Spin-coating composition comprising a carbon material, a metal organic compound and a solvent, and method for producing a metal oxide film over a substrate - Patent Application 20070122997

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 using the same to form a metal oxide film over a substrate. The present invention also relates to a method for fabricating a device using the composition. [Background technology]

[0002] Metal oxide films are useful in a variety of applications, such as lithography hard masks, underlayers for antireflective coatings, and electro-optical devices in the semiconductor industry.

[0003] As an example, photoresist ("resist") compositions are used in microlithography processes to produce miniaturized electronic components, such as in the manufacture of computer chips and integrated circuits. Typically, a thin coating of a resist composition is applied to a substrate, such as a silicon wafer used to manufacture integrated circuits. The coated substrate is then baked to remove a desired amount of solvent from the resist. The resist film on the substrate is then imagewise exposed to actinic radiation, such as visible light, ultraviolet light, extreme ultraviolet light, electron beam, particle beam, and X-ray radiation, and developed to form a pattern. The radiation causes a chemical change in the exposed areas of the resist. The exposed film is treated with a developer to dissolve and remove either the radiation-exposed or unexposed areas of the resist.

[0004] The trend towards smaller semiconductor devices has led to the use of new resists sensitive to shorter wavelengths of radiation, as well as advanced multi-level systems, to overcome the challenges associated with such miniaturization.

[0005] An underlayer containing a large amount of refractory components can be used as a hard mask, an antireflective coating. Hard masks are useful when the overlying resist cannot provide sufficient resistance to the dry etch used to transfer an image to the underlying semiconductor substrate. In such circumstances, materials called hard masks are used, whose etch resistance is high enough to transfer any pattern formed on them to the underlying semiconductor substrate. This is possible because the organic resist is different from the underlying hard mask and can be subjected to an etching gas mixture that allows the image in the resist to be transferred to the underlying hard mask. This patterned hard mask can then be used to transfer the image from the hard mask to the semiconductor substrate using appropriate etching conditions and gas mixtures, a task that the resist itself cannot accomplish using a single etching process.

[0006] In these circumstances, compositions comprising multi-ligand substituted metal compounds and solvents have been investigated, which are useful as air-stable precursors to high-K metal oxides and can produce metal hardmask films. See, for example, U.S. Patent No. 6,233,999.

[0007] Certain organic carbon materials have been investigated to provide compounds with good heat resistance and coatings that can fill gaps well, flatten well, and reduce film shrinkage. For example, see Patent Document 2. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] International Publication No. 2019 / 048393

[0009] [Patent Document 2] International Publication No. 2019 / 121480 Summary of the Invention [Problem to be solved by the invention]

[0010] technical challenges

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

[0012] The invention described below solves at least one of these problems. [Means for solving the problem]

[0013] Means to resolve

[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 formula (A1): [ka] (In the formula, Ar 11 is unsubstituted or R 11 Replaced by C 6-60 is a hydrocarbon, R 11 is C 1-20 of linear, branched or cyclic, C 1-20 alkyl, amino or alkylamino; R 12 is I, Br or CN, p 11 is a number between 0 and 5, and p 12 is a number between 0 and 1, and q 11 is a number between 0 and 5, and q 12 is a number between 0 and 1, and r 11 is a number between 0 and 5, and s 11 is a number between 0 and 5, where p 11 , q 11 and r 11 is not 0 at the same time); The solvent (C) comprises an organic solvent; and 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.

[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) may be included that do not substantially alter the effectiveness of the composition.

[0016] In another embodiment, the composition consists of components (A), (B), and (C), as described above. In such an embodiment, the total amount of (A), (B), and (C) is about 100% by weight, but may include other minor and / or trace amounts of additives, the presence of which in small amounts does not substantially alter the effectiveness of the composition. For example, in one such embodiment, the composition may contain 2% by weight or less of additives. In another embodiment, the composition may contain 1% by weight or less of additives. In a further embodiment, the composition may contain 0.05% by weight or less of additives.

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

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

[0019] The present invention also provides (3) a method for producing a resist film, which comprises applying a resist composition onto the metal oxide film produced as described above.

[0020] The present invention provides a method for producing a resist pattern, comprising: (4) exposing the resist film produced 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 producing a processed substrate, comprising: (7) etching using the resist pattern produced as described above; and (8) processing the substrate:

[0022] The present invention provides a device manufacturing method that includes the above-described method for manufacturing a processed substrate.

[0023] Effect 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 cracking. The metal oxide film formed from the spin coating composition exhibits good etching resistance. The solute in the spin coating composition reduces precipitation. The density of the metal oxide film increases. The metal oxide film exhibits good coatability on the substrate. The mask and the metal oxide film pattern after use 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. Excessive internal stress and pattern wiggling can be suppressed.

[0025] Description of the Embodiments

[0026] The above summary and the following detailed description are provided to illustrate the invention and are not intended to limit the invention as claimed.

[0027] definition

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

[0029] Use of the singular includes the plural, and the words "a," "an," and "the" mean "at least one." Furthermore, use of the term "including," as well as "includes" and "included," is not limiting. Also, terms such as "element" or "component" include both an element or component that comprises one unit and an element or component that comprises one or more units.

[0030] The term "and / or" refers to any combination of any of the elements in question, including the use of a single element.

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

[0032] The terms "about" or "approximately," when used in connection with a measurable, numerical variable, refer to the indicated value of the variable and to any value of the variable that is within experimental error of the stated value (e.g., within a 95% confidence limit for the mean) or within a percentage of the stated value (e.g., ±10%, ±5%), whichever is greater.

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

[0034] When the polymer described herein has multiple types of repeating units, these repeating units are copolymerized. The copolymerization may be any selected from alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, and any combination thereof. When the polymer or resin is represented by a chemical structure, the n, m, etc. in parentheses indicate the number of repeating units.

[0035] Temperatures mentioned herein are in 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 mass%, preferably about 10 to about 75 mass%, more preferably about 10 to about 50 mass%. In a further embodiment, the spin-coating composition consists essentially of these components. In yet another embodiment, the spin-coating composition consists essentially of these components.

[0038] In another aspect, the present invention provides the use of the composition for spin coating, preferably over a substrate; more preferably onto a substrate. The present invention provides the use of the composition for spin coating, preferably over a substrate, to form a coating; preferably, to subsequently form a film.

[0039] In a preferred embodiment, the spin-on metal hard mask composition can consist essentially of the spin-coating composition of the present invention. In another preferred embodiment, the spin-on metal hard mask composition can consist essentially of the spin-coating composition of the present invention. The resulting film 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 that they are dissolved, the resulting composition can be filtered to remove impurities and / or small debris. A known filter 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). [ka]

[0043] In (A1), Ar 11 is unsubstituted or R 11 Replaced by C6-60 It is a hydrocarbon. Preferably, Ar 11 excludes fused aromatic rings. 11 is preferably 9,9-diphenylfluorene, 9-phenylfluorene, phenyl, C 6-60 A linear polyphenylene or a branched polyphenylene ether, each of which is independently R 11 may be substituted with.

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

[0045] When the carbon material (A) is composed of multiple units (A1), R 11 can act as a linker to connect the units (A1) together. 11 Single or multiple (preferably single) R replacing 11 can exist.

[0046] In one unit (A1), a group enclosed in brackets (e.g., p 11 (group enclosed in brackets with an R 11 In this case, R 11 is a linker between the group and Ar 11 and can be combined.

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

[0048] p 11 is a number from 0 to 5. The carbon material (A) has two types of units (A1) as its constituent elements, and both Ar 11is phenyl, while Ar 11 Above p 11 is 1, and the other Ar 11 Above p 11 It may be one aspect of the present invention that p is 2. In such a case, p 11 = 1.5. The same numbering convention is used herein unless otherwise stated.

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

[0050] p 12 is a number of 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; and even more preferably 1. 11 =0 is also one aspect of the present invention.

[0052] q 12 is a number of 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; and even more preferably 1. 11 =0 is also one aspect 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; and even more preferably 1. 11 =0 is also one aspect of the present invention.

[0055] p 11 , q 11 and r 11 are not 0 at the same time.

[0056] The unit (A1) according to the present invention may be a unit (A1-1), (A1-2) and / or (A1-3) represented by the formula (A1-1), (A1-2) and / or (A1-3), each of which will be explained in detail below.

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

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

[0059] Ar 21 is C 6-50 An aromatic hydrocarbon ring; preferably phenyl. Without wishing to be bound by theory, Ar 21 When is phenyl, it is believed that 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, C 6-50 A single bond bonding to an aromatic hydrocarbon ring, hydrogen, or other unit; preferably, each independently a single bond bonding to a phenyl, hydrogen, or other unit; more preferably, each independently a single bond bonding to a phenyl or other unit; even more preferably, each independently a phenyl.

[0061] The term "other unit" in "single bond bonded to other unit" does not include the unit in which the single bond exists. However, if the carbon material (A) has multiple units (A1), the single bond may be bonded to other units (A1) (not the unit (A1) in which the single bond exists, but one unit (A1) that is not self-crosslinked). The same rule applies in this specification unless otherwise specified.

[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 bond to each other and form an aromatic ring with adjacent benzenes. For example, two R 24 can be bonded to each other to form a naphthyl ring with adjacent benzenes.

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

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

[0065] R 12 , p 11 , p 12 , q 11 , q 12 , r 11 and s 11 The definitions and / or forms of are each independently the same as above.

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

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

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

[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 p 11 +q 11 +r 11 =1 to 4.

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

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

[0072] n 31 , n 32 , m 31 and m32 are each independently an integer of 0 to 6; preferably an integer of 0 to 3. 31 +n 32 In one preferred embodiment of the present invention, L is 5 or 6. 31 If is a single bond, m 31 = 1. L 32 If 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 each independently the same as 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: [ka]

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

[0076] Ar 41 is C 6-50 Aromatic hydrocarbons; preferably Ar 41 is phenyl.

[0077] R 41 and R 42 are each independently, C 1-10 Alkyl (preferably C 1-6 Optionally, R 41 and R 42 constitutes a cyclic hydrocarbon; preferably, R 41 and R 42constitutes a saturated hydrocarbon ring.

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

[0079] L 41 is C 6-50 A single bond bonding to an arylene or other unit; preferably a single bond bonding to a phenylene or other unit; more preferably a single bond bonding to another unit.

[0080] R 12 , p 11 , p 12 , q 11 , q 12 , r 11 and s 11 The definitions and / or forms of are each 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: [ka]

[0082] When the carbon material (A) is a polymer, the film produced from the composition of the present invention has high heat resistance. In a preferred embodiment, (i) the main chain of the carbon material (A) does not contain any secondary or tertiary carbon atoms, or (ii) the total amount of secondary and tertiary carbon atoms 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 in 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 %; and even more preferably about 0 mol %, or 0 mol %), based on all components used in the synthesis. An example of an aldehyde derivative is formaldehyde. In one preferred embodiment of the present invention, a ketone derivative is used to obtain a polymer of the carbon material (A) that contains almost no or almost no secondary and tertiary carbon atoms in its main chain.

[0084] It is possible to synthesize a polymer so that it contains little or no secondary carbon atoms and / or tertiary carbon atoms. In one preferred embodiment of the present invention, when the carbon material (A) is a polymer, the polymer does not contain any secondary or tertiary carbon atoms (other than the terminal ends of the polymer, which may acceptably contain secondary and / or tertiary carbon atoms). Without wishing to be bound by theory, it is believed that such polymers have solubility and that the films formed have improved heat resistance. It is acceptable for the terminal ends of the polymer to have secondary and / or tertiary carbon atoms.

[0085] In one embodiment of the present invention, when the carbon material (A) is a polymer, the main chain of the polymer preferably does not contain an ether linker (-O-) or a sulfone linker (-S(=O)2-). Here, the term "linker" refers to a component that connects units together. Terminal modifications with such units are permitted, for example, hydroxy groups. Without wishing to be bound by theory, it is believed that such polymers exhibit good solubility.

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

[0087] In the present 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 is instead a low molecular weight compound, its molecular weight can be measured using liquid chromatography-mass spectrometry (LC-MASS).

[0089] In one embodiment of the present invention, the molecular weight of the carbon material (A) is about 500 to about 6,000; preferably about 600 to about 5,500; more preferably about 700 to about 5,000; and even more preferably 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 embodiment, the carbon material (A) consists essentially of the repeating unit (A1). In another preferred embodiment, the carbon material (A) consists of the repeating unit (A1). In one embodiment of the present invention, the carbon material (A) does not contain repeating units other than the unit (A1).

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

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

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

[0094] Cy 51 is C 5-30A cyclic 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; even more preferably fluorene or adamantane; and even more preferably fluorene.

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

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

[0097] Carbon materials (A), units (A3)

[0098] The unit (A3) is represented by the formula (A3). [ka]

[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 straight chain alkyl, C6 straight chain alkyl, tertiary butyl, or phenyl; even 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 linear alkyl, tertiary butyl, or phenyl; more preferably, hydrogen or phenyl; even more preferably, hydrogen.

[0103] R 62 C 1-6 Alkyl or C 6-14 aryl, and R 63 C 1-6 Alkyl or C 6-14 When R is aryl, 62 and R 63 are optionally linked to each other to form a hydrocarbon ring.

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

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

[0106] Each Cy is surrounded by a dashed line. 64 , Cy 65 and Cy 66 At least one of the rings is adjacent to an aromatic hydrocarbon ring Ph 62 It is an aromatic hydrocarbon ring fused with the aromatic hydrocarbon ring Ph. 62 The total number of carbon atoms is preferably C 10-14 ; more preferably, C 10 is.

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

[0108] For example, the following compound can have the structure of formula (A3) as the unit (A3): 61 and aromatic hydrocarbon ring Cy 63 and are fused to each other to form a naphthyl ring (C 10 ) and OH is an aromatic hydrocarbon ring Cy 63 It is bonded to Ar 61 is a single bond, and Ar 62 and R 63 are each phenyl, and Ar 62 and R 63 are linked together to form a hydrocarbon ring (fluorene): [ka]

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

[0110] When the carbon material (A) is a polymer, the repeating numbers of the units (A1), (A2), and (A3) are each n A1 , n A2 and n A3 and n A1 >0%.

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

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

[0113] n A3 / (n A1 +n A2 +n A3 ) is preferably about 0 to about 99%; more preferably about 10 to about 50%; and even more preferably about 20 to about 40%. In one embodiment 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 ) / n totalis preferably about 80 to about 100%; more preferably about 90 to about 100%; and even more preferably about 95 to about 100%. In one preferred embodiment of the present invention, (n A1 +n A2 +n A3 ) / n total =100%.

[0116] For example, the following polymer can be interpreted as an alternating copolymer having units (A1), (A2), and (A3), respectively, in that 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 ((n A1 +n A2 +n A3 ) / n total =100%. [ka]

[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 thereof. In one embodiment of the present invention, the metal organic compound (B) is a mixture of multiple metal organic compounds each having the structure represented by (B).

[0119] Without being bound by theory, it is believed that containing only metal components in the film is not desirable because cracks often occur, and that the carbon material (A) is a good solute because it can avoid precipitation with the metal.

[0120] Without being bound by theory, it is further believed that when forming the metal oxide film of the present invention, the carbon component (derived in part or in whole from the carbon material (A)) can be located in the voids between the polymers made from the metal organic compound (B); increase the film density (mass density, more preferably atomic number density); and contribute to etching resistance.

[0121] The metal organic compound (B) is represented by the formula (B): [ka]

[0122] M is a tetravalent metal. M is preferably at least one selected from the group consisting of 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 Al, Zr, Hf, and Ti; and even more preferably Al, Ti, and Zr.

[0123] n 71 is an integer between 1 and 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 having at least two carbons (B)-2, a second organic moiety, and any combination of any of these. Without wishing to be bound by theory, it is believed that R 71 and / or R 74 can contribute to the solubility of the metal organic compound (B), and R 72 and / or R73 is believed to be cleaved to provide additional polymerization attachment points.

[0125] In formula (B), R 71 , R 72 , R 73 and R 74 wherein at least one moiety is selected from the group consisting of: [ka]

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

[0127] R 75 is C 2-10 Alkylene, C 3-12 Branched alkylene, C 5-12 Cycloalkylene, C containing a C=C double bond 2-10 Alkylene, C containing a C=C double bond 3-12 Branched alkylene and C containing C=C double bonds 5-12 Cycloalkylene; preferably C 2-10 Alkylene, C containing a C=C double bond 2-10 Alkylene, and C 5-12 Cycloalkylene; more preferably, C 2-10 In another aspect of the invention, R 75 is a C containing a C=C double bond 2-10 In another aspect of the invention, R 75 is C 5-12 It is a cycloalkylene.

[0128] R 76 is hydrogen or alkyloxycarbonyl represented by formula (B)-11. [ka]

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

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

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

[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 aspect of the invention, R 78 and R 79 However, each independently, C 1-8 Alkyloxy, C 3-12 Branched alkyloxy, or C 6-16 It is preferably aryl.

[0133] R 80 is C 1-8 Alkyl, C 6-16aryl, hydroxy, and siloxanes having structure (B)-2-1; preferably, methyl, ethyl, propyl, butyl, t-butyl, and siloxanes having structure (B)-2-1; more preferably, methyl, and siloxanes having structure (B)-2-1; even more preferably, methyl: [ka]

[0134] R 81 is hydrogen, C 1-8 Alkyl, hydroxy substituted C 1-8 Alkyl, C 6-16 aryl, and silyl moieties having the structure (B)-2-1-1; preferably hydrogen, C 1-8 alkyl, and silyl moieties having the structure (B)-2-1-1; more preferably hydrogen, C 1-4 R is selected from the group consisting of alkyl, and a silyl moiety having the structure (B)-2-1-1; even more preferably, hydrogen, and a silyl moiety having the structure (B)-2-1-1. 81 C 1-4 It is an aspect of the present invention that R is selected from the group consisting of alkyl, and a silyl moiety having the structure (B)-2-1-1. 81 is methyl or t-butyl; preferably, methyl. [ka]

[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 selected from the group consisting of methyl, ethyl, propyl, butyl, t-butyl, methoxy and phenyl; more preferably methyl, t-butyl and phenyl; and even more preferably methyl.

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

[0137] p 81 represents the number of repeating units in the siloxane portion (B)-2-1. In one embodiment 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 selected from the group consisting of methyl, ethyl, propyl, butyl, t-butyl, and phenyl; more preferably methyl, t-butyl, and phenyl; and even more preferably methyl.

[0139] The second organic moiety is C 2-8 Alkyl, C 2-8 Alkyl carboxy, C 6-20 Arylcarboxy, fluorenylcarboxy, fluorinated C 2-8 Alkyl carboxy, C 2-8 Alkyl sulfonyl, fluorinated C 2-8 alkylsulfonyl, and any combination thereof.

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

[0141] In one embodiment 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), which comprises an organic solvent. The solvent (C) cannot consist solely of an inorganic solvent, such as water.

[0144] In a preferred embodiment of the present invention, 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 combination thereof.

[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; 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, and 2,6-dimethylheptanol. Monoalcohol solvents such as diol-4, n-decanol, cyclohexanol, benzyl alcohol, phenylmethylcarbinol, 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 fenchone;Ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, dimethyl dioxane, 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 ether solvents such as 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 combination of any of these solvents may 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 of these are preferred in terms of storage stability of the solution.

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

[0148] When 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; even more preferably about 80:20 to about 20:80; and even more preferably about 70:30 to about 30:70.

[0149] The amount of water in solvent (C) is preferably 0.1% by mass or less, and more preferably 0.01% by mass or less. In view of the relationship with other layers or coatings, it is preferable that solvent (C) does not contain water. In one embodiment of the present invention, the amount of water in solvent (C) is preferably 0.00% by mass.

[0150] In one embodiment 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 mass%, preferably about 10 to about 75 mass%, more preferably about 10 to about 50 mass%.

[0151] Surfactant (D)

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

[0153] In one embodiment 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 alkylaryl 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; and 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), which is selected from the group consisting of a crosslinking agent, an acid generator, a radical generator, a photopolymerization initiator, a substrate adhesion promoter, and an antifoaming agent.

[0157] In one embodiment of the present invention, the mass ratio of the other additives (E) to the mass of the metal organic compound (B) is preferably about 0.05 to about 10 mass%, more preferably about 0.10 to about 5 mass%, and even more preferably about 0.10 to about 2 mass%. In one embodiment of the present invention, the spin coating composition does not contain any of these additives (E) (0 mass%).

[0158] Metal oxide film formation

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

[0160] For clarity, numbers in parentheses indicate the order of steps, e.g., step 1 occurs before step 2. This rule also applies to other steps described herein unless otherwise indicated.

[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 an underlying layer being interposed between the substrate and the applied composition. Hereinafter, the term "above" includes "in direct contact" and "through a layer" unless otherwise specified.

[0162] The substrate surface on which the composition is to be deposited can be pretreated, for example, with a 1,1,1,3,3,3-hexamethyldisilazane solution. The top surface of the substrate can be flat or uneven. The substrate can be patterned or unpatterned. The substrate can be a single-layer substrate or a multilayer substrate consisting of multiple substrate layers. In one form of the present invention, the top surface of the substrate is a patterned semiconductor. The semiconductor can be composed of an oxide, a nitride, a metal, or 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, YO3, GaN, TiN, TaN, Si3N4, NbN, Cu, Ta, W, Hf, and Al.

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

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

[0165] In one embodiment of the present invention, the heating conditions are selected from the range of about 200 to about 800°C (preferably, about 250 to about 750°C; more preferably, about 300 to about 700°C; even more preferably, about 350 to about 650°C; and 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; and even more preferably, about 60 to about 90 seconds). Heating can be performed in separate steps (step baking). For example, heating can be performed in two steps or three steps. For example, it is preferred that the first heating is performed at about 200 to about 300°C for about 30 to about 120 seconds, and the second heating is performed at about 300 to about 500°C for about 60 to about 180 seconds.

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

[0167] In one embodiment of the present invention, a spin-coating composition is applied to an underlayer (e.g., a spin-on carbon layer, a planarizing layer) or a substrate containing a topographical feature. In this embodiment of the present invention, the metal oxide film formed has a thickness sufficient to cover the topography; and chemical strippers or fluorinated plasma etching can be used to create a filled topography in which the metal oxide film is flush with the top of the topography. 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 embodiment of the present invention, the metal content of the metal oxide film is about 5 to about 85 mass % (more preferably about 10 to about 50 mass %; even more preferably about 15 to about 40 mass %) based on the total mass of the film. The metal content in the metal oxide film can be measured by Rutherford backscattering spectroscopy / hydrogen forward scattering spectroscopy (RBS / HFS).

[0169] Formation of a resist layer

[0170] The present invention further comprises: (3) Applying a resist composition onto the metal oxide film produced by the above method. The present invention provides a method for producing a resist film comprising the steps of: The term "above a 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 possibility of an intermediate layer (e.g., bottom antireflective coating, BARC) being interposed between the metal oxide film and the applied resist composition. The intermediate layer can include a single layer or multiple layers. Another layer (e.g., top antireflective coating, TARC) may be formed on the resist film.

[0171] Known methods can be used for application, 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 vary depending on the resist composition used, but 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 performed on a hot plate for about 10 to about 180 seconds, preferably about 30 to about 90 seconds, or in a high-temperature gas atmosphere (e.g., in a clean oven) for about 1 to about 30 minutes. The formed resist film preferably has 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] Resist pattern formation

[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. The present invention provides a method for producing a resist pattern, comprising the steps of:

[0174] The resist composition undergoes a reaction under irradiation through a mask. Preferably, ArF exposure can be performed using immersion lithography. When the resist composition is a positive resist, the irradiated portion increases resistance to dissolution by a developer. The wavelength of the irradiating 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). KrF excimer laser (248 nm), ArF excimer laser (193 nm), or extreme ultraviolet light (13.5 nm) are preferred; ArF excimer laser is more preferred. Another preferred embodiment of the present invention is when this composition is used in a process using EUV or ArF immersion. These wavelengths may vary within ±1%.

[0175] After the exposure, if desired, post-exposure baking (PEB) can be performed. The PEB temperature is selected from the range of about 80 to about 150°C (preferably, about 90 to about 140°C), and the PEB heating time 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 carried out using a developer. The developer used for development to form a resist pattern is preferably an aqueous solution of TMAH at a concentration of about 2.38% by mass (with a concentration variation of ±1% allowed). 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 puddle development can be used.

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

[0178] Substrate processing

[0179] The present invention provides (7) Etching using the resist pattern produced by the above method; and (8) processing the substrate. The present invention provides a method for producing a processed substrate, comprising:

[0180] As mentioned above, the fabricated multilayer structure may have an underlayer and / or an intermediate layer. The left-to-right direction in the following list corresponds to the bottom-to-top direction in the multilayer structure (including the resist pattern): i. Substrate / underlayer / metal oxide film / intermediate layer / resist pattern; ii. Substrate / metal oxide film / interlayer / resist pattern; iii. substrate / metal oxide film / resist pattern; and / or iv. Substrate / underlayer / metal oxide film / resist pattern.

[0181] The layers and / or metal oxide film under the resist pattern can be patterned using the resist pattern as a mask. For pattern formation, known techniques such as etching (dry etching) can be used.

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

[0183] In one form, dry etching can be performed with O2, CF4, CHF3, Cl2, or BCl3, with O2 or F4 being the preferred gases 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 N, NF, O, a rare gas, Cl, HBr, or any mixture thereof can be used to etch the metal oxide film and obtain the metal oxide film.

[0185] One method of the present invention for processing a substrate is described below: i. forming a metal oxide film as described above; ii. applying a BARC onto the metal oxide film; iii. applying a resist composition onto the BARC; iv. forming a resist pattern as described above; v. Etching through the BARC unprotected by the resist pattern down to the metal oxide film using a fluorinated plasma; vi. etching through the metal oxide film unprotected by the BARC and resist pattern down to the substrate using a chlorine plasma to produce a patterned metal oxide film; vii. Etching the substrate in areas not protected by the patterned metal oxide film using a fluorinated plasma.

[0186] After processing the substrate, the pattern and / or layers above / on top of the pattern may be removed by known methods.

[0187] Device fabrication

[0188] The present invention provides a method for manufacturing a device, comprising manufacturing a substrate processed as described above. Preferably, the method for manufacturing a device further comprises: (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 the chips are connected to lead frames and packaged with resin.Preferably, the device is a semiconductor device, a solar cell chip, an organic light-emitting diode, or an inorganic light-emitting diode.One preferred form of the device of the present invention is a semiconductor device. [Example]

[0190] The present invention will now be described with reference to the following examples, which are for illustrative purposes only and are not intended to limit the scope of the present invention.

[0191] Reference is now made to more specific embodiments of the present disclosure and experimental results that provide support for such embodiments. Examples are presented below to more fully illustrate the disclosed subject matter, but should not be construed as limiting the disclosed subject matter in any way.

[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 in the specific examples provided herein without departing from the spirit or scope of the disclosed subject matter. Therefore, the disclosed subject matter, including the description provided by the following examples, is intended to cover modifications and variations of the disclosed subject matter that come within the scope of the appended claims and their equivalents.

[0193] Preparation Example 1 of Example Composition 1

[0194] Component A1 (2.0% by mass), B1 (7.9% by mass) [ka] and surfactant MEGAFACE® R-41 (0.1 wt%, DIC) are added to a solvent mixture of PGMEA (63 wt%) and PGME (27 wt%). The liquid is mixed with a stirrer at room temperature for 10 minutes. Visually confirm that all solutes have dissolved. The resulting liquid is filtered through a 0.2 μm fluorinated resin filter to obtain Example Composition 1.

[0195] The polymers used are obtained in the same manner as described in WO2019 / 121480A1, 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 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 amounts are changed as described in Table 1: [ka]

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

[0199] The resulting composition has the following characteristics: [Table 1]

[0200] In Table 1 and the following tables, the numbers in parentheses refer to the amount by weight of each component in the composition.

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

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

[0203] Metal oxide film formation examples of Example compositions 2 to 4, and metal oxide film comparative formation examples 1 and 2 of Comparative compositions 1 and 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] Solubility evaluation

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

[0207] Crack evaluation

[0208] The presence of cracks on the surface of the metal oxide film made from each composition was evaluated by visual inspection. The evaluation results are shown in Table 2. In Table 2, "A" means that no cracks were observed, and "B" means that cracks were observed. Since Comparative Compositions 1 and 2 were evaluated as B in the crack evaluation, compositions other than these were used for further evaluation.

[0209] Film thickness measurement

[0210] The thickness of each metal oxide film was measured using a cross-sectional photograph of the wafer taken with a 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 using a K-Alpha Plus (Thermo Scientific) under the conditions of Ar gas, ion energy: 3 keV, and time: 2 minutes.

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

[0214] Etching resistance evaluation

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

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

[0217] While the present invention has been described and illustrated with a certain degree of particularity, it will be understood that the disclosure is by way of example only and that numerous modifications in the conditions and sequence of steps can be made by those skilled in the art without departing from the spirit and scope of the invention.

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 Formula 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 aromatic ring with adjacent benzene, 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. 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, if desired, be 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) 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 coating 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 ５－１２ cycloalkylene containing a C═C double bond, and 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 Formula 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 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 Formula 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) **Claim 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. **Claim 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. **Claim 8** The spin-coating composition according to any one of claims 1 to 7, further comprising a surfactant (D). **Claim 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. **Claim 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. **Claim 11** A spin-on metal hard mask composition comprising the spin-coating composition according to any one of claims 1 to 10. **Claim 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 the above steps. **Claim 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. **Claim 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 the above steps. **Claim 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 the steps of:

16. A method for manufacturing a processed substrate, comprising: （７） etching a resist pattern produced by the method according to claim 15; and processing the substrate A method comprising the steps of:

17. A method for manufacturing a device, comprising: forming wiring on a processed substrate produced by the method according to claim 16 A method comprising the steps of:

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 photoinitiator, 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 photoinitiator, a substrate adhesion enhancer, an antifoaming agent, and combinations thereof.

Images