Organic film-forming material, pattern forming method, compound and polymer

Abstract

The present invention relates to an organic film-forming material, a pattern-forming method, and a compound and a polymer. The problem to be solved by the present invention is to provide an organic film-forming material and a compound and a polymer suitable for the organic film-forming material. This problem is solved by providing an organic film-forming material containing: (A) a compound represented by the following formula (1) and / or a polymer having a repeating unit represented by the following formula (4); and (B) an organic solvent. In the formula (1), AR1, AR2, AR3, AR4, AR5, and AR6 are benzene rings or naphthalene rings, and R1 is any one of the groups represented by the following formula (2). n represents an integer of 1 to 2, and W is a divalent organic group having 2 to 50 carbon atoms. In the formula (4), AR1, AR2, AR3, AR4, AR5, AR6, R1, n, and W are the same as described above; R2 and R3 are hydrogen atoms or organic groups having 1 to 20 carbon atoms, and R2 and R3 may also form a cyclic organic group by bonding within the molecule.

Description

Technical Field

[0001] The present invention relates to a coating-type organic film-forming material suitable for fine processing in manufacturing steps of semiconductor elements and the like, and a patterning method suitable for 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), extreme ultraviolet rays (EUV, 13.5 nm), electron beam (EB), and X-ray exposure using the organic film-forming material. Prior Art

[0002] In recent years, with the high integration and high speed of semiconductor elements, miniaturization of pattern rules has been sought. In lithography using optical exposure, which is currently used as a general technology, various technologies have been developed regarding how to perform fine and high-precision pattern processing on the light source used.

[0003] Regarding the light source for lithography used in resist pattern formation, optical exposure using g-rays (436 nm) or i-rays (365 nm) of a mercury lamp has been widely used in parts with low integration. On the other hand, in parts with high integration and the need for miniaturization, lithography using KrF excimer laser (248 nm) and ArF excimer laser (193 nm) with shorter wavelengths has also been put into practical use. In the most advanced era where further miniaturization is required, lithography using extreme ultraviolet rays (EUV, 13.5 nm) has also approached practical use.

[0004] If the line width of the resist pattern progresses like this, it is well known that 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) becomes large, and pattern collapse occurs due to the surface tension of the developer during development. Therefore, when forming a pattern with a high aspect ratio on a substrate with height differences, the multi-layer resist method of forming a pattern by laminating films with different dry etching characteristics is known to be excellent. A two-layer resist method (Patent Document 1, etc.) has been developed, which combines a photoresist layer based on a silicon-containing photosensitive polymer and a lower layer based on 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, etc.) that combines a photoresist layer based on an organic photosensitive polymer used in the single-layer resist method, a lower layer based on a silicon-based polymer or a silicon-based CVD film, and an organic layer based on an organic polymer.

[0005] In the three-layer resist method, first, a pattern of a photoresist layer is transferred onto a silicon-containing lower layer using a fluorocarbon-based dry etching gas. Then, using this pattern as a mask, a dry etching using an oxygen-based dry etching gas is performed to transfer a pattern onto an organic film mainly composed of carbon and hydrogen. Next, using this as a mask, pattern formation is performed on a substrate to be processed by dry etching. However, in semiconductor device manufacturing processes after the 20 nm era, when a pattern is transferred onto a substrate to be processed by dry etching using this organic film pattern as a hard mask, distortion or bending is observed in this organic film pattern.

[0006] Regarding a carbon hard mask directly formed on a substrate to be processed, an amorphous carbon (hereinafter referred to as CVD-C) film obtained by a CVD method using methane gas, ethane gas, acetylene gas, etc. as raw materials is common. Regarding this CVD-C film, it is known that hydrogen atoms in the film can be extremely reduced, which is very effective for the above-mentioned distortion or bending of the pattern. However, it is also known that when there are height differences on the substrate to be processed, it is difficult to fill such height differences to be flat on the characteristic surface of the CVD process. Therefore, if a substrate to be processed with height differences is filled with a CVD-C film and then patterned with a photoresist, due to the influence of the height differences of the substrate to be processed, height differences will occur on the coating surface of the photoresist, and as a result, the film thickness of the photoresist will become uneven, and the focus tolerance and pattern shape during lithography will deteriorate.

[0007] On the other hand, when an organic film, which is a carbon hard mask directly formed on a substrate to be processed, is formed by a spin coating method, it is known to have the advantage of filling the height differences of a substrate with height differences to be flat. If the substrate is planarized with this organic film material, the film thickness variations of the silicon-containing lower layer and the photoresist formed thereon can be suppressed, the focus tolerance of lithography can be expanded, and a normal pattern can be formed.

[0008] Therefore, there is a demand for an organic film material and a method for forming an organic film that have high etching resistance during dry etching of a substrate to be processed and can form an organic film with high flatness on the substrate to be processed using a spin coating method.

[0009] Conventionally, among such organic film materials, condensation resin materials formed using carbonyl compounds such as ketones and aldehydes or aromatic alcohols as condensing agents for phenol-based and naphthol-based compounds have been known as materials for forming organic films used in the multilayer resist method. For example, bisphenol fluorene novolac resins described in Patent Document 2, bisphenol compounds and their novolac resins described in Patent Document 3, novolac resins of adamantane phenol compounds described in Patent Document 4, bisnaphthol compounds and their novolac resins described in Patent Document 5, etc. can be exemplified. Although the resins used in such materials are composed mainly of skeletons such as naphthalene, fluorene, and adamantane with high carbon density, it is impossible to avoid the deterioration of etching resistance caused by oxygen atoms due to phenolic hydroxyl groups.

[0010] In addition, regarding resins for organic film materials that do not contain heteroatoms such as oxygen so as not to impair etching resistance, resins having a fluorene structure described in Patent Document 6 are exemplified. However, since a cured film is formed by using a composition added with a crosslinking agent such as a hydroxymethyl compound, even if the carbon content of the resin is increased, the etching resistance is impaired due to the crosslinking agent having a low carbon content.

[0011] Furthermore, regarding organic film materials for improving etching resistance, organic film materials having a benzopyran structure introduced as shown in Patent Document 7 have been explored, but there is still room for improvement in various physical properties required for organic film materials such as heat resistance and etching resistance. Also, the shape of the substrate to be processed has become complicated, and various materials are used for the material of the substrate to be processed itself, and an organic film material with excellent process tolerance is required.

[0012] Prior Art Documents

[0013] Patent Documents

[0014] [Patent Document 1] Japanese Patent Laid-Open No. 6-118651

[0015] [Patent Document 2] Japanese Patent Laid-Open No. 2005-128509

[0016] [Patent Document 3] Japanese Patent Laid-Open No. 2006-293298

[0017] [Patent Document 4] Japanese Patent Laid-Open No. 2006-285095

[0018] [Patent Document 5] Japanese Patent Laid-Open No. 2010-122656

[0019] [Patent Document 6] WO2013-047106

[0020] [Patent Document 7] WO2017-208796 Summary of the Invention

[0021] Problems to be Solved by the Invention

[0022] The present invention has been made in view of the above facts, and an object thereof is to provide an organic film-forming material that can exhibit high etching resistance and excellent twist resistance without impairing the carbon content of the resin itself, and to provide a patterning method using the organic film-forming material, and a compound and a polymer suitable for such an organic film-forming material.

[0023] Means for Solving the Problems

[0024] In order to solve the above problems, the present invention provides an organic film-forming material containing:

[0025] (A) A compound represented by the following general formula (1) and / or a polymer having a repeating unit represented by the following general formula (4), and

[0026] (B) An organic solvent.

[0027] [Chemical formula 1]

[0028]

[0029] In the above general formula (1), AR1, AR2, AR3, AR4, AR5 and AR6 are benzene rings or naphthalene rings, and R1 is any one of the groups represented by the following formula (2). n represents an integer of 1 to 2, and W is a divalent organic group having 2 to 50 carbon atoms.

[0030] [Chemical formula 2]

[0031]

[0032] [Chemical formula 3]

[0033]

[0034] In the above general formula (4), AR1, AR2, AR3, AR4, AR5, AR6, R1, n and W are the same as those described above. R2 and R3 are hydrogen atoms or organic groups having 1 to 20 carbon atoms, and R2 and R3 may also form a cyclic organic group by bonding within the molecule.

[0035] The compound of the present invention represented by the above general formula (1) forms a main skeleton with a structure containing a large amount of condensed aromatic ring structures with a high carbon content, and can further form a dense organic film with a high carbon density by the crosslinking action of the benzopyran ring structure. Therefore, if it is an organic film forming material using the compound of the present invention, an organic film with high twist resistance (bending resistance) and high dry etching resistance can be formed, which is effective when used as an organic film material. Further, by using a polymer having a repeating unit such as the above general formula (4), there will be no deterioration of etching resistance, and a dense organic film can be formed by improving the curability, and it becomes an organic film forming material that can form a film without depending on the substrate material and shape. Further, if it is a mixture of the compound of the above general formula (1) and a polymer having a repeating unit represented by the above general formula (4), various physical properties required when using an organic film, such as filling / planarization characteristics and escape gas caused by sublimates, can be adjusted within an appropriate range.

[0036] Moreover, the aforementioned compound is preferably a compound represented by the following general formula (3).

[0037] [Chemical formula 4]

[0038]

[0039] AR5, AR6, R1 and n in the above general formula (3) are the same as those described above.

[0040] By introducing such a structure, the etching resistance and twist resistance can be further improved.

[0041] Further, the aforementioned polymer is preferably a polymer having a repeating unit represented by the following general formula (5).

[0042] [Chemical formula 5]

[0043]

[0044] AR5, AR6, R1, R2, R3 and n in the above general formula (5) are the same as those described above.

[0045] By using a polymer having such a repeating unit, the handling properties such as solubility in an organic solvent can also be improved.

[0046] In addition, the weight average molecular weight of the aforementioned polymer is preferably 1000 to 10000.

[0047] If it is an organic film forming material containing a polymer having a weight average molecular weight within such a range, the solubility in an organic solvent will not be impaired and the escape gas during baking can be suppressed.

[0048] Moreover, the aforementioned organic solvent is preferably a mixture of one or more organic solvents with a boiling point below 180 degrees and one or more organic solvents with a boiling point of 180 degrees or more.

[0049] When the above-mentioned organic solvent is the above-mentioned mixture, by imparting the thermal fluidity of the organic film brought about by adding a high-boiling solvent to the above-mentioned compound and / or polymer, the organic film-forming material becomes one having a high degree of burying / planarizing characteristics.

[0050] It is preferably further contained one or more of (C) an acid generator, (D) a surfactant, (E) a crosslinking agent, and (F) a plasticizer.

[0051] When it is an organic film-forming material containing the above-mentioned additives, it has better coating properties and burying / planarizing characteristics.

[0052] The present invention provides a patterning method, which is a method for forming a pattern on a substrate to be processed; an organic film is formed on the substrate to be processed using the above-mentioned organic film-forming material, a silicon-containing antireflective underlayer film is formed on the organic film using a silicon-containing antireflective underlayer film material, a photoresist upper layer film is formed on the silicon-containing antireflective underlayer film using a photoresist composition, a circuit pattern is formed on the photoresist upper layer film, the patterned photoresist upper layer film is used as a mask and the above-mentioned silicon-containing antireflective underlayer film is pattern-transferred by etching, the pattern-transferred silicon-containing antireflective underlayer film is used as a mask and the above-mentioned organic film is pattern-transferred by etching, and then the pattern is formed on the above-mentioned substrate to be processed by etching using the pattern-transferred organic film as a mask.

[0053] The patterning method using the above three-layer resist process can form a fine pattern on the substrate to be processed with high precision.

[0054] Furthermore, the present invention provides a patterning method, which is a method for forming a pattern on a substrate to be processed; an organic film is formed on the substrate to be processed using the above-mentioned organic film-forming material, a silicon-containing antireflective underlayer film is formed on the organic film using a silicon-containing antireflective underlayer film material, an organic antireflective film is formed on the silicon-containing antireflective underlayer film, a photoresist upper layer film is formed on the organic antireflective film using a photoresist composition to form a four-layer film structure, a circuit pattern is formed on the photoresist upper layer film, the patterned photoresist upper layer film is used as a mask and the above-mentioned organic antireflective film and the above-mentioned silicon-containing antireflective underlayer film are pattern-transferred by etching, the pattern-transferred silicon-containing antireflective underlayer film is used as a mask and the above-mentioned organic film is pattern-transferred by etching, and then the substrate to be processed is etched using the pattern-transferred organic film as a mask to form a pattern on the substrate to be processed.

[0055] The patterning method using the above four-layer resist process can form a fine pattern on the substrate to be processed with higher precision.

[0056] In addition, the present invention provides a pattern formation method, which is a method for forming a pattern on a substrate to be processed; an organic film is formed on the substrate to be processed using the above-mentioned organic film forming material, an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film, a resist upper layer film is formed on the inorganic hard mask using a photoresist composition, a circuit pattern is formed on the resist upper layer film, the patterned resist upper layer film is used as a mask and the pattern is transferred to the aforementioned inorganic hard mask by etching, the transferred patterned inorganic hard mask is used as a mask and the pattern is transferred to the aforementioned organic film by etching, and then the transferred patterned organic film is used as a mask and the substrate to be processed is etched to form the pattern on the substrate to be processed.

[0057] The pattern formation method using the three-layer resist process can form a fine pattern on the substrate to be processed with high precision.

[0058] Moreover, the present invention provides a pattern formation method, which is a method for forming a pattern on a substrate to be processed; an organic film is formed on the substrate to be processed using the above-mentioned organic film forming material, an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film, an organic anti-reflection film is formed on the inorganic hard mask, a resist upper layer film is formed on the organic anti-reflection film using a photoresist composition to form a four-layer film structure, a circuit pattern is formed on the resist upper layer film, the patterned resist upper layer film is used as a mask and the pattern is transferred to the aforementioned organic anti-reflection film and the aforementioned inorganic hard mask by etching, the transferred patterned inorganic hard mask is used as a mask and the pattern is transferred to the aforementioned organic film by etching, and then the transferred patterned organic film is used as a mask and the substrate to be processed is etched to form the pattern on the substrate to be processed.

[0059] The pattern formation method using the four-layer resist process can form a fine pattern on the substrate to be processed with higher precision.

[0060] At this time, the aforementioned inorganic hard mask is preferably formed by CVD method or ALD method.

[0061] If the above-mentioned inorganic hard mask is formed by CVD method or ALD method, a fine pattern can be formed on the substrate to be processed with higher precision.

[0062] The pattern formation method of the aforementioned resist upper layer film is preferably: pattern formation by optical lithography with a wavelength of 10 nm or more and 300 nm or less, direct drawing by electron beam, nanoimprinting, or a combination of these methods.

[0063] If the above method is used as the method for forming a circuit pattern on the above resist upper layer film, a fine pattern can be formed on the substrate to be processed with higher precision.

[0064] In the aforementioned pattern forming method, the development method is preferably development using an alkali developer or an organic solvent.

[0065] If development using an alkali developer or an organic solvent is used as the development method, a fine pattern can be formed on the substrate to be processed with higher precision.

[0066] The aforementioned substrate to be processed is preferably a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, or a metal oxynitride film.

[0067] In the present invention, for the aforementioned substrate to be processed, the above-mentioned ones can be used, for example.

[0068] The aforementioned metal is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, cobalt, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, manganese, molybdenum, ruthenium, or an alloy thereof.

[0069] They can be used as the above-mentioned metal. If the organic film forming material of the present invention is used in this way to perform pattern formation, the pattern of the upper layer photoresist can be transferred and formed on the substrate to be processed with high precision.

[0070] The present invention provides a compound represented by the following general formula (1).

[0071] [Chemical formula 6]

[0072]

[0073] In the above general formula (1), AR1, AR2, AR3, AR4, AR5, and AR6 are benzene rings or naphthalene rings, and R1 is any one of the groups represented by the following formula (2). n represents an integer from 1 to 2, and W is a divalent organic group having 2 to 50 carbon atoms.

[0074] [Chemical formula 7]

[0075]

[0076] If it is a compound represented by the general formula (1), since it contains a plurality of condensed aromatic ring structures and fused ring structures, it becomes a compound for an organic film forming material that can form an organic film with excellent heat resistance, twist resistance, and dry etching resistance.

[0077] The aforementioned compound is preferably represented by the following general formula (3).

[0078] [Chemical formula 8]

[0079]

[0080] AR5, AR6, R1, and n in the above general formula (3) are the same as those described above.

[0081] By using such a compound, the etching resistance and the twist resistance can be further improved.

[0082] Furthermore, the present invention provides a polymer having a repeating unit represented by the following general formula (4).

[0083] [Chemical formula 9]

[0084]

[0085] In the above general formula (4), AR1, AR2, AR3, AR4, AR5 and AR6 are benzene rings or naphthalene rings, and R1 is any one of the groups represented by the following formula (2). n represents an integer of 1 to 2, and W is a divalent organic group having 2 to 50 carbon atoms. R2 and R3 are hydrogen atoms or organic groups having 1 to 20 carbon atoms, and R2 and R3 may also form a cyclic organic group by bonding within the molecule.

[0086] [Chemical formula 10]

[0087]

[0088] Since such a repeating unit contains a plurality of cardo structures, when used as a polymer for forming an organic film, various physical properties that are mutually balanced, such as etching resistance, heat resistance, filling characteristics, planarization characteristics, solvent solubility, and film-forming properties, can be taken into account.

[0089] The aforementioned polymer preferably has a repeating unit represented by the following general formula (5).

[0090] [Chemical formula 11]

[0091]

[0092] AR5, AR6, R1, R2, R3 and n in the above general formula (5) are the same as those described above.

[0093] By providing such a repeating unit, the carbon density is increased, and it becomes a polymer for forming an organic film having excellent etching resistance and twist resistance.

[0094] Effects of the Invention

[0095] As described above, since the compound or polymer of the present invention forms a main skeleton using a structure containing a large number of condensed aromatic rings, it is effective for forming an organic film with excellent etching resistance and twist resistance. Further, the organic film forming material containing the compound or polymer is an effective material for forming an organic film having excellent etching resistance, twist resistance, and also having many characteristics such as heat resistance, filling / planarization characteristics, etc. Therefore, for example, it is extremely effective as an organic film forming material in multi-layer resist processes such as a two-layer resist process, a three-layer resist process using a silicon-containing resist underlayer film, or a four-layer resist process using a silicon-containing resist underlayer film and an organic antireflection film. Further, in the case of the pattern forming method of the present invention, in a multi-layer resist process, a fine pattern can be formed with high precision on a substrate to be processed. BRIEF DESCRIPTION OF THE DRAWINGS

[0096] Figure 1 (A) to (F) are explanatory diagrams of an example of a pattern forming method of the present invention using a three-layer resist process.

[0097] Figure 2 Explanatory diagram of the planarization characteristic evaluation method in the examples. DETAILED DESCRIPTION OF THE INVENTION

[0098] There is a need for an organic film forming material that can exhibit high etching resistance and excellent twist resistance without damaging the carbon content of the resin itself, a pattern forming method using the organic film forming material, and compounds and polymers suitable for such an organic film forming material.

[0099] The inventors of the present application found that since the compound or polymer of the present invention forms a main skeleton using a structure containing a large number of condensed aromatic rings, it becomes an effective compound or polymer for forming an organic film with excellent etching resistance and twist resistance, and thus completed the present invention.

[0100] That is, the present invention is an organic film forming material containing:

[0101] (A) a compound represented by the following general formula (1) and / or a polymer having a repeating unit represented by the following general formula (4), and

[0102] (B) an organic solvent.

[0103] [Chemical Formula 12]

[0104]

[0105] In the above general formula (1), AR1, AR2, AR3, AR4, AR5, and AR6 are benzene rings or naphthalene rings, and R1 is any one of the groups represented by the following formula (2). n represents an integer of 1 to 2, and W is a divalent organic group having 2 to 50 carbon atoms. ​​

[0106] [Chemical formula 13]

[0107]

[0108] [Chemical formula 14]

[0109]

[0110] In the above general formula (4), AR1, AR2, AR3, AR4, AR5, AR6, R1, n, and W are the same as described above. R2 and R3 are hydrogen atoms or organic groups having 1 to 20 carbon atoms, and R2 and R3 may also form a cyclic organic group by bonding within the molecule.

[0111] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto.

[0112] <Compound for organic film-forming material>

[0113] The compound for an organic film-forming material of the present invention is a compound represented by the following general formula (1).

[0114] [Chemical formula 15]

[0115]

[0116] In the above general formula (1), AR1, AR2, AR3, AR4, AR5, and AR6 are benzene rings or naphthalene rings, and R1 is any one of the groups represented by the following formula (2). n represents an integer of 1 to 2, and W is a divalent organic group having 2 to 50 carbon atoms.

[0117] [Chemical formula 16]

[0118]

[0119] The W in the above general formula (1) is a divalent organic group having 2 to 50 carbon atoms, and specific examples of the structure thereof include those shown below.

[0120] [Chemical formula 17]

[0121]

[0122] The dotted line represents an atomic bond.

[0123] The fluorene-type partial structure formed by AR1, AR2 or AR3, AR4 in the above general formula (1) can be exemplified as follows. Among them, AR1, AR2, AR3, and AR4 are benzene rings, and it is particularly preferable when it becomes fluorene.

[0124] [Chemical formula 18]

[0125]

[0126] The dotted line represents an atomic bond.

[0127] In the above general formula (1), AR5 and AR6 represent a benzene ring or a naphthalene ring, and AR5, AR6 and the 9-position of fluorene form a benzopyran-type heterocyclic structure. The following may be exemplified as specific structures.

[0128] [Chemical formula 19]

[0129]

[0130] AR1, AR2, AR3, AR4, R1, n, and W in the above formula are the same as described above.

[0131] R1 is any one of the groups represented by the above formula (2). Further, the group represented by the general formula (2) is a substituent for improving solubility in a solvent, polymerizability, and curability, and from the viewpoint of improving curability, ethynyl or propargyloxy is particularly preferred.

[0132] Since the compound of the present invention has a condensed aromatic ring structure such as fluorene and a benzopyran-type heterocyclic structure, it not only has high etching resistance and excellent heat resistance, but also can form a dense film due to its thermosetting property.

[0133] In addition, the compound of the present invention is preferably a compound represented by the following general formula (3).

[0134] [Chemical formula 20]

[0135]

[0136] AR5, AR6, R1, and n in the above general formula (3) are the same as described above.

[0137] The compound represented by the above general formula (3) may be exemplified as the following specific examples, and it is particularly preferred when AR5 and AR6 are naphthalene rings.

[0138] [Chemical formula 21]

[0139]

[0140] [Chemical formula 22]

[0141]

[0142] [Chemical formula 23]

[0143]

[0144] [Method for producing compound]

[0145] As an example of the method for producing the compound represented by the general formula (1) of the present invention, it can be synthesized by using the cyclization reaction with dehydration of the following phenols and fluorenols composed of AR1, AR2, AR3, AR4 and W. AR1, AR2, AR3, AR4, R1, n, W in the following formula are the same as described above, and ARx represents a benzene ring or a naphthalene ring.

[0146] [Chemical formula 24]

[0147]

[0148] The above compound can usually be obtained in an organic solvent in the presence of an acid catalyst at room temperature or, if necessary, under cooling or heating. As the acid catalyst to be used, inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acid can be used; organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; Lewis acids such as aluminum chloride, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium(IV) methoxide, titanium(IV) ethoxide, titanium(IV) isopropoxide, and titanium(IV) oxide can be used.

[0149] There is no particular limitation on the solvent to be used, and examples thereof include alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane; chlorinated solvents such as dichloromethane, chloroform, dichloroethane, and trichloroethylene; hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and cumene; nitriles such as acetonitrile; ketones such as acetone, ethyl methyl ketone, and isobutyl methyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and hexamethylphosphoric triamide, and they can be used alone or in combination of two or more.

[0150] Regarding the reaction method, there are methods of charging phenols, fluorenols, and an acid catalyst as a catalyst all at once; methods of adding the catalyst all at once or in portions after dispersing or dissolving phenols and fluorenols, or adding them dropwise after diluting with a solvent; methods of adding fluorenols or phenols all at once or in portions after dispersing or dissolving the catalyst, or adding them dropwise after diluting with a solvent. At this time, not only one kind of phenol and fluorenol can be used, but two or more kinds can also be used. Although it also depends on the reactivity of the phenol, when the amount of fluorenol is 1 mole, it is advisable to use 2 moles or more of the phenol. After the reaction is completed, in order to remove the catalyst used in the reaction, it can be diluted in an organic solvent, followed by liquid separation and washing, and the target product can be recovered.

[0151] Regarding the organic solvent used at this time, if it can dissolve the target substance and still separate into two layers when mixed with water, there is no particular limitation. 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 dichloromethane, chloroform, dichloroethane, and trichloroethylene; and mixtures thereof. The cleaning water used at this time may be the so-called deionized water or ultrapure water. The number of cleaning times may be 1 or more. Even if the cleaning is carried out more than 10 times, the corresponding cleaning effect may not necessarily be obtained. Therefore, it is preferably about 1 to 5 times.

[0152] In order to remove the acidic components in the system during liquid-liquid separation cleaning, cleaning can also be carried out with an alkaline aqueous solution. Regarding the base, specifically, examples include hydroxides of alkali metals, carbonates of alkali metals, hydroxides of alkaline earth metals, carbonates of alkaline earth metals, ammonia, and organic ammonium salts.

[0153] In addition, in order to remove metal impurities or base components in the system during liquid-liquid separation cleaning, cleaning can also be carried out with an acidic aqueous solution. Regarding the acid, specifically, examples include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropolymeric acid; organic acids such as oxalic acid, fumaric acid, maleic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid, etc.

[0154] The above-mentioned liquid-liquid separation cleaning using an alkaline aqueous solution or an acidic aqueous solution can be either one alone or carried out in combination. It is more ideal to carry out the liquid-liquid separation cleaning in the order of alkaline aqueous solution and acidic aqueous solution from the perspective of removing metal impurities.

[0155] After the above-mentioned liquid-liquid separation cleaning using an alkaline aqueous solution or an acidic aqueous solution, cleaning with neutral water can also be carried out continuously. The number of cleaning times may be 1 or more, and it is preferably about 1 to 5 times. Neutral water may be the above-mentioned deionized water, ultrapure water, etc. The number of cleaning times may be 1 or more, but sometimes the base components and acidic components may not be removed when the number of times is small. Even if the cleaning is carried out more than 10 times, the corresponding cleaning effect may not necessarily be obtained. Therefore, it is preferably about 1 to 5 times.

[0156] In addition, the reaction product after the liquid-liquid separation operation can be concentrated and dried or crystallized under reduced pressure or normal pressure to recover it in the form of a powder. However, in order to improve the operability when preparing the organic film-forming material, it can also be made into a solution state with an appropriate concentration in advance. The concentration at this time is preferably 0.1 to 50% by mass, and more preferably 0.5 to 30% by weight. If it is such a concentration, the viscosity is not likely to become too high, so the operability can be prevented from being damaged. Also, since the amount of the solvent is not excessive, it is economical.

[0157] Regarding the solvent at this time, if it is a compound that can dissolve other compounds, there is no particular limitation. Specific examples include: ketones such as cyclohexanone and methyl-2-pentyl 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 monoter-butyl ether acetate. These can be used alone or in combination of two or more.

[0158] <Polymer for organic film-forming material>

[0159] The polymer for the organic film-forming material of the present invention is a polymer having a repeating unit represented by the following general formula (4).

[0160] [Chemical formula 25]

[0161]

[0162] In the above general formula (4), AR1, AR2, AR3, AR4, AR5, AR6, R1, n, and W are the same as described above. R2 and R3 are hydrogen atoms or organic groups having 1 to 20 carbon atoms, and R2 and R3 may also form a cyclic organic group by bonding within the molecule.

[0163] They are polymers obtained by using the compound represented by the above general formula (1). Due to the use of the aforementioned compound, they have excellent heat resistance, etching resistance, and thermosetting properties. Moreover, since they are polymers having repeating units rather than monomers, the amount of off-gas components is small. Also, since they are polymers having a molecular weight distribution, the crystallinity is relatively mild and an improvement in film-forming properties can be expected.

[0164] The partial structure formed by R2 and R3 in the repeating unit constituting the above general formula (4) is such that R2 and R3 are hydrogen atoms or organic groups having 1 to 20 carbon atoms, and R2 and R3 may also form a cyclic organic group by bonding within the molecule. Specific examples are as follows. Among the following, considering the ease of obtaining raw materials, methylene is more desirable.

[0165] [Chemical formula 26]

[0166]

[0167] The dotted line represents an atomic bond.

[0168] In addition, the polymer for the organic film-forming material of the present invention is preferably a polymer having a repeating unit represented by the following general formula (5).

[0169] [Chemical 27]

[0170]

[0171] AR5, AR6, R1, R2, R3, n in the above general formula (5) are the same as those described above.

[0172] They are polymers obtained using the compound represented by the above general formula (3).

[0173] In addition, the Mw (weight-average molecular weight) of the polymer described above is preferably 1000 to 10000, more preferably 1000 to 5000. In addition, the molecular weight can be obtained in the form of the weight-average molecular weight (Mw) converted to polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as the mobile phase.

[0174] If it is in such a molecular weight range, the solubility in organic solvents can be ensured, and the sublimates generated during baking can be suppressed. Also, since the polymer for the organic film-forming material has good thermal fluidity, when blended with the material, it can not only well fill the fine structures formed on the substrate, but also form an organic film that makes the whole substrate flat.

[0175] [Method for manufacturing polymer]

[0176] Regarding the means for obtaining the polymer used in the organic film-forming material of the present invention, it can be obtained by the polycondensation reaction of the compound represented by the general formula (1) with aldehydes or ketones. AR1, AR2, AR3, AR4, AR5, AR6, W, R1, R2, R3, n in the following formula are the same as those described above (when any one or both of R2 and R3 are hydrogen atoms, it represents the polycondensation with aldehyde, and in other cases, it represents the polycondensation with ketone).

[0177] [Chemical 28]

[0178]

[0179] The polycondensation reaction can generally be obtained in an organic solvent in the presence of an acid catalyst at room temperature or, if necessary, under cooling or heating. Regarding the acid catalyst used, inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropoly acid can be used; organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dimethoxydibutyltin, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium(IV) methoxide, titanium(IV) ethoxide, titanium(IV) isopropoxide, and titanium(IV) oxide can be used.

[0180] As for the solvents used, examples of alcohols include methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerin, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.; examples of ethers include diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, etc.; examples of chlorine-based solvents include dichloromethane, chloroform, dichloroethane, trichloroethylene, etc.; examples of hydrocarbons include hexane, heptane, benzene, toluene, xylene, cumene, etc.; examples of nitriles include acetonitrile, etc.; examples of ketones include acetone, ethyl methyl ketone, isobutyl methyl ketone, etc.; examples of esters include ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate, etc.; examples of aprotic polar solvents include dimethyl sulfoxide, N,N-dimethylformamide, hexamethylphosphoric triamide, etc. These can be used alone or in combination of two or more.

[0181] Regarding the reaction method and the polymer recovery method, the methods described in the manufacturing method of the compound represented by the above general formula (1) can be used.

[0182] [Another Method of the Manufacturing Method of the Compound and the Polymer]

[0183] Furthermore, when the substituent represented by R1 in the compound or polymer used in the organic film-forming material of the present invention is propargyl ether, examples include a method of using a compound or polymer having a hydroxyl group as an intermediate and performing propargylation, etc. There is no particular limitation for a reaction capable of introducing a propargyl ether group, and examples include a substitution reaction using a halide or tosylate, mesylate having a propargyl group and a base catalyst. In the following formula, X represents a halogen, tosyl group or mesyl group, and AR1, AR2, AR3, AR4, AR5, AR6, W, R2, R3, n are the same as described above.

[0184] [Chemical Formula 29]

[0185]

[0186] [Chemical Formula 30]

[0187]

[0188] Examples of the base catalyst used in the substitution reaction include inorganic base compounds such as sodium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, potassium phosphate, etc.; organic amine compounds such as triethylamine, pyridine, N-methylmorpholine, etc. These can be used alone or in combination of two or more.

[0189] The solvent used at this time is not particularly limited as long as it is a solvent inactive to the above reaction, for example: ether solvents such as diethyl ether, tetrahydrofuran, dioxane; aromatic solvents such as benzene, toluene, xylene; acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, water, etc., which can be used alone or in combination.

[0190] The reaction method and the method for recovering the compound or polymer can be carried out by the method described in the method for producing the compound represented by the general formula (1).

[0191] In the preparation of the compound or polymer used in the organic film forming material obtained by this method, various halides, toluenesulfonates and mesylate salts can be used alone or in combination according to the required performance. For example, those having a side chain structure that contributes to the improvement of planarization characteristics and those having a hard aromatic ring structure that contributes to etching resistance and heat resistance can be combined in any proportion. Therefore, the organic film forming material using these polymers can have both the embedding / planarization characteristics and the etching resistance to a high degree.

[0192] As described above, the compound or polymer for an organic film forming material of the present invention can provide an organic film forming material that can exhibit high etching resistance and excellent warp resistance.

[0193] <Organic film forming material>

[0194] The present invention can also provide an organic film-forming material comprising (A) the compound for an organic film-forming material of the present invention and / or a polymer and (B) an organic solvent.

[0195] [(A) Compound and / or polymer of the present invention]

[0196] In the organic film-forming material of the present invention, the compound or polymer for an organic film-forming material of the present invention can be used alone or in combination of two or more.

[0197] Furthermore, the present invention preferably contains at least one selected from the above-mentioned compounds for organic film-forming materials and polymers.

[0198] With such a mixture, various physical properties required when using an organic film, such as filling / planarization characteristics and dissipated gas resulting from sublimation, can be adjusted within appropriate ranges.

[0199] [(B) Organic solvent]

[0200] Regarding the organic solvent used in the organic film-forming material applicable to the present invention, there is no particular limitation as long as it can dissolve the above-mentioned compound and / or polymer (base polymer) and can dissolve these when containing an acid generator, a crosslinking agent, other additives, etc. described later. Specifically, solvents with a boiling point of less than 180°C such as those described in paragraphs

[0091] to

[0092] of Japanese Patent Laid-Open 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 them can be preferably used. The blending amount of the organic solvent is preferably 200 to 10,000 parts, more preferably 300 to 5,000 parts, relative to 100 parts of the above-mentioned (A) compound and / or polymer.

[0201] If such an organic film-forming material is used, it can be coated by spin coating. Moreover, since it contains the compound and / or polymer for the organic film-forming material of the present invention as described above, it will become an organic film-forming material having good dry etching resistance, heat resistance, and a high level of filling / planarization characteristics at the same time.

[0202] In addition, in the organic film-forming material of the present invention, in terms of organic solvents, a high-boiling solvent with a boiling point of 180°C or higher (a mixture of a solvent with a boiling point below 180°C and a solvent with a boiling point of 180°C or higher) can also be added to the solvents with a boiling point below 180°C. Regarding high-boiling organic solvents, if they can dissolve the compounds and / or polymers for forming the organic film, there are no particular restrictions on hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc. Specific examples can be exemplified as follows: 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 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, glycerol, 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 monobutyl ether, diethylene glycol monoiso-butyl 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 monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl 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-butanediol diacetate, 1,6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, etc. They can be used alone or in combination.

[0203] The boiling point of the above high-boiling solvent can be appropriately selected in accordance with the temperature for heat-treating the organic film-forming material. The boiling point of the added high-boiling solvent is preferably 180°C to 300°C, more preferably 200°C to 300°C. If the boiling point is such, there is no concern about excessive volatilization during baking (heat treatment) due to too low a boiling point, so sufficient thermal fluidity can be obtained. Also, if the boiling point is such, the boiling point will not be too high, and there will be no situation where it remains in the film without volatilization after baking, so there is no concern about adversely affecting film physical properties such as etching resistance.

[0204] Further, when using the above-mentioned high-boiling solvent, the blending amount of the high-boiling solvent is preferably 1 to 30 parts by mass relative to 100 parts by mass of the solvent having a boiling point of less than 180°C. If the blending amount is such, there is no concern that the blending amount is too small to impart sufficient thermal fluidity during baking, or that the blending amount is too large and remains in the film, leading to deterioration of film physical properties such as etching resistance.

[0205] If it is such an organic film-forming material, since thermal fluidity brought about by adding a high-boiling solvent is imparted to the above-mentioned organic film-forming material, it becomes an organic film-forming composition having a high level of filling / planarization characteristics.

[0206] [(C) Acid generator]

[0207] In the organic film-forming material of the present invention, in order to further promote the curing reaction, a (C) acid generator can be added. Acid generators include those that generate acid by thermal decomposition and those that generate acid by light irradiation, and either can be added. Specifically, materials described in paragraphs

[0061] to

[0085] of Japanese Patent Laid-Open No. 2007-199653 can be added, but are not limited thereto.

[0208] The above-mentioned 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, more preferably 0.1 to 10 parts, relative to 100 parts of the aforementioned compound and / or polymer (A).

[0209] [(D) Surfactant]

[0210] In the organic film-forming material of the present invention, in order to improve coatability during spin coating, a (D) surfactant can be added. As the surfactant, for example, those described in

[0142] to

[0147] of Japanese Patent Laid-Open No. 2009-269953 can be used. When adding the surfactant, the addition amount is preferably 0.01 to 10 parts, more preferably 0.05 to 5 parts, relative to 100 parts of the aforementioned compound and / or polymer (A).

[0211] [(E) Crosslinking agent]

[0212] Further, in the organic film-forming material of the present invention, in order to improve the curability and further suppress the mutual mixing with the upper layer film, a crosslinking agent may be added. The crosslinking agent is not particularly limited, and various known crosslinking agents of various systems can be widely used. As examples thereof, hydroxymethyl or alkoxymethyl type crosslinking agents of polynuclear phenols, melamine-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, and epoxy-based crosslinking agents can be exemplified. When adding a crosslinking agent, the addition amount is preferably 1 to 100 parts, more preferably 5 to 50 parts, relative to 100 parts of the aforementioned compound and / or polymer (A).

[0213] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylated melamine, hexabutoxymethylated melamine, their alkoxy and / or hydroxy substituents, and their partial self-condensates. Specific examples of the glycoluril-based crosslinking agent include tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, their alkoxy and / or hydroxy substituents, and their partial self-condensates. Specific examples of the benzoguanamine-based crosslinking agent include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxy substituents, and their partial self-condensates. Specific examples of the urea-based crosslinking agent include dimethoxymethylated dimethoxyethyleneurea, its alkoxy and / or hydroxy substituents, and their partial self-condensates. Specific examples of the β-hydroxyalkylamide-based crosslinking agent include N,N,N',N'-tetrakis(2-hydroxyethyl)adipamide. Specific examples of the isocyanurate-based crosslinking agent include triglycidyl isocyanurate, triallyl isocyanurate. Specific examples of the aziridine-based crosslinking agent include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane, 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate]. Specific examples of the oxazoline-based crosslinking agent include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis-4,5-diphenyl-2-oxazoline, 2,2'-methylenebis-4-phenyl-2-oxazoline, 2,2'-methylenebis-4-tert-butyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), 2-isopropenyl oxazoline copolymer. Specific examples of the epoxy-based crosslinking agent include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether.

[0214] Specific examples of the polynuclear phenol-based crosslinking agent include the compound represented by the following general formula (6).

[0215] [Chemical Formula 31]

[0216]

[0217] In the formula, Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. R5 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. q is an integer of 1 to 5.

[0218] Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. q is an integer of 1 to 5, more preferably 2 or 3. Specifically, Q can be exemplified by a group formed by removing q hydrogen atoms from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, eicosane. R5 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specifically, the alkyl group having 1 to 20 carbon atoms can be exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, eicosyl, and is preferably a hydrogen atom or a methyl group.

[0219] Examples of the compound represented by the above general formula (6) can be specifically exemplified by the following compounds. Among them, from the viewpoints of improving the hardening property and film thickness uniformity of the organic film, it is preferably the hexa-methoxymethylated product of triphenylmethane, triphenylethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene.

[0220] [Chemical formula 32]

[0221]

[0222] [Chemical formula 33]

[0223]

[0224] R5 is as described above.

[0225] [(F) Plasticizer]

[0226] Further, in the organic film-forming material of the present invention, in order to further improve the planarization / embedding property, a plasticizer can be added. The plasticizer is not particularly limited, and various known plasticizers can be widely used. Examples thereof include low-molecular compounds such as phthalates, adipates, phosphates, trimellitates, and citrates; polymers such as polyether-based, polyester-based, and polyacetal-based polymers described in JP-A-2013-253227. When adding a plasticizer, the addition amount is preferably 1 to 100 parts, more preferably 5 to 30 parts, relative to 100 parts of the aforementioned compound and / or polymer (A).

[0227] Further, in the organic film-forming material of the present invention, as an additive that imparts filling / planarization characteristics in the same manner as a plasticizer, for example, a liquid additive having a polyethylene glycol or polypropylene glycol structure, or a thermal decomposable polymer having a weight reduction rate of 40% by mass or more between 30°C and 250°C and a weight average molecular weight of 300 to 200,000 can be desirably used. The thermal decomposable polymer preferably contains repeating units having an acetal structure represented by the following general formulas (DP1) and (DP1a).

[0228] [Chemical formula 34]

[0229]

[0230] In the formula, R6 is a hydrogen atom or a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms which may be substituted. Y1 is a saturated or unsaturated divalent organic group having 2 to 30 carbon atoms.

[0231] [Chemical formula 35]

[0232]

[0233] In the formula, R 6a is an alkyl group having 1 to 4 carbon atoms. Y a is a saturated or unsaturated divalent hydrocarbon group having 4 to 10 carbon atoms and may also have an ether bond. n represents the average number of repeating units and is 3 to 500.

[0234] [(G) Other components]

[0235] In the organic film-forming material of the present invention, other compounds or polymers may be further blended. The blended compound or polymer will play a role in mixing with the organic film-forming material of the present invention and improving the film-forming property of spin coating or the filling property on a substrate having height differences.

[0236] Examples of such materials include: phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3,5-diphenylphenol, 2-naphthol, 3-naphthol, 4-naphthol, 4-tritylphenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, catechol, 4-tert-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-tert-butyl-5-methylphenol, pyrogallol, thymol, isothymol, 4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2'-dimethyl-4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2'-diallyl-4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2'-difluoro-4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2'-diphenyl-4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2'-dimethoxy-4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 3,3,3',3',4,4'-hexamethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 2,3,2',3'-tetrahydro-(1,1')-spirobiindene-5,5'-diol, 5,5'-dimethyl-3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol, and dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, methyl 3-hydroxynaphthalene-2-carboxylate, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthene, biphenyl, bisphenol, triphenol, dicyclopentadiene, indane, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborn-2-ene, phenolic resins such as α-pinene, β-pinene, limonene, polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthene, polynorbornene, polycyclodecene, polytetracyclododecene, polytricyclodecene, poly(meth)acrylate and their copolymers.Alternatively, it is also possible to blend the naphthol dicyclopentadiene copolymer described in Japanese Patent Application Laid-Open No. 2004-205685, the bisphenol fluorene novolak resin described in Japanese Patent Application Laid-Open No. 2005-128509, the acenaphthene copolymer described in Japanese Patent Application Laid-Open No. 2005-250434, the fullerene having a phenol group described in Japanese Patent Application Laid-Open No. 2006-227391, the bisphenol compound and its novolak resin described in Japanese Patent Application Laid-Open No. 2006-293298, the novolak resin of the adamantane phenol compound described in Japanese Patent Application Laid-Open No. 2006-285095, the binaphthol compound and its novolak resin described in Japanese Patent Application Laid-Open No. 2010-122656, the fullerene resin compound described in Japanese Patent Application Laid-Open No. 2008-158002, and the like.

[0237] The blending amount of the above-described compound or polymer for blending is preferably 0 to 1,000 parts by mass, more preferably 0 to 500 parts by mass, relative to 100 parts by mass of the organic film-forming material of the present invention.

[0238] In addition, the organic film-forming material of the present invention can be used alone or in combination of two or more. The above-described organic film-forming material can be used for uses such as an organic film material or a planarization material for manufacturing a semiconductor device.

[0239] Furthermore, the organic film-forming material of the present invention is extremely effective as an organic film material for a multilayer resist process such as a two-layer resist process, a three-layer resist process using a silicon-containing lower layer film, or a four-layer resist process using a silicon-containing inorganic hard mask lower layer film and an organic antireflection film.

[0240] (Organic film-forming method)

[0241] The present invention provides a method for forming an organic film that serves as a multilayer resist film used in lithography or an organic film that functions as a planarization film for semiconductor manufacturing, using the above-described organic film-forming material.

[0242] The organic film-forming method using the organic film-forming material of the present invention coats the above-described organic film-forming material on a substrate to be processed by a spin coating method or the like. By using a spin coating method or the like, good filling characteristics can be obtained. After spin coating, baking (heat treatment) is performed in order to evaporate the solvent, prevent mixing with the upper resist film or the lower resist film, and promote the crosslinking reaction. The baking is preferably performed in the range of 100°C or higher and 600°C or lower, for 10 to 600 seconds, and more preferably in the range of 200°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 set to 600°C or lower, and more preferably 500°C or lower.

[0243] Furthermore, in the organic film forming method using the organic film forming material of the present invention, the organic film forming material of the present invention can also be coated on a substrate to be processed by a spin coating method or the like, and the organic film forming material can be calcined and hardened in an environment with an oxygen concentration of 0.1% or more and 21% or less to form an organic film.

[0244] By calcining the organic film forming material of the present invention in such an oxygen environment, a sufficiently hardened film can be obtained. The environment during baking may be air. In order to reduce oxygen, it is preferable to previously enclose inert gases such as N2, Ar, and He because it can prevent the oxidation of the organic film. In order to prevent oxidation, the oxygen concentration must be controlled, preferably at 1000 ppm or less, and more preferably at 100 ppm or less. Preventing the oxidation of the organic film during baking is preferable because there will be no increase in absorption or decrease in etching resistance.

[0245] In the organic film forming method using the organic film forming material of the present invention as described above, due to its excellent filling / planarization characteristics, a flat hardened film can be obtained regardless of the unevenness of the substrate to be processed. Therefore, it is extremely effective when forming a flat hardened film on a substrate to be processed having a structure or height difference of 30 nm or more.

[0246] In addition, the thickness of the organic film such as the organic film or the planarization film for semiconductor device manufacturing is appropriately selected, preferably 30 to 20,000 nm, and particularly preferably 50 to 15,000 nm.

[0247] (Pattern Forming Method)

[0248] The present invention provides a pattern forming method, which is a pattern forming method in the form of a three-layer resist process using the organic film forming material as described above to form a pattern on a substrate to be processed; at least the organic film forming material of the present invention is used on the substrate to be processed to form an organic film, a silicon-containing resist underlayer film material is used on the organic film to form a silicon-containing resist underlayer film, a resist upper layer film material composed of a photoresist composition is used on the silicon-containing resist underlayer film to form a resist upper layer film and form a multi-layer resist film. After exposing the pattern circuit area of the resist upper layer film, it is developed with a developer to form a resist pattern on the resist upper layer film. The obtained resist pattern is used as an etching mask, and the pattern is transferred to the silicon-containing resist underlayer film by etching. The obtained silicon-containing resist underlayer film pattern is used as an etching mask, and the pattern is transferred to the aforementioned organic film by etching. Then, the obtained organic film pattern is used as an etching mask, and the pattern is transferred to the aforementioned substrate to be processed by etching.

[0249] In the above three-layer resist process, since the silicon-containing resist underlayer film exhibits etching resistance to oxygen or hydrogen, in the above three-layer resist process, it is advisable to use an etching gas mainly composed of oxygen or hydrogen to perform dry etching of the organic film using the silicon-containing resist underlayer film as a mask.

[0250] Regarding the silicon-containing resist underlayer film of the above three-layer resist process, a polysiloxane-based underlayer film can also be ideally used. By making the silicon-containing resist underlayer film have an antireflection effect, reflection can be suppressed. Especially for 193 nm exposure, if a material containing a large amount of aromatic groups and having a high etching selectivity with respect to the substrate is used for the organic film, the k value will increase and the substrate reflection will increase. However, by making the silicon-containing resist underlayer film have absorption that results in an appropriate k value, reflection can be suppressed, and the substrate reflection can be controlled to 0.5% or less. Regarding the silicon-containing resist underlayer film having an antireflection effect, for 248 nm and 157 nm exposure, a polysiloxane crosslinked with pendant anthracene by acid or heat can be ideally used, and for 193 nm exposure, a polysiloxane crosslinked with pendant phenyl or a light-absorbing group having a silicon-silicon bond by acid or heat can be ideally used.

[0251] Also, a four-layer resist process using an organic antireflection film is also ideal. At this time, at least on the substrate to be processed, an organic film is formed using the organic film forming material of the present invention, a silicon-containing resist underlayer film is formed on the organic film using a silicon-containing resist underlayer film material, an organic antireflection film is formed on the silicon-containing resist underlayer film, and an upper resist film is formed on the organic antireflection film using a resist upper film material of a photoresist composition to form a multilayer resist film. After exposing the pattern circuit region of the above upper resist film, development is performed using a developer to form a resist pattern on the above upper resist film. The obtained resist pattern is used as an etching mask, and the pattern is transferred to the above organic antireflection film and the above silicon-containing resist underlayer film by etching. The obtained silicon-containing resist underlayer film pattern is used as an etching mask, and the pattern is transferred to the above organic film by etching. Then, the obtained organic film pattern is used as an etching mask, and the pattern is transferred to the above substrate to be processed by etching, and a semiconductor device circuit pattern can be formed on the substrate.

[0252] Alternatively, the silicon-containing resist underlayer film can be replaced with an inorganic hard mask. In this case, an organic film is formed on at least the substrate to be processed using the organic film-forming material of the present invention. An inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film. On the inorganic hard mask, a resist upper layer film material composed of a photoresist composition is used to form a resist upper layer film. After the pattern circuit region of the resist upper layer film is exposed, it is developed with a developer to form a resist pattern on the resist upper layer film. The obtained resist pattern is used as an etching mask, and the pattern is transferred to the inorganic hard mask by etching. The obtained inorganic hard mask pattern is used as an etching mask, and the pattern is transferred to the organic film by etching. Then, the obtained organic film pattern is used as an etching mask, and the pattern is transferred to the substrate to be processed by etching, so that a semiconductor device circuit pattern can be formed on the substrate.

[0253] When forming an inorganic hard mask on the organic film as described above, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. For example, regarding the formation method of the silicon nitride film, it is described in Japanese Patent Laid-Open No. 2002-334869 and International Publication No. 2004 / 066377. The film thickness of the inorganic hard mask is preferably 5 to 200 nm, more preferably 10 to 100 nm. Further, for the inorganic hard mask, an SiON film having a high antireflection film effect can be most preferably used. Since the substrate temperature during the formation of the SiON film reaches 300 to 500°C, the organic film must withstand a temperature of 300 to 500°C. The organic film-forming material used in the present invention has high heat resistance and can withstand a high temperature of 300°C to 500°C, so an inorganic hard mask formed by a CVD method or an ALD method and an organic film formed by a spin coating method can be combined.

[0254] Alternatively, a four-layer resist process using an organic antireflection film is also ideal. In this case, an organic film is formed on at least the substrate to be processed using the organic film-forming material of the present invention. An inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film. An organic antireflection film is formed on the inorganic hard mask. On the organic antireflection film, a resist upper layer film material of a photoresist composition is used to form a resist upper layer film to form a multilayer resist film. After the pattern circuit region of the resist upper layer film is exposed, it is developed with a developer to form a resist pattern on the resist upper layer film. The obtained resist pattern is used as an etching mask, and the pattern is transferred to the organic antireflection film and the inorganic hard mask by etching. The obtained inorganic hard mask pattern is used as an etching mask, and the pattern is transferred to the organic film by etching. Then, the obtained organic film pattern is used as an etching mask, and the pattern is transferred to the substrate to be processed by etching, so that a semiconductor device circuit pattern can be formed on the substrate.

[0255] As described above, a photoresist film can also be formed on the inorganic hard mask as the upper resist film, and an organic anti-reflective coating (BARC) can be spin-coated on the inorganic hard mask, and a photoresist film can be formed thereon. Especially when using a SiON film as the inorganic hard mask, through the two-layer anti-reflective film of the SiON film and the BARC, reflection can be suppressed even in immersion exposure with a high NA exceeding 1.0. Another advantage of forming the BARC is that it has the effect of reducing the tailing of the photoresist pattern on the SiON film.

[0256] In the above three-layer resist process, the upper resist film can be either positive or negative, and the same composition as the commonly used photoresist composition can be used. After spin-coating the photoresist composition, pre-baking is carried out, preferably in the range of 60 to 180 °C for 10 to 300 seconds. Thereafter, exposure is carried out according to the usual method, followed by post-exposure baking (PEB) and development to obtain a resist pattern. In addition, the thickness of the upper resist film is not particularly limited, preferably 30 to 500 nm, and particularly preferably 50 to 400 nm.

[0257] Also, the exposure light is high-energy radiation with a wavelength of 300 nm or less. Specifically, excimer lasers of 248 nm, 193 nm, and 157 nm, soft X-rays of 3 to 20 nm, electron beams, X-rays, etc. can be cited.

[0258] Regarding the pattern formation method of the above upper resist film, it is preferably set to pattern formation by optical lithography using light with a wavelength of 10 nm or more and 300 nm or less, direct drawing using an electron beam, nanoimprinting, or a combination of these methods.

[0259] Also, the development method in the above pattern formation method is preferably development using alkali development or an organic solvent.

[0260] Then, the obtained resist pattern is used as a mask and etching is carried out. The etching of the silicon-containing lower resist film and the inorganic hard mask in the three-layer resist process is carried out using a fluorocarbon-based gas with the upper resist pattern as a mask. Thereby, a silicon-containing lower resist film pattern and an inorganic hard mask pattern are formed.

[0261] Then, the obtained silicon-containing lower resist film pattern and inorganic hard mask pattern are used as masks, and etching processing of the organic film is carried out.

[0262] Subsequent etching of the substrate to be processed can also be carried out by conventional methods. For example, if the substrate to be processed is SiO2, SiN, or a silicon dioxide-based low dielectric constant insulating film, etching using a fluorocarbon (FLON)-based gas as the main component is carried out. If it is p-Si, Al, or W, etching using a chlorine-based or bromine-based gas as the main component is carried out. When etching the substrate using a fluorocarbon (FLON)-based gas, the silicon-containing resist underlayer film pattern in the three-layer resist process will be peeled off simultaneously with the substrate processing. When etching the substrate using a chlorine-based or bromine-based gas, peeling of the silicon-containing resist underlayer film pattern requires additional dry etching peeling using a fluorocarbon (FLON)-based gas after the substrate processing.

[0263] The organic film obtained using the organic film-forming material of the present invention has the characteristic of excellent etching resistance during etching of these substrates to be processed.

[0264] In addition, the substrate to be processed is not particularly limited, and substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., or those with a processed layer formed on the substrate can be used. As the processed layer, various Low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, etc., and their barrier films can be used. Generally, a thickness of 50 to 10,000 nm can be formed, and particularly, a thickness of 100 to 5,000 nm can be formed. In addition, when forming the processed layer, different materials can be used for the substrate and the processed layer.

[0265] The substrate to be processed is preferably a semiconductor device substrate or one formed by depositing any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film on the semiconductor device substrate. More specifically, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., or those with the above metal films, etc., formed on the substrate as the processed layer can be used, but are not limited thereto.

[0266] As the processed layer, various Low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, etc., and their barrier films can be used. Generally, a thickness of 50 to 10,000 nm can be formed, and particularly, a thickness of 100 to 5,000 nm can be formed. In addition, when forming the processed layer, different materials can be used for the substrate and the processed layer.

[0267] In addition, the metal constituting the substrate to be processed is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, ruthenium, or their alloys.

[0268] Further, a substrate to be processed is preferably a substrate to be processed having a structure or height difference of 30 nm or more.

[0269] For an example of a three-layer resist process, use Figure 1 Specifically exemplified as follows. In the case of a three-layer resist process, as Figure 1 shown in (A), after forming an organic film 3 on a processed layer 2 laminated on a substrate 1 using the organic film forming material of the present invention, a silicon-containing lower resist film 4 is formed, and an upper resist film 5 is formed thereon.

[0270] Then, as Figure 1 shown in (B), the used portion 6 of the upper resist film 5 is exposed, and PEB and development are performed to form a resist pattern 5a ( Figure 1 shown in (C)). Using the obtained resist pattern 5a as a mask, the silicon-containing lower resist film 4 is etched using a CF-based gas to form a silicon-containing lower resist film pattern 4a ( Figure 1 shown in (D)). After removing the resist pattern 5a, the obtained silicon-containing lower resist film pattern 4a is used as a mask and the organic film 3 is etched with oxygen plasma to form an organic film pattern 3a ( Figure 1 shown in (E)). After removing the silicon-containing lower resist film pattern 4a, the organic film pattern 3a is used as a mask and the processed layer 2 is etched to form a pattern 2a ( Figure 1 shown in (F)).

[0271] When using an inorganic hard mask, the silicon-containing lower resist film 4 is an inorganic hard mask. When applying BARC, a BARC layer is provided between the silicon-containing lower resist film 4 and the upper resist film 5. Etching of BARC may sometimes be continuously performed before etching of the silicon-containing lower resist film 4, or only etching of BARC may be performed, and then the etching apparatus etc. may be changed to perform etching of the silicon-containing lower resist film 4.

[0272] Thus, if it is the pattern forming method of the present invention, a fine pattern can be formed with high precision on a substrate to be processed in a multi-layer resist process.

[0273] [Examples]

[0274] Hereinafter, synthesis examples, examples and comparative examples are exemplified to more specifically explain the present invention, but the present invention is not limited by them. In addition, regarding the molecular weight and dispersity, the weight average molecular weight (Mw), number average molecular weight (Mn) in terms of polystyrene converted by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase are determined, and the dispersity (Mw / Mn) is obtained.

[0275] [Synthesis of Compounds and Polymers for Organic Film Forming Materials]

[0276] In the synthesis of compounds (A1) to (A7) for the organic film-forming material and compound (R1) for the comparative example, phenols (B1) to (B5) and fluorene alcohols (C1) to (C4) shown below were used.

[0277] Phenols:

[0278] [Chemical formula 36]

[0279]

[0280] Fluorene alcohols:

[0281] [Chemical formula 37]

[0282]

[0283] (Synthesis Example 1)

[0284] Synthesis of compound (A1)

[0285] [Chemical formula 38]

[0286]

[0287] Under a nitrogen atmosphere, 22.8 g of phenol (B1), 30.0 g of fluorene alcohol (C1), and 200 g of 1,2-dichloroethane were added, and a homogeneous dispersion was prepared at an internal temperature of 50 °C. 15.4 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 50 °C for 6 hours. After the reaction was completed, it was cooled to room temperature, 400 ml of MIBK (methyl isobutyl ketone) was added, and it was washed 6 times with 100 ml of pure water, and the organic layer was dried under reduced pressure. 150 g of THF was added to the residue to form a homogeneous solution, and then crystallization was carried out in 500 g of methanol. The precipitated crystals were separated by filtration, washed twice with 200 g of methanol and recovered. The recovered crystals were vacuum dried at 70 °C to obtain compound (A1).

[0288] When the weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained.

[0289] (A1): Mw = 720, Mw / Mn = 1.04

[0290] (Synthesis Example 2)

[0291] Synthesis of compound (A2)

[0292] [Chemical formula 39]

[0293]

[0294] In a nitrogen atmosphere, 32.9 g of phenols (B2), 20.0 g of fluorenols (C2), and 200 g of 1,2-dichloroethane were added, and a homogeneous dispersion was prepared at an internal temperature of 50 °C. 9.9 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 50 °C for 6 hours. After the reaction was completed, it was cooled to room temperature, 400 ml of MIBK was added, and it was washed 6 times with 100 ml of pure water, and the organic layer was dried under reduced pressure. After adding 150 g of THF to the residue to form a homogeneous solution, crystallization was carried out in 500 g of IPE (diisopropyl ether). The precipitated crystals were separated by filtration, washed 2 times with 300 g of methanol and recovered. The recovered crystals were vacuum-dried at 70 °C to obtain compound (A2).

[0295] When the weight-average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained.

[0296] (A2): Mw = 840, Mw / Mn = 1.06

[0297] (Synthesis Example 3)

[0298] Synthesis of compound (A3)

[0299] [Chemical Formula 40]

[0300]

[0301] In a nitrogen atmosphere, 24.4 g of phenols (B4), 20.0 g of fluorenols (C2), and 200 g of 1,2-dichloroethane were added, and a homogeneous dispersion was prepared at an internal temperature of 50 °C. 9.9 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 50 °C for 6 hours. After the reaction was completed, it was cooled to room temperature, 350 ml of MIBK was added, and it was washed 6 times with 100 ml of pure water, and the organic layer was dried under reduced pressure. After adding 180 g of THF to the residue to form a homogeneous solution, crystallization was carried out in 500 g of methanol. The precipitated crystals were separated by filtration, washed 2 times with 200 g of methanol and recovered. The recovered crystals were vacuum-dried at 70 °C to obtain compound (A3).

[0302] When the weight-average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained.

[0303] (A3): Mw = 890, Mw / Mn = 1.04

[0304] (Synthesis Example 4)

[0305] Synthesis of compound (A4)

[0306] [Chemical Formula 41]

[0307]

[0308] In a nitrogen atmosphere, 21.9 g of phenols (B1), 30.0 g of fluorenols (C3), and 100 g of 1,2-dichloroethane were added, and a homogeneous dispersion was prepared at an internal temperature of 50°C. 14.8 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 50°C for 6 hours. After the reaction was completed, it was cooled to room temperature, 400 ml of MIBK was added, and it was washed 6 times with 100 ml of pure water. The organic layer was dried under reduced pressure. After adding 200 g of THF to the residue to form a homogeneous solution, crystallization was carried out in 500 g of methanol. The precipitated crystals were separated by filtration, washed twice with 200 g of methanol and recovered. The recovered crystals were dried under vacuum at 70°C to obtain compound (A4).

[0309] When the weight-average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained.

[0310] (A4): Mw = 710, Mw / Mn = 1.03

[0311] (Synthesis Example 5)

[0312] Synthesis of Compound (A5)

[0313] [Chemical Formula 42]

[0314]

[0315] In a nitrogen atmosphere, 32.9 g of phenols (B3), 20.0 g of fluorenols (C3), and 100 g of 1,2-dichloroethane were added, and a homogeneous dispersion was prepared at an internal temperature of 50°C. 9.9 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 50°C for 6 hours. After the reaction was completed, it was cooled to room temperature, 400 ml of MIBK was added, and it was washed 6 times with 100 ml of pure water. The organic layer was dried under reduced pressure. After adding 100 g of THF to the residue to form a homogeneous solution, crystallization was carried out in 500 g of IPE. The precipitated crystals were separated by filtration, washed twice with 200 g of methanol and recovered. The recovered crystals were dried under vacuum at 70°C to obtain compound (A5).

[0316] When the weight-average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained.

[0317] (A5): Mw = 900, Mw / Mn = 1.06

[0318] (Synthesis Example 6)

[0319] Synthesis of Compound (A6)

[0320] [Chemical Formula 43]

[0321]

[0322] In a nitrogen atmosphere, 18.1 g of phenols (B1), 30.0 g of fluorenols (C4), and 100 g of 1,2-dichloroethane were added, and a homogeneous dispersion was prepared at an internal temperature of 50 °C. 12.3 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 50 °C for 6 hours. After the reaction was completed, it was cooled to room temperature and 400 ml of MIBK was added, and it was washed 6 times with 100 ml of pure water, and the organic layer was dried under reduced pressure. After adding 200 g of THF to the residue to form a homogeneous solution, crystallization was carried out in 500 g of methanol. The precipitated crystals were separated by filtration, washed twice with 200 g of methanol and recovered. The recovered crystals were vacuum-dried at 70 °C to obtain compound (A6).

[0323] When the weight-average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained.

[0324] (A6): Mw = 850, Mw / Mn = 1.05

[0325] (Synthesis Example 7)

[0326] Synthesis of compound (A7)

[0327] [Chemical formula 44]

[0328]

[0329] In a nitrogen atmosphere, 27.3 g of phenols (B2), 20.0 g of fluorenols (C4), and 200 g of 1,2-dichloroethane were added, and a homogeneous dispersion was prepared at an internal temperature of 50 °C. 8.2 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 50 °C for 6 hours. After the reaction was completed, it was cooled to room temperature and 400 ml of MIBK was added, and it was washed 6 times with 100 ml of pure water, and the organic layer was dried under reduced pressure. After adding 200 g of THF to the residue to form a homogeneous solution, crystallization was carried out in 500 g of IPE. The precipitated crystals were separated by filtration, washed twice with 200 g of methanol and recovered. The recovered crystals were vacuum-dried at 70 °C to obtain compound (A7).

[0330] When the weight-average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained.

[0331] (A7): Mw = 950, Mw / Mn = 1.07

[0332] (Synthesis Example 8)

[0333] Synthesis of polymer (A8)

[0334] [Chemical formula 45]

[0335]

[0336] In a nitrogen atmosphere, 20.0 g of compound (A2), 1.47 g of 37% aqueous formaldehyde solution, and 100 g of 1,2-dichloroethane were added, and a homogeneous solution was prepared at an internal temperature of 50°C. 2.5 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 50°C for 8 hours. After the reaction was completed, it was cooled to room temperature and 300 ml of MIBK was added, and it was washed 6 times with 100 ml of pure water, and the organic layer was dried under reduced pressure. After adding 100 g of THF to the residue and preparing a homogeneous solution, crystallization was carried out in 300 g of hexane. The precipitated crystals were separated by filtration, washed 2 times with 200 g of hexane and recovered. The recovered crystals were vacuum-dried at 70°C to obtain polymer (A8).

[0337] When the weight-average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained.

[0338] (A8): Mw = 3300, Mw / Mn = 1.68

[0339] (Synthesis Example 9)

[0340] Synthesis of polymer (A9)

[0341] [Chemical Formula 46]

[0342]

[0343] In a nitrogen atmosphere, 20.0 g of compound (A5), 2.84 g of 2-naphthaldehyde, and 100 g of 1,2-dichloroethane were added, and a homogeneous solution was prepared at an internal temperature of 50°C. 2.5 g of methanesulfonic acid was slowly added, and the reaction was carried out at an internal temperature of 50°C for 8 hours. After the reaction was completed, it was cooled to room temperature and 300 ml of MIBK was added, and it was washed 6 times with 100 ml of pure water, and the organic layer was dried under reduced pressure. After adding 100 g of THF to the residue and preparing a homogeneous solution, crystallization was carried out in 300 g of hexane. The precipitated crystals were separated by filtration, washed 2 times with 200 g of hexane and recovered. The recovered crystals were vacuum-dried at 70°C to obtain polymer (A9).

[0344] When the weight-average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained.

[0345] (A9): Mw = 3400, Mw / Mn = 1.76

[0346] (Synthesis Example 10)

[0347] Synthesis of polymer (A10)

[0348] [Chemical Formula 47]

[0349]

[0350] In a nitrogen atmosphere, 20.0 g of compound (A7), 3.31 g of 9-fluorenone, and 100 g of 1,2-dichloroethane were added and made into a homogeneous dispersion at an internal temperature of 50 °C. A mixed solution of 2.2 g of methanesulfonic acid and 0.73 g of 3-mercaptopropionic acid prepared in advance was slowly added, and the reaction was carried out at an internal temperature of 70 °C for 12 hours. After the reaction was completed, it was cooled to room temperature and 300 ml of MIBK was added, and it was washed 6 times with 100 ml of pure water, and the organic layer was dried under reduced pressure. After adding 100 g of THF to the residue and making it into a homogeneous solution, crystallization was carried out with 300 g of IPE. The precipitated crystals were separated by filtration, washed 2 times with 200 g of IPE and recovered. The recovered crystals were vacuum-dried at 70 °C to obtain polymer (A10).

[0351] When the weight-average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained.

[0352] (A10): Mw = 4300, Mw / Mn = 1.86

[0353] (Synthesis Example 11)

[0354] Synthesis of polymer (A11)

[0355] [Chemical Formula 48]

[0356]

[0357] In a nitrogen atmosphere, 10.0 g of polymer (A8), 7.1 g of potassium carbonate, and 50 g of dimethylformamide were added and made into a homogeneous dispersion at an internal temperature of 50 °C. 4.6 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50 °C for 24 hours. After the reaction was completed, it was cooled to room temperature and 200 ml of MIBK was added, and it was washed 6 times with 100 ml of pure water, and the organic layer was dried under reduced pressure. 200 ml of methyl isobutyl ketone and 100 g of pure water were added to the reaction solution to dissolve the precipitated salt, and the separated aqueous layer was removed. Then, the organic layer was washed 2 times with 50 g of 3% aqueous nitric acid solution and 6 times with 50 g of pure water, and then the organic layer was dried under reduced pressure. After adding 40 g of THF to the residue and making it into a homogeneous solution, crystallization was carried out with 150 g of methanol. The precipitated crystals were separated by filtration, washed 2 times with 100 g of methanol and recovered. The recovered crystals were vacuum-dried at 70 °C to obtain polymer (A11).

[0358] When the weight-average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained.

[0359] (A11): Mw = 3700, Mw / Mn = 1.73

[0360] (Synthesis Example 12)

[0361] Synthesis of Polymer (A12)

[0362] [Chemical Formula 49]

[0363]

[0364] Under a nitrogen atmosphere, 10.0 g of polymer (A9), 6.1 g of potassium carbonate, and 50 g of dimethylformamide were added, and a homogeneous dispersion was prepared at an internal temperature of 50°C. 3.9 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. After the reaction was completed, it was cooled to room temperature, 200 ml of MIBK was added, and it was washed 6 times with 100 ml of pure water, and the organic layer was dried under reduced pressure. 200 ml of methyl isobutyl ketone and 100 g of pure water were added to the reaction solution to dissolve the precipitated salt, and the separated aqueous layer was removed. Then, the organic layer was washed 2 times with 50 g of 3% aqueous nitric acid solution and 6 times with 50 g of pure water, and the organic layer was dried under reduced pressure. 40 g of THF was added to the residue to form a homogeneous solution, and then crystallized with 150 g of methanol. The precipitated crystals were separated by filtration, washed 2 times with 100 g of methanol and recovered. The recovered crystals were vacuum dried at 70°C to obtain polymer (A12).

[0365] When the weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, the following results were obtained.

[0366] (A12): Mw = 3800, Mw / Mn = 1.85

[0367] (Synthesis Example 13)

[0368] Synthesis of Compound (R1) for Comparative Example

[0369] [Chemical Formula 50]

[0370]

[0371] In a nitrogen atmosphere, 10.0 g of a phenol (B5) which is a diol compound, 13.8 g of 9-ethynyl-9-fluorenol, 14.1 g of trimethyl orthoformate, and 250 g of 1,2-dichloroethane were made into a homogeneous solution at a liquid temperature of 80 °C, and then 3.4 g of pyridinium p-toluenesulfonate was added, and the reaction was carried out at a liquid temperature of 80 °C for 12 hours. After cooling to room temperature, 300 ml of MIBK was added, the organic layer was washed 5 times with 100 g of pure water, and then the organic layer was dried under reduced pressure. After adding 50 g of THF to the residue and making it into a homogeneous solution, 200 g of methanol was added to precipitate crystals. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain compound (R1).

[0372] When the weight-average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained.

[0373] (R1): Mw = 900, Mw / Mn = 1.04

[0374] (Synthesis Example 14)

[0375] Synthesis of Compound (R2) for Comparative Example

[0376] [Chemical Formula 51]

[0377]

[0378] In a nitrogen atmosphere, 80 g of 2,7-dipropynyloxy naphthalene, 22 g of 37% formaldehyde solution, and 250 g of 1,2-dichloroethane were made into a homogeneous solution at a liquid temperature of 70 °C, and then 5 g of methanesulfonic acid was slowly added, and the reaction was carried out at a liquid temperature of 80 °C for 12 hours. After cooling to room temperature, 500 ml of MIBK was added, the organic layer was washed 5 times with 200 g of pure water, and then the organic layer was dried under reduced pressure. After adding 300 g of THF to the residue and making it into a homogeneous solution, 2000 g of hexane was added to reprecipitate the polymer. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain compound (R2).

[0379] When the weight-average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, the following results were obtained.

[0380] (R2): Mw = 2900, Mw / Mn = 1.57

[0381] A summary of the Mw and Mw / Mn results of the compounds and polymers (A1) to (A12) used in the examples and the compounds (R1) and (R2) used in the comparative examples is shown in Tables 1 to 4.

[0382] [Table 1]

[0383]

[0384] [Table 2]

[0385]

[0386] [Table 3]

[0387]

[0388] [Table 4]

[0389]

[0390] [Preparation of Organic Film-Forming Materials (UDL-1 to 16, Comparative UDL-1 to 2)]

[0391] By using the above-mentioned compounds and / or polymers (A1) to (A12) and (R1), (R2), 1,6-diacetoxyhexane (S1) with a boiling point of 260 °C and tripropylene glycol monomethyl ether (S2) with a boiling point of 242 °C as high-boiling solvents, and dissolving them in propylene glycol monomethyl ether acetate (PGMEA) containing 0.1% by mass of PF-6320 (manufactured by OMNOVA Solutions Inc.) in the proportions shown in Table 5, and then filtering through a 0.1-μm fluororesin filter, organic film-forming materials (UDL-1 to 16, Comparative UDL-1 to 2) were prepared respectively.

[0392] [Table 5]

[0393]

[0394] [Solvent Resistance Measurement of Example 1 (Examples 1-1 to 1-16, Comparative Examples 1-1 to 1-2)]

[0395] The above-prepared UDL-1 to 16 and Comparative UDL-1 to 2 were coated on a silicon substrate. In the atmosphere, after baking at 350 °C for 60 seconds, the film thickness was measured. Then, PGMEA solvent was dropped on it and left for 30 seconds, followed by spin drying and baking at 100 °C for 60 seconds to evaporate the PGMEA, and the film thickness before and after the PGMEA treatment was measured. The residual film rate was calculated using the film thickness after film formation and the film thickness after the PGMEA treatment. The results are shown in Table 6.

[0396] [Table 6]

[0397]

[0398] As shown in Table 6, the organic films (Examples 1-1 to 1-16) using the compounds and / or polymers of the present invention had a residual film rate of 99.5% or more after PGMEA treatment, and underwent a crosslinking reaction due to heat treatment and exhibited sufficient solvent resistance. In particular, when comparing Examples 1-1 to 1-4, 13, 14 which are single-molecule compounds with Comparative Example 1-1, it can be seen that the crosslinked part of the compound in Comparative Example 1-1 is only the benzopyran ring. In contrast, the compounds of the present invention also have crosslinked parts at the terminal substituents. Therefore, the film loss of Examples 1-1 to 1-4, 13, 14 is small, and the hardening due to heat proceeds efficiently.

[0399] [Example 2 Heat Resistance Evaluation (Examples 2-1 to 2-16, Comparative Examples 2-1 to 2-2)]

[0400] The above-mentioned organic film-forming materials (UDL-1 to 16, Comparative UDL-1 to 2) were respectively coated on a silicon substrate and calcined in the atmosphere at 350 °C for 60 seconds to form a 200-nm coating film, and the film thickness A was measured. The substrate was further calcined at 450 °C for 10 minutes under a nitrogen gas flow in which the oxygen concentration was controlled below 0.2%, and the film thickness B was measured. Their results are shown in Table 7.

[0401] [Table 7]

[0402]

[0403] As shown in Table 7, it can be seen that for the organic film-forming materials of the present invention (Examples 2-1 to 2-16), the film thickness reduction after calcination at 450 °C was still less than 5%. The organic film-forming materials of the present invention maintained the film thickness before high-temperature baking even after calcination at 450 °C and had excellent heat resistance. In particular, it can be seen that in Examples 2-2 to 2-16 in which an aromatic ring structure rather than an alkyl group was introduced into the linking group, the residual film rate remained above 99% and the heat resistance was improved. On the other hand, in Comparative Example 2-1, as a result of Example 1, it can be seen that the heat resistance was worse than that of Examples 2-1 to 2-16 due to insufficient crosslinking density. In Comparative Example 2-2, although the film hardening property was sufficient as shown in the results of Example 1, the polymer had poor heat resistance because of the poor rigidity of the partial structure constituting the repeating unit.

[0404] [Example 3 Hardness Measurement (Examples 3-1 to 3-16, Comparative Examples 3-1 to 3-2)]

[0405] The prepared UDL-1 to 16 and Comparative UDL-1 to 2 were coated on a silicon substrate and baked at 350 °C for 60 seconds in the atmosphere to form a coating film with a film thickness of 200 nm. Nanoindentation tests were performed on these films using a NANOINDENTER SA2 type device manufactured by TOYO Corporation to measure the hardness of the above coating films, and the results are shown in Table 8.

[0406] [Table 8]

[0407] Organic Film-Forming Material Hardness (GPa) Example 3-1 UDL-1 0.65 Example 3-2 UDL-2 0.62 Example 3-3 UDL-3 0.71 Example 3-4 UDL-4 0.72 Example 3-5 UDL-5 0.69 Example 3-6 UDL-6 0.65 Example 3-7 UDL-7 0.63 Example 3-8 UDL-8 0.61 Example 3-9 UDL-9 0.61 Example 3-10 UDL-10 0.69 Example 3-11 UDL-11 0.68 Example 3-12 UDL-12 0.66 Example 3-13 UDL-13 0.63 Example 3-14 UDL-14 0.70 Example 3-15 UDL-15 0.68 Example 3-16 UDL-16 0.61 Comparative Example 3-1 Comparative UDL-1 0.54 Comparative Example 3-2 Comparative UDL-2 0.63

[0408] As shown in Table 8, in Examples 3-1 to 3-16, films with a hardness of 0.6 or more could be formed, and it was confirmed that films denser and stronger than Comparative Example 3-1 could be formed. This is the result taught by the results of Example 1. Also, in Comparative Example 3-2, since the hardening property was sufficient as shown by the results of Example 1, although the heat resistance was poor as shown by the results of Example 2, it had a hardness of 0.6 or more.

[0409] [Example 4 Etching Test (Examples 4-1 to 4-16, Comparative Examples 4-1 to 4-2)]

[0410] [Etching Test Using CF4 / CHF3-Based Gas]

[0411] The prepared UDL-1 to 16 and Comparative UDL-1 to 2 were coated on a silicon substrate and baked at 350 °C for 60 seconds in the atmosphere to form an organic film with a film thickness of 200 nm, and then an etching test using CF4 / CHF3-based gas was performed under the following conditions. At this time, a dry etching device TE-8500 manufactured by Tokyo Electron Limited was used to obtain the film thickness difference of the polymer film before and after etching, and the etching rate (nm / min.) was calculated. The results are shown in Table 9.

[0412] The etching conditions are as follows.

[0413]

[0414] [Etching Test Using O2-Based Gas]

[0415] In the same manner as above, UDL-1 to 16 and Comparative UDL-1 to 2 were coated on a silicon substrate, and in an air environment, baked at 350 °C for 60 seconds in the atmosphere to form an organic film with a film thickness of 200 nm, and then an etching test using O2-based gas was performed under the following conditions. At this time, a dry etching device TE-8500 manufactured by Tokyo Electron Limited was used to obtain the film thickness difference of the polymer film before and after etching, and the etching rate (nm / min.) was calculated. The results are presented in Table 9 in combination with those of the CF4 / CHF3-based gas.

[0416] The etching conditions are as described below.

[0417]

[0418]

[0419] In the etching tests of the above CF4 / CHF3-based gas and O2-based gas, the smaller the etching rate, the better the etching resistance of the film.

[0420] [Table 9]

[0421]

[0422] As can be seen from Table 9, compared with Comparative Examples 4-1 and 4-2, in any of the etching tests of the CF4 / CHF3-based gas and O2-based gas, the etching rate values of the Examples are smaller than those of the Comparative Examples, and films with excellent etching resistance are formed.

[0423] [Example 5 Pattern Etching Test (Examples 5-1 to 5-16, Comparative Examples 5-1 to 5-2)]

[0424] The above-prepared UDL-1 to 16 and Comparative UDL-1 to 2 were coated on a 300-mm diameter silicon wafer substrate with a 200-nm thick SiO2 film. In the atmosphere, an organic film with a thickness of 200 nm was formed by baking at 350 °C for 60 seconds. A silicon-containing anti-resist underlayer film material (SOG-1) was coated thereon and baked at 220 °C for 60 seconds to form a 35-nm thick silicon-containing anti-resist underlayer film. Then, an anti-resist upper layer film material (ArF SL resist) was coated thereon and baked at 105 °C for 60 seconds to form a 100-nm thick anti-resist upper layer film. An immersion protective film material (TC-1) was coated on the anti-resist upper layer film and baked at 90 °C for 60 seconds to form a 50-nm thick protective film.

[0425] Regarding the anti-resist upper layer film material (ArF SL resist), it was prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) in a solvent containing 0.1 mass% of FC-430 (manufactured by Sumitomo 3M Co., Ltd.) in the ratio shown in Table 10, and then filtering through a 0.1-μm fluororesin filter.

[0426] [Table 10]

[0427]

[0428] The structural formulas of the polymer (RP1), acid generator (PAG1), and basic compound (Amine1) used are as shown below.

[0429] [Chemical Formula 52]

[0430]

[0431] Regarding the immersion protective film material (TC-1), it is prepared by dissolving the protective film polymer (PP1) in an organic solvent at the ratio shown in Table 11 and then filtering it through a filter made of fluororesin with a pore size of 0.1 μm.

[0432] [Table 11]

[0433]

[0434] The structural formula of the polymer (PP1) used is as follows.

[0435] [Chemical Formula 53]

[0436]

[0437] Regarding the silicon-containing anti-reflective lower layer film material (SOG-1), the polymer represented by the ArF silicon-containing intermediate film polymer (SiP1) and the crosslinking catalyst (CAT1) are dissolved in an organic solvent containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Limited) at the ratio shown in Table 12, and then filtered through a filter made of fluororesin with a pore size of 0.1 μm to prepare the silicon-containing anti-reflective lower layer film material (SOG-1).

[0438] [Table 12]

[0439]

[0440] The structural formulas of the ArF silicon-containing intermediate film polymer (SiP1) and the crosslinking catalyst (CAT1) used are as follows.

[0441] [Chemical Formula 54]

[0442]

[0443] Then, using an ArF immersion exposure apparatus (manufactured by Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% half-tone phase shift mask), exposure is performed while changing the exposure amount, baked at 100 °C (PEB) for 60 seconds, and then developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds to obtain a positive line and space pattern with an anti-reflective line width ranging from 50 nm to 30 nm at a pitch of 100 nm.

[0444] Then, using the etching device Telius manufactured by Tokyo Electron Limited, processing of the silicon-containing resist underlayer film using the resist pattern formed by dry etching as a mask, processing of the organic film using the silicon-containing resist underlayer film as a mask, and processing of the SiO2 film using the organic film as a mask were carried out.

[0445] The etching conditions are as follows.

[0446] Transfer conditions of the resist pattern onto the SOG film.

[0447]

[0448] Transfer conditions of the SOG film pattern onto the organic film.

[0449]

[0450] Transfer conditions of the organic film pattern onto the SiO2 film.

[0451]

[0452]

[0453] The pattern cross-section was observed with a scanning electron microscope (S-4700) manufactured by Hitachi, Ltd., and the shapes were compared and summarized in Table 13.

[0454] [Table 13]

[0455]

[0456] As confirmed in Table 13, as described in the results of the organic film-forming materials of the present invention (Examples 5-1 to 5-16), in any case, the resist upper layer film pattern was finally well transferred to the substrate. The organic film-forming material of the present invention can be ideally used as an organic film material by the multilayer resist method. Also, the pattern size after substrate transfer changes with the resist line width formed by exposure. In Comparative Example 5-1, pattern distortion occurred at a line width of about 40 nm, while in Examples 5-1 to 5-16 using the compound and / or polymer of the present invention, the pattern size did not distort up to 35 nm or less, and it was determined to have high distortion resistance. As known for the compound and polymer of the present invention, by using an organic film capable of forming a dense and high-strength film with a hardness exceeding 0.60 GPa, high distortion resistance can be obtained.

[0457] [Example 6 Planarization Property Evaluation (Examples 6-1 to 6-13, Comparative Example 6-1)]

[0458] The organic film-forming materials (UDL-2 to 3, 5 to 8, 10 to 16, Comparative UDL-2) were respectively coated on a SiO2 substrate with a large isolated groove pattern (groove width: 10 μm, groove depth: 0.10 μm). Figure 2 After calcining at 350 °C for 60 seconds in the atmosphere, the height difference ( Figure 2 delta in Figure 2 ) between the groove part and the non-groove part of the organic film was observed using an NX10 atomic force microscope (AFM) manufactured by Park Systems Corporation. The results are shown in Table 14. In this evaluation, the smaller the height difference, the better the planarization characteristics. In addition, in this evaluation, a groove pattern with a depth of 0.10 μm was planarized using an organic film-forming material with a film thickness of approximately 0.2 μm, and relatively strict evaluation conditions were adopted to evaluate the quality of the planarization characteristics.

[0459] [Table 14]

[0460]

[0461] As shown in Table 14, it was confirmed that the organic film-forming material of the present invention has a smaller height difference between the groove part and the non-groove part of the organic film compared to Comparative Example 6-1, and excellent planarization characteristics. As described in Example 2, this is because the polymer of the present invention has excellent heat resistance, so the shrinkage of the film caused by baking is suppressed. Also, when Examples 6-10 to 6-13 containing a high-boiling solvent were compared with Examples 6-1 to 6-3 and 6-6 without a high-boiling solvent, it was found that the planarization was improved due to the addition of the high-boiling solvent. Further, when Examples 6-7 to 6-9 in which a polymer and a compound were mixed were compared with Examples 6-3 to 6-5 containing only a polymer, it was found that the planarization was improved. As in the results of Examples 1 to 5 described above, the planarization can be improved without sacrificing various physical properties required for the organic film, such as solvent resistance, heat resistance, twist resistance, and etching resistance.

[0462] As described above, the organic film-forming material of the present invention has excellent heat resistance, high etching resistance, and twist resistance during etching, and is extremely effective for a multilayer resist process for ultra-fine and high-precision pattern processing, and is particularly effective as an organic film for a three-layer resist process.

[0463] Explanation of Reference Numerals

[0464] 1: Substrate

[0465] 2: Layer to be processed

[0466] 2a: Pattern formed on the substrate

[0467] 3: Organic film

[0468] 3a: Organic film pattern

[0469] 4: Silicon-containing resist underlayer film

[0470] 4a: Pattern of silicon-containing resist underlayer film

[0471] 5: Resist upper layer film

[0472] 5a: Resist pattern

[0473] 6: Used part

[0474] 7: Organic film

[0475] 8: SiO2 substrate

[0476] delta: Height difference

Claims

1. An organic film-forming material, characterized by containing: (A) A compound represented by the following general formula (1) and / or a polymer having a repeating unit represented by the following general formula (4), and (B) An organic solvent; In the general formula (1), AR1, AR2, AR3, AR4, AR5 and AR6 are benzene rings or naphthalene rings, and R1 is any one of the groups represented by the following formula (2); n represents an integer of 1 to 2, and W is any one of the structures shown in the following [Chemical Formula 17]; [Chemical Formula 17] The dotted line represents an atomic bond; In the general formula (4), AR1, AR2, AR3, AR4, AR5, AR6, R1, n and W are the same as described above; R2 and R3 together with the carbon atom to which they are bonded form a group in the following [Chemical Formula 26], [Chemical Formula 26] The dotted line represents an atomic bond.

2. The organic film-forming material according to claim 1, wherein, The compound is a compound represented by the following general formula (3); In the general formula (3), AR5, AR6, R1 and n are the same as described above.

3. The organic film-forming material according to claim 1 or 2, wherein, The polymer is a polymer having a repeating unit represented by the following general formula (5); In the general formula (5), AR5, AR6, R1, R2, R3 and n are the same as described above.

4. The organic film-forming material according to claim 1 or 2, wherein, The weight-average molecular weight of the polymer is 1000 to 10000.

5. The organic film-forming material according to claim 1 or 2, wherein, The organic solvent is a mixture of one or more organic solvents with a boiling point below 180 °C and one or more organic solvents with a boiling point of 180 °C or higher.

6. The organic film-forming material according to claim 1 or 2, further containing one or more of (C) an acid generator, (D) a surfactant, (E) a crosslinking agent, and (F) a plasticizer.

7. A pattern forming method, which is a method for forming a pattern on a substrate to be processed, characterized in that: An organic film is formed on the substrate to be processed using the organic film-forming material according to any one of claims 1 to 6, a silicon-containing anti-reflective coating material is used to form a silicon-containing anti-reflective coating on the organic film, a photoresist composition is used to form a photoresist upper layer on the silicon-containing anti-reflective coating, a circuit pattern is formed on the photoresist upper layer, the patterned photoresist upper layer is used as a mask and the silicon-containing anti-reflective coating is pattern-transferred by etching, the pattern-transferred silicon-containing anti-reflective coating is used as a mask and the organic film is pattern-transferred by etching, and then the pattern-transferred organic film is used as a mask and the pattern is formed on the substrate to be processed by etching.

8. A pattern forming method, which is a method for forming a pattern on a substrate to be processed, characterized in that: An organic film is formed on a substrate to be processed using the organic film forming material according to any one of claims 1 to 6. A silicon-containing anti-reflective coating underlayer film is formed on the organic film using a silicon-containing anti-reflective coating underlayer film material. An organic anti-reflective film is formed on the silicon-containing anti-reflective coating underlayer film. A resist upper layer film is formed on the organic anti-reflective film using a photoresist composition to form a four-layer film structure. A circuit pattern is formed on the resist upper layer film. Using the patterned resist upper layer film as a mask, the organic anti-reflective film and the silicon-containing anti-reflective coating underlayer film are pattern-transferred by etching. Using the pattern-transferred silicon-containing anti-reflective coating underlayer film as a mask, the organic film is pattern-transferred by etching. Then, using the pattern-transferred organic film as a mask, the substrate to be processed is etched to form a pattern on the substrate to be processed.

9. A pattern forming method, which is a method for forming a pattern on a substrate to be processed, characterized in that: An organic film is formed on a substrate to be processed using the organic film forming material according to any one of claims 1 to 6. An inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film. A resist upper layer film is formed on the inorganic hard mask using a photoresist composition. A circuit pattern is formed on the resist upper layer film. Using the patterned resist upper layer film as a mask, the pattern is transferred to the inorganic hard mask by etching. Using the pattern-transferred inorganic hard mask as a mask, the pattern is transferred to the organic film by etching. Then, using the pattern-transferred organic film as a mask, the substrate to be processed is etched to form a pattern on the substrate to be processed.

10. A pattern forming method, which is a method for forming a pattern on a substrate to be processed, characterized in that: An organic film is formed on a substrate to be processed using the organic film forming material according to any one of claims 1 to 6. An inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film. An organic anti-reflective film is formed on the inorganic hard mask. A resist upper layer film is formed on the organic anti-reflective film using a photoresist composition to form a four-layer film structure. A circuit pattern is formed on the resist upper layer film. Using the patterned resist upper layer film as a mask, the pattern is transferred to the organic anti-reflective film and the inorganic hard mask by etching. Using the pattern-transferred inorganic hard mask as a mask, the pattern is transferred to the organic film by etching. Then, using the pattern-transferred organic film as a mask, the substrate to be processed is etched to form a pattern on the substrate to be processed.

11. The pattern forming method according to claim 9 or 10, wherein, The inorganic hard mask is formed by CVD method or ALD method.

12. The pattern forming method according to any one of claims 7 to 10, wherein, The method for forming the pattern of the resist upper layer film is: pattern formation by optical lithography with a wavelength of 10 nm or more and 300 nm or less, direct drawing by an electron beam, nanoimprinting, or a combination of these methods.

13. The pattern forming method according to any one of claims 7 to 10, wherein, The developing method in the pattern forming method is development using an alkali developer or an organic solvent.

14. The pattern forming method according to any one of claims 7 to 10, wherein, The substrate to be processed is a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, or a metal oxynitride film.

15. The pattern forming method according to claim 14, wherein, The metal is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, cobalt, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, manganese, molybdenum, ruthenium or their alloys.

16. A compound, characterized in that it is represented by the following general formula (1): In the general formula (1), AR1, AR2, AR3, AR4, AR5 and AR6 are benzene rings or naphthalene rings, and R1 is any one of the groups represented by the following formula (2); n represents an integer from 1 to 2, and W is any one of the structures shown in the following [Chemical Formula 17]; [Chemical Formula 17] The dotted line represents an atomic bond.

17. The compound according to claim 16, wherein, The compound is represented by the following general formula (3); AR5, AR6, R1 and n in the general formula (3) are the same as those described above.

18. A polymer, characterized in that: It has a repeating unit represented by the following general formula (4); In the general formula (4), AR1, AR2, AR3, AR4, AR5 and AR6 are benzene rings or naphthalene rings, and R1 is any one of the groups represented by the following formula (2); n represents an integer from 1 to 2, and W is any one of the structures shown in the following [Chemical Formula 17]; R2 and R3 together with the carbon atom to which they are bonded form a group in the following [Chemical Formula 26]; [Chemical Formula 17] The dotted line represents an atomic bond; [Chemical Formula 26] The dotted line represents an atomic bond.

19. The polymer according to claim 18, wherein, The polymer has a repeating unit represented by the following general formula (5); AR5, AR6, R1, R2, R3 and n in the general formula (5) are the same as those described above.

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