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

Abstract

The present invention relates to a spin-on composition comprising a carbon material and a metal organic compound. The present invention also relates to methods of using the same to form metal oxide films over a substrate and to fabricate devices.

Description

Technical Field

[0001] This 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 over a substrate using the composition. The invention also relates to a method for manufacturing a device using the composition. Background Technology

[0002] Metal oxide films can be used in a variety of applications, such as photolithography hard masks, as underlayers for anti-reflective coatings, and in electro-optic devices in the semiconductor field.

[0003] As an example, photoresist / photoresist (“resist”) compositions are used in microlithography processes in the manufacture of computer chips and integrated circuits to fabricate miniaturized electronic components. Typically, a thin coating of the 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 the required amount of solvent from the resist. The resist film on the substrate is then exposed in an image-like manner to photochemical radiation, such as visible light, ultraviolet light, extreme ultraviolet light, electron beams, particle beams, and X-ray radiation, and developed to form a pattern. The radiation induces a chemical transformation in the exposed areas of the resist. The exposed coating is treated with a developer solution to dissolve and remove the irradiated or unexposed areas of the resist.

[0004] The trend toward miniaturization of semiconductor devices has led to the use of new photoresists that are sensitive to increasingly shorter radiation wavelengths, and has also led to the use of complex multi-stage systems to overcome the difficulties associated with this miniaturization.

[0005] A base layer containing a significant amount of heat-resistant elements can be used as a hard mask and an anti-reflective coating. Hard masks are useful when the upper resist layer cannot provide sufficiently high resistance to dry etching used to transfer an image to the underlying semiconductor substrate. In this case, a material called a hard mask is used, which has high enough etch resistance to transfer any pattern created on it to the underlying semiconductor substrate. This is possible because organic resists differ from the underlying hard mask, and an etching gas mixture can be found that allows the image in the resist to be transferred to the underlying hard mask. This patterned hard mask can then be used with the gas mixture under appropriate etch conditions to transfer the image from the hard mask to the semiconductor substrate, a task that the photoresist itself cannot accomplish with a single etch process.

[0006] In these cases, compositions comprising multiligand-substituted metal compounds and solvents were investigated, which can be used as air-stabilized precursors for high-k metal oxides and can be used to fabricate metal hard mask films. See, for example, Patent Document 1.

[0007] Certain organic carbon materials have been investigated to provide compounds with good heat resistance, as well as coatings that can effectively fill gaps, provide good planarization, and reduce film shrinkage. See, for example, Patent Document 2.

[0008] Citation List

[0009] [Patent Document 1] WO2019 / 048393A1

[0010] [Patent Document 2] WO2019 / 121480A1 Summary of the Invention

[0011] Technical issues

[0012] One or more significant issues requiring improvement have been identified, including: insufficient solute solubility; insufficient solute heat resistance; cracking in the metal oxide film; insufficient etch resistance of the metal oxide film; potential precipitation during preparation; low density of the metal oxide film; insufficient coatability of the composition and / or the metal oxide film; difficulty in removing the pattern from the substrate; potential mixing of the metal oxide film with adjacent coatings; difficulty in fine patterning of the metal oxide film; insufficient gap filling in the composition; insufficient surface flatness of the film; insufficient film hardness; high internal stress of the film; and frequent pattern twisting.

[0013] The present invention described below solves at least one of these problems.

[0014] Solution to the problem

[0015] The present invention provides a spin-coating composition comprising a carbon material (A), an organometallic compound (B), and a solvent (C), wherein the carbon material (A) comprises a unit (A1) represented by formula (A1):

[0016]

[0017] Ar 11 Is it unsubstituted or substituted with R? 11 C 6-60 hydrocarbon,

[0018] R 11 It is C 1-20 Straight-chain, branched, or cyclic alkyl, amino, or alkylamino groups.

[0019] R 12 Is it I, Br, or CN?

[0020] p 11 p is an integer between 0 and 5. 12 q is an integer between 0 and 1. 11 q is an integer between 0 and 5. 12r is an integer between 0 and 1. 11 s is an integer between 0 and 5. 11 The integers are between 0 and 5, provided that p is an integer. 11 q 11 and r 11 Do not both be 0;

[0021] Solvent (C) includes organic solvents; and

[0022] The mass of carbon material (A) and the mass of organometallic compound (B) are approximately 5 to approximately 100% by mass.

[0023] In another embodiment, the composition consists essentially of components (A), (B), and (C) as described above. In such an embodiment, the total amount of (A), (B), and (C) need not be equal to 100% by weight, and may include other components (e.g., additional solvents, including water, common additives, and / or impurities) that do not substantially alter the effectiveness of the composition.

[0024] In another embodiment, the composition comprises components (A), (B), and (C) as described above. In such an embodiment, the total amount of (A), (B), and (C) is approximately 100% by weight, but may include other small and / or trace amounts of additives so small that they are substantially absent, which may alter the effectiveness of the composition. For example, in one such embodiment, the composition may contain 2% by weight or less of the additive. In another embodiment, the composition may contain 1% by weight or less of the additive. In a further embodiment, the composition may contain 0.05% by weight or less of the additive.

[0025] The present invention also provides a spin-coated metal hard mask composition.

[0026] The present invention provides a method for manufacturing a metal oxide film, comprising (1) spin coating the above spin coating composition onto a substrate; and (2) heating the spin coating composition to form a metal oxide film.

[0027] The present invention provides a method for manufacturing a resist coating, comprising: (3) applying a resist composition over a metal oxide film manufactured as above.

[0028] The present invention provides a method for manufacturing a resist pattern, comprising: (4) exposing the resist coating manufactured above to radiation light; (5) developing the exposed resist coating with a developer; and (6) removing the developer from the substrate.

[0029] The present invention provides a method for manufacturing a treated substrate, comprising: (7) etching with a resist pattern manufactured as above; and (8) treating the substrate.

[0030] The present invention provides a method for manufacturing a device, including the method for manufacturing a treated substrate as described above.

[0031] The effects of the invention

[0032] The solute in the spin-coating composition exhibits good solubility in solvent (C). The solute in the spin-coating composition exhibits good heat resistance. Metal oxide films made from the spin-coating composition show reduced cracking. Metal oxide films made from the spin-coating composition exhibit good etch resistance. The solute in the spin-coating composition reduces precipitation. The metal oxide film increases its density. The metal oxide film exhibits good coatability on the substrate. Patterns in the metal oxide film previously used as masks can be easily removed. The metal oxide film reduces mixing with adjacent coatings (e.g., resist coatings). 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 / or pattern distortion can be suppressed.

[0033] Description of the implementation plan

[0034] The above overview and the following detailed description are provided to illustrate the invention and are not intended to limit the scope of the claimed invention. Detailed Implementation

[0035] definition

[0036] Throughout this specification, unless explicitly limited or stated otherwise, the following definitions, symbols, units, abbreviations, and terms have the meanings given in the following definitions, descriptions, and examples.

[0037] The use of the singular includes the plural, and "a," "an," and "the" mean "at least one." Furthermore, the use of the term "comprising" and other forms such as "containing" and "containing" is not restrictive. Similarly, terms such as "element" or "component" cover both elements or components that contain one unit and elements or components that contain more than one unit.

[0038] The term “and / or” refers to any combination of the above elements, including the use of a single element.

[0039] When a numerical range is described using "to", "-", or "~", the range includes the numbers before and after the "to", "-", or "~", and the units of the two numbers are the same. For example, "5 to 25 mol%" means "5 mol% or more and 25 mol% or less".

[0040] The term “about” or “approximately”, when used in conjunction with a measurable numerical variable, refers to the indicated value of the variable and all values ​​of the variable within the experimental error of the indicated value (e.g., within the 95% confidence limit of the mean) or within a percentage of the indicated value (e.g., ±10%, ±5%), whichever is greater.

[0041] The "C" used in this article x-y “C” x -C y "and "C x Terms like "" indicate the number of carbon atoms in a molecule or substituent. For example, "C" 1-6 "Alkyl" refers to an alkyl chain having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0042] When the polymers described herein have multiple types of repeating units, these repeating units are copolymerized. The copolymer can be any form 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. outside the parentheses indicate the number of repetitions.

[0043] The temperature unit used in this article is Celsius. For example, "20 degrees" means "20 degrees Celsius".

[0044] Spin-coating composition

[0045] This invention provides a spin-coating composition comprising a carbon material (A), an organometallic compound (B), and a solvent (C). The mass ratio of carbon material (A) to organometallic 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 another embodiment, the spin-coating composition consists essentially of these components. In yet another embodiment, the spin-coating composition consists of these components.

[0046] In another embodiment, the present invention provides the use of the composition for spin coating: preferably over a substrate; more preferably on a substrate. The present invention provides the use of a composition spin-coated over a substrate to form a coating; preferably subsequently forming a film.

[0047] In a preferred embodiment, the spin-coated metal hard mask composition may consist substantially of the spin-coating composition of the present invention. In another preferred embodiment, the spin-coated metal hard mask composition may consist of the spin-coating composition of the present invention. It can be said that the film subsequently made with the composition of the present invention is preferably a metal hard mask film.

[0048] After all components are added to the solvent (C) and dissolution is confirmed, the resulting composition can be filtered to remove impurities and / or small debris. Known filters can be used in the preparation.

[0049] Carbon material (A), unit cell (Al)

[0050] The carbon material (A) of the present invention comprises a unit (A1) represented by formula (A1):

[0051]

[0052] In (A1), Ar 11 Is it unsubstituted or substituted with R? 11 C 6-60 Hydrocarbons. Ar is preferred. 11 Excluding fused aromatic rings. Ar 11 Preferably, it contains 9,9-diphenylfluorene, 9-phenylfluorene, phenyl, or C. 6-60 Linear polystyrene or branched polystyrene, which can each independently replace R 11 .

[0053] R 11 It is C 1-20 Straight-chain, branched, or cyclic alkyl, amino, or alkylamino groups. R 11 C is preferred 1-10 Straight-chain, branched, or cyclic alkyl groups, or alkylamino groups; more preferably C 1-3 Straight-chain alkyl, cyclopentyl, cyclohexyl or dimethylamino.

[0054] When carbon material (A) is composed of multiple (A1) units, R 11 It can be used as a connecting base and combined with the unit (A1). There can be one or more (preferably one) R. 11 Replace an Ar 11 .

[0055] In a unit (A1), groups enclosed in parentheses (e.g., those subscripted p) 11 The group enclosed in brackets can interact with R 11 Combined. In this case, R 11 As a linker, it intervenes and interacts with this group and Ar. 11 Combine.

[0056] R 12 It is I, Br or CN; preferably I or Br; more preferably I.

[0057] p 11 The numbers are 0 to 5. One embodiment of the present invention may involve carbon material (A) composed of two types of units (Al) one after another, Ar... 11 All are phenyl, one of which is Ar 11 p on 11 For 1, another Ar 11 p on 11The value is 2. In this case, the overall value of p is 2. 11 =1.5. Unless otherwise specified, the same numbering conventions will be used throughout this specification.

[0058] p 11 Preferably 0, 1, 2, or 3; more preferably 0, 1, or 2; even more preferably 1. 11 =0 is also a form of the present invention.

[0059] p 12 It is a number from 0 to 1; preferably 0 or 1; more preferably 1.

[0060] q 11 The value is a number from 0 to 5; preferably 0, 1, 2, or 3; more preferably 0, 1, or 2; and even more preferably 1. q 11 =0 is also an aspect of this invention.

[0061] q 12 It is a number from 0 to 1; preferably 0 or 1; more preferably 1.

[0062] r 11 The number is 0 to 5; preferably 0, 1, 2 or 3; more preferably 0, 1 or 2; and even more preferably 1. 11 =0 is also a form of the present invention.

[0063] s 11 The number is 0 to 5; preferably 0, 1, 2, or 3; more preferably 0, 1, or 2; and even more preferably 1. 11 =0 is also a form of the present invention.

[0064] p 11 q 11 and r 11 Do not take 0 at the same time.

[0065] According to the invention, the unit (A1) can be a unit (A1-1), (A1-2) and / or (A1-3) represented by formula (A1-1), (A1-2) and / or formula (A1-1). Detailed explanation follows.

[0066] As one implementation, the preferred formula (A1) is formula (A1-1). It is not desirable to be bound by theory, but it is believed that the unit (A1-1) in the carbon material (A) can contribute to solubility and / or prevent precipitation.

[0067] Unit (A1-1) is represented by equation (A1-1):

[0068]

[0069] Ar 21 It is C 6-50Aromatic ring; preferably phenyl. Not wanting to be bound by theory, I believe that when Ar... 21 When it is phenyl, good effects can be expected, such as the solubility of carbon material (A) and the ability to form thick films (e.g., ≥ about 1 micrometer, more preferably ≥ about 1.5 micrometers).

[0070] R 21 R 22 and R 23 Each is C independently 6-50 An aromatic ring, hydrogen, or a single bond bonded to another unit; preferably, each independently is a phenyl, hydrogen, or a single bond bonded to another unit; more preferably, each independently is a phenyl, or a single bond bonded to another unit; even more preferably, each independently is a phenyl.

[0071] The term "another unit" in "a single bond bonded to another unit" does not include the unit in which the single bond resides. However, in the case of a carbon material (A) having multiple units (A1), a single bond may be bonded to another unit (A1) (not the unit (A1) in which the single bond resides, nor a self-crosslinking within a unit (A1)). Unless otherwise specified, the same convention applies hereinafter to this specification.

[0072] R 24 and R 25 Each is C independently 1-4 Alkyl groups, optionally multiple R groups 24 and / or R 25 They can combine with each other to form an aromatic ring with an adjacent benzene. For example, two R... 24 They can combine with each other to form a naphthalene ring with the adjacent benzene.

[0073] n 21 It is an integer from 0 to 1; preferably 0.

[0074] n 24 and n 25 Each is an integer from 0 to 3; preferably 0, 1 or 2; more preferably 0 or 2, and even more preferably 0.

[0075] R 12 p 11 p 12 q 11 q 12 r 11 and s 11 The definitions and / or implementation schemes are each independently the same as those described above.

[0076] For example, the compound on the lower left is a carbon material (A), which can be interpreted as being composed of one unit (A1) and one unit (A2), where Ar 11 It is 9,9-diphenylfluorene, p 11=2, p 12 =1, q 11 =r 11 =s 11 =0. As shown in the lower right figure, the key indicated by the arrow is not used to bond to another unit. Cy in equation (A2) 51 It is 9-phenylfluorene.

[0077]

[0078] Unintentionally limiting the scope of the invention, exemplary embodiments of the carbon material (A) comprising unit (A1-1) include:

[0079]

[0080]

[0081] As a more specific implementation, unit (A1-1) can be unit (A1-1-1). Unit (A1-1-1) is represented by equation (A1-1-1):

[0082]

[0083] p 11 p 12 q 11 q 12 and r 11 The definitions and / or implementation schemes are each independently the same as those described above and p 11 +q 11 +r 11 =1 to 4.

[0084] Unit (A-2) is represented by equation (A-2):

[0085]

[0086] L 31 and L 32 Each is independently a single bond or a phenylene group; preferably, each is independently a single bond.

[0087] n 31 n 32 m 31 and m 32 Each is an independent integer from 0 to 6; preferably an integer from 0 to 3. 31 +n 32 =5 or 6 is a preferred embodiment of the present invention. L 31 When it is a single bond, m 31 =1. L 32 When it is a single bond, m 32 =1.

[0088] R 12 p 11 p 12 q 11 q 12 r 11 and s 11 The definitions and / or implementation schemes are each independently the same as those described above.

[0089] Unintentionally limiting the scope of the invention, exemplary embodiments of the carbon material (A) comprising units (A1-2) include:

[0090]

[0091] Unit (A-3) is represented by equation (A-3):

[0092]

[0093] Ar 41 It is C 6-50 Aromatics; preferably Ar 41 It is phenyl.

[0094] R 41 and R 42 Each is C independently 1-10 Alkyl (preferably C) 1-6 Straight-chain alkyl). Optionally, R 41 and R 42 It can form cyclic hydrocarbons; R is preferred. 41 and R 42 It forms a saturated hydrocarbon ring.

[0095] The carbon atom at position 41 is a quaternary carbon atom.

[0096] L 41 It is C 6-50 arylene, or a single bond bonded to another unit; preferably phenylene, or a single bond bonded to another unit; more preferably a single bond bonded to another unit.

[0097] R 12 p 11 p 12 q 11 q 12 r 11 and s 11 The definitions and / or implementation schemes are each independently the same as those described above.

[0098] Unintentionally limiting the scope of the invention, exemplary embodiments of the carbon material (A) comprising units (A1-3) include:

[0099]

[0100] When the carbon material (A) is a polymer, the film made from the composition of the present invention has high heat resistance. In its preferred embodiment, (i) the main chain of the carbon material (A) does not contain secondary or tertiary carbon atoms, or (ii) the total amount of secondary and tertiary carbon atoms contained in the main chain of the carbon material (A) is low.

[0101] In a preferred embodiment of the invention, when the carbon material (A) is a polymer, the amount of 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%; further preferably about 0 to about 5 mol%; further preferably about 0 mol% or 0 mol%) based on all components used in the synthesis. An example of an aldehyde derivative is formaldehyde. The use of ketone derivatives is one of the preferred embodiments of the invention in order to obtain a polymer of carbon material (A) containing little or no secondary and tertiary carbon atoms in the main chain.

[0102] Polymers can be synthesized to contain few or no secondary and / or tertiary carbon atoms. As a preferred embodiment of the invention, when the carbon material (A) is a polymer, the polymer does not contain secondary or tertiary carbon atoms (except that the ends of the polymer may acceptably contain secondary and / or tertiary carbon atoms). It is not desirable to be bound by theory, but it is believed that such polymers are soluble and that the resulting films have improved heat resistance. It is acceptable for the polymer ends to have secondary and / or tertiary carbon atoms.

[0103] As one embodiment of the invention, when the carbon material (A) is a polymer, it is preferred that the polymer backbone does not contain ether linkages (-O-) or sulfone linkages (-S(=O)2-). Here, the term "linking group" refers to a component bonded to multiple units. Terminal modifications with these units, such as hydroxyl groups, are acceptable. It is not desirable to be bound by theory, but it is believed that such a polymer exhibits good solubility.

[0104] When the carbon material (A) is a polymer, the weight-average molecular weight (Mw) is used as its molecular weight.

[0105] In this application, Mw can be measured by gel permeation chromatography (GPC). In a suitable example of this measurement, the GPC column is set to approximately 40°C; tetrahydrofuran is used as the elution solvent at a flow rate of approximately 0.6 mL / min; and monodisperse polystyrene is used as the standard.

[0106] When the carbon material (A) is not a polymer but a low molecular weight compound, its molecular weight can be measured using LC-MASS.

[0107] As one embodiment of the present invention, the carbon material (A) has a molecular weight of 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.

[0108] The carbon material (A) of the present invention may or may not contain repeating units other than unit (A1). In a preferred embodiment, the carbon material (A) is substantially composed of repeating units (A1). In another preferred embodiment, the carbon material (A) is composed of repeating units (A1). One aspect of the present invention is that the carbon material (A) does not contain repeating units other than unit (A1).

[0109] Carbon material (A), unit (A2)

[0110] The carbon material (A) of the present invention may further comprise unit (A2) and / or unit (A3).

[0111] Unit (A2) is represented by equation (A2):

[0112]

[0113] Cy 51 It is C 5-30 Cyclic hydrocarbon ring; preferably 9-phenylfluorene, 9,9-diphenylfluorene, adamantane, phenyl, naphthyl, anthracene, phenanthrene, benzene, biphenyl, pyrene, leucine or perylene; more preferably fluorene, 9-phenylfluorene, 9,9-diphenylfluorene or adamantane; further preferably fluorene or adamantane; even more preferably fluorene.

[0114] As one embodiment of the present invention, formula (A2) is equivalent to formula (A2-1):

[0115]

[0116] Cy 51 The definition and / or implementation scheme are the same as those described above.

[0117] Carbon material (A), unit (A3)

[0118] Unit (A3) is represented by equation (A3):

[0119]

[0120] Ar 61 It is a single key, C 1-6 Alkyl, C 6-12 cycloalkyl or C 6-14 Aryl; preferably single bond, C 1-6Alkyl or phenyl; more preferably single bond, straight-chain C3 alkyl, straight-chain C6 alkyl, tert-butyl or phenyl; even more preferably single bond or phenyl; even more preferably phenyl.

[0121] Ar 62 It is C 1-6 Alkyl, C 6-12 cycloalkyl or C 6-14 Aryl; preferably isopropyl, tert-butyl, C6 cycloalkyl, phenyl, naphthyl, phenanthrene or biphenyl; more preferably phenyl.

[0122] R 61 and R 62 Each is C independently 1-6 Alkyl, hydroxyl, halogen or cyano; preferably methyl, ethyl, propyl, isopropyl, tert-butyl, hydroxyl, fluorine, chlorine or cyano; more preferably methyl, hydroxyl, fluorine or chlorine.

[0123] R 63 It is hydrogen, C 1-6 Alkyl or C 6-14 Aryl group; preferably hydrogen, C 1-6 Alkyl or phenyl; more preferably hydrogen, methyl, ethyl, straight-chain C5 alkyl, tert-butyl or phenyl; more preferably hydrogen or phenyl; even more preferably hydrogen.

[0124] When Ar 62 It is C 1-6 Alkyl or C 6-14 Aryl and R 63 It is C 1-6 Alkyl or C 6-14 Aryl 62 and R 63 They can optionally connect to each other to form a hydrocarbon ring.

[0125] r 61 and r 62 Each number is independently a number from 0 to 5; preferably 0 or 1; more preferably 0.

[0126] Cy enclosed by dashed lines 61 Cy 62 and Cy 63 At least one of the rings is an adjacent aromatic ring Ph 61 A fused aromatic ring. This aromatic ring and the aromatic ring Ph 61 The preferred total number of carbon atoms is C 10-14 More preferably, C 10 .

[0127] Cy enclosed by dashed lines 64 Cy 65 and Cy 66 At least one of the rings is an adjacent aromatic ring Ph62 A fused aromatic ring. This aromatic ring and the aromatic ring Ph 62 The preferred total number of carbon atoms is C 10-14 More preferably, C 10 .

[0128] In equation (A3), R 61 R 62 The bonding positions with OH are not restricted.

[0129] For example, the following compounds can have a structure of formula (A3) as unit (A3). That is, an aromatic ring Ph 61 and aromatic ring Cy 63 They fuse together to form naphthalene rings (C 10 ), OH is bonded to the aromatic ring Cy 63 Up. Ar 61 It's a single bond, Ar 62 and R 63 Each is a phenyl group, while Ar... 62 and R 63 They connect to form a hydrocarbon ring (fluorene):

[0130]

[0131] Unintentionally limiting the scope of the invention, exemplary embodiments of unit (A3) include:

[0132]

[0133] When the carbon material (A) is a polymer, the number of repetitions of unit (A1), unit (A2), and unit (A3) are respectively represented as n. A1 n A2 and n A3 And n A1 >0%.

[0134] n A1 / (n A1 +n A2 +n A3 Preferably, it is 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%.

[0135] n A2 / (n A1 +n A2 +n A3 Preferably, it is 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 invention, n A2 / (n A1 +n A2 +nA3 ) = 0%.

[0136] n A3 / (n A1 +n A2 +n A3 Preferably, it is 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 invention, n A3 / (n A1 +n A2 +n A3 ) = 0%.

[0137] When the carbon material (A) is a polymer, n total This indicates the total number of repetitions.

[0138] (n A1 +n A2 +n A3 ) / n total Preferably about 80% to about 100%; more preferably about 90% to about 100%; even more preferably about 95% to about 100%. In a preferred embodiment of the invention, (n A1 +n A2 +n A3 ) / n total =100%.

[0139] For example, the following polymers can be interpreted as alternating copolymers having units (A1), (A2), and (A3), respectively. 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 ) = approximately 1 / 3 (approximately 33%), while (n A1 +n A2 +n A3 ) / n total =100%.

[0140]

[0141] Organometallic compounds (B)

[0142] The spin-coating composition of the present invention comprises an organometallic compound (B). The organometallic compound (B) is preferably an organometallic complex containing a hydrolyzable group, a hydrolysis product of an organometallic complex containing a hydrolyzable group, a hydrolysis-condensation product of an organometallic complex containing a hydrolyzable group, or any combination thereof. As one embodiment of the present invention, the organometallic compound (B) is a mixture of various organometallic compounds each having the structure shown in (B).

[0143] I do not want to be bound by theory and believe that including only metal components in the membrane is not good because cracking may occur frequently; carbon materials (A) can serve as a good solute because they can avoid precipitation with metals.

[0144] Without being bound by theory, it is further believed that when manufacturing the metal oxide film of the present invention, the carbon component (some or all derived from carbon material (A)) can be located in the empty space between polymers made of organometallic compounds (B); this can increase the film density (mass density, more preferably atomic number density); and can provide etch resistance.

[0145] Organometallic compounds (B) can be represented by the following formula (B):

[0146]

[0147] M is a metal with a valence state of tetrad (4). Preferably, M is 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; even more preferably Al, Ti and Zr.

[0148] n 71 It is an integer from 1 to 20.

[0149] R 71 R 72 R 73 and R 74 Each is independently selected from the group consisting of a first organic moiety (B)-1, a silicon-containing organic moiety (B)-2 having at least two carbon atoms, a second organic moiety, and any combination thereof. While not wishing to be bound by theory, it is believed that R... 71 and / or R 74 It can help increase the solubility of organometallic compounds (B); R 72 and / or R 73 It can be cleaved and become a further polymerization point.

[0150] In equation (B), R 71 R 72R 73 and R 74 At least one part is selected from the group consisting of:

[0151]

[0152] The first organic part (B)-1 is represented by equation (B-1):

[0153]

[0154] R 75 From C 2-10 Alkylene, C 3-12 Branched alkylene, C 5-12 Cycloalkylene, C containing C=C double bonds 2-10 Alkylene, C containing C=C double bonds 3-12 Branched alkylene groups and C=C double bonds 5-12 Selected from the group consisting of cycloalkylene groups; preferably C 2-10 Alkylene, C containing C=C double bonds 2-10 Alkylene, C 5-12 Cycloalkylene; more preferably C 2-10 Alkylene. In another embodiment of the invention, R 75 It is a C containing a C=C double bond. 2-10 Alkylene. In another embodiment of the invention, R 75 It is C 5-12 Cycloalkylene.

[0155] R 76 It is hydrogen or an alkoxycarbonyl group represented by formula (B)-1-1.

[0156]

[0157] As one embodiment of the present invention, R 76 The alkoxy carbonyl group is preferably C 1-8 Alkoxycarbonyl; more preferably C 2-6 alkoxycarbonyl; further preferred C 3-4 Alkoxycarbonyl group.

[0158] R 77 It is C 1-8 Alkyl; preferably C 2-6 Alkyl; preferably C 3-4 alkyl.

[0159] The silicon-containing organic moiety (B)-2 having at least 2 carbon atoms is represented by formula (B)-2:

[0160]

[0161] R78 and R 79 Each independently from C 1-8 Alkyl, C 3-12 Branched alkyl, C 1-8 Alkoxy, C 3-12 Branched alkoxy groups and C 6-16 Selected from the group consisting of aryl groups; preferably methyl, ethyl, propyl, butyl, and tert-butyl. In another embodiment of the invention, R is preferred. 78 and R 79 Each independently is C 1-8 Alkoxy, C 3-12 Branched alkoxy or C 6-16 Aryl.

[0162] R 80 From C 1-8 Alkyl, C 6-16 Selected from the group consisting of aryl, hydroxyl, and siloxanes having the structure (B)-2-1; preferably methyl, ethyl, propyl, butyl, tert-butyl, and siloxanes having the structure (B)-2-1; more preferably methyl, and siloxanes having the structure (B)-2-1; further preferably methyl:

[0163]

[0164] R 81 From hydrogen, C 1-8 Alkyl groups, substituted C groups with hydroxyl groups 1-8 Alkyl, C 6-116 Selected from the group consisting of aryl groups and silyl moieties having the structure (B)-2-1-1; preferably hydrogen, C 1-8 Alkyl groups and silyl groups having the structure (B)-2-1-1; more preferably hydrogen, C 1-4 Alkyl groups and silyl groups having the structure (B)-2-1-1; more preferably hydrogen and silyl groups having the structure (B)-2-1-1. Another aspect of the invention is R. 81 Selected from C 1-4 Alkyl groups and silyl groups having the structure (B)-2-1-1. Another embodiment of the invention is R. 81 It is methyl or tert-butyl; methyl is preferred.

[0165]

[0166] R 84 and R 85 Each independently from C 1-8 Alkyl, C 3-12 Branched alkyl, C 1-8 Alkoxy, C 3-12 Branched alkoxy groups and C 6-16Selected from the group consisting of aryl groups; preferably methyl, ethyl, propyl, butyl, tert-butyl, methoxy, and phenyl; more preferably methyl, tert-butyl, and phenyl; and even more preferably methyl.

[0167] R 86 From C 1-8 Alkyl and C 6-16 Selected from the group consisting of aryl groups; preferably methyl, ethyl, propyl, butyl, tert-butyl, and phenyl; more preferably methyl, tert-butyl, and phenyl; and even more preferably methyl.

[0168] p 81 This indicates the number of repeating units in the siloxane moiety (B)-2-1. As one embodiment of the invention, p... 81 =1 to 500; preferably 1 to 200; more preferably 1 to 50.

[0169] R 82 and R 83 Each independently from C 1-8 Alkyl, C 3-12 Branched alkyl, C 1-8 Alkoxy, C 3-12 Branched alkoxy groups and C 6-16 Selected from the group consisting of aryl groups; preferably methyl, ethyl, propyl, butyl, tert-butyl, and phenyl; more preferably methyl, tert-butyl, and phenyl; and even more preferably methyl.

[0170] The second organic component is derived from C 2-8 Alkyl, C 2-8 alkyl carboxyl group, C 6-20 Aryl carboxyl, fluorenyl carboxyl, C fluoride 2-8 alkyl carboxyl group, C 2-8 Alkyl sulfonyl, fluorinated C 2-8 Selected from the group consisting of alkylsulfonyl groups and any combination thereof.

[0171] Unintentionally limiting the scope of the invention, exemplary embodiments of the organometallic compound (B) include:

[0172]

[0173]

[0174]

[0175]

[0176]

[0177] In one embodiment of the invention, the mass ratio of the organometallic compound (B) 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.

[0178] Solvent (C)

[0179] 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 solely of an inorganic solvent such as water.

[0180] In a preferred embodiment of the invention, the solvent (C) is selected from the group consisting of aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, monohydric alcohol solvents, polyhydric alcohol solvents, ketone solvents, ether solvents, ester solvents, nitrogen-containing solvents, sulfur-containing solvents, and any combination thereof.

[0181] Examples of solvents (C) include: aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methyl ethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, and isobutylbenzene; and monohydric alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, 2-ethylhexanol, n-nonanol, 2,6-dimethylheptanol-4, n-decanol, cyclohexanol, and benzene. Methanol, benzyl alcohol, diacetone alcohol, and cresol; polyol solvents, such as ethylene glycol, propylene glycol, 1,3-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerol; ketone solvents, such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, trimethyl nonanone, cyclohexanone, cyclopentanone, methyl cyclohexanone, 2,4-pentanedione, acetone-based acetone, acetophenone, and fentanyl ketone; ether solvents, such as diethyl ether, isopropyl 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 diethyl 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, e.g. Examples of solvents include diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-butyl propionate, methyl lactate, ethyl lactate (EL), γ-butyrolactone, n-butyl lactate, n-pentyl 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 these solvents may also be used.

[0182] Specifically, 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 solution storage stability.

[0183] In terms of the coatability and / or solubility of the solute, PGME, PGMEA, EL, and combinations of any two solvents selected therefrom are preferred. Therefore, a combination of PGMEA and PGME is more preferred as the solvent (C).

[0184] 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; even more preferably about 80:20 to about 20:80; and even more preferably about 70:30 to about 30:70.

[0185] The amount of water in solvent (C) is preferably 0.1% by mass or less, more preferably about 0.01% by mass or less. Considering its relationship with another layer or coating, solvent (C) is preferably water-free. In one embodiment of the invention, the amount of water in solvent (C) is preferably 0.00% by mass.

[0186] As one embodiment of the present invention, the mass ratio of 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.

[0187] Surfactant (D)

[0188] The spin-coating composition of the present invention may contain a surfactant (D) which can be used to reduce pinholes or streaks in the coating and to increase the coatability and / or solubility of the composition.

[0189] In one embodiment of the invention, the mass ratio of surfactant (D) to organometallic 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.

[0190] 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; sorbitol fatty acid ester compounds, such as sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol trioleate, and sorbitol tristearate; and polyoxyethylene sorbitol fatty acid ester compounds, such as polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, and polyoxyethylene sorbitol tristearate. Other examples of surfactants include: fluorosurfactants such as EFTOP (trade names) EF301, EF303 and EF352 (Tohkem Products Corporation), MEGAFACE (trade names) F171, F173, R-08, R-30, R-41 and R-2011 (DICC Corporation), Fluorad FC430 and FC431 (Sumitomo 3M), AsahiGuard (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).

[0191] Additives (E)

[0192] The spin-coating composition of the present invention may further comprise an additive (E) in addition to a surfactant (D). Such an additive may be selected from the group consisting of crosslinking agents, acid generators, free radical generators, photopolymerization initiators, agents that enhance adhesion to substrates, and defoamers.

[0193] In one embodiment of the invention, the mass ratio of other additives (E) to organometallic compound (B) is preferably from about 0.05 to about 10% by mass; more preferably from about 0.10 to about 5% by mass; and even more preferably from about 0.10 to about 2% by mass. In one embodiment of the invention, the spin-coating composition is free of (0% by mass) these additives (E).

[0194] Formation of metal oxide films

[0195] The present invention provides a method for manufacturing a metal oxide film, comprising (1) spin coating the above spin coating composition onto a substrate; and (2) heating the spin coating composition to prepare a metal oxide film.

[0196] Although described for clarity, the numbers in parentheses reflect the order of the steps. For example, step (1) is performed before step (2). Unless otherwise explicitly stated, this convention applies to the other steps described herein.

[0197] Preferably, the heating conditions are about 150 to about 400°C and / or about 30 to about 120 seconds. The term "over the substrate" can mean that the applied spin-coating composition can form a coating directly on the substrate (i.e., in direct contact with the substrate), but also includes the possibility of an underlayer being inserted between the substrate and the applied composition. The term "over" hereinafter includes both "direct contact" and "intermediate layer" unless otherwise specified.

[0198] The surface of the substrate on which the composition is disposed can be pretreated, for example, by using a 1,1,1,3,3,3-hexamethyldisilazane solution. The upper 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 composed of multiple substrate layers. In one embodiment of the 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 substrate surface 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.

[0199] Due to the difficult-to-process nature of the organometallic compound (B) component in the composition of the present invention, the resulting metal oxide film exhibits good etch resistance to various plasmas and allows the pattern to be etched and transferred into the substrate.

[0200] Spin-coating compositions are applied using appropriate application methods, such as spin coaters or coating machines.

[0201] As one embodiment of the invention, the heating conditions are selected from a range of about 200 to about 800°C (preferably about 250 to about 750°C, more preferably about 300 to about 700°C, further preferably about 350 to about 650°C, more preferably about 400 to about 600°C), and / or the heating time is selected from a range of about 30 to about 240 seconds (preferably about 40 to about 150 seconds, more preferably about 50 to about 120 seconds, more preferably about 60 to about 90 seconds). Heating can be performed in a single step (stage baking). For example, heating can be two-step heating or three-step heating. For example, preferably, 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.

[0202] Heating can be performed in an air atmosphere, the oxygen concentration of which can be reduced to prevent oxidation of the spin-coated 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 lower (preferably about 100 ppm or lower). The atmosphere can be changed in multiple heating steps. Heating in an N2 atmosphere is one embodiment of the invention.

[0203] In one embodiment of the invention, a spin-coating composition is applied to an underlayer (e.g., a spin-coated carbon layer, a planarization layer) or substrate containing topographical features. As an embodiment of the invention, the formed metal oxide film has a thickness sufficient to cover the topographical features; chemical stripping agents or fluorinated plasma etching can be used to produce filled topographical features, wherein the metal oxide film is flush with the top of the topographical features. The topographical features may have an aspect ratio of about 1 to about 10 and / or a critical dimension (CD) of about 5 nm to about 100 nm.

[0204] In a preferred embodiment of the invention, the metal content of the metal oxide film accounts for about 5 to about 85% by mass of the total mass of the film (more preferably about 10 to about 50% by mass; even more preferably about 15 to about 40% by mass). The metal content in the metal oxide film can be measured by Rutherford backscattering spectroscopy / hydrogen forward scattering (RBS / HFS).

[0205] Formation of resist layer

[0206] The present invention also provides a method for manufacturing a resist coating, comprising (3) applying a resist composition over a metal oxide film manufactured by the above method. The term "over a metal oxide film" can mean that the applied resist composition can form a resist coating directly on the metal oxide film (i.e., in direct contact with the metal oxide film), but also includes the possibility that an intermediate layer (e.g., a bottom anti-reflective coating, BARC) can be inserted between the metal oxide film and the applied resist composition. The intermediate layer can comprise a single layer or multiple layers. Other layers (e.g., a top anti-reflective coating, TARC) can be formed on the resist coating.

[0207] Known methods can be used for application, such as spin coating. The applied resist composition can be baked to remove the solvent from the composition, thereby forming a resist coating. The baking temperature can vary depending on the resist composition to be used, and is preferably from about 70 to about 150°C (more preferably from about 90 to about 150°C, and even more preferably from about 100 to about 140°C). When carried out on a hot plate, it can be carried out for about 10 to about 180 seconds, preferably from about 30 to about 90 seconds, or when carried out in a hot atmosphere (e.g., in a clean oven), it can be carried out for about 1 to about 30 minutes. The thickness of the formed resist coating is preferably from about 0.40 to about 5.00 μm (more preferably from about 0.40 to about 3.00 μm, and even more preferably from about 0.50 to about 2.00 μm).

[0208] Formation of resist patterns

[0209] The present invention provides a method for manufacturing a resist pattern, comprising (4) exposing a resist coating manufactured by the above method to radiation light; (5) developing the exposed resist coating with a developer; and (6) removing the developer from the substrate.

[0210] The resist composition reacts under irradiation through certain masks. Preferably, immersion lithography can be used in ArF exposure. When the resist composition is positive-tonal, the irradiated portion increases its resistance to developer dissolution. The wavelength of the radiation light used for exposure is not limited. Exposure is preferably performed using light with 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 embodiments; KrF excimer laser is more preferred. Using this composition in processes using EUV or immersion ArF is another preferred embodiment of the invention. These wavelengths can vary within ±1%.

[0211] If necessary, post-exposure baking (PEB) can be performed after exposure. The temperature of PEB is selected from about 80 to about 150°C (preferably about 90 to about 140°C), and the heating time of PEB is selected from about 0.3 to about 5 minutes (preferably about 0.5 to about 2 minutes).

[0212] Next, development is performed using a developer. An aqueous solution of approximately 2.38% by mass (accepting ±1% concentration variation) of TMAH is preferably used as the developer for developing the resist pattern. Additives such as surfactants may be added to the developer. The temperature of the developer is typically selected from a range of about 5 to about 50°C (preferably about 25 to about 40°C), and the development time is typically selected from a range of about 10 to about 300 seconds (preferably about 30 to about 90 seconds). Known methods such as immersion development can be used as the development method.

[0213] After development, the developer can be removed by known methods (e.g., liquid replacement or spin drying). As one embodiment of the invention, the resist pattern can be cleaned by replacing the developer with water or a cleaning solution. The substrate can then be dried, for example, by spin drying.

[0214] Treatment substrate

[0215] The present invention provides a method for manufacturing a treated substrate, comprising (7) etching a resist pattern manufactured by the above method, and (8) treating the substrate.

[0216] As mentioned above, a multilayer structure can have a bottom layer and / or intermediate layers. The left-to-right direction in the following list corresponds to the bottom-to-top direction in the multilayer structure (including the resist pattern):

[0217] i. Substrate / Underlayer / Metal oxide film / Intermediate layer / Resist pattern;

[0218] ii. Substrate / Metal oxide film / Intermediate layer / Resist pattern;

[0219] iii. Substrate / metal oxide film / resist pattern; and / or

[0220] iv. Substrate / Underlayer / Metal oxide film / Resist pattern.

[0221] The layer and / or metal oxide film beneath the resist pattern can be patterned using the resist pattern as a mask. Known techniques such as etching (dry etching) can be used for pattern formation.

[0222] For example, an intermediate layer can be etched using a resist pattern as an etching mask, and then the resulting intermediate layer pattern, which serves as an etching mask, can be used to etch the metal oxide film and substrate of the present invention to form a pattern on the substrate. Alternatively, a mask oxide film can be etched using a resist pattern or an interlayer pattern as an etching mask to obtain a metal oxide film pattern. Then, the resulting metal oxide film pattern, which serves as an etching mask, can be used to etch the underlayer, and then the resulting underlayer pattern, which serves as an etching mask, can be used to etch the substrate to form a pattern on the substrate.

[0223] As one implementation, dry etching can be performed using O2, CF4, CHF3, Cl2, or BCl3. O2 or CF4 are preferred gases for organic coatings / layers.

[0224] In one embodiment, a metal oxide film can be obtained by etching a metal oxide film in a gas atmosphere of about 100 to about 10,000 W (more preferably about 200 to about 5,000 W) and / or in any mixture of N2, NF3, O2, rare gases, Cl2, HBr or any of the above.

[0225] The following describes a method for processing a substrate according to the present invention:

[0226] i. Form a metal oxide film as described above.

[0227] ii. Coat BARC onto the metal oxide film,

[0228] iii. Apply the resist composition to the BARC.

[0229] iv. Form the resist pattern as described above,

[0230] v. Etching with fluorinated plasma through the BARC not protected by the resist pattern down to the metal oxide film.

[0231] vi. Etching with chlorine plasma through the unprotected metal oxide film and the resist pattern down to the substrate to produce a patterned metal oxide film.

[0232] vii. Etching with fluorinated plasma into those areas of the substrate not protected by the patterned metal oxide film.

[0233] After the substrate has been treated, patterns and / or layers on or above it can be removed by known methods.

[0234] Device manufacturing

[0235] The present invention provides a method for manufacturing a device, comprising the above-described method for manufacturing a treated substrate. Preferably, the method for manufacturing a device further comprises (9) forming wiring in the treated substrate. Preferably, the substrate is a stepped substrate.

[0236] After the device is formed, if necessary, the substrate is cut into sheets, which are then connected to a lead frame and encapsulated with resin. Preferably, the device is a semiconductor device, a solar cell, an organic light-emitting diode (OLED), or an inorganic light-emitting diode. A preferred embodiment of the device of the present invention is a semiconductor device.

[0237] Example

[0238] The invention will be described below by way of inventive examples. These embodiments are given for illustrative purposes only and are not intended to limit the scope of the invention.

[0239] Reference will now be made to more specific embodiments of this disclosure and experimental results supporting those embodiments. The embodiments given below are provided to illustrate the disclosed subject matter more fully and should not be construed as limiting the disclosed subject matter in any way.

[0240] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed subject matter and the specific embodiments 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 embodiments, is intended to cover modifications and variations of the disclosed subject matter that fall within the scope of any claims and their equivalents.

[0241] Preparation Example 1 of Composition 1 of the Invention

[0242]

[0243] Components A1 (2.0 wt%), B1 (7.9 wt%), and surfactant were added. R-41 (0.1% by mass, DIC) was added to a solvent composed of PGMEA (63% by mass) and PGME (27% by mass). The liquid was mixed with a stirrer for 10 minutes at room temperature. Visual confirmation was made that all solutes were dissolved. The resulting liquid was filtered through a 0.2-micron fluorinated resin filter to obtain composition 1 of the invention.

[0244] The polymers used were obtained in the same manner as described in WO2019 / 121480A1, JP2019-86545A and WO2019 / 048393A1.

[0245] Preparation Examples 2-4 of Invention Compositions 2-4 and Comparative Preparation Examples 1-2 of Comparative Compositions 1-2

[0246] Except for changing the components (using components A2, A3, A4, and cA1) and / or the amounts as described in Table 1, the preparation was carried out in the same manner as in Preparation Example 1 above:

[0247]

[0248] Visual inspection confirmed that all solutes in each composition were dissolved. The resulting liquids were filtered through a 0.2-micron fluorinated resin filter to obtain inventive compositions 2-4 and comparative compositions 1-2.

[0249] The resulting composition has the following characteristics:

[0250] Invention Example Composition 1 A1(2.0) M1(7.9) Invention Example Composition 2 A2(2.0) M1(7.9) Invention Example Composition 3 A3(2.0) M1(7.9) Invention Example Composition 4 A4(2.0) M1(7.9) Comparative composition 1 - M1(9.9) Comparative composition 2 cA1(2.0) M1(7.9)

[0251] Table 1

[0252] In Table 1 and the following tables, the numbers in parentheses represent the mass of each component in the composition.

[0253] Example 1 of metal oxide film formation of composition 1 in the invention

[0254] The inventive composition 1 was spin-coated onto a bare Si wafer at 1,500 rpm using a CLEAN TRACK ACT 12 (Tokyo Electron). The wafer was then baked at 250°C for 60 seconds in an air atmosphere, followed by a further baking at 400°C for 120 seconds in a N2 atmosphere to obtain a metal oxide film.

[0255] Examples of metal oxide film formation of inventive compositions 2-4 and comparative preparation examples 1-2 of comparative compositions 1-2

[0256] Except for changing the composition of the inventive example or the comparative example, the metal oxide film is formed in the same manner as in Example 1.

[0257] Solubility assessment

[0258] The solubility of each composition was assessed by visual verification. The assessment results are shown in Table 2. In Table 2, "A" indicates that the solute in the composition is completely dissolved; "B" indicates that the solute in the composition is not completely dissolved and remains in the solvent.

[0259] Cracking assessment

[0260] The presence of cracks on the surface of the metal oxide films made from each composition was assessed by visual inspection. The assessment results are shown in Table 2. In Table 2, "A" indicates no cracks were detected; "B" indicates cracks were detected. Because comparative compositions 1 and 2 were rated B in the crack assessment, the compositions other than them were used for the following further assessment.

[0261] Measurement of film thickness

[0262] The thickness of each metal oxide film was measured using cross-sectional photographs of the wafer taken with a JSM-7100F (JEOL Ltd). The measurement results are shown in Table 2.

[0263] Evaluation of Ar sputtering resistance

[0264] Metal oxide films were sputtered on wafers using the K-Alpha Plus (Thermo Scientific) device under Ar gas, ion energy of 3 keV, and for 2 minutes.

[0265] For the metal oxide films before and after sputtering, the film thickness was measured as described above. The thickness difference was obtained, and the thickness reduction per unit time was calculated. The evaluation results are shown in Table 2.

[0266] Etching resistance assessment

[0267] Dry etching of metal oxide films on wafers was performed using an NE-5000N (ULVAC) etching apparatus under the following conditions: 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.

[0268] For the metal oxide films before and after etching, the film thickness was measured as described above. The thickness difference was obtained, and the thickness reduction per unit time was calculated. The evaluation results are shown in Table 2.

[0269]

[0270] Table 2

[0271] Although the present invention has been described and illustrated with a certain degree of specificity, it should be understood that this disclosure is by way of example only, and those skilled in the art can make various changes to the conditions and order of steps without departing from the spirit and scope of the invention.

Claims

1. A spin-coating composition comprising a carbon material (A), an organometallic compound (B), and a solvent (C), wherein... (i) The carbon material (A) comprises a unit (A1) represented by formula (A1-1): (A1-1) in Ar 21 It is C 6-50 Aromatic rings, R 21 R 22 and R 23 Each is C independently 6-50 Aromatic rings, hydrogen, or single bonds bonded to another unit. R 24 and R 25 Each is C independently 1-4 Alkyl group, multiple R 24 and / or R 25 They either do not combine with each other, or they combine with each other to form an aromatic ring with the adjacent benzene. n 21 n is an integer between 0 and 1. 24 and n 25 Each is an independent integer between 0 and 3, and R 12 Is it I, Br, or CN? p 11 p is an integer between 0 and 5. 12 q is an integer between 0 and 1. 11 q is an integer between 0 and 5. 12 r is an integer between 0 and 1. 11 s is an integer between 0 and 5. 11 It is an integer between 0 and 5, and The condition is p 11 q 11 and r 11 Do not both be 0; (ii) The solvent (C) contains an organic solvent; and (iii) The mass ratio of carbon material (A) to organometallic compound (B) is 5 to 100 by mass.

2. The spin-coating composition according to claim 1, wherein the carbon material (A) further comprises one or more of the following: (iv) Unit (A2) represented by equation (A2): (A2), Cy 51 It is C 5-30 cyclic hydrocarbon rings; and (v) Element (A3) represented by equation (A3): (A3), in: Ar 61 It is a single key, C 1-6 Alkyl, C 6-12 cycloalkyl or C 6-14 Aryl, Ar 62 It is C 1-6 Alkyl, C 6-12 cycloalkyl or C 6-14 Aryl, R 61 and R 62 Each is C independently 1-6 Alkyl, hydroxyl, halogen, or cyano groups R 63 It is hydrogen, C 1-6 Alkyl or C 6-14 Aryl, When Ar 62 It is C 1-6 Alkyl or C 6-14 Aryl and R 63 It is C 1-6 Alkyl or C 6-14 Aryl 62 and R 63 They either do not connect to each other, or they connect to each other to form a hydrocarbon ring. r 61 and r 62 Each is an independent integer between 0 and 5. Cy enclosed by dashed lines 61 Cy 62 and Cy 63 At least one of the rings is an adjacent aromatic ring Ph 61 Fused aromatic rings, and Cy enclosed by dashed lines 64 Cy 65 and Cy 66 At least one of the rings is an adjacent aromatic ring Ph 62 Fused aromatic rings.

3. The spin-coating composition according to any one of claims 1 to 2, wherein the organometallic compound (B) is an organometallic complex containing a hydrolyzable group, a hydrolysis product of an organometallic complex containing a hydrolyzable group, a hydrolysis-condensation product of an organometallic complex containing a hydrolyzable group, or any combination thereof.

4. The spin-coating composition according to any one of claims 1 to 3, wherein the organometallic compound (B) is represented by the following formula (B); (B) in: M is a metal with a valence state of tetrad (4) and is at least one selected from the group consisting of Zr, Ta, Hf, Ti, Sn, Pb, Nb, Mo, Ge and W. n 71 It is the number from 1 to 20, and R 71 R 72 R 73 and R 74 Each independently selects from the following groups: (a) The first organic part (B)-1, represented by equation (B)-1: (B)-1, in: R 75 From C 2-10 Alkylene, C 3-12 Branched alkylene, C 5-12 Cycloalkylene, C containing C=C double bonds 2-10 Alkylene, C containing C=C double bond 3-12 Branched alkylene groups and C=C double bonds 5-12 Selected from the group consisting of cycloalkylene groups, and R 76 It is hydrogen or an alkoxy carbonyl group represented by formula (B)-1-1: (B)-1-1 Where R 77 It is C 1-8 alkyl; (b) A silicon-containing organic moiety (B)-2 having at least two carbon atoms, represented by formula (B)-2: (B)-2, in: R 78 and R 79 Each independently from C 1-8 Alkyl, C 3-12 Branched alkyl, C 1-8 Alkoxy, C 3-12 Branched alkoxy groups and C 6-16 Select from the group consisting of aryl groups; R 80 From C 1-8 Alkyl, C 6-16 Choose from the group consisting of aryl, hydroxyl, and siloxanes having the structure (B)-2-1: (B)-2-1, in: R 81 From hydrogen, C 1-8 Alkyl groups, substituted C groups with hydroxyl groups 1-8 Alkyl, C 6-16 Selected from the group consisting of aryl groups and silyl moieties having the structure (B)-2-1-1: (B)-2-1-1 Where: R 84 and R 85 Each independently from C 1-8 Alkyl, C 3-12 Branched alkyl, C 1-8 Alkoxy, C 3-12 Branched alkoxy groups and C 6-16 Selected from the group consisting of aryl groups; R 86 From C 1-8 Alkyl and C 6-16 Select from the group consisting of aryl groups; R 82 and R 83 Each independently from C 1-8 Alkyl, C 3-12 Branched alkyl, C 1-8 Alkoxy, C 3-12 Branched alkoxy groups and C 6-16 Selected from the group consisting of aryl groups; while p 81 Indicates the number of repeating units in the siloxane moiety (B)-2-1; and (c) The second organic part, which is derived from C 2-8 Alkyl, C 2-8 alkyl carboxyl group, C 6-20 Aryl carboxyl, fluorenyl carboxyl, C fluoride 2-8 alkyl carboxyl group, C 2-8 Alkyl sulfonyl, fluorinated C 2-8 Alkyl sulfonyl groups, and any combination thereof, are selected from the group consisting of alkyl sulfonyl groups and any of these groups. (d) Any combination of (a), (b) and (c).

5. The spin-coating composition according to any one of claims 1 to 4, wherein the solvent (C) is selected from the group consisting of aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, monohydric alcohol solvents, polyhydric alcohol solvents, ketone solvents, ether solvents, ester solvents, nitrogen-containing solvents, sulfur-containing solvents, and any combination thereof.

6. The spin-coating composition according to any one of claims 1 to 5 further comprises a surfactant (D).

7. The spin-coating composition according to any one of claims 1 to 6 further comprises another additive (E) selected from the group consisting of crosslinking agents, acid generators, free radical generators, photopolymerization initiators, agents that enhance adhesion to substrates, defoamers, and combinations thereof.

8. The spin-coating composition according to any one of claims 1 to 7, wherein the carbon material (A) has a molecular weight of 500 to 4,000.

9. The spin-coating composition according to any one of claims 1 to 8, wherein the mass ratio of the organometallic compound (B) to the total mass of the spin-coating composition is 5 to 100% by mass. in, The mass ratio of solvent (C) to the total mass of the spin-coating composition is 5% to 100% by mass. and The mass ratio of surfactant (D) to organometallic compound (B) is 5 to 100 by mass.

10. A spin-coated metal hard mask composition, comprising the spin-coating composition according to any one of claims 1 to 9.

11. A method for manufacturing a metal oxide film, comprising: (1) Spin-coating the spin-coating composition according to any one of claims 1 to 9 onto a substrate; and (2) The spin-coating composition is heated to prepare a metal oxide film, wherein the heating is performed at 200 to 800 °C and / or for 30 to 240 seconds.

12. The method according to claim 11, wherein the metal content of the metal oxide film is 10 to 85% of the total mass of the film.

13. A method for manufacturing a resist coating, comprising: (3) Applying a resist composition over a metal oxide film manufactured by any one of claims 11 to 12.

14. A method for manufacturing a resist pattern, comprising: (4) Expose the resist coating manufactured according to the method of claim 13 to radiation light; (5) Develop the exposed resist coating with a developer; and (6) Remove the developer from the substrate.

15. A method of manufacturing a treated substrate, comprising: (7) Etching the resist pattern manufactured by the method of claim 14; and (8) Treat the substrate.

16. A method of manufacturing a device, comprising: (9) Forming wiring in a treated substrate manufactured by the method of claim 15, wherein the substrate is a stepped substrate.

17. The spin-coating composition according to claim 1, wherein the spin-coating composition is substantially composed of a carbon material (A), an organometallic compound (B), and a solvent (C).

18. The spin-coating composition according to claim 1, wherein the spin-coating composition is substantially composed of a carbon material (A), an organometallic compound (B), a solvent (C), and a surfactant (D).

19. The spin-coating composition according to claim 1, wherein the spin-coating composition is substantially composed of a carbon material (A), an organometallic compound (B), a solvent (C), a surfactant (D), and an additive (E), said additive (E) being selected from the group consisting of crosslinking agents, acid generators, free radical generators, photopolymerization initiators, agents that enhance adhesion to substrates, defoamers, and combinations thereof.

20. The spin-coating composition according to claim 1, wherein the spin-coating composition comprises a carbon material (A), an organometallic compound (B), and a solvent (C).

21. The spin-coating composition according to claim 1, wherein the spin-coating composition comprises a carbon material (A), an organometallic compound (B), a solvent (C), and a surfactant (D).

22. The spin-coating composition according to claim 1, wherein the spin-coating composition comprises a carbon material (A), an organometallic compound (B), a solvent (C), a surfactant (D), and an additive (E), said additive (E) being selected from the group consisting of crosslinking agents, acid generators, free radical generators, photopolymerization initiators, agents that enhance adhesion to substrates, defoamers, and combinations thereof.

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