KR20130029040A - Method for producing semiconductor element substrate - Google Patents

Abstract

Performing a plasma treatment on the surface of the semiconductor element or on the surface of the semiconductor layer included in the semiconductor element; and forming a passivation film made of an organic material on the surface of the semiconductor element subjected to the plasma treatment or on the surface of the semiconductor layer. Is done.

Description

Method for manufacturing a semiconductor device substrate {METHOD FOR PRODUCING SEMICONDUCTOR ELEMENT SUBSTRATE}

This invention relates to the manufacturing method of the semiconductor element board | substrate which performs a hydrogen plasma process with respect to a semiconductor layer, and forms the passivation film using an organic material.

Semiconductor device substrates are widely used in electronic products. For example, a thin film transistor is a switching element having a terminal called a gate electrode, a source electrode, and a drain electrode, and is widely applied to an active element of an active matrix substrate of a display element such as an active matrix liquid crystal display or an organic EL.

In the conventional thin film transistor, the passivation film which consists of a silicon nitride film (SiNx film) was formed by the sputtering method, vapor deposition method, and CVD method on the semiconductor element or the semiconductor layer surface contained in a semiconductor element. Moreover, it processed to the surface of a semiconductor layer for the purpose of the adhesive improvement of the SiNx film | membrane and the semiconductor layer which consists of a-Si.

For example, Patent Document 1 discloses that after performing a hydrogen plasma treatment on a semiconductor layer, performing a nitrogen plasma treatment to improve the adhesion between the semiconductor layer and the passivation film and to reduce the off-leak current. However, in the case of using an inorganic material for the passivation film as in Patent Literature 1, it is necessary to perform the film formation in a state where the material is plasmaized or ionized in vacuum, resulting in a problem that the equipment becomes large and the operation becomes complicated. there was.

In this case, since a problem of etching failure occurs when the nitrogen plasma treatment is not performed after the hydrogen plasma treatment, it is necessary to perform the nitrogen plasma treatment after the hydrogen plasma treatment. In addition, when an inorganic material is used for the passivation film, a resist is required when forming the contact hole, which increases the number of steps compared with the case where an organic material is used for the passivation film. That is, the process of apply | coating a resist and the process of peeling a resist after dry etching are needed. On the other hand, when using an organic material for a passivation film, since it is not necessary to use a resist, the number of processes can be reduced. Moreover, when an inorganic material is used, the thickness of the passivation film which can be formed on a specific layer is limited and it is difficult to form a flat passivation film.

In addition, Non-Patent Document 1 discloses that a plasma treatment is performed on a passivation film by using SiNx to suppress an initial off-leak current. However, when this semiconductor element substrate is used for the active matrix substrate of the display element, high reliability is required. That is, not only the initial off-leak current but also when used under severe conditions, it is required to suppress the off-leak current and to improve the TFT lifetime.

In addition, since SiNx has a function of terminating the dangling bond (see, for example, Patent Document 2), the plasma treatments in Patent Document 1 and Non-Patent Document 1 mainly aim to terminate the dangling bond. Will not.

Japanese Laid-Open Patent Publication 2003-37269 International Publication No. 2009/057444

 Pei Ming Chen, Wan Yu Lo, Chuan Sheng Wei, Jing Jie Shih, Chih Hung Shih, Mao Song Chen, Feng Yuan Gen, and Tom Huang, “The effects of back-channel treatment on electrical characteristic of a-Si: H TFT device ”, International Display Workshop＇ 07, p1951-1953

An object of the present invention is to provide a method for producing a semiconductor device substrate, which can produce a highly reliable semiconductor device substrate.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said objective, in the manufacturing method of a semiconductor element board | substrate, a dangling bond is performed by performing a plasma process on the surface of a semiconductor element or the surface of the semiconductor layer contained in a semiconductor element. By forming a passivation film containing an organic material on the surface of the semiconductor element subjected to the plasma treatment or the surface of the semiconductor element subjected to the plasma treatment, the rise of the off-leak current can be suppressed even under high temperature, high humidity, and excellent device reliability. I found out.

In other words, according to the present invention,

(1) a step of performing a plasma treatment on a surface of a semiconductor element or a surface of a semiconductor layer included in the semiconductor element, and forming a passivation film made of an organic material on the surface of the semiconductor element or the surface of the semiconductor layer subjected to the plasma treatment Method for manufacturing a semiconductor device substrate comprising a

(2) The method for producing a semiconductor element substrate according to (1), wherein the plasma treatment is a hydrogen plasma treatment.

(3) The semiconductor element or the semiconductor layer is manufactured by a process including forming a gate electrode, a gate insulating film, a semiconductor layer and a source / drain electrode on a substrate, and forming a channel region. The manufacturing method of the semiconductor element substrate as described in (1) or (2),

(4) The said organic material is a resin composition containing resin, The manufacturing method of the semiconductor element substrate in any one of (1)-(3) characterized by the above-mentioned.

(5) The said plasma process is the processing time of 1 to 10 minutes, The manufacturing method of the semiconductor element substrate in any one of (1)-(4) characterized by the above-mentioned.

According to the manufacturing method of the semiconductor element substrate which concerns on this invention, a highly reliable semiconductor element substrate can be manufactured.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the process of the manufacturing method of the semiconductor element substrate which concerns on embodiment of this invention.
2 is a diagram showing a step of a method of manufacturing a semiconductor element substrate according to the embodiment of the present invention.
3 is a diagram showing a passivation film according to an embodiment of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, the manufacturing method of the semiconductor element substrate which concerns on this invention is demonstrated with reference to drawings. In addition, to the extent that the accompanying drawings can understand the invention, only the shape, size and arrangement of the components are schematically illustrated, by which the present invention is not particularly limited. Therefore, the elements unnecessary for the description of the present invention are omitted, and the shape, the dimension ratio, and the like of each of the illustrated elements do not necessarily reflect the actual ones. In addition, it is apparent to those skilled in the art that the present invention can be substituted, modified, and changed in various forms without departing from the technical spirit of the present invention described in the claims.

First, as shown to Fig.1 (a), the gate electrode 22 is formed on the insulating substrate 21, such as a glass substrate, by sputtering method. Next, using the photoresist (not shown) as a mask, the gate electrode 22 is patterned by dry etching or wet etching as shown in FIG. 1 (b). Subsequently, as shown in FIG. 1C, the gate insulating film 23, the semiconductor layer 24 made of amorphous silicon, and the impurity-added semiconductor layer 25 are deposited in order by the CVD method. Subsequently, as shown in FIG. 1 (d), the semiconductor layer 24 and the impurity-added semiconductor layer 25 are patterned by dry etching or wet etching using a photoresist (not shown) as a mask. An island-like semiconductor structure composed of the 24 and the impurity-added semiconductor layer 25 is formed.

(Omic layer)

Next, as shown to Fig.2 (a), the source-drain electrode 26 is formed by sputtering method. Subsequently, using the photoresist (not shown) as a mask, the source and drain electrodes 26 are patterned by etching as shown in Fig. 2B to form the source and drain electrodes 27 and 28. . That is, the source electrode 27 and the drain electrode 28 are formed by separating the source and drain electrodes 26 by patterning, and the source and drain electrodes 26, the source electrodes 27, and the drain electrodes 28 are formed. All are made of the same material. Generally, although the etching of a source-drain electrode is performed by wet etching, it may be dry etching.

Subsequently, the impurity-added semiconductor layer 25 is etched using the photoresist, not shown, which has been reduced by patterning of the source and drain electrodes 26 as it is as a mask. A channel region is formed as shown in Fig. 2C. In general, although the etching of the impurity-added semiconductor layer is performed by dry etching, it may be wet etching. Here, the channel region refers to the impurity-added semiconductor layer 30 in the region where the source electrode 27 and the source electrode exist. The semiconductor layer of the part sandwiched between the gate electrode side edge part and the impurity addition semiconductor layer 31 in the area | region where a drain electrode 28 and a drain electrode exist is shown. That is, the semiconductor layer at the portion indicated by the arrow sandwiched between the dotted lines in Fig. 2C is the channel region 29.

Next, the photoresist (not shown) used at the time of patterning is removed using a peeling liquid. Since organic residues may remain on the substrate during the removal or contamination may occur, the photoresist may be peeled off using a stripping solution, followed by a cleaning process using UV irradiation or CF ₄ or N based mainly on oxygen. _It is possible to generate | generate a plasma using the gas which mixed ₂ etc., and to suitably incorporate the ashing process, the combination process, etc. which use the produced | generated oxygen radical.

Next, a hydrogen plasma treatment is performed on the channel region 29 to terminate the dangling bond. It is preferable to perform a hydrogen plasma process for 1 to 10 minutes, and when performing a hydrogen plasma process, you may apply a bias of several hundred W or less, Preferably it is 200 W or less. Moreover, since the process of performing a plasma process and the process of surface-treating the said plasma process surface again with hydrofluoric acid are preferable because the reliability of a thin film transistor may improve more.

Next, the passivation film which consists of organic materials is formed. In the present invention, the passivation film made of an organic material is not particularly limited, but can be formed by a plasma CVD method, a vapor deposition method, a film lamination method, a coating method, or the like. Among them, a film lamination method or a coating method is preferable, and a coating method is more preferable at the point which can form a film simply and efficiently.

When a passivation film formed of an organic material is formed by a coating method, a thin film transistor having high reliability can be manufactured in a simple and short time process. Moreover, it is preferable to form a film by the resin composition containing resin and an organic solvent.

A coating method is a method of removing a solvent after apply | coating a resin composition on the board | substrate with which the coarse thin film transistor is formed until the process of removing the oxide film of the semiconductor layer surface of a channel region. As a method of apply | coating a resin composition on the said board | substrate, the spray method, the spin coat method, the roll coat method, the die coat method, the doctor blade method, the rotation coating method, the bar coating method, the screen printing method, etc. are mentioned, for example. Can be. Solvent removal is performed by drying a coating film, Preferably it heat-drys. In that case, although drying temperature can be suitably selected according to the kind and compounding agent of each component, it is 30-250 degreeC normally. Although drying time can be suitably selected according to the kind and compounding ratio of each component, it is 0.5 to 150 minutes normally.

The film lamination method is a method of applying a resin composition onto a substrate for B stage film formation such as a resin film or a metal film, removing a solvent to obtain a B stage film, and then laminating the B stage film on the substrate. . Solvent removal is performed by drying, preferably heat-drying, the board | substrate for B stage film formation after application | coating. In that case, although drying conditions can be suitably selected according to the kind and compounding ratio of each component, drying temperature is 30-150 degreeC normally, and drying time is 0.5-90 minutes normally. Film lamination can be performed using compression machines, such as a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator.

As a result, a passivation film made of an organic material is formed on the substrate on which the thin film transistor is formed. The thickness of the passivation film is usually 0.1 to 100 µm, preferably 0.5 to 50 µm, more preferably 0.5 to 30 µm, and most preferably 0.5 to 10 µm. When the passivation film has a film thickness in the above range, it is possible to easily manufacture a thin film transistor having high reliability even in a harsh atmosphere. If the passivation film is too thin, the protective performance is poor, the reliability deteriorates, or the yield deteriorates due to particles at the time of manufacture. When too thick, the stress of a passivation film will increase and protection performance will fall and reliability will deteriorate.

In the case of a passivation film made of an inorganic material, the film thickness is restricted to 200 to 400 nm. Therefore, as shown to Fig.3 (a), the passivation film 32 which consists of organic materials can be planarized compared with the passivation film 33 which consists of inorganic materials shown to Fig.3 (b).

It is preferable that the passivation film which consists of organic materials used by this invention is formed of the resin composition containing resin (A) and an organic solvent (B).

In this invention, resin (A) is not specifically limited, For example, cyclic olefin resin, acrylic resin, acrylamide resin, polysiloxane, epoxy resin, phenol resin, cardo resin, polyimide, polyamideimide, poly Carbonate, a polyethylene terephthalate, resin containing the unit of the monomer represented by following General formula (1), etc. are mentioned. Especially, it is preferable to contain at least 1 sort (s) chosen from the group which consists of a cyclic olefin resin, an acrylic resin, a cardo resin, a polysiloxane, and a polyimide resin, and among these, a cyclic olefin resin from a reliability viewpoint of a thin film transistor. More preferably, the cyclic olefin resin is particularly preferably a cyclic olefin resin having a protonic polar group or a resin containing a unit (e) of a monomer represented by the general formula (1).

(In said formula (1), R <_1> represents a C5-C16 branched alkyl group.)

These resins may be used independently, respectively, or may use 2 or more types together.

The protonic polar group refers to a group containing an atom in which a hydrogen atom is directly bonded to an atom belonging to group 15 or group 16 of the periodic table. The atoms belonging to the group 15 or 16 of the periodic table are preferably atoms belonging to the first or second cycles of the group 15 or 16 of the periodic table, more preferably an oxygen atom, a nitrogen atom or a sulfur atom, Especially preferably, it is an oxygen atom.

Specific examples of the protonic polar group include polar groups having oxygen atoms such as hydroxyl group, carboxyl group (hydroxycarbonyl group), sulfonic acid group, and phosphoric acid group; primary amino group, secondary amino group, primary amide group, secondary amide Polar groups which have nitrogen atoms, such as group (imide group); Polar groups which have sulfur atoms, such as a thiol group; These etc. are mentioned. Among these, those having an oxygen atom are preferable, and more preferably a carboxy group.

In the present invention, the number of protic polar groups bonded to the cyclic olefin resin having a protic polar group is not particularly limited, and different types of protic polar groups may be included.

In the present invention, the cyclic olefin resin is a homopolymer or copolymer of an cyclic olefin monomer having an alicyclic structure and a carbon-carbon double bond. The cyclic olefin resin may have a unit derived from monomers other than the cyclic olefin monomer.

In the total structural units of the cyclic olefin resin, the proportion of the cyclic olefin monomer unit is usually 30 to 100% by weight, preferably 50 to 100% by weight, more preferably 70 to 100% by weight.

In the cyclic olefin resin having a protonic polar group, the protonic polar group may be bonded in a cyclic olefin monomer unit or in a monomer unit other than the cyclic olefin monomer, but is bonded in a cyclic olefin monomer unit. desirable.

As a monomer for constructing the cyclic olefin resin which has a protonic polar group, the cyclic olefin monomer (a) which has a protonic polar group, the cyclic olefin monomer (b) which has polar groups other than a protonic polar group, and does not have a polar group And cyclic olefin monomers (c) and monomers (d) other than cyclic olefins (these monomers are simply referred to as monomers (a) to (d) below). Here, the monomer (d) may have a protic polar group or polar groups other than this, and does not need to have a polar group at all.

In the present invention, the cyclic olefin resin having a protic polar group is preferably composed of a monomer (a), a monomer (b) and / or a monomer (c), and is preferably composed of a monomer (a) and a monomer (b). More preferably.

As a specific example of the monomer (a), 5-hydroxycarbonyl bicyclo [2.2.1] hept-2-ene and 5-methyl-5-hydroxycarbonyl bicyclo [2.2.1] hept-2- N, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-dihydroxycarbonylbicyclo [2.2.1] hept-2-ene, 9- Hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 Carboxyl group-containing cyclic olefins such as] dodeca-4-ene and 9,10-dihydroxycarbonyltetracyclo [6.2.1.1 ^{3,6 2,7} ] dodeca-4-ene; 5- (4 -Hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 9- (4-hydroxy Hydroxyphenyl) tetracyclo [6.2.1.1 ^{3,6 2,7} ] dodeca-4-ene, 9-methyl-9- (4-hydroxyphenyl) tetracyclo [6.2.1.1 ^3,6 .0 ^{2 , 7],} and the like hydroxyl group-containing cyclic olefin such as dodeca-4-yen And, among the cyclic olefin containing a carboxy group is preferred. These cyclic olefin monomers (a) which have a protonic polar group may be used independently, respectively and may be used in combination of 2 or more type.

As a specific example of polar groups other than a protonic polar group which the cyclic olefin monomer (b) which has polar groups other than a protonic polar group is ester group (alkoxycarbonyl group and an aryloxycarbonyl group are named generically), N-substituted imide group And epoxy groups, halogen atoms, cyano groups, carbonyloxycarbonyl groups (acid anhydride residues of dicarboxylic acids), alkoxy groups, carbonyl groups, tertiary amino groups, sulfone groups, acryloyl groups and the like. Especially, ester group, N-substituted imide group, and cyano group are preferable, ester group and N-substituted imide group are more preferable, and N-substituted imide group is especially preferable. Specific examples of the monomer (b) include the following cyclic olefins.

As a cyclic olefin which has ester group, 5-acetoxy bicyclo [2.2.1] hept-2-ene, 5-methoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5, for example. -Methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 9-acetoxytetracyclo [6.2.1.1 ^{3,6 2,7} ] dodeca-4-ene, 9- Methoxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-ethoxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca- 4-ene, 9-n-propoxycarbonyltetracyclo [6.2.1.1 ^{3,6 2,7} ] dodeca-4-ene, 9-isopropoxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-n-butoxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-methyl-9-meth Oxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-methyl-9-ethoxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] Dodeca-4-ene, 9-methyl-9-n-propoxycarbonyltetracyclo [6.2.1.1 ^{3,6 2,7} ] dodeca-4-ene, 9-methyl-9- Isopropoxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-methyl-9-n-butoxycarbonyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 ^{3,6 2,7} ] dodeca-4-ene, 9-methyl-9- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 ^{3,6.0 2,7} ] dodeca-4-ene and the like.

Examples of the cyclic olefin having an N-substituted imide group include, for example, N-phenylbicyclo [2.2.1] hept-5-ene 2, 3-dicarboxyimide and N- (2-ethylhexyl) -1 Isopropyl-4-methylbicyclo [2.2.2] oct-5-ene-2,3-dicarboxyimide, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene- 2, 3-dicarboxyimide, N-[(2-ethylbutoxy) ethoxypropyl] -bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide, etc. are mentioned.

As the cyclic olefin having a cyano group, for example, 9-cyanotetracyclo [6.2.1.1 ^{3,6.0 2,7} ] dodeca-4-ene, 9-methyl-9-cyanotetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 5-cyanobicyclo [2.2.1] hept-2-ene, and the like.

As the cyclic olefin having a halogen atom, for example, 9-chlorotetracyclo [6.2.1.1 ^{3,6.0 2,7} ] dodeca-4-ene, 9-methyl-9-chlorotetracyclo [6.2 .1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene and the like.

The cyclic olefin monomers (b) which have polar groups other than these protonic polar groups may be used independently, respectively, and may be used in combination of 2 or more type.

Specific examples of the cyclic olefin monomer (c) having no polar group include bicyclo [2.2.1] hept-2-ene (also referred to as "norbornene") and 5-ethyl-bicyclo [2.2.1 ] Hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [ 2.2.1] hept-2-ene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 ^2,6 ] deca-3, 8-diene (common name: dicyclopenta Diene), tetracyclo [10.2.1.0 ^2,11 .0 ^4,9 ] pentadeca-4,6,8,13-tetraene, tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca- 4-ene (also called "tetracyclododecene"), 9-methyl-tetracyclo [6.2.1.1 ^{3,6.0 2,7} ] dodeca-4-ene, 9-ethyl-tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-methylidene-tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-ethylidene-tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-vinyl-tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene , 9-propenyl-tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, pentacyclo [9.2.1.1 ^{3,9 2,10} ] ^pentadeca -5, 12- Dienes, cyclopentene, cyclopentadiene, 9-phenyl-tetracyclo [6.2.1.1 ^{3,6 2,7} ] dodeca-4-ene, tetracyclo [9.2.1.0 ^{2,10 3,8} ] Tetradeca-3,5,7,12-tetraene, pentacyclo [9.2.1.1 ^{3,9 2,10} ] pentadeca-12-ene and the like. The cyclic olefin monomers (c) which do not have any of these polar groups may be used alone, or may be used in combination of two or more thereof.

Specific examples of the monomer (d) other than the cyclic olefin include chain olefins. As the chain olefin, for example, ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1- Α-olefins having 2 to 20 carbon atoms such as hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; 1,4-hexa And non-conjugated dienes such as diene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene. Monomers (d) other than these cyclic olefins can be used individually or in combination of 2 or more types, respectively.

The cyclic olefin resin which has a protonic polar group used for this invention is obtained by superposing | polymerizing a monomer (a) with the monomer chosen from monomer (b)-(d) as needed. You may further hydrogenate the polymer obtained by superposition | polymerization. Hydrogenated polymer is also contained in the cyclic olefin resin which has a protonic polar group used for this invention.

Moreover, the cyclic olefin resin which has a protic polar group used by this invention introduce | transduces a protic polar group into a cyclic olefin resin which does not have a protonic polar group using a well-known modifier, and performs hydrogenation as needed. It can also be obtained by the method. Hydrogenation may be performed with respect to the polymer before introduction of a protonic polar group. Moreover, you may modify | denature again and introduce | transduce protonic polar group into cyclic olefin resin which has a protonic polar group. The polymer which does not have a protic polar group can be obtained by superposing | polymerizing combining the said monomers (b)-(d) arbitrarily.

As a modifier for introducing a protic polar group, a compound having a carbon-carbon unsaturated bond reactive with a protic polar group is usually used in one molecule. Specific examples of such compounds include acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, ellidic acid, erucic acid, brassidic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, Unsaturated carboxylic acids such as atroic acid and cinnamic acid; allyl alcohol, methyl vinyl methanol, crotyl alcohol, metalyl alcohol, 1-phenylethen-1-ol, 2-propene-1-ol, 3-butene- 1-ol, 3-butene-2-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-butene-1-ol, 2-methyl-3-buten-2-ol, 2- Unsaturated alcohols such as methyl-3-buten-1-ol, 4-penten-1-ol, 4-methyl-4-penten-1-ol and 2-hexen-1-ol; and the like. The modification reaction of the cyclic olefin resin using this modifier is in accordance with a conventional method, and is usually carried out in the presence of a radical generator.

The polymerization method for polymerizing the monomer (a) with the monomer selected from monomers (b) to (d) may be in accordance with a conventional method, for example, a ring-opening polymerization method or an addition polymerization method is employed.

As a polymerization catalyst, metal complexes, such as molybdenum, ruthenium, osmium, are used suitably, for example. These polymerization catalysts may be used alone or in combination of two or more. The amount of the polymerization catalyst is in the molar ratio of the metal compound: cyclic olefin in the polymerization catalyst, and is usually in the range of 1: 100 to 1: 2,000,000, preferably 1: 500 to 1: 1,000,000, more preferably 1: 1,000 to 1: 500,000. to be.

Hydrogenation of the polymer obtained by superposing | polymerizing each monomer is normally performed using a hydrogenation catalyst. As a hydrogenation catalyst, what is generally used at the time of hydrogenation of an olefin compound can be used, for example. Specifically, a Ziegler-type homogeneous catalyst, a noble metal complex catalyst, a supported noble metal catalyst, and the like can be used.

Among these hydrogenation catalysts, noble metal complex catalysts such as rhodium and ruthenium are preferable because side reactions such as functional groups are not modified and carbon-carbon unsaturated bonds in the main chain in the polymer can be selectively hydrogenated. Particularly preferred is a nitrogen-containing heterocyclic carbene compound or a ruthenium catalyst coordinated with phosphines with high electron donation.

The hydrogenation rate of the principal chain of a hydrogenated polymer is 90% or more normally, Preferably it is 95% or more, More preferably, it is 98% or more. When the hydrogenation rate is in this range, resin (A) is especially excellent in heat resistance and suitable. The hydrogenation rate of resin (A) can be measured by <^1> H-NMR spectrum. For example, it can obtain | require as a ratio with respect to the number of moles of carbon-carbon double bonds before hydrogenation of the number of moles of hydrogenated carbon-carbon double bonds.

In this invention, as cyclic olefin resin which has a protonic polar group, it is especially preferable to have a structural unit represented by Formula (2) as shown below, and the structural unit represented by Formula (2) and a formula ( It is more suitable to have a structural unit represented by 3).

[In Formula (2), R ¹ ～ R ⁴ Are each independently a hydrogen atom or a -X _n -R 'group (X is a divalent organic group; n is 0 or 1; R' is an alkyl group which may have a substituent, an aromatic group which may have a substituent, or Protonic polar group). R ¹ ～ R ⁴ At least one is a -X _n -R 'group _wherein R' is a protonic polar group. m is an integer of 0 to 2.

[In formula (3), R ⁵ ～ R ⁸ Is an arbitrary combination, together with the two carbon atoms to which they are bonded, to form a 3 to 5 membered heterocyclic structure containing an oxygen atom or a nitrogen atom as ring constituent atoms, which is attached to the heterocyclic ring You may have a substituent. k is an integer of 0 to 2.]

 In general formula (2), a methylene group, an ethylene group, a carbonyl group, etc. are mentioned as an example of the bivalent organic group represented by X.

The alkyl group which may have a substituent represented by R 'is a linear or branched C1-C7 alkyl group normally, A methyl group, an ethyl group, n-propyl group, isopropyl group etc. are mentioned as an example. . The aromatic group which may have a substituent is a C6-C10 aromatic group normally, As an example, a phenyl group, benzyl group, etc. are mentioned. Examples of the substituent of these alkyl groups and aromatic groups include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group; phenyl group, xylyl group, tolyl group, C6-C12 aryl groups, such as a naphthyl group; These etc. are mentioned.

Examples of the protonic polar group represented by R 'include the groups described above. In general formula (3), R ⁵ ～ R ⁸ In this arbitrary combination, an epoxy structure etc. are mentioned as a 3-membered heterocyclic structure formed with the two carbon atoms to which they are bonded. Similarly, examples of the 5-membered heterocyclic structure include dicarboxylic acid anhydride structures [-C (= O) -OC (= O)-] and dicarboxyimide structures [-C (= O) -NC (= O). )-] And the like. As an example of the substituent couple | bonded with the said hetero ring, a phenyl group, a naphthyl group, anthracenyl group, etc. are mentioned.

Although the acrylic resin used by this invention is not specifically limited, The homopolymer or copolymer which makes at least 1 selected from a carboxylic acid which has an acrylic group, the carboxylic acid anhydride which has an acrylic group, or an epoxy group containing acrylate compound a monomer is desirable.

Specific examples of the carboxylic acid having an acrylic group include (meth) acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutamic acid, and the like; Specific examples of the carboxylic acid anhydride having an acrylic group include maleic anhydride. And citraconic anhydride; specific examples of the epoxy group-containing acrylate compound include glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, and α- n-butyl glycidyl acrylate, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α- Ethylacrylic acid-6,7-epoxyheptyl; and the like.

Among these, (meth) acrylic acid, maleic anhydride, glycidyl methacrylate, methacrylic acid-6, 7-epoxyheptyl and the like are preferable. In the present invention, "(meth)" means either methacryl or acryl.

The acrylic resin may be a copolymer of at least one monomer selected from unsaturated carboxylic acid, unsaturated carboxylic anhydride and epoxy group-containing unsaturated compound with other acrylate monomers or copolymerizable monomers other than acrylate. As another acrylate monomer, methyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, ethylhexyl (meth) acrylate, decyl ( Alkyl (meth) acrylates such as meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate; hydroxyethyl (meth) acrylate, 2-hydroxy Hydroxyalkyl (meth) acrylates such as propyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate; phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) Phenoxyalkyl (meth) acrylates, such as acrylate; Alkoxyalkyl (meth) acrylates, such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate; Polyethyleneglycol mono (meth) Acrylic ray Polyalkylene glycol (meth) acrylates such as ethoxy diethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, and phenoxy polyethylene glycol (meth) acrylate; cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, bornyl (meth) acrylate, iso Cycloalkyl (meth) acrylates, such as bornyl (meth) acrylate and tricyclo decanyl (meth) acrylate; benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc. are mentioned. Among these, butyl (meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and the like are preferable.

Although it will not restrict | limit especially if it is a compound copolymerizable with the carboxylic acid which has the said acryl group, the carboxylic anhydride which has an acryl group, or an epoxy group containing acrylate compound as a monomer which can copolymerize other than an acrylate, For example, vinylbenzyl methyl ether, Vinyl group containing radically polymerizable compounds, such as vinylglycidyl ether, styrene, (alpha) -methylstyrene, butadiene, and isoprene, are mentioned. These compounds may be used independently, respectively and may be used in combination of 2 or more type. The polymerization method of the said monomer is according to a conventional method, For example, suspension polymerization method, emulsion polymerization method, solution polymerization method, etc. are employ | adopted.

Cardo resin is resin which has a cardo structure, ie, the skeleton structure which two cyclic structures couple | bonded with the quaternary carbon atom which comprises the cyclic structure. Typical of the cardo structure is a benzene ring bonded to a fluorene ring.

Specific examples of the skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenyl fluorene skeleton, and a fluorene skeleton having an epoxy group. And fluorene skeletons having an acryl group.

The cardo resin used by this invention superposes | polymerizes and forms by reaction of the functional period in which the skeleton which has this cardo structure is couple | bonded with it, and is formed. The cardo resin has a structure (cardo structure) in which the main chain and the bulky side chain are connected by one element, and have a cyclic structure in a direction substantially perpendicular to the main chain.

An example of the cardo structure which has an epoxyglycidyl ether structure is shown to Formula (4).

(In formula (4), n represents the integer of 0-10.)

Examples of the monomer having a cardo structure include a bis (glycidyloxyphenyl) fluorene type epoxy resin; a condensate of a bisphenol fluorene type epoxy resin and acrylic acid; 9,9-bis (4-hydroxyphenyl) Cardo structure-containing bisphenols such as fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; 9,9-bis (sia) such as 9,9-bis (cyanomethyl) fluorene Noalkyl) fluorenes; 9,9-bis (aminoalkyl) fluorenes such as 9,9-bis (3-aminopropyl) fluorene; Although cardo resin is a polymer obtained by superposing | polymerizing the monomer which has a cardo structure, the copolymer with another monomer which can be copolymerized may be sufficient. The polymerization method of the said monomer should just follow a conventional method.

Although the structure of the polysiloxane used by this invention is not specifically limited, Preferably the polysiloxane obtained by mixing and reacting 1 or more types of organosilane represented by Formula (5) is reacted.

R ₉ of Formula (5) Represents hydrogen, a C1-C10 alkyl group, a C2-C10 alkenyl group, a C6-C15 aryl group, and several R <_9> May be the same or different, respectively. Moreover, all these alkyl groups, alkenyl groups, and aryl groups may have a substituent, and may be an unsubstituted body which does not have a substituent, and can be selected according to the characteristic of a composition. As a specific example of an alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2,2,2 -Trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, 3-mercaptopropyl A group and 3-isocyanate propyl group are mentioned. As a specific example of an alkenyl group, a vinyl group, 3-acryloxypropyl group, and 3-methacryloxypropyl group are mentioned. As a specific example of an aryl group, a phenyl group, tolyl group, p-hydroxyphenyl group, 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, 4-hydroxy-5- (p -Hydroxyphenylcarbonyloxy) pentyl group and a naphthyl group are mentioned.

R <_10> of Formula (5) represents hydrogen, a C1-C6 alkyl group, a C1-C6 acyl group, or a C6-C15 aryl group, and some R <_10> may be same or different, respectively. Moreover, all these alkyl groups and acyl groups may have a substituent, and the unsubstituted group which does not have a substituent may be sufficient, and can be selected according to the characteristic of a composition. As a specific example of an alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group is mentioned. An acetyl group is mentioned as an example of an acyl group. A phenyl group is mentioned as an example of an aryl group. N of Formula (5) represents the integer of 0-3. It is tetrafunctional silane when n = 0, trifunctional silane when n = 1, bifunctional silane when n = 2, and monofunctional silane when n = 3.

As a specific example of the organosilane represented by Formula (5), tetrafunctional silanes, such as tetramethoxysilane and tetraethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyl Triethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxy Silane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, p-hydride Hydroxyphenyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltri Methoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane Trifunctional silanes such as 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane; dimethyldimethoxysilane, Bifunctional silanes such as dimethyldiethoxysilane, dimethyldiacetoxysilane, din-butyldimethoxysilane and diphenyldimethoxysilane; monofunctional silanes such as trimethylmethoxysilane and trin-butylethoxysilane; Can be mentioned.

Among these organosilanes, trifunctional silane is preferably used from the viewpoint of crack resistance and hardness of the resin film obtained from the resin composition of the present invention. Moreover, these organosilanes may be used individually or may be used in combination of 2 or more type.

The polysiloxane in this invention is obtained by hydrolyzing and partial condensation of the organosilane mentioned above. General methods can be used for hydrolysis and partial condensation. For example, a solvent, water, and a catalyst, if necessary, are added to the mixture and stirred by heating. While stirring, you may distill off hydrolysis by-products (alcohols, such as methanol) and condensation by-products (water) by distillation as needed.

The polyimide used by this invention can be obtained by heat-processing the polyimide precursor obtained by making tetracarboxylic anhydride and diamine react. Precursors for obtaining a polyimide resin include polyamic acid, polyamic acid ester, polyisoimide, polyamic acid sulfonamide, and the like.

Specific examples of the acid dianhydride that can be used as a raw material of the polyimide include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyl tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl Propane 2 anhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane 2 anhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane 2 anhydride, bis (3,4-dicarboxyphenyl Methane 2 anhydride, bis (2,3-dicarboxyphenyl) methane 2 anhydride, bis (3,4-dicarboxyphenyl) sulfone 2 anhydride, bis (3,4-dicarboxyphenyl) ether 2 anhydride, 1,2 , 5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetraca Aromatic tetracarboxylic acids 2 such as acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane 2 anhydride And an aliphatic tetracarboxylic dianhydride such as butanetetracarboxylic dianhydride and 1,2,3,4-cyclopentane tetracarboxylic dianhydride. These acid dianhydrides can be used individually or in combination of 2 or more types.

As a specific example of the diamine which can be used as a raw material of a polyimide, 3,4'- diamino diphenyl ether, 4,4'- diamino diphenyl ether, 3,4'- diamino diphenylmethane, 4,4 V-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodi Phenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4- Aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis'4- (4-aminophenoxy) phenyl 'ether, 1,4-bis ( 4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3'-tetramethyl-4,4'-diaminobiphenyl , 3, 3 ′, 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl, or an alkyl group on these aromatic rings And compounds substituted with halogen atoms, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine and the like. These diamines can be used individually or in combination of 2 or more types.

The polyimide used by this invention is synthesize | combined by a well-known method. That is, tetracarboxylic dianhydride and diamine are selectively combined, and N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide and hexamethyl phosph are selectively combined. It is synthesize | combined by a well-known method, such as making it react in polar solvents, such as porotriamide, (gamma) -butyrolactone, and a cyclopentanone.

Resin containing the unit (e) of the monomer represented by General formula (1) used by this invention contains cyclic olefin resin containing the unit (e) obtained by superposing | polymerizing the monomer represented by following General formula (1). to be.

(In the formula (1), R ₁ Represents a branched alkyl group having 5 to 16 carbon atoms.)

In said general formula (1), R <_1> is a C5-C16 branched alkyl group, For example, 1-methylbutyl group, 2-methylbutyl group, 1-methylpentyl group, 1-ethylbutyl group, 2 -Methylhexyl group, 2-ethylhexyl group, 4-methylheptyl group, 1-methylnonyl group, 1-methyl tridecyl group, 1-methyl tetradecyl group, etc. are mentioned. Among these, a C6-C14 branched alkyl group is preferable and C7-C10 branched alkyl group is more preferable at the point which is more excellent in heat resistance and the solubility to an organic solvent. If the carbon number is 4 or less, the solubility in an organic solvent is inferior, and if the carbon number is 17 or more, there is a problem in that the heat resistance is inferior, and the patterned resin film is melted by heat to lose the pattern.

As a specific example of the monomer represented by the said General formula (1), N- (1-methylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3- dicarboxyimide and N- (2- Methylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-methylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboxyimide, N- (2-methylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-ethylbutyl) -bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboxyimide, N- (2-ethylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1- Methylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-methylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboxyimide, N- (3-methylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-butylpentyl) -bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboxyimide, N- (2-butylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1- Methylheptyl) -bicyclo [2.2.1] T-5-ene-2,3-dicarboxyimide, N- (2-methylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (3-methyl Heptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4-methylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3- Dicarboxyimide, N- (1-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-ethylhexyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (3-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-propyl Pentyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-propylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3- Dicarboxyimide, N- (1-methyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-methyloctyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (3-methyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4-methyl Octyl) -bicyclo [2.2.1] hept-5-ene-2,3-dica Boxiimide, N- (1-ethylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-ethylheptyl) -bicyclo [2.2.1] hept -5-ene 2,3-dicarboxyimide, N- (3-ethylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4-ethylheptyl) -Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-propylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyi Mead, N- (2-propylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (3-propylhexyl) -bicyclo [2.2.1] hept- 5-ene-2,3-dicarboxyimide, N- (1-methylnonyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-methylnonyl) -Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (3-methylnonyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyi Mead, N- (4-methylnonyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (5-methylnonyl) -bicyclo [2.2.1] hept- 5-ene-2,3-dicarboxyimide, N- (1-ethyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-ethyloctyl) -bicyclo [2.2.1] hept-5- En-2,3-dicarboxyimide, N- (3-ethyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4-ethyloctyl) -ratio Cyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-methyldecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-methyldodecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-methylundecyl) -bicyclo [2.2.1] hept- 5-ene-2,3-dicarboxyimide, N- (1-methyldodecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-methyltri Decyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-methyltetradecyl) -bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboxyimide, N- (1-methylpentadedecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, etc. are mentioned. In addition, these may be used independently, respectively and may be used in combination of 2 or more type.

Although it does not specifically limit as a manufacturing method of the monomer represented by the said General formula (1), For example, by the amidation reaction of a corresponding amine and 5-norbornene-2,3- dicarboxylic anhydride, You can get it. Moreover, the obtained monomer can be efficiently isolated by isolate | separating and refine | purifying the reaction liquid of an amidation reaction by a well-known method.

The content ratio of the unit (e) of the monomer represented by the general formula (1) in the resin (A) is preferably 10 to 90 mol% based on the total monomer units. When the content rate of the unit (e) of the monomer represented by the said General formula (1) is too small, there exists a possibility that the solubility with respect to the organic solvent of resin (A) may become inadequate, When too much, the radiation sensitivity of a resin composition will fall, There exists a possibility that melt | dissolution residue may arise at the time of image development.

In addition, the more preferable range of the content rate of the unit (e) of the monomer represented by the said General formula (1) changes with kinds of the passivation film comprised by the resin composition used by this invention. Specifically, when the passivation film is formed of a resin composition containing a radiation sensitive compound and is a passivation film subjected to patterning by photolithography, the unit (e) of the monomer represented by the general formula (1) As for a content rate, it is more preferable that it is 30-60 mol%, and it is especially preferable that it is 40-50 mol%. On the other hand, when the passivation film is a passivation film in which the patterning by photolithography is not performed, it is more preferable that the content rate of the unit (e) of the monomer represented by the said General formula (1) is 20-80 mol%, 30 It is especially preferable that it is-70 mol%.

It is preferable that the unit of the monomer copolymerizable with the monomer represented by the said General formula (1) copolymerized. As a monomer which can be copolymerized, the cyclic olefin monomer (a) which has a protonic polar group mentioned above, the cyclic olefin monomer (b) which has polar groups other than the protonic polar group except the monomer represented by General formula (1), and a polar group The cyclic olefin monomer (c) which does not have a, and monomers (d) other than a cyclic olefin are mentioned.

Moreover, the ring-opening polymer which ring-opened-polymerized the at least 1 sort (s) of the monomer represented by the said General formula (1), and the copolymerizable monomer used as needed may be sufficient.

As the polymerization catalyst, for example, metal complexes such as molybdenum, ruthenium and osmium are preferably used. These polymerization catalysts may be used alone or in combination of two or more.

Moreover, you may hydrogenate with respect to the polymer obtained by superposing | polymerizing each monomer using a hydrogenation catalyst. As a hydrogenation catalyst, what is generally used at the time of hydrogenation of an olefin compound as mentioned above can be used, for example. Specifically, a Ziegler-type homogeneous catalyst, a noble metal complex catalyst, a supported noble metal catalyst, and the like can be used. Among these hydrogenation catalysts, noble metal complex catalysts such as rhodium and ruthenium are preferable, in that side reactions such as functional groups are not modified and carbon-carbon unsaturated bonds of the main chain in the polymer can be selectively hydrogenated. Particularly preferred is a nitrogen-containing heterocyclic carbene compound or a ruthenium catalyst coordinated with phosphines with high electron donation.

The weight average molecular weight (Mw) of resin (A) used by this invention is 1,000-1,000,000 normally, Preferably it is 1,500-100,000, More preferably, it is the range of 2,000-10,000.

The molecular weight distribution of the resin (A) is usually 4 or less, preferably 3 or less, and more preferably 2.5 or less in a weight average molecular weight / number average molecular weight (Mw / Mn) ratio.

The weight average molecular weight (Mw) and molecular weight distribution of resin (A) can be measured using a gel permeation chromatography. For example, it can obtain | require as a polystyrene conversion molecular weight using solvents, such as tetrahydrofuran, as an eluent.

The organic solvent (B) used in the present invention is not particularly limited. Specific examples thereof include alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol; ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, and di Alkylene glycol monoethers such as ethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene Alkylene glycol dialkyl ethers such as glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether; propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene Glycol monoethyl Alkylene glycol monoalkyl ether esters such as ether acetate; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, cyclohexanone and cyclopentanone Alcohols such as methanol, ethanol, propanol, butanol and 3-methoxy-3-methylbutanol; cyclic ethers such as tetrahydrofuran and dioxane; cello such as methyl cellosolve acetate and ethyl cellosolve acetate Sorbesters; aromatic hydrocarbons such as benzene, toluene and xylene; ethyl acetate, butyl acetate, ethyl lactate, 2-hydroxy-2-methylpropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, γ Esters such as butyrolactone; amides such as N-methylformamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-methylacetamide, and N, N-dimethylacetamide Dimethyl sulfoxide The sulfoxides; and the like. Among these, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, cyclopentanone and N-methyl-2-pyrrolidone are preferable.

These organic solvents (B) may be used independently, respectively, or may use 2 or more types together. The amount of the organic solvent (B) used is usually 20 to 10,000 parts by weight, preferably 50 to 5,000 parts by weight, and more preferably 100 to 1,000 parts by weight with respect to 100 parts by weight of the resin.

In the resin composition used by this invention, it is preferable to contain the compound (C) which has an acidic group further. Although the compound (C) which has an acidic group is not specifically limited, Preferably they are an aliphatic compound, an aromatic compound, and a heterocyclic compound, More preferably, they are an aromatic compound and a heterocyclic compound. These compounds (C) can be used individually or in combination of 2 types or more, respectively.

Although the number of acidic groups is not specifically limited, It is preferable to have two or more acidic groups, and it is especially preferable to have two acidic groups. The acidic groups may be the same or different from each other.

The acidic group may be an acidic functional group, and specific examples thereof include strong acidic groups such as sulfonic acid group and phosphoric acid group, and weakly acidic groups such as carboxyl group, thiol group and carboxymethylenethio group. Among these, a carboxyl group, a thiol group or a carboxymethylenethio group is preferable, and a carboxyl group is especially preferable. Moreover, it is preferable that acid dissociation constant pKa exists in the range of 3.5 or more and 5.0 or less among these acidic groups. In addition, when there are two or more acidic groups, let 1st dissociation constant pKa1 be an acid dissociation constant. In addition, pKa is under lean conditions, an aqueous solution, the acid dissociation constant ^{_{Ka = [H 3 O +]}} - a / [BH] [B]. BH represents an organic acid here and B <^-> represents the conjugate base of an organic acid. pKa is pKa = -logKa. Moreover, the measuring method of pKa can measure a hydrogen ion concentration using a pH meter, for example, and can calculate it from the density | concentration of this substance, and a hydrogen ion concentration.

In this invention, the passivation film formed from the resin composition of this invention by using the compound (C) which has these acidic groups is excellent in the reliability improvement of a thin film transistor.

In the present invention, the compound (C) may have a substituent other than an acidic group. Such substituents include, in addition to hydrocarbon groups such as alkyl groups and aryl groups, halogen atoms; alkoxy groups, aryloxy groups, acyloxy groups, heterocyclic oxy groups; amino groups substituted with alkyl groups or aryl groups or heterocyclic groups, acylamino groups, and right. Raid groups, sulfamoylamino groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups; polar groups having no protons such as alkylthio groups, arylthio groups, heterocyclic thio groups; hydrocarbon groups substituted with polar groups having no protons Etc. can be mentioned.

Specific examples of the compound (C) include methane acid, ethanic acid, propanoic acid, butanoic acid, pentanic acid, butanoic acid, pentanic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, glycolic acid, glycerin Acids, ethane diacids (also called oxalic acids), propane diacids (also called malonic acids), butane diacids (also called succinic acids), pentane diacids, hexane diacids (also called adipic acids) 2-cyclohexanedicarboxylic acid, 2-oxopropanoic acid, 2-hydroxybutanediic acid, 2-hydroxypropanetricarboxylic acid, mercaptosuccinic acid, dimercaptosuccinic acid, 2,3-dimercapto-1 -Propanol, 1,2,3-trimercaptopropane, 2,3,4-trimercapto-1-butanol, 2,4-dimercapto-1,3-butanediol, 1,3,4-trimer Aliphatic compounds such as capto-2-butanol, 3,4-dimercapto-1,2-butanediol, 1,5-dimercapto-3-thiapentane; benzoic acid, p-hydroxybenzenecarboxylic acid, o- Hydroxybenzenecarboxylic acid, 2-naph Lencarboxylic acid, methylbenzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, 3-phenylpropanoic acid, 2-hydroxybenzoic acid, dihydroxybenzoic acid, dimethoxybenzoic acid, benzene-1,2-dicarboxylic acid (also called "phthalic acid") Benzene-1,3-dicarboxylic acid (also called "isophthalic acid"), benzene-1,4-dicarboxylic acid (also called "terephthalic acid"), benzene-1,2,3-tricar Acid, benzene-1,2,4-tricarboxylic acid, benzene-1,3, 5-tricarboxylic acid, benzenehexacarboxylic acid, biphenyl-2,2'-dicarboxylic acid, 2- (Carboxymethyl) benzoic acid, 3- (carboxymethyl) benzoic acid, 4- (carboxymethyl) benzoic acid, 2- (carboxycarbonyl) benzoic acid, 3- (carboxycarbonyl) benzoic acid, 4- (carboxycarbonyl) benzoic acid, 2 Mercaptobenzoic acid, 4-mercaptobenzoic acid, 2-mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimer Captobenzene, 1,4-dimercap Tobenzene, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 1,2,3-trimercaptobenzene, 1,2, 4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3, 5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) Aromatic compounds such as benzene; nicotinic acid, isnicotinic acid, 2-proic acid, pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole -3,4-dicarboxylic acid, imidazole-2,4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3 5-membered heterocyclic compound containing nitrogen atoms such as, 4-dicarboxylic acid and pyrazole-3,5-dicarboxylic acid; thiophene-2,3-dicarboxylic acid, thiophene-2,4 -Dicarboxylic acid, thio Phen-2,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole-2,5-dicarboxylic acid, thiazole- 4,5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole-3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-dica Carboxylic acid, 1,3,4-thiadiazole-2,5-dicarboxylic acid, 3-amino-5-mercapto-1,2,4-thiadiazole, 2-amino-5-mercapto -1,3,4-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, 3- ( 5-mercapto-1,2,4-thiadiazol-3-ylsulfanyl) succinic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylsulfanyl) succinic acid, (5- Mercapto-1,2,4-thiadiazol-3-ylthio) acetic acid, (5-mercapto-1,3,4-thiadiazol-2-ylthio) acetic acid, 3- (5-mercapto -1,2,4-thiadiazol-3-ylthio) propionic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylthio) propionic acid, 3- (5-mercapto -1,2,4-thiadiazole-3-ylthio) succinic acid, 2- (5-mercapto -1,3,4-thiadiazol-2-ylthio) succinic acid, 4- (3-mercapto-1,2,4-thiadiazol-5-yl) thiobutanesulfonic acid, 4- (2-mer 5-membered heterocyclic compounds containing a nitrogen atom and a sulfur atom such as capto-1,3,4-thiadiazol-5-yl) thiobutanesulfonic acid; pyridine-2,3-dicarboxylic acid, pyridine-2, 4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5-dicarboxylic acid , Pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, pyri Midine-2,4-dicarboxylic acid, pyrimidine-2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2 , 3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, triazine-2,4-dicarboxylic acid, 2-diethylamino-4, 6-dimercapto-s-triazine, 2-dipropylamino-4,6-di Lecapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, 2,4,6 And 6-membered heterocyclic compounds containing nitrogen atoms such as -trimercapto-s-triazine; and the like. Among these, from the viewpoint of further improving the stability of the thin film transistor, it is preferable that the number of acidic groups is two or more, and two are particularly preferable.

Examples of the compound having two acid groups include ethane diacid, propane diacid, butane diacid, pentane diacid, hexane diacid, 1,2-cyclohexanedicarboxylic acid, and benzene-1,2-dicarboxylic acid (also referred to as "phthalic acid"). Benzene-1,3-dicarboxylic acid (also called "isophthalic acid"), benzene-1,4-dicarboxylic acid (also called "terephthalic acid") biphenyl-2,2'-dicarboxylic Acid, 2- (carboxymethyl) benzoic acid, 3- (carboxymethyl) benzoic acid, 4- (carboxymethyl) benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, 2-mercapto-6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,4-naphthalenedithiol, 1,5 Aromatic compounds having two acid groups, naphthalenedithiol, 2,6-naphthalenedithiol and 2,7-naphthalenedithiol; pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid , Pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dica Carboxylic acid, imidazole-2,4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxyl Acid, pyrazole-3,5-dicarboxylic acid, thiophene-2,3-dicarboxylic acid, thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, tee Offen-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole-2,5-dicarboxylic acid, thiazole-4,5-dicarboxylic acid, isothiazole -3,4-dicarboxylic acid, isothiazole-3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid, 1,3,4-thiadia Sol-2,5-dicarboxylic acid, (5-mercapto-1,2,4-thiadiazol-3-ylthio) acetic acid, (5-mercapto-1,3,4-thiadiazole- 2-ylthio) acetic acid, pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid , Pyridine-3,4-dicarboxylic acid, pyridine-3,5-dicarboxylic acid, pyridazine-3,4-dicarboxylic acid, pyridazine 3,5-dicarboxylic acid Acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine-2,5-dicarboxylic acid, Pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyridine-2, Heterocyclic compounds having two acidic groups of 6-dicarboxylic acid and triazine-2,4-dicarboxylic acid;

By using these compounds, the effect of making the stability of the thin film transistor which has an organic passivation film formed from a resin composition further favorable can be acquired.

In this invention, content of the compound (C) which has an acidic group in the resin composition to be used is 1-45 weight part normally with respect to 100 weight part of resin (A), Preferably it is 1.5-30 weight part, More preferably, Is in the range of 2 to 15 parts by weight. When the usage-amount of the compound (C) which has an acidic group exists in this range, even if the resin composition is stored after manufacture, the resin composition excellent in liquid stability which causes the change of the physical property of a resin composition and does not change the characteristic of a resin composition will be You can get it.

In the present invention, the resin composition to be used also has one atom selected from a silicon atom, a titanium atom, an aluminum atom, and a zirconium atom, and also has a hydrocarbyloxy group or a hydroxyl group bonded to the atom (D) It is preferable that it contains).

Moreover, among the said compounds (D), the compound which has a hydrocarbyloxy group couple | bonded with the silicon atom or the titanium atom is preferable. Moreover, it is preferable that the said hydrocarbyloxy group is a C1-C18 hydrocarbyloxy group.

Moreover, it is especially preferable that compound (D) has a functional group which can react with a protonic polar group, when resin (A) has a protonic polar group. It is preferable that it is an isocyanate group, a mercapto group, an epoxy group, or an amino group, and, as for the functional group which can react with this protonic polar group, it is more preferable that it is an epoxy group.

Specific examples of the compound (D) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane and tetra-n-butoxysilane, Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i- Propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyl Limethoxysilane, n-decyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltri Ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloro Propyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltri Ethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyl Triethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyl Trimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidepropyltrimethoxysilane , 3-ureapropyltriethoxysilane, 3-ethyl (trimethoxysilylpropoxymethyl) oxetane, 3-ethyl (triethoxysilylpropoxymethyl) oxetane, 3-triethoxysilyl-N- Trialkoxysilanes such as (1,3-dimethyl-butylidene) propylamine and bis (triethoxysilylpropyl) tetrasulfide, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyl Diethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di -n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di -n-heptyl diethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyl diethoxysilane, diphenyldimethoxy Silane, diphenyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane Methyltriacetyloxysilane, dimethyldiacetyloxysilane, in addition to dialkoxysilanes such as 3-acryloxypropylmethyldiethoxysilane and N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane Silicon atom-containing compounds such as -12-414, KBP-44 (manufactured by Shin-Etsu Chemical Co., Ltd.), 217 FLAKE, 220 FLAKE, 233 FLAKE, z 6018 (manufactured by Torre Dow Corning Corporation); (tetra-i-propoxycitane, Tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxy Octylene glycolate, di-i-propoxy bis (acetylacetonato) titanium, propanedioxytitaniumbis (ethylacetoacetate), tri-n-butoxy titanium monostearate, di-i-propoxytitadis Tearate, titanium stearate, di-i-propoxycitanediisostearate, (2-n-butoxycarbonylbenzoyloxy) tributoxy titanium, di-n-butoxy bis (triethanol amina) titanium In addition, titanium atom containing compounds, such as the Frenakuto series (made by Ajinomoto Fine Techno Co., Ltd.); aluminum atom containing compounds, such as (acetoalkoxy aluminum diisopropylate); (tetra normal propoxy zirconium, tetranormal butoxy zirconium, Zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), zirconium dibu And zirconium atom-containing compounds such as oxybis (ethylacetoacetate), zirconium tetraacetylacetonate and zirconium tributoxy stearate).

As said compound (D), among these, a silicon atom containing compound and a titanium atom containing compound are preferable, and what has a functional group which can react with a protonic polar group is especially preferable. By having the said functional group, stability of a thin film transistor is further improved.

As a compound which has a functional group which can react with the said protonic polar group, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, n-2- (aminoethyl) -3-aminopropyl trimethoxy Silane, n-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltrie Methoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxy Cyclohexyl) ethyltriethoxysilane, 3-ureidepropyltrimethoxysilane, 3-ureidepropyltriethoxysilane, 3-triethoxysilyl-n- (1,3-dimethyl-butylidene) propyl Particular preference is given to amines, n-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane. These compounds (D) can be used individually or in combination of 2 types or more, respectively.

Content of the compound (D) in the resin composition used for this invention is 1-40 weight part with respect to 100 weight part of binder resin (A), Preferably it is 3-30 weight part, More preferably, it is 5-25 weight part Range. If the amount of the compound (D) is in this range, the stability of the thin film transistor can be further improved.

In the resin composition used for this invention, what further contains a radiation sensitive compound (E) is preferable.

The radiation sensitive compound (E) used by this invention is a compound which can cause a chemical reaction by irradiation of radiation, such as an ultraviolet-ray or an electron beam. In this invention, it is preferable that a radiation sensitive compound (E) can control the alkali solubility of the resin film formed from a resin composition.

In this invention, it is preferable to use a photo-acid generator as a radiation sensitive compound (E).

Examples of the radiation-sensitive compound (E) include azide compounds such as acetophenone compounds, triarylsulfonium salts, and quinonediazide compounds, and the like, and preferably azide compounds, particularly preferably quinonediazide. Compound.

As a quinone diazide compound, the ester compound of the compound which has quinone diazide sulfonic-acid halide and phenolic hydroxyl group can be used, for example. Specific examples of the quinone diazide sulfone acid halide include 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-benzoquinone diazide -5-sulfonic acid chloride etc. are mentioned. Representative examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [ 1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol etc. are mentioned.

Examples of the compound having a phenolic hydroxyl group other than these include 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone and 2-bis (4-hydroxyphenyl) propane , Tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, furnace And oligomers obtained by copolymerizing a compound having one or more oligomers of phenol resins and phenolic hydroxyl groups with dicyclopentadiene.

Among these, condensates of 1,2-naphthoquinone diazide-5-sulfonic acid chloride and a compound having a phenolic hydroxyl group are preferable, and 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl More preferred are condensates of) -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol).

As a photo-acid generator, in addition to a quinone diazide compound, an onium salt, a halogenated organic compound, the (alpha), (alpha)-bis (sulfonyl) diazomethane type compound, the (alpha)-carbonyl- (alpha)-sulfonyl diazomethane type compound, Known ones such as sulfone compounds, organic acid ester compounds, organic acid amide compounds and organic acid imide compounds can be used.

These radiation sensitive compounds can be used individually or in combination of 2 types or more, respectively. Content of the radiation sensitive compound (E) in the resin composition used for this invention is 1-100 weight part with respect to 100 weight part of resin (A), Preferably it is 5-50 weight part, More preferably, it is 10-40 weight It is a range of wealth. When the usage-amount of a radiation sensitive compound (E) exists in this range, when patterning the resin film which consists of resin compositions formed on arbitrary board | substrates, the solubility difference with respect to the developing solution of a radiation irradiation part and a non-irradiation part becomes large, and patterning by development is easy. Moreover, since radiation sensitivity becomes high, it is suitable.

In this invention, it is preferable to further contain a crosslinking agent (F) as a component of a resin composition. As a crosslinking agent (F), what has 2 or more, preferably 3 or more functional groups which can react with resin (A) is used. Although the functional group which a crosslinking agent (F) has can react with the functional group, unsaturated bond, etc. in binder resin, it will not specifically limit, It is preferable that it can react with a protonic polar group.

As such a functional group, an amino group, a hydroxyl group, an epoxy group, an isocyanate group, etc. are mentioned, for example, More preferably, they are an amino group, an epoxy group, and an isocyanate group, More preferably, it is an epoxy group.

As a specific example of a crosslinking agent (F), Aliphatic polyamines, such as hexamethylenediamine; Aromatic polyamines, such as 4,4'- diamino diphenyl ether and diamino diphenyl sulfone; 2, 6-bis (4'- Azides, such as azide benzal) cyclohexanone and 4,4'- diazide diphenyl sulfone; Polyamides, such as nylon, polyhexamethylenediamine terephthalamide, and polyhexamethylene isophthalamide; N, N Melamines such as N ', N', N ', N', and N '-(hexaalkoxymethyl) melamine; glycols such as N, N', N ', and N'-(tetraalkoxymethyl) glycoluril Acrylate compounds such as ethylene glycol di (meth) acrylate; isocyanates such as hexamethylene diisocyanate polyisocyanate, isophorone diisocyanate polyisocyanate, tolylene diisocyanate polyisocyanate, hydrogenated diphenylmethane diisocyanate Cyanate compound; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di (hydroxymethyl) norbornane; 1,3,4-trihydroxycyclohexane; bisphenol A epoxy resin , Epoxy compounds such as bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, polyphenol type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether and epoxy acrylate polymer; Can be.

As a specific example of such an epoxy compound, the trifunctional epoxy compound (brand name "XD-1000", the Nippon Kayaku Co., Ltd. product) which makes a dicyclopentadiene skeleton, [2, 2-bis (hydroxymethyl) 1- 1,2-epoxy-4- (2-oxyranyl) cyclohexane adduct of butanol (15 functional alicyclic epoxy resin having cyclohexane skeleton and terminal epoxy group, trade name "EHPE3150", manufactured by Daicel Chemical Industries, Ltd.), epoxy -Cyclohexene-1,2-dicarboxylic acid bis (3-cyclohexenylmethyl) formula (epsilon) -caprolactone (aliphatic cyclic trifunctional epoxy resin, a brand name "Eporide GT301", the Daicel Chemical Industries Corporation make), Epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) formula (epsilon) -caprolactone (aliphatic cyclic tetrafunctional epoxy resin, a brand name "Eporide GT401", the Daicel Chemical Industry Co., Ltd. product), 3, 4- Epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene Epoxy compound which has alicyclic structure, such as a carboxylate (brand name "Cerroside 2021P", the Daicel Chemical Co., Ltd. make); aromatic amine type polyfunctional epoxy compound (brand name "H-434", Toto Kasei Kogyo Co., Ltd.), cresol furnace Volacic polyfunctional epoxy compound (brand name "EOCN-1020", the Nippon Kayaku Co., Ltd. product), phenol novolak-type polyfunctional epoxy compound (Epicoat 152, 154, Japan epoxy resin company make), polyfunctional epoxy compound which has naphthalene skeleton (Brand name EXA-4700, Dainippon Ink Chemical Co., Ltd.), a chain alkyl polyfunctional epoxy compound (brand name "SR-TMP", manufactured by Sakamoto Pharmaceutical Co., Ltd.), polyfunctional epoxy polybutadiene (brand name "Eporide PB 3600", die Cell Chemical Industry Co., Ltd.), glycidyl polyether compound of glycerin (brand name "SR-GLG", Sakamoto Pharmaceutical Co., Ltd. product), diglycerin polyglycidyl ether Epoxy compounds which do not have alicyclic structure, such as a compound (brand name "SR-DGE", the Sakamoto Pharmaceutical Co., Ltd. make, a polyglycerol polyglycidyl ether compound (brand name "SR-4 GL", the Sakamoto Pharmaceutical Co., Ltd. make), etc.); Can be.

Among these, an epoxy compound is preferable, and since an epoxy compound which has an alicyclic structure makes stability of the thin film transistor which has an organic passivation film formed from this resin composition more preferable, it is more preferable.

Although the molecular weight of a crosslinking agent (F) is not specifically limited, Usually, 100-100,000, Preferably 500-50,000, More preferably, it is 1,000-10,000. Crosslinking agents can be used individually or in combination of 2 types or more, respectively.

Content of the crosslinking agent (F) in the resin composition used for this invention is 0.1-200 weight part normally with respect to 100 weight part of resin (A), Preferably it is 1-150 weight part, More preferably, it is 5-100 It is the range of weight part. When the usage-amount of a crosslinking agent exists in this range, sufficient heat resistance can be obtained and it is preferable.

Other resins such as sensitizers, surfactants, latent acid generators, antioxidants, light stabilizers, antifoaming agents, pigments, dyes, etc., as desired, as long as the effects of the present invention are not impaired in the resin composition used in the present invention. You may contain a compounding agent;

Specific examples of the sensitizer include 2H-pyrid- (3,2-b) -1,4-oxazine-3 (4H)-warm, 10H-pyrid- (3,2-b) -1, 4-benzothiazines, urasols, hydantoin, barbituric acid, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, maleimide, and the like.

In this invention, it is preferable to contain surfactant as a component of a resin composition.

Surfactant is used for the purpose of prevention of striation (coating tape), improvement of developability, etc. Specific examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and the like. Polyoxyethylene aryl ethers; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; fluorine-based surfactants; silicone-based surfactants; methacrylic acid copolymerization system Surfactant; Acrylic acid copolymer type surfactant; These etc. are mentioned.

Potential acid generators are used for the purpose of improving the heat resistance and chemical resistance of the resin composition of the present invention. Specific examples thereof include sulfonium salts, benzothiazolium salts, ammonium salts, phosphonium salts, and the like which are cationic polymerization catalysts that generate an acid by heating. Among these, sulfonium salt and benzothiazolium salt are preferable.

As antioxidant, a phenolic antioxidant, phosphorus antioxidant, sulfur-type antioxidant, lactone-type antioxidant, etc. which are used by the normal polymer can be used. For example, 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3- (3 ', 5'-di-t-butyl) as phenols -4'-hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5 L-methyl-2'-hydroxybenzyl) -4-methylphenylacrylate, 4,4'-butylidene-bis- (3-methyl-6-t-butylphenol), 4,4'-thio-bis (3-methyl-6-t-butylphenol), pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], alkylated bisphenol, etc. are mentioned. Examples of the phosphorus antioxidant include triphenyl phosphite, trisphosphite (nonylphenyl), and sulfur-based dilauryl thiodipropionate.

In this invention, it is preferable to contain an optical stabilizer as a component of a resin composition. The light stabilizer can be used to trap radicals generated by light such as ultraviolet absorbers such as benzophenone series, salicylic acid ester series, benzotriazole series, cyanoacrylate series, metal complex salt series, and hindered amine series (HALS). It may be. Among these, HALS is a compound which has a piperidine structure, and since it has little coloring and stability is good with respect to the composition of this invention, it is preferable. Specific examples of the compound include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl 1, 2,3,4-butane tetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, etc. are mentioned.

The preparation method of the resin composition used for this invention is not specifically limited, Each constituent component of a resin composition, ie, resin (A), an organic solvent (B), and the other component used as needed is a well-known method. What is necessary is just to mix.

Although the mixing method is not specifically limited, It is preferable to mix the solution or dispersion liquid obtained by melt | dissolving or disperse | distributing each structural component of a resin composition to an organic solvent (B). Thereby, the resin composition of this invention is obtained in the form of a solution or a dispersion liquid.

The method of melt | dissolving or disperse | distributing each structural component of the resin composition used for this invention in the organic solvent (B) may be according to a conventional method. Specifically, it can carry out using stirring using a stirrer and a magnetic stirrer, a high speed homogenizer, a disper, a planetary stirrer, a biaxial stirrer, a ball mill, three rolls, etc. Moreover, after melt | dissolving or disperse | distributing each component in the organic solvent (B), you may filter using a filter etc. which have a pore diameter of about 0.5 micrometer, for example.

Solid content concentration at the time of melt | dissolving or disperse | distributing each structural component of the resin composition used for this invention in an organic solvent (B) is 1-70 weight% normally, Preferably it is 5-60 weight%, More preferably, it is 10-50 Weight percent. When solid content concentration exists in this range, dissolution stability, the coating property on a board | substrate, the film thickness uniformity of the resin film formed, a flatness, etc. can be highly balanced.

In the present invention, after the passivation film is formed on the substrate having the thin film transistor which has been subjected to the step of removing the oxide film on the surface of the semiconductor layer in the channel region, the passivation film can be crosslinked.

Crosslinking of the passivation film formed on the said board | substrate can be performed by the crosslinking reaction of resin (A), Preferably a crosslinking agent is used. Although crosslinking should just select a method suitably according to the kind of crosslinking agent, it carries out by heating normally. A heating method can be performed using a hotplate, oven, etc., for example. Heating temperature is 180-250 degreeC normally, and a heating time is suitably selected by the size and thickness of a passivation film | membrane, a used apparatus, etc., For example, when using a hotplate, when using an oven for 5 to 90 minutes normally, Usually, it is 30 to 120 minutes. You may perform heating in inert gas atmosphere as needed. As an inert gas, what is necessary is just to contain oxygen and not to oxidize a passivation film, For example, nitrogen, argon, helium, neon, xenon, krypton, etc. are mentioned. Among these, nitrogen and argon are preferable, and nitrogen is especially preferable. In particular, an inert gas having an oxygen content of 0.1 vol% or less, preferably 0.01 vol% or less, in particular nitrogen, is suitable. These inert gases can be used individually or in combination of 2 types or more, respectively.

In the present invention, the passivation film may be patterned. Patterning of the passivation film formed on the board | substrate, for example, the method of dry-etching using a photoresist as a mask, or the radiation-sensitive substance is contained in the resin composition, and active radiation is formed in the resin film formed using this resin composition. It can be performed by a method of forming a latent image pattern using the method, and presenting the latent image pattern using a developer.

The activating radiation is not particularly limited as long as it can activate the photoacid generator to change the alkali solubility of the crosslinkable composition containing the photoacid generator. Specifically, light rays such as ultraviolet rays having a single wavelength such as ultraviolet rays, g rays or i rays, KrF excimer laser light, ArF excimer laser light, and particle beams such as electron beams can be used. As a method of forming a latent image pattern by selectively irradiating these active radiations in a pattern form, for example, ultraviolet rays, g rays, i rays, KrF excimer laser light, The method of irradiating light rays, such as ArF excimer laser beam, through a desired mask pattern, the method of drawing by particle beams, such as an electron beam, etc. can be used. When using a light ray as active radiation, it may be single wavelength light or mixed wavelength light. Irradiation conditions are suitably selected according to the actinic radiation used, For example, when using the light of 200-450 nm of wavelengths, irradiation amount is 10-1,000 mJ / cm <2> normally, Preferably it is the range of 50-500 mJ / cm <2>. It is determined by irradiation time and illuminance. After irradiating active radiation in this way, the resin film is heat-processed for about 1 to 2 minutes at the temperature of about 60-130 degreeC as needed.

Next, the latent image pattern formed on the passivation film is developed and made to present. In this invention, such a process is called "patternation" and a patterned passivation film is called "patternation passivation film." As a developing solution, the aqueous solution of an alkaline compound is used normally. As an alkaline compound, an alkali metal salt, an amine, and an ammonium salt can be used, for example. The alkaline compound may be an inorganic compound or an organic compound. Specific examples of these compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and sodium metasilicate; aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine and di-n Secondary amines such as -propylamine; tertiary amines such as triethylamine and methyldiethylamine; agents such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline Quaternary ammonium salts; alcohol amines such as dimethylethanolamine and triethanolamine; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undeca-7-ene, 1,5-diazabicyclo [4.3. Cyclic amines such as 0] nona-5-ene and N-methylpyrrolidone; These alkaline compounds can be used individually or in combination of 2 types or more, respectively.

As an aqueous medium of an alkaline aqueous solution, water; water-soluble organic solvents, such as methanol and ethanol, can be used. The alkaline aqueous solution may be obtained by adding an appropriate amount of a surfactant and the like.

As a method of bringing a developing solution into contact with the passivation film which has a latent image pattern, methods, such as a paddle method, a spray method, and a dipping method, are used, for example. The image development is usually 0-100 degreeC, Preferably it is 5-55 degreeC, More preferably, it is suitably selected in the range for 30 to 180 second normally in 10-30 degreeC.

In this manner, after the target patterned passivation film is formed, the substrate can be rinsed with a rinse liquid in order to remove the development residues on the substrate, the rear surface of the substrate, and the substrate end as necessary. After the rinse treatment, the remaining rinse liquid is removed by compressed air or compressed nitrogen.

Moreover, in order to deactivate a photo-acid generator as needed, actinic radiation can also be irradiated to the whole board | substrate surface which has a patterned passivation film. For the irradiation of the actinic radiation, the method exemplified in the formation of the latent image pattern can be used. You may heat a passivation film | membrane simultaneously with or after irradiation. As a heating method, the method of heating a board | substrate in a hotplate or oven is mentioned, for example. Temperature is 100-300 degreeC normally, Preferably it is the range of 120-200 degreeC.

In this invention, after forming patterning resin on a board | substrate, crosslinking reaction of patterning resin can be performed. What is necessary is just to perform bridge | crosslinking similarly to the bridge | crosslinking of the passivation film formed on the board | substrate mentioned above.

According to the manufacturing method of the semiconductor element substrate which concerns on this invention, a highly reliable semiconductor element substrate can be manufactured.

The thin film transistor obtained by the manufacturing method of this invention can be used for display apparatuses, such as an active-matrix liquid crystal display and an active-matrix organic EL. In addition, since the passivation film is flat in the semiconductor element manufactured by the manufacturing method according to the present invention, the brightness can be improved in the display device. In addition, the power consumption can be reduced. In addition, the life of the thin film transistor can be improved.

Moreover, since the passivation film which consists of organic materials is low dielectric constant, RC delay can be suppressed.

Example

An Example and a comparative example are given to the following, and this invention is demonstrated more concretely. "Part" and "%" in each case are "weight part" and "weight%", respectively, unless there is particular notice.

Each characteristic was evaluated by the following method.

(1) thin film transistor characteristics

The change of the current between source and drain with respect to the change of the gate voltage of the measurement sample (substrate with a thin film transistor) immediately after manufacture was measured using the semiconductor parameter analyzer (4156A by Agilent). A voltage of 10 V was applied between the source electrode and the drain electrode, and the minimum value of the inter-source drain current when the gate voltage was changed every 0.2 V in the range of -10 V to 15 V was observed as the off-leak current value. Subsequently, the sample for a measurement was installed in the constant temperature / humidity tank (Prectas PR-2KP by Espek Co., Ltd.) set to the temperature of 60 degreeC and 90% of humidity. After installation, the off-leak current value is measured by the above method every 20 hours up to 100 hours and after every 100 hours, and the time when the off-leak current value reaches 1.0 × 10 ⁻¹¹ A is used as the thin film transistor characteristic. Observed. According to this analysis, the longer the thin film transistor characteristics, the higher the reliability of the thin film transistor.

(Production Example 1)

N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2, 40 mol% of 3-dicarboxyimide (NEHI), and 8-hydroxycarbonyltetracyclo [4.4.0.1 ^{2 , 5} .1 ^7,10] dodeca-3-ene (TCDC) 100 parts monomer mixture consisting of 60 mol%, 1,5-hexadiene part 2, (1,3-dimethyl-imidazole-2-ylidene sleepy (Tricyclohexylphosphine) benzylidene ruthenium chloride (synthesized by the method described in Org. Lett., Vol. 1, p. 953, 1999) 0.02 part by glass, and 400 parts of diethylene glycol methylethyl ether by nitrogen It injected into the pressure resistant reactor and reacted at 80 degreeC for 4 hours, stirring, and obtained the polymerization reaction liquid. And the obtained polymerization reaction liquid was put into the autoclave, it stirred at 150 degreeC and hydrogen pressure of 4 Mpa for 5 hours, and hydrogenated reaction was obtained, and the solution of cyclic olefin resin was obtained. As for the polymerization conversion rate of cyclic olefin resin in the obtained solution, 9150%, the weight average molecular weight were 7150, the number average molecular weight was 4690, the molecular weight distribution was 1.52, and the hydrogenation rate was 99.7%.

Next, 2 parts of pyrazine-2,3- dicarboxylic acids and a radiation sensitive compound as a compound which has an acidic group in the solution (amount which cyclic olefin resin in a solution adds 100 parts) of the cyclic olefin resin obtained as mentioned above. As 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2 mol) 30 parts of condensates (Toyo Synthetic Industries, Ltd., "TS 200"), 30 parts of methyl ether-ized melamine resin (Cytec Industries, Ltd., "Cymel 370") as a crosslinking agent, 3, 4- epoxycyclohexenylmethyl-3 ' 30 parts of 4,4'-epoxycyclohexene carboxylate (made by Daicel Chemical Industry Co., Ltd., "Cerroside 2021P"), and epoxidized butane tetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) modified ε-capro 10 parts of lactones (made by Daicel Chemical Industry Co., Ltd., "Eporide GT 401"), pentaerythritol as antioxidant 1 part of toltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (made by Chiba Specialty Chemicals, "Irganox 1010"), and a solution as surfactant The silicone type surfactant (Shin-Etsu Silicone Co., Ltd. make, "KP-341") of the quantity which becomes a concentration in 300 ppm was added, 100 parts of diethylene glycol methyl ethyl ether was further added, and it stirred and mixed. After stirring for 30 minutes, this solution was filtered with the filter made from polytetrafluoroethylene of the pore diameter of 0.45 micrometer, and the resin composition ((alpha)) which has radiation sensitivity including the cyclic olefin resin was prepared.

(Production Example 2)

20 parts of styrene, 25 parts of butyl methacrylate, 25 parts of 2-ethylhexyl acrylate, 30 parts of methacrylic acid, 0.5 parts of 2,2-azobisisobutyronitrile, and 300 parts of propylene glycol monomethyl ether acetate, It injected into the substituted glass pressure reactor, and made it react at 80 degreeC for 4 hours, stirring in nitrogen stream. And the obtained reaction solution was concentrated by the rotary evaporator, and the solution of acrylic resin was obtained by 35% of solid content concentration. As for the polymerization conversion ratio of the acrylic resin in the obtained solution, the weight average molecular weight was 15000, the number average molecular weight was 6500, and the molecular weight distribution was 2.31.

Next, 3-glycidoxypropyltrimethoxysilane (Torre) as a compound having a hydrocarbyloxy group bonded to a silicon atom in a solution of the acrylic resin obtained as described above (amount in which the acrylic resin in the solution is 100 parts added) 10 parts of Dow Corning, Ltd., 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane (1 mol) and 1, as a radiation sensitive compound 30 parts of condensates of 2-naphthoquinone diazide-5-sulfonic acid chloride (2 mol) (Toyo Synthetic Industry Co., Ltd., "TS 200") and methyl ether melamine resin (manufactured by Cytec Industries, Ltd., Cymel 350) as a crosslinking agent. ) 50 parts, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as an antioxidant (manufactured by Chiba Specialty Chemicals, "Irganox 1010" 1 part, and an amount of silicone having a concentration of 300 ppm by weight as a surfactant Surface active agent (Shin-Etsu Silicone Co., Ltd., "KP-341") was added, and propylene glycol monomethyl ether were mixed and stirred to further added 100 parts of acetate. After stirring for 30 minutes, this solution was filtered with the filter made of polytetrafluoroethylene of the pore diameter of 0.45 micrometer, and the resin composition ((beta)) which has radiation sensitivity including the acrylic resin was prepared.

(Example 1)

On the glass substrate (Corning Corporation, product name Corning 1737), a 200 nm-thick chromium film which becomes a gate electrode was formed by sputtering method. Subsequently, in order to pattern the chromium film to form a gate electrode, a positive photoresist (ZPP-1800U3 manufactured by Nippon Xeon Co., Ltd.) used as a mask for etching is applied on the chromium film by a spin coating method, and a hot plate is used. By removing the solvent, a 1.5 탆 resist film was formed. Next, the exposure process and the image development process were performed, and the resist film was patterned. Subsequently, using a diammonium nitrate as an etching solution, the chromium film was patterned by wet etching to form a gate electrode. Next, the resist film was removed using the peeling liquid of the mixed solution (MEA / DMSO = 7/3) of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO).

Next, a 450 nm thick silicon nitride film covering the gate electrode to be a gate insulating film, a 250 nm thick a-Si layer (amorphous silicon layer) to be a semiconductor layer, and a 50 nm thick n + to be an impurity-added semiconductor layer Si layers were formed in turn by the CVD method, respectively. Next, in order to pattern the semiconductor layer and the impurity-added semiconductor layer into islands, a positive photoresist (ZPP-1800U3 manufactured by Nippon Xeon Co., Ltd.) used as an etching mask is applied onto the impurity-added semiconductor layer by a spin coating method, The solvent film was removed using a hot plate to form a resist film of 1.5 mu m. Next, the resist film was patterned through the exposure process and the image development process. Subsequently, the impurity-added semiconductor layer and the semiconductor layer were patterned on an island by dry etching. Next, the resist film was removed with a stripping solution of a mixed solution of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO) (MEA / DMSO = 7/3). Subsequently, the hydrogen plasma treatment was performed for 5 minutes in the state which biased 100 W by the apparatus for hydrogen plasma processing (the apparatus which improved the Dipole Ring Magnet (made by Tokyo Electron Co., Ltd.) so that a plasma treatment was possible). Subsequently, the board | substrate which passed until the said process was rinsed with ultrapure water for 30 second, and the ultrapure water adhered at the time of rinse was removed from the substrate surface using nitrogen. Next, the said resin composition ((alpha)) which becomes a passivation film containing an organic material is apply | coated on the board | substrate which passed the said process by the spin coating method, and it heat-drys at 90 degreeC for 2 minutes using a hotplate (prebaking) To form a resin film having a thickness of 2.5 m. Subsequently, the resin film was irradiated with ultraviolet light with a light intensity of 5 mW / cm 2 at 365 nm for 40 seconds through a mask of a hole pattern of 10 μm × 10 μm. Subsequently, using 0.4 wt% of tetramethylammonium hydroxide aqueous solution, the development treatment was carried out at 23 ° C. for 90 seconds, followed by rinsing with ultrapure water for 30 seconds to form a contact hole pattern, followed by heating at 230 ° C. for 60 minutes (post Bake). This obtained the thin film transistor in which the patterned organic passivation film was formed.

(Example 2)

A thin film transistor with a patterned organic passivation film was obtained in the same manner as in Example 1 except that the bias was 0 W in the hydrogen plasma treatment.

(Example 3)

The thin film transistor in which the patterned organic passivation film was formed by the method similar to Example 2 except having used the resin composition ((beta)) instead of the resin composition ((alpha)) was obtained.

(Comparative Example 1)

Except not performing a hydrogen plasma process, it carried out similarly to Example 1, and produced the thin film transistor in which the patterned organic passivation film was formed and evaluated.

(Comparative Example 2)

A thin film transistor was produced and evaluated in the same manner as in Example 1 except that the passivation film was changed to a silicon nitride film (SiNx film) formed by CVD using silane gas and ammonium gas as raw materials.

(Comparative Example 3)

Except not performing a hydrogen plasma process, it carried out similarly to the comparative example 2, and manufactured the thin film transistor, and evaluated.

(Comparative Example 4)

Except not performing the hydrogen plasma process, the thin film transistor in which the patterned organic passivation film was formed similarly to Example 3 was produced, and it evaluated.

Moreover, Table 1 also showed the result of evaluation about the following characteristics.

(2) aperture ratio

The ratio of the area of the wiring portion and the portion of the thin film transistor substrate to the light passing except for the transistor portion was determined as the aperture ratio. The higher the aperture ratio, the better the brightness.

(3) Passivation film manufacturing process number after TFT manufacture

After manufacturing a thin film transistor by the process shown to FIG. 1 (a)-FIG. 2 (c), the number of processes required before obtaining the thin film transistor in which the patterned passivation film was formed was compared.

That is, in Examples 1 to 3, six steps of (i) hydrogen plasma treatment, (ii) cleaning, (iv) coating, (iv) exposure, (v) development and (iv) bake are required. In Comparative Examples 1 and 4, five steps of (i) cleaning, (ii) coating, (iv) exposure, (iv) development, and (v) baking are required. In Comparative Example 2, (i) cleaning, (ii) formation of a SiNx film by CVD method, (i) cleaning, (iv) coating, (v) exposure, (iv) development, (iv) baking, (iv) Eight steps of dry etching are required. In Comparative Example 3, (i) hydrogen plasma treatment, (ii) cleaning, (i) formation of SiNx film by CVD method, (i) cleaning, (v) coating, (iv) exposure, (iv) development, Nine processes of (i) bake and (iii) dry etching are required.

(4) relative dielectric constant and RC delay

After the resin composition containing the organic materials prepared in Production Examples 1 and 2 was applied on a silicon wafer by spin coating, it was heated and dried (prebaked) at 90 ° C. for 2 minutes using a hot plate to obtain a film thickness. A 2.5 μm resin film was formed. Subsequently, it heated for 60 minutes at 230 degreeC, and obtained the test sample which consists of a silicon wafer with a resin film containing an organic material.

Further, a silicon nitride film (SiNx film) formed by CVD method using silane gas and ammonium gas as a raw material was formed on a silicon wafer, and heated and dried (prebaked) at 90 ° C. for 2 minutes using a hot plate. A resin film having a thickness of 120 nm was formed. Subsequently, it heated for 60 minutes at 230 degreeC, and obtained the test sample which consists of a silicon wafer with a SiNx film | membrane formed. And the dielectric constant of the resin film and SiNx film was measured at 10 kPa (room temperature) according to JIS C 6481 using the obtained test sample. The lower the dielectric constant, the better.

The RC delay was calculated by the following equation and calculated as the RC delay time (DT) by calculating the time until the input signal was set at 10 V and a voltage of 97% was reached at the terminal of the data line at a full high-vision of 65 inches.

V (t) = V (1-exp [t / RC])

V: input voltage, t: time, R: resistance of data wiring, C: parasitic capacitance of data wiring

From the results in Table 1, it was found that the thin film transistors subjected to hydrogen plasma treatment and using an organic material for the passivation film did not deteriorate even in a harsh atmosphere and were very reliable. Moreover, the thin film transistor substrate using the passivation film which consists of organic materials was easy to manufacture because there were few processes, and compared with using the passivation film which contains SiNx which is an inorganic material. In addition, since the passivation film containing an organic material has a high aperture ratio, it is excellent in brightness and low in dielectric constant, and thus, RC delay can be suppressed.

21: substrate
22: gate electrode
23: gate insulating film
24: semiconductor layer
25 impurity-added semiconductor layer
26 source / drain electrodes
27: source electrode
28; Drain electrode
29: channel area
30: impurity-added semiconductor layer in region where source electrode is present
31 impurity-added semiconductor layer in region where drain electrode is present
32: passivation film containing organic materials
33: Passivation film containing inorganic material

Claims (5)

Performing a plasma treatment on the surface of the semiconductor element or the surface of the semiconductor layer included in the semiconductor element;
Forming a passivation film made of an organic material on the surface of the semiconductor element or the surface of the semiconductor layer subjected to the plasma treatment
The manufacturing method of the semiconductor element substrate containing a. The method of claim 1,
And said plasma treatment is a hydrogen plasma treatment. 3. The method according to claim 1 or 2,
The semiconductor element or the semiconductor layer,
Forming a gate electrode, a gate insulating film, a semiconductor layer, and a source / drain electrode on the substrate;
A process comprising forming a channel region
It is manufactured by the manufacturing method of the semiconductor element substrate. The method according to any one of claims 1 to 3,
The said organic material is a resin composition containing resin, The manufacturing method of the semiconductor element substrate characterized by the above-mentioned. The method according to any one of claims 1 to 4,
The plasma treatment is a processing time of 1 to 10 minutes.

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