A spin coating composition comprising a carbon material, a metal organic compound, and a solvent, and a method for manufacturing a metal oxide film over a substrate

Abstract

The present invention relates to a spin-coating composition comprising a carbon material and a metal organic compound, as well as to a method for forming a metal oxide film over a substrate and a method for manufacturing a device using the same.

Description

Technical Field

[0001] The present invention relates to a spin coating composition comprising a carbon material and a metal organic compound, and a method for forming a metal oxide film above a substrate using the same. The present invention further relates to a method for manufacturing a device using this composition.

Background Art

[0002] Metal oxide films are useful for various applications, for example, lithography hard masks, underlayers for antireflection films, and electro-optical devices in the semiconductor field.

[0003] As an example, a photoresist (hereinafter referred to as "resist") composition is used in a microlithography process for manufacturing miniaturized electronic components such as in the manufacture of computer chips and integrated circuits. Generally, a thin film of the resist composition is applied to a substrate such as a silicon wafer used for manufacturing an integrated circuit. Next, the coated substrate is baked to remove a desired amount of solvent from the resist. Next, the resist film on the substrate is imagewise exposed with actinic rays such as visible light, ultraviolet light, extreme ultraviolet light, electron beams, particle beams, and X-rays, and developed to form a pattern. The radiation causes a chemical change in the exposed area of the resist. The exposed film is treated with a developer to dissolve and remove either the radiation-exposed area or the unexposed area of the resist.

[0004] Semiconductor devices tend to be miniaturized, and in order to overcome the difficulties associated with such miniaturization, new resists that are sensitive to even shorter wavelengths of radiation, as well as the use of advanced multi-level systems, have been used.

[0005] A lower layer containing a large amount of heat-resistant components can be used as an anti-reflection film as a hard mask. The hard mask is useful when the resist on it cannot provide sufficient resistance to dry etching used to transfer an image to the underlying semiconductor substrate. In such an environment, a material called a hard mask is used, and its etching resistance is high enough to transfer any pattern formed on it to the underlying semiconductor substrate. This is possible because the organic resist is different from the underlying hard mask and because an etching gas mixture that can transfer the image in the resist to the underlying hard mask can be applied. Then, this patterned hard mask can be used to transfer the image from the hard mask to the semiconductor substrate using appropriate etching conditions and gas mixtures, which was an issue that could not be achieved by the resist itself in a single etching process.

[0006] Under these environments, compositions comprising a metal compound substituted with a plurality of ligands and a solvent have been studied, which are useful as air-stable precursors to high-K metal oxides and can form metal hard mask films. See, for example, Patent Document 1.

[0007] Certain organic carbon materials have been studied to provide compounds with good heat resistance and coatings capable of good filling of gaps, good planarization, and reduction of film shrinkage. See, for example, Patent Document 2.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

[0009]

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0010] Technical problems

[0011] It has been found that one or more important problems that need improvement still exist, including the following: insufficient solubility of the solute; insufficient heat resistance of the solute; cracking of the metal oxide film; insufficient etching resistance of the metal oxide film; precipitation may occur during preparation; low density of the metal oxide film; insufficient coatability of the composition and / or the metal oxide film; the pattern of the metal oxide film is not easily removed from the substrate; intermixing may occur between the metal oxide film and an adjacent film; fine patterning of the metal oxide film is difficult; insufficient gap filling of the composition; insufficient surface flatness of the film; insufficient hardness of the film; high internal stress of the film; and pattern wiggling often occurs.

[0012] The present invention described below solves at least one of these problems.

Means for Solving the Problems

[0013] Means for solving

[0014] The present invention provides a spin coating composition comprising a carbon material (A), a metal organic compound (B) and a solvent (C), wherein the carbon material (A) comprises a unit (A1) represented by the formula (A1)

Chemical formula

[0015] In another form, as described above, the composition consists essentially of components (A), (B) and (C). In such a form, the total amount of (A), (B) and (C) is not necessarily 100% by weight, and other components (e.g., additional solvents including water, common additives and / or impurities) that do not substantially change the effectiveness of the composition can be included.

[0016] In another form, as described above, the composition consists of components (A), (B) and (C). In such a form, the total amount of (A), (B) and (C) is about 100% by weight, but other minor and / or trace additives that do not substantially change the effectiveness of the composition can be included even if present in small amounts. For example, in one such form, the composition can contain up to 2% by weight of additives. In another form, the composition can contain up to 1% by weight of additives. In a further form, the composition can contain up to 0.05% by weight of additives.

[0017] The present invention also provides a spin-on metal hard mask composition.

[0018] The present invention provides a method for manufacturing a metal oxide film, comprising: (1) spin-coating a spin-coating composition above a substrate; and (2) heating the spin-coating composition to form a metal oxide film.

[0019] The present invention provides a method for manufacturing a resist film, comprising: (3) applying a resist composition above the metal oxide film manufactured as described above.

[0020] The present invention provides a method for manufacturing a resist pattern, comprising: (4) exposing the resist film manufactured as described above to radiation; (5) developing the exposed resist film with a developer; and (6) removing the developer from the substrate.

[0021] The present invention provides a method for manufacturing a processed substrate, comprising: (7) etching using the resist pattern manufactured as described above; and (8) processing the substrate.

[0022] The present invention provides a method for manufacturing a device, comprising the method for manufacturing a processed substrate described above.

[0023] Advantages of the Invention

[0024] The solute in the spin coating composition exhibits good solubility in the solvent (C). The solute in the spin coating composition exhibits good heat resistance. The metal oxide film formed from the spin coating composition reduces cracks. The metal oxide film formed from the spin coating composition exhibits good etching resistance. The solute of the spin coating composition reduces precipitation. It increases the density of the metal oxide film. The metal oxide film exhibits good coatability onto the substrate. The metal oxide film pattern after use with the mask can be easily removed. The metal oxide film reduces intermixing with adjacent films (e.g., resist films). Fine patterning of the metal oxide film is possible. The spin coating composition exhibits good gap filling properties. The metal oxide film has good flatness. The metal oxide film has high hardness. It can suppress excessive increase in internal stress and pattern wiggling.

[0025] Description of Embodiments

[0026] The above summary and the following details are provided to explain the present invention and are not intended to limit the invention described in the claims. Detailed Description

[0027] Definitions

[0028] Throughout this specification, defined symbols, units, abbreviations, and terms have the meanings given in the following definitions, descriptions, and examples, unless explicitly limited or stated otherwise.

[0029] The use of the singular form includes the plural form, and the words "a", "an", and "the" mean "at least one". Further, the use of the term "including", like "includes" and "included", is not limiting. Also, terms such as "element" or "component" include both an element or component consisting of one unit and an element or component consisting of one or more units.

[0030] The term "and / or" indicates any combination of any of the respective elements, including the use of a single element.

[0031] In this specification, when a numerical range is specified by "-", "to" or "~", the numerical range includes both of the numbers shown before and after these "-", "to" or "~", and the unit is common to the two numerical values. For example, "5~25 mol%" means "5 mol% or more and 25 mol% or less".

[0032] When the term "about" or "approximately" is used in relation to a measurable numerical variable, it means the indicated value of the variable, and also means all variable values greater than either within the experimental error of the indicated value (for example, within the 95% confidence limit relative to the average) or within the range of a percentage of the indicated value (for example, ±10%, ±5%).

[0033] As used in this specification, "C x-y ", "C x -C y " and "C x " and the like mean the number of carbon atoms in the molecule or in the substituent. For example, "C 1~6 alkyl" means an alkyl chain having 1 to 6 carbons (for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0034] When the polymers described in this specification have multiple types of repeating units, these repeating units copolymerize. The copolymerization can be any selected from alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, and any combination of any of these. When representing a polymer or resin by a chemical structure, n, m, etc. appended in parentheses mean the number of repetitions.

[0035] The unit of temperature described in this specification is degrees Celsius. For example, "20 degrees" means "20 degrees Celsius".

[0036] Spin coating composition

[0037] The present invention provides a spin-coating composition comprising a carbon material (A), a metal-organic compound (B), and a solvent (C). The mass ratio of the carbon material (A) to the mass of the metal-organic compound (B) is about 5 to about 100% by mass; preferably, about 10 to about 75% by mass; more preferably, about 10 to about 50% by mass. In a further form, the spin-coating composition consists essentially of these components. In yet another form, the spin-coating composition consists of these components.

[0038] In another form, the present invention preferably provides for the use of a composition for spin-coating above a substrate; more preferably, on a substrate. The present invention provides for the use of a composition for spin-coating above a substrate for forming a film; preferably, for forming a film later.

[0039] In a preferred form, the spin-on metal hard mask composition can consist essentially of the spin-coating composition of the present invention. In another preferred form, the spin-on metal hard mask composition can consist of the spin-coating composition of the present invention. It can be said that the film after being produced by the composition of the present invention is preferably a metal hard mask film.

[0040] After adding all the components to the solvent (C) and confirming dissolution, the resulting composition can be filtered to remove impurities and / or small fragments. Known filters can be used for this preparation.

[0041] Carbon material (A), unit (A1)

[0042] The carbon material (A) of the present invention comprises a unit (A1) represented by formula (A1).

Chemical formula

[0043] In (A1), Ar 11 is unsubstituted or C substituted with R 11 substituted with6-60 It is a hydrocarbon. Preferably, it is Ar 11 Excludes condensed aromatic rings. Ar 11 Preferably, it is 9,9-diphenylfluorene, 9-phenylfluorene, phenyl, C 6-60 Linear polyphenylene, or branched polyphenylene ether, and each of these can be independently substituted with R 11 if necessary.

[0044] R 11 is a linear, branched or cyclic alkyl, amino or alkylamino of C 1-20 . R 11 Preferably, it is a linear, branched or cyclic alkyl, or alkylamino of C 1-10 ; more preferably, it is linear alkyl of C 1-3 , cyclopentyl, cyclohexyl, or dimethylamino.

[0045] When the carbon material (A) consists of a plurality of units (A1), R 11 can be interposed as a linker to bond the units (A1) to each other. One Ar 11 can have a single or a plurality of (preferably single) R 11 substituting it.

[0046] In one unit (A1), a group enclosed in parentheses (for example, a group enclosed in parentheses with p 11 attached) can be bonded to R 11 . In this case, R 11 can be interposed as a linker to bond that group to Ar 11 .

[0047] R 12 is I, Br or CN; preferably, it is I or Br; more preferably, it is I.

[0048] p 11 is a number from 0 to 5. When the carbon material (A) consists of one each of two types of units (A1), and both Ar 11is phenyl, and one of the Ars 11 the p on 11 is 1, and the other Ar 11 the p on 11 is 2, which can be one form of the present invention. In such a case, the overall p 11 = 1.5. In this specification, unless otherwise specified, the same numbering rule is used.

[0049] p 11 is preferably 0, 1, 2, or 3; more preferably 0, 1, or 2; even more preferably 1. p 11 = 0 is also one form of the present invention.

[0050] p 12 is a number from 0 to 1; preferably 0 or 1; more preferably 1.

[0051] q 11 is a number from 0 to 5; preferably 0, 1, 2, or 3; more preferably 0, 1, or 2; even more preferably 1. q 11 = 0 is also one form of the present invention.

[0052] q 12 is a number from 0 to 1; preferably 0 or 1; more preferably 1.

[0053] r 11 is a number from 0 to 5; preferably 0, 1, 2, or 3; more preferably 0, 1, or 2; even more preferably 1. r 11 = 0 is also one form of the present invention.

[0054] s 11 is a number from 0 to 5; preferably 0, 1, 2, or 3; more preferably 0, 1, or 2; even more preferably 1. s 11 = 0 is also one form of the present invention.

[0055] p 11 , q 11 and r 11 are not simultaneously 0.

[0056] The unit (A1) according to the present invention can be the units (A1-1), (A1-2) and / or (A1-3) represented by the formulas (A1-1), (A1-2) and / or (A1-3). Each of them will be described in detail below.

[0057] In one form, preferably, the formula (A1) is the formula (A1-1). Without wishing to be bound by theory, it is considered that the unit (A1-1) in the carbon material (A) contributes to solubility and / or can avoid precipitation.

[0058] The unit (A1-1) is represented by the formula (A1-1).

Chemical formula

[0059] Ar 21 is a C 6-50 aromatic hydrocarbon ring; preferably phenyl. Without wishing to be bound by theory, when Ar 21 is phenyl, good effects such as the solubility of the carbon material (A) and the ability to form a thick film (for example, about 1 μm or more, more preferably about 1.5 μm or more) can be expected.

[0060] R 21 , R 22 and R 23 are each independently a C 6-50 aromatic hydrocarbon ring, hydrogen, or a single bond connecting to another unit; preferably, each is independently phenyl, hydrogen, or a single bond connecting to another unit; more preferably, each is independently phenyl or a single bond connecting to another unit; still more preferably, each is independently phenyl.

[0061] The term "other unit" in "single bond that binds to another unit" does not include one unit in which a single bond exists. However, when the carbon material (A) has a plurality of units (A1), the single bond can bind to other units (A1) (not the unit (A1) in which a single bond exists, and not self-crosslinked in one unit (A1)). Unless otherwise specified, the same rules apply throughout this specification.

[0062] R 24 and R 25 are each independently, C 1-4 alkyl, and optionally, a plurality of R 24 and / or R 25 can be bonded to each other to form an aromatic ring with adjacent benzene. For example, two R 24 can be bonded to each other to form a naphthyl ring with adjacent benzene.

[0063] n 21 is an integer from 0 to 1; preferably, 0.

[0064] n 24 and n 25 are each independently, an integer from 0 to 3; preferably, 0, 1 or 2; more preferably, 0 or 2; even more preferably, 0.

[0065] R 12 , p 11 , p 12 , q 11 , q 12 , r 11 and s 11 are each independently defined and / or in the same form as above.

[0066] For example, the lower left compound can be interpreted as a carbon material (A) composed of one unit (A1) and one unit (A2), where Ar 11 is 9,9-diphenylfluorene, p 11 = 2, p 12 = 1, q 11 = r 11 = s11 It is 0. As shown in the lower right, the bond indicated by the arrow is not used to bond to other units.

Chemical formula

[0067] Although not intended to limit the scope of the present invention, specific examples of the carbon material (A) containing the unit (A1-1) include the following.

Chemical formula

[0068] In a more specific form, the unit (A1-1) can be the unit (A1-1-1). The unit (A1-1-1) is represented by the formula (A1-1-1):

Chemical formula

[0069] p 11 、p 12 、q 11 、q 12 and r 11 The definitions and / or forms of are each independently the same as above, and also p 11 +q 11 +r 11 = 1 to 4.

[0070] The unit (A-2) is represented by the formula (A-2):

Chemical formula

[0071] L 31 and L 32 are each independently a single bond or phenylene: preferably, each independently a single bond.

[0072] n 31 、n 32 、m 31 and m32 is, independently of each other, an integer from 0 to 6; preferably, an integer from 0 to 3. n 31 + n 32 = 5 or 6 is one preferred form of the present invention. L 31 When L is a single bond, m 31 = 1. L 32 When L is a single bond, m 32 = 1.

[0073] R 12 , p 11 , p 12 , q 11 , q 12 , r 11 and s 11 The definitions and / or forms of are, independently of each other, the same as those described above.

[0074] Although not intended to limit the scope of the present invention, specific examples of the carbon material (A) comprising the unit (A1-2) include the following:

Chemical formula

[0075] The unit (A-3) is represented by the formula (A-3):

Chemical formula

[0076] Ar 41 is C 6-50 aromatic hydrocarbon; preferably, Ar 41 is phenyl.

[0077] R 41 and R 42 are, independently of each other, C 1-10 alkyl (preferably, C 1-6 linear alkyl). Optionally, R 41 and R 42 form a cyclic hydrocarbon; preferably, R 41 and R 42It constitutes a saturated hydrocarbon ring.

[0078] * The carbon atom at the 41st position is a quaternary carbon atom.

[0079] L 41 is a single bond connecting to an arylene, or other unit; preferably, a single bond connecting to a phenylene, or other unit; more preferably, a single bond connecting to other units. 6-50 is a single bond connecting to an arylene, or other unit; preferably, a single bond connecting to a phenylene, or other unit; more preferably, a single bond connecting to other units.

[0080] R 12 , p 11 , p 12 , q 11 , q 12 , r 11 and s 11 The definitions and / or forms of are, respectively, independently, the same as above.

[0081] Although not intended to limit the scope of the present invention, specific examples of the carbon material (A) comprising the unit (A1-3) include the following:

Chemical formula

[0082] When the carbon material (A) is a polymer, the film produced from the composition of the present invention has high heat resistance. In its preferred form, (i) the main chain of the carbon material (A) does not contain a secondary carbon atom or a tertiary carbon atom, or (ii) the total amount of the secondary carbon atoms and tertiary carbon atoms contained in the main chain of the carbon material (A) is small.

[0083] In one preferred embodiment of the present invention, when the carbon material (A) is a polymer, the amount of the aldehyde derivative used during the synthesis of the carbon material (A) is about 0 to about 30 mol% (more preferably, about 0 to about 15 mol%; even more preferably, about 0 to about 5 mol%; still more preferably, about 0 mol% or 0 mol%) based on all the components used in the synthesis. An example of the aldehyde derivative is formaldehyde. In order to obtain a polymer of the carbon material (A) that contains no or almost no secondary and tertiary carbon atoms in the main chain, it is one of the preferred embodiments of the present invention to use a ketone derivative.

[0084] It is possible to synthesize a polymer so as to contain hardly any or no secondary and / or tertiary carbon atoms. As one preferred embodiment of the present invention, when the carbon material (A) is a polymer, the polymer contains no secondary or tertiary carbon atoms (except at the ends of the polymer that can acceptably contain secondary and / or tertiary carbon atoms). Although not wishing to be bound by theory, such polymers are considered to have solubility and the formed films to have improved heat resistance. The ends of the polymer are tolerated to have secondary and / or tertiary carbon atoms.

[0085] As one embodiment of the present invention, when the carbon material (A) is a polymer, it is preferable that the main chain of the polymer does not contain an ether linker (-O-) or a sulfone linker (-S(=O)2-). Here, the term "linker" means a component that binds units together. Terminal modification with such units is tolerated, for example, a hydroxy group. Although not wishing to be bound by theory, such polymers are considered to exhibit good solubility.

[0086] When the carbon material (A) is a polymer, the weight average molecular weight (Mw) is used as its molecular weight.

[0087] In this application, Mw can be measured by gel permeation chromatography (GPC). In a preferred example of this measurement, the GPC column is set at about 40 °C; tetrahydrofuran is used as the elution solvent at about 0.6 mL / min; and monodisperse polystyrene is used as the standard.

[0088] When the carbon material (A) is not a polymer but instead a low molecular weight compound, its molecular weight can be measured using liquid chromatography mass spectrometry (LC-MASS).

[0089] In one form of the present invention, the molecular weight of the carbon material (A) is from about 500 to about 6,000; preferably from about 600 to about 5,500; more preferably from about 700 to about 5,000; still more preferably from about 800 to about 5,000.

[0090] The carbon material (A) of the present invention may or may not contain repeating units other than the unit (A1). In a preferred form, the carbon material (A) consists essentially of the repeating unit (A1). In another preferred form, the carbon material (A) consists of the repeating unit (A1). The fact that the carbon material (A) does not contain repeating units other than the unit (A1) is one form of the present invention.

[0091] Carbon material (A), unit (A2)

[0092] The carbon material (A) of the present invention can further comprise the unit (A2) and / or the unit (A3).

[0093] The unit (A2) is represented by the formula (a2).

Chemical formula

[0094] Cy 51 is C 5-30Cyclic hydrocarbon ring; preferably, 9-phenylfluorene, 9,9-diphenylfluorene, adamantane, phenyl, naphthyl, anthracene, phenanthrene, fluoranthene, triphenylene, pyrene, chrysene, or perylene; more preferably, fluorene, 9-phenylfluorene, 9,9-diphenylfluorene, or adamantane; still more preferably, fluorene or adamantane; even more preferably, fluorene.

[0095] In one embodiment of the present invention, formula (A2) is formula (A2-1).

Chemical formula

[0096] Cy 51 The definition and / or form of is the same as above.

[0097] Carbon material (A), unit (A3)

[0098] Unit (A3) is represented by formula (A3).

Chemical formula

[0099] Ar 61 is a single bond, C 1-6 alkyl, C 6-12 cycloalkyl, or C 6-14 aryl; preferably, a single bond, C 1-6 alkyl, or phenyl; more preferably, a single bond, C3 linear alkyl, C6 linear alkyl, tertiary butyl, or phenyl; still more preferably, a single bond or phenyl; even more preferably, phenyl.

[0100] Ar 62 is C 1-6 alkyl, C 6-12 cycloalkyl, or C 6-14Aryl; preferably isopropyl, tertiary butyl, C6 cycloalkyl, phenyl, naphthyl, phenanthryl, or biphenyl; more preferably phenyl.

[0101] R 61 and R 62 are each independently C 1-6 alkyl, hydroxy, halogen or cyano; preferably methyl, ethyl, propyl, isopropyl, tertiary butyl, hydroxy, fluorine, chlorine, or cyano; more preferably methyl, hydroxy, fluorine, or chlorine.

[0102] R 63 is hydrogen, C 1-6 alkyl, or C 6-14 aryl; preferably hydrogen, C 1-6 alkyl, or phenyl; more preferably hydrogen, methyl, ethyl, C5 straight-chain alkyl, tertiary butyl, or phenyl; even more preferably hydrogen or phenyl; still more preferably hydrogen.

[0103] Ar 62 is C 1-6 alkyl or C 6-14 aryl, and R 63 is C 1-6 alkyl or C 6-14 aryl, then Ar 62 and R 63 may optionally be joined to each other to form a hydrocarbon ring.

[0104] r 61 and r 62 are each independently a number from 0 to 5; preferably 0 or 1; more preferably 0.

[0105] Each, at least one of the Cy rings enclosed by a broken line 61 , Cy 62 and Cy 63 is adjacent to the aromatic hydrocarbon ring Ph 61It is an aromatic hydrocarbon ring condensed with. The total number of carbon atoms of the aromatic hydrocarbon ring and the aromatic hydrocarbon ring Ph 61 is preferably C 10-14 ; more preferably C 10 .

[0106] Each of Cy 64 , Cy 65 and Cy 66 at least one of the rings is an aromatic hydrocarbon ring condensed with the adjacent aromatic hydrocarbon ring Ph 62 . The total number of carbon atoms of the aromatic hydrocarbon ring and the aromatic hydrocarbon ring Ph 62 is preferably C 10-14 ; more preferably C 10 .

[0107] In formula (A3), the bonding positions of R 61 , R 62 and OH are not limited.

[0108] For example, the following compounds can have the structure of formula (A3) as unit (A3). That is, the aromatic hydrocarbon ring Ph 61 and the aromatic hydrocarbon ring Cy 63 are condensed with each other to form a naphthyl ring (C 10 ), and OH is bonded to the aromatic hydrocarbon ring Cy 63 . Ar 61 is a single bond, Ar 62 and R 63 are each phenyl, and Ar 62 and R 63 are bonded to each other to form a hydrocarbon ring (fluorene):

Chemical formula

[0109] Although not intended to limit the scope of the present invention, specific examples of unit (A3) include the following.

Chemical formula

[0110] When the carbon material (A) is a polymer, the number of repetitions of units (A1), (A2), and (A3) is n A1 , n A2 and n A3 respectively, and n A1 > 0%.

[0111] n A1 / (n A1 + n A2 + n A3 ) is preferably from about 1 to about 100%; more preferably from about 10 to about 100%; still more preferably from about 20 to about 100%; even more preferably from about 30 to about 100%.

[0112] n A2 / (n A1 + n A2 + n A3 ) is preferably from about 0 to about 99%; more preferably from about 10 to about 50%; still more preferably from about 20 to about 40%. In one form of the present invention, n A2 / (n A1 + n A2 + n A3 ) = 0%.

[0113] n A3 / (n A1 + n A2 + n A3 ) is preferably from about 0 to about 99%; more preferably from about 10 to about 50%; still more preferably from about 20 to about 40%. In one form of the present invention, n A3 / (n A1 + n A2 + n A3 ) = 0%.

[0114] When the carbon material (A) is a polymer, n total represents the total number of repetitions therein.

[0115] (n A1 + n A2 + n A3 ) / ntotal is preferably about 80% to about 100%; more preferably about 90% to about 100%; even more preferably about 95% to about 100%. In one preferred form of the present invention, (n A1 + n A2 + n A3 ) / n total = 100%.

[0116] For example, the following polymers can be interpreted as alternating copolymers each having units (A1), units (A2), and units (A3) in this order. In such an embodiment, n A1 / (n A1 + n A2 + n A3 ), n A2 / (n A1 + n A2 + n A3 ), n A3 / (n A1 + n A2 + n A3 ) = about 1 / 3 (about 33%), and also, ((n A1 + n A2 + n A3 ) / n total = 100%. [Chemical formula]

[0117] Metal-organic compound (B)

[0118] The spin-coating composition of the present invention comprises a metal-organic compound (B). The metal-organic compound (B) is preferably a metal-organic complex containing a hydrolyzable group, a hydrolysis product of a metal-organic complex containing a hydrolyzable group, a hydrolysis condensation product of a metal-organic complex containing a hydrolyzable group, or any combination of these. As one form of the present invention, the metal-organic compound (B) is a mixture of a plurality of metal-organic compounds each having a structure represented by (B).

[0119] Although not bound by theory, having only a metal component in the film is not good because cracks often occur. Also, carbon material (A) is considered to be good as a solute because precipitation with a metal can be avoided.

[0120] Although not bound by theory, further, when forming the metal oxide film of the present invention, the carbon component (derived in part or in whole from carbon material (A)) can be located in the voids between the polymers made from metal organic compound (B); increase the film density (mass density, more preferably, atomic number density); and is considered to be able to contribute to the etching resistance.

[0121] Metal organic compound (B) is represented by formula (B):

Chemical formula

[0122] M is a tetravalent metal. M is preferably Al, Zr, Ta, Hf, Ti, Sn, Pb, Nb, Mo, Ge, and W; more preferably Al, Zr, Hf, Ti, Ta, Nb, and Sn; even more preferably at least one selected from the group consisting of Al, Zr, Hf, and Ti; still more preferably at least one selected from the group consisting of Al, Ti, and Zr.

[0123] n 71 is an integer from 1 to 20.

[0124] R 71 、R 72 、R 73 and R 74 are each independently selected from the group consisting of a first organic moiety (B)-1, a silicon-containing organic moiety (B)-2 having at least 2 carbons, a second organic moiety, and any combination of these. Although not wishing to be bound by theory, R 71 and / or R 74 can contribute to the solubility of metal organic compound (B), and R 72 and / or R73 It is cleaved and considered to be a further polymerization crosslinking point.

[0125] In formula (B), R 71 , R 72 , R 73 and R 74 At least one part is selected from the group consisting of the following.

Chemical formula

[0126] The first organic moiety (B)-1 is represented by formula (B)-1.

Chemical formula

[0127] R 75 is C 2-10 alkylene, C 3-12 branched alkylene, C 5-12 cycloalkylene, C=C double bond-containing C 2-10 alkylene, C=C double bond-containing C 3-12 branched alkylene, and C=C double bond-containing C 5-12 cycloalkylene; preferably, C 2-10 alkylene, C=C double bond-containing C 2-10 alkylene, and C 5-12 cycloalkylene; more preferably, C 2-10 alkylene selected from the group consisting of. In another form of the present invention, R 75 is C=C double bond-containing C 2-10 alkylene. In another form of the present invention, R 75 is C 5-12 cycloalkylene.

[0128] R 76 is hydrogen, or alkyloxycarbonyl represented by formula (B)-l-l.

Chemical formula

[0129] In one form of the present invention, R 76 The alkyloxycarbonyl of is preferably C 1-8 alkyloxycarbonyl; more preferably C 2-6 alkyloxycarbonyl; even more preferably C 3-4 alkyloxycarbonyl.

[0130] R 77 is C 1-8 alkyl; preferably C 2-6 alkyl; preferably C 3-4 alkyl.

[0131] The silicon-containing organic moiety (B)-2 having at least 2 carbons is represented by formula (B)-2.

Chemical formula

[0132] R 78 and R 79 are each independently C 1-8 alkyl, C 3-12 branched alkyl, C 1-8 alkyloxy, C 3-12 branched alkyloxy, and C 6-16 aryl; preferably selected from the group consisting of methyl, ethyl, propyl, butyl and t-butyl. In another form of the present invention, R 78 and R 79 are each independently preferably C 1-8 alkyloxy, C 3-12 branched alkyloxy, or C 6-16 aryl.

[0133] R 80 is C 1-8 alkyl, C 6-16Siloxanes having aryl, hydroxy, and structure (B)-2-1; preferably, siloxanes having methyl, ethyl, propyl, butyl, t-butyl, and structure (B)-2-1; more preferably, siloxanes having methyl and structure (B)-2-1; even more preferably selected from the group consisting of methyl:

Chemical formula

[0134] R 81 is hydrogen, C 1-8 alkyl, C substituted with hydroxy 1-8 alkyl, C 6-16 aryl, and a silyl moiety having structure (B)-2-1-1; preferably, hydrogen, C 1-8 alkyl, and a silyl moiety having structure (B)-2-1-1; more preferably, hydrogen, C 1-4 alkyl, and a silyl moiety having structure (B)-2-1-1; even more preferably selected from the group consisting of hydrogen and a silyl moiety having structure (B)-2-1-1. R 81 being C 1-4 alkyl, and a silyl moiety having structure (B)-2-1-1 is also one form of the present invention. R 81 being methyl or t-butyl; preferably, being methyl is another form of the present invention:

Chemical formula

[0135] R 84 and R 85 are each independently C 1-8 alkyl, C 3-12 branched alkyl, C 1-8 alkyloxy, C 3-12 branched alkyloxy, and C 6-16Aryl; preferably, methyl, ethyl, propyl, butyl, t-butyl, methoxy and phenyl; more preferably, methyl, t-butyl and phenyl; even more preferably, selected from the group consisting of methyl.

[0136] R 86 is C 1-8 alkyl and C 6-16 aryl; preferably, methyl, ethyl, propyl, butyl, t-butyl, and phenyl; more preferably, methyl, t-butyl, and phenyl; even more preferably, selected from the group consisting of methyl.

[0137] p 81 represents the number of repeating units in the siloxane moiety (B)-2-1. As one form of the present invention, p 81 = 1 to 500; preferably, 1 to 200; more preferably, 1 to 50.

[0138] R 82 and R 83 are each independently C 1-8 alkyl, C 3-12 branched alkyl, C 1-8 alkyloxy, C 3-12 branched alkyloxy, and C 6-16 aryl; preferably, methyl, ethyl, propyl, butyl, t-butyl, and phenyl; more preferably, methyl, t-butyl, and phenyl; even more preferably, selected from the group consisting of methyl.

[0139] The second organic moiety is C 2-8 alkyl, C 2-8 alkyl carboxy, C 6-20 aryl carboxy, fluorenyl carboxy, fluorinated C 2-8 alkyl carboxy, C 2-8 alkylsulfonyl, fluorinated C 2-8 alkylsulfonyl, and any combination thereof selected from the group consisting of.

[0140] Although it is not intended to limit the scope of the present invention, specific examples of the metal organic compound (B) include the following.

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[0141] In one form of the present invention, the mass ratio of the metal organic compound (B) to the total mass of the spin coating composition is about 5 to about 100 mass%; preferably, about 10 to about 75 mass%; more preferably, about 10 to about 50 mass%.

[0142] Solvent (C)

[0143] The spin coating composition of the present invention comprises a solvent (C), and the solvent (C) comprises an organic solvent. The solvent (C) cannot consist of only an inorganic solvent, such as water.

[0144] It is a preferred form of the present invention that the solvent (C) is selected from the group consisting of aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, monoalcohol solvents, polyol solvents, ketone solvents, ether solvents, ester solvents, nitrogen-containing solvents, sulfur-containing solvents, and any arbitrary combination of these.

[0145] Examples of the solvent (C) include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methyl ethyl ketone, n-propylbenzene, i-propylbenzene, diethylbenzene, and i-butylbenzene; monoalcohol solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, 2-ethylhexanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, cyclohexanol, benzyl alcohol, phenylmethyl carbinol, diacetone alcohol, and cresol; polyol solvents such as ethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin; ketone solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, and phencon;Ether solvents such as ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran; ester solvents such as diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-butyl propionate, methyl lactate, ethyl lactate (EL), γ-butyrolactone, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; nitrogen-containing solvents such as n-methylformamide; and sulfur-containing solvents such as dimethyl sulfide. Any arbitrary combination of these solvents can also be used.;

[0146] In particular, cyclohexanone, cyclopentanone, PGME, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, PGMEA, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, γ-butyrolactone, EL, and any combination thereof are preferred in terms of the storage stability of the solution.

[0147] Regarding coatability and / or solubility of the solute, PGME, PGMEA, EL, and any combination of two solvents selected therefrom are preferred. For this purpose, a combination of PGMEA and PGME is more preferred as the solvent (C).

[0148] When the solvent (C) is a combination of two organic solvents, the mass ratio of the first solvent to the second solvent is preferably about 95:5 to about 5:95; more preferably about 90:10 to about 10:90; still more preferably about 80:20 to about 20:80; even more preferably about 70:30 to about 30:70.

[0149] The amount of water in the solvent (C) is preferably 0.1% by mass or less, and more preferably 0.01% by mass or less. From the relationship with another layer or film, it is preferred that the solvent (C) does not contain water. As one form of the present invention, the amount of water in the solvent (C) is preferably 0.00% by mass.

[0150] As one form of the present invention, the mass ratio of the solvent (C) to the total mass of the spin coating composition is about 5 to about 100% by mass; preferably about 10 to about 75% by mass; more preferably about 10 to about 50% by mass.

[0151] Surfactant (D)

[0152] The spin coating composition of the present invention can include a surfactant (D), which is useful for reducing pinholes or striations in the film and increasing the coatability and / or solubility of the composition.

[0153] In one form of the present invention, the mass ratio of the surfactant (D) to the mass of the metal organic compound (B) is about 5 to about 100 mass%; preferably, about 10 to about 75 mass%; more preferably, about 10 to about 50 mass%.

[0154] Examples of surfactants include polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ether compounds such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymer compounds; sorbitan fatty acid ester compounds such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan fatty acid ester compounds such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan tristearate. Other examples of surfactants include fluorosurfactants such as F-Top (trade name) EF301, EF303, and EF352 (Tochem Products), MEGAFACE (trade name) F171, F173, R-08, R-30, R-41, and R-2011 (DIC), Fluorad FC430 and FC431 (Sumitomo 3M), Asahi Guard (trade name) AG710 (Asahi Glass), and Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (Asahi Glass); and organosiloxane polymers such as KP341 (Shin-Etsu Chemical).

[0155] Additive (E)

[0156] The spin coating composition of the present invention may further comprise an additive (E) other than the surfactant (D). Such additives are selected from the group consisting of crosslinking agents, acid generators, radical generators, photoinitiators, substrate adhesion enhancers, and defoaming agents.

[0157] In one embodiment of the present invention, the mass ratio of the other additive (E) to the mass of the metal organic compound (B) is preferably from about 0.05 to about 10% by mass; more preferably from about 0.10 to about 5% by mass; still more preferably from about 0.10 to about 2% by mass. In one embodiment of the present invention, the spin coating composition contains none (0% by mass) of these additives (E).

[0158] Formation of Metal Oxide Film

[0159] The present invention provides (1) spin coating the above spin coating composition above a substrate; and (2) heating the spin coating composition to form a metal oxide film and provides a method for producing a metal oxide film comprising the steps.

[0160] For clarity of explanation, the numbers in parentheses indicate the order of the steps. For example, step 1 is performed before step 2. This rule applies to the other steps described in this specification unless otherwise specified.

[0161] Preferably, the heating conditions are about 150 to about 400 °C and / or about 30 to about 120 seconds. The term "above the substrate" not only indicates that the applied spin coating composition can form a film directly on the substrate (i.e., in direct contact with the substrate), but also includes the possibility of interposing a lower layer between the substrate and the applied composition. The above term "above" includes "in direct contact" and "through a layer" hereinafter unless otherwise specified.

[0162] The substrate surface on which the composition is disposed can be pretreated, for example, with a 1,1,1,3,3,3 - hexamethyldisilazane solution. The upper surface of the substrate may be flat or non - flat. The substrate can be a patterned substrate or an unpatterned substrate. The substrate can be a single - layer substrate or a multi - layer substrate composed of a plurality of substrate layers. In one form of the present invention, the uppermost surface of the substrate is a patterned semiconductor. The semiconductor can be composed of oxides, nitrides, metals, and any combination thereof. The surface of the substrate is preferably selected from the group consisting of Si, Ge, SiGe, Si3N4, TaN, SiO2, TiO2, Al2O3, SiON, HfO2, T2O5, HfSiO4, Y2O3, GaN, TiN, TaN, Si3N4, NbN, Cu, Ta, W, Hf, and Al.

[0163] Due to the heat resistance of the content of the metal - organic compound (B) in the composition of the present invention, the formed metal oxide film has good etching resistance to various plasmas, and the pattern can be etched and transferred to the substrate.

[0164] The spin - coat composition is applied by appropriate application means such as a spin coater or a coater.

[0165] It is one form of the present invention that the heating conditions are selected from the range of about 200 to about 800 °C (preferably about 250 to 750 °C; more preferably about 300 to about 700 °C; still more preferably about 350 to about 650 °C; even more preferably about 400 to about 600 °C), and / or the heating time is selected from the range of about 30 to about 240 seconds (preferably about 40 to about 150 seconds; more preferably about 50 to about 120 seconds; even more preferably about 60 to about 90 seconds). The heating can be carried out in separate steps (step baking). For example, the heating can be two - step heating or three - step heating. For example, it is preferable that the first heating is carried out at about 200 to about 300 °C for about 30 to about 120 seconds, and the second heating is carried out at about 300 to about 500 °C for about 60 to about 180 seconds.

[0166] Heating can be carried out in an air atmosphere, and the oxygen concentration can be reduced to prevent oxidation of the spin coating composition and the formed metal oxide film. For example, by introducing an inert gas (N2, Ar, He, or a mixture thereof) into the atmosphere, the oxygen concentration can be adjusted to about 1,000 ppm or less (preferably, about 100 ppm or less). The atmosphere can be changed in a plurality of heating steps. Heating in an N2 atmosphere is one form of the present invention.

[0167] In one form of the present invention, the spin coating composition is applied to a substrate including a lower layer (e.g., a spin-on carbon layer, a planarization layer) or a topographical feature. As a form of the present invention, the formed metal oxide film has a thickness sufficient to cover this topography; and a filled topography where the metal oxide film is on the same surface as the top of the topography can be generated using a chemical stripping solution or fluorinated plasma etching. This topography can have an aspect ratio of about 1 to about 10 and / or a critical dimension (CD) of about 5 nm to about 100 nm.

[0168] In a preferred form of the present invention, the metal content of the metal oxide film is about 5 to about 85% by mass (more preferably, about 10 to about 50% by mass; even more preferably, about 15 to about 40% by mass) based on the total mass of the film. The metal content in the metal oxide film can be measured by Rutherford backscattering spectrometry / hydrogen forward scattering spectrometry (RBS / HFS).

[0169] Formation of a resist layer

[0170] The present invention further provides (3) applying a resist composition above the metal oxide film produced by the above method and provides a method for manufacturing a resist film comprising the same. The term "above the metal oxide film" not only indicates that the applied resist composition can form a resist film directly on the metal oxide film (i.e., in direct contact with the metal oxide film), but also includes the ability to interpose an intermediate layer (e.g., an underlying antireflective film, BARC) between the metal oxide film and the applied resist composition. The intermediate layer can include a single layer or multiple layers. Other layers (e.g., an upper antireflective film, TARC) may be formed on the resist film.

[0171] Known methods can be used for applications such as spin coating. The applied resist composition can be baked to remove the solvent in the composition and form a resist film. The baking temperature can be varied depending on the resist composition used, which is preferably about 70 to about 150 °C (more preferably about 90 to about 150 °C; even more preferably about 100 to about 140 °C). This can be carried out for about 10 to about 180 seconds when on a hot plate; preferably about 30 to about 90 seconds, or for about 1 to about 30 minutes when in a high-temperature gas atmosphere (e.g., in a clean oven). The formed resist film can preferably have a thickness of about 0.40 to about 5.00 μm (more preferably about 0.40 to about 3.00 μm; even more preferably about 0.50 to about 2.00 μm).

[0172] Formation of a resist pattern

[0173] The present invention provides (4) exposing the resist film produced by the above method to radiation; (5) developing the exposed resist film with a developer; and (6) removing the developer from the substrate and provides a method for manufacturing a resist pattern comprising the above.

[0174] The resist composition undergoes a reaction under irradiation through a certain mask. Preferably, in the case of ArF exposure, immersion lithography technology can be used. When the resist composition is positive, the irradiated portion increases its resistance to dissolution by the developer. The wavelength of the irradiation light used for exposure is not limited. The exposure is preferably performed with light having a wavelength of about 13.5 to about 365 nm (preferably, about 13.5 to about 248 nm). A KrF excimer laser (248 nm), an ArF excimer laser (193 nm), or extreme ultraviolet light (13.5 nm) is a preferred form; an ArF excimer laser is more preferred. It is also another preferred form of the present invention that this composition is used in a process using EUV or immersion ArF. These wavelengths may vary within ±1%.

[0175] After exposure, if desired, a post-exposure bake (PEB) can be performed. The temperature of the PEB is selected from the range of about 80 to about 150 °C (preferably, about 90 to about 140 °C), and the heating time of the PEB is selected from the range of about 0.3 to about 5 minutes (preferably, about 0.5 to about 2 minutes).

[0176] Next, development is performed using a developer. As the developer used for the development of resist pattern formation, an aqueous solution of about 2.38 mass% (allowing a concentration change of ±1%) TMAH is preferred. Additives such as surfactants can be added to the developer. The temperature of the developer is typically selected from the range of about 5 to about 50 °C (preferably, about 25 to about 40 °C), and the development time is typically selected from the range of about 10 to about 300 seconds (preferably, about 30 to about 90 seconds). As the development method, a known method such as paddle development can be used.

[0177] After development, the developer is removed by a known method (e.g., liquid replacement, spin drying). As one form of the present invention, the resist pattern can be washed with water or a cleaning solution when replacing the developer with water and / or a cleaning solution. Thereafter, the substrate can be dried, for example, by a spin drying method.

[0178] Processing of the substrate

[0179] The present invention relates to (7) etching using the resist pattern manufactured by the above method; and (8) processing the substrate and provides a method for manufacturing a processed substrate comprising the same.

[0180] As described above, in the manufactured multilayer structure, a lower layer and / or an intermediate layer can be present. The direction from left to right in the following list corresponds to the bottom-to-top direction in the multilayer structure (including the resist pattern): i. substrate / lower layer / metal oxide film / intermediate layer / resist pattern; ii. substrate / metal oxide film / intermediate layer / resist pattern; iii. substrate / metal oxide film / resist pattern; and / or iv. substrate / lower layer / metal oxide film / resist pattern.

[0181] Each layer under the resist pattern and / or the metal oxide film can be patterned via the resist pattern as a mask. For patterning, known techniques such as etching (dry etching) can be used.

[0182] For example, the intermediate film may be etched via the resist pattern as an etching mask, and then the obtained intermediate layer pattern may be used as an etching mask to etch the metal oxide film and the substrate of the present invention to form a pattern on the substrate. Alternatively, the mask oxide film may be etched using the resist pattern or the intermediate layer pattern as an etching mask to obtain a metal oxide film pattern. Then, the obtained metal oxide film pattern may be used as an etching mask to etch the lower layer, and then the obtained lower layer pattern may be used as an etching mask to etch the substrate to form a pattern on the substrate.

[0183] In one form, dry etching can be performed with O2, CF4, CHF3, Cl2, or BCl3. O2 or F4 is a preferred gas for organic films / layers.

[0184] In one embodiment, an RF discharge power of about 100 to about 10,000 W (more preferably, about 200 to about 5,000 W) and / or a gas atmosphere of N2, NF3, O2, noble gas, Cl2, HBr, or any arbitrary mixture thereof can be used to etch a metal oxide film and obtain a metal oxide film.

[0185] One method of the present invention for processing a substrate is described below: i. Form a metal oxide film as described above, ii. Apply a BARC on the metal oxide film, iii. Apply a resist composition on the BARC, iv. Form a resist pattern as described above, v. Using fluorinated plasma, etch through the BARC not protected by the resist pattern until reaching the metal oxide film, vi. Using chlorine plasma, etch through the BARC and the metal oxide film not protected by the resist pattern until reaching the substrate to generate a patterned metal oxide film, vii. Using fluorinated plasma, etch the substrate in the regions not protected by the patterned metal oxide film.

[0186] After processing the substrate, the pattern and / or the layer on / above the pattern can be removed by known methods.

[0187] Manufacture of Device

[0188] The present invention provides a method for manufacturing a device, which includes a method for manufacturing a substrate processed as described above. Preferably, the method for manufacturing a device further includes: (9) forming wiring on the processed substrate. Preferably, the substrate is a stepped substrate.

[0189] After forming the device, the substrate is cut into chips as needed, and these chips are connected to a lead frame and packaged with resin. Preferably, the device is a semiconductor device, a solar cell chip, an organic light-emitting diode, and an inorganic light-emitting diode. One preferred form of the device of the present invention is a semiconductor device.

Example

[0190] Hereinafter, the present invention will be described by way of examples. These examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[0191] Next, refer to more specific forms of the present disclosure and experimental results providing support for such forms. The examples are presented below to more fully illustrate the disclosed subject matter, but should not be construed as in any way limiting the disclosed subject matter.

[0192] It will be apparent to those skilled in the art that various modifications and variations can be made in the disclosed subject matter and the specific examples provided herein without departing from the spirit or scope of the disclosed subject matter. Accordingly, the disclosed subject matter, including the descriptions provided by the following examples, is intended to cover modifications and variations of the disclosed subject matter within the scope of the claims and their equivalents.

[0193] Preparation Example 1 of Example Composition 1

[0194] Component A1 (2.0% by mass), B1 (7.9% by mass)

Chemical formula

[0195] The polymers used are obtained in the same manner as described in WO2019 / 121480Al, JP2019-86545A and WO2019 / 048393A1.

[0196] Preparation Examples 2 to 4 of Example Compositions 2 to 4 and Comparative Preparation Examples 1 to 2 of Comparative Example Compositions 1 to 2

[0197] The preparation is carried out in the same manner as in Example 1 above, except that the components (using components A2, A3, A4 and cAl) and / or the amounts are changed as described in Table 1:

Chemical formula

[0198] Visually confirm that all solutes in each composition are dissolved. The resulting liquid is filtered through a 0.2 μm fluorinated resin filter to obtain Example Compositions 2 to 4 and Comparative Example Compositions 1 to 2.

[0199] The resulting compositions have the following characteristics:

Table 1

[0200] In Table 1 and each of the following tables, the numbers in parentheses mean the amounts by mass% of each component in the composition.

[0201] Example of forming a metal oxide film of Example Composition 1

[0202] Example Composition 1 is spin-coated onto a Si bare wafer at 1,500 rpm using a clean track ACT12 (Tokyo Electron). The wafer is baked at 250 °C for 60 seconds in an air atmosphere and then baked at 400 °C for 120 seconds in an N2 atmosphere to obtain a metal oxide film.

[0203] Examples of metal oxide film formation for Examples 2 to 4 and Comparative examples of metal oxide film formation for Comparative Examples 1 to 2

[0204] The formation is carried out in the same manner as in Metal Oxide Film Formation Example 1, except that the Example composition or the Comparative Example composition is changed.

[0205] Evaluation of solubility

[0206] The solubility of each composition is evaluated by visual confirmation. The evaluation results are shown in Table 2. In Table 2, "A" means that the solute in the composition is completely dissolved, and "B" means that the solute in the composition is not completely dissolved and remains in the solvent.

[0207] Evaluation of cracks

[0208] The presence of cracks on the surface of the metal oxide film prepared from each composition is evaluated by visual confirmation. The evaluation results are shown in Table 2. In Table 2, "A" means that no cracks are confirmed, and "B" means that cracks are confirmed. Since Comparative Compositions 1 and 2 are evaluated as B in the crack evaluation, the other compositions are used for the following further evaluation.

[0209] Measurement of film thickness

[0210] The film thickness of each metal oxide film is measured from a cross-sectional photograph of the wafer taken with JSM-7100F (JEOL Ltd.). The measurement results are shown in Table 2.

[0211] Evaluation of Ar sputtering resistance

[0212] The metal oxide film on the wafer is sputtered with an Ar gas, ion energy: 3 keV, and for 2 minutes using an apparatus K-Alpha Plus (Thermo Scientific).

[0213] For the metal oxide film before and after sputtering, the film thickness is measured as described above. A difference in thickness is obtained, and the decrease in thickness per unit time is calculated. The evaluation results are shown in Table 2.

[0214] Evaluation of Etching Resistance

[0215] The metal oxide film on the wafer is dry-etched by an etching apparatus NE-5000N (ULVAC) under the conditions of chamber pressure: 0.17 mT, RF power: 200 W, gas flow rate: CF4 (50 sccm), Ar (35 sccm), and O2 (4 sccm), and time: 30 seconds.

[0216] For the metal oxide film before and after etching, the film thickness is measured as described above. A difference in thickness is obtained, and the decrease in thickness per unit time is calculated. The evaluation results are shown in Table 2. [Table 2]

[0217] The present invention has been described and illustrated with a certain degree of particularity, but the disclosure is only by way of example and it is understood that those skilled in the art can make numerous changes in the conditions and the order of steps without departing from the spirit and scope of the present invention. Some aspects of the present invention are shown below. [Aspect 1] A spin coating composition comprising a carbon material (A), a metal organic compound (B), and a solvent (C), (i) The carbon material (A) comprises a unit (A1) represented by the formula (A1) [Chemical Formula] (wherein, Ar 11 is an unsubstituted or R 11 -substituted C 6-60 hydrocarbon, R 11 is a C 1-20linear, branched or cyclic alkyl, amino or alkylamino, R 12 is I, Br or CN, p 11 is an integer from 0 to 5, p 12 is an integer from 0 to 1, q 11 is an integer from 0 to 5, q 12 is an integer from 0 to 1, r 11 is an integer from 0 to 5, and s 11 is an integer from 0 to 5, provided that p 11 、q 11 and r 11 are not both 0 at the same time); (ii) The solvent (C) comprises an organic solvent; and (iii) The mass ratio of the carbon material (A) to the mass of the metal organic compound (B) is about 5 to about 100% by mass, preferably about 10 to about 75% by mass, more preferably about 10 to about 50% by mass. [Aspect 2] The formula (A1) is (i) Formula (A1-1):

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Claims

1. A spin coating composition comprising a carbon material (A), a metal organic compound (B), and a solvent (C), wherein (i) the carbon material (A) comprises a unit (A1) represented by formula (A1-1) 【Chemical 2】 (wherein Ar₂₁ is a C₆₋₅₀ aromatic hydrocarbon ring, R₂₁, R₂₂, and R₂₃ are each independently a C₆₋₅₀ aromatic hydrocarbon ring, hydrogen, or a single bond bonding to another unit, R₂₄ and R₂₅ are each independently a C₁₋₄ alkyl, and optionally, a plurality of R₂₄ and / or R₂₅ can bond to each other to form an adjacent benzene and an aromatic ring, n₂₁ is an integer from 0 to 1, n₂₄ and n₂₅ are each independently an integer from 0 to 3, and R₁₂ is I, Br, or CN, p₁₁ is an integer from 0 to 5, p₁₂ is an integer from 0 to 1, q₁₁ is an integer from 0 to 5, q₁₂ is an integer from 0 to 1, r₁₁ is an integer from 0 to 5, and s₁₁ is an integer from 0 to 5, provided that p₁₁, q₁₁, and r₁₁ are not simultaneously 0); (ii) the solvent (C) comprises an organic solvent; and (iii) the mass ratio of the carbon material (A) to the mass of the metal organic compound (B) is 5 to 100% by mass.

2. The spin coating composition according to claim 1, wherein when the carbon material (A) is a polymer, the polymer substantially does not contain or does not contain secondary carbon atoms and tertiary carbon atoms except at the terminal positions of the polymer.

3. When the carbon material (A) is (iv) a unit (A2) represented by formula (A2): [Chemical Formula 5] (wherein Cy ５１ is a C ５－３０ cyclic hydrocarbon ring); and (v) a unit (A3) represented by formula (A3): 【Chemical Formula 6】 (wherein Ar ６１ is a single bond, C １－６ alkyl, C ６－１２ cycloalkyl, or C ６－１４ aryl, and Ar ６２ is C １－６ alkyl, C ６－１２ cycloalkyl, or C ６－１４ aryl, and R ６１ and R ６２ are each independently C １－６ alkyl, hydroxy, halogen or cyano, R ６３ is hydrogen, C １－６ alkyl, or C ６－１４ aryl, and Ar ６２ is C １－６ alkyl or C ６－１４ aryl, and when R ６３ is C １－６ alkyl or C ６－１４ aryl, Ar ６２ and R ６３ may be optionally joined to each other to form a hydrocarbon ring, r ６１ and r ６２ are each independently an integer from 0 to 5, Cy surrounded by a broken line ６１ , Cy ６２ and Cy ６３ At least one of the rings is an aromatic hydrocarbon ring condensed with an adjacent aromatic hydrocarbon ring Ph ６１ and Cy surrounded by a broken line ６４ , Cy ６５ and Cy ６６ At least one of the rings is an aromatic hydrocarbon ring condensed with an adjacent aromatic hydrocarbon ring Ph ６２ (which is an aromatic hydrocarbon ring condensed with) The spin coating composition according to any one of claims 1 to 2, further comprising one or more of the above.

4. The spin coating composition according to any one of claims 1 to 3, wherein the metal organic compound (B) is a metal organic complex containing a hydrolyzable group, a hydrolysis product of a metal organic complex containing a hydrolyzable group, a hydrolysis condensation product of a metal organic complex containing a hydrolyzable group, or any combination thereof.

5. The spin coat composition according to any one of claims 1 to 4, wherein the metal organic compound (B) is represented by the following formula (B). 【Chemical Formula 7】 (wherein M is a tetravalent metal, n ７１ is a number from 1 to 20, and R ７１ 、R ７２ 、R ７３ and R ７４ are each independently, (a) The first organic moiety (B)-1 represented by formula (B)-1: 【Chemical 8】 (In the formula, R ７５ is selected from the group consisting of C ２－１０ alkylene, C ３－１２ branched alkylene, C ５－１２ cycloalkylene, C alkylene containing a C═C double bond, C ２－１０ alkylene containing a C═C double bond, C ３－１２ branched alkylene, and C alkylene containing a C═C double bond, and ５－１２ is selected from the group consisting of cycloalkylene R ７６ is hydrogen or an alkyloxycarbonyl represented by formula (B)-1-1: [Chemical Formula 9] (In the formula, R ７７ is C １－８ alkyl)); (b) A silicon-containing organic moiety (B)-2 having at least two carbons, represented by formula (B)-2: 【Chemical 10】 (In the formula, R ７８ and R ７９ are each independently selected from the group consisting of C １－８ alkyl, C ３－１２ branched alkyl, C １－８ alkyloxy, C ３－１２ branched alkyloxy, and C ６－１６ aryl; R ８０ is selected from the group consisting of C １－８ alkyl, C ６－１６ aryl, hydroxy, and siloxanes having structure (B)-2-1: 【Chemical Formula 11】 (In the formula, R ８１ is selected from the group consisting of hydrogen, C １－８ alkyl, C alkyl substituted with hydroxy １－８ alkyl, C ６－１６ aryl, and a silyl moiety having structure (B)-2-1-1: 【Chemical 12】 (In the formula, R ８４ and R ８５ are each independently selected from the group consisting of C １－８ alkyl, C ３－１２ branched alkyl, C １－８ alkyloxy, C ３－１２ branched alkyloxy, and C ６－１６ aryl; and R ８６ is selected from the group consisting of C １－８ alkyl and C ６－１６ aryl); R ８２ and R ８３ are each independently selected from the group consisting of C １－８ alkyl, C ３－１２ branched alkyl, C １－８ alkyloxy, C ３－１２ branched alkyloxy, and C ６－１６ aryl; and p ８１ represents the number of repeating units in the siloxane moiety (B)-2-1)); and (c) C ２－８ alkyl, C ２－８ alkyl carboxy, C ６－２０ aryl carboxy, fluorenyl carboxy, fluorinated C ２－８ alkyl carboxy, C ２－８ alkyl sulfonyl, fluorinated C ２－８ alkyl sulfonyl, and a second organic moiety selected from the group consisting of any combination of any of these, and (d) Any combination of (a), (b), and (c) (selected from the group consisting of)

6. The spin-coating composition according to claim 5, wherein M is at least one selected from the group consisting of Zr, Ta, Hf, Ti, Sn, Pb, Nb, Mo, Ge, and W.

7. The spin-coating composition according to any one of claims 1 to 6, wherein the solvent (C) is selected from the group consisting of aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, monoalcohol solvents, polyol solvents, ketone solvents, ether solvents, ester solvents, nitrogen-containing solvents, sulfur-containing solvents, and any arbitrary combination thereof.

8. The spin-coating composition according to any one of claims 1 to 7, further comprising a surfactant (D).

9. The spin-coating composition according to any one of claims 1 to 8, wherein the molecular weight of the carbon material (A) is 500 to 4,000.

10. The mass ratio of the metal-organic compound (B) to the total mass of the spin-coating composition is 5 to 75% by mass; the mass ratio of the solvent (C) to the total mass of the spin-coating composition is 5 to 75% by mass; and the mass ratio of the surfactant (D) to the mass of the metal-organic compound (B) is 5 to 100% by mass. The spin-coating composition according to any one of claims 1 to 9.

11. A spin-on metal hard mask composition comprising the spin-coating composition according to any one of claims 1 to 10.

12. A method for manufacturing a metal oxide film, comprising: (1) spin-coating the spin-coating composition according to any one of claims 1 to 10 above the substrate; and (2) heating the spin-coating composition to form a metal oxide film A method comprising.

13. The method according to claim 12, wherein the metal content of the metal oxide film is 10 to 85% by mass based on the total mass of the film.

14. A method for manufacturing a resist film, comprising: (3) applying a resist composition above the metal oxide film manufactured by the method according to any one of claims 12 to 13 A method comprising.

15. A method for manufacturing a resist pattern, comprising: Exposing a resist film produced by the method according to claim 14 to radiant light; Developing the exposed resist film with a developer; and Removing the developer from the substrate A method comprising.

16. A method for manufacturing a processed substrate, （７） Etching a resist pattern produced by the method according to claim 15 ; and (8) Processing the substrate A method comprising.

17. A method for manufacturing a device, (9) Forming a wiring on a processed substrate produced by the method according to claim 16 A method comprising.

18. The spin-coating composition according to claim 1, wherein the spin-coating composition consists essentially of a carbon material (A), a metal organic compound (B), and a solvent (C).

19. The spin-coating composition according to claim 1, wherein the spin-coating composition consists essentially of a carbon material (A), a metal organic compound (B), a solvent (C), and a surfactant (D).

20. The spin-coating composition according to claim 1, wherein the spin-coating composition consists essentially of a carbon material (A), a metal organic compound (B), a solvent (C), a surfactant (D), and an additive (E) selected from the group consisting of a crosslinking agent, an acid generator, a radical generator, a photopolymerization initiator, a substrate adhesion enhancer, an antifoaming agent, and combinations thereof.

21. The spin-coating composition according to claim 1, wherein the spin-coating composition consists of a carbon material (A), a metal organic compound (B), and a solvent (C).

22. The spin-coating composition according to claim 1, wherein the spin-coating composition consists of a carbon material (A), a metal organic compound (B), a solvent (C), and a surfactant (D).

23. The spin-coating composition according to claim 1, wherein the spin-coating composition consists of a carbon material (A), a metal organic compound (B), a solvent (C), a surfactant (D), and an additive (E) selected from the group consisting of a crosslinking agent, an acid generator, a radical generator, a photopolymerization initiator, a substrate adhesion enhancer, an antifoaming agent, and combinations thereof.

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