Composition for forming interstitial material

Abstract

A composition for forming an interstitial material, which contains a solvent and at least one of a compound and a polymer having a structure represented by formula (1) and a carbonyl bond. (In formula (1), R1 and R2 each independently represent a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1-13 carbon atoms, or a halogen atom,-COOR11 (R11 represents a hydrogen atom or an alkyl group having 1-4 carbon atoms). ) or-COO-. When there are two or more R3s, the two or more R3s may be the same as or different from each other. And R3 represents a methoxy group, an alkyl group having 1-13 carbon atoms, or a halogen atom. And n1 represents an integer of 0-4. And n2 represents an integer of 0 or 1. Wherein the total of n1 and n2 is 4 or less. And X1 represents an ether bond or an ester bond. And X2 represents an ether bond or an ester bond. And * represents a binding bond. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a gap filler-forming composition preferably used in a process for producing a redistribution layer of a semiconductor device, a gap filler cured product, a method for producing a redistribution layer, and a method for producing a printed circuit board. Background Art

[0002] With the demand for miniaturization, high performance and low price of electronic equipment, the wiring circuit substrates carrying semiconductor chips are becoming miniaturized and multi-layered, and the high-density mounting of electronic components on the wiring circuit substrates is progressing, along with the miniaturization and multi-terminalization of semiconductor chips. With the multi-terminalization of semiconductor chips and the narrowing of the pitch of these terminals, there is also a demand for fine wiring on multi-layer circuit substrates.

[0003] In multilayer circuit substrates, various forms such as packaging substrates, wafer-level packaging (WLP), and silicon interposers are known. Generally speaking, in the wiring layer of the build-up substrate used for the packaging substrate, the redistribution layer of the wafer-level packaging, etc., a semi-additive (SAP) method that can achieve fine wiring compared to the subtractive method is applied. In the case of forming multilayer wiring, there are methods of stacking wiring by the semi-additive method, and methods of contacting and connecting wiring to each other with interposer plugs by the photosensitive hole forming method or the inlay method (for example, refer to Patent Document 1).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2011-249483 Summary of the invention

[0007] Problems to be solved by the invention

[0008] A redistribution layer having an insulating layer, wiring formed on the surface of the insulating layer, and a through hole formed inside the insulating layer is manufactured, for example, by a dual damascene process. Dual damascene is a technique for simultaneously forming wiring and forming through holes by burying through holes. Here, a manufacturing process of a redistribution layer using a dual damascene process is described using a diagram.

[0009] Figure 1A to Figure 1K This is a schematic diagram for explaining an example of a dual damascene process.

[0010] First, prepare the substrate 101 ( Figure 1A Next, a photosensitive resin layer 102 is formed on the substrate 101 ( Figure 1B The photosensitive resin layer 102 used here is a photosensitive resin layer that will later function as an insulating layer, for example, a photosensitive polyimide. Next, through holes ( Figure 1C Next, a barrier / seed layer 103 serving as both a barrier layer and a seed layer is formed on the surface of the photosensitive resin layer 102 ( Figure 1D The barrier / seed layer 103 is, for example, a two-layer structure in which the lower layer is a Ti layer and the upper layer is a Cu layer. Next, a plating resist 104 ( Figure 1E Next, the plating resist 104 is formed into a desired pattern by photolithography ( Figure 1F ). Next, plating is performed in the gaps between the desired patterned plating resist 104 to form a plating layer 105 ( Figure 1G ). The plating layer 105 is formed at the position that will later become the through hole and the position that will become the wiring. The plating layer 105 is, for example, a Cu layer. Next, the plating resist 104 is removed by etching. In this way, the plating layer 105 becomes the through hole 105a formed inside the photosensitive resin layer 102 as an insulating layer, and the wiring 105b formed on the surface of the photosensitive resin layer 102 ( Figure 1H Next, the exposed barrier / seed layer 103 is removed ( Fig. 1I ). In this way, Fig. 1I As shown, a redistribution layer including a photosensitive resin layer 102 (insulating layer), through holes 105 a formed inside the photosensitive resin layer 102 , and wirings 105 b formed on the surface of the photosensitive resin layer 102 is formed.

[0011] Next, a photosensitive resin layer 106 (insulating layer) is formed on the photosensitive resin layer 102 (insulating layer) in which the through hole 105a and the wiring 105b are formed. Figure 1J Next, through holes are formed in the photosensitive resin layer 106 by photolithography ( Figure 1K ). Next, proceed with Figure 1D to Figure 1I By doing so, the redistribution layer can be made into a multi-layer structure.

[0012] Here, the metal such as Cu constituting the through hole 105a and the wiring 105b is easy to migrate to the insulating layer. Therefore, a barrier / seed layer 103 having a function of preventing migration is formed. Figure 1I to Figure 1K As shown in FIG. 1 , the barrier / seed layer 103 is formed only on the lower side of the through hole 105a and the wiring 105b on the upper surface of the photosensitive resin layer 102, and the barrier / seed layer 103 is not formed on the side surfaces of the through hole 105a and the wiring 105b, which occupy a large area among the surfaces of the through hole 105a and the wiring 105b. Therefore, the prevention of migration is insufficient.

[0013] The present invention aims to provide a gap-filling material composition which can be suitably used for temporarily filling through-holes of an insulating layer when forming a redistribution layer, a gap-filling material cured product using the gap-filling material composition, and a method for producing a printed circuit board using the gap-filling material composition.

[0014] Means for solving problems

[0015] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved, thereby completing the present invention having the following gist.

[0016] That is, the present invention includes the following aspects.

[0017] [1] A gap-filler-forming composition comprising at least one of a compound and a polymer and a solvent, wherein the compound and the polymer have a structure represented by the following formula (1) and a carbonyl bond.

[0018]

[0019] (In formula (1), R 1 and R 2 Each independently represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms, a halogen atom, -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ) or -COO-.

[0020] R 3 represents a methoxy group, an alkyl group having 1 to 13 carbon atoms, or a halogen atom. 3 When there are 2 or more, 2 or more R 3 It can be the same or different.

[0021] n1 represents an integer of 0 to 4. n2 represents an integer of 0 or 1. However, the total of n1 and n2 is 4 or less.

[0022] X 1 It represents an ether bond or an ester bond.

[0023] X 2 It represents an ether bond or an ester bond.

[0024] * indicates a bond. )

[0025] [2] The gap-filler-forming composition according to [1], wherein the compound and the polymer have at least one of a structure represented by the following formula (2) and a structure represented by the following formula (3) as the structure having the carbonyl bond.

[0026]

[0027] (In formula (2), X 11 It represents a group represented by any one of the following formulae (2-1) to (2-4). 1 and Z 2 Each independently represents a single bond or a divalent group represented by the following formula (2-5) (wherein *3 in formula (2-5) represents a bond to the nitrogen atom in formula (2).) 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each independently represents a hydrogen atom, a methyl group or an ethyl group. * represents a bond.

[0028] In formula (3), Q 1 A represents a divalent organic group having an aromatic hydrocarbon ring. 11 , A 12 , A 13 , A 14 , A 15 and A 16 Each independently represents a hydrogen atom, a methyl group or an ethyl group. n11 and n12 represent integers of 0 or 1. At least one of n11 and n12 is 1. * represents a bond. )

[0029]

[0030] (In formulas (2-1) to (2-3), R 1 ~R 5 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. 1 With R 2 They may be bonded to each other to form a ring having 3 to 6 carbon atoms. 3 With R 4 They may be bonded to each other to form a ring having 3 to 6 carbon atoms.

[0031] In formula (2-4), Z 3 A represents a single bond or a divalent group represented by the following formula (2-5) (wherein *3 in formula (2-5) represents a bond to the nitrogen atom in formula (2-4).) 7 , A 8 and A 9Each independently represents a hydrogen atom, a methyl group or an ethyl group.

[0032] * represents a bond. *1 represents a bond to a carbon atom in formula (2). *2 represents a bond to a nitrogen atom in formula (2).

[0033]

[0034] (In formula (2-5), m1 is an integer of 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer of 0 to 2. When m3 is 1, m1 and m2 are not simultaneously 0. *3 represents a bond to a nitrogen atom in formula (2) or (2-4). *4 represents a bond to a carbon atom in formula (2) or (2-4).)

[0035] [3] The gap-filling material forming composition according to [2], wherein Q 1 It is represented by the following formula (3-1) or formula (3-2).

[0036]

[0037] (In formulas (3-1) to (3-2), R 21 ~R 23 Each independently represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an alkynyloxy group having 2 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. * represents a bond.

[0038] In formula (3-1), n3 represents 0 or 1. When n3 is 0, n21 represents an integer from 0 to 4. When n3 is 1, n21 represents an integer from 0 to 6. 21 When there are 2 or more, 2 or more R 21 It can be the same or different.

[0039] In formula (3-2), Z 4 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms. n22 and n23 each independently represent an integer of 0 to 4. 22 When there are 2 or more, 2 or more R 22 Can be the same or different. 23 When there are 2 or more, 2 or more R 23 Can be the same or different.)

[0040] [4] The gap-filling material-forming composition according to any one of [1] to [3], wherein R 1 Indicates cyano or -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ).

[0041] [5] The gap-filling material-forming composition according to any one of [1] to [4], wherein R 2 Indicates cyano, -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ) or -COO-.

[0042] [6] The gap-filling material-forming composition according to any one of [1] to [5], wherein X 1 Represents an ether bond.

[0043] [7] The gap-filler-forming composition according to any one of [1] to [6], wherein n2 represents 0.

[0044] [8] The gap-filler-forming composition according to any one of [1] to [7], which contains a crosslinking agent.

[0045] [9] The gap-filler-forming composition according to any one of [1] to [8], which is used for temporary filling of through holes in an insulating layer when forming a redistribution layer.

[0046]

[10] A gap filler cured product, formed by applying the gap filler forming composition according to any one of [1] to [9] to a substrate, followed by firing.

[0047]

[11] The solidified material according to

[10] , which can be removed by a chemical solution.

[0048]

[12] A method for producing a redistribution layer, comprising the step of filling a through-hole of an insulating layer with a gap-filler cured product formed from the gap-filler-forming composition according to any one of [1] to [9].

[0049]

[13] The method for producing a redistribution layer according to

[12] , further comprising, after the step of filling the through-holes, a step of removing the cured product of the gap-filling material using a chemical solution.

[0050]

[14] A method for manufacturing a printed circuit board, the method comprising the step of manufacturing a redistribution layer.

[0051] The step of producing the redistribution layer includes the step of filling the through-holes of the insulating layer with a gap-filler cured product formed from the gap-filler-forming composition according to any one of [1] to [9].

[0052]

[15] The method for manufacturing a printed circuit board according to

[14] , further comprising, after the step of filling the through-holes, a step of removing the cured product of the gap-filling material with a chemical solution.

[0053] Effects of the Invention

[0054] According to the present invention, there can be provided a gap-filling material composition suitable for temporarily filling through-holes in an insulating layer when forming a redistribution layer, a gap-filling material cured product using the gap-filling material composition, and a method for producing a wiring circuit board using the gap-filling material composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1A This is a schematic diagram for explaining an example of a dual damascene process (part 1).

[0056] Figure 1B This is a schematic diagram for explaining an example of a dual damascene process (part 2).

[0057] Figure 1C This is a schematic diagram for explaining an example of a dual damascene process (part 3).

[0058] Figure 1D This is a schematic diagram for explaining an example of a dual damascene process (part 4).

[0059] Figure 1E This is a schematic diagram for explaining an example of a dual damascene process (part 5).

[0060] Figure 1F It is a schematic diagram for explaining an example of a dual damascene process (part 6).

[0061] Figure 1G 7 is a schematic diagram for explaining an example of a dual damascene process.

[0062] Figure 1H It is a schematic diagram for explaining an example of a dual damascene process (part 8).

[0063] Fig. 1I 9 is a schematic diagram for explaining an example of a dual damascene process.

[0064] Figure 1J FIG. 10 is a schematic diagram for explaining an example of a dual damascene process.

[0065] Figure 1K FIG. 11 is a schematic diagram for explaining an example of a dual damascene process.

[0066] Figure 2AThis is a schematic diagram (part 1) for explaining one embodiment of the present invention (formation of a redistribution layer using a dual damascene process).

[0067] Figure 2B This is a schematic diagram (part 2) for explaining one embodiment of the present invention (formation of a redistribution layer using a dual damascene process).

[0068] Figure 2C This is a schematic diagram (part 3) for explaining one embodiment of the present invention (formation of a redistribution layer using a dual damascene process).

[0069] Figure 2D This is a schematic diagram (part 4) for explaining one embodiment of the present invention (formation of a redistribution layer using a dual damascene process).

[0070] Figure 2E It is a schematic diagram (part 5) for explaining one embodiment of the present invention (formation of a redistribution layer using a dual damascene process).

[0071] Figure 2F It is a schematic diagram (part 6) for explaining one embodiment of the present invention (formation of a redistribution layer using a dual damascene process).

[0072] Figure 2G It is a schematic diagram (part 7) for explaining one embodiment of the present invention (formation of a redistribution layer using a dual damascene process).

[0073] Figure 2H It is a schematic diagram (part 8) for explaining one embodiment of the present invention (formation of a redistribution layer using a dual damascene process).

[0074] Fig.2I It is a schematic diagram (No. 9) for explaining one embodiment of the present invention (formation of a redistribution layer using a dual damascene process).

[0075] Figure 2J It is a schematic diagram (No. 10 ) for explaining one embodiment of the present invention (formation of a redistribution layer using a dual damascene process).

[0076] Figure 2K It is a schematic diagram (No. 11) for explaining one embodiment of the present invention (formation of a redistribution layer using a dual damascene process).

[0077] Figure 3 This is a SEM photograph of Example 1 when evaluating the embedding property and planarization property.

[0078] Figure 4 This is a SEM photograph of Example 2 when evaluating the embedding property and planarization property.

[0079] Figure 5 This is a SEM photograph of Example 3 when evaluating the embedding property and planarization property.

[0080] Figure 6 This is a SEM photograph of Example 4 when evaluating the embedding property and planarization property.

[0081] Figure 7 This is a SEM photograph of Comparative Example 1 when evaluating the embedding property and planarization property. DETAILED DESCRIPTION

[0082] (Gap-filler-forming composition)

[0083] The gap-filler-forming composition of the present invention contains at least one of a compound and a polymer, and a solvent, wherein the compound and the polymer have a structure represented by the following formula (1) and a carbonyl bond.

[0084]

[0085] (In formula (1), R 1 and R 2 Each independently represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms, a halogen atom, -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ) or -COO-.

[0086] R 3 represents a methoxy group, an alkyl group having 1 to 13 carbon atoms, or a halogen atom. 3 When there are 2 or more, 2 or more R 3 It can be the same or different.

[0087] n1 represents an integer of 0 to 4. n2 represents an integer of 0 or 1. However, the total of n1 and n2 is 4 or less.

[0088] X 1 It represents an ether bond or an ester bond.

[0089] X 2 It represents an ether bond or an ester bond.

[0090] * indicates a bond. )

[0091] The gap-filler-forming composition of the present invention can be suitably used for temporary filling of through holes in an insulating layer when a redistribution layer is produced.

[0092] By using the gap-filling material-forming composition of the present invention to temporarily bury the through-holes of the insulating layer when making a redistribution layer, through-holes and wirings with barrier layers formed not only on the lower surface but also on the side surfaces can be formed in the redistribution layer. As a result, the migration of metal from the through-holes and wirings to the insulating layer can be reduced, forming a highly reliable redistribution layer. It can be preferably used as a gap-filling material in a dual damascene process.

[0093] Details will be used later Figure 2A to Figure 2K Provide explanation.

[0094] <Compounds and polymers>

[0095] The compound and polymer contained in the gap-filler-forming composition (hereinafter, sometimes referred to as "specific compound and polymer") have a structure represented by the following formula (1) and a carbonyl bond.

[0096] It should be noted that, in the present invention, the distinction between a compound and a polymer does not need to be particularly clear. For example, as long as it is a substance having a structure shown in formula (1) and a carbonyl bond, it can be low molecular weight, high molecular weight, single composition, or have a molecular weight distribution (for example, the polydispersity (weight average molecular weight / number average molecular weight) can exceed 1).

[0097] <<Structure represented by formula (1)>>

[0098]

[0099] (In formula (1), R 1 and R 2 Each independently represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms, a halogen atom, -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ) or -COO-.

[0100] R 3 represents a methoxy group, an alkyl group having 1 to 13 carbon atoms, or a halogen atom. 3 When there are 2 or more, 2 or more R 3 It can be the same or different.

[0101] n1 represents an integer of 0 to 4. n2 represents an integer of 0 or 1. However, the total of n1 and n2 is 4 or less.

[0102] X 1 It represents an ether bond or an ester bond.

[0103] X 2 It represents an ether bond or an ester bond.

[0104] * indicates a bond. )

[0105] Since the structure represented by formula (1) has absorption of ultraviolet rays (e.g., i-rays (365 nm)), the gap-filling material cured product obtained from the gap-filling material forming composition has an anti-reflection function. Therefore, it is possible to prevent the poor patterning of the photoresist layer when a photoresist layer is formed on the gap-filling material cured product and photolithography is performed. That is, the gap-filling material forming composition of the present invention can also be said to be a composition for forming an anti-reflection layer or a composition for forming an ultraviolet-proof reflection layer.

[0106] As R in formula (1) 1 ~R 3 The alkyl group having 1 to 13 carbon atoms in the group includes, for example, an alkyl group having 1 to 6 carbon atoms.

[0107] Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, isopropyl group, n-butyl group, and cyclohexyl group.

[0108] As R in formula (1) 11 Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, isopropyl, and n-butyl.

[0109] As X in formula (1) 1 , preferably represents an ether bond.

[0110] As R in formula (1) 1 , preferably represents cyano or -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ).

[0111] As R in formula (1) 2 , preferably represents cyano, -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ) or -COO-.

[0112] As n2 in formula (1), 0 is preferred.

[0113] <<Carbonyl bond>>

[0114] The specific compound and polymer have a carbonyl bond in addition to the structure shown in formula (1). Since the specific compound and polymer have a carbonyl bond, the gap filler cured product obtained from the gap filler forming composition has excellent removability. Therefore, the gap filler forming composition can be suitable for temporary embedding of the through hole of the insulating layer when making the redistribution layer.

[0115] The cured product of the gap-filling material is removed by, for example, wet etching or dry etching using an alkaline organic solvent.

[0116] The carbon atom of the carbonyl bond (-CO-) can be bonded to a carbon atom, can be bonded to an oxygen atom, or can be bonded to a nitrogen atom. Therefore, the carbonyl bond can be a carbonyl bond in an ester group (-COO-), a carbonyl bond in an amide group (-CO-NH-), a carbonyl bond in an isocyanuric acid skeleton, or a carbonyl bond in a hydantoin skeleton.

[0117] There is no particular limitation on the amount of carbonyl bonds in the specific compound or polymer.

[0118] The specific compound and polymer preferably have at least one of a structure represented by the following formula (2) and a structure represented by the following formula (3) as a structure having a carbonyl bond.

[0119]

[0120] (In formula (2), X 11 It represents a group represented by any one of the following formulae (2-1) to (2-4). 1 and Z 2 Each independently represents a single bond or a divalent group represented by the following formula (2-5) (wherein *3 in formula (2-5) represents a bond to the nitrogen atom in formula (2).) 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each independently represents a hydrogen atom, a methyl group or an ethyl group. * represents a bond.

[0121] In formula (3), Q 1 A represents a divalent organic group having an aromatic hydrocarbon ring. 11 , A 12 , A 13 , A 14 , A 15 and A 16 Each independently represents a hydrogen atom, a methyl group or an ethyl group. n11 and n12 represent integers of 0 or 1. At least one of n11 and n12 is 1. * represents a bond. )

[0122]

[0123] (In formulas (2-1) to (2-3), R 1 ~R 5Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. 1 With R 2 They may be bonded to each other to form a ring having 3 to 6 carbon atoms. 3 With R 4 They may be bonded to each other to form a ring having 3 to 6 carbon atoms.

[0124] In formula (2-4), Z 3 A represents a single bond or a divalent group represented by the following formula (2-5) (wherein *3 in formula (2-5) represents a bond to the nitrogen atom in formula (2-4).) 7 , A 8 and A 9 Each independently represents a hydrogen atom, a methyl group or an ethyl group.

[0125] * represents a bond. *1 represents a bond to a carbon atom in formula (2). *2 represents a bond to a nitrogen atom in formula (2).

[0126]

[0127] (In formula (2-5), m1 is an integer of 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer of 0 to 2. When m3 is 1, m1 and m2 are not simultaneously 0. *3 represents a bond to a nitrogen atom in formula (2) or (2-4). *4 represents a bond to a carbon atom in formula (2) or (2-4).)

[0128] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0129] In this specification, the alkyl group is not limited to a straight chain, and may be a branched chain or a cyclic chain. Examples of the straight chain or branched chain alkyl group include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a n-hexyl group, etc. Examples of the cyclic alkyl group (cycloalkyl group) include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.

[0130] In the present specification, examples of the alkoxy group include a methoxy group, an ethoxy group, an n-pentyloxy group, an isopropoxy group, and the like.

[0131] In the present specification, examples of the alkylthio group include a methylthio group, an ethylthio group, a n-pentylthio group, an isopropylthio group, and the like.

[0132] In the present specification, examples of the alkenyl group include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl.

[0133] In the present specification, examples of the alkynyl group include groups in which the double bond of the alkenyl group exemplified in the above-mentioned "alkenyl group" is replaced with a triple bond.

[0134] In the present specification, examples of the alkenyloxy group include vinyloxy, 1-propenyloxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, and prenyloxy.

[0135] In the present specification, examples of the alkynyloxy group include a 2-propynyloxy group, a 1-methyl-2-propynyloxy group, a 2-methyl-2-propynyloxy group, a 2-butynyloxy group, and a 3-butynyloxy group.

[0136] In the present specification, examples of the acyl group include an acetyl group and a propionyl group.

[0137] In the present specification, examples of the aryloxy group include a phenoxy group and a naphthoxy group.

[0138] In the present specification, examples of the arylcarbonyl group include a phenylcarbonyl group and the like.

[0139] In the present specification, examples of the aralkyl group include a benzyl group and a phenethyl group.

[0140] In the present specification, examples of the alkylene group include a methylene group, an ethylene group, a 1,3-propylene group, a 2,2-propylene group, a 1-methylethylene group, a 1,4-butylene group, a 1-ethylethylene group, a 1-methylpropylene group, a 2-methylpropylene group, a 1,5-pentylene group, a 1-methylbutylene group, a 2-methylbutylene group, a 1,1-dimethylpropylene group, a 1,2-dimethylpropylene group, a 1-ethylpropylene group, a 2-ethylpropylene group, a 1,6-hexylene group, a 1,4-cyclohexylene group, a 1,8-octylene group, a 2-ethyloctylene group, a 1,9-nonylene group, and a 1,10-decylene group.

[0141] As R in formulas (2-1) to (2-3) 1 ~R 5 The alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom includes, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkoxyalkyl group having 3 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and an alkylthioalkyl group having 2 to 10 carbon atoms.

[0142] Furthermore, the alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom may contain two or more oxygen atoms or sulfur atoms.

[0143] As Q in formula (3) 1 , preferably represented by the following formula (3-1) or formula (3-2).

[0144]

[0145] (In formulas (3-1) to (3-2), R 21 ~R 23 Each independently represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an alkynyloxy group having 2 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. * represents a bond.

[0146] In formula (3-1), n3 represents 0 or 1. When n3 is 0, n21 represents an integer from 0 to 4. When n3 is 1, n21 represents an integer from 0 to 6. 21 When there are 2 or more, 2 or more R 21 It can be the same or different.

[0147] In formula (3-2), Z 4 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms. n22 and n23 each independently represent an integer of 0 to 4. 22 When there are 2 or more, 2 or more R 22 Can be the same or different. 23 When there are 2 or more, 2 or more R 23 Can be the same or different.)

[0148] Examples of the following formula (2X) in the formula (2) include the structures exemplified below.

[0149]

[0150] (In formula (2X), X 11 , Z 1 and Z 2 Each of them is the same as X in formula (2) 11 , Z 1 and Z 2 The meaning is the same. * indicates a bond. )

[0151]

[0152]

[0153] (* indicates a bond.)

[0154] Examples of the following formula (3X) in the formula (3) include the structures exemplified below.

[0155]

[0156] (In formula (3X), Q 1 , n11 and n12 are respectively related to Q in formula (3) 1 , n11 and n12 have the same meaning. At least one of n11 and n12 is 1. * represents a bond. )

[0157]

[0158] (* indicates a bond.)

[0159] <<Other structures>>

[0160] The specific compound and polymer may have a structure other than the structure represented by formula (1) and the carbonyl bond. As such a structure, a structure represented by the following formula (E) is preferred from the viewpoint of improving crosslinking efficiency and removability.

[0161]

[0162] (In formula (E), X 21 Represents -COO-, -OCO-, -O-, -S- or -NR a -, R a represents a hydrogen atom or a methyl group. 21 A represents a directly bonded or substituted alkylene group having 1 to 4 carbon atoms. 21 ~A 23 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted, or an aryl group having 6 to 40 carbon atoms which may be substituted. * represents a bond. )

[0163] In formula (E), Y 21 , and A 21 ~A 23 Here, "may be substituted" means that a part or all of the hydrogen atoms present in the substituted functional group may be independently substituted by, for example, a hydroxyl group, a halogen atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group or an alkoxy group having 1 to 9 carbon atoms.

[0164] As X 21 , preferably -S-.

[0165] As Y 21 The alkylene group having 1 to 4 carbon atoms which may be substituted is not particularly limited, but a methylene group is preferred.

[0166] As A 21 ~A 23 The aryl group having 6 to 40 carbon atoms which may be substituted is not particularly limited, and examples thereof include phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl.

[0167] As for the specific compound and polymer, as the compound having the structure represented by formula (1) and a carbonyl bond, a compound represented by the following formula (1-2) is preferred.

[0168]

[0169] (In formula (1-2), Z 1 , Z 2 , A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each of them is related to Z in formula (2) 1 , Z 2 , A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Same meaning.

[0170] Z 3 , A 7 , A 8 and A 9 Each of them is related to Z in formula (2-4) 3 , A 7 , A 8 and A 9 Same meaning.

[0171] Y 1 , Y 2 and Y 3 Each independently represents a structure represented by the following formula (1X) or a structure represented by the following formula (E). 1 ~Y 3At least one of them represents the structure represented by formula (1X).

[0172]

[0173] (In formula (1X), X 1 , R 3 and n1 are respectively the same as X in formula (1) 1 , R 3 Same meaning as n1. 1 and R 2 Each independently represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms, a halogen atom or -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ) * represents a bond. )

[0174] The specific compound and polymer preferably have at least one of the structure represented by the following formula (1-3) and the structure represented by the following formula (1-4) as the structure having "the structure represented by the formula (1) and a carbonyl bond". The structure represented by the formula (1-3) may be a repeating unit in the polymer. The structure represented by the formula (1-4) may be a repeating unit in the polymer.

[0175]

[0176] (In formula (1-3) and formula (1-4), X 1 , R 3 and n1 are respectively the same as X in formula (1) 1 , R 3 Has the same meaning as n1.

[0177] In formula (1-3), X 11 , Z 1 , Z 2 , A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each of them is the same as X in formula (2) 11 , Z 1 , Z 2 , A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Same meaning.

[0178] In formula (1-3), R 1 represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms, a halogen atom, or -COOR11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ).

[0179] In formula (1-4), Q 1 , A 11 , A 12 , A 13 , A 14 , A 15 , A 16 , n11 and n12 are respectively related to Q in formula (3) 1 , A 11 , A 12 , A 13 , A 14 , A 15 , A 16 , n11 and n12 have the same meaning. At least one of n11 and n12 is 1.

[0180] * indicates a bond. )

[0181] The weight average molecular weight of the compound or polymer is, for example, 300 to 100,000, preferably 300 to 50,000, more preferably 300 to 10,000, particularly preferably 300 to 5,000.

[0182] An example of a method for producing a specific compound and a polymer will be described.

[0183] One example of the specific compound and polymer can be obtained by, for example, the following reactions (I) to (IV).

[0184] (I): A reaction in which a compound represented by the following formula (1A) is reacted with a compound represented by the following formula (2A), and then an active methylene compound (Ra-CH2-Rb) is reacted with the obtained reaction product.

[0185] (II): A reaction in which a compound represented by the following formula (1A), a compound represented by the following formula (2A), and a compound represented by the following formula (EA) are reacted, and then an active methylene compound (Ra-CH2-Rb) is reacted with the obtained reaction product.

[0186] By using active methylene compounds such as malononitrile, malonic acid, and malonate in these reactions, the aldehyde group can be converted into a "-CH=C(Ra)(Rb)" group by Knoevenagel condensation. Ra and Rb are, for example, cyano, -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ).

[0187]

[0188] (In formula (1A), X 1A It represents a hydroxyl group or a carboxyl group.

[0189] In formula (1A), R 3 and n1 are respectively the same as R in formula (1) 3 Has the same meaning as n1.

[0190] In formula (2A), Z 1 , Z 2 , A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each of them is related to Z in formula (2) 1 , Z 2 , A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Same meaning.

[0191] In formula (2A), Z 3 , A 7 , A 8 and A 9 Each of them is related to Z in formula (2-4) 3 , A 7 , A 8 and A 9 Same meaning.

[0192] In formula (EA), X 21 , Y 21 , A 21 , A 22 and A 23 Each of them is the same as X in formula (E) 21 , Y 21 , A 21 , A 22 and A 23 Same meaning.)

[0193] (III): reacting a compound represented by the following formula (1B) with at least one of a compound represented by the following formula (2B) and a compound represented by the following formula (3B).

[0194] (IV): Reaction of a compound represented by the following formula (1C) with at least one of a compound represented by the following formula (2B) and a compound represented by the following formula (3B).

[0195]

[0196] (In formula (1B), X 1A It represents a hydroxyl group or a carboxyl group.

[0197] In formula (1B), R 3 and n1 are respectively the same as R in formula (1) 3 Same meaning as n1. 1 represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms, a halogen atom, or -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ).

[0198] In formula (1C), R 3 and n1 are respectively the same as R in formula (1) 3 Same meaning as n1. 1 and R 2 Each independently represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms, a halogen atom or -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ).

[0199] In formula (2B), X 11 , Z 1 , Z 2 , A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each of them is the same as X in formula (2) 11 , Z 1 , Z 2 , A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Same meaning.

[0200] In formula (3B), Q 1 , A 11 , A 12 , A 13 , A 14 , A 15 , A 16 , n11 and n12 are respectively related to Q in formula (3) 1 , A 11 , A 12 , A 13 , A 14 , A 15, A 16 , n11 and n12 have the same meaning. Wherein, at least one of n11 and n12 is 1. )

[0201] Examples of the compound represented by formula (1A) include 4-hydroxybenzaldehyde and p-formylbenzoic acid, etc. These may be used alone or in combination of two or more.

[0202] Examples of the compound represented by formula (1B) include α-cyano-4-hydroxycinnamic acid and the like.

[0203] Examples of the compound represented by formula (1C) include the following compounds.

[0204]

[0205] In the formula, Me represents a methyl group.

[0206] Examples of the compound represented by formula (2A) or formula (2B) include the following compounds.

[0207]

[0208]

[0209]

[0210] Examples of the compound represented by formula (3A) include the following compounds.

[0211]

[0212]

[0213] Examples of the compound represented by formula (EA) include thioglycerol and the like.

[0214] Reactions (I) to (VI) can be carried out in the presence of a catalyst, for example, tetrabutyl bromide Ethyltriphenylphosphine bromide That kind of season The amount of the catalyst used can be selected from a range of 0.1 to 10% by mass relative to the total mass of the reaction raw materials used in the reaction. The temperature and time for the reaction can be selected from the range of 80 to 160° C. and 2 to 50 hours for the best conditions.

[0215] The content of the specific compound and polymer in the gap-filling material forming composition is not particularly limited, but is preferably 5% to 99% by mass, more preferably 10% to 98% by mass, and particularly preferably 20% to 95% by mass, relative to the film-constituting components in the gap-filling material forming composition.

[0216] The film-constituting components refer to the components other than the solvent in the gap-filler-forming composition.

[0217] <Cross-linking agent>

[0218] The gap-filler-forming composition preferably contains a cross-linking agent.

[0219] The crosslinking agent contained as an optional component in the gap-filler-forming composition has, for example, a functional group that reacts independently of itself.

[0220] Examples of the crosslinking agent include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (tetramethoxymethyl glycoluril) (POWDERLINK [registered trademark] 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea.

[0221] Furthermore, the crosslinking agent may be a nitrogen-containing compound described in International Publication No. 2017 / 187969, which has 2 to 6 substituents represented by the following formula (1d) bonded to a nitrogen atom in one molecule.

[0222]

[0223] (In formula (1d), R1 represents a methyl group or an ethyl group. * represents a bond to a nitrogen atom.)

[0224] The nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1d) in one molecule may be a glycoluril derivative represented by the following formula (1E).

[0225]

[0226] (In formula (1E), four R1s each independently represent a methyl group or an ethyl group, and R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)

[0227] Examples of the glycoluril derivative represented by the above formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0228]

[0229] The nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1d) in one molecule can be obtained by reacting a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (2d) bonded to a nitrogen atom in one molecule with at least one compound represented by the following formula (3d).

[0230]

[0231] (In formula (2d) and formula (3d), R1 represents a methyl group or an ethyl group, and R4 represents an alkyl group having 1 to 4 carbon atoms. * represents a bond to a nitrogen atom.)

[0232] The glycoluril derivative represented by the above formula (1E) can be obtained by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the above formula (3d).

[0233] The nitrogen-containing compound having 2 to 6 substituents represented by the formula (2d) in one molecule is, for example, a glycoluril derivative represented by the following formula (2E).

[0234]

[0235] (In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represents an alkyl group having 1 to 4 carbon atoms.)

[0236] Examples of the glycoluril derivatives represented by the above formula (2E) include compounds represented by the following formulas (2E-1) to (2E-4). Further examples of the compounds represented by the above formula (3d) include compounds represented by the following formulas (3d-1) and (3d-2).

[0237]

[0238] Regarding the nitrogen-containing compound having 2 to 6 substituents represented by formula (1d) bonded to a nitrogen atom in one molecule, the entire disclosure of WO2017 / 187969 is incorporated herein by reference.

[0239] Furthermore, the crosslinking agent may be a crosslinking compound described in International Publication No. 2014 / 208542 and represented by the following formula (G-1) or formula (G-2).

[0240]

[0241] (Where Q 1 Represents a single bond or m1-valent organic group, R 1 and R4 Each represents an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms having an alkoxy group having 1 to 10 carbon atoms, and R 2 and R 5 Each represents a hydrogen atom or a methyl group, R 3 and R 6 Each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0242] n1 represents an integer of 1≤n1≤3, n2 represents an integer of 2≤n2≤5, n3 represents an integer of 0≤n3≤3, n4 represents an integer of 0≤n4≤3, and n1, n2, n3, n4 represent integers of 3≤(n1+n2+n3+n4)≤6.

[0243] n5 represents an integer of 1≤n5≤3, n6 represents an integer of 1≤n6≤4, n7 represents an integer of 0≤n7≤3, n8 represents an integer of 0≤n8≤3, and n5, n6, n7, n8 represent integers of 2≤(n5+n6+n7+n8)≤5.

[0244] m1 represents an integer from 2 to 10. )

[0245] The crosslinkable compound represented by the above formula (G-1) or (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or (G-4) with an ether compound containing a hydroxyl group or an alcohol having 2 to 10 carbon atoms.

[0246]

[0247] (Where Q 2 Represents a single bond or an m2-valent organic group. 8 , R 9 , R 11 and R 12 Each represents a hydrogen atom or a methyl group, R 7 and R 10 Each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0248] n9 represents an integer of 1≤n9≤3, n10 represents an integer of 2≤n10≤5, n11 represents an integer of 0≤n11≤3, n12 represents an integer of 0≤n12≤3, and n9, n10, n11, n12 represent integers of 3≤(n9+n10+n11+n12)≤6.

[0249] n13 represents an integer of 1≤n13≤3, n14 represents an integer of 1≤n14≤4, n15 represents an integer of 0≤n15≤3, n16 represents an integer of 0≤n16≤3, and n13, n14, n15, n16 represent integers of 2≤(n13+n14+n15+n16)≤5.

[0250] m2 represents an integer from 2 to 10. )

[0251] Examples of the compounds represented by the above formula (G-1) and formula (G-2) are shown below.

[0252]

[0253]

[0254]

[0255] Examples of the compounds represented by formula (G-3) and formula (G-4) are shown below.

[0256]

[0257]

[0258] In the formula, Me represents a methyl group.

[0259] The entire disclosure of International Publication No. 2014 / 208542 is incorporated herein by reference.

[0260] When a crosslinking agent is used, the content ratio of the crosslinking agent in the gap-filler-forming composition is not particularly limited, but is, for example, 1 to 50% by mass, preferably 5 to 40% by mass, based on the specific compound and the polymer.

[0261] <Curing catalyst>

[0262] As the curing catalyst contained as an optional component in the gap-filling material forming composition, either a thermal acid generator or a photoacid generator may be used, but a thermal acid generator is preferably used.

[0263] Examples of the thermal acid generator include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridine - p-Toluenesulfonate (pyridine -p-Toluenesulfonic acid), pyridine Phenolsulfonic acid, pyridine -p-Hydroxybenzenesulfonic acid (pyridinium phenolsulfonate Salt), pyridine - Sulfonic acid compounds and carboxylic acid compounds such as trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, and hydroxybenzoic acid.

[0264] Examples of the photoacid generator include: Salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds, etc.

[0265] As Salt compounds, for example, diphenyl iodide Hexafluorophosphate, diphenyl iodide Trifluoromethanesulfonate, diphenyl iodide Nonafluorobutane sulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphorsulfonate, bis(4-tert-butylphenyl)iodide Camphorsulfonate and bis(4-tert-butylphenyl)iodide Trifluoromethanesulfonate and other iodine Sulfonium salt compounds, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.

[0266] Examples of the sulfonyl imide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0267] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0268] The curing catalyst may be used alone or in combination of two or more.

[0269] When a curing catalyst is used, the content ratio of the curing catalyst is, for example, 0.1 mass % to 50 mass %, and preferably 1 mass % to 30 mass % based on the cross-linking agent.

[0270] <Solvent>

[0271] The gap-filler forming composition contains a solvent.

[0272] As the solvent, an organic solvent generally used in a chemical solution for a semiconductor photolithography process is preferred. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, 2 ethyl-hydroxyisobutyrate, ethyl ethoxylate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

[0273] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred, and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0274] <Other ingredients>

[0275] A surfactant may be further added to the gap-filling material-forming composition in order to prevent pinholes, streaks, and the like from being generated and to further improve the coating properties on uneven surfaces.

[0276] Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as sorbitan tristearate, Eftop EF301, EF303, EF352 (trade names of Tokem Projects), Megaphac F171, F173, R-30 (trade names of DIC Corporation), Fluoro FC430, FC 431 (manufactured by Sumitomo Slide Group, trade name), Asahigard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., trade name), etc., organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0277] The amount of these surfactants blended is not particularly limited, but is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the gap-filler-forming composition.

[0278] These surfactants may be added alone or in combination of two or more.

[0279] The film-constituting components contained in the gap-filler-forming composition, that is, the components excluding the solvent, are, for example, 0.01% by mass to 30% by mass of the gap-filler-forming composition.

[0280] The gap-filling material-forming composition of the present invention is prepared, for example, by mixing a specific compound and at least one of a polymer and a solvent by a known method. In order to be used as a gap-filling material-forming composition, it is necessary to be in a uniform solution state. In order to remove metal impurities, foreign matter, etc. present in the composition, the prepared composition is preferably filtered through a filter or the like.

[0281] One of the criteria for evaluating whether the gap-filling material forming composition is in a uniform solution state is to observe the permeability of a specific microfilter. The gap-filling material forming composition of the present invention preferably presents a uniform solution state when passing through microfilters with pore sizes of 0.1 μm, 0.05 μm, 0.03 μm, 0.02 μm, and 0.01 μm.

[0282] The material of the above-mentioned microfilter includes fluororesins such as PTFE (polytetrafluoroethylene), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), PE (polyethylene), UPE (ultra-high molecular weight polyethylene), PP (polypropylene), PSF (polysulfone), PES (polyethersulfone), and nylon, but PTFE (polytetrafluoroethylene) is preferred.

[0283] The gap-filler-forming composition of the present invention is suitably used for temporarily filling through holes in an insulating layer when forming a redistribution layer.

[0284] The so-called rewiring layer is a layer for electrically connecting the semiconductor chip and the external lead-out electrode or electrically connecting two external lead-out electrodes to each other. The rewiring layer used in the present invention has, for example, through holes and wirings.

[0285] It is preferred that the insulating layer used for temporarily embedding the through-holes has the through-holes and does not have grooves for forming wiring.

[0286] The material of the insulating layer is not particularly limited, and examples thereof include inorganic insulating materials and organic insulating materials.

[0287] Examples of the inorganic insulating material include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, yttrium oxide, lanthanum oxide, hafnium oxide, zirconium oxide, silicon nitride, aluminum nitride, and mixtures thereof.

[0288] Examples of the organic insulating material include polyimide, polyamide, polyacrylate, polyvinyl alcohol, novolac resin, liquid crystal polymer, polybenzoic acid, Azoles, polyesters, etc.

[0289] The thickness of the insulating layer is not particularly limited, but is preferably 0.1 μm to 30 μm, more preferably 0.5 μm to 25 μm, and particularly preferably 1 μm to 20 μm.

[0290] The opening area of ​​the through hole is not particularly limited, but is preferably 0.1 μm to 30 μm, more preferably 0.2 μm to 25 μm, and particularly preferably 0.3 μm to 20 μm in terms of equivalent circle diameter. The equivalent circle diameter is the diameter of a circle having the same area as the opening to be targeted.

[0291] The aspect ratio of the through hole (thickness of the insulating layer / equivalent circular diameter of the opening of the through hole) is not particularly limited, but is preferably 0.1-20, more preferably 0.2-15, and particularly preferably 0.3-10.

[0292] The thickness of the insulating layer and the opening area of ​​the through hole can be obtained by, for example, observation with a scanning electron microscope.

[0293] (Filling material cured product)

[0294] The gap filler cured product of the present invention is formed by applying the gap filler-forming composition of the present invention onto a substrate and then firing the coating.

[0295] The substrate to which the gap-filler-forming composition is applied is not particularly limited, and examples thereof include a substrate having an insulating layer in which a through-hole is formed.

[0296] The substrate may be an insulating layer itself in which through holes are formed, or may be a substrate further having a layer or a base material under the insulating layer. Examples of the layer include a redistribution layer.

[0297] Examples of the material of the substrate include metals and resins. Examples of metals include copper and resins. Examples of resins include polyimide and the like.

[0298] As a method for applying the gap filling material forming composition to the substrate, there is no particular limitation, and for example, a suitable coating method such as a spin coater and a coater can be cited. Then, the gap filling material cured product is formed by baking (firing) using a heating means such as a hot plate. As baking conditions, it is appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 120°C to 350°C, and the baking time is 0.5 minutes to 30 minutes, and more preferably, the baking temperature is 150°C to 300°C, and the baking time is 0.8 minutes to 10 minutes.

[0299] The cured product of the gap filling material can be removed by, for example, a chemical solution. Examples of the chemical solution include organic solvents. The chemical solution may contain an acidic compound or a basic compound in addition to the organic solvent.

[0300] Examples of the organic solvent include dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, ethylene glycol, propylene glycol, and diethylene glycol dimethyl ether.

[0301] Examples of the acidic compound include inorganic acids and organic acids. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and the like. Examples of the organic acid include p-toluenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, acetic acid, propionic acid, trifluoroacetic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthoic acid, and the like.

[0302] Examples of the basic compound include inorganic bases and organic bases. Examples of the inorganic base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and amines such as ethanolamine, propylamine, diethylaminoethanol and ethylenediamine.

[0303] The organic solvent used in the chemical solution may be used alone or in combination of two or more.

[0304] In addition, the acidic compound or the basic compound used in the drug solution may be used alone or in combination of two or more.

[0305] The amount of the acidic compound or the basic compound blended is, for example, 0.01 to 20% by mass, preferably 0.1 to 5% by mass, and particularly preferably 0.2 to 1% by mass, based on the drug solution.

[0306] The chemical solution is preferably an organic solvent containing a basic compound (basic organic solvent), and particularly preferably a mixed solution containing dimethyl sulfoxide and tetramethylammonium hydroxide.

[0307] Examples of commercially available alkaline organic solvents include ST-120 (Tokyo Ohka Kogyo Co., Ltd.).

[0308] (Method for manufacturing a rewiring layer, and method for manufacturing a wiring circuit board)

[0309] The method for producing a redistribution layer of the present invention includes a step of filling a through hole.

[0310] The method for producing a printed circuit board of the present invention includes a step of producing a redistribution layer. The step of producing a redistribution layer is the method for producing a redistribution layer of the present invention.

[0311] The step of filling the through-holes is a step of filling the through-holes of the insulating layer with a gap-filler cured product formed from the gap-filler-forming composition of the present invention.

[0312] One embodiment of a method for producing a redistribution layer and a method for producing a printed circuit board will be described using drawings.

[0313] Figure 2A to Figure 2KThis is a schematic diagram for explaining formation of a redistribution layer using a dual damascene process.

[0314] First, a laminate having a support 1 and an insulating layer 2 thereon is prepared. Figure 2A ). A through hole is formed in the insulating layer 2. The insulating layer 2 used here is, for example, a non-photosensitive insulating layer. Examples of the material of the insulating layer include polyimide, polybenzoic acid, and polyisocyanate. Azoles, liquid crystal polymers, silicon oxide, etc.

[0315] The through hole is formed by, for example, photolithography. For example, a photoresist pattern is formed on the insulating layer, and the insulating layer is etched using the pattern as a mask, thereby forming the through hole.

[0316] The thickness of the insulating layer is not particularly limited, but is preferably 0.1 μm to 30 μm, more preferably 0.5 μm to 25 μm, and particularly preferably 1 μm to 20 μm.

[0317] The opening area of ​​the through hole is not particularly limited, but is preferably 0.1 μm to 30 μm, more preferably 0.2 μm to 25 μm, and particularly preferably 0.3 μm to 20 μm in terms of equivalent circle diameter.

[0318] The aspect ratio of the through hole (thickness of the insulating layer / equivalent circular diameter of the opening of the through hole) is not particularly limited, but is preferably 0.1-20, more preferably 0.2-25, and particularly preferably 0.3-10.

[0319] The support 1 is not particularly limited as long as it can support the insulating layer 2, and examples thereof include a substrate and a redistribution layer.

[0320] Examples of the material of the substrate include metals and resins. Examples of metals include copper and resins. Examples of resins include polyimide and the like.

[0321] Next, the gap-filling material forming composition of the present invention is applied onto the insulating layer 2 and fired to form a gap-filling material cured product 3 ( Figure 2B Since the gap-filling material forming composition enters into the through-hole, the formed gap-filling material cured product 3 fills the through-hole.

[0322] The coating method is not particularly limited, and examples thereof include the coating methods mentioned in the description of the cured product of the gap-filling material of the present invention.

[0323] The firing conditions are not particularly limited, and examples thereof include the firing conditions mentioned in the description of the cured product of the gap-filling material of the present invention.

[0324] Next, unnecessary portions of the cured filler material 3 on the insulating layer 2 are removed ( Figure 2C Specifically, the cured filler material 3 on the insulating layer 2, except for the cured filler material 3 filling the through-hole, is removed. The unnecessary cured filler material 3 is removed by, for example, wet etching or dry etching using an alkaline organic solvent.

[0325] Next, a photoresist layer 4 ( 200 Å) is formed on the insulating layer 2 in which the through holes are filled with the gap-filling material cured product 3 to process the insulating layer 2 into a desired shape. Figure 2D ). The photoresist used for the photoresist layer 4 is not particularly limited as long as it is a photoresist that can be removed after the insulating layer 3 is processed into a desired shape, and examples thereof include photoresists used for microprocessing, i-ray photoresists, KrF excimer laser photoresists, ArF excimer laser photoresists, etc. The photoresist may be a positive photoresist or a negative photoresist. The thickness of the photoresist layer 4 is not particularly limited, and examples thereof include 0.5 μm to 3 μm, etc.

[0326] Next, the photoresist layer 4 is processed into a predetermined pattern shape by photolithography using exposure and development. Figure 2E At this time, the cured filler material 3 filling the through-hole has an anti-reflection function, thereby preventing the photoresist layer 4 in contact with the cured filler material 3 from having a poor pattern formation.

[0327] Next, using the patterned photoresist layer 4 as a mask, a groove for forming wiring (wiring forming groove 5b) is formed in the insulating layer 2 by etching. At this time, the gap filling material cured product 3 filling the through hole is also removed, and a through hole for forming a through hole (through hole forming through hole 5a) is formed. Figure 2F ). As an etching method for forming the wiring forming groove 5b, for example, dry etching can be cited. In addition, as a method for removing the gap filling material solidified product 3 filling the through hole, for example, wet etching using an alkaline organic solvent can be cited. It should be noted that, by etching for forming the wiring forming groove 5b, a part or all of the gap filling material solidified product 3 filling the through hole can be removed from the through hole.

[0328] The width of the wiring forming groove is not particularly limited, and is preferably 0.05 μm to 30 μm, more preferably 0.1 μm to 20 μm, and particularly preferably 0.2 μm to 10 μm. The width of the wiring forming groove is, in other words, the length of the wiring forming groove in the width direction perpendicular to the thickness direction of the insulating layer.

[0329] The depth of the wiring forming groove is not particularly limited, and is preferably 0.05 μm to 5 μm, more preferably 0.1 μm to 4 μm, and particularly preferably 0.2 μm to 3 μm. The depth of the wiring forming groove is, in other words, the length of the wiring forming groove in the thickness direction of the insulating layer.

[0330] The depth of the wiring forming groove is not particularly limited, and can be, for example, 1 / 50 or more, 1 / 30 or more, or 1 / 20 or more of the thickness of the insulating layer. In addition, the depth of the wiring forming groove can be less than 1 / 1, 1 / 2 or less, or 1 / 10 of the thickness of the insulating layer.

[0331] The width of the wiring forming groove corresponds to the width of wiring in wiring described later.

[0332] The depth of the wiring forming groove corresponds to the height of wiring in wiring described later.

[0333] Next, a barrier / seed layer 6 ( 5a ) serving as both a barrier layer and a seed layer is formed on the surface of the insulating layer 2 having the through hole 5a for forming a via hole and the groove 5b for forming a wiring line. Figure 2G The barrier / seed layer 6 is, for example, a two-layer structure in which the lower layer is a Ti layer and the upper layer is a Cu layer. The barrier / seed layer 6 is also formed on the surface of the insulating layer 2 in the through hole 5a for forming a through hole and the groove 5b for forming a wiring.

[0334] Next, a plating layer 7 is formed on the barrier / seed layer 6 ( Figure 2H ). The plating layer 7 is, for example, a Cu layer. The plating layer 7 is formed in such a way that the plating layer 7 fills the through hole 5a for forming the through hole and the groove 5b for forming the wiring. The plating layer 7 is formed, for example, by electrolytic plating. It should be noted that the plating layer 7 may also be formed by electroless plating. In this case, since it is not necessary to form a seed layer, a barrier layer is formed instead of the barrier / seed layer 6.

[0335] Next, the plating layer 7 and the barrier / seed layer 6 on the upper surface of the insulating layer 2 are removed ( Fig.2I ). The plating layer 7 and the barrier / seed layer 6 on the upper surface of the insulating layer 2 are removed by, for example, CMP (chemical mechanical polishing). In this way, the plating material filling the through hole 5a for forming the through hole and the groove 5b for forming the wiring is electrically independent, forming the through hole 7a and the wiring 7b ( Fig.2I ).

[0336] Through the above, Fig.2I As shown, a redistribution layer including the insulating layer 2, the through-holes 7a formed inside the insulating layer 2, and the wirings 7b formed inside the insulating layer 2 is obtained.

[0337] In this rewiring layer, since the barrier layer is formed not only on the bottom surface of the through hole 7a and the wiring 7b but also on the side surface, it is possible to prevent the metal constituting the through hole and the wiring from migrating to the insulating layer compared to the case where the barrier layer is only formed on the bottom surface of the through hole and the wiring.

[0338] Furthermore, in the redistribution layer, the wiring 7b is formed inside the insulating layer 2 and does not fly out from the surface of the insulating layer 2. In other words, in the redistribution layer, the through hole and the wiring through hole are exposed on the surface of the insulating layer, and the exposed surface of the through hole, the exposed surface of the wiring, and the surface of the insulating layer form a flat surface. Therefore, the thickness of the redistribution layer is uniform. When the redistribution layer with uniform thickness is stacked to obtain a laminate, a laminate with excellent flatness can be obtained.

[0339] Furthermore, an insulating layer 8 ( Figure 2J The insulating layer 8 is, for example, a non-photosensitive insulating layer. Next, a through hole ( Figure 2K ). Next, proceed with Figure 2B to Figure 2I By doing so, the redistribution layer can be made into a multi-layer structure.

[0340] Example

[0341] Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples, but the present invention is not limited only to the following examples.

[0342] The apparatus and the like used for measuring the weight average molecular weight of the polymer obtained in the following synthesis example are shown.

[0343] ·Device: HLC-8320GPC manufactured by Higashikata Co., Ltd.

[0344] ·GPC column: Shodex〔registered trademark〕 ·Asahipak〔registered trademark〕(Showa Denko K.K.)

[0345] Column temperature: 40°C

[0346] Flow rate: 0.35mL / min

[0347] ·Eluent: Tetrahydrofuran (THF)

[0348] · Standard sample: Polystyrene (Tosoh Corporation)

[0349] <Synthesis example 1>

[0350] 9.00 g of a triazine epoxy compound (product name: TEPIC, manufactured by Nissan Chemical Co., Ltd., epoxy functionality: 10.03 eq. / kg), 5.51 g of 4-hydroxybenzaldehyde, 6.78 g of p-formaldehyde benzoic acid, and tetrabutyl bromide were added. 1.53g, and 34.23g of propylene glycol monomethyl ether were added to a reaction flask, and heated under reflux for 23 hours under a nitrogen atmosphere. Then, a solution obtained by dissolving 5.96g of malononitrile in 32.93g of propylene glycol monomethyl ether was added to the system, and further heated under reflux for 4 hours. The resulting reaction product was equivalent to formula (A-1), and the weight average molecular weight Mw measured by GPC in terms of polystyrene was 900.

[0351]

[0352] (L1, L2 and L3 each represent a bond, and L1 together with L2 or L3 represents a single bond.)

[0353] <Synthesis example 2>

[0354] 5.00 g of a triazine epoxy compound (product name: TEPIC, manufactured by Nissan Chemical Co., Ltd., epoxy functionality: 10.03 eq. / kg), 4.26 g of 4-hydroxybenzaldehyde, 2.71 g of thioglycerol, and tetrabutyl bromide were added. 0.51g, and 49.92g of propylene glycol monomethyl ether were added to a reaction flask, and heated under reflux for 6 hours under a nitrogen atmosphere. Next, a solution obtained by dissolving 1.56g of malononitrile in 4.0g of propylene glycol monomethyl ether was added to the system, and further heated under reflux for 4 hours. The resulting reaction product was equivalent to formula (A-2), and the weight average molecular weight Mw measured by GPC in terms of polystyrene was 1300.

[0355]

[0356] (L1, L2 and L3 each represent a bond, and L1 together with L2 or L3 represents a single bond.)

[0357] <Synthesis Example 3>

[0358] 10.00 g of diglycidyl terephthalate (product name: EX-711, manufactured by Nagase Chemtex Co., Ltd.), 6.86 g of α-cyano-4-hydroxycinnamic acid, and tetrabutyl bromide were mixed. 0.59 g of propylene glycol monomethyl ether and 69.80 g of propylene glycol monomethyl ether were added to a reaction flask, and heated and stirred at an internal temperature of 105° C. for 24 hours under a nitrogen atmosphere. The obtained reaction product corresponded to formula (A-3), and the weight average molecular weight Mw measured by GPC in terms of polystyrene was 1930.

[0359]

[0360] <Synthesis Example 4>

[0361] 10.00 g of monoallyl diglycidyl isocyanurate (product name: MA-DGIC, manufactured by Shikoku Chemical Industry Co., Ltd.), 7.12 g of α-cyano-4-hydroxycinnamic acid, and tetrabutyl bromide were added. 0.61 g of propylene glycol monomethyl ether and 70.89 g of propylene glycol monomethyl ether were added to a reaction flask, and heated and stirred at an internal temperature of 105° C. for 24 hours under a nitrogen atmosphere. The obtained reaction product corresponded to formula (A-4), and the weight average molecular weight Mw measured by GPC in terms of polystyrene was 2671.

[0362]

[0363] <Comparative Synthesis Example 1>

[0364] 15.00 g of phenol novolac epoxy resin (product name: DEN, manufactured by Daw Chemika, epoxy functionality: 5.55 eq. / kg), 10.17 g of 4-hydroxybenzaldehyde, and tetrabutyl bromide were mixed. 1.41g, and 39.87g of propylene glycol monomethyl ether were added to a reaction flask, and heated under reflux for 24 hours under a nitrogen atmosphere. Then, a solution obtained by dissolving 5.50g of malononitrile in 34.99g of propylene glycol monomethyl ether was added to the system, and further heated under reflux for 4 hours. The resulting reaction product was equivalent to formula (A-5), and the weight average molecular weight Mw measured by GPC in terms of polystyrene was 2100.

[0365]

[0366] <Example 1>

[0367] To 3.65 g of a solution (solid content: 16.9% by mass) of the reaction product of the above formula (A-1) were added 0.12 g of tetramethoxymethyl glycoluril as a crosslinking agent and pyridine as a crosslinking catalyst. - 0.006 g of p-toluenesulfonate, 1.16 g of propylene glycol monomethyl ether, and 1.05 g of propylene glycol monomethyl ether acetate were added to prepare a gap-filling material-forming composition.

[0368] <Example 2>

[0369] To 3.75 g of a solution (solid content: 16.5% by mass) of the reaction product of the above formula (A-2), 0.12 g of tetramethoxymethyl glycoluril as a crosslinking agent and pyridine as a crosslinking catalyst were added. - 0.006 g of p-toluenesulfonate, 1.16 g of propylene glycol monomethyl ether, and 1.05 g of propylene glycol monomethyl ether acetate were added to prepare a gap-filling material-forming composition.

[0370] <Example 3>

[0371] To 3.22 g of a solution (solid content: 19.2% by mass) of the reaction product of the above formula (A-3) were added 0.12 g of tetramethoxymethyl glycoluril as a crosslinking agent and pyridine as a crosslinking catalyst. - 0.006 g of p-toluenesulfonate, 1.60 g of propylene glycol monomethyl ether, and 1.05 g of propylene glycol monomethyl ether acetate were added to prepare a gap-filling material-forming composition.

[0372] <Example 4>

[0373] To 3.24 g of a solution (solid content: 19.1% by mass) of the reaction product of the above formula (A-4), 0.12 g of tetramethoxymethyl glycoluril as a crosslinking agent and pyridine as a crosslinking catalyst were added. - 0.006 g of p-toluenesulfonate, 1.58 g of propylene glycol monomethyl ether, and 1.05 g of propylene glycol monomethyl ether acetate were added to prepare a gap-filling material-forming composition.

[0374] <Comparative Example 1>

[0375] To 2.62 g of a solution (solid content: 28.8% by mass) of the reaction product of the above formula (A-5) were added 0.47 g of hexamethoxymethylmelamine as a cross-linking agent, 0.02 g of p-toluenesulfonic acid as a cross-linking catalyst, 6.01 g of propylene glycol monomethyl ether, and 0.88 g of ethyl lactate to prepare a composition for forming a gap filling material.

[0376] 〔Evaluation of optical constants〕

[0377] The gap-filling material-forming composition prepared in Examples 1 to 4 and Comparative Example 1 was applied to a silicon wafer using a spin coater so that the film thickness of the obtained film was about 50 nm, and baked (fired) on a hot plate at 200° C. for 90 seconds. The obtained film was measured for n value (refractive index) and k value (attenuation coefficient) at 365 nm (i-ray wavelength) using a spectroscopic ellipsometer (VUV-VASE, manufactured by JA Woolam). The results are shown in Table 1.

[0378] [Table 1]

[0379] n / k(365nm) Example 1 1.83 / 0.23 Example 2 1.75 / 0.24 Example 3 1.78 / 0.21 Example 4 1.79 / 0.20 Comparative Example 1 1.83 / 0.35

[0380] Examples 1 to 4 and Comparative Example 1 have appropriate n and k values ​​at 365 nm. In a photolithography process using radiation such as i-rays, it has an antireflection function that can suppress reflection (standing waves) from a base substrate that is a factor of an undesired resist pattern.

[0381] [Resistant solvent resistance test]

[0382] As an evaluation of resistance to anti-etching solvents (organic solvents), the gap filling material forming composition prepared in Examples 1 to 4 and Comparative Example 1 was applied to a silicon wafer and heated at 150°C for 180 seconds to form a film. Next, it was immersed in OK73 diluent (Tokyo Ohka Industry Co., Ltd.) at room temperature for 1 minute, and the removability of the film after immersion was observed. The results are shown in Table 2. It should be noted that when the film is removed (when the film is peeled off), it is judged to have no resistance to anti-etching solvents (organic solvents), and when the film is not removed (when the film is not peeled off), it is judged to have resistance.

[0383] [Table 2]

[0384] Removability of coating film with OK73 thinner Example 1 No peeling Example 2 No peeling Example 3 No peeling Example 4 No peeling Comparative Example 1 No peeling

[0385] From the above results, the gap-filler-forming compositions of Examples 1 to 4 and Comparative Example 1 were not removed (peeled off) by the OK73 diluent, and therefore can be said to have good chemical resistance to these organic solvents (resist solvents).

[0386] [Removability test for wet etching solution]

[0387] As an evaluation of the removability to a wet etching solution (alkaline organic solvent), the gap filling material forming composition prepared in Examples 1 to 4 and Comparative Example 1 was applied to a copper substrate and heated at 150°C for 180 seconds to form a film with a thickness of 100 nm. Next, the copper substrate on which the film was formed was immersed in ST-120 (Tokyo Ohka Industry Co., Ltd.) as an alkaline organic solvent at 70°C for 10 minutes, and the removability of the film after immersion was visually observed. The results are shown in Table 3. It should be noted that when the film was removed (when the film was peeled off), it was judged to have good removability (peeling property) to the alkaline organic solvent, and when the film was not removed (when the film was not peeled off), it was judged to have poor removability (peeling property).

[0388] [Table 3]

[0389]

[0390] According to the above results, the gap-filling material-forming compositions of Examples 1 to 4 obtained sufficient removability of the film on the copper substrate to the wet etching solution (alkaline organic solvent) as compared with the gap-filling material-forming composition of Comparative Example 1. That is, the film obtained from the gap-filling material-forming composition of Example 1 can show good removability (peelability) to the wet etching solution, and is therefore useful in a semiconductor manufacturing process in which the film is removed by a wet etching solution.

[0391] [Burying and planarization properties in uneven substrates]

[0392] As an evaluation of the embedding property and planarization property of the high-contrast substrate, the gap-filling material forming composition prepared in Examples 1 to 4 and Comparative Example 1 was applied to a hole substrate having holes with a depth of 1.6 μm and a diameter of 0.36 μm, and heated at 200°C for 180 seconds to form a film. The embedding property and planarization property of the hole substrate were then observed using a cross-sectional SEM. The results are shown in Figure 3 to Figure 7 middle.

[0393] According to the observation results of cross-sectional SEM, the gap-filling material forming compositions of Examples 1 to 4 have good embedding properties and planarization properties in the hole substrate, and no voids inside the hole are observed. However, in Comparative Example 1, a gap is formed at the interface between the hole substrate and the film, and the film peels off when the substrate is cut and observed by SEM, and the film inside the hole cannot be observed. That is, the film obtained from the gap-filling material forming compositions of Examples 1 to 4 can show good embedding properties in the hole substrate, and is therefore useful in the semiconductor manufacturing process of planarizing the high-low substrate.

[0394] Explanation of symbols

[0395] 1 Support

[0396] 2 Insulation layer

[0397] 3. Cured filling material

[0398] 4 Photoresist layer

[0399] 5a Through hole for through hole formation

[0400] 5b Wiring formation groove

[0401] 6. Barrier / Seed Layer

[0402] 7 Plating

[0403] 7a through hole

[0404] 7b wiring

[0405] 8 Insulation layer

[0406] 101 substrate

[0407] 102 photosensitive resin layer

[0408] 103 barrier / seed layer

[0409] 104 Plating Resist

[0410] 105 coating

[0411] 105a Through hole

[0412] 105b Wiring

[0413] 106 photosensitive resin layer.

Claims

1. A gap-filling material-forming composition comprising at least one of a compound and a polymer and a solvent, wherein the compound and the polymer have a structure represented by the following formula (1) and a carbonyl bond, In formula (1), R 1 and R 2 Each independently represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms, a halogen atom, -COOR 11 or -COO-, where R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 3 represents a methoxy group, an alkyl group having 1 to 13 carbon atoms, or a halogen atom; in R 3 When there are 2 or more, 2 or more R 3 It can be the same or different; n1 represents an integer of 0 to 4; n2 represents an integer of 0 or 1; wherein, The sum of n1 and n2 is less than 4; X 1 represents an ether bond or an ester bond; X 2 represents an ether bond or an ester bond; * indicates a bonding bond.

2. The gap-filling material-forming composition according to claim 1, wherein the compound and the polymer have at least one of a structure represented by the following formula (2) and a structure represented by the following formula (3) as the structure having the carbonyl bond, In formula (2), X 11 represents a group represented by any one of the following formulae (2-1) to (2-4); Z 1 and Z 2 Each independently represents a single bond or a divalent group represented by the following formula (2-5), wherein: *3 in formula (2-5) represents a bond to the nitrogen atom in formula (2); A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each independently represents a hydrogen atom, a methyl group or an ethyl group; * represents a bond; In formula (3), Q 1 A represents a divalent organic group having an aromatic hydrocarbon ring; 11 , A 12 , A 13 , A 14 , A 15 and A 16 Each independently represents a hydrogen atom, a methyl group or an ethyl group; n11 and n12 represent integers of 0 or 1; wherein at least one of n11 and n12 is 1; * represents a bond; In formulas (2-1) to (2-3), R 1 ~R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent group selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms; R 1 With R 2 can combine with each other to form a ring with 3 to 6 carbon atoms; R 3 With R 4 They can combine with each other to form a ring with 3 to 6 carbon atoms; In formula (2-4), Z 3 represents a single bond or a divalent group represented by the following formula (2-5), wherein *3 in the formula (2-5) represents a bond to the nitrogen atom in the formula (2-4); A 7 , A 8 and A 9 each independently represents a hydrogen atom, a methyl group or an ethyl group; * represents a bond; *1 represents a bond to a carbon atom in formula (2); *2 represents a bond to a nitrogen atom in formula (2); In formula (2-5), m1 is an integer from 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer from 0 to 2; wherein, when m3 is 1, m1 and m2 are not simultaneously 0; *3 represents a bond to the nitrogen atom in formula (2) or (2-4); *4 represents a bond to the carbon atom in formula (2) or (2-4).

3. The gap-filling material-forming composition according to claim 2, wherein Q 1 It is represented by the following formula (3-1) or formula (3-2), In formulas (3-1) to (3-2), R 21 ~R 23 Each independently represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an alkynyloxy group having 2 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms; * represents a bond; In formula (3-1), n3 represents 0 or 1; when n3 is 0, n21 represents an integer from 0 to 4; when n3 is 1, n21 represents an integer from 0 to 6; 21 When there are 2 or more, 2 or more R 21 It can be the same or different; In formula (3-2), Z 4 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms; n22 and n23 each independently represent an integer of 0 to 4; in R 22 When there are 2 or more, 2 or more R 22 Can be the same or different; in R 23 When there are 2 or more, 2 or more R 23 It can be the same or different.

4. The gap-filling material-forming composition according to claim 1, wherein R 1 Indicates cyano or -COOR 11 , R 11 It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

5. The gap-filling material-forming composition according to claim 1, wherein R 2 Indicates cyano, -COOR 11 or -COO-, R 11 It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

6. The gap-filling material-forming composition according to claim 1, wherein X 1 Represents an ether bond. 7 . The gap-filling material-forming composition according to claim 1 , wherein n2 represents 0. The gap-filler-forming composition according to claim 1 , comprising a crosslinking agent. 9 . The gap-filler-forming composition according to claim 1 , which is used for temporary filling of through holes in an insulating layer when forming a redistribution layer. 10 . A gap-filler cured product, which is formed by applying the gap-filler-forming composition according to claim 1 to a substrate, followed by firing. The solidified material according to claim 10 , which can be removed by a chemical solution. 12 . A method for producing a redistribution layer, comprising the step of filling a through-hole of an insulating layer with a gap-filler cured product formed from the gap-filler-forming composition according to claim 1 . 13 . The method for manufacturing a redistribution layer according to claim 12 , further comprising, after the step of filling the through-holes, a step of removing the cured product of the gap-filling material with a chemical solution.

14. A method for manufacturing a printed circuit board, comprising the step of manufacturing a redistribution layer. The step of manufacturing the redistribution layer includes the step of filling the through-holes of the insulating layer with a gap-filler cured product formed from the gap-filler-forming composition according to any one of claims 1 to 9. 15 . The method for manufacturing a printed circuit board according to claim 14 , further comprising, after the step of filling the through-holes, a step of removing the cured product of the gap-filling material with a chemical solution.

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