TWI511201B - Semiconductor element, semiconductor substrate, radiation-sensitive resin composition, protective film and display element - Google Patents

Description

Semiconductor element, semiconductor substrate, radiation sensitive resin composition, protective film, and display element

The present invention relates to a semiconductor element, a semiconductor substrate, a radiation sensitive resin composition, a protective film, and a display element.

A liquid crystal display element which is a display element is formed by sandwiching liquid crystal on a pair of substrates. An alignment film is provided on the surface of each substrate to control the alignment of the liquid crystal. Next, an alignment change occurs in the liquid crystal by applying an electric field between the substrates. In the liquid crystal display element, light is partially transmitted or shielded corresponding to the alignment of the liquid crystal. The liquid crystal display element utilizes such characteristics to display an image. The liquid crystal display element has an advantage of being thinner or lighter than the display element of the conventional CRT method.

In the development of the liquid crystal display element, it is used as a display element of a computer or a clock centered on a character display or the like. Then, the development of the simple matrix method makes it easy to display the dot matrix, and the use is expanded to display elements of a notebook computer. Then, through the development of a TFT (Thin Film Transistor) which is a semiconductor element, an active matrix type liquid crystal display was developed. Show components. In addition, it is possible to achieve good image quality with excellent contrast or response performance, and further, it can also be used for monitors of desktop computers, etc., by overcoming problems such as high definition, colorization, and widening of viewing angle. . Recently, it has been possible to realize a wider viewing angle, high-speed response of liquid crystal, improvement in display quality, and the like, and to use it as a thin display element for television.

Then, in recent years, the liquid crystal display element has been further improved in performance, and for example, it has been possible to provide a large screen for a large-sized television or to use a flexible substrate. Therefore, even in the TFT which is a main component of the liquid crystal display element, the performance of the TFT is improved.

Previously, TFTs which are semiconductor elements have been used for the use of amorphous germanium or polycrystalline germanium in semiconductor layers. Recently, it has become possible to form at a lower temperature and to form it on a flexible substrate such as a resin substrate, and in order to obtain a desired degree of mobility, a new structure TFT has been studied.

For example, Patent Document 1 discloses a technique of using a TFT of a transparent oxide semiconductor in a semiconductor layer. In the TFT described in Patent Document 1, IGZO (Indium Gallium Zinc Oxide) is used for the semiconductor layer. Next, a flexible active matrix type liquid crystal display element which makes formation of a TFT at a low temperature and which forms a TFT on a resin substrate lacking heat resistance can be provided.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-165529

However, in the case of using a semiconductor of an oxide semiconductor on a semiconductor layer, there is a problem of light resistance. Specifically, in the case of using a semiconductor layer of an oxide semiconductor, there is a case where it is absorbed in an ultraviolet region or the like. Therefore, when the semiconductor element using the semiconductor element is irradiated with light from outside, the resistance at the time of OFF is lowered, and when a switching element as a display element is used, it is considered that a sufficient ON/OFF ratio cannot be obtained. Therefore, in the case where the semiconductor element is used for a liquid crystal display element, there is a problem that the characteristics are deteriorated due to the influence of light from the outside.

Although the problem of deterioration of characteristics due to such light irradiation is different in degree, it is considered to be a problem even if a conventional amorphous germanium or the like is used for a semiconductor element of a semiconductor layer. Therefore, in a semiconductor element, in particular, a semiconductor element used for a display element such as a liquid crystal display element, we have sought a technique for improving light resistance.

The present invention has been made in view of the above problems, that is, an object of the present invention is to provide a semiconductor element which can reduce the deterioration of characteristics due to the influence of light.

Further, an object of the present invention is to provide a semiconductor substrate having a semiconductor element which is reduced in characteristics due to influence of light, and which is suitable for formation of a display element.

Further, an object of the present invention is to provide a radiation sensitive resin composition which is used for forming a protective film of a semiconductor element which is reduced in characteristics due to influence of light.

Next, an object of the present invention is to provide a protective film for a semiconductor element which is reduced in characteristics due to effects of light.

Further, an object of the present invention is to provide a display element having a semiconductor element which is reduced in characteristics due to influence of light.

A first aspect of the invention is a semiconductor device comprising: a semiconductor layer; and an electrode disposed on the first surface of the semiconductor layer, wherein a protective film is disposed between the semiconductor layer and the electrode, the protective film comprising: a resin; and at least one of a quinonediazide compound and a hydrazine carboxylic acid.

In the first aspect of the invention, the resin is preferably one selected from the group consisting of an acrylic resin having a carboxyl group, a polyimine resin, a polyoxyalkylene oxide, and a novolak resin.

In the first aspect of the present invention, preferably, the through hole is provided in the protective film, and the connection between the first surface of the semiconductor layer and the electrode is performed through the through hole.

In a first aspect of the present invention, a bottom gate semiconductor device is preferably provided with a gate electrode provided on a second surface of a semiconductor layer via a gate insulating film, and a source electrode and a germanium electrode. On the first side.

In the first aspect of the invention, the semiconductor layer is preferably formed using an oxide composed of at least one of indium (In), zinc (Zn), and tin (Sn).

In the first aspect of the invention, the semiconductor layer is formed using at least one of zinc oxide (ZnO), indium gallium zinc oxide (IGZO), zinc tin oxide (ZTO), and indium zinc oxide (IZO).

In the first aspect of the invention, the semiconductor layer is preferably made of bismuth (Si).

A second aspect of the present invention relates to a semiconductor substrate including: a substrate; and a plurality of gate wirings and a plurality of data wirings disposed on the substrate and formed at intersections of a plurality of gate wirings and a plurality of data wirings In the matrix-shaped pixel, a semiconductor element having a semiconductor layer and an electrode provided on the first surface of the semiconductor layer is provided, and a protective film is provided between the semiconductor layer and the electrode, and the protective film contains a resin and a second At least one of an azide compound and a hydrazine carboxylic acid.

In the second aspect of the invention, the resin is preferably one selected from the group consisting of an acrylic resin having a carboxyl group, a polyimine resin, a polysiloxane, and a novolak resin.

In the second aspect of the invention, it is preferable that the protective film is provided with a through hole, and the first surface of the semiconductor layer is connected to the electrode via the through hole.

A second aspect of the present invention is preferably a bottom gate type semiconductor device having a gate electrode provided on a second surface of a semiconductor layer via a gate insulating film. The source electrode and the germanium electrode are provided on the first surface.

In a second aspect of the invention, a semiconductor layer is preferably formed using an oxide comprising at least one of indium (In), zinc (Zn) and tin (Sn).

In the second aspect of the present invention, it is preferable that the semiconductor layer is formed using at least one of zinc oxide (ZnO), indium gallium zinc oxide (IGZO), zinc tin oxide (ZTO), and indium zinc oxide (IZO).

In the second aspect of the invention, it is preferable that the semiconductor layer is made of bismuth (Si).

A third aspect of the present invention relates to a radiation sensitive resin composition characterized by being used for forming a protective film of a semiconductor element according to a first aspect of the present invention, characterized in that it contains a resin and a ruthenium. Azide compound.

A fourth aspect of the invention relates to a protective film characterized by the radiation sensitive linear resin composition of the third aspect of the invention.

A fifth aspect of the invention relates to a display element characterized by using the semiconductor element of the first aspect of the invention.

According to the first aspect of the invention, it is possible to obtain a semiconductor element which is reduced in characteristics due to the influence of light.

According to the second aspect of the present invention, the semiconductor element has a semiconductor element, and the characteristics due to the influence of light can be reduced, and a semiconductor substrate suitable for the formation of the display element can be obtained.

According to the third aspect of the present invention, a radiation can be obtained The linear resin composition is used for forming a protective film of a semiconductor element in which the characteristics due to the influence of light are reduced.

According to the fourth aspect of the present invention, it is possible to obtain a protective film of a semiconductor element which is reduced in characteristics due to effects of light.

According to the fifth aspect of the present invention, a liquid crystal display element having a semiconductor element which is reduced in characteristics due to the influence of light can be obtained.

1‧‧‧Semiconductor components

2‧‧‧Semiconductor layer

3‧‧‧ source electrode

4‧‧‧汲 electrode

5‧‧‧Protective film

6‧‧‧through holes

10, 22, 45‧‧‧ substrates

11‧‧‧ gate electrode

12‧‧‧Brake insulation film

21‧‧‧Semiconductor substrate

23‧‧‧Data wiring

24‧‧ ‧ gate wiring

25‧‧‧pixel electrode

30‧‧‧Color filter substrate

36‧‧‧Coloring pattern

37‧‧‧Black matrix

38‧‧‧Protective layer

40‧‧‧Color filters

41‧‧‧Common electrode

42‧‧‧Alignment film

43‧‧‧LCD

44‧‧‧Polar plate

46‧‧‧ Sealing material

47‧‧‧ Backlight

100‧‧‧Liquid display components

Fig. 1 is a schematic cross-sectional view showing the structure of a semiconductor element of the present embodiment.

Fig. 2 is a plan explanatory plan view showing a configuration of an important part of a semiconductor substrate of the present embodiment.

Fig. 3 is a schematic cross-sectional view showing the structure of an important part of a liquid crystal display element of the present embodiment.

[Formation of the Invention]

The semiconductor element of the embodiment of the present invention will be described below. Next, a semiconductor substrate formed using the semiconductor element and a display element liquid crystal display element having the semiconductor element will be described.

Further, in the present invention, the "radiation" irradiated during exposure includes visible light, ultraviolet light, far ultraviolet rays, X-rays, charged particle lines, and the like.

Embodiment 1.

<semiconductor component>

Fig. 1 is a schematic cross-sectional view showing the structure of a semiconductor element of the present embodiment.

Fig. 1 shows an example in which the semiconductor element 1 of the present embodiment is provided on one surface of the substrate 10.

The semiconductor element 1 has a semiconductor layer 2 and an electrode which is provided on the upper surface side of the first layer of the semiconductor layer 2 and is provided on the first surface. The electrode includes a source electrode 3 and a germanium electrode 4.

In the semiconductor element 1 , a protective film 5 is disposed between the semiconductor layer 2 and the source electrode 3 and the germanium electrode 4 . As described later in detail, the protective film 5 is formed using a resin. Therefore, the through hole 6 is provided in the protective film 5, and the first surface of the semiconductor layer 2 is electrically connected to the source electrode 3; and the first surface of the semiconductor layer 2 is electrically connected to the germanium electrode 4, Each is carried out via a corresponding through hole 6 .

The semiconductor element 1 of the first embodiment has the gate electrode 11 via the gate insulating film 12 on the second surface of the semiconductor layer 2 on the lower surface side of the first drawing. In other words, in the semiconductor element 1, the gate electrode 11 is disposed on the substrate 10, and the gate insulating film 12 is formed on the gate electrode 11. The semiconductor layer 2 is disposed on the gate electrode 11 via the gate insulating film 12, and has a source electrode 3 and a germanium electrode 4 connected to the semiconductor layer 2. The semiconductor element 1 constitutes a bottom gate type semiconductor element.

Further, the semiconductor element according to the embodiment of the present invention is not limited to the bottom gate type shown in Fig. 1. On the first surface side of the surface on the upper side of the semiconductor layer, a gate electrode is provided via a gate insulating film, and a first gate type can be formed on the first surface thereof, and a source electrode and a gate electrode connected to the surface are disposed. pole.

In the semiconductor element 1 shown in FIG. 1, the gate electrode 11 is formed on the substrate 10 by a vapor deposition method, a sputtering method, or the like to form a metal thin film, and can be formed by patterning by an etching process. Further, a metal oxide conductive film or an organic conductive film may be patterned for use.

Examples of the material of the metal thin film constituting the gate electrode 11 include metals such as Al, Mo, Cr, Ta, Ti, Au, and Ag, and alloys such as Al-Nd and APC (Ag/Pd/Cu) alloy. . Next, as the metal thin film, a laminated film of a laminated film of Al (aluminum) and Mo (molybdenum) or the like can be used.

Examples of the material of the metal oxide conductive film constituting the gate electrode 11 include tin oxide, zinc oxide, indium oxide, ITO (Indium Tin Oxide), and zinc indium oxide (IZO). Metal oxide conductive film.

Further, examples of the material of the organic conductive film include conductive organic compounds such as polyaniline, polythiophene, and polypyrrole, or a mixture thereof.

The thickness of the gate electrode 11 is preferably from 10 nm to 1000 nm.

The gate insulating film 12 which is disposed so as to cover the gate electrode 11 can be formed by forming an oxide film or a nitride film by a sputtering method, a CVD method, a vapor deposition method, or the like. The gate insulating film 12 can be formed, for example, of a metal oxide such as SiO ₂ or a metal nitride such as SiN. Further, it may be composed of an organic material such as a polymer material. The film thickness of the gate insulating film 12 is preferably 10 nm to 10 μm, particularly in the case of using an inorganic material such as a metal oxide, preferably 10 nm to 1000 nm, and in the case of using an organic material, preferably 50 nm to 10 μm.

The source electrode 3 and the ruthenium electrode 4 connected to the semiconductor layer 2 are formed of a conductive film constituting the electrodes, and a sputtering method, a CVD method, a vapor deposition method, or the like is used in addition to a printing method or a coating method. After the formation, it can be formed by patterning by photolithography or the like. Examples of the constituent material of the source electrode 3 and the tantalum electrode 4 include metals such as Al, Mo, Cr, Ta, Ti, Au, and Ag; alloys such as Al-Nd and APC, tin oxide, and zinc oxide. Conductive metal oxides such as indium oxide, ITO, indium zinc oxide (IZO), AZO (doped aluminum zinc oxide), and GZO (gallium dopant zinc oxide), polyaniline, polythiophene, polypyrrole, etc. Conductive organic compound.

The thickness of the source electrode 3 and the germanium electrode 4 is preferably from 10 nm to 1000 nm.

The semiconductor layer 2 of the semiconductor device 1 of the present embodiment can be formed, for example, by using a germanium (Si) material such as a-Si (amorphous germanium) or microcrystalline germanium.

Further, the semiconductor layer 2 of the semiconductor device 1 of the present embodiment can be formed using an oxide. Examples of the oxide which can be applied to the semiconductor layer 2 of the present embodiment include a single crystal oxide, a polycrystalline oxide, an amorphous oxide, and a mixture thereof. Examples of the polycrystalline oxide include zinc oxide (ZnO) and the like.

The amorphous oxide which can be applied to the semiconductor layer 2 is an amorphous oxide containing at least one element of indium (In), zinc (Zn), and tin (Sn).

Specific examples of the amorphous oxide which can be applied to the semiconductor layer 2 include Sn-In-Zn oxide, In-Ga-Zn oxide (IGZO: indium gallium zinc oxide), and In-Zn-Ga-. Mg oxide, Zn-Sn oxidation (ZTO: zinc tin oxide), In oxide, Ga oxide, In-Sn oxide, In-Ga oxide, In-Zn oxide (IZO: indium zinc oxide), Zn-Ga oxide, Sn- In-Zn oxide or the like. Further, in the above case, the composition ratio of the constituent materials is not necessarily 1:1, and the composition ratio of the desired characteristics can be selected.

When the semiconductor layer 2 of an amorphous oxide is used, for example, when IGZO or ZTO is used, an IGZO target or a ZTO target is used, and a semiconductor layer is formed by a sputtering method or a vapor deposition method, and a photolithography method or the like is used. The patterning process is performed by a photoresist process and an etching process. The thickness of the semiconductor layer 2 using an amorphous oxide is preferably from 1 nm to 1000 nm.

By using the oxides exemplified above, the semiconductor layer 2 having high mobility can be formed at a low temperature, and the semiconductor device 1 of the present embodiment can be provided.

Next, examples of the oxide which is particularly preferable for forming the semiconductor layer 2 of the semiconductor device 1 of the present embodiment include zinc oxide (ZnO), indium gallium zinc oxide (IGZO), zinc tin oxide (ZTO), and oxidation. Indium zinc (ZIO).

By using these oxides, the semiconductor element 1 has a semiconductor layer 2 excellent in mobility and is formed at a lower temperature, and can exhibit a high ON/OFF ratio.

In the semiconductor device 1 of the present embodiment, the protective film 5 is disposed between the semiconductor layer 2 and the source electrode 3 and the germanium electrode 4. The protective film 5 of the present embodiment includes an insulating organic film as described later, and includes a resin formed of a radiation-sensitive resin composition containing a resin and a quinonediazide compound.

The protective film 5 is connected to the gate electrode 11 and the gate insulating film 12, and the semiconductor The radiation-sensitive resin composition of the present embodiment is applied onto the substrate 10 formed of the bulk layer 2 or the like, and is formed by heat-hardening after being patterned as necessary for formation of the through holes 6. The formed protective film 5 may contain a quinonediazide compound, and in this case, excellent light blocking properties can be achieved.

Therefore, in the semiconductor element 1 of the present embodiment having the protective film 5 between the semiconductor layer 2 and the source electrode 3 and the germanium electrode 4, the effect of the protective film 5 is effective, and the light shielding of the semiconductor layer 2 is possible. Next, in the semiconductor device 1 of the present embodiment, the light-shielding effect of the protective film 5 can reduce the deterioration of the characteristics due to the influence of light.

In this case, as the element formed using the semiconductor element, as described above, for example, a liquid crystal display element is used, but in the case of a liquid crystal display element, a semiconductor substrate having a TFT which is a semiconductor element, and a color filter having a color filter Manufactured by sandwiching liquid crystal between color filter substrates. Next, a backlight unit is usually disposed on the side of the semiconductor substrate, and high contrast image display is possible.

Therefore, on the semiconductor substrate side of the liquid crystal display element, it is necessary to easily transmit light from the backlight unit (transparency), and it is not appropriate to provide a protective film having a light-shielding property.

However, in the semiconductor device 1 of the present embodiment, by using the protective film 5 containing the quinonediazide compound, the balance between the transparency and the light-shielding property required for the liquid crystal display device or the like can be appropriately controlled.

The quinonediazide compound changes its molecular structure upon exposure to become a hydrazine carboxylic acid, and has a property called photofading property which changes the light absorption property of the molecule.

Therefore, in the semiconductor device 1 of the present embodiment, the protective film 5 is formed. After that, in the case where the transparency is inconvenient, the protective film 5 can be irradiated with light only, and transparency can be modulated. Therefore, at least one of the quinonediazide compound and the hydrazine carboxylic acid is contained in the protective film 5 together with the resin.

As described above, in the semiconductor element 1 of the present embodiment, the protective film 5 exhibits a unique effect and is a very important component. Therefore, the formation of the protective film 5 of the semiconductor device 1 of the present embodiment will be described in more detail. In particular, the radiation sensitive resin composition used for the formation of the protective film 5 will be described in detail.

<Inductive Radiation Resin Composition>

In the semiconductor device of the present embodiment, the radiation sensitive resin composition of the present embodiment used for the production of the protective film of the constituent member contains a resin and a quinonediazide compound as essential components. The resin is preferably a resin having alkali developability. By having such a composition, the film formed of the radiation sensitive resin composition of the present embodiment can have excellent patterning properties and light blocking properties after formation. Next, the radiation sensitive resin composition of the present embodiment may contain a curing accelerator for promoting curing of the formed film, and may further contain other optional components as long as the effects of the present invention are not impaired.

The resin contained in the radiation sensitive resin composition of the present embodiment is preferably one selected from the group consisting of an acrylic resin having a carboxyl group, a polyimide resin, a polysiloxane, and a novolak resin. The various resins having a carboxyl group-containing acrylic resin, a polyimide resin, a polyoxyalkylene, and a novolac resin, which are preferred as the resin, will be described in more detail below.

[Acrylic resin with carboxyl group]

A preferred carboxyl group-containing acrylic resin as the resin preferably contains a constituent unit having a carboxyl group and a constituent unit having a polymerizable group. In this case, it is not particularly limited as long as it is a constituent unit having a carboxyl group and a constituent unit having a polymerizable group and has alkali developability.

The constituent unit having a polymerizable group is preferably selected from the group consisting of at least one of a constituent unit having an epoxy group and a constituent unit having a (meth)acryloxy group. The acrylic resin having a carboxyl group can form a cured film having excellent surface hardenability and deep hardenability by containing the above specific constituent unit, and the protective film of the present embodiment can be formed.

A constituent unit having a (meth) acryloxy group can be formed by a method in which an epoxy group in a copolymer reacts (meth)acrylic acid; a carboxyl group in the copolymer gives an epoxy group; a method for reacting a (meth) acrylate; a method of reacting a hydroxyl group in a copolymer to a (meth) acrylate having an isocyanate group; and reacting an hydroxyester of (meth) acrylate with an acid anhydride moiety in the copolymer The method or the like is formed. Among these, a method of reacting a carboxyl group in a copolymer with a (meth) acrylate having an epoxy group is particularly preferred.

An acrylic resin comprising a constituent unit having a carboxyl group and a constituent unit having an epoxy group as a polymerizable group may be at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (A1) (hereinafter also referred to as It is synthesized by copolymerizing "the compound (A1)") and an epoxy group-containing unsaturated compound (A2) (hereinafter also referred to as "(A2) compound"). In this case, the acrylic resin having a carboxyl group is a copolymer comprising: And a constituent unit formed of at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides; and a constituent unit formed of the epoxy group-containing unsaturated compound.

An acrylic resin having a carboxyl group, for example, by copolymerizing a compound (A1) to which a carboxyl group-containing constituent unit is supplied and a compound (A2) to which an epoxy group-containing constituent unit is supplied, in the presence of a polymerization initiator in a solvent, It can be manufactured. Further, a hydroxyl group-containing unsaturated compound (A3) (hereinafter also referred to as "(A3) compound") to which a hydroxyl group-containing constituent unit is added may be further added to obtain a copolymer. Further, in the production of an acrylic resin having a carboxyl group, a compound (A4) is further added together with the above compound (A1), compound (A2) and compound (A3) (from the above compounds (A1), (A2) and ( The unsaturated compound of the constituent unit other than the constituent unit of A3) can be used as a copolymer. Each compound is described in detail below.

[Compound (A1)]

The compound (A1) may, for example, be an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an anhydride of an unsaturated dicarboxylic acid or a mono[(meth)acryloxyalkylalkyl]ester of a polyvalent carboxylic acid.

Examples of the unsaturated monocarboxylic acid include acrylate, methacrylic acid, crotonic acid and the like.

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid.

The anhydride of the unsaturated dicarboxylic acid may, for example, be an anhydride of the compound exemplified as the above dicarboxylic acid.

Among the compounds (A1), acrylic acid, methacrylic acid, maleic anhydride, and acrylic acid, methacrylic acid, and cis are preferred. The butenedic anhydride is more preferably copolymerized, has solubility in an aqueous alkali solution, and is easy to obtain.

These compounds (A1) may be used singly or in combination of two or more.

The use ratio of the compound (A1) is preferably from 5% by mass to 30% by mass, based on the total of the compound (A1) and the compound (A2) (any compound (A3) and the compound (A4) which may be required), more preferably It is 10% by mass to 25% by mass. By setting the use ratio of the compound (A1) to 5% by mass to 30% by mass, the solubility of the acrylic resin having a carboxyl group in the aqueous alkali solution can be optimized, and an insulating film excellent in radiation sensitivity can be obtained.

[Compound (A2)]

The compound (A2) which is a radically polymerizable epoxy group-containing unsaturated compound. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) or an oxetanyl group (1,3-epoxy structure).

Examples of the unsaturated compound having an oxiranyl group include, for example, glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, and 3,4-epoxy acrylate. Butyl ester, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyglycol Ester, o-vinylbenzyl epoxidized propyl ether, m-vinyl benzyl epoxidized propyl ether, p-vinylbenzyl epoxidized propyl ether, 3,4-epoxycyclohexyl methacrylate, and the like. Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl epoxidized ether, m-vinyl benzyl Base ring Oxypropyl propyl ether, p-vinylbenzyl epoxidized propyl ether, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl acrylate, etc., which are resistant to solvents such as copolymerization reactivity and insulating film. The viewpoint of sex and the like is preferred.

Examples of the unsaturated compound having an oxetanyl group include 3-(acryloxymethyl) propylene oxide, 3-(acryloxymethyl)-2-methyl propylene oxide, and 3 -(propylene oxime methyl)-3-ethyl propylene oxide, 3-(acryloxymethyl)-2-phenyl propylene oxide, 3-(2-propenyl oxiranyl) propylene oxide, 3-(2-propenyloxyethyl)-2-ethyl propylene oxide, 3-(2-propenyl oxiranyl)-3-ethyl propylene oxide, 3-(2-propenyl oxirane Acrylate such as 2-phenyl propylene oxide; 3-(methacrylofluorenyloxy) propylene oxide, 3-(methacryloxymethyl)-2-methyl propylene oxide, 3 -(methacryloyloxymethyl)-3-ethyl propylene oxide, 3-(methacrylofluorenyloxy)-2-phenyl propylene oxide, 3-(2-methylpropene oxime Propylene oxide, 3-(2-methylpropenyloxyethyl)-2-ethyl propylene oxide, 3-(2-methylpropenyloxyethyl)-3-ethyl propylene oxide, 3-(2-methylpropenyloxyethyl)-2-phenyl propylene oxide, 3-(2-methylpropenyloxyethyl)-2,2-difluoropropylene oxide, etc. Ester and the like.

Among the compounds (A2), preferred are glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3-(methacryloxymethyl)-3-ethyl epoxy Propane. These compounds (A2) may be used singly or in combination of two or more.

The use ratio of the compound (A2) is preferably from 5% by mass to 60% by mass, based on the total of the compound (A1) and the compound (A2) (any compound (A3) and the compound (A4) which may be required), more preferably For 10 masses % to 50% by mass. By using the use ratio of the compound (A2) at 5% by mass to 60% by mass, the protective film of the present embodiment having excellent curability and the like can be formed.

[Compound (A3)]

The compound (A3) may, for example, be a (meth) acrylate having a hydroxyl group, a (meth) acrylate having a phenolic hydroxyl group, or hydroxystyrene.

Examples of the acrylate having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate.

Examples of the methacrylate having a hydroxyl group include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, and A. 6-hydroxyhexyl acrylate or the like.

Examples of the acrylate having a phenolic hydroxyl group include 2-hydroxyphenyl acrylate and 4-hydroxyphenyl acrylate. Examples of the methacrylate having a phenolic hydroxyl group include 2-hydroxyphenyl methacrylate and 4-hydroxyphenyl methacrylate.

In the case of hydroxystyrene, o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene are preferred. These compounds (A3) may be used singly or in combination of two or more.

The use ratio of the compound (A3) is preferably from 1% by mass to 30% by mass, based on the total of the compound (A1), the compound (A2) and the compound (A3) (any compound (A4) may be required), more preferably It is 5 mass% to 25% by mass.

[Compound (A4)]

The compound (A4) is not particularly limited as long as it is an unsaturated compound other than the above compound (A1), the compound (A2) and the compound (A3). Examples of the compound (A4) include a chain alkyl ester of methacrylic acid, a cyclic alkyl methacrylate, an alkyl chain acrylate, a cyclic alkyl acrylate, an aryl methacrylate, an aryl acrylate, and the like. An unsaturated compound such as an unsaturated dicarboxylic acid diester, a maleimide compound, an unsaturated aromatic compound, a conjugated diene or a tetrahydrofuran skeleton, and other unsaturated compounds.

Examples of the chain alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, butyl methacrylate, and butyl methacrylate. 2-ethylhexyl acrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like.

Examples of the cyclic alkyl methacrylate include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, and tricyclo [ 0.45.1.0 ^2,6 ]nonane-8- Base ester, tricyclo[meth] methacrylate [5.2.1.0 ^2,6 ]decane-8-oxoethyl ester, methacrylic acid Ester and the like.

Examples of the chain alkyl acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, butyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, N-lauryl acrylate, tridecyl acrylate, n-stearyl acrylate, and the like.

Examples of the cyclic alkyl acrylate include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate, and tricyclobutyl acrylate [ 5.2.1.0 ^2,6 ]decane-8-yloxyethyl ester, acrylic acid Ester and the like.

Examples of the aryl methacrylate include phenyl methacrylate and benzyl methacrylate.

Examples of the aryl acrylate include phenyl acrylate, benzyl acrylate, and the like.

Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate, and the like.

Examples of the maleimide compound include N-phenyl maleimide, N-cyclohexyl maleimide, and N-benzyl maleimide. , N-(4-hydroxyphenyl) maleimide, N-(4-hydroxybenzyl) maleimide, N-ammonium imino-3-butane Imino benzoate, N-succinimide-4-butyleneimine butyrate, N-succinimide-6-m-butyleneimine hexanoate, N - amber succinimide-3-synylene diimide propionate, N-(9-acridinyl) maleimide, and the like.

Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.

Examples of the conjugated diene include 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

Examples of the unsaturated compound containing a tetrahydrofuran skeleton include, for example, tetrahydrofurfuryl methacrylate, 2-methylpropenyloxy-propionic acid tetrahydrofurfuryl ester, and 3-(methyl)acryloxytetrahydrofuran-2- Ketones, etc.

Examples of the other unsaturated compound include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, and methyl group. Acrylamide, vinyl acetate, and the like.

Among the compounds (A4), a linear alkyl methacrylate, a cyclic alkyl methacrylate, an aryl methacrylate, a maleimide compound, a tetrahydrofuran skeleton, or an unsaturated aromatic compound is preferred. , a cyclic alkyl acrylate. Among these are especially styrene, methyl methacrylate, butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, trimethyl methacrylate [5.2.1.0 ^2,6 ]decane -8-yl ester, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenyl maleimide, N-cyclohexyl maleimide, methacrylic acid The hydroquinone ester is preferably a point which is soluble in copolymerization reactivity and an aqueous alkali solution.

These compounds (A4) may be used singly or in combination of two or more.

The use ratio of the compound (A4) is preferably from 10% by mass to 80% by mass based on the total of the compound (A1), the compound (A2) and the compound (A4) (and any compound (A3)).

[Polyimide resin]

A preferred polyimine resin which is a resin used in the radiation-sensitive resin composition of the present embodiment has a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group in a constituent unit of the polymer. At least one polyimine resin in the group. By having such an alkali-soluble group in the constituent unit, it is possible to suppress the occurrence of residue in the exposed portion at the time of alkali development. Further, when the constituent unit has a fluorine atom, it is preferable to provide water repellency at the interface of the film during the development of the aqueous alkali solution, thereby suppressing penetration of the interface. The content of fluorine atoms in the polyimide resin in order to fully obtain the prevention The penetration effect of the interface is preferably 10% by mass or more, and is preferably 20% by mass or less from the viewpoint of solubility in an aqueous alkali solution.

The resin used in the radiation-sensitive resin composition of the present embodiment is preferably a polyimine resin, and is preferably a structural unit represented by the following formula (I-1).

In the above formula (I-1), R ¹ represents an organic group of 4 to 14 valence, and R ² represents an organic group of 2 to 12 valence.

R ³ and R ⁴ represent a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group or a thiol group, and each may be the same or different. a and b represent an integer from 0 to 10.

In the above formula (I-1), R ¹ represents a residue of a tetracarboxylic dianhydride, and is an organic group of 4 to 14 valence. Among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferred.

Examples of the tetracarboxylic dianhydride include 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, and 2,2. ',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid Dihydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-double (3,4 -dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis (2, 3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)anthracene Dihydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 3,3',4,4'-di Benzoquinonetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)ruthenium anhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}anthracene A dianhydride or an acid dianhydride of the structure shown below. These may also be used in two or more types.

R ⁵ represents an oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ . R ⁶ and R ⁷ represent a hydrogen atom, a hydroxyl group or a thiol group.

In the above formula (I-1), R ² represents a residue of a diamine and is a divalent to 12-valent organic group. Among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferred.

Specific examples of the diamine include 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 3,3. '-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl hydrazine, 3,4'- Diaminodiphenyl hydrazine, 4,4'-diaminodiphenyl hydrazine, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4 '-Diaminodiphenyl sulfide, meta-phenylenediamine, p-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene, 9,9-bis(4-aminobenzene) The diamine or the like having the structure shown below is preferably. These may also be used in two or more types.

R ⁵ represents an oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ . R ⁶ to R ⁹ represent a hydrogen atom, a hydroxyl group or a thiol group.

Further, in order to improve the adhesion to the substrate, an aliphatic group having a decane structure can be copolymerized in R ¹ or R ² without lowering the heat resistance. Specifically, the diamine component may be exemplified by bis(3-aminopropyl)tetramethyldioxane, bis(p-aminophenyl)octamethylpentaoxane, etc., from 1 mol% to 10 mol. Ear co-polymerized and the like.

In the above formula (I-1), R ³ and R ⁴ represent a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group or a thiol group. a and b represent an integer from 0 to 10. From the viewpoint of the stability of the obtained radiation sensitive resin composition, a and b are preferably 0, and a and b are preferably 1 or more from the viewpoint of solubility in an aqueous alkali solution.

By adjusting the amount of the alkali-soluble group of R ³ and R ⁴ and changing the rate of dissolution of the aqueous alkali solution, it is possible to obtain a radiation-sensitive resin composition having a moderate dissolution rate by adjusting this.

In the case where both of R ³ and R ⁴ are phenolic hydroxyl groups, in order to set the dissolution rate of the 2.38 mass % aqueous solution of tetramethylammonium hydroxide (TMAH) in a more suitable range, it is preferred to make (a) polyazide. The amount of phenolic hydroxyl groups of the amine resin (a) contains from 2 moles to 4 moles in 1 kg. By making the amount of the phenolic hydroxyl group in this range, a higher sensitivity and high contrast radiation-sensitive resin composition can be obtained.

Further, the polyimine having the structural unit represented by the above formula (I-1) preferably has an alkali-soluble group at the terminal of the main chain. This polyimine has a high alkali solubility. Specific examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a thiol group, and the like. The introduction of the alkali-soluble group into the end of the main chain can be carried out by having an alkali-soluble group at the terminal blocking agent. As the terminal blocking agent, a monoamine, an acid anhydride, a monocarboxylic acid, a monobasic acid chlorine compound, a mono-active ester compound or the like can be used.

Preferred as the monoamine used as the terminal blocking agent is 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy- 5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy- 7-Aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy- 5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid , 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-amino group Phenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, and the like. These two or more types can also be used.

In the case of using an acid anhydride, a monocarboxylic acid, a monobasic acid chlorine compound, or a mono-active ester compound as a terminal blocking agent, phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexane dicarboxylic anhydride, and 3- are preferable. Anhydride such as hydroxyphthalic anhydride; 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1 -hydroxy-5-carboxynaphthalene, 1-hydrothio-7-carboxynaphthalene, 1-hydrothio-6-carboxynaphthalene, 1-hydrothio-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4- a monocarboxylic acid such as carboxybenzenesulfonic acid and a monobasic acid chlorine compound in which the carboxyl group is acid chlorinated; a citric acid, a citric acid, a maleic acid, a cyclohexanedicarboxylic acid, a 1,5-dicarboxylate a monobasic acid chlorine compound in which a carboxyl group of naphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene or the like is acid-chlorinated; An active ester compound or the like obtained by the reaction with N-hydroxybenzotriazole or N-hydroxy-5-northene-2,3-dicarboxylimenimine. It is also possible to use these two or more types.

The introduction ratio of the monoamine used in the terminal blocking agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 60 mol% or less, particularly preferably 50 mol%, to the total amine component. %the following. The introduction ratio of the acid anhydride, the monocarboxylic acid, the monobasic acid chlorine compound or the mono-active ester compound as the terminal blocking agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, more preferably 5 mol% or more. It is 100 mol% or less, and particularly preferably 90 mol% or less. It is also possible to introduce a plurality of different terminal groups by using a plurality of terminal blocking agents.

In the polyimine having the structural unit represented by the above formula (I-1), the number of repeating units is preferably 3 or more, more preferably 5 or more, and It is preferably 200 or less, more preferably 100 or less. As long as it is within this range, the use of a thick film of the photosensitive resin composition of the present invention is feasible.

In the present embodiment, the polyimine resin is preferably a constituent unit represented by the above formula (I-1), or a copolymer or a mixture with other constituent units. In this case, it is preferred that the constituent unit represented by the formula (I-1) contains 10% by mass or more of the entire polyimine resin. When it is 10% by mass or more, shrinkage during thermal curing can be suppressed, and it is suitable for production of a thick film. The type and amount of the constituent unit used for copolymerization or mixing are preferably in a range that does not impair the heat resistance of the polyimide obtained by the final heat treatment. For example, benzo Oxazole, benzimidazole, benzothiazole and the like. These constituent units are preferably 70% by mass or less of the polyimine resin.

In the present embodiment, a preferred polyimine resin is obtained by, for example, obtaining a polyimine precursor using a known method, and subjecting the precursor to imidization using a known hydrazine imidization reaction method. To synthesize. In the well-known synthesis method of polyiminoimine precursor, one part of the diamine is replaced with a monoamine which is a terminal blocking agent, or a part of the acid dianhydride is replaced with a monocarboxylic acid, an acid anhydride, a unitary one which is a terminal blocking agent. The acid chloride compound and the mono-active ester compound are obtained by reacting an amine component with an acid component. For example, there are the following methods: a method of reacting a tetracarboxylic dianhydride with a diamine compound (a part of which is substituted with a monoamine) at a low temperature; and a tetracarboxylic dianhydride (a part of an acid anhydride, a monobasic acid chlorine compound or a single activity) at a low temperature a method of reacting an ester compound with a diamine compound; a method of obtaining a diester by using a tetracarboxylic dianhydride and an alcohol, followed by reacting a diamine (partially substituted with a monoamine) with a condensing agent; Taking a tetracarboxylic dianhydride and an alcohol to obtain a diester, Thereafter, the residual dicarboxylic acid is subjected to acid chlorination, a method of reacting with a diamine (partially substituted with a monoamine), and the like.

Further, the ruthenium imidization ratio of the polyimine resin can be easily obtained by, for example, the following method. First, the polymer of the infrared absorption spectrum was measured, the peak absorption of the imine XI is due to the polyimide (near 1780 cm ^-1, near 1377 cm ^-1) of the present. Thereafter, the polymer was subjected to heat treatment at 350 ° C for 1 hour, and the infrared absorption spectrum was measured, and the peak intensity near 1377 cm ^{-1 was} compared to calculate the content of the quinone imine group in the polymer before the heat treatment, thereby obtaining the quinone imine. Rate.

In the present embodiment, the ruthenium imidization ratio of the polyimide resin is preferably 80% or more from the viewpoint of chemical resistance and high shrinkage residual film ratio.

Further, in the present embodiment, the terminal blocking agent which is preferably introduced into the polyimide resin can be easily detected by the following method. For example, by dissolving a polyimine which introduces a terminal blocking agent in an acidic solution, the amine component and the acid anhydride component which are constituent units of the polyimine are decomposed and subjected to gas chromatography (GC) or NMR measurement. The terminal blocking agent used in the present invention can be easily detected. In addition, the polymer component introduced into the terminal blocking agent can be easily detected by directly measuring it by thermal decomposition gas chromatography (PGC) or infrared spectroscopy and 13 C-NMR spectroscopy.

[polyoxyalkylene]

The resin used in the radiation sensitive resin composition of the present embodiment is preferably a polyoxyalkylene oxide-based polyoxyalkylene having a radical reactive functional group. In the case of a polyoxyalkylene having a radically reactive functional group, as long as it is a compound having a compound having a siloxane coupling The main chain or side chain of the compound and a radical reactive functional group are not particularly limited. In this case, the polyoxyalkylene can be hardened by radical polymerization to suppress the hardening shrinkage to a minimum. The radically reactive functional group may, for example, be an unsaturated organic group such as a vinyl group, an α-methylvinyl group, an acrylonitrile group, a methacryl fluorenyl group or a styryl group. Among these, since the hardening reaction proceeds smoothly, it is preferred to have an acrylonitrile group or a methacrylonitrile group.

The polyoxynonane which is preferable in the embodiment is preferably a hydrolyzed condensate of a hydrolyzable decane compound. The hydrolyzable decane compound constituting the polyoxyalkylene is preferably a hydrolyzable decane compound comprising a hydrolyzable decane compound (s1) represented by the following formula (S-1) (hereinafter also referred to as a compound (s1)) And a hydrolyzable decane compound (s2) (hereinafter also referred to as (s2) compound) represented by the following formula (S-2).

In the above formula (S-1), R ¹¹ is an alkyl group having 1 to 6 carbon atoms. R ¹² is an organic group containing a radical reactive functional group. p is an integer from 1 to 3. However, in the case where R ¹¹ and R ¹² are plural, a plurality of R ¹¹ and R ¹² are independent.

In the above formula (S-2), R ¹³ is an alkyl group having 1 to 6 carbon atoms. R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, an epoxy group, an amine group or an isocyanate group. n is an integer from 0 to 20. q is an integer from 0 to 3. However, in the case where R ¹³ and R ¹⁴ are plural, a plurality of R ¹³ and R ¹⁴ are independent.

In the present invention, the "hydrolyzable decane compound" means that it is usually hydrolyzed by heating at room temperature (about 25 ° C) to about 100 ° C in the presence of no catalyst or excess water. A sterol group or a compound which can form a base of a decane condensate. In the hydrolysis reaction of the hydrolyzable decane compound represented by the above formula (S-1) and the above formula (S-2), a part of the hydrolyzability may remain in the unhydrolyzed state in the produced polyoxyalkylene. Here, the "hydrolyzable group" means the above-mentioned group which is hydrolyzable to produce a sterol group or a group which forms a siloxane condensate. Further, in the radiation-sensitive resin composition, a part of the hydrolyzable decane compound has a part or all of the hydrolyzable group in the molecule in an unhydrolyzed state, and does not condense with other hydrolyzable decane compound, but in a monomer state. Residue is also possible. Further, the "hydrolysis condensate" means a hydrolysis condensate in which a sterol group of a part of the hydrolyzed decane compound is condensed with each other. The compound (s1) and the compound (s2) will be described in detail below.

[compound (s1)]

In the above formula (S-1), R ¹¹ is an alkyl group having 1 to 6 carbon atoms. R ¹² is an organic group containing a radical reactive functional group. p is an integer from 1 to 3. However, in the case where R ¹¹ and R ^{12 are} plural, a plurality of R ¹¹ and R ¹² are independent of each other.

The alkyl group having 1 to 6 carbon atoms of the above-mentioned R ¹¹ may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a butyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of easiness of hydrolysis. From the viewpoint of the above p, from the viewpoint of the hydrolysis condensation reaction, it is preferably 1 or 2, more preferably 1.

The organic group having a radically reactive functional group may be a linear, branched or cyclic carbon number of 1 to 12 which is substituted with one or more hydrogen atoms by the above-mentioned radical reactive functional group. An alkyl group, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and the like. When there are a plurality of R ¹² in the same molecule, the lines are independent. Further, the organic group represented by R ¹² may have a hetero atom. Examples of such an organic group include an ether group, an ester group, a sulfide group and the like.

Examples of the compound (s1) in the case of p=1 include ethylene trimethoxy decane, ethylene triethoxy decane, ethylene tripropoxy decane, o-styrene trimethoxy decane, and o-styrene triethyl ethane. Oxy decane, m-styrene trimethoxy decane, m-styrene triethoxy decane, p-styrene trimethoxy decane, p-styrene triethoxy decane, allyl trimethoxy decane, allyl tri Ethoxy decane, methacryl oxime trimethoxy decane, methacryl oxime triethoxy decane, methacryl oxiranium tripropoxy decane, propylene oxime trimethoxy decane, propylene oxime triethoxy Base decane, propylene oxime tripropoxy decane, 2-methyl propylene oxiranyl trimethoxy decane, 2-methyl propylene oxiranyl triethoxy decane, 2-methyl propylene oxirane ethyl Propoxy oxane, 3-methacryl oxime propyl trimethoxy decane, 3-methyl propylene oxypropyl triethoxy decane, 3-methyl propylene oxypropyl tripropoxy decane, 2-propene Oxyxyethyltrimethoxydecane, 2-propenyloxyethyltriethoxydecane, 2-propenyloxyethyltripropoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, 3-propenyloxypropyltripropoxydecane, 3-methylpropenyloxypropyltrimethoxydecane , 3-methacryloxypropyltriethoxydecane, 3-methacryloxypropyltripropoxydecane, trifluoropropyltrimethoxydecane, trifluoropropyltriethoxydecane, three Fluorobutyl A trialkoxydecane compound such as trimethoxydecane or 3-(trimethoxydecane)propyl succinic anhydride.

The compound (s1) in the case of p=2 may, for example, be ethylene methyl dimethoxydecane, ethylene methyl diethoxy decane, ethylene phenyl dimethoxy decane, vinyl phenyl diethylene. a dialkoxy decane compound such as oxydecane, allylmethyldimethoxydecane, allylmethyldiethoxydecane or phenyltrifluoropropyldimethoxydecane.

The compound (s1) in the case of p = 3 may, for example, be allyldimethylmethoxydecane, allyldimethylethoxydecane, divinylmethylmethoxydecane, or the like. Ethylene methyl ethoxy decane, 3-methyl propylene oxypropyl dimethyl methoxy decane, 3- propylene oxypropyl dimethyl methoxy decane, 3-methyl propylene oxy propyl Phenylmethoxy decane, 3-propenyl propyloxypropyl diphenyl methoxy decane, 3,3'-dimethyl propylene oxypropyl dimethoxy decane, 3,3'-dipropylene oxime Propyldimethoxydecane, 3,3',3"-trimethylpropenyloxypropylmethoxydecane, 3,3',3"-tripropenyloxypropylmethoxydecane, dimethyl A monoalkoxydecane compound such as a trifluoropropyl methoxydecane.

Among these compounds (s1), ethylene trimethoxydecane, p-styrene triethoxy decane, and 3-methyl propylene oxime are preferred because they can achieve scratch resistance and the like at a high level and improve condensation reactivity. Oxypropyltrimethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltriethoxydecane, 3- (Trimethoxydecane) propyl succinic anhydride.

[compound (s2)]

In the above formula (S-2), R ¹³ is an alkyl group having 1 to 6 carbon atoms. R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, an epoxy group, an amine group or an isocyanate group. n is an integer from 0 to 20. q is an integer from 0 to 3. However, in the case where each of R ¹³ and R ¹⁴ is plural, a plurality of R ¹³ and R ¹⁴ are each independently.

The alkyl group having 1 to 6 carbon atoms of the above-mentioned R ¹³ may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a butyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of easiness of hydrolysis. From the viewpoint of the above q, from the viewpoint of the hydrolysis condensation reaction, it is preferably 1 or 2, more preferably 1.

In the case where the above R ¹⁴ is an alkyl group having 1 to 20 carbon atoms, the alkyl group thereof may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group or a secondary butyl group. , tertiary butyl, n-pentyl, 3-methylbutyl, 2-methylbutyl, 1-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 4-methylpentyl , 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl Base, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethylbutyl, n-heptyl, 5-methylhexyl, 4-methylhexyl, 3- Methylhexyl, 2-methylhexyl, 1-methylhexyl, 4,4-dimethylpentyl, 3,4-dimethylpentyl, 2,4-dimethylpentyl, 1,4- Dimethylpentyl, 3,3-dimethylpentyl, 2,3-dimethylpentyl, 1,3-dimethylpentyl, 2,2-dimethylpentyl, 1,2- Dimethylpentyl, 1,1-dimethylpentyl, 2,3,3-trimethylbutyl, 1,3,3-trimethylbutyl, 1,2,3-trimethylbutyl Base, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl, 2-methylheptyl, 1-methylheptyl, 2- Ethylhexyl, positive Base, n-decyl, n-decyl, n-dodeyl, n-tridecyl, n-tetradecyl, n-heptyl, n-hexyl, n-heptyl, n-octadecyl, n-xenyl Wait. It is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

In the case of the compound (s2) in the case of q = 0, for example, a decane compound substituted with four hydrolyzable groups, tetramethoxy decane, tetraethoxy decane, tetrabutoxy decane, and tetra are mentioned. - n-propoxy decane, tetra-isopropoxy decane, and the like.

In the case of the compound (s2) in the case of q = 1, the decane compound substituted with one non-hydrolyzable group and three hydrolyzable groups may, for example, be methyltrimethoxydecane or methyltriethyl. Oxy decane, methyl triisopropoxy decane, methyl tributoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl tri-isopropoxy decane, ethyl tributoxy Decane, butyltrimethoxydecane, phenyltrimethoxydecane, tolyltrimethoxydecane, naphthyltrimethoxydecane,phenyltriethoxydecane,naphthyltriethoxydecane,aminotrimethoxy Base decane, aminotriethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy, γ-glycidoxypropyltrimethoxydecane, 3-isocyanopropyltrimethoxy Basear, 3-isocyanopropyltriethoxydecane, o-tolyltrimethoxydecane, m-tolyltrimethoxydecane, p-tolyltrimethoxydecane, and the like.

In the case of the compound (s2) in the case of q=2, as the decane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups, for example, dimethyldimethoxydecane or diphenyl is exemplified. Dimethoxy decane, xylyl dimethoxy decane, dibutyl dimethoxy decane, and the like.

In the case of the compound (s2) in the case of q = 3, the decane compound substituted with three non-hydrolyzable groups and one hydrolyzable group may, for example, be trimethylmethoxydecane or triphenyl. Methoxy decane, top three Phenylmethoxydecane, tributylmethoxydecane, and the like.

In the compound (s2), a decane compound substituted with four hydrolyzable groups and a decane compound substituted with one non-hydrolyzable group and three hydrolyzable groups are more preferable, and one non-non- A decane compound substituted with a hydrolyzable group and three hydrolyzable groups. Examples of the particularly preferred hydrolyzable decane compound include tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, methyl tri-isopropoxy decane, and methyl tributoxy decane. , phenyl trimethoxy decane, tolyl trimethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl triisopropoxy decane, ethyl tributoxy decane, butyl trimethoxy Basear, gamma-glycidoxypropyltrimethoxydecane, naphthyltrimethoxydecane, gamma-aminopropyltrimethoxydecane, and gamma-isocyanatepropyltrimethoxydecane. These hydrolyzable decane compounds may be used singly or in combination of two or more.

The compound (s1) is preferably more than 5 mol% in terms of the mixing ratio of the above compound (s1) and the compound (s2). When the compound (s1) is 5 mol% or less, the exposure sensitivity when forming a protective film as a cured film is low, and the abrasion resistance of the obtained protective film tends to be lowered.

[Hydrolysis condensation of compound (s1) and compound (s2)]

The conditions for the hydrolysis and condensation of the above compound (s1) and the compound (s2) are as long as at least a part of the compound (s1) and the compound (s2) are hydrolyzed, and the hydrolyzable group is converted into a sterol group, and is produced. The condensation reaction is not particularly limited, and an example is carried out as follows.

In the case of the water to be subjected to the hydrolysis condensation reaction, water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment, or distillation is preferably used. By using such refined water, side reactions can be suppressed, and Increase the reactivity of hydrolysis. In terms of the amount of water used, the total amount of the hydrolyzable groups of the above compound (s1) and the compound (s2) is 1 mole, preferably 0.1 mole to 3 moles, more preferably 0.3 mole to 2 moles. Ears, especially from 0.5 to 1.5 moles. By using such an amount of water, the reaction rate of hydrolysis condensation can be optimized.

Examples of the solvent to be hydrolyzed and condensed include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, and propylene glycol monoalkyl ether acetates. Ester, propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, other esters, and the like. These solvents may be used alone or in combination of two or more.

Among these solvents, preferred are ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, butyl methoxyacetate, and particularly preferably diethyl ethane. Alcohol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl methoxyacetate.

The hydrolysis condensation reaction is preferably carried out in an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resin, various Lewis acids, etc.); Medium (for example, ammonia, primary amines, secondary amines, tertiary amines, nitrogen compounds such as pyridine; basic ion exchange resins; hydroxides such as sodium hydroxide; carbonates such as potassium carbonate; sodium acetate It is carried out in the presence of a catalyst such as a carboxylate; various Lewis bases or the like or an alkoxide (for example, zirconium alkoxide, alkoxytitanium or alkoxyaluminum). For example, in the case of alkoxy aluminum, triisopropoxide can be used. In terms of the amount of the catalyst to be used, from the viewpoint of promoting the hydrolysis condensation reaction, the monomer of the 1 mol hydrolyzable decane compound is preferably 0.2 mol. Below the ear, it is preferably from 0.00001 to 0.1 mol.

The weight average molecular weight (hereinafter referred to as "Mw") of the converted polystyrene by GPC (gel permeation chromatography) of the above hydrolysis-condensation product is preferably from 500 to 10,000, more preferably from 1,000 to 5,000. By setting Mw to 500 or more, the film forming property of the radiation sensitive resin composition of the present embodiment can be improved. On the other hand, by setting Mw to 10000 or less, it is possible to prevent deterioration in developability of the radiation sensitive resin composition.

The number average molecular weight of the polystyrene (hereinafter referred to as "Mn") in terms of GPC of the above hydrolysis-condensation product is preferably from 300 to 5,000, more preferably from 500 to 3,000. By setting the Mn of the polyoxyalkylene to the above range, the curing reactivity at the time of curing of the coating film of the radiation-sensitive resin composition of the present embodiment can be improved.

The molecular weight distribution "Mw/Mn" of the hydrolysis-condensation product is preferably 3.0 or less, more preferably 2.6 or less. By setting the Mw/Mn of the hydrolysis condensate of the compound (s1) and the compound (s2) to 3.0 or less, the developability of the obtained protective film can be improved. The radiation-sensitive linear resin composition containing polyoxyalkylene has little occurrence of development residue during development, and can easily form a desired pattern shape.

[Novolak resin]

As the resin which can be used in the radiation-sensitive resin composition of the present embodiment, a preferred novolac resin is obtained by polycondensing a phenol with an aldehyde such as formalin by a known method.

The phenol which is a preferred novolac resin in the present embodiment may, for example, be a phenol or a pair. Phenol, room Phenol, o-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5- Xylenol, 2,3,4-trimethyl phenol, 2,3,5-trimethyl phenol, 3,4,5-trimethyl phenol, 2,4,5-trimethyl phenol, methylene bisphenol, methylene double pair Phenol, resorcinol, catechol, 2-methyl resorcinol, 4-methyl resorcinol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, Methoxyphen, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-cresol, p-acetol, 2,3-diethylphenol, 2,5-diethylphenol, p-propofol, α-naphthalene Phenol, β-naphthol and the like. These may also be used in two or more types.

Further, in the present embodiment, examples of the aldehyde to obtain a preferred novolac resin include formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like in addition to formalin. These may also be used in two or more types.

The preferred weight average molecular weight of the novolac resin of the resin used in the radiation sensitive resin composition of the present embodiment is 2,000 to 50,000, more preferably 3,000 to 30,000 in terms of GPC (gel permeation chromatography). 40000.

[醌 叠 azide compound]

The radiation sensitive resin composition of the present embodiment contains a quinonediazide compound as an essential component together with the above resin. Thereby, the radiation sensitive resin composition of the present embodiment can be used as a positive radiation sensitive resin composition. Next, the light shielding property of the protective film after formation can be provided. Further, the transparency of the formed protective film can be adjusted by photofading performance.

The quinonediazide compound is a quinonediazide compound of a carboxylic acid generated by irradiation of radiation. In the case of a quinonediazide compound, a phenolic compound or an alcoholic compound (hereinafter referred to as "mother core") and 1,2- can be used. a condensate of naphthoquinonediazidesulfonic acid halide.

Examples of the above-mentioned mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydrohydroxybenzophenone, (polyhydroxyphenyl)alkane, and other parent cores.

Examples of the trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone and the like.

Examples of the tetrahydroxybenzophenone include 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4. '-Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone Wait.

The pentahydroxybenzophenone may, for example, be 2,3,4,2',6'-pentahydroxybenzophenone or the like.

Examples of hexahydrodihydroxybenzophenone include 2,4,6,3',4',5'-hexahydrohydroxybenzophenone, 3,4,5,3',4',5'- Hexahydrohydroxybenzophenone and the like.

Examples of the (polyhydroxyphenyl)alkane include bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, ginseng(p-hydroxyphenyl)methane, 1,1. 1-paran (p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1, 3-paraxyl (2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-{4-(1-[4-hydroxyphenyl]-1-methyl Ethylethyl)phenyl}ethylidene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl -1,1'-helical biguanide-5,6,7,5',6',7'-hexanol, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan (fravane) and so on.

For other parent cores, for example, 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxy Chromium, 1-[1-{3-(1-[4-hydroxyphenyl]-1-methylethyl)-4,6-dihydroxyphenyl}-1-methylethyl]- 3-[1-{3-(1-[4-Hydroxyphenyl]-1-methylethyl)-4,6-dihydroxyphenyl}-1-methylethyl]benzene, 4,6- Bis{1-(4-hydroxyphenyl)-1-methylethyl}-1,3-dihydroxybenzene and the like.

Among these cores, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-paraxyl (p-hydroxyphenyl)ethane, 4,4'-[1-{4 can be suitably used. -(1-[4-Hydroxyphenyl]-1-methylethyl)phenyl}ethylidene]bisphenol.

In the case of 1,2-naphthoquinonediazidesulfonic acid halide, 1,2-naphthoquinonediazidesulfonium chloride is preferred. Examples of the 1,2-naphthoquinonediazidesulfonium chloride include 1,2-naphthoquinonediazide-4-sulfonyl chloride and 1,2-naphthoquinonediazide-5-sulfonyl chloride. Wait. Among these, 1,2-naphthoquinonediazide-5-sulfonyl chloride is more preferable.

In the condensation reaction of a phenolic compound or an alcoholic compound (nuclear core) with a 1,2-naphthoquinonediazidesulfonic acid halide, the number of OH groups in the phenolic compound or the alcoholic compound is preferably 30 moles. From % to 85 mol%, more preferably from 1,50 nath to 70 mol% of 1,2-naphthoquinonediazidesulfonic acid halide. The condensation reaction can be carried out by a known method.

Further, in the case of the quinonediazide compound, the 1,2-naphthoquinonediazidesulfonate oxime amine having the ester bond of the above-exemplified nucleus is changed to a guanamine bond, and for example, 2, 3 may be suitably used. 4-Triaminobenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid decylamine and the like.

These quinonediazide compounds may be used singly or in combination of two or more. The use ratio of the quinonediazide compound in the radiation sensitive resin composition of the present embodiment is preferably 5 parts by mass to 100 parts by mass, more preferably 10 parts by mass to 50 parts by mass, per 100 parts by mass of the resin. By making the use ratio of the quinonediazide compound in the above range, The difference in solubility between the irradiated portion and the unirradiated portion of the radiation serving as the aqueous alkali solution of the developer is increased, and the patterning performance can be improved. Further, the solvent resistance of the protective film obtained by using the radiation-sensitive resin composition can be improved.

[Other ingredients]

The radiation sensitive resin composition of the present embodiment contains a resin and a quinonediazide compound as essential components, and may contain a curing accelerator, a thermal acid generator, or other optional components.

The curing accelerator is a compound which promotes the function of curing the film by the radiation-sensitive resin composition of the present embodiment.

The thermal acid generator releases a compound which acts as an acidic active material of a catalyst when the resin is hardened by application of heat.

The radiation-sensitive resin composition of the present embodiment may contain other optional components such as a surfactant, a storage stabilizer, a binding aid, and a heat resistance improving agent, as needed, without departing from the effects of the present invention. These optional components may be used singly or in combination of two or more.

<Modulation method of radiation sensitive resin composition>

The radiation sensitive resin composition of the present embodiment is prepared by uniformly mixing a resin and a quinonediazide compound. Further, in the case where a curing accelerator, a thermal acid generator, or other optional component which can be added as needed is contained, it is prepared by uniformly mixing a resin and a quinonediazide compound with the components. The radiation sensitive resin composition is preferably dissolved in a suitable solvent and used in the form of a solution. The solvent may be used singly or in combination of two or more.

The solvent used for the preparation of the radiation sensitive resin composition of the present embodiment is a product obtained by uniformly dissolving an essential component and an optional component and not reacting with each component. Examples of such a solvent include an alcohol, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol monoalkyl ether, a diethylene glycol dialkyl ether, a dipropylene glycol dialkyl ether, and a propylene glycol monoalkane. Ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone, ester, and the like.

The content of the solvent is not particularly limited, and it is preferable that the total concentration of each component of the solvent for removing the radiation sensitive resin composition is 5% by mass from the viewpoint of coatability and stability of the radiation sensitive resin composition. The amount to 50% by mass is more preferably 10% by mass to 40% by mass. In the case of modulating the solution of the radiation-sensitive resin composition, it is possible to set a solid content concentration (a component other than the solvent in the composition solution) in accordance with the value of the desired film thickness in the above-mentioned concentration range.

The solution-like composition thus prepared is preferably used in the formation of the protective film of the present embodiment after filtration using a micropore filter having a pore diameter of about 0.5 μm or the like.

<Method of Forming Protective Film>

In the protective film of the semiconductor device of the present embodiment, the radiation sensitive resin composition of the present embodiment is applied to a substrate on which a gate electrode, a gate insulating film, and a semiconductor layer are formed, and a through hole is formed. After patterning, it is formed by heat curing. The protective film formed is preferably composed of a quinonediazide compound, and has a light-shielding property in this case.

The method of forming the protective film will be described in more detail below.

In the formation of the protective film of the semiconductor device of the present embodiment, first, the coating film of the radiation sensitive resin composition of the present embodiment is formed on the substrate. On the substrate, a gate electrode, a gate insulating film, a semiconductor layer, and the like are formed in accordance with a known method. For example, in the semiconductor layer or the like, the semiconductor film formation and the photolithography method are repeatedly formed on the substrate in accordance with the method described in Patent Document 1 or the like.

On the substrate, the radiation-sensitive resin composition of the present embodiment is applied onto the surface on which the semiconductor layer or the like is formed, and then pre-baked to evaporate the solvent to form a coating film.

In the coating method of the radiation sensitive resin composition, for example, a spray method, a roll coating method, a spin coating method (also referred to as a spin coating method or a spinner method), or a slit coating method (slit die coating) may be employed. A suitable method such as a method of coating, a bar coating method, or an inkjet coating method. Among these, from the viewpoint of forming a film having a uniform thickness, a spin coating method or a slit coating method is preferred.

The prebaking conditions differ depending on the type of the component constituting the radiation sensitive resin composition, the blending ratio, and the like, but it is preferably carried out at a temperature of 70 ° C to 120 ° C for a period of time due to heating of a hot plate or an oven. The device varies, and is approximately 1 minute to 15 minutes.

Next, at least a part of the coating film formed as described above is irradiated with radiation. At this time, it is necessary to irradiate only a part of the coating film via the pattern mask, which corresponds to, for example, formation of a desired through hole and formation of a desired shape.

For the radiation used for irradiation, visible light can be cited. Line, ultraviolet light, far ultraviolet light, etc. Among them, radiation having a wavelength in the range of 200 nm to 550 nm is preferable, and radiation containing ultraviolet rays of 365 nm is more preferable.

The amount of radiation (exposure amount), which is measured by an illuminance meter (manufactured by OAI model 356, manufactured by Optical Associates Inc.) at a wavelength of 365 nm of the radiation, can be set to 10 J/m ² to 10000 J/m ² . It is preferably 100J / m ² to 5000J / m ^2, more preferably 200J / m ² to 3000J / m ^2.

Thereafter, the coating film after the radiation irradiation is developed to remove unnecessary portions, and a coating film having a through hole having a predetermined shape is obtained.

For the developer to be used for development, an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate or the like or a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide or choline may be used; An aqueous solution of a basic compound such as 8-diazabicyclo-[5.4.0]-7-undecene or 1,5-diazabicyclo-[4.3.0]-5-nonene. An aqueous solution of the above basic compound may be added in an appropriate amount to a water-soluble organic solvent such as methanol or ethanol. Further, the surfactant may be added in an appropriate amount or in combination with the addition of the above-mentioned water-soluble organic solvent.

The developing method may be any one of a liquid-filling method, a dipping method, a rinsing method, and a spraying method, and the developing time may be set at a normal temperature for 5 seconds to 300 seconds, preferably at a normal temperature of 10 seconds to 180 seconds. The subsequent development process, for example, after 30 seconds to 90 seconds of running water washing, is dried by compressed air or compressed nitrogen to obtain a desired pattern.

Next, the coating film having the through holes formed in a predetermined shape is hardened by a suitable heating means such as a hot plate or an oven (also referred to as post-bake drying). grilled). Thereby, the protective film of this embodiment as a cured film can be obtained. The thickness of the insulating film of the protective film is preferably from 10 nm to 1000 nm. In the protective film, a through hole disposed at a desired position is formed as described above.

According to the radiation sensitive resin composition of the present embodiment, the setting hardening temperature is preferably from 100 ° C to 250 ° C, and the curing temperature can be set to 200 ° C or lower by the effect of the hardening accelerator added or the like. The hardening time is preferably, for example, 5 minutes to 30 minutes on the hot plate, and 30 minutes to 180 minutes in the oven.

After the protective film of the present embodiment is formed, the source electrode and the germanium electrode are formed on the protective film in accordance with a known method, whereby the semiconductor device of the present embodiment can be manufactured. The source electrode and the ruthenium electrode can be formed by a method such as a sputtering method, a CVD method, or a vapor deposition method, in addition to a printing method or a coating method, in accordance with a known method. Patterning by light lithography or the like is formed.

Embodiment 2.

<Semiconductor substrate>

Fig. 2 is a plan view showing a schematic configuration of an important part of a semiconductor substrate of the present embodiment.

As shown in FIG. 2, in the semiconductor substrate 21 of the present embodiment, the data wiring 23 and the gate wiring 24 are arranged in an array on the substrate 22. The semiconductor element 1 of the above-described embodiment is disposed in the vicinity of the intersection of the data line 23 and the gate line 24. The source electrode (not shown in FIG. 2) of the semiconductor element 1 is connected to the data line 23, and the gate electrode 11 is connected to Brake wiring 24. In this way, each pixel divided on the semiconductor substrate 21 is formed. The semiconductor substrate 21 of the present embodiment is a display element such as a liquid crystal display element The composition is suitable.

The material of the substrate 22 may, for example, be a glass substrate such as soda lime glass or alkali-free glass, or ruthenium, polyethylene terephthalate, polybutylene terephthalate or polyether oxime. A resin substrate such as polycarbonate, aromatic polyamine, polyamidimide or polyimine. Further, in the substrates, pretreatment such as drug treatment, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum vapor deposition or the like is performed in advance as desired.

In the semiconductor substrate 21 of the present embodiment, the data wiring 23 is electrically connected to the source electrode of the semiconductor element 1, and the pixel electrode 25 is electrically connected to the germanium electrode (not shown in FIG. 2) of the semiconductor element 1. . Further, the data wiring 23 can also serve as a source electrode, and the pixel electrode 25 can also serve as a germanium electrode.

Next, when the scan signal is supplied to the gate wiring 24 in the semiconductor substrate 21 of the present embodiment, the semiconductor element 1 is on. The image signal from the data wiring 23 is supplied to the pixel electrode 25 via the on-via semiconductor element 1. Here, the gate wirings 24 are arranged side by side in the vertical direction in FIG. 2, and the data wirings 23 are arranged side by side in the left-right direction in FIG. Next, the pixel electrode 25 having a desired shape is disposed in a region (pixel) surrounded by the adjacent gate wiring 24 and the adjacent one of the pair of data wirings 23. Further, although the shape of the pixel electrode 25 shown in Fig. 2 is a solid plate shape, as will be described later, in the case where the display element of the present embodiment is a liquid crystal display element of the IPS mode or the FFS mode, it can be made into a pattern. Sinking comb, etc.

Embodiment 3.

<Liquid crystal display element>

Fig. 3 is a schematic cross-sectional view showing the structure of an important part of a liquid crystal display element of the present embodiment.

The liquid crystal display element 100 shown in Fig. 3 of the display device is an active matrix type TN (Twisted Nematic) mode color liquid crystal display device comprising the semiconductor substrate 21 of the above-described embodiment.

The liquid crystal display element 100 has a structure in which the semiconductor substrate 21 having the semiconductor element 1 and the color filter substrate 30 on which the color filter 40 is formed are opposed to each other via a liquid crystal 43 of a nematic phase which is twisted by 90°.

As shown in FIG. 3, on the semiconductor substrate 21, the semiconductor element 1 of the present embodiment and the transparent pixel electrode including ITO are provided on the side of the semiconductor substrate 21 in contact with the liquid crystal 43 of the transparent substrate 22 (not shown in FIG. 3). They are arranged in an array and constitute each pixel. Next, on the surface in contact with the liquid crystal 43 of the semiconductor substrate 21, an alignment film 42 for controlling the alignment of the liquid crystals 43 is provided.

In the color filter substrate 30, a colored pattern 36 or the like is disposed on the side in contact with the liquid crystal 43 of the transparent substrate 45, and the color filter 40 is formed. The color filter 40 has a red, green, and blue colored pattern 36 disposed in the pixel region and a black matrix 37 surrounding the patterns. The color filter substrate 30 has a protective layer 38 on the colored pattern 36 of the color filter 40. Next, the color filter substrate 30 has a transparent common electrode 41 including ITO and an alignment film 42 for controlling the alignment of the liquid crystal 43 on the protective layer 38.

An alignment film 42 for controlling the alignment of the liquid crystals 43 is provided on each of the semiconductor substrate 21 and the color filter substrate 30 as described above. Orientation film In the case where necessary, for example, the alignment treatment such as the polishing treatment or the optical alignment treatment by the polarized light irradiation is performed, and the uniform alignment of the liquid crystals 43 sandwiched between the semiconductor substrate 21 and the color filter substrate 30 is realized.

The polarizing plate 44 is disposed on the opposite side of the semiconductor substrate 21 and the color filter substrate 30 on the side in contact with the liquid crystal 43. The distance between the semiconductor substrate 21 and the color filter substrate 30 is preferably 2 μm to 10 μm, and these are fixed to each other by the sealing material 46 provided on the peripheral portion.

In Fig. 3, reference numeral 47 is a backlight from a backlight unit (not shown) that is directed toward the liquid crystal 43. As the backlight unit, a structure in which a fluorescent tube such as a Cold Cathode Fluorescent Lamp (CCFL) and a diffusion plate are combined can be used. Further, a backlight unit using a white LED as a light source can also be used. In the case of a white LED, for example, a combination of a red LED, a green LED, and a blue LED, a white LED that obtains white light in a mixed color, a combination of a blue LED, a red LED, and a green phosphor, and a white color in a mixed color White LED; combine blue LED, red illuminating phosphor and green illuminating phosphor, obtain white LED with white light in mixed color; obtain white white light with mixed color of blue LED and YAG fluorescent body LED; combined blue LED, orange illuminating phosphor, green illuminating phosphor, white LED with white color in combination; combined ultraviolet LED, red illuminating phosphor, green luminescent phosphor, and blue illuminating illuminating The light body obtains a white light white LED or the like in a mixed color.

The liquid crystal display element 100 of the present embodiment may be an STN (Super Twisted) in addition to the TN mode described above. Nematic)) mode, IPS (In-Planes Switching) mode, FFS (Fringe Field Switching) mode, VA (Vertical Alignment) mode or OCB (optical compensation birefringence) Optically Compensated Birefringence)) LCD mode such as mode.

The semiconductor element of the semiconductor substrate of the liquid crystal display device of the present embodiment has the protective film of the present embodiment between the semiconductor layer, the source electrode, and the germanium electrode, and the effect is that the semiconductor layer can be shielded from light. Therefore, the semiconductor element of the liquid crystal display element of the present embodiment can reduce the characteristics due to the influence of light. As a result, the liquid crystal display element of the present embodiment can suppress deterioration in display quality due to the influence of light.

[Examples]

The embodiments of the present invention are described in detail below based on the embodiments, but the invention is not limited by the examples.

<Modulation of Radiation-Linear Resin Composition>

Synthesis Example 1

[Synthesis of Resin (α-I)]

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ether were charged. Next, 13 parts by mass of methacrylic acid, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of α-methyl-p-hydroxystyrene, 10 parts by mass of styrene, and 12 parts by mass of tetrahydroanthracene methacrylate were charged. Ester, 15 parts by mass of N-cyclohexylmethyleneimine and 10 parts by mass of n-lauryl methacrylate, after being substituted by nitrogen, while slowly stirring, the temperature of the solution is raised to The temperature was maintained at 70 ° C for 5 hours, and polymerization was carried out to obtain a solution containing a resin (α-I) as a copolymer. The resin of the copolymer (α-I) has a Mw of 8,000.

Synthesis Example 2

[Synthesis of Resin (α-II)]

Under dry nitrogen flow, 29.30 g (0.08 mol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane (Central Glass), 1.24 g (0.005 mol) of 1,3-double (3) -aminopropyl)tetramethyldioxane, 3.27 g (0.03 mol) of 3-aminophenol (Tokyo Chemical Industry Co., Ltd.) as a terminal blocking agent, dissolved in 80 g of N-methyl-2-pyrrolidine Ketone (hereinafter referred to as NMP). Here, 31.2 g (0.1 mol) of bis(3,4-dicarboxyphenyl)ether dianhydride (Manac) was added together with 20 g of NMP, and reacted at 20 ° C for 1 hour, followed by reaction at 50 ° C. 4 hours. Thereafter, 15 g of xylene was added, and water was azeotroped together with xylene while stirring at 150 ° C for 5 hours. After the completion of the stirring, the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C for 20 hours to obtain a polymer resin (α-II) having a structure represented by the following formula.

Synthesis Example 3

[Synthesis of Resin (α-III)]

In a container with a stirrer, 20 parts by mass of propylene glycol monomethyl ether was charged, followed by 70 parts by mass of methyltrimethoxydecane, and 30 masses. The toluene trimethoxy decane was heated to a solution temperature of 60 °C. After the solution temperature reached 60 ° C, 0.15 parts by mass of phosphoric acid, 19 parts by mass of ion-exchanged water was charged, and the mixture was heated to 75 ° C for 4 hours. Further, by setting the solution temperature to 40 ° C and evaporating while maintaining the temperature, methanol which is generated by ion exchange water and hydrolysis condensation can be removed. From the above, a resin (α-III) which is a siloxane polymer which is a hydrolysis condensate is obtained. The Mw of the siloxane polymer (α-III) has a Mw of 5,000.

Example 1

[Modulation of Radiation-Linear Resin Composition (β-I)]

A solution containing the resin (α-I) of Synthesis Example 1 (corresponding to 100 parts by mass (solid content) copolymer), and 30 parts by mass of 4,4'-[1-{ as a quinonediazide compound 4-(1-[4-hydroxyphenyl]-1-methylethyl)phenyl}ethylidene]bisphenol (1.0 mol), and 2 parts by mass of benzyl-4- as a thermal acid generator The hydroxyphenylmethyl sulfonium hexafluorophosphate was mixed, dissolved in diethylene glycol ethyl methyl ether, and filtered through a membrane filter having a diameter of 0.2 μm to prepare a radiation sensitive resin composition (β-I).

Example 2

[Modulation of Radiation-Linear Resin Composition (β-II)]

In 8 g of the resin (α-II) of Synthesis Example 2, 2 g of a novolac resin (trade name, XPS-4958G, and the like) was added. Phenol/pair Phenol ratio = 55/45 (weight ratio), Qunrong Chemical Industry Co., Ltd.). Further, as a thermally crosslinkable compound which undergoes a crosslinking reaction by heat, 2.4 g of a compound represented by the following formula (β1) and 0.6 g of a compound represented by the following formula (β2) are added, and 2 g of quinone is added. The nitrogen compound (β3) was dissolved in γ-butyrolactone as a solvent, and then filtered through a membrane filter having a diameter of 0.2 μm to prepare a radiation sensitive resin composition (β-II).

Example 3

[Modulation of radiation sensitive resin composition (β-III)]

In the solution containing the oxirane polymer-containing resin (α-III) obtained in Synthesis Example 3 (corresponding to 100 parts by mass of the amount of the siloxane polymer (solid content)), 12 parts by mass was added as the bismuth stack. 4,4'-[1-{4-(1-[4-hydroxyphenyl]-1-methylethyl)phenyl}ethylidene]bisphenol (1.0 mol) and 1,2 as a nitrogen compound a condensate of naphthoquinonediazide-5-sulfonyl chloride (3.0 mol), and 0.1 part by mass of a fluorine-type surfactant (FTX-218, manufactured by Neos) as a surfactant, and adding propylene glycol monomethyl The radiation-sensitive linear resin composition (β-III) was prepared by setting the solid content to 25% by mass.

<Formation and Evaluation of Protective Film>

Example 4

[Protective film formed from a radiation sensitive resin composition (β-I)]

On the alkali-free glass substrate, the radiation-sensitive resin composition (β-I) prepared in Example 1 was applied by a spinner, and then pre-baked on a hot plate at 90 ° C for 2 minutes to form a coating film. Next, the obtained coating film was irradiated with a high-pressure mercury lamp at an exposure amount of 700 J/m ² , and developed at a temperature of 25° C. for 60 seconds with a 0.4% by mass aqueous solution of tetramethylammonium hydroxide. Next, in the oven, a protective film was formed by post-baking at a hardening temperature of 230 ° C and a hardening time of 30 minutes.

Example 5

[Protective film formed from a radiation sensitive resin composition (β-II)]

On the alkali-free glass substrate, the radiation-sensitive resin composition (β-II) prepared in Example 2 was applied by a spinner, and then pre-baked on a hot plate at 90 ° C for 2 minutes to form a coating film. Next, the obtained coating film was irradiated with a high-pressure mercury lamp at an exposure amount of 1000 J/m ² , and developed at a temperature of 25° C. for 150 seconds with a 0.4% by mass aqueous solution of tetramethylammonium hydroxide. Next, post-baking was performed in an oven at a hardening temperature of 230 ° C and a hardening time of 30 minutes to form a protective film.

Example 6

[Protective film formed from a radiation sensitive resin composition (β-III)]

On the alkali-free glass substrate, the radiation-sensitive resin composition (β-III) prepared in Example 3 was coated with a spinner, and then pre-baked on a hot plate at 100 ° C for 2 minutes to form a coating film. Next, a high-pressure mercury lamp was used for the obtained coating film, and the radiation was irradiated at an exposure amount of 800 J/m ² , and developed at a temperature of 25° C. for 80 seconds with a 0.4% by mass aqueous solution of tetramethylammonium hydroxide. Next, a protective film was formed by post-baking in a baking oven at a hardening temperature of 230 ° C and a hardening time of 30 minutes.

Example 7

[Evaluation of heat resistance]

The protective film of the formation method of Example 4 was further heated in an oven at 230 ° C for 20 minutes, and the film thickness before and after the heating was measured by a stylus type film thickness measuring machine (Alpha-Step IQ, KLA Tencor Co., Ltd.). . Next, the residual film ratio (film thickness after treatment/film thickness before treatment × 100) was calculated, and the residual film ratio was taken as heat resistance. The residual film ratio was 99%, and it was judged that the heat resistance was good.

Similarly, the protective film of the formation method of Example 5 was further heated in an oven at 230 ° C for 20 minutes, and the film thickness before and after the heating was measured by a thimble type film thickness measuring machine (Alpha-step IQ, KLATencor Co., Ltd. ) Determination. Next, the residual film ratio (film thickness after treatment/film thickness before treatment × 100) was calculated, and the residual film ratio was taken as heat resistance. The residual film ratio was 99%, and it was judged that the heat resistance was good.

Similarly, the protective film of the formation method of Example 6 was further heated in an oven at 230 ° C for 20 minutes, and the film thickness before and after the heating was measured by a thimble type film thickness measuring machine (Alpha-step IQ, KLA Tencor Co., Ltd. ) Determination. Next, the residual film ratio (film thickness after treatment/film thickness before treatment × 100) was calculated, and the residual film ratio was taken as heat resistance. The residual film ratio was 99%, and it was judged that the heat resistance was good.

Example 8

[Evaluation of light resistance]

In the protective film of the method of the present invention, a UV irradiation device (UVX-02516S1JS01, Ushio Co., Ltd.) was further irradiated with ultraviolet light of 800,000 J/m ² at an illuminance of 130 mW, and the amount of film thinning after the irradiation was examined. The film thinning amount was 2% or less, and it was judged that the light resistance was good.

In the same manner, the protective film of the formation method of Example 5 was further irradiated with ultraviolet light of 800,000 J/m ² at an illumination of 130 mW using a UV irradiation device (UVX-02516S1JS01, Ushio Co., Ltd.) to investigate the film thinning amount after the irradiation. The film thinning amount was 2% or less, and it was judged that the light resistance was good.

In the same manner as the protective film of the formation method of Example 6, a UV irradiation device (UVX-02516S1JS01, Ushio Co., Ltd.) was further irradiated with ultraviolet light of 800,000 J/m ² at an illuminance of 130 mW, and the amount of film thinning after the irradiation was examined. The film thinning amount was 2% or less, and it was judged that the light resistance was good.

<Manufacture of liquid crystal display element>

Example 9

Using the radiation sensitive resin composition (β-I) obtained in Example 1, a gate electrode and a gate insulating film were formed in accordance with a known method, and a substrate including a semiconductor layer of indium gallium zinc oxide (IGZO) was disposed thereon. Top, coated with a slot coater. The semiconductor layer on the substrate is formed by a method known in the art by forming a film of a semiconductor film by a method described in JP-A-2007-115902, followed by etching by repeated photolithography.

Thereafter, in the formation method of Example 4, a protective film having a through hole formed by patterning was formed on the semiconductor layer on the substrate.

Thereafter, an electrode such as a source electrode or a germanium electrode is formed on the protective film having the through hole according to a known method, and data wiring and gate matching are formed. After wiring such as a line, the pixel electrode is patterned and reformed to fabricate a semiconductor substrate. This semiconductor substrate has the same structure as the semiconductor substrate 21 shown in Fig. 2 described above. Therefore, the semiconductor element having the same structure as the semiconductor element 1 shown in Fig. 1 described above is provided.

Next, a color filter substrate manufactured by a known method is prepared. The color filter substrate is formed on a transparent substrate, and a minute color pattern of three colors of red, green, and blue and a black matrix are arranged in a lattice shape. Next, a transparent common electrode including ITO is formed on the protective layer.

Thereafter, a photoalignment film is formed on the obtained semiconductor substrate and the color filter substrate by using a liquid crystal alignment agent containing a photo-alignment-based radiation-sensitive polymer. In the method for forming a photo-alignment film, a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group is a liquid crystal alignment agent described in Example 6 of WO 2009/025386. A-1 was coated on each substrate with a spinner. Subsequently, the film was prebaked in a hot plate at 80 ° C for 1 minute, and then heated at 180 ° C for 1 hour in an oven substituted with nitrogen to form a coating film having a film thickness of 80 nm. Next, on the surface of the coating film, a Hg-Xe lamp and a glan-taylor prism were used, and a bright line of 313 nm was irradiated from a direction inclined by 40° with respect to the surface of the substrate in a vertical direction. The polarized ultraviolet light was 200 J/m ² , and a semiconductor substrate having a photoalignment film and a color filter substrate were produced.

The liquid crystal layer is sandwiched by the obtained semiconductor substrate with the photoalignment film and the color filter substrate, and a color liquid crystal display element is produced. In the case of the liquid crystal layer, it is composed of nematic liquid crystals, and the accompanying phase The substrate surface has a very small inclination and is approximately parallel-aligned. The liquid crystal display element has the same structure as the liquid crystal display element as shown in Fig. 3 described above. Then, even when light such as ultraviolet rays is irradiated, there is no decrease in operational characteristics, and excellent display characteristics are exhibited.

Example 10

The photosensitive resin composition (β-II) obtained in Example 2 was used, and the semiconductor layer on the substrate was patterned to form a protective film having a through hole by the formation method of Example 5. Others were the same as in the above-described Embodiment 9, and a color liquid crystal display element was produced. This liquid crystal display element has the same structure as the liquid crystal display element 100 shown in Fig. 3 described above. Then, even if light such as ultraviolet rays is irradiated, the operation characteristics are not lowered, and excellent display characteristics are exhibited.

Example 11

The photosensitive resin composition (β-III) obtained in Example 3 was used, and the semiconductor layer on the substrate was patterned to form a protective film having a through hole by the formation method of Example 6. Others were the same as in the above-described Embodiment 9, and a color liquid crystal display element was produced. This liquid crystal display element has the same structure as the liquid crystal display element 100 shown in Fig. 3 described above. Then, even when light such as ultraviolet rays is irradiated, there is no decrease in operational characteristics, and excellent display characteristics are exhibited.

The present invention is not limited to the embodiments described above, and various modifications can be made without departing from the spirit and scope of the invention.

[Industrial availability]

The semiconductor component of the present invention is used in the sense of the present invention. The radiation-sensitive resin composition is formed into a protective film or the like, whereby it can be produced by a low-temperature heat treatment, and has excellent mobility characteristics and light resistance. Therefore, it is suitable to form a resin substrate or the like which is resistant to heat, and it is suitable to provide a flexible liquid crystal display element. Moreover, since it is excellent in light resistance, it is suitable for use outdoors. Therefore, the semiconductor element, the semiconductor substrate, and the display element of the present invention are suitable for use as a display element of a portable information device in addition to a large liquid crystal TV application.

1‧‧‧Semiconductor components

2‧‧‧Semiconductor layer

3‧‧‧ source electrode

4‧‧‧汲 electrode

5‧‧‧Protective film

6‧‧‧through holes

10‧‧‧Substrate

11‧‧‧ gate electrode

12‧‧‧Brake insulation film

Claims (17)

A semiconductor device comprising: a semiconductor layer and an electrode, wherein the electrode is provided on a first surface of the semiconductor layer, wherein a protective film is disposed between the semiconductor layer and the electrode, and the protective film contains a resin and a ruthenium At least one of a diazide compound and a hydrazine carboxylic acid. The semiconductor element according to claim 1, wherein the resin is one selected from the group consisting of a carboxyl group-containing acrylic resin, a polyimide resin, a polysiloxane, and a novolak resin. The semiconductor device according to claim 1, wherein the protective film is provided with a through hole, and the first surface of the semiconductor layer is connected to the electrode via the through hole. A semiconductor device according to claim 1, comprising a bottom electrode type semiconductor device: a gate electrode provided on a second surface of the semiconductor layer via a gate insulating film; and a source electrode and a germanium electrode; It is provided on the first surface. The semiconductor device according to any one of claims 1 to 4, wherein the semiconductor layer is formed using an oxide composed of at least one of indium (In), zinc (Zn), and tin (Sn). Things. The semiconductor device according to any one of claims 1 to 4, wherein the semiconductor layer uses zinc oxide (ZnO), indium gallium zinc oxide (IGZO), zinc tin oxide (ZTO), and indium zinc oxide (IZO). At least one of the formed objects. The semiconductor device according to any one of claims 1 to 4, wherein the semiconductor layer is made of bismuth (Si). A semiconductor substrate comprising: a substrate; and a plurality of gate lines and a plurality of data lines arranged on the substrate; wherein the plurality of gate lines and the plurality of data lines intersect to form a matrix of pixels Providing a semiconductor element having a semiconductor layer and an electrode provided on the first surface of the semiconductor layer, and a protective film containing a resin, a quinonediazide compound, and a ruthenium carboxylate between the semiconductor layer and the electrode At least one of the acids. The semiconductor substrate of claim 8, wherein the resin is one selected from the group consisting of a carboxyl group-containing acrylic resin, a polyimide resin, a polyoxyalkylene, and a novolak resin. The semiconductor substrate according to claim 8 is characterized in that the protective film is provided with a through hole, and the connection between the first surface of the semiconductor layer and the electrode is performed through the through hole. The semiconductor substrate of claim 8 having the following electrode to constitute a bottom gate semiconductor device: a gate electrode provided on a second surface of the semiconductor layer via a gate insulating film; a source electrode and a germanium electrode; It is provided on the first surface. The semiconductor substrate according to any one of claims 8 to 11, wherein the semiconductor layer is used in the group consisting of indium (In), zinc (Zn) and tin (Sn). An object formed by at least one of the constituent oxides. The semiconductor substrate according to any one of claims 8 to 11, wherein the semiconductor layer uses zinc oxide (ZnO), indium gallium zinc oxide (IGZO), zinc tin oxide (ZTO), and indium zinc oxide (IZO). At least one of the formed objects. The semiconductor substrate according to any one of claims 8 to 11, wherein the semiconductor layer is made of bismuth (Si). A radiation-sensitive resin composition for use in forming a protective film for a semiconductor device according to any one of claims 1 to 7, characterized by comprising a polyfluorene resin selected from the group consisting of poly(imide) a resin of alkane and novolac resin, and a quinonediazide compound. A protective film characterized by being formed of a radiation sensitive resin composition as in claim 15 of the patent application. A display element characterized by using the semiconductor element according to any one of claims 1 to 7.