Composition, manufacturing method of cured film, manufacturing method of electronic element, and use of composition

Abstract

To provide a composition comprising a polysilazane. A manufacturing method according to the present invention may be used with a nanotechnology process to manufacture applications of semiconductor devices and display devices. For example, liquid crystals, quantum dots, or OLED displays formed on a substrate can be manufactured, and these may be controlled by a semiconductor. The preferred performance of the manufacturing method according to the present invention may be supported by at least one of the properties of high-performance materials and advanced materials. A composition comprising a polysilazane, at least one of a unit A represented by Formula (1A) or a unit B represented by Formula (1B), and a solvent.

Description

Foreignfiling text P24-235- 1 -[DESCRIPTION][Title of Invention]COMPOSITION, MANUFACTURING METHOD OF CURED FILM, MANUFACTURING METHOD OF ELECTRONIC ELEMENT, AND USE OF 5 COMPOSITION[Technical Field]

[0001] The present invention relates to a composition, a manufacturing method of a cured film, a manufacturing method of an electronic element, and use of the composition.[Background Art]

[0002] In semiconductor manufacturing, it is known that a composition containing a polysilazane is applied to a surface of a substrate to form a 15 siliceous film. An electronic device, in particular, a semiconductor device is formed of thin films such as a semiconductor film, an insulating film, and a conductive film. The siliceous film is used as a planarizing film, an etching mask in processing an insulating film, or a sacrificial film in manufacturing a metal gate or the like.20

[0003] Patent Literature 1 describes a coating composition containing perhydropolysilazane and a solvent.[Citation List][Patent Literature]

[0004] [PTL 1] JP 2011-142207 A[Summary of Invention][Technical Problem]

[0005] The inventors have recognized that one or more problems30 regarding a composition containing a polysilazane are still required to be improved. Examples thereof include the following.When Edge Bead Removal (EBR) is performed, a protrusion of theForeignfiling text P24-235-2 -composition is formed from the outer edge of the substrate toward the outside of the substrate; when EBR is performed, a protrusion of the composition is formed from the outer edge of the substrate toward the outside of the substrate, and the protrusion comes into contact with the arm 5 to generate dust; striation occurs on the surface of the coating film formed from the composition; striation occurs on the surface of the cured film; the composition has low storage stability; the cured film has high dielectric constant; the cured film has low film hardness; the cured film has poor electrical properties; a long time is required for curing; shrinkage occurs due to film curing; peeling occurs due to film curing; cracks are generated in the cured film; the cured film has low insulation properties; the cured film has high flat band voltage; the cured film has low chemical resistance; the cured film has high wet etching rate; the cured film has low heat resistance; the cured film has low acid resistance; voids are generated in the cured 15 film; adhesion to a wiring material and a silica film is low; the yield of the composition is low; and the yield of the cured film is low.

[0006] The present invention has been made on the basis of the technical background as described above, and provides a composition, a manufacturing method of a cured film, a manufacturing method of an 20 electronic element, and use of the composition.[Solution to Problem]

[0007] The composition according to one embodiment comprises:a polysilazane;a compound A comprising at least one of a unit A represented by Formula (1A) and a unit B represented by Formula (1B); anda solvent:[Chem. 1]Foreignfiling text P24-235(1A)5whereinR11is C 1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably linear C1-20 alkyl, branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, or cyclic C3-20 alkenyl; more preferably linear C1-15 alkyl or branched 10C3-15 alkyl; still more preferably linear C1-10 alkyl or branched C3-10 alkyl; and even more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl; andone or more non-adjacent -CH2- in R11are each independently optionally substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or -C≡C-; and [Chem. 2]20whereinR12is C 1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably linear C1-20 alkyl, branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, or cyclic C3-20 alkenyl; more preferably linear C1-15 alkyl or branched C3-15 alkyl; still more preferably linear C1-10 alkyl or branched C3-10 alkyl; and even more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl; R13is H, C 1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably H, linear C1-20 alkyl, branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, or cyclic C3-20 alkenyl; more preferably H, linear C1-15 alkyl, or 30branched C3-15 alkyl; still more preferably H, linear C1-10 alkyl, or branched C3-10 alkyl; and even more preferably H, methyl, ethyl, n-propyl, isopropyl,Foreignfiling text P24-235- 4 -n-butyl, or tert-butyl; andone or more non-adjacent -CH2- in R12and R13are each independently optionally substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or -C≡C-.5

[0008] The manufacturing method of a cured film according to one embodiment comprises steps (a) and (b-1) below:(a) applying the composition above a substrate to form a coating film, preferably the composition is applied above the substrate by spin coating at 200 to 4000 RPM for 0.1 to 100 seconds, more preferably at 300 to 3500 RPM for 0.3 to 70 seconds, and still more preferably at 500 to 3000 RPM for 0.5 to 40 seconds; and(b-1) heating the coating film,preferably the coating film is heated at 30 to 1100°C, more preferably at 50 to 1000°C, and still more preferably at 100 to 900°C; and preferably for 30 15 seconds to 600 minutes, more preferably for 1 to 400 minutes, still more preferably for 1.5 to 200 minutes, and even more preferably for 2 to 150 minutes.

[0009] The manufacturing method of an electronic element according to one embodiment comprises the above-mentioned method.20

[0010] The use of the composition according to one embodiment is for forming a cured film of the composition above a substrate.[Advantageous Effects of the Invention]

[0011] According to the present invention, one or more of effects set forth below can be desired.When EBR is performed, a protrusion of the composition is inhibited from being formed from the outer edge of the substrate toward the outside of the substrate; formation of a protrusion of the composition from the outer edge of the substrate toward the outside of the substrate due to EBR is inhibited, and the protrusion is prevented from coming into contact with the arm to 30 generate dust; occurrence of striation on the surface of the coating film formed from the composition can be inhibited; occurrence of striation on the surface of the cured film can be inhibited; the composition has higherForeignfiling text P24-235- 5 -storage stability; the cured film has lower dielectric constant; the cured film has higher film hardness; the cured film has improved electrical properties; the time required for curing is shortened; shrinkage due to film curing is inhibited; peeling due to film curing is inhibited; generation of cracks in the 5 cured film is inhibited; the cured film has higher insulation properties; the cured film has lower flat band voltage; the cured film has higher chemical resistance; the cured film has lower wet etching rate; the cured film has higher heat resistance; the cured film has higher acid resistance; generation of voids in the cured film is inhibited; adhesion to a wiring material and a silica film is increased; the yield of the composition is improved; and the yield of the cured film is improved.

[0012] The above description is not to be construed as disclosing all embodiments of the present invention and all advantages related to the present invention.15[Brief Description of Drawings]

[0013] [Fig. 1] FIG. 1 is an observation image of Example 1 for EBR evaluation.[Fig. 2] FIG. 2 is an observation image of Comparative Example 1 20 for EBR evaluation.[Description of Embodiments]

[0014] Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments, and various applications can be made within the spirit and scope of the present invention.

[0015] [Definitions]In the present invention, unless otherwise specifically stated, terms and symbols follow the definitions or examples described in this paragraph. 30 The singular form includes the plural form, and the terms “a” and “the” mean “at least one.” An element of a certain concept can be expressed as a plurality of types, and when an amount thereof (for example, mass% orForeignfiling text P24-235- 6 -mol%) is described, the amount means a sum of the amounts of the plurality of types.The term “and / or” includes all combinations of elements, and also includes the use of a single element.5 When a numerical range is expressed using “to” or the range includes values at both ends, and the units are the same. For example, 5 to 25 mol% is 5 mol% or more and 25 mol% or less.Notations such as “Cx-y”, “Cx to Cy” and “Cx” refer to the number of carbon atoms in a molecule or substituent. For example, C1-6 alkyl is an alkyl chain having 1 or more and 6 or less carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).As the unit of temperature, Celsius is used. For example, “20 degrees” means “20 degrees Celsius”.An “additive” means a compound itself having a relevant function. For 15 example, in the case of a base generator, the additive means a compound itself that generates a base. There may also be an embodiment in which the compound is dissolved or dispersed in a solvent and added to the composition.By “applied above a substrate” is meant that the composition of the present 20 invention may be applied directly onto the substrate or via one or more other layers. Examples of the other layers include an SOC (spin on carbon) and an adhesion enhancing film.The “polysilazane” means a polymer compound having a basic skeleton - [N-Si]- in which silicon atoms and nitrogen atoms are alternately arranged. The polysilazane also encompasses polymer compounds comprising, in addition to the basic skeleton, a siloxane bond (Si-O), a silicon-carbon bond (Si-C), or a combination thereof in the molecule. A polymer compound in which a part of the basic skeleton of a polysilazane is substituted with a siloxane bond is also called polysiloxazane. A polymer compound in which 30 a part of the basic skeleton of a polysilazane is substituted with a siliconcarbon bond is also called polycarbosilazane.The “striation” means a pattern of irregular lines, stripes, spots, and the likeForeignfiling text P24-235- 7 -visible or observable by an optical measuring device, which occurs when the composition according to the present invention is applied above a substrate. In the present invention, the striation is considered to be caused by convection of the composition that occurs during volatilization of the 5 solvent. For example, when a coating liquid is applied to a circular substrate using a spin coater, the striation occurs in a spot shape at the center of the substrate due to a small centrifugal force applied to the coating liquid, and near the outer periphery of the substrate, the striation occurs in a line or stripe shape extending toward the outer periphery.The “EBR” means a treatment for removing an excess composition near the outer periphery of a substrate having a coating film thereabove. Examples of a specific treatment method include a method of discharging, while rotating the substrate having the coating film thereabove, a liquid agent such as a thinner to the outer periphery of the substrate.15 The “solid content” means all components contained in the composition excluding the solvent.The “solid content concentration” means a value obtained by dividing the total mass of all components contained in the composition excluding the solvent by the mass of the entire composition.20

[0016] < Composition>The composition according to the present invention (hereinafter sometimes referred to as a “composition”) comprises:a polysilazane;a compound A comprising at least one of a unit A represented by Formula (1A) and a unit B represented by Formula (1B); anda solvent.[Chem. 3]30Foreignfiling text P24-2355[Chem. 4]

[0017] The composition is preferably a film forming composition, more preferably an insulating film forming composition, and still more preferably an interlayer insulating film forming composition.15

[0018] (Polysilazane)In a preferred embodiment of the present invention, the polysilazane comprises a unit represented by Formula (2).[Chem. 5]20R21, R22, and R23are each independently a single bond, H, C1-20 alkyl, C2-20 alkenyl, C6-20 aryl, or a linking group represented by any one of Formulae (a), (b), and (c); preferably a single bond, H, linear C1-20 alkyl, branched C3- 20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, cyclic C3-20 alkenyl, or a linking group represented by any one of Formulae (a), 30 (b), and (c); more preferably a single bond, H, linear C1-10 alkyl, branched C3-10 alkyl, or a linking group represented by any one of Formulae (a), (b), and (c); still more preferably a single bond, H, methyl, ethyl, n-propyl,Foreignfiling text P24-235isopropyl, n-butyl, tert-butyl, or a linking group represented by any one of Formulae (a), (b), and (c); and even more preferably a single bond, H, or a linking group represented by any one of Formulae (a), (b), and (c).When R21, R22, and R23are each independently alkyl, alkenyl, or aryl, one 5 or more non-adjacent -CH2- in R21, R22, and R23are each independently optionally substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or -C≡C-. When R21, R22, and R23are each independently alkyl, alkenyl, or aryl, preferably, -CH2- in R21, R22, and R23is not substituted with any group. R21and R22, when being each independently a single bond, are each 10independently bonded to N contained in another unit represented by Formula (2).R23, when being a single bond, is bonded to Si contained in another unit represented by Formula (2).[Chem. 6]( Ra)3-na — La— Si — (-1?)- (a)20( R^-ncl ( R=2)3-nc2 — (Lcl)— 7 Si - 0 - Si - {-Lc2}— -' 'nclx znc2Ra, Rb1, Rb2, Rc1, and Rc2are each independently H, C1-6 alkyl, C2-6 alkenyl, or C6-12 aryl; preferably H, linear C1-6 alkyl, branched C3-6 alkyl, cyclic C3-6 alkyl, linear C2-6 alkenyl, branched C3-6 alkenyl, or cyclic C3-6 alkenyl; and more preferably H, methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl.30La, Lb1, Lb2, Lc1, and Lc2are each independently C1-8 alkylene or C6-14arylene; preferably linear C1-8 alkylene, branched C3-8 alkylene, or cyclic C3-Foreignfiling text P24-235- 10 -8 alkylene; more preferably linear C1-5 alkylene or branched C3-5 alkylene; and still more preferably methylene, ethylene, linear propylene, or branched propylene.One or more non-adjacent -CH2- in La, Lb1, Lb2, Lc1, and Lc2are each 5 independently optionally substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH- or -C≡C-. Preferably, -CH2- in La, Lb1, Lb2, Lc1, and Lc2is not substituted with any group.na is 1 to 3, and preferably 1.nb1 and nb2 are each independently 1 or 2, preferably 1.nc1 and nc2 are each independently 1 to 3, preferably 1.p and q are each independently 1 to 3, preferably 1.Among bonds of the linking group represented by Formula (a), (b), or (c), a bond that is not bonded to Si contained in the unit represented by Formula (2) is bonded to Si contained in another unit represented by Formula (2).15

[0019] Specific examples of the linking group represented by Formula (a) are as follows.2030Foreignfiling text_P24-235- 11 - [Chem. 7]I CH, C; H5CH, H, H, I H, H, H; H; I H, H, — C^-C‘-Si— C -c - — c -c -Si— C -c‘- 5 I I C; Hj CH;CH,1‘ CH, i " CH; CH; H, H, H, | H, H, H, — C -C -C -Si— C -C -C - I CH, i “ CH, hCH2C2H2— CH2~ CH,~ Si — CH2— CH2— -CH -CH2-Si-CH2-CH2- CH3C2H3CH3C6H5- CH2- CH2- Si- CH2— CH2- - CH2- CH2~ Si-CH2- CH2- CH2CH2CH; CH2CH3C3HS-CH2-CH -CH -Si-CH2-CH2-CH - -CH2-CH - CH -Si-CH2-CH2-CH2- CH3C3H5CH3C6H5-CH2-CH2-CH -Si-CH2-CH2-CH2- -CH2-CH2- CH2-Si-CH2-CH2- CH - CH; CH; CH; CH; CH; CH;I I 30Foreignfiling text P24-235- 12 -

[0020] Specific examples of the linking group represented by Formula (b) are as follows.[Chem. 8]H2 H2 H2H2 H2 5 — c -c C -c - H->? Si, SixH2CH’X ZCH2 \XCH2-CH2— Q -Q C C-C - Si Si H2H2H2- CH2- CH2XCH2>’ CH2— CHHx XCH2-CH2- Hx^CH2^ ^CH—CH Si Si Si Si -CH2-CH2X SCH / ^CH2-CH2- -CH2-CH2X'■'CHZXHCH3^XCH2 X.XCH2-CH2- Si Six-CH2-CH2X XCH2X XCH315

[0021] Specific examples of the linking group represented by Formula (c) are as follows.[Chem. 9]H2H2I^3H3H2H220 — c -c — si-o-si— c -c - CH2CH2CH3CH3CH2CH2— CH2— CH2~ Si — O-Si -CH2- CH2-I I CH3CH3

[0022] Interpretation of Formula (2) will be described in detail using the following example of a partial structure of the polysilazane.30Foreignfiling text P24-235- 13 -5

[0023] As for the structure in the dashed frame (A), in Formula (2), R21can be read as H, and R22and R23can each be read as a single bond. R22is a single bond bonded to N contained in another unit represented by Formula (2), and R23is a single bond bonded to Si contained in another unit represented by Formula (2).

[0024] As for the structure in the dashed frame (B), in Formula (2), R21can be read as a single bond, R22can be read as a linking group represented by Formula (a), and R23can be read as H. R21is a single bond bonded to N 30 contained in another unit represented by Formula (2).Furthermore, in Formula (a), Racan be read as C2alkyl (ethyl), Lacan beForeignfiling text P24-235- 14 -read as C2alkylene (ethylene), and na can be read as 1. The bond at the lowermost part of the structure in the dashed frame (B) corresponds to, among bonds of the linking group represented by Formula (a), a bond that is not bonded to Si contained in the unit represented by Formula (2). The 5 bond is bonded to Si contained in another unit represented by Formula (2).

[0025] The polysilazane may comprise a unit not represented by Formula (2) (hereinafter, the unit is referred to as a “different unit I”).When the number of units represented by Formula (2) is represented by nn and the total number of all the units contained in the polysilazane is represented by np, nn / np is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more.It is also a preferred embodiment of the present invention that nn / np is 100%, that is, the polysilazane does not contain the different unit I.The “unit” as used herein does not include a terminal group.15

[0026] The polysilazane may comprise only one type of the unit represented by Formula (2), or may comprise two or more types thereof. In a case where a plurality of Raare contained in one unit, Ramay be of only one type or two or more types. It is preferable that all of Rain one unit are identical. The same applies to Rb1, Rb2, Rc1, and Rc2.20

[0027] The polysilazane preferably comprises at least one terminal group represented by Formula (2-1), and more preferably all terminal groups of the polysilazane are represented by Formula (2-1).-SiR24R25R26(2-1)R24, R25, and R26are each independently H, OH, C1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably H, OH, linear C1-20 alkyl, branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, cyclic C3-20 alkenyl, or C6-20 aryl; more preferably H, OH, linear C1-15 alkyl, or branched C3-15 alkyl; still more preferably H, OH, linear C1-10 alkyl, or branched C3-10 alkyl; and even more preferably H, OH, or methyl.30 One or more non-adjacent -CH2- in R24, R25, and R26are each independently optionally substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -Foreignfiling text P24-235- 15 -O-CO-O-, or -C = C-. Preferably, -CH2- in R24, R25, and R26is not substituted with any group.When R24, R25, and R26are each independently alkyl, alkenyl, or aryl, one or more H in R24, R25, and R26are each independently optionally substituted 5with -OH, -COOH, or -SO2H. Preferably, H in R24, R25, and R26is not substituted with any group.

[0028] In a preferred aspect of the present invention, the polysilazane is polyperhydropolysilazane (PHPS). PHPS is a polysilazane consisting only of Si, N, and H. In PHPS, apart from the Si-N bond, all elements bonded to Si or N are H.PHPS is substantially free of other elements such as carbon or oxygen, and preferably free of them. PHPS comprises a chain structure, a cyclic structure, or a crosslinked structure, and preferably comprises a chain structure.15

[0029] In a preferred embodiment of the present invention, the polysilazane is PHPS, and comprises a unit represented by Formula (2) in which R21, R22, and R23are H.In a still more preferred embodiment of the present invention, the polysilazane is PHPS, and comprises a unit represented by Formula (2) in 20which R21, R22, and R23are H, and a terminal group represented by Formula (2-1) in which R24, R25, and R26are H.

[0030] It is considered that when the polysilazane is PHPS, the composition can be more uniformly applied above the substrate, and the cured film has improved heat resistance.

[0031] The mass average molecular weight (Mw) of the polysilazane is preferably 1000 to 30000, more preferably 1200 to 28000, and still more preferably 1500 to 25000.In the present invention, the Mw is measured by gel permeation chromatography (GPC) using polystyrene standards. The measurement is 30carried out under measurement conditions of a flow rate of 0.5 mL / min and a column temperature of 40°C using monodisperse polystyrene as aForeignfiling text P24-235- 16 -standard sample and tetrahydrofuran as a developing solvent, and then the Mw is calculated as a relative molecular weight to the standard sample. It is considered that when the Mw of the polysilazane is 1000 or more, the coating film of the composition applied above the substrate has improved 5 mechanical strength. It is considered that when the Mw of the polysilazane is 30000 or less, the composition can be more uniformly applied above the substrate.

[0032] The content of the polysilazane is preferably 5 to 50 mass%, more preferably 8 to 45 mass%, and still more preferably 10 to 40 mass% with respect to the total mass of the composition.

[0033] It is considered that when the content of the polysilazane is 5 mass% or more with respect to the total mass of the composition, the coating film of the composition applied above the substrate has improved mechanical strength. It is considered that when the content of the15 polysilazane is 50 mass% or less with respect to the total mass of the composition, the composition can be more uniformly applied above the substrate.

[0034] (Compound A)The compound A comprises at least one of a unit A represented by20 Formula (1 A) or a unit B represented by Formula (1B).[Chem. 11]R11is C 1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably linear C1-20 alkyl, branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, or cyclic C3-20 alkenyl; more preferably linear C1-15 alkyl or branched 30C3-15 alkyl; still more preferably linear C1-10 alkyl or branched C3-10 alkyl; and even more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl.Foreignfiling text P24-235- 17 -One or more non-adjacent -CH2- in R11are each independently optionally substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or -C = C-.Preferably, -CH2- in R11is not substituted with any group.[Chem. 12]5R12is C 1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably linear C1-20 alkyl, branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, or cyclic C3-20 alkenyl; more preferably linear C1-15 alkyl or branched C3-15 alkyl; still more preferably linear C1-10 alkyl or branched C3-10 alkyl; and even more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl.15R13is H, C 1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably H, linear C1-20 alkyl, branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, or cyclic C3-20 alkenyl; more preferably H, linear C1-15 alkyl, or branched C3-15 alkyl; still more preferably H, linear C1-10 alkyl, or branched C3-10 alkyl; and even more preferably H, methyl, ethyl, n-propyl, isopropyl, 20n-butyl, or tert-butyl.One or more non-adjacent -CH2- in R12and R13are each independently optionally substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or -C = C-. Preferably, -CH2- in R12and R13is not substituted with any group.

[0035] When a composition comprising a polysilazane and a solvent is applied above a substrate and EBR is performed, a protrusion of the composition (hereinafter simply referred to as a “protrusion”) may be formed from the outer edge of the substrate toward the outside of the substrate. When a coating film or a cured film is formed above a substrate 30 using a composition comprising a polysilazane and a solvent, striation (hereinafter simply referred to as “striation”) may occur on the surface of the coating film or the cured film.Foreignfiling text P24-235- 18 -Since the composition according to the present invention comprises the compound A, it is considered that the solid content in the composition has lower solubility in a liquid agent such as a thinner used in EBR. Therefore, it is considered that the formation of the protrusion is inhibited when the EBR 5 is performed. In addition, since the composition according to the present invention comprises the compound A, it is considered that convection of the composition that occurs during volatilization of the solvent is inhibited (hereinafter referred to as “convection inhibition”), and thus the occurrence of striation is inhibited.

[0036] In a preferred embodiment of the present invention, the compound A comprises a unit B represented by Formula (1B), in which R12and R13are methyl.When the compound A comprises a unit B represented by Formula (1B), in which R12and R13are methyl, it is considered that the compound A has a 15 linear structure with fewer branches. Therefore, it is considered that the effective area of the convection inhibition expands linearly from the compound A (hereinafter referred to as “linear expansion of the effect”), and thus broadens, whereby the occurrence of striation is further inhibited.

[0037] The meaning of Oo.s in Formula (1 A) and Formula (1B) will be 20 described herein in detail. The structure of the compound A has, as a basic skeleton, a network in which Si and O are continuously bonded. An example of the network is illustrated below.[Chem. 13]30Foreignfiling text P24-235- 19 -5In the above network, one 0 atom is bonded to two Si atoms. Therefore, the repeating unit indicated by the dashed line cannot be expressed as a 15 unit containing a Si-0 bond. Therefore, the unit is expressed as in Formula (1 A) using the expression Oo.s for convenience. The same applies to Formula (1B).

[0038] The compound A may comprise only one type of the unit represented by Formula (1A), or may comprise two or more types thereof.20 The same applies to the unit represented by Formula (1B).

[0039] The compound A may comprise a unit not represented by either of Formula (1 A) and Formula (1B) (hereinafter, the unit is referred to as a “different unit II”).When the total number of the units represented by Formula (1A) and the units represented by Formula (1B) is represented by nA + B and the total number of all the units contained in the compound A is represented by ntotai, nA + B / ntotalis preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more.It is also a preferred embodiment of the present invention that nA + B / ntotalis 30 100%, that is, the compound A does not contain the different unit II.The “unit” as used herein does not include a terminal group.Foreignfiling text P24-235- 20 -

[0040] The compound A preferably comprises at least one terminal group represented by Formula (3), and preferably all terminal groups of the compound (A) are represented by Formula (3).-SiR31R32R33(3)5 R31is C 1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably linear C1-20 alkyl, branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, or cyclic C3-20 alkenyl; more preferably linear C1-15 alkyl or branched C3-15 alkyl; still more preferably linear C1-10 alkyl or branched C3-10 alkyl; and even more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl. R32is H, C 1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably H, linear C1-20 alkyl, branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, or cyclic C3-20 alkenyl; more preferably H, linear C1-15 alkyl, or branched C3-15 alkyl; still more preferably H, linear C1-10 alkyl, or branched C3-10 alkyl; and even more preferably H, methyl, ethyl, n-propyl, isopropyl, 15 n-butyl, or tert-butyl.R33is H, OH, C1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably H, OH, linear C1-20 alkyl, branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, or cyclic C3-20 alkenyl; more preferably H, OH, linear C1-15 alkyl, or branched C3-15 alkyl; still more preferably H, OH, linear C1-10 20 alkyl, or branched C3-10 alkyl; and even more preferably H, OH, or methyl.One or more non-adjacent -CH2- in R31, R32, and R33are each independently optionally substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, - O-CO-O-, or -C = C-. Preferably, -CH2- in R31, R32, and R33is not substituted with any group.When R33is alkyl, alkenyl, or aryl, one or more H in R33are optionally substituted with -OH, -COOH, or -SO2H. Preferably, H in R33is not substituted with any group.

[0041] In a preferred embodiment of the present invention, the compound A comprises at least one terminal group represented by Formula (3), in 30which R31, R32, and R33are methyl.When the compound A comprises at least one terminal group representedForeignfiling text P24-235- 21 -by Formula (3), in which R31, R32, and R33are methyl, it is considered that the change in interfacial tension caused by the interaction between the terminal group and the polysilazane can be further suppressed (hereinafter referred to as “stabilization of interfacial tension”). Therefore, it is5 considered that the occurrence of striation is further inhibited.

[0042] In a more preferred embodiment of the present invention, the compound A comprises a unit B represented by Formula (1B), in which R12and R13are methyl, and further comprises at least one terminal group represented by Formula (3), in which R31, R32, and R33are methyl.When the compound A comprises a unit B represented by Formula (1B), in which R12and R13are methyl, and at least one terminal group represented by Formula (3), in which R31, R32, and R33are methyl, in addition to the linear expansion of the effect, and stabilization of interfacial tension, it is considered that the occurrence of striation is further inhibited, for the 15 following reasons.The fact that the terminal groups of the compound A and the functional groups of its side chains are identical can further suppress the difference in interfacial tension within the film, thereby contributing to the additional inhibition of striation.20

[0043] The compound A may comprise only one type of the terminal group represented by Formula (3), or may comprise two or more types thereof.

[0044] In a preferred aspect of the present invention, the compound A comprises the unit represented by Formula (1A) and at least one terminal group represented by Formula (3), and R32and R33are each independently C1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably linear C1-20 alkyl, branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, or cyclic C3-20 alkenyl; more preferably linear C1-15 alkyl or branched C3-15 alkyl; still more preferably linear C1-10 alkyl or branched C3-10 alkyl; and even more preferably methyl.30

[0045] In a preferred aspect of the present invention, the compound A comprises the unit represented by Formula (1B) and at least one terminal group represented by Formula (3), and at least one of R32or R33is H.Foreignfiling text P24-235- 22 -

[0046] The Mw of the compound A is preferably 100 to 80000, more preferably 300 to 60000, still more preferably 500 to 50000, even more preferably 1000 to 48000, and particularly preferably from 5000 to 45000. In another preferred embodiment of the present invention, the Mw of the 5 compound A is preferably 100 to 100000, more preferably 1500 to 98000, still more preferably 3000 to 95000, even more preferably 3500 to 90000.

[0047] It is considered that when the Mw of the compound A is 100 or more, formation of the protrusion and / or the occurrence of striation can be further inhibited. It is considered that when the Mw of the compound A is 80000 or less, the composition can be more uniformly applied above the substrate.

[0048] In the compound A, the ratio of the total number of units A and units B to the number of terminal groups is preferably 1.2 to 2.5, more preferably 1.3 to 2.4, still more preferably 1.4 to 2.0, and even more preferably 1.5 to 15 1.7.

[0049] The surface tension of the compound A is preferably 15 to 30 mN / m, more preferably 18 to 27 mN / m, still more preferably 19 to 25 mN / m, and even more preferably 20 to 22 mN / m.In the present invention, the surface tension of the compound A is20 determined as follows.A dibutyl ether solution of the compound A is prepared so that the solution has a concentration of the compound A of 5 mass%. The solution is uniformly applied onto a glass slide and dried overnight at room temperature to form a coating film.The contact angles of water (surface free energy dispersion: 21.8 mN / m, surface free energy polarity: 51.0 mN / m) and diiodomethane (surface free energy dispersion: 50.8 mN / m, surface free energy polarity: 0 mN / m) with respect to the coating film are measured in an atmosphere of 25°C.The surface tension of the compound A is calculated by the Owens and 30 Wendt equation using the obtained values of the contact angles of water and diiodomethane.Foreignfiling text P24-235- 23 -

[0050] It is considered that when the ratio of the total number of units A and units B to the number of terminal groups of the compound A and the surface tension of the compound A are each within the above-mentioned range, the compound A can be prevented from forming an island-like 5 isolated phase in the coating film of the composition of the present invention. This is considered to be due to the fact that the unit A and the unit B of the compound A contain a hydrophobic group, while the polysilazane contains a hydrophilic polar group.

[0051] The content of the compound A is preferably 0.001 to 10 mass%, more preferably 0.003 to 7 mass%, still more preferably 0.005 to 5 mass%, even more preferably 0.007 to 3 mass%, and particularly preferably 0.008 to 2 mass% with respect to the total mass of the composition.

[0052] It is considered that when the content of the compound A is 0.001 mass% or more with respect to the total mass of the composition, formation 15 of the protrusion and / or the occurrence of striation can be further inhibited.It is considered that when the content of the compound A is 10 mass% or less with respect to the total mass of the composition, the composition can be more uniformly applied above the substrate.

[0053] The solvent is not particularly limited. The solvent is preferably one 20 or more selected from the group consisting of aromatic compounds, more preferably benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, and triethylbenzene; saturated hydrocarbon compounds, more preferably n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i- heptane, n-octane, i-octane, n-nonane, i-nonane, n-decane, cyclohexane, methylcyclohexane, ethylcyclohexane, decahydronaphthalene, and p- menthane; unsaturated hydrocarbon compounds, more preferably cyclohexene and dipentene; ether compounds, more preferably dipropyl ether, dibutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and anisole; ester compounds, more preferably 30 n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, and ethyl lactate; and ketone compounds, more preferably methyl isobutyl ketone; still more preferably dipropyl ether, dibutyl ether, propylene glycolForeignfiling text P24-235-24 -monomethyl ether, propylene glycol monomethyl ether acetate, or anisole; and even more preferably dibutyl ether.

[0054] The content of the solvent is preferably 65 to 95 mass%, more preferably 70 to 90 mass%, and still more preferably 75 to 85 mass% with 5 respect to the total mass of the composition.

[0055] It is considered that when the content of the solvent is 65 mass% or more with respect to the total mass of the composition, the composition can be more uniformly applied above the substrate.It is considered that when the content of the solvent is 95 mass% or less with respect to the total mass of the composition, convection of the composition that occurs during volatilization of the solvent is further inhibited, and thus striation can be further inhibited.

[0056] The boiling point of the solvent is preferably 60 to 200°C, more preferably 70 to 180°C, still more preferably 80 to 160°C, and even more 15 preferably 80 to 145°C. The boiling point of the solvent in the present invention is the boiling point at 1 atm.

[0057] It is considered that when the boiling point of the solvent is 60°C or more, the solubility of the solid content in the composition is rendered further lower in the liquid agent used in EBR, and thus the formation of the 20 protrusion can be further inhibited. It is also considered that convection of the composition that occurs during volatilization of the solvent is further inhibited, and thus striation can be further inhibited.It is considered that when the boiling point of the solvent is 200°C or less, the coating film of the composition can be more efficiently cured.

[0058] The absolute value of the surface tension difference ratio determined by the following formula is preferably 0.01 to 0.20, more preferably 0.01 to 0.18, and still more preferably 0.01 to 0.17.Surface tension difference ratio = (surface tension of compound A at 25°C - surface tension of solvent at 25°C) / surface tension of compound A at 25°C 30 It is considered that when the surface tension difference ratio is within the above-mentioned range, the polysilazane is prevented from beingForeignfiling text P24-235- 25 -separated in the composition, and the polysilazane can impart appropriate viscosity to the composition in conjunction with the solvent.

[0059] (Additive)The composition can further comprise an additive. Examples of the additive 5 include silanol condensation catalysts, fluorine-containing compounds, adhesion promoters, anti-corrosion additives, crosslinking agents, dispersants, fillers, functional dyes (e.g., those that bring about functional effects such as electrical conductivity, thermal conductivity, and magnetic properties), nanoparticles, optical dyes (e.g., those that bring about optical effects such as color tone, refractive index, and a pearlescent effect), particles that reduce thermal expansion, polymerization initiators, polymerization inhibitors, primers, rheology modifiers (e.g., thickeners), and binding enhancers. The additive is different from the polysilazane, the compound A, and the solvent.15 The content of the additive (in the case where a plurality of additives are used, the total content thereof) is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, still more preferably 0 to 1 part by mass, and even more preferably 0 to 0.5 parts by mass with respect to 100 parts by mass of the polysilazane. It is also a preferred embodiment that the 20 composition does not contain an additive.

[0060] The additive is different from the above-mentioned polysilazane, compound A, and solvent.

[0061] Examples of the silanol condensation catalyst include a photoacid generator, a photobase generator, a thermal acid generator, and a thermal base generator. In the present invention, the photoacid generator or the photobase generator refers to a compound that generates an acid or a base by causing bond cleavage upon exposure to light. Herein, examples of the light include visible light, ultraviolet rays, infrared rays, X-rays, electron beams, a-rays, and y-rays. In the present invention, the thermal 30 acid generator or the thermal base generator refers to a compound that generates an acid or a base by causing bond cleavage due to heat. TheForeignfiling text P24-235- 26 -generated acid or base is considered to contribute to a polymerization reaction of a siloxane compound.

[0062] Examples of the photoacid generator include diazomethane compounds, triazine compounds, sulfonic acid esters, iodonium salts such 5 as diphenyliodonium salts, sulfonium salts such as triphenylsulfonium salts, ammonium salts, phosphonium salts, and sulfonimide compounds.

[0063] Examples of the photobase generator include polysubstituted amide compounds having an amido group, lactams, and imide compounds; and ionic photobase generators containing, as an anion, an amide anion, a methide anion, a borate anion, a phosphate anion, a sulfonate anion, or a carboxylate anion.

[0064] Examples of the thermal acid generator include aliphatic sulfonic acids and salts thereof; aliphatic carboxylic acids such as citric acid, acetic acid, and maleic acid, and salts thereof; aromatic carboxylic acids such as 15 benzoic acid and phthalic acid, and salts thereof; aromatic sulfonic acids and salts thereof; aromatic diazonium salts; and phosphonic acids and salts thereof.

[0065] Examples of the thermal base generator include compounds that generate a base, such as imidazoles and tertiary amines.20

[0066] Examples of the fluorine-containing compound include fluorine- containing surfactants having a fluorinated hydrocarbon group and a hydrophilic group, such as MEGAFACE (DIC), Fluorad (3M), and Surflon (AGC SEIMI CHEMICAL).

[0067] The composition can comprise other surfactants other than the fluorine-containing surfactants. Examples of the other surfactants include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0068] The nanoparticles may be selected from particles of nitrides, titanates, diamond, oxides, sulfides, sulfites, sulfates, silicates, and carbides. The nanoparticles may optionally be surface modified with a 30 capping agent. The particle diameter of the nanoparticles may be, for example, 1 to 100 nm, 1 to 50 nm, or 1 to 25 nm. The particle diameter can be measured by any standard method known to those skilled in the art.Foreignfiling text P24-235- 27 -

[0069] Examples of the polymerization initiator include a polymerization initiator that generates an acid, a base, or a radical by radiation, and a polymerization initiator that generates an acid, a base, or a radical by heat. Herein, examples of the radiation include visible light, ultraviolet rays, 5 infrared rays, X-rays, electron beams, a-rays, and y-rays.

[0070] Examples of a photoradical generator include azo-based, peroxide- based, acylphosphine oxide-based, alkylphenone-based, oxime ester- based, and titanocene-based generators. Among these, alkylphenone- based, acylphosphine oxide-based, and oxime ester-based generators are preferable, and 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy- cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4- (2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1 -propan-1 -one, 2-hydroxy-1 - {4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1 -(4-methylthiophenyl)-2-morpholinopropan-1 -one, 2-benzyl-2- 15 dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2- [(4-methylphenyl)methyl]-1 -[4-(4-morpholinyl)-phenyl]-1 -butanone, 2,4,6- trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)- phenyl-phosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O- benzoyloxime), ethanone, 1 -[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- 20 yl]-, 1-(O-acetyloxime), and the like can be used.

[0071] Examples of the polymerization inhibitor include ultraviolet absorbers, and nitrones, nitrogen oxide radicals, hydroquinones, catechols, phenothiazines, phenoxazines, hindered amines, and derivatives thereof. Specifically, methylhydroquinone, catechol, 4-t-butylcatechol, 3- methoxycatechol, phenothiazine, chlorpromazine, phenoxazine, TINUVIN 144, 292, and 5100 (BASF) as hindered amines, TINUVIN 326, 328, 384-2, 400, and 477 (BASF) as ultraviolet absorbers, and the like can be used.

[0072] The binding enhancer has an effect of preventing the coating film from being peeled off from the substrate due to the applied stress when the 30 composition according to one embodiment is applied above the substrate to form a coating film and the coating film is cured by heating. As the binding enhancer, an imidazole compound, a silane coupling agent, and the like areForeignfiling text P24-235- 28 -preferable. Examples of the imidazole compound include 2- hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2- hydroxyimidazole, imidazole, 2-mercaptoimidazole, and 2-aminoimidazole.

[0073] Examples of the silane coupling agent include an epoxysilane 5 coupling agent, an aminosilane coupling agent, and a mercaptosilane coupling agent. Specifically, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropyltriethoxysilane, N-(2-aminoethyl)-3- aminopropyltrimethoxysilane, N-2-(aminoethyl)-3- aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino- propyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3- chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- isocyanatopropyltriethoxysilane, and the like can be used.

[0074] Moreover, as the silane coupling agent, a silane compound having an acid group can be used. Examples of the acid group include a carboxy 15 group, an acid anhydride group, and a phenolic hydroxy group.

[0075] Since the composition can form a cured film having excellent film hardness and electrical properties, the composition is useful as a composition for manufacturing an electronic element, particularly as a composition for manufacturing a semiconductor element. The composition 20 can be used, for example, for forming a cured film above a substrate.Examples of the substrate include a silicon substrate, a glass substrate, and a resin film.

[0076] Considering that the composition is used for manufacturing an electronic element, or for manufacturing a semiconductor element in a more preferred embodiment, the composition preferably has a small content of an alkali metal and an alkaline earth metal. The total concentration of the alkali metal and the alkaline earth metal in the composition is preferably 1 ppm or less, more preferably 100 ppb or less, and still more preferably 10 ppb or less.30

[0077] < Manufacturing Method of Cured Film>The manufacturing method of a cured film according to one embodiment comprises steps (a) and (b-1):Foreignfiling text P24-235- 29 -(a) applying the composition above a substrate to form a coating film; and (b-1) heating the coating film.

[0078] The formation of the coating film in the step (a) can be performed by any method known as a method for applying a composition. Specific 5 examples thereof include dip coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, and slit coating, and spin coating is preferable.

[0079] When the coating film is formed by spin coating, the composition is applied above the substrate by spin coating preferably at 200 to 4000 RPM, more preferably at 300 to 3500 RPM, and still more preferably at 500 to 3000 RPM.When the coating film is formed by spin coating, the composition is applied above the substrate by spin coating while maintaining the rotation preferably for 0.1 to 100 seconds, more preferably for 0.3 to 70 seconds, 15 and still more preferably for 0.5 to 40 seconds.

[0080] Examples of the substrate include a silicon substrate, a glass substrate, and a resin film.

[0081] In the step (b-1), the coating film is heated preferably at 30 to 1100°C, more preferably at 50 to 1000°C, and still more preferably at 100 to 20 900°C; and preferably for 30 seconds to 600 minutes, more preferably for 1 to 400 minutes, still more preferably for 1.5 to 200 minutes, and even more preferably for 2 to 150 minutes. The coating film can be dried and cured by heating. The heating can be performed using, for example, at least one selected from a hot plate and a clean oven.

[0082] The heating may be performed in multiple separate stages. For example, after drying of the coating film, curing can be allowed to proceed at a higher temperature. The heating may be performed by combining curing with prebaking, annealing (also referred to as post-baking), or a combination of both.30 When the heating is separately performed in a first stage (b-1 -1 ) and a second stage (b-1 -2), the heating in the first stage (b-1 -1 ) is preferably performed at 30 to 300°C, more preferably at 40 to 250°C, and still moreForeignfiling text P24-235- 30 -preferably at 50 to 200°C; and preferably for 30 seconds to 30 minutes, more preferably for 1 to 10 minutes, still more preferably for 1.5 to 5 minutes, and even more preferably for 2 to 3 minutes. The heating in the second stage (b-1-2) is preferably performed at 250 to 1100°C, more 5 preferably at 300 to 1000°C, and still more preferably at 350 to 900°C; and preferably for 1 to 600 minutes, more preferably for 5 to 400 minutes, still more preferably for 10 to 200 minutes, and even more preferably for 30 to 150 minutes.

[0083] The process of sequentially performing the step (a) and the heating in the first stage (b-1-1 ) may be repeated twice or more so that the obtained coating film may have a desired film thickness.

[0084] The heating in the step (b-1) can be performed in an atmosphere containing oxygen, air, or an inert gas such as nitrogen. When the heating is performed in multiple separate stages, the stages may be performed in 15 different atmospheres.In a preferred embodiment of the present invention, the heating in the step (b-1) is performed in an atmosphere in which the oxygen partial pressure is 0.5 to 1 time the total pressure.In another preferred embodiment of the present invention, the heating in the 20 step (b-1) is performed in an atmosphere in which the nitrogen partial pressure is 0.5 to 1 time the total pressure.It is preferable that a part of the heating in the step (b-1) is performed in an atmosphere in which the nitrogen partial pressure is 0.5 to 1 time the total pressure. For example, in the step (b-1), the heating in the first stage (b-1- 1) may be performed in an air atmosphere, and the heating in the second stage (b-1-2) may be performed in an atmosphere in which the nitrogen partial pressure is 0.5 to 1 time the total pressure.

[0085] The manufacturing method of a cured film may further comprise a step (b-2) simultaneously with the step (b-1) and / or after the step (b-1): 30 (b-2) irradiating the coating film with ultraviolet rays.Foreignfiling text P24-235- 31 -

[0086] The wavelength of the ultraviolet rays is preferably 13.5 to 248 nm, more preferably 50 to 240 nm, still more preferably 100 to 230 nm, and even more preferably 150 to 225 nm.

[0087] The intensity of the ultraviolet rays is preferably 0.10 to 3 J / cm2, 5 more preferably 0.15 to 2 J / cm2, still more preferably 0.20 to 1.5 J / cm2, and even more preferably 0.30 to 1.0 J / cm2.

[0088] Examples of the light source used for ultraviolet irradiation include a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a xenon lamp, a laser diode, and an LED.

[0089] < Cured Film>The cured film according to one embodiment is a cured product of the composition. The cured film can be obtained, for example, by the above- mentioned manufacturing method.

[0090] The film thickness of the cured film is preferably 0.1 to 3000 nm, 15 more preferably 1 to 1500 nm, still more preferably 2 to 1200 nm, and even more preferably 3 to 1000 nm. In the present invention, the film thickness of the cured film is a value measured by an ellipsometer M-2000 (J. A.Woollam).

[0091] Since the cured film has excellent film hardness and electrical 20 properties, the cured film is useful as an insulating film of an electronic element. The cured film can be used, for example, as a surface protective film, a buffer coat film, and an interlayer insulating film of a semiconductor element.

[0092] Electronic Element>The electronic element according to one embodiment comprises a cured film. Examples of the electronic element include semiconductor elements; and electronic components such as a capacitor and a printed circuit board. In the manufacture of an electronic element, the cured film can be manufactured by the above-mentioned manufacturing method.30

[0093] Manufacturing Method of Electronic Element>The manufacturing method of an electronic element according to oneForeignfiling text P24-235- 32 -embodiment of the present invention comprises the above-mentioned manufacturing method of a cured film.

[0094] < Use of Composition>The use of the composition according to one embodiment of the present 5 invention is for forming a cured film of the composition above a substrate.[Examples]

[0095] The present invention will be described by way of examples as follows. The embodiments of the present invention are not limited to these examples.

[0096] In the following examples, the Mw is measured by GPC using polystyrene standards. GPC is performed using Waters ACQUITY APC System (Nihon Waters), and a Shodex GPC HK-401 column and a Shodex GPC HK-404L column (Shoko Science). The measurement is carried out 15 under measurement conditions of a flow rate of 0.5 mL / min and a column temperature of 40°C using monodisperse polystyrene as a standard sample and tetrahydrofuran as a developing solvent, and then the Mw is calculated as a relative molecular weight to the standard sample.

[0097] Unless otherwise specified, all the steps in the examples are 20 performed at room temperature.

[0098] < Synthesis of Polysilazane lntermediate>The inside of a 10 L reaction vessel equipped with a cooling condenser, a mechanical stirrer, and a temperature controller is purged with dry nitrogen. To the reaction vessel, 7350 g of dehydrated pyridine is added, and the contents are cooled to -3°C. Upon addition of 500 g of dichlorosilane, a white solid mixture (SiH2Cl2·2C5H5N) is produced. It is confirmed that the mixture has a temperature of -3°C or less, and then 350 g of ammonia is slowly blown into the mixture with stirring. The mixture is stirred for 30 minutes, and dry nitrogen is blown into the liquid layer for 30 minutes to 30 remove excess ammonia. In the dry nitrogen atmosphere, the obtained slurry-like product is pressure-filtered using a 0.2 pm filter made of PTFE to obtain 6000 mL of a filtrate. To the filtrate, 2640 g of dehydrated xylene isForeignfiling text P24-235- 33 -added, pyridine is distilled off using an evaporator, and the filtrate is concentrated. A xylene solution of a polysilazane intermediate having a solid content concentration of 39.8 mass% is obtained. The obtained polysilazane intermediate has a Mw of 1399 in terms of polystyrene.5

[0099] < Synthesis of Polysilazane A>The inside of a 10 L reaction vessel equipped with a cooling condenser, a mechanical stirrer, and a temperature controller is purged with dry nitrogen. To the reaction vessel, 4710 g of dehydrated pyridine, 150 g of dehydrated xylene, and 1650 g of the polysilazane intermediate are added. The mixture is stirred to be uniform under bubbling with a nitrogen gas at 0.5 NL / min. The modification reaction is performed at 100°C for 9 hours, and pyridine is distilled off to obtain a solution of a polysilazane A having a solid content concentration of 40 mass%. The obtained polysilazane A has a Mw of 3294.15

[0100] Preparation of Composition>As the compound A, a: methyl group-terminated polysilsesquioxane (Mw: 41000), b: H-terminated polydimethylsiloxane (Mw: 6000), c: H-terminated polydimethylsiloxane (Mw: 28000), d: methylphenylpolysiloxane KF-53 (Shin-Etsu Chemical), e: decamethylcyclopentasiloxane, f1: CH3-terminated polydimethylsiloxane (Mw: 1200), f2: CH3-terminated polydimethylsiloxane (Mw: 3700), f3: CH3-terminated polydimethylsiloxane (Mw: 15000), f4: CH3-terminated polydimethylsiloxane (Mw: 18000), f5: CH3-terminated polydimethylsiloxane (Mw: 60000), or f6: CH3-terminated polydimethylsiloxane (Mw: 88000) is used.Each of these compounds (a to e, and f1 to f6) as the compound A is added in the parts by mass shown in Table 1 with respect to 100 parts by mass of the polysilazane A to the polysilazane A solution. Dibutyl ether is added as a solvent so that the content of the polysilazane A is 20 mass% with respect to the total amount of the composition, and the mixture is stirred 30 with a mechanical stirrer. The compositions of Examples 1 to 32 and Comparative Example 1 shown in Table 1 are obtained.Foreignfiling text P24-235- 34 -

[0101] The structure of each of the compounds as the compound A is as follows.a:[Chem. 14]5In the formula, R = methyl,b, c:[Chem. 15]CH3CH3CH3H^SI-O-’SFO-SHHCH 3d:[Chem. 16]CH3CH3?6H5CH3H3C““Si~-0- _Si__0...Si—0- ~Si~CH '3CH3CH3C6H5CH3m ne:30[Chem. 17]Foreignfiling text P24-235- 35 -5[Chem. 18]

[0102] < Formation of Coating Film>The composition is applied by spin coating using Mark 8 (Tokyo Electron). The composition of Example 1 is dropped onto an 8-inch silicon wafer and applied by successively maintaining the rotation speed at 500 RPM for 0.5 seconds, at 1000 RPM for 20 seconds, and at 2500 RPM for 8 seconds. 15 While rotating the silicon wafer to which the composition is applied, a rinse solvent HC-100 (Merck Electronics) is discharged toward the outer periphery of the silicon wafer to perform EBR. The rotation is performed by successively maintaining the rotation speed at 800 RPM for 10 seconds, and at 3000 RPM for 10 seconds. The resulting film is baked at 150°C for 3 20 minutes to obtain a coating film of Example 1. The coating films of Examples 2 to 32 and Comparative Example 1 are also obtained in the same manner.

[0103] < EBR Evaluation>Using an optical microscope Eclipse L300N (Nikon Solutions), a range of 1650 pm x 2200 pm at an arbitrary position on the outer edge of the coating film of Example 1 is observed. On the basis of the observation results, the EBR is evaluated according to the following criteria. The coating films of Examples 2 to 32 and Comparative Example 1 are also subjected to the same evaluation.30 A: The maximum distance of the protrusion extending outward from the outer edge of the coating film in the horizontal direction (radial direction of the wafer) is less than 1000 angstroms.Foreignfiling text P24-235- 36 -B: The maximum distance of the protrusion extending outward from the outer edge of the coating film in the horizontal direction (radial direction of the wafer) is 1000 angstroms or more and less than 2000 angstroms. C: The maximum distance of the protrusion extending outward from the 5 outer edge of the coating film in the horizontal direction (radial direction of the wafer) is 2000 angstroms or more.The results are shown in Table 1.

[0104] Evaluation of Coating Film Surface>Using Eclipse L300N, a range of 1650 pm x 2200 pm at an arbitrary position on the surface of the coating film of Example 1 is observed. On the basis of the observation results, the surface of the coating film is evaluated according to the following criteria. The coating films of Examples 2 to 32 and Comparative Example 1 are also subjected to the same evaluation. A: No striation is observed on the surface of the coating film.15 B: Slight striation is observed on the surface of the coating film.C: Striation is clearly observed on the surface of the coating film.The results are shown in Table 1. The observation images of Example 1 and Comparative Example 1 for EBR evaluation are presented in FIG. 1 and FIG. 2, respectively.2030Foreignfiling text P24-235

[0105] [Table 1]Compound A Content2)EBR Surface evaluatio evaluation of Type Content Polysilazane A Compound An coating film ComparativeNone - 20% 0% C C Example 15 Example 1 a 0.01 20% 0.002% A B Example 2 a 0.1 20% 0.02% A A Example 3 a 1 20% 0.2% A A Example 4 b 0.01 20% 0.002% A A Example 5 b 0.1 20% 0.02% A A Example 6 b 1 20% 0.2% A A Example 7 c 0.01 20% 0.002% A A Example 8 c 0.1 20% 0.02% A A Example 9 c 1 20% 0.2% A A Example 10 d 0.1 20% 0.02% A B Example 11 d 1 20% 0.2% A A Example 12 e 0.01 20% 0.002% B B Example 13 e 0.1 20% 0.02% B B Example 14 e 1 20% 0.2% B B Example 15 fl 0.01 20% 0.002% A B Example 16 fl 0.1 20% 0.02% A B Example 17 fl 1 20% 0.2% A B Example 18 f2 0.01 20% 0.002% A A Example 19 f2 0.1 20% 0.02% A A Example 20 f2 1 20% 0.2% A A Example 21 f3 0.01 20% 0.002% A A Example 22 f3 0.1 20% 0.02% A A Example 23 f3 1 20% 0.2% A A Example 24 f4 0.01 20% 0.002% A A Example 25 f4 0.1 20% 0.02% A A Example 26 f4 1 20% 0.2% A A Example 27 f5 0.01 20% 0.002% A A Example 28 f5 0.1 20% 0.02% A A Example 29 f5 1 20% 0.2% A A Example 30 f6 0.01 20% 0.002% A A Example 31 f6 0.1 20% 0.02% A AExample 32 f6 1 20% 0.2% A A 1) parts by mass with respect to 100 parts by mass of polysilazane2) mass% with respect to composition30

Claims

Foreignfiling text P24-235- 38 -[CLAIMS]

1. A composition comprising:a polysilazane;5 a compound A comprising at least one of a unit A represented by Formula (1 A) and a unit B represented by Formula (1B); anda solvent:[Chem. 1]whereinR11is C 1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably linear C1-20 alkyl, branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, or cyclic C3-20 alkenyl; more preferably linear C1-15 alkyl or branched C3-15 alkyl; still more preferably linear C1-10 alkyl or branched C3-10 alkyl; and even more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl; andone or more non-adjacent -CH2- in R11are each independently optionally substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or -C≡C-; and [Chem. 2]wherein30R12is C 1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably linear C1-20 alkyl, branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20Foreignfiling text P24-235- 39 -alkenyl, or cyclic C3-20 alkenyl; more preferably linear C1-15 alkyl or branched C3-15 alkyl; still more preferably linear C1-10 alkyl or branched C3-10 alkyl; and even more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl; R13is H, C 1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably H, linear C1-20 alkyl, 5 branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, or cyclic C3-20 alkenyl; more preferably H, linear C1-15 alkyl, or branched C3-15 alkyl; still more preferably H, linear C1-10 alkyl, or branched C3-10 alkyl; and even more preferably H, methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl; andone or more non-adjacent -CH2- in R12and R13are each independently optionally substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or -C=C-.

2. The composition according to claim 1, wherein the polysilazane comprises a unit represented by Formula (2):[Chem. 3]whereinR21, R22, and R23are each independently a single bond, H, C1-20 alkyl, C2-20 alkenyl, C6-20 aryl, or a linking group represented by any one of Formulae (a), (b), and (c); preferably a single bond, H, linear C1-20 alkyl, branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, cyclic C3-20 alkenyl, or a linking group represented by any one of Formulae (a), (b), and (c); more preferably a single bond, H, linear C1-10 alkyl, branched C3-10 alkyl, or a linking group represented by any one of Formulae (a), (b), and (c); still more preferably a single bond, H, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert30butyl, or a linking group represented by any one of Formulae (a), (b), and (c);Foreignfiling text P24-235- 40 -and even more preferably a single bond, H, or a linking group represented by any one of Formulae (a), (b), and (c);when R21, R22, and R23are each independently alkyl, alkenyl, or aryl, one or more non-adjacent -CH2- in R21, R22, and R23are each independently optionally 5 substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or -C=C-;R21and R22, when being each independently a single bond, are each independently bonded to N contained in another unit represented by Formula (2); andR23, when being a single bond, is bonded to Si contained in another unit represented by Formula (2); and[Chem. 4]( R.a)s-na-La— Si > — ka)~ (a)2-nbi ( Rb2)2-nb2r H I-2>p—vSIribif nd') I nc2\' y '3-nd / 3-nc2 I > I / x (C)— ( Lc*) — - S i - 0 - S i - r Lc2) > -' 'ndv znc2whereinRa, Rb1, Rb2, Rc1, and Rc2are each independently H, C1-6 alkyl, C2-6 alkenyl, or C6-12 aryl; preferably H, linear C1-6 alkyl, branched C3-6 alkyl, cyclic C3-6 alkyl, linear C2-6 alkenyl, branched C3-6 alkenyl, or cyclic C3-6 alkenyl; and more preferably H, methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl;La, Lb1, Lb2, Lc1, and Lc2are each independently C1-8 alkylene or C6-14arylene; 30 preferably linear C1-8 alkylene, branched C3-8 alkylene, or cyclic C3-8 alkylene;more preferably linear C1-5 alkylene or branched C3-5 alkylene; and still more preferably methylene, ethylene, linear propylene, or branched propylene;Foreignfiling text P24-235- 41 -one or more non-adjacent -CH2- in La, Lb1, Lb2, Lc1, and Lc2are each independently optionally substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -0- CO-O-, -CH=CH- or -C≡C-;na is 1 to 3;5 nb1 and nb2 are each independently 1 to 2;nc1 and nc2 are each independently 1 to 3;p and q are each independently 1 to 3; andamong bonds of the linking group represented by Formula (a), (b), or (c), a bond that is not bonded to Si contained in the unit represented by Formula (2) is bonded to Si contained in another unit represented by Formula (2).

3. The composition according to claim 1 or 2, wherein a content of the compound A is 0.001 to 10 mass%, preferably 0.003 to 7 mass%, more preferably 0.005 15 to 5 mass%, still more preferably 0.007 to 3 mass%, and even more preferably 0.008 to 2 mass% with respect to a total mass of the composition.

4. The composition according to any one of claims 1 to 3, wherein the compound 20 A has a mass average molecular weight of 100 to 80000, preferably 300 to 60000, more preferably 500 to 50000, still more preferably 1000 to 48000, and even more preferably 5000 to 45000.

5. The composition according to any one of claims 1 to 4, wherein the compound A comprises at least one terminal group represented by Formula (3), and preferably all terminal groups of the compound (A) are represented by Formula (3):-SiR31R32R33(3)30 whereinR31is C 1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably linear C1-20 alkyl, branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20Foreignfiling text P24-235- 42 -alkenyl, or cyclic C3-20 alkenyl; more preferably linear C1-15 alkyl or branched C3-15 alkyl; still more preferably linear C1-10 alkyl or branched C3-10 alkyl; and even more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl; R32is H, C 1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably H, linear C1-20 alkyl, 5 branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, or cyclic C3-20 alkenyl; more preferably H, linear C1-15 alkyl, or branched C3-15 alkyl; still more preferably H, linear C1-10 alkyl, or branched C3-10 alkyl; and even more preferably H, methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl; R33is H, OH, C1-20 alkyl, C2-20 alkenyl, or C6-20 aryl; preferably H, OH, linear C1- 20 alkyl, branched C3-20 alkyl, cyclic C3-20 alkyl, linear C2-20 alkenyl, branched C3- 20 alkenyl, or cyclic C3-20 alkenyl; more preferably H, OH, linear C1-15 alkyl, or branched C3-15 alkyl; still more preferably H, OH, linear C1-10 alkyl, or branched C3-10 alkyl; and even more preferably H, OH, or methyl;one or more non-adjacent -CH2- in R31, R32, and R33are each independently 15 optionally substituted with -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or -C=C-;andwhen R33is alkyl, alkenyl, or aryl, one or more H in R33are optionally substituted with -OH, -COOH, or -SO2H.20

6. The composition according to any one of claims 1 to 5, wherein the compound A comprises a unit B represented by Formula (1B), in which R12and R13are methyl.

7. The composition according to claim 5 or 6, the compound A comprises at least one terminal group represented by Formula (3), in which R31, R32, and R33are methyl.30

8. The composition according to any one of claims 1 to 7, wherein the polysilazane is polyperhydropolysilazane.Foreignfiling text P24-235- 43 -

9. The composition according to any one of claims 1 to 8, wherein the compound A has a ratio of a total number of units A and units B to a number of terminal 5 groups of 1.2 to 2.5, preferably 1.3 to 2.4, more preferably 1.4 to 2.0, and still more preferably 1.5 to 1.7.

10. The composition according to any one of claims 1 to 9, wherein the solvent is one or more selected from the group consisting of benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, n-pentane, i- pentane, n-hexane, i-hexane, n-heptane, i-heptane, n-octane, i-octane, n- nonane, i-nonane, n-decane, cyclohexane, methylcyclohexane, ethylcyclohexane, decahydronaphthalene, p-menthane, cyclohexene,15 dipentene, dipropyl ether, dibutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, anisole, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, ethyl lactate, and methyl isobutyl ketone; preferably dipropyl ether, dibutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or anisole; and more20 preferably dibutyl ether.

11. The composition according to any one of claims 1 to 10, wherein a content of the solvent is 65 to 95 mass%, preferably 70 to 90 mass%, and more preferably 75 to 85 mass% with respect to a total mass of the composition.

12. The composition according to any one of claims 1 to 11, wherein an absolute value of a surface tension difference ratio determined by a formula shown 30 below is 0.01 to 0.20, preferably 0.01 to 0.18, and more preferably 0.01 to 0.17:surface tension difference ratio = (surface tension of compound A at 25°C - surface tension of solvent at 25°C) / surface tension of compound A at 25°C.Foreignfiling text P24-235- 44 -

13. The composition according to any one of claims 1 to 12, wherein the compound A has a surface tension of 15 to 30 mN / m, preferably 18 to 27 5 mN / m, more preferably 19 to 25 mN / m, and still more preferably 20 to 22 mN / m.

14. A manufacturing method of a cured film, the method comprising steps (a) and (b-1) below:(a) applying the composition described in any one of claims 1 to 13 above a substrate to form a coating film,preferably, wherein the composition is applied above the substrate by spin coating at 200 to 4000 RPM for 0.1 to 100 seconds, more preferably at 300 to 15 3500 RPM for 0.3 to 70 seconds, and still more preferably at 500 to 3000 RPM for 0.5 to 40 seconds; and(b-1) heating the coating film,preferably, wherein the coating film is heated at 30 to 1100°C, more preferably at 50 to 1000°C, and still more preferably at 100 to 900°C; and preferably for 20 30 seconds to 600 minutes, more preferably for 1 to 400 minutes, still more preferably for 1.5 to 200 minutes, and even more preferably for 2 to 150 minutes.

15. The manufacturing method of a cured film according to claim 14, further comprising a step (b-2) simultaneously with the step (b-1) and / or after the step (b-1):(b-2) irradiating the coating film with ultraviolet rays having a wavelength of 13.5 to 248 nm, preferably 50 to 240 nm, more preferably 100 to 230 nm, and 30 still more preferably 150 to 225 nm.

16. Foreignfiling text P24-235-45 -The manufacturing method of a cured film according to claim 15, wherein the ultraviolet rays have an intensity of 0.10 to 3 J / cm2, preferably 0.15 to 2 J / cm2, more preferably 0.20 to 1.5 J / cm2, and still more preferably 0.30 to 1.0 J / cm2.5

17. The manufacturing method of a cured film according to any one of claims 14 to 16, wherein the heating in the step (b-1) is performed in an atmosphere in which an oxygen partial pressure is 0.5 to 1 time a total pressure.

18. The manufacturing method of a cured film according to any one of claims 14 to 16, wherein the heating in the step (b-1) is performed in an atmosphere in which a nitrogen partial pressure is 0.5 to 1 time a total pressure.15

19. A manufacturing method of an electronic element, the method comprising the method described in any one of claims 14 to 18.

20. 20 Use of the composition described in any one of claims 1 to 13 for forming a cured film above a substrate.30

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