comparison of silicon intermediate film coatability evaluation between 250 °C bake and 350 °C bake: Examples 3-1 to 3-54 and Comparative Examples 3-1 to 3-2] An organic film was formed on a silicon wafer substrate in the same manner as the above method, except that the silicon wafer coated with the composition for forming an organic film was heated at 250 °C for 60 seconds. The composition for forming an organic film (UDL-24 to 77 and Comparative UDL-16 to 17) was used. Then, 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. And the state of the coating film of the silicon-containing resist intermediate film was visually observed and evaluated.

[0316] When the state of the coating film was good, it was rated as good; when dewetting occurred, it was rated as bad.

[0317] In this evaluation, in order to evaluate the superiority or inferiority of the coatability of the silicon-containing resist intermediate film, severe evaluation conditions were set with the film thickness of the silicon intermediate film being 10 nm. The results are shown in Tables 13 to 14.

[0318] Also, the evaluation results of the coatability of the silicon intermediate film at 350 °C baking shown in Tables 13 to 14 are those obtained in Example 2.

[0319] As the silicon-containing resist intermediate film material (SOG1), a propylene glycol ethyl ether solution of the same polymer as that used in Example 2 was prepared. The polymer solution used for the evaluation of the coatability of the silicon-containing resist intermediate film was 0.5% by weight.

[0320] [Table 13]

[0321] [Table 14]

[0322] As shown in Tables 13 to 14, it was confirmed that the coating property of the silicon-containing resist intermediate film after film formation by baking at 250 °C of the composition for forming an organic film (UDL-24 to 77) which is an example of the present invention is excellent. Further, the contact angle at the time of baking at 250 °C was 64 degrees or more and less than 80 degrees. On the other hand, in Comparative Examples 3-1 to 3-2 which are the ratios of the structures outside the above range, in the low temperature region where thermal decomposition does not occur at the benzyl position, the contact angle was high, resulting in deterioration of the coating property of the silicon-containing resist intermediate film. By adjusting the ratio α of the PEG chain such as the structure represented by the above formula (B2-1) and the ratio β of the fluorine substituent such as the structure represented by the above formula (B2-2) to the above range, even in the low temperature region where thermal decomposition does not occur at the benzyl position, due to the sufficient presence of the PEG chain, the contact angle can be adjusted, so that it was confirmed that it becomes a composition for forming an organic film excellent in the coating property of an intermediate film such as a silicon-containing resist intermediate film.

[0323] [Pattern formation test: Examples 4-1 to 4-113] An organic cured film was formed on a SiO2 wafer substrate using the composition for forming an organic film (UDL-1 to 113) 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 having 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 having 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 having a film thickness of 50 nm.

[0324] As the silicon-containing resist intermediate film material (SOG1), a 2% solution of the following polymer in propylene glycol ethyl ether was prepared.

[0325] [Chemical formula]

[0326] 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 15, and filtering through a 0.1-μm fluororesin filter.

[0327]

Table 15

[0328] The polymer (RP1), the acid generator (PAG1), and the basic compound (Amine1) are shown below.

Chemical formula

[0329] The immersion protective film material (TC-1) was prepared by dissolving a polymer (PP1) in an organic solvent at the ratios shown in Table 16, and filtering through a 0.1-μm fluororesin filter.

Table 16

[0330] The polymer (PP1) is shown below.

Chemical formula

[0331] 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% by 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.

[0332] Next, using an etching apparatus Telius manufactured by Tokyo Electron, with the upper resist film pattern as a mask, the silicon-containing resist intermediate film was dry-etched (pattern transfer) 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.

[0333] (Transfer conditions of the upper resist 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

[0334] (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

[0335] (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

[0336] 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 17 to 20.

[0337]

Table 17

[0338]

Table 18

[0339]

Table 19

[0340]

Table 20

[0341] As shown in Tables 17 to 20, in Examples 4-1 to 4-113 using the organic film-forming compositions (UDL-1 to 113) of the examples of the present invention, the resist upper layer film patterns were all finally well transferred to the SiO2 wafer substrate, and it was confirmed that the organic film-forming compositions of the examples of the present invention are suitably used for fine processing by the multilayer resist method.

[0342] From the above, it can be seen that the organic film-forming composition of the present invention has excellent film-forming properties, high embedding characteristics, and excellent hump suppression properties, and is excellent in the coatability of the silicon-containing resist intermediate film, so it is extremely useful as an organic film material used in the multilayer resist process. Further, in the pattern forming method of the present invention using the organic film-forming composition of the present invention, it is possible to embed holes and trenches with a very high aspect ratio without gaps and to form fine patterns with high precision, and since an organic film with suppressed humps can be formed, it can be seen that semiconductor elements and the like can be efficiently manufactured.

[0343] Furthermore, from the results of the above-described embodiments, it can be seen that the surfactant of the present invention is suitable for forming 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. Also, it can be seen that by using the surfactant of the present invention, an organic film-forming composition capable of forming an organic film on which an intermediate film, for example, a silicon-containing intermediate film, can be formed with excellent coatability can be realized.

[0344] This specification includes the following aspects. [1] An organic film-forming composition, comprising: (A) A material for forming an organic film, (B) An aryl benzyl ether compound having a partial structure represented by the following general formula (B1), and (C) A solvent, and characterized in that it contains them.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[10] The method for forming a pattern according to [8] or [9], characterized in that 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, according to any one of [6] to

[10] . The pattern formation method described.

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

[11] . The pattern formation method described.

[13] The method for forming a pattern according to any one of [6] to

[12] , characterized in that 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 oxide carbide film, and a metal oxide nitride film are formed on the semiconductor device substrate.

[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 formation method according to

[13] , characterized in that such a material is used.

[15] A surfactant comprising an aryl benzyl ether compound having a partial structure represented by the following general formula (B1).

Chemical formula

Chemical formula

Chemical formula

[16] The surfactant according to

[15] , characterized in that the aryl benzyl ether compound is a compound represented by the following general formula (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

[17] The surfactant according to

[15] or

[16] , characterized in that the weight average molecular weight of the aryl benzyl ether compound is 1000 to 30000.

[0345] Note that the present invention is not limited to the above-described embodiments. The above-described embodiments are examples, 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 symbols

[0346] 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... Lower substrate, 8... Organic film.

Claims

1. A composition for forming an organic film, comprising: (A) a material for forming an organic film, a benzyl aryl ether compound having a partial structure represented by the following general formula (B1), and a solvent (C), and characterized in that it is a composition for forming an organic film. 【Chemical 1】 (wherein R １ is a group represented by the following formula (B2-1) or any fluorine-containing group represented by the following formula (B2-2), and among the structures constituting the R １ when the ratio of the group represented by the following formula (B2-1) is α and the ratio of the fluorine-containing group represented by the following formula (B2-2) is β, it satisfies the relationship of α + β = 1, 0.1 ≦ α ≦ 0.5, 0.5 ≦ β ≦ 0.

9. 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 to another atom.) 【Chemical 2】 (In the formula, the broken line represents a bond with an oxygen atom in the above formula (B1), n is 1 to 6, and it may have one or two of the structures represented by the above formula (B2-1).) 【Chemical Formula 3】 (In the formula, the broken line represents a bond with an oxygen atom in the above formula (B1), and it may have one or two of the structures represented by the above formula (B2-2).)

2. The composition for forming an organic film according to claim 1, wherein the (B) benzyl aryl ether compound is a compound represented by the following general formula (B3), (B4), (B6), (B8), (B10), or (B11). 【Chemical Formula 4】 (In the formula, R １ is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2). Among the structures constituting the said R １ , when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationship of α + β = 1, 0.1 ≦ α ≦ 0.5, and 0.5 ≦ β ≦ 0.

9. 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. When a1 is 0, b1 is 1 to 5 and c1 is 0 to 4. When a1 is 1, b1 is 1 to 7 and c1 is 0 to 6.) 【Chemical Formula 5】 (In the formula, R １ is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2). Among the structures constituting the above R １ , when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.

9. R ２ is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, and R ４ is a single bond or any 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 and c2 is 0 to 4. When a2 is 1, b2 is 1 to 7 and c2 is 0 to 6. ) [Chemical Formula 6] 【Chemical Formula 7】 (In the formula, R １ is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2). Among the structures constituting the said R １ , when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationships of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.

9. 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 and c3 is 0 to 4. When a3 is 1, b3 is 1 to 7 and c3 is 0 to 6.) 【Chemical 8】 【Chemical Formula 9】 (In the formula, R １ is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2). Among the structures constituting the R １ , when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.

9. 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 10】 (In the formula, R １ is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2), and among the structures constituting the above R １ when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationships of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9.) 【Chemical 11】 (In the formula, R １ is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2). Among the structures constituting the above R １ , when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationships of α + β = 1, 0.1 ≦ α ≦ 0.5, and 0.5 ≦ β ≦ 0.

9. 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 Formula 12】 (In the formula, R １ is a group represented by the above formula (B2-1) or any group containing fluorine represented by the above formula (B2-2). Among the structures constituting the R １ , when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationships of α + β = 1, 0.1 ≦ α ≦ 0.5, and 0.5 ≦ β ≦ 0.

9. 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) benzyl aryl ether compound is 1000 to 30000.

4. The composition for forming an organic film according to claim 1, wherein the content of the (B) benzyl aryl ether compound is 0.01 parts 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 a manufacturing process of a semiconductor device, comprising: spin-coating the composition for forming an organic film according to any one of claims 1 to 4 on a substrate to be processed to obtain a coating film, and curing the coating film by heat treatment at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to form an organic film.

6. 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, 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 characterized by forming a pattern 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 characterized by forming a pattern 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 characterized by forming a pattern 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, the 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, the 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 formation method characterized by this.

10. The pattern formation method according to claim 8, 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 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 formation method according to claim 6, characterized by this.

13. The workpiece is a semiconductor device substrate or a substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxynitride film, and a metal oxynitride film is formed on the semiconductor device substrate. The pattern formation 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 formation method according to claim 13, characterized by using such a material.

15. A surfactant composed of an aryl benzyl ether compound having a partial structure represented by the following general formula (B1). 【Chemical 13】 (wherein, R １ is a group represented by the following formula (B2-1) or any fluorine-containing group represented by the following formula (B2-2), and among the structures constituting the R １ when the ratio of the group represented by the following formula (B2-1) is α and the ratio of the fluorine-containing group represented by the following formula (B2-2) is β, it satisfies the relationship of α + β = 1, 0.1 ≦ α ≦ 0.5, 0.5 ≦ β ≦ 0.

9. 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 to another atom.) 【Chemical 14】 (In the formula, the broken line indicates a bond with an oxygen atom in the above formula (B1), n is 1 to 6, and it may have one kind or two kinds of the structures represented by the above formula (B2-1).) 【Chemical 15】 (In the formula, the broken 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 (B2-2).)

16. The surfactant according to claim 15, wherein the aryl benzyl ether compound is a compound represented by the following general formulas (B3), (B4), (B6), (B8), (B10), or (B11). 【Chemical 16】 (In the formula, R １ is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2). Among the structures constituting the above R １ , when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationships of α + β = 1, 0.1 ≦ α ≦ 0.5, and 0.5 ≦ β ≦ 0.

9. 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. When a1 is 0, b1 is 1 to 5 and c1 is 0 to 4. When a1 is 1, b1 is 1 to 7 and c1 is 0 to 6.) 【Chemical 17】 (In the formula, R １ is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2). Among the structures constituting the above R １ , when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.

9. R ２ is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, and R ４ is a single bond or any 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 and c2 is 0 to 4. When a2 is 1, b2 is 1 to 7 and c2 is 0 to 6.) 【Chemical Formula 18】 【Chemical 19】 (wherein, R １ is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2), and among the structures constituting the above R １ , when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationship of α + β = 1, 0.1 ≦ α ≦ 0.5, 0.5 ≦ β ≦ 0.

9. 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, and when a3 is 1, b3 is 1 to 7, c3 is 0 to 6.). 【Chemical 20】 【Chemical 21】 (In the formula, R １ is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2). Among the structures constituting the R １ , when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationships of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.

9. 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 22】 (In the formula, R １ is a group represented by the above formula (B2-1) or any group containing fluorine represented by the above formula (B2-2). Among the structures constituting the above R １ , when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationships of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9.) 【Chemical 23】 (In the formula, R １ is a group represented by the above formula (B2-1) or any group containing fluorine represented by the above formula (B2-2). Among the structures constituting the above R １ , when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the group containing fluorine represented by the above formula (B2-2) is β, it satisfies the relationship of α + β = 1, 0.1 ≦ α ≦ 0.5, and 0.5 ≦ β ≦ 0.

9. 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 24】 (wherein, R １ is a group represented by the above formula (B2-1) or any fluorine-containing group represented by the above formula (B2-2), and among the structures constituting the above R １ when the ratio of the group represented by the above formula (B2-1) is α and the ratio of the fluorine-containing group represented by the above formula (B2-2) is β, it satisfies the relationships of α + β = 1, 0.1 ≦ α ≦ 0.5, and 0.5 ≦ β ≦ 0.

9. R ８ is a hydrogen atom or a methyl group, and b6 is from 1 to 5.)

17. The surfactant according to claim 15 or 16, wherein the weight average molecular weight of the aryl benzyl ether compound is from 1000 to 30000.

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