JP2008024900A - Benzoxazole precursor, resin composition and coating varnish, resin film, and semiconductor device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductor device with excellent reliability by using a coating varnish which has good preservability and can be used for producing a resin film lowered in permittivity. <P>SOLUTION: This benzoxazole precursor comprises an aromatic compound having an aminohydroxyphenyl group, a carboxy group and a group comprising a diamondoid structure. The benzoxazole precursor has a structure expressed by general formula (1), wherein X is a group comprising one or more diamondoid structure(s); Ar<SB>1</SB>and Ar<SB>2</SB>each represents an aromatic group; m<SB>1</SB>and m<SB>2</SB>each denotes an integer of 0-4; m<SB>3</SB>denotes 0 or 1; Y is hydrogen or a group comprising a diamondoid structure, provided that when m<SB>3</SB>is 0, Y is a group comprising the diamondoid structure. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a benzoxazole precursor, a resin composition, a coating varnish using the same, a resin film, and a semiconductor device.

Various types of CVD films and films made of coating materials have been applied as semiconductor interlayer insulating films. In order to achieve a further lower dielectric constant, these insulating films are mainly made porous. Consideration is being made. As a method of making the insulating film porous, a thermally decomposable component (porogen) is introduced into the insulating film material by mixing or bonding to a resin in the material, and in the heating and baking step at the time of forming the insulating film, There is a method of decomposing porogen and forming pores. However, in the porous formation by such a method, the pores existing in the film have a size of several nanometers to several tens of nanometers, and these pores are connected independently rather than independently. For this reason, the strength of the insulating film is inevitably lowered, and various problems due to holes are pointed out in the semiconductor process. As a specific example, peeling or destruction of an insulating film occurs in CMP or a package process, and in a damascene process, metal penetrates into a hole in an insulating film during metallization after etching the insulating film. In other words, the reliability of the device is lowered, and in the ashing or wet cleaning process, gas or cleaning liquid penetrates into the pores and causes a problem. As a method for solving these problems, studies have been made to introduce a process such as pore sealing. However, there is a concern that the number of steps increases and the manufacturing cost increases.
On the other hand, in the insulating film material, since the resin chain takes a branched structure, the polymer chains do not come close to each other. Therefore, the volume fraction occupied by the polymer chains in the bulk polymer is lowered, so that the dielectric constant is lowered. (For example, refer to Patent Document 1), however, gelation is likely to occur during synthesis, solubility during synthesis, storage stability during varnish, etc. are poor, and it is very difficult to handle. .
JP 2001-332543 A

In view of such a background, the present invention provides a benzoxazole precursor having good storage stability and solubility when made into a varnish, and having a dielectric constant reduced without making it porous when made into a resin film. It is in providing the resin composition containing.
An object of the present invention is to provide a coating varnish having good storage stability and having a reduced dielectric constant when formed into a resin film.
The present invention can provide a resin film having a low dielectric constant, and provides a semiconductor device having excellent reliability by using the resin film.

（式中のＸは、少なくとも１つ以上のダイヤモンドイド構造より構成される基を示し、Ａｒ₁及びＡｒ₂は、芳香族基を示し、ｍ₁及びｍ₂は、０以上、４以下の整数を示し、ｍ₃は、０又は１を示す。また、Ｙは水素原子又はダイヤモンドイド構造より構成される基を示し、ｍ₃＝０のとき、Ｙはダイヤモンドイド構造より構成される基である。）
（３） 前記ベンゾオキサゾール前駆体は、少なくとも２つのアミノヒドロキシフェニル基を有する化合物（Ａ）を含んで構成されるものである第（１）項又は第（２）項に記載のベンゾオキサゾール前駆体。
（４） 前記ベンゾオキサゾール前駆体は、少なくとも３つのアミノヒドロキシフェニル基を有する化合物（Ａ）を含んで構成されるものである第（１）項乃至第（３）項のいずれか１項に記載のベンゾオキサゾール前駆体。
（５） 前記ベンゾオキサゾール前駆体は、少なくとも２つのカルボキシル基を有する化合物（Ｂ）を含んで構成されるものである第（１）項乃至第（４）項のいずれか１項に記載のベンゾオキサゾール前駆体。
（６） 前記ベンゾオキサゾール前駆体は、架橋基を有するものである第（１）項乃至第（５）項のいずれか１項に記載のベンゾオキサゾール前駆体。
（７） 第（１）項乃至第（６）項のいずれか１項に記載のベンゾオキサゾール前駆体を含む樹脂組成物。
（８） 第（１）項乃至第（６）項のいずれか１項に記載のベンゾオキサゾール前駆体又は第（７）項に記載の樹脂組成物を有機溶媒に溶解させたコーティングワニス。
（９） 第（１）項乃至第（６）項のいずれか１項に記載のベンゾオキサゾール前駆体、第（７）項に記載の樹脂組成物、又は第（８）項に記載のコーティングワニスより構成される樹脂膜。
（１０） 第（９）項に記載の樹脂膜を有する半導体装置。
（１１） 前記樹脂膜は、層間絶縁膜及び／又は保護膜として有するものである第（１０）項に記載の半導体装置。
（１２） 前記樹脂膜は、半導体基板の所定の位置に、請求項８に記載のコーティングワニスを塗布して塗膜を形成し、前記塗膜を、加熱及び／又は活性放射線を照射することにより硬化して得られたものである第（１０）項又は第（１１）項に記載の半導体装置。 It has been found that the present invention can be achieved by the following items (1) to (12).
(1) A benzoxazole precursor comprising an aromatic compound (C) having an aminohydroxyphenyl group, a carboxyl group, and a group composed of a diamondoid structure.
(2) The benzoxazole precursor according to item (1), wherein the benzoxazole precursor has a structure represented by the general formula (1).

(X in the formula represents a group composed of at least one diamondoid structure, Ar ₁ and Ar ₂ represent an aromatic group, and m ₁ and m ₂ are integers of 0 or more and 4 or less. M ₃ represents 0 or 1. Y represents a group composed of a hydrogen atom or a diamondoid structure, and when m ₃ = 0, Y represents a group composed of a diamondoid structure. .)
(3) The benzoxazole precursor according to (1) or (2), wherein the benzoxazole precursor includes a compound (A) having at least two aminohydroxyphenyl groups. .
(4) The benzoxazole precursor according to any one of items (1) to (3), comprising the compound (A) having at least three aminohydroxyphenyl groups. Benzoxazole precursor.
(5) The benzoxazole precursor according to any one of (1) to (4), wherein the benzoxazole precursor includes a compound (B) having at least two carboxyl groups. Oxazole precursor.
(6) The benzoxazole precursor according to any one of items (1) to (5), wherein the benzoxazole precursor has a crosslinking group.
(7) A resin composition comprising the benzoxazole precursor according to any one of items (1) to (6).
(8) A coating varnish obtained by dissolving the benzoxazole precursor according to any one of items (1) to (6) or the resin composition according to item (7) in an organic solvent.
(9) The benzoxazole precursor according to any one of items (1) to (6), the resin composition according to item (7), or the coating varnish according to item (8) A resin film composed of
(10) A semiconductor device having the resin film according to item (9).
(11) The semiconductor device according to item (10), wherein the resin film has an interlayer insulating film and / or a protective film.
(12) The resin film is formed by applying the coating varnish according to claim 8 to a predetermined position of a semiconductor substrate to form a coating film, and heating and / or irradiating the coating film with actinic radiation. The semiconductor device according to (10) or (11), which is obtained by curing.

According to the present invention, when used as a varnish, the solubility and storage stability are good, and when used as a resin film, the dielectric constant is reduced without making it porous, and various processes when applied as a resin film of a semiconductor device. A benzoxazole precursor having compatibility and a resin composition containing the precursor can be provided.
According to the present invention, it is possible to provide a coating varnish that has good storage stability, has a reduced dielectric constant when used as a resin film, and is compatible with various process suitability when applied as a resin film of a semiconductor device.
According to the present invention, a resin film having a low dielectric constant and good adhesion can be provided, and a semiconductor device using the resin film is excellent in connection reliability and has low signal loss and wiring delay.

Hereinafter, the benzoxazole precursor, resin composition, coating varnish, resin film and semiconductor device of the present invention will be described.
The benzoxazole precursor of the present invention includes an aromatic compound (C) having an aminohydroxyphenyl group (first functional group), a carboxyl group (second functional group), and a group composed of a diamondoid structure. Is a precursor composed of As a result, when it is used as a varnish, it has good solubility and storage stability, and when it is used as a resin film, the dielectric constant is reduced without making it porous, so that it can be used as a resin film for semiconductor devices. Both sexes can be achieved.

  The benzoxazole precursor of the present invention includes an aromatic compound (C) having the aminohydroxyphenyl group (first functional group), a carboxyl group (second functional group), and a group composed of a diamondoid structure; And the compound (A) having at least two aminohydroxyphenyl groups, and the benzoxazole precursor of the present invention contains the aminohydroxyphenyl group (first functional group). And an aromatic compound (C) having a carboxyl group (second functional group) and a group composed of a diamondoid structure, and a compound (B) having at least two carboxyl groups or at least two aminohydroxyphenyls A compound (A) having a group and a compound (B) having at least two carboxyl groups. It may be. Thereby, the said characteristic can be made more favorable.

  In the present invention, the aromatic compound (C) having an aminohydroxyphenyl group, a carboxyl group, and a group composed of a diamondoid structure includes an aminohydroxyphenyl group or an aminohydroxyphenyl group and an aromatic group, a carboxyl group, Any group may be used as long as it is composed of a group composed of a diamondoid structure. For example, one or two or more substituents composed of the diamondoid structure are formed on the phenyl group of the aminohydroxyphenyl group. The substituent constituted by the diamondoid structure is substituted with hydrogen on the phenyl group, or through a group such as a substituent wherein the carboxyl group is constituted by the diamondoid structure, The thing couple | bonded with the said phenyl group etc. are mentioned. Thereby, a polybenzoxazole precursor having a low relative dielectric constant and good solubility can be obtained.

  The group composed of the diamondoid structure is a group composed of at least one diamondoid structure, and the diamondoid structure is a polycyclic structure having an adamantane structure as a minimum unit. Specifically, an adamantyl group, a diamantyl group, a triamantyl group, a tetramantyl group, a pentamantyl group, a hexamantyl group, a heptamantyl group, an octamantyl group, a nonamantyl group, a decamantyl group, an undecamantyl group, and the like, and further, the polycyclic Examples include a group having a plurality of groups having a skeletal structure. Adamantyl group, etc. undecapeptide adamantyl group, and the like, but not limited thereto. As a result, a resin having a low relative dielectric constant can be obtained.

  The hydrogen atom in the diamondoid structure may be substituted with an aliphatic group, an aromatic group and a fluorine atom. Examples of the aliphatic group that may be substituted with the hydrogen atom include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; and an alkoxy group such as a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Alkenyl groups such as vinyl group, propenyl group and butenyl group; alkynyl groups such as ethynyl group, propynyl group and butynyl group; alicyclic groups such as cyclopentyl group, cyclohexyl group, adamantyl group, diamantyl group and biadamantyl group Examples of the aromatic group that may be substituted for the hydrogen atom include, but are not limited to, a phenyl group, a naphthyl group, a phenoxy group, and a naphthoxy group. It is not something. Moreover, the hydrogen atom in the aliphatic group and aromatic group which may be substituted with the hydrogen atom may be substituted with a fluorine atom. By these, the resin which has solubility and heat resistance can be obtained.

Examples of the aromatic group include a phenyl group, a biphenyl group, a phenyl ether group, a naphthyl group, a binaphthyl group, and a fluorenyl group. On these aromatic groups, a group composed of the diamondoid structure may be substituted.
Examples of the group containing a group composed of the diamondoid structure and an aromatic group include a group in which a group composed of the diamondoid structure and the aromatic group are bonded.
In these, inclusion of the diamondoid structure is preferable for obtaining a resin having a low relative dielectric constant.

Specific examples of the aromatic compound (C) having an aminohydroxyphenyl group (first functional group), a carboxyl group (second functional group) and a group composed of a diamondoid structure used in the present invention include, for example, 1- (3-amino-4-hydroxyphenyl) -3-carboxyadamantane, 1- (3-amino-4-hydroxyphenyl)-(3-carboxy-5,7-dimethyladamantane), 1- (3- Amino-4-hydroxyphenyl) -3-carboxydiamantane, 1- (3-amino-4-hydroxyphenyl) -3-carboxytriamantane, 3- (3-amino-4-hydroxyphenyl) -3′-carboxy -(1,1'-biadamantane) and 3- (3-amino-4-hydroxyphenyl) -3'-carboxy- (5,5 ', 7,7'- Such Toramechiru 1,1'-biadamantane), compound amino hydroxyphenyl group and a carboxyl group is directly bonded to diamondoid structure,
1- (4- (4-amino-3-hydroxyphenoxy) -phenyl) -3-carboxyadamantane, 1- (4- (4-amino-3-hydroxyphenoxy) -phenyl)-(3-carboxy-5, 7-dimethyladamantane, 1- (4- (4-amino-3-hydroxyphenoxy) -phenyl) -3-carboxydiamantane, 1- (4- (4-amino-3-hydroxyphenoxy) -phenyl) -3 -Carboxytriamantane, 3- (4- (4-amino-3-hydroxyphenoxy) -phenyl) -3'-carboxy- (1,1'-biadamantane), 3- (4- (4-amino-3) -Hydroxyphenoxy) -phenyl) -3'-carboxy- (5,5 ', 7,7'-tetramethyl-1,1'-biadamantane), 1- (4- (2-adamanti) -4-amino-3-hydroxyphenoxy) -phenyl) -3-carboxyadamantane, 1- (4- (2- (3,5-dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) -phenyl ) -3-carboxyadamantane, 1- (4- (2-adamantyl-4-amino-3-hydroxyphenoxy) -phenyl) -3-carboxydiamantane, 1- (4- (2- (3,5-dimethyl) -1-adamantyl) -4-amino-3-hydroxyphenoxy) -phenyl) -3-carboxydiamantane, 1- (4- (2-adamantyl-4-amino-3-hydroxyphenoxy) -phenyl) -3- Carboxytriamantane, 1- (4- (2- (3,5-dimethyl-1-adamantyl) -4-amino-3-hydroxypheno Cis) -phenyl) -3-carboxytriamantane, 3- (4- (2-adamantyl-4-amino-3-hydroxyphenoxy) -phenyl) -3′-carboxy- (1,1′-biadamantane), 3- (4- (2- (3,5-dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) -phenyl) -3′-carboxy- (1,1′-biadamantane), 3- (4- (2-adamantyl-4-amino-3-hydroxyphenoxy) -phenyl) -3′-carboxy- (5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane) and 3 -(4- (2- (3,5-dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) -phenyl) -3'-carboxy- (5,5 ', 7,7'-tetramethyl -1,1'-bia daman Tan), etc., an aminohydroxyphenyl group is bonded to the diamondoid structure via an aromatic group (phenyl ether structure), and a carboxyl group is directly bonded to the diamondoid structure,
1- (3-amino-4-hydroxyphenyl) -3- (4- (carboxyphenoxy) phenyl) adamantane, 1- (3-amino-4-hydroxyphenyl) -3- (4- (carboxyphenoxy) phenyl) -5,7-dimethyladamantane, 1- (3-amino-4-hydroxyphenyl) -3- (4- (carboxyphenoxy) phenyl) diamantane, 1- (3-amino-4-hydroxyphenyl) -3- ( 4- (carboxyphenoxy) phenyl) triamantane, 3- (3-amino-4-hydroxyphenyl) -3 ′-(4- (carboxyphenoxy) phenyl)-(1,1′-biadamantane) and 3- ( 3-Amino-4-hydroxyphenyl) -3 '-(4- (carboxyphenoxy) phenyl)-(5,5', 7,7'-tetra Chill-1,1'-biadamantane) etc., amino hydroxyphenyl group is directly bonded to the diamondoid structure, compound carboxyl group bonded to diamondoid structure via an aromatic group (phenyl ether structure),
1- (4- (4-amino-3-hydroxyphenoxy) phenyl) -3- (4-carboxyphenyl) adamantane, 1- (4- (4-amino-3-hydroxyphenoxy) phenyl) -3- (4 -Carboxyphenyl) -5,7-dimethyladamantane, 1- (4- (4-amino-3-hydroxyphenoxy) phenyl) -3- (4-carboxyphenyl) diamantane, 1- (4- (4-amino- 3-hydroxyphenoxy) phenyl) -3- (4-carboxyphenyl) triamantane, 3- (4- (4-amino-3-hydroxyphenoxy) phenyl) -3 ′-(4-carboxyphenyl)-(1, 1'-biadamantane), 3- (4- (4-amino-3-hydroxyphenoxy) phenyl) -3 '-(4-carboxyphenyl)-(5 5 ′, 7,7′-tetramethyl-1,1′-biadamantane), 1- (4- (2-adamantyl-4-amino-3-hydroxyphenoxy) phenyl) -3- (4-carboxyphenyl) Adamantane, 1- (4- (2- (3,5-dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -3- (4-carboxyphenyl) adamantane, 1- (4- ( 2-adamantyl-4-amino-3-hydroxyphenoxy) phenyl) -3- (4-carboxyphenyl) -5,7-dimethyladamantane, 1- (4- (2- (3,5-dimethyl-1-adamantyl) ) -4-amino-3-hydroxyphenoxy) phenyl) -3- (4-carboxyphenyl) -5,7-dimethyladamantane, 1- (4- (2-adamanti) -4-amino-3-hydroxyphenoxy) phenyl) -3- (4-carboxyphenyl) diamantane, 1- (4- (4-amino-3-hydroxyphenoxy) phenyl) -3- (4-carboxyphenyl) tria Mantane, 1- (4- (2- (3,5-dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -3- (4-carboxyphenyl) diamantane, 1- (4- ( 4-Amino-3-hydroxyphenoxy) phenyl) -3- (4-carboxyphenyl) triamantane, 3- (2-adamantyl-4- (4-amino-3-hydroxyphenoxy) phenyl) -3 '-(4 -Carboxyphenyl)-(1,1′-biadamantane), 3- (2- (3,5-dimethyl-1-adamantyl) -4- (4-a No-3-hydroxyphenoxy) phenyl) -3 '-(4-carboxyphenyl)-(1,1'-biadamantane), 3- (4- (2-adamantyl-4-amino-3-hydroxyphenoxy) phenyl ) -3 ′-(4-carboxyphenyl)-(5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane) and 3- (4- (2- (3,5-dimethyl-) 1-adamantyl) -4-amino-3-hydroxyphenoxy) phenyl) -3 ′-(4-carboxyphenyl)-(5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane) and the like A compound in which the aminohydroxyphenyl group is bonded to the diamondoid structure through an aromatic group (phenyl ether structure), and the carboxyl group is bonded to the diamondoid structure through an aromatic group (phenyl structure);
1,3-bis (1-adamantyl) -4- (4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene, 1,3-bis (3,5-dimethyl-1-adamantyl) ) -4- (4-Amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene, 1,3-bis (1-diamantyl) -4- (4-amino-3-hydroxyphenoxy)- 6- (4-Carboxyphenoxy) -benzene, 1,3-bis (1-triamantyl) -4- (4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene, 1,3- Bis (3- (1,1′-biadamantyl))-4- (4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene, 1,3-bis (3- (5,5 ′, 7,7′-tetramethyl-1,1′-biadamantyl))-4- (4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene 1,3-bis (1-adamantyl) -4- (2-adamantyl-4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene, 1,3-bis (1-adamantyl) -4- (2- (3,5-dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene, 1,3-bis (3,5-dimethyl -1-adamantyl) -4- (2-adamantyl-4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene, 1,3-bis (3,5-dimethyl-1-a Mantyl) -4- (2- (3,5-dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene, 1,3-bis (1-diamantyl) ) -4- (2-adamantyl-4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene, 1,3-bis (1-diamantyl) -4- (2- (3,5 -Dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene, 1,3-bis (1-triamantyl) -4- (2-adamantyl-4-amino -3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene, 1,3-bis (1-triamantyl) -4- (2- (3,5-dimethyl) 1-adamantyl) -4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene, 1,3-bis (3- (1,1′-biadamantyl))-4- (2- Adamantyl-4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene, 1,3-bis (3- (1,1′-biadamantyl))-4- (2- (3 5-Dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene, 1,3-bis (3- (5,5 ′, 7,7′-tetra) Methyl-1,1′-biadamantyl))-4- (2-adamantyl-4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene and 1,3-bis (3- (5 , 5 ', 7, 7'-tetramethyl-1,1'-biadamantyl))-4- (2- (3,5-dimethyl-1-adamantyl) -4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) ) -Benzene and other compounds in which an aminohydroxyphenyl group and a carboxyl group are bonded to a diamondoid structure via an aromatic group (phenyl ether structure),
1- (2-adamantyl-4-amino-5-hydroxyphenoxy) -4-carboxybenzene, 1- (2- (3,5-dimethyl-1-adamantyl) -4-amino-5-hydroxyphenoxy) -4 -Carboxybenzene, 1- (2-diamantyl-4-amino-5-hydroxyphenoxy) -4-carboxybenzene, 1- (2-triamantyl-4-amino-5-hydroxyphenoxy) -4-carboxybenzene, 1- (2- (3- (1,1′-Biadamantyl) -4-amino-5-hydroxyphenoxy) -4-carboxybenzene and 1- (2- (3- (5,5 ′, 7,7′- 1,1′-biadamantyl) -4-amino-5-hydroxyphenoxy) -4-carboxybenzene and the like, and resorcinol-derived compounds. However, one or more of these compounds can be used.
In the above, an alkyl group or a fluoroalkyl group may be bonded to an aromatic group such as a diamondoid structure, a phenyl structure, or a phenyl ether structure.

Examples of the compound (A) having at least two aminohydroxyphenyl groups used in the present invention include, as examples of bisaminophenol compounds, diamino-dihydroxybenzene, diamino-dihydroxy-biphenyl, diamino-dihydroxy-diphenyl ether and 9 , 9-bis (3-amino-4-hydroxyphenyl) fluorene, a common aromatic bisaminophenol compound such as 2,2′-bis [4- (3-hydroxy-4-aminophenoxy)]-5, 5′-bis (1-adamantyl) -biphenyl, 2,2′-dihydroxy-3,3′-diamino-5,5′-bis (1-adamantyl) -biphenyl, 2,2′-dihydroxy-3,3 '-Diamino-5,5'-bis (3,5-dimethyl-1-adamantyl) -biphenyl, 3-biphenyl [4- (3-hydroxy-4-aminophenoxy)]-4,6-bis (1-adamantyl) -benzene, 1,3-bis [4- (3-hydroxy-4-aminophenoxy)]-4, 6-bis (3,5-dimethyl-1-adamantyl) -benzene and 1,3-bis [4- (3-hydroxy-4-aminophenoxy)]-4,6-bis (5,5 ′, 7, Bisaminophenol compounds having a diamondoid structure such as 7′-tetramethyl-3,3′-1-biadamantyl) -benzene, etc.
Examples of the compound (A) having at least three aminohydroxyphenyl groups include tris- (3-amino-4-hydroxyphenyl) amine, tris- (3-amino-4-hydroxyphenyl) methane, tetrakis- Three or more aminohydroxyphenyl groups such as (3-amino-4-hydroxyphenyl) methane and tris- (3-amino-4-hydroxyphenyl) silane and tetrakis- (3-amino-4-hydroxyphenyl) silane Compound directly bonded to element group, tris- [4- (3-hydroxy-4-aminophenoxy) -phenyl] amine, tris- [4- (3-hydroxy-4-aminophenoxy) -phenyl] methane, tetrakis- [4- (3-hydroxy-4-aminophenoxy) -phenyl] methane, tris Three or more aminohydroxyphenyl groups are phenyl ether, such as [4- (3-hydroxy-4-aminophenoxy) -phenyl] silane and tetrakis- [4- (3-hydroxy-4-aminophenoxy) -phenyl] silane. 1,3,5-tris (3-amino-4-hydroxyphenyl) adamantane, 1,3,5,7-tetrakis (3-amino-4-hydroxyphenyl) adamantane And three or more aminohydroxyphenyl groups directly attached to the diamondoid structure, such as 3,3 ′, 5,5′-tetrakis- (3-amino-4-hydroxy-phenyl) -1,1′-biadamantane Compound 1,3,5-tris [4- (3-hydroxy-4-amino-phenoxy) -phenyl] -adamantane, 1 3,5,7-tetrakis [4- (3-hydroxy-4-aminophenoxy-) phenyl] adamantane and 3,3 ′, 5,5′-tetrakis- [4- (3-hydroxy-4-aminophenoxy) -Phenyl] -1,1'-biadamantane and the like include a compound in which three or more aminohydroxyphenyl groups are bonded to a diamondoid structure via a phenyl ether structure, and has two or more aminohydroxyphenyl groups. If it is a thing, it is not limited to these, However, It is more preferable that it is a thing which has 2 or more and 4 or less aminohydroxyphenyl group. One or two or more of these compounds can be used. Moreover, in order to obtain a branched structure, a benzoxazole precursor having at least three aminohydroxyphenyl groups is more preferable. By using a branched structure, the dielectric constant can be further reduced when a resin film is used.
An alkyl group or a fluoroalkyl group may be bonded to an aromatic group such as the diamondoid structure, the phenyl structure, or the phenyl ether structure.
Examples of the element group include elements such as nitrogen, carbon and silicon, and groups composed of the elements such as aromatic groups and aliphatic groups.

Examples of the compound (B) having at least two carboxyl groups used in the present invention are shown. First, as a compound having two carboxylic acids, adamantyl-1,3-dicarboxylic acid, 1,1′-biadamantyl-3,3′-dicarboxylic acid and 3,3 ′, 5,5′-tetramethyl- ( 1,1′-biadamantyl) -3,3′-dicarboxylic acid and other carboxylic acids in which the carboxyl group is directly bonded to the diamondoid structure, isophthalic acid, phthalic acid, terephthalic acid, biphenyl-dicarboxylic acid and biphenyl ether-dicarboxylic acid Examples thereof include aromatic carboxylic acids such as acids, adipic acid, aliphatic carboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and the compounds having at least three carboxylic acids include adamantyl-1 , 3,5-tricarboxylic acid, 1,1′-biadamantyl-3,3 ′, 5-tricarboxylic acid Examples include adamantyl-1,3,5,7-tetracarboxylic acid and 1,1′-biadamantyl-3,3 ′, 5,5′-tetracarboxylic acid, which have two or more of the carboxyl groups. If it exists, it is not limited to these, but it is more preferable that it has 2 or more and 4 or less carboxyl groups. One or two or more of these compounds can be used. Further, in the benzoxazole precursor, one having at least three carboxyl groups is more preferable for obtaining a branched structure. By using a branched structure, the dielectric constant can be further reduced when a resin film is used.
An alkyl group or a fluoroalkyl group may be bonded to the diamondoid structure.

Examples of the carboxyl group include carboxylic acid-derived groups such as a carboxyl group, a carboxylic acid ester group, and a carboxylic acid chloride group.
When the compound having a carboxylic acid derivative group is used, an aromatic having an aminohydroxyphenyl group (first functional group), a carboxyl group (second functional group), and a group composed of a diamondoid structure as exemplified above. In the compound (C) and the compound (B) carboxylic acid having at least two carboxyl groups, the ester compound obtained by converting the carboxyl group into the carboxylic acid ester group, and the carboxyl group is converted into the carboxylic acid chloride group. It can be used as a carboxylic acid derivative such as a prepared chloride compound. Examples of the ester compound include an activity obtained by converting a carboxyl group in the carboxylic acid into a carboxylic acid active ester group such as a phenyl ester group, a 2-pyridyl ester group, a succinimide ester group, and an N-hydroxy-benzotriazole ester group. An ester compound can be used.

In the present invention, the bridging group means a group having a triple bond, a double bond, etc., and an ethynyl group, an aromatic substituted ethynyl group, a butadiynyl group, an aromatic substituted butadiynyl group, a propargyl group, an aromatic substituted propargyl group, A vinyl group, an allyl group, etc. are shown. The aromatic compound (C) having the aminohydroxyphenyl group (first functional group), the carboxyl group (second functional group), and a group composed of a diamondoid structure, and having at least three aminohydroxyphenyl groups As the compound (A) and the compound (B) having at least two carboxyl groups, those obtained by bonding these crosslinking groups can be used. As a result, the heat resistance of the benzoxazole precursor and the process compatibility when manufacturing a semiconductor device can be further improved. These cross-linking groups can be appropriately selected in consideration of the necessary cross-linking temperature and cross-linking density when cross-linking with the cross-linking group.
Examples of the compound having a crosslinking group include ethynylisophthalic acid, phenylethynylisophthalic acid, 4-phenylethynyl-phenoxy-isophthalic acid, butadiynyl-isophthalic acid, phenyl in the case of the compound (B) having at least two carboxyl groups. -Butadiynyl-isophthalic acid, propargylisophthalic acid, phenylpropargylisophthalic acid, vinylisophthalic acid, allylisophthalic acid and 4- (1-adamantyl) -phenylethynylisophthalic acid, but are not limited thereto.
The aromatic compound (C) having the aminohydroxyphenyl group (first functional group), the carboxyl group (second functional group), and a group composed of a diamondoid structure, and at least two aminohydroxyphenyl groups Similarly, a compound having a crosslinking group may also be used in the compound (A) having.

  As a method for synthesizing the benzoxazole precursor of the present invention, an aromatic compound having the aminohydroxyphenyl group (first functional group), the carboxyl group (second functional group), and a group composed of a diamondoid structure. (C) and optionally derived from the aminohydroxyphenyl group, the carboxyl group and the carboxyl group in the compound (A) having at least two aminohydroxyphenyl groups and the compound (B) having at least two carboxyl groups Reactions with groups that can be used can be used.

  As an example of the reaction method in the synthesis method, a direct polycondensation method in which the aminohydroxyphenyl group and the carboxyl group are reacted using a polycondensation agent such as triphenyl phosphite is preferable. Depending on the storage stability of the aromatic compound (C) having a group (first functional group), a carboxyl group (second functional group) and a group composed of a diamondoid structure, it is derived from the carboxyl group. A polycondensation reaction with a carboxylic acid active ester group (for example, phenyl ester, 2-pyridyl ester, succinimide ester, N-hydroxy-benzotriazole ester, etc.) as a group, or from the aminohydroxyphenyl group and the carboxyl group Polycondensation reaction with carboxylic acid chloride as the derived group It can be used, resulting benzoxazole precursor has a weight average molecular weight, preferably from 1,000～1000,000. More preferably, it is 3,000-150,000. Although it can be used outside the range of the weight average molecular weight, if the molecular weight is low, the heat resistance may be lowered, and if it is high, the varnish stability may be lowered.

  In the above synthesis, for example, a reaction between aromatic compounds (C) having an aminohydroxyphenyl group, a carboxyl group, and a group composed of a diamondoid structure, an aminohydroxyphenyl group, a carboxyl group, and a diamondoid structure are included. Reaction of an aromatic compound (C) having a group with a compound (A) having at least two aminohydroxyphenyl groups, an aromatic having a group composed of an aminohydroxyphenyl group, a carboxyl group and a diamondoid structure The benzoxazole precursor of the present invention can be obtained by reacting the group compound (C) with the compound (B) having at least two carboxyl groups and combining these.

  Examples of the benzoxazole precursor thus obtained include those having a benzoxazole structure, and specific examples include those having a structure represented by the general formula (1).

X in the formula (1) represents a group composed of at least one diamondoid structure, Ar ₁ and Ar ₂ represent an aromatic group, and m ₁ and m ₂ are 0 or more and 4 or less. M ₃ represents 0 or 1. Y represents a group composed of a hydrogen atom or a diamondoid structure, and when m ₃ = 0, Y is a group composed of a diamondoid structure.
The group composed of the diamondoid structure, the aromatic group, or the group composed of the diamondoid structure and the group containing an aromatic group is composed of an aminohydroxyphenyl group, a carboxyl group, and a diamondoid structure. And those similar to those in the aromatic compound (C) having a group.

  Benzoxazole obtained in the reaction of an aromatic compound (C) having an aminohydroxyphenyl group, a carboxyl group and a group composed of a diamondoid structure and a compound (A) having at least two aminohydroxyphenyl groups Specific examples of the precursor include those containing a structure represented by the general formula (2). However, the example of the structure represented by the general formula (2) is an example using a compound having three aminohydroxyphenyl groups.

X, Y, Ar ₁ , Ar ₂ , m ₁ and m ₂ in formula (2) are the same as those in formula (1), and S is a compound having at least two aminohydroxyphenyl groups Groups other than the aminohydroxyphenyl group constituting (A) are shown.

  Also, a benzoxazole precursor obtained by a reaction between an aromatic compound (C) having an aminohydroxyphenyl group, a carboxyl group, and a group composed of a diamondoid structure and a compound (B) having at least two carboxyl groups Specific examples include those containing a structure represented by the general formula (3). However, the example of the structure represented by the general formula (3) is an example using a compound having three carboxyl groups.

X, Y, Ar ₁ , Ar ₂ , m ₁ and m ₂ in the formula (3) are the same as those in the formula (1), and T is a compound having at least two carboxyl groups (B ) Is a group other than the carboxyl group constituting.

In the above synthesis method, the end of the benzoxazole precursor can be sealed with a compound (D) having one aminohydroxyphenyl group or one carboxyl group. These sealing agents may have the above diamondoid structure or a crosslinking group.
Examples of the compound having one aminohydroxyphenyl group include 2-amino-phenol, 2-amino-4- (1-adamantyl) phenol, and 2-amino-4- (3,5-dimethyl-1-adamantyl). ) Phenol and the like, and examples of the aminophenol having a crosslinking group include phenylethynyl-2-amino-phenol and (4-phenyl-butadiynyl) -2-amino-phenol.
Examples of the compound having one carboxyl group include acetic acid, benzoic acid, adamantyl-benzoic acid, adamantyl-1-carboxylic acid, 3,5-dimethyl-adamantyl-1-carboxylic acid, and biadamantyl-3-carboxylic acid. And 5,5 ′, 7,7′-tetramethyl-1,1′-biadamantyl-3-carboxylic acid, and the carboxylic acid having a bridging group includes ethynylbenzoic acid and phenylethynylbenzoic acid. And (1-adamantyl) phenylethynyl-benzoic acid, 4- [4- (3,5-dimethyl-1-adamantyl) -phenylethynyl] -benzoic acid, (4-phenyl-butadiynyl) benzoic acid, and the like.
These end groups can be selected in view of the required level of heat resistance, dielectric constant and solubility.

The resin composition of the present invention contains the above-mentioned benzoxazole precursor, and further, if necessary, a surfactant, a coupling agent typified by a silane, and oxygen radicals and sulfur radicals by heating. Additives such as generated radical initiators and catalysts such as disulfides can be used.
Moreover, it can also be used as a photosensitive resin composition by adding a naphthoquinone diazide compound or the like as a photosensitive agent to the resin composition. By using the benzoxazole precursor together with a naphthoquinone diazide compound as a photosensitizer, it can be used as a positive photosensitive resin composition. When the benzoxazole precursor has a group containing a photocrosslinkable group such as a methacryloyl group, it can be used as a negative photosensitive resin composition by using a photoinitiator.
The resin composition of the present invention can be obtained by appropriately blending the above components and mixing them.

The benzoxazole precursor and the resin composition of the present invention are soluble in an organic solvent and can provide a uniform resin solution to form a coating varnish. Examples of the organic solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy Propionate, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, tetrahydride Furan, can be used anisole and mesitylene, be other than these, any organic solvent capable of dissolving or dispersing, it can be used. These organic solvents may be used alone or in combination of two or more.
The amount of solvent used in preparing the coating varnish is not particularly limited as long as it is an amount capable of completely dissolving the benzoxazole precursor and the resin composition, but can be appropriately adjusted according to the application. Generally, the solvent content in the varnish is preferably about 70 to 98% by weight.

Next, the resin film will be described.
The resin film of the present invention is suitable as an interlayer insulating film of a wiring layer or a via layer in semiconductor applications. In addition to the interlayer insulating film, as a material constituting a semiconductor multilayer wiring structure, for example, the uppermost part of the multilayer wiring Protective film for protecting the surface from the outside, etching stopper film for stopping the etching of the interlayer insulating film, cap film and barrier film for preventing Cu diffusion constituting the wiring layer, adhesion imparting for improving the adhesion between the interlayer insulating film and the base Although it is suitable for a film etc., it is not limited to these.

The resin film of the present invention is obtained using the benzoxazole precursor, the resin composition, or the coating varnish as described above, and is excellent in adhesion to various substrates, electrical characteristics, and mechanical characteristics. The thickness of the interlayer insulating film is not particularly limited, but can be arbitrarily adjusted according to the purpose of application, but is generally formed in the range of 0.001 to 20 μm.
Moreover, as a use of the resin film of this invention, the cover coat of a flexible copper clad board, a soldering resist film, a liquid crystal aligning film, an adhesive bond layer etc. are mentioned besides the said use, for example.

As a method for producing the resin film of the present invention, for example, a varnish is prepared by dissolving the benzoxazole precursor or the resin composition in an organic solvent such as cyclohexanone, and the varnish is prepared with an appropriate support, for example, It is applied to an organic base material such as a polyester film, a metal plate such as copper foil, a semiconductor substrate such as a silicon wafer or a ceramic substrate, and the like to form a coating film.
Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like.

  Thereafter, the coating film is dried, subjected to heat treatment, and the solvent is removed to obtain a resin film. The benzoxazole precursor is cured by a condensation reaction by heating following the solvent removal. Further, when the benzoxazole precursor has a crosslinking group, the benzoxazole precursor is subjected to a crosslinking reaction to form a benzoxazole resin as a benzoxazole resin or It can be set as the resin film comprised with the resin composition containing it.

In addition, if the benzoxazole precursor converted into a resin is dissolved in an organic solvent, the benzoxazole precursor is converted into a benzoxazole resin in advance and dissolved in an organic solvent to prepare a varnish. By this method, a resin film can be obtained. In that case, in the heat processing of a coating film, since the process of converting a benzoxazole resin precursor into resin is not required, heat processing time can be shortened.
In the condensation reaction and the crosslinking reaction in the above step, actinic radiation can be irradiated in addition to the method using heating, and it is more preferable to use both in combination. Examples of the active radiation include active energy rays such as microwaves, visible light, UV light, and X-rays, and electron beams.
Further, the resin film of the present invention may be formed by directly applying to the substrate by the above method, or the resin film formed on the support may be used as a dry film by peeling from the support. it can.

Next, a semiconductor device will be described based on a preferred embodiment.
FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device of the present invention.
The semiconductor device 100 includes a semiconductor substrate 1 on which elements are formed, a silicon nitride film 2 provided on the upper side of the semiconductor substrate 1 (upper side in FIG. 1), an interlayer insulating film 3 provided on the silicon nitride film 2, and A copper wiring layer 4 covered with a barrier layer 6 is provided.
A recess corresponding to the pattern to be wired is formed in the interlayer insulating film 3, and a copper wiring layer 4 is provided in the recess.
In addition, a reforming treatment layer 5 is provided between the interlayer insulating film 3 and the copper wiring layer 4.
A hard mask layer 7 is formed on the upper side of the interlayer insulating film 3 (on the side surface opposite to the silicon nitride film 2).
The interlayer insulating film 3 can be formed by directly applying a varnish on the silicon nitride film 2 of the semiconductor substrate 1, but a dry film of a resin film is prepared in advance. It can also be formed so as to be laminated on one silicon nitride film 2. More specifically, a coating varnish containing the benzoxazole precursor or the resin composition obtained above is directly applied onto the silicon nitride film 2 of the semiconductor substrate 1 to form a coating film, and then heated and / or It can be formed by irradiation with actinic radiation and curing. When a dry film is used, a dry varnish is formed by forming a resin layer on the substrate and drying it in advance using the coating varnish containing the benzoxazole precursor or resin composition obtained above. Can be laminated on the silicon nitride film 2 of the semiconductor substrate 1 and cured by heating and / or irradiation with actinic radiation.
In the above description, the example of forming on the silicon nitride film 2 has been described, but the position where the resin film is formed is not limited to this.

In the present embodiment, the semiconductor device 100 using the interlayer insulating film 3 has been described. However, the present invention is not limited to this. The semiconductor device of the present invention uses the interlayer insulating film as described above, and thus has dimensions. The connection reliability is excellent because of its high accuracy and sufficient insulation.
In addition, since the interlayer insulating film as described above has excellent adhesion to the wiring layer, the connection reliability of the semiconductor device can be further improved.
In addition, since the interlayer insulating film as described above has excellent dielectric characteristics, signal loss of the semiconductor device can be reduced.
In addition, since the interlayer insulating film as described above has excellent dielectric characteristics, wiring delay can be reduced.

(Example)
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.

(1) Synthesis of 3- (3-amino-4-hydroxyphenyl) -3′-carboxy- (5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane) 1-bromo-3 3-bromo-5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane by coupling reaction with magnesium in diethyl ether and subsequent bromination reaction from 1,5-dimethyladamantane (Reference: IIPe051, Polymer Preprints, Japan Vol. 50, No.2 (2001) p277). This bromide is then converted to 5,5 ′, 7,7′-tetramethyl-1,1′-biadamantyl-3-dicarboxylic acid by carboxylation of Koch-Haaf (reaction with formic acid in concentrated sulfuric acid). (Ludek Vodicka, Josef Janku and Jiri Burkhard, Collection Czechoslovak Chem. Commun. Vol. 48 (1983), p1162-1172). Next, methyl 3-bromo-5,5 ′, 7,7′-tetramethyl-1,1′-biadamantyl-3′-carboxylate was synthesized by methyl esterification reaction and bromination reaction. And Friedel-Crafts reaction with phenol and FeCl ₃ (Reference: Yaw-Terng Chern and Hann-Chyan Shiue, Macromolecules 1997, 30, 4646-4651), followed by nitration with nitric acid, Pd-C catalyst and hydrogen 3- (3-amino-4-hydroxyphenyl) -3′-carboxy- (5,5 ′, 7,7′-tetramethyl-1,1 by reduction reaction with '-Biadamantane) was synthesized.

(2) Synthesis of benzoxazole precursor:
Under a nitrogen gas flow, 3- (3-amino-4-hydroxyphenyl) -3′-carboxy- (5,5 ′, 7,7′-tetramethyl-1,1′-) obtained in (1) above was obtained. 42.3 g (0.1 mol) of biadamantane) was dissolved in 200 g of dried N-methyl-2-pyrrolidone, 17.4 g (0.22 mol) of pyridine was added, and the mixture was cooled to −15 ° C. and phosphorous acid. 46.5 g (0.15 mol) of triphenyl was added little by little. After completion of dropping, the mixture was stirred at −15 ° C. for 1 hour, returned to room temperature, and stirred at room temperature for 2 hours. The reaction solution was dropped into 4 liters of distilled water in small droplets, and the precipitate was collected and dried to obtain a benzoxazole resin precursor.
It was 20,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using the Tosoh Corporation gel permeation chromatograph (GPC).

(3) Production of Resin Film The benzoxazole resin precursor was dissolved in N-methyl-2-pyrrolidone and filtered through a Teflon (registered trademark) filter to obtain a varnish for coating. This varnish was applied onto a silicon wafer using a spin coater. Then, it heated in order of 90 degreeC / 1 minute, 250 degreeC / 1 hour, 350 degreeC / 1 hour in oven of nitrogen atmosphere, and obtained the resin film.

(1) Synthesis of 2-amino-4- (3,5-dimethyl-1-adamantyl) -phenol Friedel-Crafts reaction of 1-bromo-3,5-dimethyl-adamantane and phenol with FeCl ₃ (reference: Yaw-Terng Chern and Hann-Chyan Shiue, Macromolecules 1997, 30, 4646-4651), followed by nitration with nitric acid, reduction with Pd-C catalyst and hydrogen, 2-amino-4- (3,5- Dimethyl-1-adamantyl) -phenol was obtained.

(2) Synthesis of 4- [4- (3,5-dimethyl-1-adamantyl) -phenylethynyl] -benzoic acid Friedel-Crafts of 1-bromo-3,5-dimethyl-adamantane and phenol with FeCl ₃ Reaction (reference: Yaw-Terng Chern and Hann-Chyan Shiue, Macromolecules 1997, 30, 4646-4651), and further with trifluoromethanesulfonic anhydride, 1-trifluoromethanesulfonyloxy-4- (3,5 -Dimethyl-1-adamantyl-benzene was synthesized, and coupled with 3-methyl-1-butyn-3-ol and deprotected with an alkali metal hydroxide to give 1-ethynyl-4- (3,5 -Dimethyl-1-adamantyl-benzene was obtained (reference: JP 2002-201158).
Next, by acetylene coupling reaction of the obtained 1-ethynyl-4- (3,5-dimethyl-1-adamantyl) -benzene and methyl 4-bromo-benzoate, hydrolysis with an alkali metal hydroxide, 4- [4- (3,5-dimethyl-)-1-adamantyl-phenylethynyl] -benzoic acid was obtained (reference: JP 2002-201158).

(3) Synthesis of benzoxazole precursor and production of resin film 3- (3-amino-4-hydroxyphenyl) -3′-carboxy- (5) obtained in (1) of Example 1 under a nitrogen gas flow , 5 ′, 7,7′-tetramethyl-1,1′-biadamantane) 47.8 g (0.1 mol) was dissolved in 200 g of dried N-methyl-2-pyrrolidone, and 17.4 g (0 .22 mol) was added and then cooled to −15 ° C., and 46.5 g (0.15 mol) of triphenyl phosphite was added little by little. After completion of dropping, the mixture was stirred at −15 ° C. for 1 hour, returned to room temperature, and stirred at room temperature for 2 hours. Thereafter, 2.71 g (0.01 mol) of 2-amino-4- (3,5-dimethyl-1-adamantyl) phenol obtained in (1) above was added and stirred at room temperature for 2 hours. Thereafter, 3.85 g (0.01 mol) of 4- [4- (3,5-dimethyl-1-adamantyl) -phenylethynyl] -benzoic acid obtained in (2) above was added and stirred at room temperature for 2 hours. . The reaction solution was dropped into 4 liters of distilled water in small droplets, and the precipitate was collected and dried to obtain a benzoxazole resin precursor.
It was 24,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.
A resin film was prepared and evaluated in the same manner as in Example 1.

(1) Synthesis of 1,3-bis (3,5-dimethyl-1-adamantyl) -4- (4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene 1-hydroxy-3 2,4- (3,5-dimethyl- (1-adamantyl))-1-hydroxy-5-methoxybenzene was synthesized by the reaction of 1-bromobenzene with 1-bromo-3,5-dimethyl-adamantane, Etherification reaction with 4-fluorobenzonitrile, methoxy group cleavage reaction with boron tribromide, hydrolysis of nitrile to carboxylic acid and methyl esterification (Reference: Guey-Sheng Liou, Sheng-Huei Hsiao, Macromol. Chem. Phys. 201, 42-48 (2000)) according to 1-hydroxy-3- (4-carboxymethyl-phenoxy) -4,6-bis (3,5-dimethyl-1-adamantyl) benze. It was obtained.
Next, etherification reaction of this compound with 2-benzyloxy-4-fluoronitrobenzene, conversion to carboxylic acid by hydrolysis of methyl carboxylate, deprotection of hydroxyl group with Pd-C catalyst and hydrogen, and nitro group 1,3-bis (3,5-dimethyl-1-adamantyl) -4- (4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene was synthesized by the reduction reaction of (Reference : Yoshio Imai, Yasumasa Maeda, Hisashi Takeuchi, Ki-Hong Park, Masa-aki Kakimoto, Toshikazu Kurosaki, Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 40, 2656-2662 (2002).
(2) Synthesis of 3,3 ′, 5,5′-tetrakis (3-amino-4-hydroxy-phenyl) -1,1′-biadamantane From 1-bromo-adamantane, magnesium was used in diethyl ether. 3,3′-5,5′-tetrabromo-1,1′-biadamantane was synthesized by a coupling reaction followed by bromination (Reference: IIPe051, Polymer Preprints, Japan Vol. 50, No. 2 (2001) p277). Next, the Friedel-Crafts reaction of this tetrabromo compound and phenol with FeCl ₃ (reference: Yaw-Terng Chern and Hann-Chyan Shiue, Macromolecules 1997, 30, 4646-4651), followed by nitration with nitric acid, Pd− 3,3 ′, 5,5′-tetrakis (3-amino-4-hydroxy-phenyl) -1,1′-biadamantane was synthesized by a reduction reaction with C catalyst and hydrogen.

(3) Synthesis of 5,5 ′, 7,7′-tetramethyl-1,1′-biadamantyl-3-carboxylic acid Magnesium was used in 1-bromo-3,5-dimethyladamantane in diethyl ether. 3-Bromo-5,5 ′, 7,7′-tetramethyl-1,1′-biadamantane was synthesized by a coupling reaction followed by a bromination reaction (reference: IIPe051, Polymer Preprints, Japan Vol. 50, No. 2 (2001) p277). This bromide is then converted to 5,5 ′, 7,7′-tetramethyl-1,1′-biadamantyl-3-dicarboxylic acid by carboxylation of Koch-Haaf (reaction with formic acid in concentrated sulfuric acid). (Ludek Vodicka, Josef Janku and Jiri Burkhard, Collection Czechoslovak Chem. Commun. Vol. 48 (1983), p1162-1172).

(4) Synthesis of benzoxazole precursor and production of resin film 1,3-bis (3,5-dimethyl-1-adamantyl) -4- (4-amino) obtained in (1) above under a nitrogen gas flow -3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene 66.2 g (0.1 mol), 3,3 ′, 5,5′-tetrakis (3-amino-4) obtained in (2) above After dissolving 0.349 g (0.0005 mol) of -hydroxy-phenyl) -1,1'-biadamantane in 200 g of dry N-methyl-2-pyrrolidone and adding 17.4 g (0.22 mol) of pyridine. The mixture was cooled to −15 ° C., and 46.5 g (0.15 mol) of triphenyl phosphite was added little by little. After completion of dropping, the mixture was stirred at −15 ° C. for 1 hour, returned to room temperature, and stirred at room temperature for 2 hours. Thereafter, 5.77 g (0.015 mol) of 5,5 ′, 7,7′-tetramethyl-1,1′-biadamantyl-3-carboxylic acid obtained in (3) above was added, and the mixture was stirred at room temperature for 2 hours. Stir. The reaction solution was dropped into 4 liters of distilled water in small droplets, and the precipitate was collected and dried to obtain a benzoxazole resin precursor.
It was 66,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.
A resin film was prepared and evaluated in the same manner as in Example 1.

(1) Synthesis of 1,1′-biadamantyl-3,3 ′, 5,5′-tetracarboxylic acid From 1-bromo-adamantane, a coupling reaction using magnesium in diethyl ether, followed by bromination By the reaction, 3,3 ′, 5,5′-tetrabromo-1,1′-biadamantane was synthesized (reference: IIPe051, Polymer Preprints, Japan Vol. 50, No. 2 (2001) p277).
Next, this tetrabrominated product was subjected to carboxylation of Koch-Haaf (reaction with formic acid in concentrated sulfuric acid) to obtain 1,1′-biadamantyl-3,3 ′, 5,5′-tetracarboxylic acid ( Reference: Ludek Vodicka, Josef Janku and Jiri Burkhard, Collection Czechoslovak Chem. Commun. Vol. 48 (1983), p1162-1172)

(2) Synthesis of benzoxazole precursor and production of resin film 3- (3-amino-4-hydroxyphenyl) -3′-carboxy- (5) obtained in (1) of Example 1 under a nitrogen gas flow , 5 ′, 7,7′-tetramethyl-1,1′-biadamantane) 47.8 g (0.1 mol), 1,1′-biadamantyl-3,3 ′, 5 obtained in (1) above. , 5′-tetracarboxylic acid (0.446 g, 0.001 mol) was dissolved in 200 g of dried N-methyl-2-pyrrolidone, 17.4 g (0.22 mol) of pyridine was added, and then cooled to −15 ° C. Then, 46.5 g (0.15 mol) of triphenyl phosphite was added little by little. After completion of dropping, the mixture was stirred at −15 ° C. for 1 hour, returned to room temperature, and stirred at room temperature for 2 hours. Thereafter, 1.63 g (0.015 mol) of 2-amino-phenol was added and stirred at room temperature for 2 hours. The reaction solution was dropped into 4 liters of distilled water as a small droplet, and the precipitate was collected and dried to obtain a benzoxazole resin precursor.
It was 41,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.
A resin film was prepared and evaluated in the same manner as in Example 1.

(1) Synthesis of 1,3-bis [4- (3-hydroxy-4-aminophenoxy)]-4,6-bis (3,5-dimethyl-1-adamantyl) -benzene Resorcinol and 1-bromo-3 4,6-bis (3,5-dimethyl-adamantyl) -resorcinol by reaction with 1,5-dimethyl-adamantane, etherification reaction with 2-benzyloxy-4-fluoronitrobenzene, Pd-C catalyst and 1,3-bis [4- (3-hydroxy-4-aminophenoxy)]-4,6-bis (3,5-dimethyl-1-adamantyl) by deprotection of hydroxyl group with hydrogen and reduction reaction of nitro group ) -Benzene was synthesized (Reference: Yoshio Imai, Yasumasa Maeda, Hisashi Takeuchi, Ki-Hong Park, Masa-aki Kakimoto, Toshikazu Kurosaki, Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 40, 2656-2662 (2002)).

(2) Synthesis of benzoxazole precursor and production of resin film 1,3-bis (3,5-dimethyl-1-adamantyl) -4- () obtained in (1) of Example 3 under a nitrogen gas flow 4-amino-3-hydroxyphenoxy) -6- (4-carboxyphenoxy) -benzene 33.1 g (0.05 mol), 1,3-bis [4- (3-hydroxy-4) obtained in (1) above -Aminophenoxy)]-4,6-bis (3,5-dimethyl-1-adamantyl) -benzene 32.4 g (0.05 mol) and 1,1′-biadamantyl obtained in (1) of Example 4 −3,3 ′, 5,5′-tetracarboxylic acid 4.46 g (0.01 mol) was dissolved in 200 g of dried N-methyl-2-pyrrolidone, and 17.4 g (0.22 mol) of pyridine was added. After cooling to -15 ° C, 46.5 g (0.15 mol) of triphenyl phosphite was added little by little. After completion of dropping, the mixture was stirred at −15 ° C. for 1 hour, returned to room temperature, and stirred at room temperature for 2 hours. Thereafter, 1.83 g (0.015 mol) of benzoic acid was added and stirred at room temperature for 2 hours. The reaction solution was dropped into 4 liters of distilled water as a small droplet, and the precipitate was collected and dried to obtain a benzoxazole resin precursor.
It was 53,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.
A resin film was prepared and evaluated in the same manner as in Example 1.

(1) Synthesis of benzoxazole precursor and production of resin film 3- (3-amino-4-hydroxyphenyl) -3′-carboxy- (5) obtained in (1) of Example 1 under a nitrogen gas flow , 5 ′, 7,7′-tetramethyl-1,1′-biadamantane) 47.8 g (0.1 mol) and 3,3 ′, 5,5′-tetrakis obtained in (2) of Example 3 0.349 g (0.0005 mol) of (3-amino-4-hydroxy-phenyl) -1,1′-biadamantane was dissolved in 200 g of dried N-methyl-2-pyrrolidone, and 17.4 g (0. 22 mol) was added, and the mixture was cooled to −15 ° C., and 46.5 g (0.15 mol) of triphenyl phosphite was added little by little. After completion of dropping, the mixture was stirred at −15 ° C. for 1 hour, returned to room temperature, and stirred at room temperature for 2 hours. Thereafter, 1.83 g (0.015 mol) of benzoic acid was added and stirred at room temperature for 2 hours. The reaction solution was dropped into 4 liters of distilled water in small droplets, and the precipitate was collected and dried to obtain a benzoxazole resin precursor.
It was 46,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.
A resin film was prepared and evaluated in the same manner as in Example 1.

(Comparative Example 1)
(1) Synthesis of 4,6-bis (3,5-dimethyl-1-adamantyl) -1,3-bis (4-carboxy-phenoxy) -benzene Resorcinol and 1-bromo-3,5-dimethyl-adamantane 4,6-bis (3,5-dimethyl-adamantyl) -resorcinol, followed by etherification with 4-fluorobenzonitrile, followed by hydrolysis of the nitrile to carboxylic acid, 4,6-bis (3,5-dimethyl-1-adamantyl) -1,3-bis (4-carboxy-phenoxy) -benzene was synthesized (reference: Guey-Sheng Liou, Sheng-Huei Hsiao, Macromol. Chem). Phys. 201, 42-48 (2000)).

(2) Synthesis of benzoxazole precursor and production of resin film 1,3-bis [4- (3-hydroxy-4-aminophenoxy)]-4 obtained in Example 5 (1) under a nitrogen gas flow , 6-Bis (3,5-dimethyl-1-adamantyl) -benzene 64.9 g (0.1 mol), 1,3-bis (4-carboxy-phenoxy) -4,6- 67.5 g (0.1 mol) of bis (3,5-dimethyl-1-adamantyl) -benzene was dissolved in 200 g of dried N-methyl-2-pyrrolidone, and 17.4 g (0.22 mol) of pyridine was added. Thereafter, the mixture was cooled to −15 ° C., and 46.5 g (0.15 mol) of triphenyl phosphite was added little by little. After completion of dropping, the mixture was stirred at −15 ° C. for 1 hour, returned to room temperature, and stirred at room temperature for 2 hours. The reaction solution was dropped into 4 liters of distilled water in small droplets, and the precipitate was collected and dried to obtain a benzoxazole resin precursor.
It was 23,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.
A resin film was prepared and evaluated in the same manner as in Example 1.

(Comparative Example 2)
(1) Synthesis of 1,3-bis (4-amino-3-hydroxyphenoxy) benzene In a 300 mL eggplant flask, 9.9 g of 1,3-dihydroxybenzene, 44.4 g of 2-benzyloxy-4-fluoronitrobenzene, carbonic acid 37.3 g of potassium, 150 mL of N, N-dimethylformamide and a stirrer were added, and the mixture was heated and stirred at 135 ° C. for 12 hours under a nitrogen stream. After the reaction solution was filtered, it was added to 1 L of ion exchange water. The precipitated solid was collected by filtration, further stirred in 1 L of ion exchange water for 1 hour, and then dried under reduced pressure to obtain 42.3 g of 1,3-bis (4-nitro-3-benzyloxyphenoxy) benzene. Obtained.
Next, in a 300 mL eggplant flask, 42.0 g of 1,3-bis (4-nitro-3-benzyloxyphenoxy) benzene obtained above, 2.00 g of 10% palladium-activated carbon, 200 mL of N, N-dimethylformamide. And a stirring bar was added, and the mixture was stirred at 25 ° C. for 24 hours in a hydrogen atmosphere. After the reaction solution was filtered, it was added to 1 L of ion exchange water. The precipitated solid was collected by filtration, further stirred in 1 L of ion exchange water for 1 hour, and then dried under reduced pressure to obtain 30.5 g of 1,3-bis (4-amino-3-hydroxyphenoxy) benzene. It was.
(2) Synthesis of adamantane-1,3,5,7-tetracarboxylic acid tetrachloride Tetrabromide was obtained from bromination of adamantane, and this tetrabromide was then converted to Koch-Haaf carboxylation (with formic acid in concentrated sulfuric acid). To obtain adamantane-1,3,5,7-tetracarboxylic acid (Ludek Vodicka, Josef Janku and Jiri Burkhard, Collection Czechoslovak Chem. Commun. Vol. 48 (1983), p1162-1172). Next, the target adamantane-1,3,5,7-tetracarboxylic acid tetrachloride was obtained by acid chloride using thionyl chloride (reference: Kenneth A Burdett, Synthesis, June 1991, p441-442). ).
(3) Synthesis of benzoxazole precursor and production of resin film Under nitrogen gas flow, 32.43 g (0.1 mol) of 1,3-bis (4-amino-3-hydroxyphenoxy) benzene obtained in (1) above. ) Is dissolved in 200 g of dried N-methyl-2-pyrrolidone, 17.4 g (0.22 mol) of pyridine is added, and the mixture is cooled to −15 ° C. and adamantyl-1,3, obtained in (2) above. 18.5 g (0.048 mol) of 5,7-tetracarboxylic acid tetrachloride was added little by little. After completion of dropping, the mixture was stirred at −15 ° C. for 1 hour, returned to room temperature, and stirred at room temperature for 2 hours. Thereafter, 2.11 g (0.015 mol) of benzoic acid chloride was added, and the mixture was further stirred at room temperature for 2 hours. The reaction solution was dropped into 4 liters of distilled water as a small droplet, and the precipitate was collected and dried to obtain a benzoxazole resin precursor.
It was 32,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.
A resin film was prepared and evaluated in the same manner as in Example 1.

(Comparative Example 3)
(1) Synthesis of 3,5-bis (3-hydroxy-4-amino-phenoxy) -benzoic acid Etherification reaction of 2-benzyloxy-4-fluoronitrobenzene with methyl 3,5-dihydroxy-benzoate, carvone Conversion to carboxylic acid by hydrolysis of methyl acid, deprotection of hydroxyl group with Pd-C catalyst and hydrogen and reduction reaction of nitro group, 3,5-bis (3-hydroxy-4-amino-phenoxy) -benzoic acid (Reference: Yoshio Imai, Yasumasa Maeda, Hisashi Takeuchi, Ki-Hong Park, Masa-aki Kakimoto, Toshikazu Kurosaki, Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 40, 2656-2662 (2002) ).
(2) Synthesis of benzoxazole precursor and production of resin film Under a nitrogen gas flow, 36.8 g of 3,5-bis (3-hydroxy-4-amino-phenoxy) -benzoic acid obtained in (1) above ( 0.1 mol) and 6.3 g (0.03 mol) of trimesic acid were dissolved in 200 g of dried N-methyl-2-pyrrolidone, and 17.4 g (0.22 mol) of pyridine was added, followed by cooling to −15 ° C. Then, 46.5 g (0.15 mol) of triphenyl phosphite was added little by little. After completion of dropping, the mixture was stirred at −15 ° C. for 1 hour, returned to room temperature, and stirred at room temperature for 2 hours. Thereafter, 18.3 g (0.015 mol) of benzoic acid was added and stirred at room temperature for 2 hours. The reaction solution was dropped into 4 liters of distilled water as a small droplet, and the precipitate was collected and dried to obtain a benzoxazole resin precursor.
It was 87,000 when the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was calculated | required in polystyrene conversion using Tosoh Corporation GPC.
A resin film was prepared and evaluated in the same manner as in Example 1.

Film characteristics The following evaluation was performed on the resin films obtained in Examples 1 to 6 and Comparative Examples 1 to 3. The evaluation items are shown together with the method. The obtained results are shown in Table 1.
1. Varnish storage solubility 1 g of polybenzoxazole resin precursor and 3 g of cyclohexanone were precisely weighed in a glass sample container with a lid, stirred for 1 hour with a stirrer, and examined for appearance after 1 week at room temperature. If there was no change in the appearance, such as precipitates, it was marked as ◯.

2. Heat resistance Heat resistance was evaluated by the glass transition temperature and the thermal decomposition temperature. The glass transition temperature was measured using a dynamic viscoelasticity measuring device (DMS6100 manufactured by Seiko Instruments Inc.) for nitrogen gas at 300 mL / min. Under the flow, the heating rate is 3 ° C./min. The measurement was performed under conditions of a frequency of 1 Hz, and the peak top temperature of tan δ was defined as the glass transition temperature.
The thermal decomposition temperature was determined by using a TG / DTA measuring device (TG / DTA220 manufactured by Seiko Instruments Co., Ltd.) for the obtained resin film. Under the flow, the heating rate is 10 ° C./min. The temperature at which the weight loss reached 5% was defined as the thermal decomposition temperature.

3. Relative permittivity Based on JIS-K6911, the capacity of the adhesive film for a semiconductor was measured using a HP-4284A Precision LCR meter manufactured by Hewlett-Packard at a frequency of 100 kHz, and the relative permittivity was calculated by the following formula.
Relative permittivity = (capacitance measurement value × film thickness) / (vacuum permittivity × measurement area)

As is apparent from Table 1, Examples 1 to 6 were excellent in varnish storage, low dielectric constant, and excellent heat resistance.
Further, Comparative Example 1 has a low glass transition temperature and a high dielectric constant, and Comparative Examples 2 and 3 have poor varnish storage properties, a considerably high dielectric constant, and poor properties.

Next, the interlayer insulating film and the semiconductor device will be described.
(Examples 7 and 8)
A silicon nitride layer is formed on a semiconductor substrate, and the coating varnish obtained in the production of the resin films of Example 1 and Example 3 is applied on the silicon nitride layer. A heat treatment was performed at 0 ° C. for 1 hour to form an interlayer insulating film having a thickness of 0.3 μm.
Next, a metal wiring was formed so as to form a predetermined pattern on the interlayer insulating film, thereby obtaining a semiconductor device.

Next, the wiring delay rate was evaluated for the obtained semiconductor device.
A semiconductor device of Example 7 obtained by using the resin film of Example 2, a semiconductor device of Example 8 obtained by using the resin film of Example 3, and SiO ₂ having the same configuration as this semiconductor device. The degree of wiring delay with a semiconductor device having an insulating film was compared. As the evaluation standard, the signal delay time obtained by conversion from the transmission frequency of the ring oscillator was adopted. As a result of comparing the two, the semiconductor device obtained by the present invention has less wiring delay, the speed of Example 7 is improved by about 14%, and the speed of Example 8 is improved by about 20%. Was confirmed.

FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Silicon nitride film 3 Interlayer insulation film 4 Copper wiring layer 5 Modification process layer 6 Barrier layer 7 Hard mask layer 100 Semiconductor device

Claims (12)

  A benzoxazole precursor comprising an aromatic compound (C) having an aminohydroxyphenyl group, a carboxyl group, and a group composed of a diamondoid structure. The benzoxazole precursor according to claim 1, wherein the benzoxazole precursor has a structure represented by the general formula (1).

(X in the formula represents a group composed of at least one diamondoid structure, Ar ₁ and Ar ₂ represent an aromatic group, and m ₁ and m ₂ are integers of 0 or more and 4 or less. M ₃ represents 0 or 1. Y represents a group composed of a hydrogen atom or a diamondoid structure, and when m ₃ = 0, Y represents a group composed of a diamondoid structure. .)   The benzoxazole precursor according to claim 1 or 2, wherein the benzoxazole precursor comprises a compound (A) having at least two aminohydroxyphenyl groups.   The benzoxazole precursor according to any one of claims 1 to 3, wherein the benzoxazole precursor includes a compound (A) having at least three aminohydroxyphenyl groups.   The benzoxazole precursor according to any one of claims 1 to 4, wherein the benzoxazole precursor includes a compound (B) having at least two carboxyl groups.   The benzoxazole precursor according to any one of claims 1 to 5, wherein the benzoxazole precursor has a crosslinking group.   The resin composition containing the benzoxazole precursor of any one of Claims 1 thru | or 6.   A coating varnish in which the benzoxazole precursor according to any one of claims 1 to 6 or the resin composition according to claim 7 is dissolved in an organic solvent.   The resin film comprised from the benzoxazole precursor of any one of Claims 1 thru | or 6, the resin composition of Claim 7, or the coating varnish of Claim 8.   A semiconductor device having the resin film according to claim 9.   The semiconductor device according to claim 10, wherein the resin film has an interlayer insulating film and / or a protective film.   The resin film is formed by applying the coating varnish according to claim 8 on a predetermined position of a semiconductor substrate to form a coating film, and the coating film is cured by heating and / or irradiation with actinic radiation. The semiconductor device according to claim 10 or 11, which is obtained.

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