JP5874230B2 - Sealing film material, sealing film and application - Google Patents

Description

  The present invention relates to a sealing film formed from an organic silicon nitride compound and its use. In particular, the present invention relates to a sealing film formed by a plasma enhanced chemical vapor deposition method (PECVD method: Plasma Enhanced Chemical Vapor Deposition method).

  In flat panel displays (hereinafter referred to as FPD) typified by liquid crystal displays and organic EL displays, a glass substrate is used as the base material of the display panel, but it is thinned, reduced in weight, improved in impact resistance, made flexible, From the viewpoint of adapting to a roll-to-roll process, there is an increasing demand for an alternative to a transparent plastic substrate. Attempts have also been made to form organic transistors using organic semiconductors on plastic substrates, and to form LSIs, Si thin film solar cells, organic dye-sensitized solar cells, and organic semiconductor solar cells.

  When the above elements are formed on a commercially available plastic substrate, the formed elements and devices such as liquid crystal elements, organic EL elements, TFT elements, semiconductor elements and solar cells are vulnerable to water and oxygen. Dark spots and missing dots occur, semiconductor elements and solar cells stop functioning and cannot be used practically. Therefore, a gas barrier plastic substrate in which a gas barrier performance against water vapor and oxygen gas is imparted to the plastic substrate is required. On the other hand, transparent plastic films imparted with gas barrier properties are increasingly used in the future as a packaging material for foodstuffs, pharmaceuticals, electronic materials, and electronic components, instead of opaque aluminum foil laminate films.

  As a method for imparting transparent gas barrier performance to a transparent plastic substrate or a transparent plastic film, there are a physical film formation method and a chemical vapor deposition method (hereinafter referred to as a CVD method).

  There exists patent document 1 as a proposal using a carbon nitride film, carbon nitride film is formed into PECVD film using methane gas and nitrogen gas, and it is set as the contact | adherence layer of a glass substrate and a resin film. Patent Document 2 discloses PECVD film formation of a carbon nitride film using an amine compound such as trimethylamine. In the semiconductor field, Patent Document 3 proposes using a carbon nitride thin film as an interlayer insulating film or a gate insulating film of a thin film transistor by using an unsaturated carbon compound such as ethylene or acetylene and nitrogen or ammonia. Further, Patent Document 4 proposes to use a carbon nitride film formed by a CVD method as a gate insulating film of a field effect transistor.

  However, in these carbon nitride film forming methods, the raw material is a two-component system, and the composition of the resulting film is not constant. In particular, the nitrogen content was not stable or the nitrogen content was low. Furthermore, when used as a gas barrier film, the film is not sufficiently dense so that the gas barrier performance against water vapor and oxygen is insufficient, or when used as an insulating film for semiconductors, the insulating properties are insufficient. We have problems such as.

JP 2004-66664 A JP-A-9-255314 JP 2004-277882 A JP 2002-270834 A

  The present invention has been made in view of the above-mentioned problems, and an object thereof is organic nitridation that can be used as a gas barrier, a barrier film for a semiconductor, an etch stop film, a hard mask film, etc., using a compound suitable for a CVD apparatus as a raw material. A silicon-containing film is formed, and a gas barrier film and a semiconductor device using the film are provided.

  The inventors of the present invention use a specific organic silicon nitride compound as a raw material, and a method of forming a sealing film by a CVD method is a preferable method for forming a dense film for a gas barrier and a semiconductor device. As a result, the present invention has been completed.

That is, the present invention is as follows.
[1] A film obtained by chemical vapor deposition using an organic silicon nitride compound having a structure in which at least one hydrogen atom is directly bonded to a silicon atom and at least one hydrogen atom is directly bonded to a nitrogen atom. A sealing film characterized by the above.
[2] The organosilicon nitride compound is represented by the following general formula (1)

（式中、Ｒ^１は水素原子、又は炭素数１〜２０の炭化水素基を表す。ｎは１乃至１０の整数を表す。）
で示される鎖状または環状構造を有する化合物である、上述の［１］に記載の封止膜。
［３］上記有機窒化ケイ素化合物が、下記一般式（２）

(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. N represents an integer of 1 to 10.)
The sealing film according to [1], which is a compound having a chain or cyclic structure represented by
[3] The organosilicon nitride compound is represented by the following general formula (2)

（式中、Ｒ^２とＲ^４は炭素数１〜２０の炭化水素基を表し、Ｒ^３とＲ^５は水素原子又は炭素数１〜２０の炭化水素基を表す。ｘは１乃至１０の整数を表す。）
で示される鎖状化合物である、上述の［１］または［２］に記載の封止膜。
［４］上記有機窒化ケイ素化合物が、下記一般式（３）

(In the formula, R ² and R ⁴ represent a hydrocarbon group having 1 to 20 carbon atoms, R ³ and R ⁵ represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, x is an integer of 1 to 10) Represents.)
The sealing film according to [1] or [2] above, which is a chain compound represented by:
[4] The organosilicon nitride compound is represented by the following general formula (3):

（式中、Ｒ^６は水素原子又は炭素数１〜２０の炭化水素基を表し、ｙは２乃至１０の整数を表す。）
で示される環状化合物である、上述の［１］または［２］に記載の封止膜。
［５］化学気相成長法が、プラズマ励起化学気相成長法である、上述の［１］乃至［４］のいずれかに記載の封止膜。
［６］化学気相成長法が、触媒化学気相成長法である、上述の［１］乃至［４］のいずれかに記載の封止膜。
［７］上述の［１］〜［６］のいずれかに記載の封止膜を、さらに熱処理、紫外線照射処理または電子線処理して得られることを特徴とする封止膜。
［８］上述の［１］〜［７］のいずれかに記載の封止膜をガスバリア層として用いることを特徴とするガスバリア部材。
［９］上述の［１］〜［７］のいずれかに記載の封止膜を含んでなることを特徴とするフラットパネルディスプレイデバイス。
［１０］上述の［１］〜［７］のいずれかに記載の封止膜を含んでなることを特徴とする半導体デバイス。
［１１］一般式（１）で示される鎖状または環状構造を有する化合物を含有することを特徴とする化学気相成長法用の封止膜材料。
［１２］一般式(１)で示される鎖状または環状構造を有する化合物が、一般式（２）で示される鎖状化合物である上述の［１１］に記載の封止膜材料。
［１３］一般式(１)で示される鎖状または環状構造を有する化合物が、一般式（３）で示される環状化合物である上述の［１１］に記載の封止膜材料。
［１４］ケイ素、炭素および窒素を含有し、表面の組成が原子比でケイ素１．０に対し、窒素含有量が０．２以上１．３３以下、炭素含有量が０以上１．０以下であり、かつ赤外吸収スペクトルの１２００〜１３００ｃｍ^−１及び２８００〜３２００ｃｍ^−１の吸収が実質的に検出限界以下である、上述の［１］〜［７］いずれかに記載の封止膜。
［１５］水透過性が５．０×１０^−３ｇ／ｍ^２・ｄａｙ以下である、上述の［１］〜［７］、［１４］いずれかに記載の封止膜。

(Wherein R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and y represents an integer of 2 to 10)
The sealing film according to [1] or [2] above, which is a cyclic compound represented by
[5] The sealing film according to any one of [1] to [4], wherein the chemical vapor deposition method is a plasma enhanced chemical vapor deposition method.
[6] The sealing film according to any one of [1] to [4], wherein the chemical vapor deposition method is a catalytic chemical vapor deposition method.
[7] A sealing film obtained by further subjecting the sealing film according to any one of [1] to [6] above to heat treatment, ultraviolet irradiation treatment, or electron beam treatment.
[8] A gas barrier member using the sealing film according to any one of [1] to [7] as a gas barrier layer.
[9] A flat panel display device comprising the sealing film according to any one of [1] to [7] above.
[10] A semiconductor device comprising the sealing film according to any one of [1] to [7] above.
[11] A sealing film material for chemical vapor deposition, comprising a compound having a chain or cyclic structure represented by the general formula (1).
[12] The sealing film material according to [11] above, wherein the compound having a chain or cyclic structure represented by the general formula (1) is a chain compound represented by the general formula (2).
[13] The sealing film material according to [11] above, wherein the compound having a chain or cyclic structure represented by the general formula (1) is a cyclic compound represented by the general formula (3).
[14] Containing silicon, carbon and nitrogen, and the composition of the surface is 1.0 to 1.33 in nitrogen content and 0 to 1.0 in carbon content with respect to silicon 1.0 in atomic ratio The sealing film according to any one of the above [1] to [7], which has an infrared absorption spectrum of absorption of 1200 to 1300 cm ⁻¹ and 2800 to 3200 cm ⁻¹ substantially below a detection limit.
[15] The sealing film according to any one of [1] to [7] and [14] above, wherein the water permeability is 5.0 × 10 ⁻³ g / m ² · day or less.

  Details of the present invention will be described below.

  In the present invention, an organic silicon nitride compound having a structure in which at least one hydrogen atom that can be used as a raw material for the CVD method is directly connected to silicon and at least one hydrogen atom is directly connected to a nitrogen atom is not particularly limited. A compound having a chain or cyclic structure represented by the general formula (1) is preferred.

In the general formula (1), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may be either saturated or unsaturated, and may be linear or branched. Any structure of a ring shape may be used. Further, those in which R ¹ are bonded to each other are also included in the scope of the present invention. When the number of carbon atoms exceeds 20, it may be difficult to procure the corresponding raw material such as organic halide, or even if it can be procured, the purity may be low.

R ¹ is preferably hydrogen, or saturated or unsaturated carbonization having 1 to 10 carbon atoms, in view of stable use in a CVD apparatus, in that the vapor pressure of the organic silicon nitride compound is not too low. A hydrogen group, for example, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an arylalkyl group, an alkylaryl group, an alkenyl group, an arylalkenyl group, an alkenylaryl group, an alkynyl group, an arylalkynyl group, an alkynylaryl The group can be mentioned. R ¹ may be the same or different.

Specific examples of R ¹ include a hydrogen atom, methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, cyclobutyl, n-pentyl, tert. -Alkyl groups such as amyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, 1-adamantyl,
Aryl groups such as phenyl, diphenyl and naphthyl; arylalkyl groups such as benzyl and methylbenzyl;
o-toluyl, m-toluyl, p-toluyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5 -Alkylaryl groups such as dimethylphenyl, 2,4,6-trimethylphenyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl,
Vinyl, allyl, 1-propenyl, 1-butenyl, 1,3-butadienyl, 1-pentenyl, cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl 1-hexenyl, cyclohexenyl, cyclooctenyl, cyclooctadienyl, 2,4-cyclohexadienyl, 2,5-cyclohexadienyl, 2,4,6-cycloheptatrienyl, 5-norbornen-2-yl, etc. An alkenyl group of
Arylalkenyl groups such as 2-phenyl-1-ethenyl,
alkenyl aryl groups such as o-styryl, m-styryl, p-styryl,
Ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 3-hexynyl, 5-hexynyl, etc. An alkynyl group of
Arylalkynyl groups such as 2-phenyl-1-ethynyl,
There may be mentioned at least one selected from the group consisting of alkynylaryl groups such as 2-ethynyl-2-phenyl.

  Particularly preferred is a hydrogen atom or a saturated hydrocarbon group having 1 to 4 carbon atoms, specifically a hydrogen atom, methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl and cyclobutyl. Of these, methyl, ethyl, and i-propyl are particularly preferable.

  In the general formula (1), n represents an integer of 1 to 10. Preferably, n is an integer of 1 to 6 in that the vapor pressure of the organic silicon nitride compound is not too low. Particularly preferably, n is an integer of 1 to 4. In particular, n = 1, 2 is preferable.

  Examples of the general formula (1) include a chain compound represented by the general formula (2).

In the general formula (2), R ² and R ⁴ use a saturated or unsaturated hydrocarbon group having a linear, branched, or cyclic structure having 1 to 20 carbon atoms similar to the above R ^1. be able to. R ³ and R ⁵ may be the same hydrogen atom as R ¹ described above, or a saturated or unsaturated hydrocarbon group having a linear, branched or cyclic structure having 1 to 20 carbon atoms. Furthermore, ^{those R 2} and ^R 4, ^{R 3} and ^{R 5} if you are bonded to each other are also within the scope of the present invention. When the number of carbon atoms exceeds 20, it may be difficult to procure the corresponding raw material such as organic halide, or even if it can be procured, the purity may be low. In view of stable use in a chemical vapor deposition apparatus, R ^{2 to} R ⁵ are preferably hydrocarbon groups having 1 to 10 carbon atoms in that the vapor pressure of the organic silicon nitride compound is not too low. , A saturated hydrocarbon group having 1 to 4 carbon atoms is more preferable, specifically, methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl and cyclobutyl. In particular, R ^{2 to} R ⁵ are preferably methyl, ethyl, or i-propyl.

R ² and R ⁴ , and R ³ and R ⁵ may be the same or different.

  In the general formula (2), x represents an integer of 1 to 10. Preferably, x is an integer of 1 to 6 in that the vapor pressure of the organic silicon nitride compound is not too low. Particularly preferably, x is an integer of 1 to 4. In particular, x = 1, 2 is preferable.

Specific examples of the compound represented by the general formula (2) include
1-methyldisilazane, 1,1-dimethyldisilazane, 1,3-dimethyldisilazane, 1,1,3-trimethyldisilazane, 1,1,3,3-tetramethyldisilazane 1-methyltrisilazane, 3-methyltrisilazane, 1,3-dimethyltrisilazane, 1,5-dimethyltrisilazane, 1,1,3-trimethyltrisilazane, 1,3,5-trimethyltrisilazane, 1,1,3,5- Tetramethyltrisilazane, 1,1,5,5-tetramethyltrisilazane, 1,1,3,5,5-pentamethyltrisilazane,
1-methyltetrasilazane, 3-methyltetrasilazane, 1,1-dimethyltetrasilazane, 1,3-dimethyltetrasilazane, 1,5-dimethyltetrasilazane, 1,7-dimethyltetrasilazane, 1,1,3- Trimethyltetrasilazane, 1,1,5-trimethyltetrasilazane, 1,1,7-trimethyltetrasilazane, 1,3,5-trimethyltetrasilazane, 1,3,7-trimethyltetrasilazane, 1,1,3 5-tetramethyltetrasilazane, 1,1,3,7-tetramethyltetrasilazane, 1,1,7,7-tetramethyltetrasilazane, 1,3,5,7-tetramethyltetrasilazane, 1,1, 3,5,7-pentamethyltetrasilazane, 1,1,3,7,7-pentamethyltetrasilazane, 1,1,3,5,7,7- Kisa methyltetrahydropyran disilazane and the like.

  Also 1-methylpentasilazane, 3-methylpentasilazane, 5-methylpentasilazane, 1,1-dimethylpentasilazane, 1,3-dimethylpentasilazane, 1,5-dimethylpentasilazane, 1,7-dimethylpentasilazane 1,9-dimethylpentasilazane, 1,1,3-trimethylpentasilazane, 1,1,5-trimethylpentasilazane, 1,1,7-trimethylpentasilazane, 1,1,9-trimethylpentasilazane, , 3,5-trimethylpentasilazane, 1,3,7-trimethylpentasilazane, 1,3,9-trimethylpentasilazane, 3,5,9-trimethylpentasilazane, 1,1,3,5-tetramethylpenta Silazane, 1,1,3,7-tetramethylpentasilazane, 1,1,3,9-tetramethylpen Silazane, 1,1,5,7-tetramethylpentasilazane, 1,1,5,9-tetramethylpentasilazane, 1,1,7,9-tetramethylpentasilazane, 1,3,5,7-tetra Methyl pentasilazane, 1,3,5,9-tetramethylpentasilazane, 1,5,7,9-tetramethylpentasilazane, 1,3,5,7,9-pentamethylpentasilazane, 1,1,3 , 5,7,9-hexamethylpentasilazane, 1,1,3,5,7,9,9-heptamethylpentasilazane.

1,3,5,7,9,11-hexamethylhexasilazane, 1,1,3,5,7,9,11,11-octamethylhexasilazane,
1,3,5,7,9,11,13-heptamethylheptasilazane, 1,1,3,5,7,9,11,13,13-nonamethylheptasilazane,
1,3,5,7,9,11,13,15-octamethyloctasilazane, 1,1,3,5,7,9,11,13,15,15-decamethyloctasilazane,
1,3,5,7,9,11,13,15,17-nonamethylnonasilazane, 1,1,3,5,7,9,11,13,15,17,17-undecamethylnonasilazane ,
1,3,5,7,9,11,13,15,17,19-decamethyldecasilazane, 1,1,3,5,7,9,11,13,15,17,19,19-dodeca Methyl decasilazane, 1,3-diethyldisilazane, 1,3-diethyl-1,3-dimethyldisilazane, 1,1,3,3-tetraethyldisilazane, 1,3,5-triethyltrisilazane, 1, 1,3,5,5-pentaethyltrisilazane, 1,3,5,7-tetraethyltetrasilazane, 1,1,3,5,7,7-hexaethyltetrasilazane, 1,3,5,7, 9-pentaethylpentasilazane, 1,1,3,5,7,9,9-heptaethylpentasilazane, 1,3,5,7,9,11-hexaethylhexasilazane, 1,1,3,5 , 7,9,11,11-octaethylhexa Than, and the like.

1,3,5,7,9,11,13-heptaethylheptasilazane, 1,1,3,5,7,9,11,13,13-nonaethylheptasilazane, 1,3,5,7 , 9,11,13,15-octaethyloctasilazane, 1,1,3,5,7,9,11,13,15,15-decaethyloctasilazane, 1,3,5,7,9,11 , 13,15,17-nonaethylnonasilazane, 1,1,3,5,7,9,11,13,15,17,17-undecaethylnonasilazane, 1,3,5,7,9, 11, 13, 15, 17, 19-decaethyldecasilazane, 1,1,3,5,7,9,11,13,15,17,19,19-dodecaethyldecasilazane,
1,3-di-n-propyldisilazane, 1,1,3,3-tetra-n-propyldisilazane, 1,3,5-tri-n-propyltrisilazane, 1,1,3,5,5-penta n-propyltrisilazane, 1,3,5,7-tetran-propyltetrasilazane, 1,1,3,5,7,7-hexa-n-propyltetrasilazane, 1,3,5,7,9- Penta n-propyl pentasilazane, 1,1,3,5,7,9,9-hepta n-propyl pentasilazane, 1,3,5,7,9,11-hexa n-propyl hexasilazane, 1,1 3,5,7,9,11,11-octa-n-propylhexasilazane.

1,3,5,7,9,11,13-hepta-n-propylheptasilazane, 1,1,3,5,7,9,11,13,13-nona-propylheptasilazane, 1,3 , 5,7,9,11,13,15-octane-propyloctasilazane, 1,1,3,5,7,9,11,13,15,15-deca-n-propyloctasilazane, 1,3 , 5,7,9,11,13,15,17-nona n-propyl nonasilazane, 1,1,3,5,7,9,11,13,15,17,17-undeca n-propyl nonasilazane 1,3,5,7,9,11,13,15,17,19-decane-propyldecasilazane, 1,1,3,5,7,9,11,13,15,17,19, 19-dodeca-propyldecasilazane,
1,3-diisopropyldisilazane, 1,3-diisopropyl-1,3-dimethyldisilazane, 1,3-diisopropyl-1,3-diethyldisilazane, 1,1,3,3-tetraisopropyldisilazane, , 3,5-triisopropyltrisilazane, 1,1,3,5,5-pentaisopropyltrisilazane, 1,3,5,7-tetraisopropyltetrasilazane, 1,1,3,5,7,7- Hexaisopropyltetrasilazane, 1,3,5,7,9-pentaisopropylpentasilazane, 1,1,3,5,7,9,9-heptaisopropylpentasilazane, 1,3,5,7,9,11 -Hexaisopropylhexasilazane, 1,1,3,5,7,9,11,11-octaisopropylhexasilazane.

1,3,5,7,9,11,13-heptaisopropylheptasilazane, 1,1,3,5,7,9,11,13,13-nonaisopropylheptasilazane, 1,3,5,7 , 9,11,13,15-octaisopropyloctasilazane, 1,1,3,5,7,9,11,13,15,15-decaisopropyloctasilazane, 1,3,5,7,9,11 , 13,15,17-nonaisopropylnonasilazane, 1,1,3,5,7,9,11,13,15,17,17-undecaisopropylnonasilazane, 1,3,5,7,9, 11, 13, 15, 17, 19-decaisopropyldecasilazane, 1,1,3,5,7,9,11,13,15,17,19,19-dodecaisopropyldecasilazane,
1,3-di-n-butyldisilazane, 1,1,3,3-tetra-n-butyldisilazane, 1,3,5-tri-n-butyltrisilazane, 1,1,3,5,5-penta n-butyltrisilazane, 1,3,5,7-tetra-n-butyltetrasilazane, 1,1,3,5,7,7-hexa-n-butyltetrasilazane, 1,3,5,7,9- Penta n-butyl pentasilazane, 1,1,3,5,7,9,9-hepta n-butyl pentasilazane, 1,3,5,7,9,11-hexa n-butyl hexasilazane, 1,1 3, 5, 7, 9, 11, 11-octane n-butyl hexasilazane.

1,3,5,7,9,11,13-hepta-n-butylheptasilazane, 1,1,3,5,7,9,11,13,13-nona-n-butylheptasilazane, 1,3 , 5,7,9,11,13,15-octa-n-butyloctasilazane, 1,1,3,5,7,9,11,13,15,15-deca-n-butyloctasilazane, 1,3 5,7,9,11,13,15,17-nona n-butyl nonasilazane, 1,1,3,5,7,9,11,13,15,17,17-undeca n-butyl nonasilazane 1,3,5,7,9,11,13,15,17,19-decane-butyldecasilazane, 1,1,3,5,7,9,11,13,15,17,19, 19-dodeca n-butyldecasilazane,
1,3-diisobutyldisilazane, 1,1,3,3-tetraisobutyldisilazane, 1,3,5-triisobutyltrisilazane, 1,1,3,5,5-pentaisobutyltrisilazane, 1,3 , 5,7-tetraisobutyltetrasilazane, 1,1,3,5,7,7-hexaisobutyltetrasilazane, 1,3,5,7,9-penta n-butylpentasilazane, 1,1,3 5,7,9,9-heptaisobutylpentasilazane, 1,3,5,7,9,11-hexaisobutylhexasilazane, 1,1,3,5,7,9,11,11-octaisobutylhexasilazane Can be given.

1,3,5,7,9,11,13-heptaisobutylheptasilazane, 1,1,3,5,7,9,11,13,13-nonaisobutylheptasilazane, 1,3,5,7 , 9,11,13,15-octaisobutyloctasilazane, 1,1,3,5,7,9,11,13,15,15-decaisobutyloctasilazane, 1,3,5,7,9,11 , 13,15,17-nonaisobutylnonasilazane, 1,1,3,5,7,9,11,13,15,17,17-undecaisobutylnonasilazane, 1,3,5,7,9, 11, 13, 15, 17, 19-decaisobutyl decacilazan, 1,1,3,5,7,9,11,13,15,17,19,19-dodecaisobutyl decacilazan,
1,3-disec. -Butyldisilazane, 1,3-disec. -Butyl-1,3-dimethyldisilazane, 1,3-disec. -Butyl-1,3-diethyldisilazane, 1,1,3,3-tetrasec. -Butyldisilazane, 1,3,5-tri sec. -Butyltrisilazane, 1,1,3,5,5-pentasec. -Butyltrisilazane, 1,3,5,7-tetra sec. -Butyltetrasilazane, 1,1,3,5,7,7-hexa sec. -Butyltetrasilazane, 1,3,5,7,9-penta sec. -Butylpentasilazane, 1,1,3,5,7,9,9-hepta sec. -Butylpentasilazane, 1,3,5,7,9,11-hexa sec. -Butyl hexasilazane, 1,1,3,5,7,9,11,11-octasec. -Butyl hexasilazane.

  1, 3, 5, 7, 9, 11, 13-hepta sec. -Butylheptasilazane, 1,1,3,5,7,9,11,13,13-nona sec. -Butylheptasilazane, 1,3,5,7,9,11,13,15-octasec. -Butyl octasilazane, 1,1,3,5,7,9,11,13,15,15-decasec. -Butyl octasilazane, 1,3,5,7,9,11,13,15,17-nona sec. -Butylnonasilazane, 1,1,3,5,7,9,11,13,15,17,17-undeca sec. -Butyl nonasilazane, 1,3,5,7,9,11,13,15,17,19-deca sec. -Butyldecasilazane, 1,1,3,5,7,9,11,13,15,17,19,19-dodeca sec. -Butyl decasilazane.

  In addition, 1,3-di tert. -Butyldisilazane, 1,3-ditert. -Butyl-1,3-dimethyldisilazane, 1,3-ditert. -Butyl-1,3-diethyldisilazane, 1,1,3,3-tetra tert. -Butyldisilazane, 1,3,5-tri tert. -Butyltrisilazane, 1,1,3,5,5-penta tert. -Butyltrisilazane, 1,3,5,7-tetra tert. -Butyltetrasilazane, 1,1,3,5,7,7-hexa tert. -Butyltetrasilazane, 1,3,5,7,9-penta tert. -Butylpentasilazane, 1,1,3,5,7,9,9-hepta tert. -Butylpentasilazane, 1,3,5,7,9,11-hexa tert. -Butyl hexasilazane, 1,1,3,5,7,9,11,11-octa tert. -Butyl hexasilazane, 1,3,5,7,9,11,13-hepta tert. -Butylheptasilazane, 1,1,3,5,7,9,11,13,13-nona tert. -Butylheptasilazane, 1,3,5,7,9,11,13,15-octa tert. -Butyl octasilazane, 1,1,3,5,7,9,11,13,15,15-deca tert. -Butyl octasilazane, 1,3,5,7,9,11,13,15,17-nona tert. -Butyl nonasilazane, 1,1,3,5,7,9,11,13,15,17,17-undeca tert. -Butylnonasilazane, 1,3,5,7,9,11,13,15,17,19-deca tert. -Butyldecasilazane, 1,1,3,5,7,9,11,13,15,17,19,19-dodeca tert. -Butyl decasilazane.

1,3-di-n-pentyldisilazane, 1,1,3,3-tetra-n-pentyldisilazane, 1,3,5-tri-n-pentyllysilazane, 1,1,3,5,5- Penta n-pentyl lysilazan, 1,3,5,7-tetra n-pentyltetrasilazane, 1,1,3,5,7,7-hexa n-pentyltetrasilazane, 1,3,5,7,9 -Penta n-pentyl pentasilazane, 1,1,3,5,7,9,9-hepta n-pentyl pentasilazane,
1,3-di tert. -Amyldisilazane, 1,1,3,3-tetra tert. Amyldisilazane, 1,3,5-tri tert. -Amyltrisilazane, 1,1,3,5,5-penta tert. -Amyltrisilazane, 1,3,5,7-tetra tert. -Amyltetrasilazane, 1,1,3,5,7,7-hexa tert. -Amyltetrasilazane, 1,3,5,7,9-penta tert. -Amylpentasilazane, 1,1,3,5,7,9,9-hepta tert. -Amyl pentasilazane,
1,3-dicyclopentyldisilazane, 1,1,3,3-tetracyclopentyldisilazane, 1,3,5-tricyclopentylrisilazane, 1,1,3,5,5-pentacyclopentylrisilazane, 1, 3,5,7-tetracyclopentyltetrasilazane, 1,1,3,5,7, hexacyclopentyltetrasilazane, 1,3,5,7,9-pentacyclopentylpentasilazane, 1,1,3,5 , 7,9,9-heptacyclopentylpentasilazane.

1,3-di-n-hexyldisilazane, 1,1,3,3-tetra-n-hexyldisilazane, 1,3,5-tri-n-hexyltrisilazane, 1,1,3,5,5- Penta n-hexyl trisilazane, 1,3,5,7-tetra n-hexyl tetrasilazane, 1,1,3,5,7,7-hexane n-hexyltetrasilazane, 1,3,5,7,9 -Penta n-hexyl pentasilazane, 1,1,3,5,7,9,9-hepta n-hexyl pentasilazane,
1,3-dicyclohexyldisilazane, 1,3-dicyclohexyl-1,3-dimethyldisilazane, 1,3-dicyclohexyl-1,3-diethyldisilazane, 1,1,3,3-tetracyclohexyldisilazane, , 3,5-tricyclohexyltrisilazane, 1,1,3,5,5-pentacyclohexyltrisilazane, 1,3,5,7-tetracyclohexyltetrasilazane, 1,1,3,5,7,7- Hexacyclohexyltetrasilazane, 1,3,5,7,9-pentacyclohexylpentasilazane, 1,1,3,5,7,9,9-heptacyclohexylpentasilazane,
1,3-di-n-heptyldisilazane, 1,1,3,3-tetra-n-heptyldisilazane, 1,3,5-tri-n-heptyllysilazane, 1,1,3,5,5-penta n-heptyl lysilazane, 1,3,5,7-tetra n-heptyltetrasilazane, 1,1,3,5,7,7-hexa-n-heptyltetrasilazane, 1,3,5,7 , 9-penta n-heptyl pentasilazane, 1,1,3,5,7,9,9-hepta n-heptyl pentasilazane.

Also, 1,3-diadamantyldisilazane, 1,1,3,3-tetraadamantyldisilazane, 1,3,5-triadamantyltrisilazane, 1,1,3,5,5-pentaadamantyllicilazane, , 3,5,7-tetraadamantyltetrasilazane, 1,1,3,5,7,7-hexaadamantyltetrasilazane, 1,3,5,7,9-pentaadamantylpentasilazane, 1,1,3 5,7,9,9-heptadamantylpentasilazane,
1,3-divinyldisilazane, 1,3-divinyl-1,3-dimethyldisilazane, 1,1,3,3-tetravinyldisilazane, 1,3,5-trivinyltrisilazane, 1,1, 3,5,5-pentavinyltrisilazane, 1,3,5,7-tetravinyltetrasilazane, 1,1,3,5,7,7-hexavinyltetrasilazane, 1,3,5,7,9 -Pentavinyl pentasilazane, 1,1,3,5,7,9,9-heptavinyl pentasilazane.

1,3-diphenyldisilazane, 1,3-diphenyl-1,3-dimethyldisilazane, 1,1,3,3-tetraphenyldisilazane, 1,3,5-triphenyltrisilazane, 1,1 , 3,5,5-pentaphenyltrisilazane, 1,3,5,7-tetraphenyltetrasilazane, 1,1,3,5,7,7-hexaphenyltetrasilazane, 1,3,5,7, 9-pentaphenylpentasilazane, 1,1,3,5,7,9,9-heptaphenylpentasilazane,
1,3,5-tritoluyltrisilazane, 1,1,3,5,5-pentatoluyltrisilazane, 1,3,5,7-tetratoluyltetrasilazane, 1,1,3,5,7,7 -Hexatoluyl tetrasilazane, 1,3,5,7,9-pentatoluyl pentasilazane, 1,1,3,5,7,9,9-heptatoluyl pentasilazane,
Can be mentioned.

  The compound represented by the general formula (2) is preferably the above-mentioned disilazanes and trisilazanes, and more preferably 1,1-dimethyl, from the viewpoint of high vapor pressure and reduction of the carbon content of the resulting thin film. Disilazane, 1,3-dimethyldisilazane, 1,1,3-trimethyldisilazane, 1,1,3,3-tetramethyldisilazane.

  Furthermore, examples of the general formula (1) include the cyclic compounds represented by the general formula (3).

In the general formula (3), R ⁶ is the same hydrogen atom as R ¹ or a saturated or unsaturated hydrocarbon group having a linear, branched or cyclic structure having 1 to 20 carbon atoms. be able to. Further, those in which R ⁶ are bonded to each other are also included in the scope of the present invention. When the number of carbon atoms exceeds 20, it may be difficult to procure the corresponding raw material such as organic halide, or even if it can be procured, the purity may be low. In consideration of stable use in a CVD apparatus, R ⁶ is preferably a hydrocarbon group having 1 to 10 carbon atoms, and preferably having 1 to 4 carbon atoms in that the vapor pressure of the organic silicon nitride compound is not too low. Saturated hydrocarbon groups are more preferred, specifically methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl and cyclobutyl. In particular, R ⁶ is preferably methyl, ethyl, or i-propyl.

R ⁶ may be the same or different.

  In the general formula (3), y represents an integer of 2 to 10. Preferably, y is an integer of 2 to 6 in that the vapor pressure of the organic silicon nitride compound is not too low. Particularly preferably, y is 3 or 4.

Specific examples of the compound represented by the general formula (3) include
1-methylcyclodisilazane, 1,3-dimethylcyclodisilazane, 1-methylcyclotrisilazane, 1,3-dimethylcyclotrisilazane, 1,3,5-trimethylcyclotrisilazane, 1-methylcyclotetrasilazane, 1,3-dimethylcyclotetrasilazane, 1,5-dimethylcyclotetrasilazane, 1,3,5-trimethylcyclotetrasilazane, 1,3,5,7-tetramethylcyclotetrasilazane, 1,3-dimethylcyclopenta Silazane, 1,5-dimethylcyclopentasilazane, 1,3,5-trimethylcyclopentasilazane, 1,3,7-trimethylcyclopentasilazane, 1,3,5,7-tetramethylcyclopentasilazane, 1,3 , 5,7,9-pentamethylcyclopentasilazane,
1,3,5,7,9,11-hexamethylcyclohexasilazane, 1,3,5,7,9,11,13-heptamethylcycloheptasilazane, 1,3,5,7,9,11 13,15-octamethylcyclooctasilazane, 1,3,5,7,9,11,13,15,17-nonamethylcyclononasilazane, 1,3,5,7,9,11,13,15, An example is 17,19-decamethylcyclodecasilazane.

  Also 1-ethylcyclodisilazane, 1,3-diethylcyclodisilazane, 1-ethylcyclotrisilazane, 1,3-diethylcyclotrisilazane, 1,3,5-triethylcyclotrisilazane, 1-ethylcyclotetrasilazane 1,3-diethylcyclotetrasilazane, 1,5-diethylcyclotetrasilazane, 1,3,5-triethylcyclotetrasilazane, 1,3,5,7-tetraethylcyclotetrasilazane, 1,3-diethylcyclopenta Silazane, 1,5-diethylcyclopentasilazane, 1,3,5-triethylcyclopentasilazane, 1,3,7-triethylcyclopentasilazane, 1,3,5,7-tetraethylcyclopentasilazane, 1,3 5,7,9-pentaethylcyclopentasilazane, 1,3,5,7,9,1 -Hexaethylcyclohexasilazane, 1,3,5,7,9,11,13-heptaethylcycloheptasilazane, 1,3,5,7,9,11,13,15-octaethylcyclooctasilazane, 1 3,5,7,9,11,13,15,17-nonaethylcyclononasilazane, 1,3,5,7,9,11,13,15,17,19-decaethylcyclodecasilazane It is done.

  1-n-propylcyclodisilazane, 1,3-din-propylcyclodisilazane, 1-n-propylcyclotrisilazane, 1,3-din-propylcyclotrisilazane, 1,3,5-tri n-propylcyclotrisilazane, 1-n-propylcyclotetrasilazane, 1,3-di-n-propylcyclotetrasilazane, 1,5-di-n-propylcyclotetrasilazane, 1,3,5-tri-n-propyl Cyclotetrasilazane, 1,3,5,7-tetra n-propylcyclotetrasilazane, 1,3-di-n-propylcyclopentasilazane, 1,5-di-n-propylcyclopentasilazane, 1,3,5- Tri-n-propylcyclopentasilazane, 1,3,7-tri-n-propylcyclopentasilazane, 1,3,5,7-tetra-n-propylcyclope Tasilazane, 1,3,5,7,9-penta-n-propylcyclopentasilazane, 1,3,5,7,9,11-hexa-n-propylcyclohexasilazane, 1,3,5,7,9, 11,13-hepta-n-propylcycloheptasilazane, 1,3,5,7,9,11,13,15-octane-propylcyclooctasilazane, 1,3,5,7,9,11,13, Examples thereof include 15,17-nona-n-propylcyclononacilazan and 1,3,5,7,9,11,13,15,17,19-deca-n-propylcyclodecasilazane.

  Also 1-isopropylcyclodisilazane, 1,3-diisopropylcyclodisilazane, 1-isopropylcyclotrisilazane, 1,3-diisopropylcyclotrisilazane, 1,3,5-triisopropylcyclotrisilazane, 1-isopropylcyclotetra Silazane, 1,3-diisopropylcyclotetrasilazane, 1,5-diisopropylcyclotetrasilazane, 1,3,5-triisopropylcyclotetrasilazane, 1,3,5,7-tetraisopropylcyclotetrasilazane, 1,3- Diisopropylcyclopentasilazane, 1,5-diisopropylcyclopentasilazane, 1,3,5-triisopropylcyclopentasilazane, 1,3,7-triisopropylcyclopentasilazane, 1,3,5,7-tetraisopropylcyclope Tasilazane, 1,3,5,7,9-pentaisopropylcyclopentasilazane, 1,3,5,7,9,11-hexaisopropylcyclohexasilazane, 1,3,5,7,9,11,13- Heptaisopropylcycloheptasilazane, 1,3,5,7,9,11,13,15-octaisopropylcyclooctasilazane, 1,3,5,7,9,11,13,15,17-nonaisopropylcyclonona Silazane, 1,3,5,7,9,11,13,15,17,19-decaisopropylcyclodecasilazane.

  1-n-butylcyclodisilazane, 1,3-din-butylcyclodisilazane, 1-n-butylcyclotrisilazane, 1,3-din-butylcyclotrisilazane, 1,3,5-tri n-butylcyclotrisilazane, 1-n-butylcyclotetrasilazane, 1,3-din-butylcyclotetrasilazane, 1,5-din-butylcyclotetrasilazane, 1,3,5-tri-n-butyl Cyclotetrasilazane, 1,3,5,7-tetra n-butylcyclotetrasilazane, 1,3-di-n-butylcyclopentasilazane, 1,5-di-n-butylcyclopentasilazane, 1,3,5- Tri-n-butylcyclopentasilazane, 1,3,7-tri-n-butylcyclopentasilazane, 1,3,5,7-tetra-n-butylcyclopentasilazane, 1,3,5,7, -Penta n-butylcyclopentasilazane, 1,3,5,7,9,11-hexa n-butylcyclohexasilazane, 1,3,5,7,9,11,13-hepta n-butylcycloheptasilazane 1,3,5,7,9,11,13,15-octa-n-butylcyclooctasilazane, 1,3,5,7,9,11,13,15,17-nona-n-butylcyclononasilazane 1,3,5,7,9,11,13,15,17,19-deca-n-butylcyclodecasilazane.

  1-isobutylcyclodisilazane, 1,3-diisobutylcyclodisilazane, 1-isobutylcyclotrisilazane, 1,3-diisobutylcyclotrisilazane, 1,3,5-triisobutylcyclotrisilazane, 1-isobutylcyclotetra Silazane, 1,3-diisobutylcyclotetrasilazane, 1,5-diisobutylcyclotetrasilazane, 1,3,5-triisobutylcyclotetrasilazane, 1,3,5,7-tetraisobutylcyclotetrasilazane, 1,3- Diisobutylcyclopentasilazane, 1,5-diisobutylcyclopentasilazane, 1,3,5-triisobutylcyclopentasilazane, 1,3,7-triisobutylcyclopentasilazane, 1,3,5,7-tetraisobutylcyclopenta Silazane, 1, 3, 5, 7, -Pentaisobutylcyclopentasilazane, 1,3,5,7,9,11-hexaisobutylcyclohexasilazane, 1,3,5,7,9,11,13-heptaisobutylcycloheptasilazane, 1,3,5 , 7,9,11,13,15-octaisobutylcyclooctasilazane, 1,3,5,7,9,11,13,15,17-nonaisobutylcyclononasilazane, 1,3,5,7,9 11, 13, 15, 17, 19-decaisobutylcyclodecasilazane.

  1-sec. -Butylcyclodisilazane, 1,3-disec. -Butylcyclodisilazane, 1-sec. -Butylcyclotrisilazane, 1,3-disec. -Butylcyclotrisilazane, 1,3,5-tri sec. -Butylcyclotrisilazane, 1-sec. -Butylcyclotetrasilazane, 1,3-disec. -Butylcyclotetrasilazane, 1,5-disec. -Butylcyclotetrasilazane, 1,3,5-tri sec. -Butylcyclotetrasilazane, 1,3,5,7-tetra sec. -Butylcyclotetrasilazane, 1,3-disec. -Butylcyclopentasilazane, 1,5-disec. -Butylcyclopentasilazane, 1,3,5-tri sec. -Butylcyclopentasilazane, 1,3,7-tri sec. -Butylcyclopentasilazane, 1,3,5,7-tetra sec. -Butylcyclopentasilazane, 1,3,5,7,9-penta sec. -Butylcyclopentasilazane, 1,3,5,7,9,11-hexa sec. -Butylcyclohexasilazane, 1,3,5,7,9,11,13-hepta sec. -Butylcycloheptasilazane, 1,3,5,7,9,11,13,15-octasec. -Butylcyclooctasilazane, 1,3,5,7,9,11,13,15,17-nona sec. -Butylcyclononasilazane, 1,3,5,7,9,11,13,15,17,19-deca sec. -Butylcyclodecasilazane.

  1-tert. -Butylcyclodisilazane, 1,3-ditert. -Butylcyclodisilazane, 1-tert. -Butylcyclotrisilazane, 1,3-di tert. -Butylcyclotrisilazane, 1,3,5-tri tert. -Butylcyclotrisilazane, 1-tert. -Butylcyclotetrasilazane, 1,3-ditert. -Butylcyclotetrasilazane, 1,5-ditert. -Butylcyclotetrasilazane, 1,3,5-tri tert. -Butylcyclotetrasilazane, 1,3,5,7-tetra tert. -Butylcyclotetrasilazane, 1,3-ditert. -Butylcyclopentasilazane, 1,5-ditert. -Butylcyclopentasilazane, 1,3,5-tri tert. -Butylcyclopentasilazane, 1,3,7-tri tert. -Butylcyclopentasilazane, 1,3,5,7-tetra tert. -Butylcyclopentasilazane, 1,3,5,7,9-penta tert. -Butylcyclopentasilazane, 1,3,5,7,9,11-hexa tert. -Butylcyclohexasilazane, 1,3,5,7,9,11,13-hepta tert. -Butylcycloheptasilazane, 1,3,5,7,9,11,13,15-octa tert. -Butylcyclooctasilazane, 1,3,5,7,9,11,13,15,17-nona tert. -Butylcyclononasilazane, 1,3,5,7,9,11,13,15,17,19-deca tert. -Butylcyclodecasilazane.

1,3-di-n-pentylcyclodisilazane, 1,3,5-tri-n-pentylcyclotrisilazane, 1,3,5,7-tetran-pentylcyclotetrasilazane, 1,3,5,7 , 9-penta-n-pentylcyclopentasilazane, 1,3,5,7,9,11-hexa-n-pentylcyclohexasilazane,
1,3-dicyclopentylcyclodisilazane, 1,3,5-tricyclopentylcyclotrisilazane, 1,3,5,7-tetracyclopentylcyclotetrasilazane, 1,3,5,7,9-pentacyclopentylcyclopenta Silazane, 1,3,5,7,9,11-hexacyclopentylcyclohexasilazane,
1,3-di tert. -Amylcyclodisilazane, 1,3,5-tri tert. -Amylcyclotrisilazane, 1,3,5,7-tetra tert. -Amylcyclotetrasilazane, 1,3,5,7,9-penta tert. -Amylcyclopentasilazane, 1,3,5,7,9,11-hexa tert. -Amylcyclohexasilazane.

Also, 1,3-di-n-hexylcyclodisilazane, 1,3,5-tri-n-hexylcyclotrisilazane, 1,3,5,7-tetra-n-hexylcyclotetrasilazane, 1,3,5,7 , 9-penta-n-hexylcyclopentasilazane, 1,3,5,7,9,11-hexa-n-hexylcyclohexasilazane,
1,3-dicyclohexylcyclodisilazane, 1,3,5-tricyclohexylcyclotrisilazane, 1,3,5,7-tetracyclohexylcyclotetrasilazane, 1,3,5,7,9-pentacyclohexylcyclopentasilazane 1,3,5,7,9,11-hexacyclohexylcyclohexasilazane,
1,3-di-n-heptylcyclodisilazane, 1,3,5-tri-n-heptylcyclotrisilazane, 1,3,5,7-tetra n-heptylcyclotetrasilazane, 1,3,5,7, 9-penta n-heptylcyclopentasilazane, 1,3,5,7,9,11-hexa n-heptylcyclohexasilazane,
1,3-diadamantylcyclodisilazane, 1,3,5-triadamantylcyclotrisilazane, 1,3,5,7-tetraadamantylcyclotetrasilazane, 1,3,5,7,9-pentaadamantyl Examples thereof include cyclopentasilazane and 1,3,5,7,9,11-hexaadamantylcyclohexasilazane.

1,3-divinylcyclodisilazane, 1,3,5-trivinylcyclotrisilazane, 1,3,5,7-tetravinylcyclotetrasilazane, 1,3,5,7,9-pentavinylcyclopenta Silazane, 1,3,5,7,9,11-hexavinylcyclohexasilazane,
1,3-diphenylcyclodisilazane, 1,3,5-triphenylcyclotrisilazane, 1,3,5,7-tetraphenylcyclotetrasilazane, 1,3,5,7,9-pentaphenylcyclopentasilazane 1,3,5,7,9,11-hexaphenylcyclohexasilazane,
1,3-ditoluylcyclodisilazane, 1,3,5-tritoluylcyclotrisilazane, 1,3,5,7-tetratoluinylcyclotetrasilazane, 1,3,5,7,9-pentatoluylcyclo Mention may be made of pentasilazane and 1,3,5,7,9,11-hexatoluylcyclohexasilazane.

  The compound represented by the general formula (3) is preferably the above cyclotrisarazanes or cyclotetrasilazanes, more preferably 1, from the viewpoint of high vapor pressure and reduction of the carbon content of the resulting thin film. 3,5-trimethylcyclotrisilazane and 1,3,5,7-tetramethylcyclopentasilazane.

  The method for producing the organic silicon nitride compounds represented by the general formulas (1) to (3) is not particularly limited. For example, it is produced by reacting a hydrogen atom, a hydrocarbon group-substituted halogenated silane compound with ammonia gas. And a method of producing a halogenated silane compound by reacting with a metal amide can be used.

  At this time, the halogenated silane compound itself may be used as the reaction medium, but an inert solvent may be used as the reaction medium. The reaction solvent that can be used is not particularly limited as long as it is used in the art, and examples thereof include n-pentane, i-pentane, n-hexane, cyclohexane, n-heptane, and n-decane. Saturated hydrocarbons, unsaturated hydrocarbons such as toluene, xylene, decene-1, diethyl ether, dipropyl ether, tert. -Ethers such as butyl methyl ether, dibutyl ether, cyclopentyl methyl ether, and tetrahydrofuran can be used.

  About the temperature of reaction in the case of manufacture, it is preferable to carry out in the range of -100-200 degreeC which is the temperature normally used industrially, Preferably, it is the range of -85-150 degreeC. The pressure conditions for the reaction can be any of under pressure, normal pressure, and reduced pressure.

  About the purification method of the synthesized organic silicon nitride compound, use a purification means such as filtration using a glass filter, sintered porous body, etc., atmospheric pressure or vacuum distillation, or column separation using silica, alumina, polymer gel, etc. Can do. At this time, these means may be used in combination as necessary.

  In the production, the method in the organometallic compound synthesis field is followed. That is, the dehydration and deoxygenation is performed in a nitrogen or argon atmosphere, and the solvent to be used and the column filler for purification are preferably subjected to a dehydration operation in advance. Further, it is preferable to remove impurities such as metal residues and particles.

  In the present invention, the compound having a chain or cyclic structure represented by the general formulas (1) to (3) can be used as a sealing film material for a CVD method.

In the present invention, the organic silicon nitride compound is formed by a CVD method and can be used as a sealing film. The sealing film contains silicon, carbon, and nitrogen. The composition of the surface is 1.0 to 1.33 with respect to silicon 1.0 by atomic ratio, the nitrogen content is 0 to 1.33, and the carbon content is 0 to 1. 0 or less, and the and the absorption of 1200～1300Cm ^-1 and 2800～3200Cm ^-1 of the infrared absorption spectrum can be obtained film is less than substantially detection limit. At this time, the composition of the surface of the film can be measured by XPS or the like.

In the infrared absorption spectrum, the absorption at 1200 to 1300 cm ⁻¹ is derived from the Si-methyl bond, and the absorption at 2800 to 3200 cm ⁻¹ indicates the presence of the hydrocarbon group at the bond end. Therefore, the fact that they are all substantially below the detection limit means that all the hydrocarbon groups in the membrane are involved in the crosslinking and are not present enough to be detected as binding ends. It is.

  In the present invention, the fact that the absorption in a specific region of the infrared absorption spectrum is substantially below the detection limit indicates that the absorption is not observed when the chart of the infrared absorption spectrum is visually observed.

Furthermore, according to the present invention, it is possible to obtain a sealing film having a water permeability of 5.0 × 10 ⁻³ g / m ² · day or less and having a very low water permeability.

  Examples of the CVD method used for film formation in the present invention include a PECVD method or a catalytic chemical vapor deposition method (Cat. CVD method). The type of PECVD method and the apparatus to be used are not particularly limited, but this PECVD method is generally used in the technical field such as semiconductor manufacturing field, liquid crystal display manufacturing field, roll-to-roll polymer film surface processing field, and the like. What is used is used.

  In the present invention, in a PECVD apparatus, an organic silicon nitride compound is vaporized by a vaporizer and introduced into a film forming chamber, applied to an electrode in the film forming chamber by a high frequency power source to generate plasma, and silicon in the film forming chamber A PECVD thin film can be formed on a substrate or the like. At this time, for the purpose of generating plasma, an inert gas such as helium, argon, krypton, neon, and xenon, and nitrogen-based gas such as ammonia, hydrazine, and nitrogen are used to improve the nitrogen content of carbon nitride. It is also within the scope of the present invention to be introduced with the compound.

  The plasma generation method of the PECVD apparatus is not particularly limited, and inductively coupled plasma, capacitively coupled plasma, ECR plasma, or the like used in the art can be used. As the plasma generation source, various types such as a parallel plate type and an antenna type can be used, and PECVD under any pressure conditions such as atmospheric pressure PECVD, reduced pressure PECVD, and pressurized PECVD can be used.

  The PECVD conditions at this time are not particularly limited, but are preferably 1.0 W to 10000 W, and more preferably 1.0 W to 2000 W.

  Specifically, a parallel plate capacitively coupled PECVD apparatus is shown in FIG. 1 as a PECVD apparatus. The parallel plate capacitively coupled PECVD apparatus shown in FIG. 1 includes a showerhead upper electrode, a lower electrode capable of controlling the temperature of the substrate in the PECVD apparatus chamber, a vaporizer apparatus for supplying a raw material compound to the chamber by vaporization, a high frequency power supply, and a matching circuit. The plasma generator comprises an exhaust system comprising a vacuum pump.

  The PECVD apparatus 1 includes a PECVD chamber 2, an upper electrode 3 having a shower head for uniformly supplying a raw material compound into the chamber, and a temperature control apparatus 8 for installing a thin film forming substrate 5 such as a Si substrate. The electrode 4 includes vaporizers 9 to 15 for vaporizing raw material compounds, a matching circuit 6 and an RF power source 7 as a plasma generation source, and an exhaust device 16 for exhausting unreacted substances and by-products in the chamber. Reference numerals 17 and 18 denote grounds.

  The matching circuit 6 and the RF power source 7 which are plasma generation sources are connected to the upper electrode 3 and generate plasma by discharge. Although it does not specifically limit about the specification of RF power supply 7, The electric power used in the said technical field is 1W-2000W, Preferably it is 10W-1000W, A frequency is 50 kHz-2.5 GHz, Preferably it is 100 kHz-100 MHz, Most preferably, it is 200 kHz- A 50 MHz RF power supply can be used.

  The control of the substrate temperature is not particularly limited, but is in the range of −90 to 1000 ° C., preferably 0 ° C. to 500 ° C.

  The vaporizer is filled with a raw material compound 13 at room temperature and normal pressure, and is provided with a container 12 having a dip pipe and a pipe 15 for pressurization with the inert gas, and a liquid flow rate for controlling the flow rate of the raw material compound 13. It comprises a control device 10, a vaporizer 9 for vaporizing the raw material compound 13, a pipe 14 for supplying the inert gas into the PECVD chamber through the vaporizer, and a gas flow rate control device 11 for controlling the flow rate thereof. . This vaporizer is connected by piping from the vaporizer 9 to the upper electrode 3 having a shower head.

  The amount of vaporization supply of the raw material compound into the chamber is not particularly limited, but is 0.1 sccm to 10000 sccm, preferably 10 sccm to 5000 sccm. The supply amount of the inert gas is not particularly limited, but is 0.1 sccm to 10,000 sccm, preferably 10 sccm to 5000 sccm.

  Specifically, an inductively coupled remote PECVD apparatus is shown in FIG. 2 as a PECVD apparatus. The inductively coupled remote PECVD apparatus shown in FIG. 2 is a plasma generator wound in a coil around the quartz at the top of the PECVD apparatus chamber, a temperature-controllable substrate installation part, and a vaporizer that vaporizes and feeds raw material compounds into the chamber. It consists of a plasma generator comprising a device, a high frequency power source and a matching circuit, and an exhaust system comprising a vacuum pump.

  The PECVD apparatus 19 includes a PECVD chamber 20, a coil 21 as a plasma generation unit, a quartz tube 22, a heater unit 23 for installing a thin film forming substrate 24 such as a Si substrate, a temperature control unit 27, and a material compound for vaporization. Vaporizers 28 to 35, a plasma generation source matching circuit 25 and an RF power source 26, and an exhaust device 36 for exhausting unreacted substances and by-products in the chamber. Reference numeral 37 denotes a ground.

  A coil around quartz, which is a plasma generation unit, is connected to a matching circuit 25 and is discharged in an antenna current magnetic field by RF current in a quartz tube to generate plasma. Although it does not specifically limit about the specification of RF power supply 26, The electric power used in the said technical field is 1W-2000W, Preferably it is 10W-1000W, A frequency is 50 kHz-2.5 GHz, Preferably it is 100 kHz-100 MHz, Most preferably, it is 200 kHz- A 50 MHz RF power supply can be used.

  The control of the substrate temperature is not particularly limited, but is in the range of −90 to 1000 ° C., preferably 0 ° C. to 500 ° C.

  The vaporizer is filled with a raw material compound 33 that is liquid at normal temperature and pressure, a container 32 having a dip pipe and a pipe 35 that is pressurized with the inert gas, and a liquid flow rate that controls the flow rate of the raw material compound 33 that is liquid. A control device 29, a vaporizer 28 for vaporizing the liquid raw material compound 33, a pipe 34 for supplying the inert gas into the PECVD chamber through the vaporizer, and a gas flow rate control device 30 for controlling the flow rate thereof. It comprises a shower head 31 for uniformly supplying the active gas and the gasified raw material compound 33 into the chamber.

  The amount of vaporization supply of the raw material compound into the chamber is not particularly limited, but is 0.1 sccm to 10000 sccm, preferably 10 sccm to 5000 sccm. The supply amount of the inert gas is not particularly limited, but is 0.1 sccm to 10,000 sccm, preferably 10 sccm to 5000 sccm.

  The raw material compound is controlled in temperature by using the PECVD apparatus exemplified above to supply an inert gas and a gasified raw material compound or a gasified raw material compound into the chamber, generating plasma by discharge with an RF power source. A film is formed on the substrate. The pressure in the chamber at this time is not particularly limited, but is 0.1 Pa to 10000 Pa, preferably 1 Pa to 5000 Pa.

  As a PECVD apparatus, a microwave PECVD apparatus is shown at 38 in FIG. A quartz chamber 39, a heater 41 and a temperature control device 42 for installing a thin film forming substrate 40 such as a Si substrate, a vaporization device 43 to 50 for vaporizing a raw material compound, and a matching circuit 51 as a microwave generation source And a microwave transmitter 52, a microwave reflector 53, and an exhaust device 54 for exhausting unreacted substances and by-products in the chamber.

  The matching circuit 51 and the microwave transmitter 52, which are microwave generation sources, are connected to the quartz chamber, and generate plasma by irradiating the quartz chamber with microwaves. Although there is no particular limitation on the frequency of the microwave, a microwave having a frequency of 1 MHz to 50 GHz, preferably 0.5 GHz to 10 GHz, particularly preferably 1 GHz to 5 MHz, which is used in this technical field, can be used. Moreover, about the microwave output, 0.1W-20000W, Preferably 1W-10000W can be used.

  The control of the substrate temperature is not particularly limited, but is in the range of −90 to 1000 ° C., preferably 0 ° C. to 500 ° C.

  The vaporizer is filled with a raw material compound 48 that is liquid at room temperature and normal pressure, and includes a container 47 that includes a dip pipe and a pipe 50 that is pressurized with the inert gas, and a liquid flow rate that controls the flow rate of the raw material compound 48 that is a liquid. A control device 44, a vaporizer 43 that vaporizes the raw material compound 48 that is a liquid, a pipe 49 for supplying the inert gas into the PECVD chamber through the vaporizer, and a gas flow rate control device 45 that controls the flow rate of the gas. It comprises a shower head 46 for uniformly supplying the active gas and the gasified raw material compound 48 into the chamber.

  The amount of vaporization supply of the raw material compound into the chamber is not particularly limited, but is 0.1 sccm to 10000 sccm, preferably 10 sccm to 5000 sccm. The supply amount of the inert gas is not particularly limited, but is 0.1 sccm to 10,000 sccm, preferably 10 sccm to 5000 sccm.

  Using the PECVD apparatus exemplified above, the raw material compound is supplied with an inert gas and a gasified raw material compound, or a gasified raw material compound is supplied into the chamber, and plasma is generated by microwave irradiation, and the temperature is controlled. A film is formed on the substrate. The pressure in the chamber at this time is not particularly limited, but is 0.1 Pa to 10000 Pa, preferably 1 Pa to 5000 Pa.

  In the present invention, the sealing film obtained from the above-mentioned organosilicon nitride compound is subjected to heat treatment, ultraviolet irradiation treatment, and electron beam treatment, whereby a sealing film with improved densification or mechanical strength can be obtained. In some cases, the film obtained by this treatment may be suitable as a gas barrier film.

  The sealing film of the present invention can be used as a gas barrier layer and is useful as a gas barrier member. Moreover, the FPD device or semiconductor device which comprises the sealing film of this invention can also be used conveniently.

  According to the present invention, a film obtained by a CVD method using an organic silicon nitride compound having a structure in which at least one hydrogen atom is directly bonded to a silicon atom and at least one hydrogen atom is directly bonded to a nitrogen atom is a sealing film As a gas barrier film and a gas barrier layer for a gas barrier substrate, a dense material with high mechanical strength can be provided.

It is the figure which showed the parallel plate capacitive coupling type PECVD apparatus. It is the figure which showed the inductive coupling type remote PECVD apparatus. It is the figure which showed the microwave PECVD apparatus.

  Examples are shown below, but the present invention is not limited to these examples.

  For the film thickness measurement, a stylus type surface profile measuring instrument Deckak 6M manufactured by ULVAC, Inc. was used. The oxygen permeability was measured by JIS K 7126-1 method, and the water permeability was measured by JIS K 7129A method or JIS K 7129 C method. The total light transmittance was measured by the JIS K 7361-1 method. The coefficient of linear expansion was 5 deg. From room temperature to 240 ° C. for an unloaded film sample in an oven. / Min. The film length was calculated by measuring the change in the film length with a CCD camera. The surface roughness was measured by tapping mode AFM using a scanning probe microscope NanoScope IIIa manufactured by Veecoo. The yellow index was measured according to JIS Z-8722 using ZE2000 manufactured by Nippon Denshoku.

Example 1 (deposition of a sealing film using 1,1,3,3-tetramethyldisilazane by a capacitively coupled PECVD apparatus)
A film was formed on a polyethylene naphthalate film substrate using the capacitively coupled PECVD apparatus shown in FIG. The film forming conditions are: vaporized 1,1,3,3-tetramethyldisilazane flow rate 50 sccm, helium gas flow rate 50 sccm, chamber internal pressure 133 Pa, substrate temperature room temperature, RF power supply power 200 W, RF power supply frequency 13.56 MHz. The film was formed for 5 minutes under the conditions.

The result was a film thickness of 3190 nm. When the gas permeability was measured, the oxygen permeability was 0.70 cc / m ² · day and the water permeability was 0.12 g / m ² · day. The total light transmittance was 91.7%, and the linear expansion coefficient was 12 ppm / deg. The surface roughness was 0.5 nm. The yellow index was 1.0.

Example 2 (deposition of a sealing film using 1,1,3,3-tetramethyldisilazane by a capacitively coupled PECVD apparatus)
A sealing film was formed in the same manner as in Example 1 except that the helium gas flow rate was changed to 50 sccm and the helium gas flow rate was 50 sccm and oxygen was 50 sccm in Example 1.

The result was a film thickness of 4360 nm. When the gas permeability was measured, the oxygen permeability was 0.35 cc / m ² · day and the water permeability was 0.01 g / m ² · day. The total light transmittance was 91.8%, and the linear expansion coefficient was 11 ppm / deg. The surface roughness was 0.6 nm. The yellow index was 0.4.

Example 3 (deposition of a sealing film using 1,1,3,3-tetramethyldisilazane by a capacitively coupled PECVD apparatus)
A sealing film was formed in the same manner as in Example 1, except that the flow rate of helium gas was changed to 50 sccm and oxygen was changed to 100 sccm, and the film was formed for 0.5 minutes.

The result was a film thickness of 385 nm. When the gas permeability was measured, the oxygen permeability was 0.01 cc / m ² · day, and the water permeability was 0.0060 g / m ² · day. The total light transmittance was 92.0%, and the linear expansion coefficient was 11 ppm / deg. The surface roughness was 0.4 nm. The yellow index was 0.4.

Further, when the composition of the formed sealing film was measured by XPS, they were Si = 24 atom%, O = 53 atom%, C = 18 atom%, and N = 5 atom%. Further, it was confirmed by infrared absorption spectrum analysis that the absorption at 1200 to 1300 cm ⁻¹ and 2800 to 3200 cm ⁻¹ was substantially below the detection limit.

Comparative Example 1 (deposition of a carbon-containing silicon oxide sealing film using hexamethyldisilazane by a capacitively coupled PECVD apparatus)
A film was formed on a polyethylene naphthalate film substrate using the capacitively coupled PECVD apparatus shown in FIG. Film formation was performed for 10 minutes under the conditions of vaporized hexamethyldisilazane flow rate 50 sccm, helium gas flow rate 50 sccm, chamber internal pressure 133 Pa, substrate temperature room temperature, RF power supply power 200 W, and RF power supply frequency 13.56 MHz. The result was a film thickness of 1370 nm. When the gas permeability was measured, the oxygen permeability was 2.73 cc / m ² · day, and the water permeability was 1.77 g / m ² · day. The total light transmittance was 83.5%, and the linear expansion coefficient was 30 ppm / deg. The surface roughness was 10 nm. The yellow index was 11.5.

Further, when the composition of the formed sealing film was measured by XPS, Si = 32 atom%, C = 64 atom%, and N = 4 atom%. Moreover, it was confirmed by infrared absorption spectrum analysis that absorption of 1200 to 1300 cm ⁻¹ and 2800 to 3200 cm ⁻¹ exist.

Comparative Example 2 (deposition of a carbon-containing silicon oxide sealing film using tetramethoxysilane by a capacitively coupled PECVD apparatus)
A film was formed on a polyethylene naphthalate film substrate using the capacitively coupled PECVD apparatus shown in FIG. Film formation was performed for 10 minutes under the conditions of vaporized tetramethoxysilane flow rate of 50 sccm, helium gas flow rate of 50 sccm, chamber internal pressure 133 Pa, substrate temperature room temperature, RF power supply power 200 W, and RF power supply frequency 13.56 MHz.

The result was a film thickness of 136 nm. When the gas permeability was measured, the oxygen permeability was 1.75 cc / m ² · day, and the water permeability was 1.67 g / m ² · day. The total light transmittance was 86.4%, and the linear expansion coefficient was 32 ppm / deg. The surface roughness was 26 nm. The yellow index was 2.4.

Comparative Example 3
When the gas permeability, total light transmittance, and linear expansion coefficient of the polyethylene naphthalate film substrate used were measured, the oxygen permeability was 21.0 cc / m ² · day, and the water permeability was 6.70 g / m ² · day. It was. The total light transmittance was 86.9%, and the linear expansion coefficient was 35 ppm / deg. The surface roughness was 1.4 nm. The yellow index was 0.4.
Example 4 (deposition of a sealing film using 1,3,5,7-tetramethylcyclotetrasilazane by a capacitively coupled PECVD apparatus)
A film was formed on a polyethylene naphthalate film substrate using the capacitively coupled PECVD apparatus shown in FIG. The film forming conditions were: vaporized 1,3,5,7-tetramethylcyclotetrasilazane flow rate 50 sccm, helium gas flow rate 50 sccm, chamber internal pressure 133 Pa, substrate temperature room temperature, RF power supply power 200 W, RF power supply frequency 13.56 MHz. The film was formed under the conditions of 2 minutes.

The result was a film thickness of 575 nm. When the gas permeability was measured, the oxygen permeability was 0.02 cc / m ² · day, and the water permeability was 0.0048 g / m ² · day. The total light transmittance was 91.7%, and the linear expansion coefficient was 11 ppm / deg. The surface roughness was 0.5 nm. The yellow index was 1.0.

Example 5 (deposition of a sealing film using 1,3,5,7-tetramethylcyclotetrasilazane by a capacitively coupled PECVD apparatus)
A sealing film was formed in the same manner as in Example 4 except that in Example 4, the flow rate of helium gas was changed to 50 sccm and the flow rate of helium gas was 50 sccm and oxygen was 50 sccm.

The result was a film thickness of 428 nm. When the gas permeability was measured, the oxygen permeability was 0.01 cc / m ² · day, and the water permeability was 0.0035 g / m ² · day. The total light transmittance was 91.9%, and the linear expansion coefficient was 10 ppm / deg. The surface roughness was 0.4 nm. The yellow index was 0.3.

Example 6 (deposition of a sealing film using 1,3,5,7-tetramethylcyclotetrasilazane by a capacitively coupled PECVD apparatus)
A sealing film was formed in the same manner as in Example 4 except that the flow rate of helium gas was changed to 50 sccm and oxygen was changed to 100 sccm and the film was formed for 0.5 minutes.

The result was a film thickness of 428 nm. When the gas permeability was measured, the oxygen permeability was 0.01 cc / m ² · day, and the water permeability was 0.0026 g / m ² · day. The total light transmittance was 92.0%, and the linear expansion coefficient was 10 ppm / deg. The surface roughness was 0.4 nm. The yellow index was 0.3.

Further, when the composition of the formed sealing film was measured by XPS, they were Si = 24 atom%, O = 49 atom%, C = 18 atom%, and N = 9 atom%. Further, it was confirmed by infrared absorption spectrum analysis that the absorption at 1200 to 1300 cm ⁻¹ and 2800 to 3200 cm ⁻¹ was substantially below the detection limit.

Reference Example 1 (Synthesis of 1,1,3,3-tetramethyldisilazane)
Under a nitrogen stream, 4.3 L of diethyl ether and 585 g (6.19 mol) of dimethylchlorosilane were charged into a 5 L four-necked flask equipped with a stirrer and cooled to 0 ° C. While maintaining the internal temperature at 0 ° C., 277 L (12.4 mol) of ammonia gas was bubbled over 9 hours to cause reaction. After the supply of ammonia was completed, the mixture was stirred at room temperature for 15 hours.

  By-product ammonium chloride was filtered off from the resulting reaction solution slurry to obtain a colorless and transparent diethyl ether solution containing 1,1,3,3-tetramethyldisilazane. The obtained diethyl ether solution was concentrated and purified by distillation under reduced pressure to obtain 285.2 g (2.18 mol) of 1,1,3,3-tetramethyldisilazane which was the target product. The conversion rate of the raw material dimethylchlorosilane to the target product was 70.3%.

Reference Example 2 (Synthesis of 1,3,5,7-tetramethylcyclotetrasilazane)
Under a nitrogen stream, 3.6 L of diethyl ether and 360 g (3.13 mol) of methyldichlorosilane were charged into a reactor in a 5 L four-necked flask equipped with a stirrer and cooled to 0 ° C. While maintaining the internal temperature at 0 ° C., 270 L (12.1 mol) of ammonia gas was bubbled and allowed to react over 9 hours. After the supply of ammonia was completed, the mixture was stirred at room temperature for 15 hours.

  By-product ammonium chloride was filtered off from the resulting reaction solution slurry to obtain a colorless and transparent diethyl ether solution containing 1,3,5,7-tetramethylcyclotetrasilazane. The obtained diethyl ether solution was concentrated and purified by distillation under reduced pressure to obtain 115.6 g (0.490 mol) of 1,3,5,7-tetramethylcyclotetrasilazane as a target product. The conversion rate of the raw material methyldichlorosilane to the target product was 62.6%.

DESCRIPTION OF SYMBOLS 1 Parallel plate capacitive coupling type PECVD apparatus 2 PECVD chamber 3 Upper electrode 4 having a shower head 4 Lower electrode 5 Substrate for thin film formation 6 Matching circuit 7 RF power supply 8 Temperature controller 9 Vaporizer 10 Liquid flow controller 11 Gas flow controller 12 Container 13 Raw material compound 14 Pipe 15 for supplying inert gas into PECVD apparatus chamber via vaporizer 15 Pipe 16 for pressurizing with inert gas 16 Exhaust apparatus 17 Earth 18 Earth 19 Inductively coupled remote PECVD apparatus 20 PECVD chamber 21 Coil 22 Quartz tube 23 Heater 24 Thin film forming substrate 25 Matching circuit 26 RF power supply 27 Temperature controller 28 Vaporizer 29 Liquid flow controller 30 Gas flow controller 31 Shower head 32 Container 33 Raw material compound 34 Inert gas via vaporizer At PECV Pipe 35 for supplying into the D apparatus chamber Pipe 35 pressurized by inert gas Exhaust device 37 Ground 38 Microwave PECVD device 39 Quartz chamber 40 Thin film forming substrate 41 Heater section 42 Temperature control device 43 Vaporizer 44 Liquid flow rate Control device 45 Gas flow control device 46 Shower head 47 Container 48 Raw material compound 49 Pipe for supplying inert gas into PECVD chamber through vaporizer 50 Pipe for pressurizing with inert gas 51 Matching circuit 52 Microwave transmitter 53 Microwave reflector 54 Exhaust device

Claims (14)

The organic silicon nitride compound is represented by the following general formula (3)

(Wherein R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and y represents an integer of 3 to 6)
A sealing film comprising a film obtained by chemical vapor deposition using a cyclic compound represented by   The sealing film according to claim 1, wherein y in the general formula (3) is 3 or 4.   The sealing film according to claim 1 or 2, wherein y in the general formula (3) is 4. The sealing film according to claim 1, wherein the chemical vapor deposition method is a plasma enhanced chemical vapor deposition method. The sealing film according to claim 1, wherein the chemical vapor deposition method is a catalytic chemical vapor deposition method. The sealing film according to claim 1, further heat treatment, the sealing film manufacturing method which comprises treating the ultraviolet irradiation treatment or electron beam. Gas barrier member, which comprises using the sealing film as claimed as a gas barrier layer to any of claims 1-5. Flat panel display device characterized by comprising a sealing film according to any one of claims 1-5. The semiconductor device characterized by comprising a sealing film according to any one of claims 1-5. The following general formula (3)

(Wherein R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and y represents an integer of 3 to 6)
A sealing film material for chemical vapor deposition characterized by containing a cyclic compound represented by the formula: The sealing film material according to claim 10, wherein y in the general formula (3) is 3 or 4. The sealing film material according to claim 10 or 11, wherein y in the general formula (3) is 4. Containing silicon, carbon, and nitrogen, the composition of the surface is 1.0 to silicon in terms of atomic ratio, the nitrogen content is 0.2 to 1.33, the carbon content is 0 to 1.0, and absorption of red absorption spectrum 1200～1300Cm ^-1 and 2800～3200Cm ^-1 is less than substantially detection limit, sealing film according to any one of claims 1-5. Water permeability is not more than ^{5.0 × 10 -3 g / m 2} · day, according to claim 1 to 5, 13 sealing film according to any one.

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