JP2015049492A - Gate insulation film, radiation-sensitive resin composition, cured film, method of forming gate insulation film, semiconductor element and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gate insulation film that can be formed by application, and has excellent transparency, heat-resistant transparency, and crack resistance, provide a radiation-sensitive resin composition for forming the gate insulation film, provide a cured film and a semiconductor element, and provide a display device having the semiconductor element.SOLUTION: A TFT 3 as a semiconductor element comprises a semiconductor layer 6, a gate electrode 4 and a gate insulation film 5. The gate insulation film 5 is formed using [A] siloxane compound, and [B] radiation-sensitive resin composition comprising photopolymerization initiator of formula (2) or formula (4). The TFT 3 is used as a switching element for the configuration of a display device.

Description

  The present invention relates to a gate insulating film, a radiation-sensitive resin composition, a cured film, a method for forming a gate insulating film, a semiconductor element, and a display device.

  A display device using a liquid crystal or an organic EL (Electro Luminescence) element has a feature of being thin and having low power consumption, and is used in various fields. In particular, an active matrix display device using a thin film transistor (TFT), which is a semiconductor element for each pixel, as a switching element is capable of displaying high-definition images and has a high contrast ratio. Is excellent. Therefore, active matrix display devices are used in televisions, monitors, notebook personal computers, etc., and are also used in display devices for portable information devices such as smartphones. Yes.

  A plurality of scanning lines and a plurality of signal lines intersecting these scanning lines via an insulating film are formed on an array substrate used for an active matrix display device. A TFT serving as a switching element for switching a pixel is provided in the vicinity of the crossing portion.

In a TFT used in a conventional active matrix display device, a scanning signal line (gate line) is formed on an insulating substrate, a gate insulating film is formed thereon, a semiconductor layer is formed thereon, and a drain electrode is formed on the semiconductor layer. Data line) and a source electrode, a transparent pixel electrode is connected to the source electrode, and a video signal voltage is supplied to the drain electrode (data line). A TFT structure in which a gate electrode is first formed on a substrate is generally called an inverted stagger structure (bottom gate structure).
Note that a TFT structure in which a drain electrode, a source electrode, and a semiconductor layer are provided and then the gate electrode is superimposed on the semiconductor layer via a gate insulating film is called a positive stagger structure (top gate structure).

  Thus, in a TFT used in a conventional active matrix display device, a gate insulating film is an important component in order to ensure transistor characteristics. The performance of the gate insulating film may greatly affect the transistor characteristics of the TFT.

Conventionally, silicon oxide (SiO ₂ ), silicon nitride (SiN), or the like, which is an inorganic material, has been used for forming the gate insulating film. Among these, silicon nitride can form a dense and highly resistant film, and is a preferable material for a gate insulating film that requires high insulation.

  Conventionally, a CVD method, which is a vacuum process, has been used to form a gate insulating film using silicon nitride. The vacuum film forming process such as the CVD method has a problem that a large-scale apparatus is required and it is difficult to cope with a large substrate, and there are problems such as improvement in productivity and cost reduction.

  Therefore, there is a need for a technique that can eliminate the vacuum process in response to the demand for a large area, high definition, and high productivity of a display device using TFTs. As one of such techniques, there is a demand for a coating-type gate insulating film having superiority in film formation and cost.

  A coating-type gate insulating film is strongly required to have characteristics such as heat resistance and light transmittance in the visible light region as well as patterning properties.

  Conventionally, with regard to the formation of a coating type gate insulating film for TFT, a material for forming it has not been sufficiently studied. On the other hand, in the field of insulating films, which is a related technical field, there is a technique using a siloxane compound obtained by hydrolysis and condensation reaction of alkoxysilane as a material having heat resistance and light transmittance in the visible light region. (For example, refer to Patent Documents 1 to 3).

JP 2013-100480 A JP 2013-512994 A JP 2008-248239 A

  However, when the above-described siloxane compound, which has been studied as a material for an insulating film, is used as a coating-type gate insulating film, for example, there are the following problems.

  Semiconductor elements such as TFTs of display devices include those using oxides such as polysilicon and IGZO, but a high-temperature treatment process of about 300 ° C. to 350 ° C. is required for their production. Therefore, the coating-type gate insulating film needs to have heat resistance that can withstand a treatment at 300 ° C. to 350 ° C. In particular, after high temperature treatment at 300 ° C. to 350 ° C., it is necessary to suppress the occurrence of cracks due to curing shrinkage of the siloxane compound.

  Further, when a semiconductor element is used for a TFT for a display device or the like, a high light transmittance in a visible light region is required so as to enable high luminance display. In addition to the heat resistance described above, excellent heat-resistant transparency is required.

  Moreover, in order to prevent deterioration of the semiconductor element, low water absorption and a low outgas amount during high temperature processing are required.

  In addition, a patterning property having a high resolution is required in accordance with a layout of a highly refined semiconductor element corresponding to a higher definition of a display device, and in particular, a photolithography property is required.

  Further, adhesion to a glass substrate of a semiconductor element or a gate electrode formed using titanium, copper, aluminum, molybdenum, or the like is required.

  As described above, the coating-type gate insulating film is required to have various characteristics so that it can be applied to a semiconductor element to provide an excellent display quality display element. For example, the coating type gate insulating film described above has been studied for an insulating film. There are many problems to be solved even if a siloxane compound is applied. In particular, compatibility between transparency and patterning properties is a problem.

  The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a gate insulating film that can be formed by coating and has excellent transparency, heat-resistant transparency, and crack resistance.

  Another object of the present invention is to provide a radiation-sensitive resin composition capable of forming a pattern having high resolution and forming a gate insulating film having excellent transparency, heat-resistant transparency and crack resistance.

  Another object of the present invention is to provide a cured film that is formed from a radiation-sensitive resin composition and has excellent transparency, heat-resistant transparency and crack resistance, and serves as a gate insulating film of a semiconductor element.

  Moreover, the objective of this invention is providing the formation method of the gate insulating film which forms a gate insulating film using a radiation sensitive resin composition.

  Moreover, the objective of this invention is providing the semiconductor element which has a gate insulating film formed using the radiation sensitive resin composition.

  Moreover, the objective of this invention is providing the display apparatus provided with the semiconductor element which has the gate insulating film formed using the radiation sensitive resin composition.

A first aspect of the present invention is a gate insulating film disposed between a semiconductor layer and a gate electrode of a semiconductor element having a semiconductor layer and a gate electrode,
[A] A siloxane compound obtained by hydrolytic condensation of a silane compound represented by the following formula (1), and [B] selected from the group of photopolymerization initiators represented by the following formula (2) and the following formula (4) The present invention relates to a gate insulating film formed using a radiation-sensitive resin composition containing at least one kind.

（式（１）中、Ｒ^１は、それぞれ独立に、炭素数１〜６のアルキル基を示し、Ｒ^２は、それぞれ独立に、水素原子、炭素数１〜２０のアルキル基、炭素数６〜１４のアリール基、（メタ）アクリロイルオキシ基、エポキシ基、３，４−エポキシシクロヘキシル基またはメルカプト基を示す。ｎは１〜３の整数を示し、ｐは０〜６の整数を示す。）

(In the formula (1), ^{R 1} each independently represent an alkyl group having 1 to 6 carbon atoms, ^{R 2} are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms 14 represents an aryl group, a (meth) acryloyloxy group, an epoxy group, a 3,4-epoxycyclohexyl group or a mercapto group, n represents an integer of 1 to 3, and p represents an integer of 0 to 6.

（式（２）中、Ｒ^１１およびＲ^１２は、それぞれ独立に、水素原子、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基、炭素数７〜３０のアリールアルキル基または炭素数２〜２０の複素環基を示す。Ｘは、酸素原子、硫黄原子またはセレン原子である。Ｒ^１３およびＲ^１４は、それぞれ独立に、水素原子、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基、炭素数７〜３０のアリールアルキル基、炭素数２〜２０の複素環基、炭素数１〜１２のフルオロアルキル基、ハロゲンまたは下記式（３）で示される基を示す。ａは１〜５の整数を示し、ｂは１〜４の整数を示す。）

(In Formula (2), R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or carbon. Represents a heterocyclic group having a number of 2 to 20. X represents an oxygen atom, a sulfur atom or a selenium atom, and R ¹³ and R ¹⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number. A 6-30 aryl group, a C7-30 arylalkyl group, a C2-C20 heterocyclic group, a C1-C12 fluoroalkyl group, a halogen or a group represented by the following formula (3) A represents an integer of 1 to 5, and b represents an integer of 1 to 4.)

（式（３）中、Ｒ^１５は、それぞれ独立に、水素原子、炭素数１〜１２のアルキル基、フェニル基またはトリル基を示す。ｋは１〜６の整数を示す。Ｒ^１６は、水素原子またはアシル基を示す。Ｒ^１７は単結合、−Ｏ−、−Ｓ−、−ＮＲ^１８−、−ＮＲ^１８ＣＯ−、−ＳＯ_２−、−ＣＯ−、−ＣＳ−、−ＯＣＯ−または−ＣＯＯ−である。Ｒ^１８は、水素原子または炭素数１〜６のアルキル基を示す。＊は結合位置を示す。）

(In Formula (3), R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group. K represents an integer of 1 to 6. R ¹⁶ represents hydrogen. R ¹⁷ represents a single bond, —O—, —S—, —NR ¹⁸ —, —NR ¹⁸ CO—, —SO ₂ —, —CO—, —CS—, —OCO— or —. COO-- R ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, * represents a bonding position.)

（式（４）中、Ｒ^１９およびＲ^２０は、それぞれ独立に、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、ハロゲンまたは水酸基を示す。ｍは１または２を示し、ｃおよびｄはそれぞれ独立に０〜５の整数を示す。）

(In Formula (4), R ¹⁹ and R ²⁰ each independently represent an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen or a hydroxyl group. M represents 1 or 2, c and d each independently represents an integer of 0 to 5.)

The second aspect of the present invention is [A] a siloxane compound obtained by hydrolytic condensation of a silane compound represented by the following formula (1), and [B] represented by the following formula (2) and the following formula (4). Including at least one selected from the group of photopolymerization initiators,
A radiation-sensitive resin composition used for forming a gate insulating film of a semiconductor element having a semiconductor layer, a gate electrode, and a gate insulating film disposed between the semiconductor layer and the gate electrode Related to things.

（式（１）中、Ｒ^１は、それぞれ独立に、炭素数１〜６のアルキル基を示し、Ｒ^２は、それぞれ独立に、水素原子、炭素数１〜２０のアルキル基、炭素数６〜１４のアリール基、（メタ）アクリロイルオキシ基、エポキシ基、３，４−エポキシシクロヘキシル基またはメルカプト基を示す。ｎは１〜３の整数を示し、ｐは０〜６の整数を示す。）

(In the formula (1), ^{R 1} each independently represent an alkyl group having 1 to 6 carbon atoms, ^{R 2} are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms 14 represents an aryl group, a (meth) acryloyloxy group, an epoxy group, a 3,4-epoxycyclohexyl group or a mercapto group, n represents an integer of 1 to 3, and p represents an integer of 0 to 6.

（式（２）中、Ｒ^１１およびＲ^１２は、それぞれ独立に、水素原子、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基、炭素数７〜３０のアリールアルキル基または炭素数２〜２０の複素環基を示す。Ｒ^１３およびＲ^１４は、それぞれ独立に、水素原子、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基、炭素数７〜３０のアリールアルキル基、炭素数２〜２０の複素環基、炭素数１〜１２のフルオロアルキル基、ハロゲンまたは下記式（３）で示される基を示す。ａは１〜５の整数を示し、ｂは１〜４の整数を示す。）

(In Formula (2), R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or carbon. R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms. An alkyl group, a heterocyclic group having 2 to 20 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, a halogen, or a group represented by the following formula (3): a represents an integer of 1 to 5; Represents an integer of ~ 4.)

（式（３）中、Ｒ^１５は、それぞれ独立に、水素原子、炭素数１〜１２のアルキル基、フェニル基またはトリル基を示す。ｋは１〜６の整数を示す。Ｒ^１６は、水素原子またはアシル基を示す。Ｒ^１７は単結合、−Ｏ−、−Ｓ−、−ＮＲ^１８−、−ＮＲ^１８ＣＯ−、−ＳＯ_２−、−ＣＯ−、−ＣＳ−、−ＯＣＯ−または−ＣＯＯ−である。Ｒ^１８は、水素原子または炭素数１〜６のアルキル基を示す。＊は結合位置を示す。）

(In Formula (3), R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group. K represents an integer of 1 to 6. R ¹⁶ represents hydrogen. R ¹⁷ represents a single bond, —O—, —S—, —NR ¹⁸ —, —NR ¹⁸ CO—, —SO ₂ —, —CO—, —CS—, —OCO— or —. COO-- R ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, * represents a bonding position.)

（式（４）中、Ｒ^１９およびＲ^２０は、それぞれ独立に、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、ハロゲンまたは水酸基を示す。ｍは１または２を示し、ｃおよびｄはそれぞれ独立に０〜５の整数を示す。）

(In Formula (4), R ¹⁹ and R ²⁰ each independently represent an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen or a hydroxyl group. M represents 1 or 2, c and d each independently represents an integer of 0 to 5.)

  In the second aspect of the present invention, [C] an oxide containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium and hafnium. It is preferable that the inorganic oxide particle which is a thing is included.

A third aspect of the present invention is a cured film formed using the radiation-sensitive resin composition of the second aspect of the present invention,
The present invention relates to a cured film that is used for a gate insulating film of a semiconductor element having a semiconductor layer, a gate electrode, and a gate insulating film disposed between the semiconductor layer and the gate electrode.

The fourth aspect of the present invention is:
(1) The process of forming a coating film on the board | substrate which has a gate electrode using the radiation sensitive resin composition of the 2nd aspect of this invention,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) It has the process of developing the coating film irradiated with the radiation, and (4) It has the process of heating the developed coating film, It is related with the formation method of the gate insulating film characterized by the above-mentioned.

  According to a fifth aspect of the present invention, there is provided a semiconductor device comprising a gate insulating film formed using the radiation-sensitive resin composition according to the second aspect of the present invention.

  According to a sixth aspect of the present invention, the gate electrode, the gate insulating film according to the first aspect of the present invention, and the semiconductor layer are arranged on the substrate in this order, and have a bottom gate structure. The present invention relates to a semiconductor device.

  According to a seventh aspect of the present invention, there is provided a display device comprising the semiconductor element according to the fifth aspect of the present invention or the semiconductor element according to the sixth aspect of the present invention.

  According to the first aspect of the present invention, a gate insulating film that can be formed by coating and has excellent transparency, heat-resistant transparency, and crack resistance is obtained.

  According to the second aspect of the present invention, a radiation-sensitive resin composition capable of forming a pattern having high resolution and forming a gate insulating film excellent in transparency, heat-resistant transparency and crack resistance is obtained. .

  According to the 3rd aspect of this invention, the cured film which is formed from a radiation sensitive resin composition, is excellent in transparency, heat-resistant transparency, and crack tolerance, and becomes a gate insulating film of a semiconductor element is obtained.

  According to the 4th aspect of this invention, the formation method of the gate insulating film which forms a gate insulating film using a radiation sensitive resin composition is obtained.

  According to the 5th aspect of this invention, the semiconductor element which has a gate insulating film formed using the radiation sensitive resin composition is obtained.

  According to the 6th aspect of this invention, the semiconductor element which has a gate insulating film formed using the radiation sensitive resin composition is obtained.

  According to the 7th aspect of this invention, the display apparatus provided with the semiconductor element which has the gate insulating film formed using the radiation sensitive resin composition is obtained.

It is sectional drawing which illustrates typically the structure of the semiconductor element of embodiment of this invention. It is sectional drawing which illustrates typically the structure of the principal part of the organic electroluminescence display of this embodiment.

The semiconductor element of the present invention is a semiconductor element having a structure in which a semiconductor layer and a gate electrode are provided, and a gate insulating film is disposed between the semiconductor layer and the gate electrode.
And the gate insulating film is
It is formed using a radiation sensitive resin composition containing [A] a siloxane compound and [B] a photopolymerization initiator.

  Below, the semiconductor element of this invention is demonstrated, and then the radiation sensitive resin composition used for forming the gate insulating film which is the main component is demonstrated in detail. And the formation method of the cured film, gate insulating film, and gate insulating film using a radiation sensitive resin composition is demonstrated.

  In the present invention, “radiation” irradiated upon exposure includes visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.

Embodiment 1. FIG.
<Semiconductor element>
FIG. 1 is a cross-sectional view schematically illustrating the structure of a semiconductor device according to an embodiment of the present invention.

  The semiconductor element according to the embodiment of the present invention shown in FIG. 1 can be a TFT 3 suitable as a switching element attached to each pixel of an active matrix display device. That is, it can be an active matrix display device having a plurality of pixels formed in a matrix, for example, a TFT 3 provided in each pixel of an organic EL display device or a liquid crystal display device.

  The TFT 3 includes a gate electrode 4 that forms part of a scanning signal line (not shown) on the substrate 2, a single-layer gate insulating film 5 that covers the gate electrode 4, and a gate insulating film on the gate electrode 4. 5 and a semiconductor layer 6 disposed via 5.

  That is, the TFT 3 is a semiconductor element having a structure including the semiconductor layer 6, the gate electrode 4, and the gate insulating film 5 having a one-layer structure disposed between the semiconductor layer 6 and the gate electrode 4. The TFT 3 has a bottom gate structure in which a gate electrode 4, a gate insulating film 5, and a semiconductor layer 6 are stacked in this order on a substrate 2.

  The TFT 3 includes a first source-drain electrode 7 that forms part of a video signal line (not shown) and is connected to the semiconductor layer 6, and a second source-drain electrode 8 that is connected to the semiconductor layer 6. It is configured.

  The gate electrode 4 can be formed by forming a metal thin film on the substrate 2 by vapor deposition or sputtering, and performing patterning using an etching process. In addition, a metal oxide conductive film or an organic conductive film can be patterned and used.

  As a material of the metal thin film constituting the gate electrode 4, for example, aluminum (Al), copper (Cu), molybdenum (Mo), chromium (Cr), tantalum (Ta), titanium (Ti), gold (Au), Mention may be made of metals such as tungsten (W) and silver (Ag), alloys of these metals, and alloys such as Al-Nd and APC alloys (silver, palladium, copper alloys). And as a metal thin film, it is also possible to use the laminated film which consists of a layer of a different material, such as a laminated film of Al and Mo.

As a material of the metal oxide conductive film constituting the gate electrode 4, metal oxide conductive films such as tin oxide, zinc oxide, indium oxide, ITO (Indium Tin Oxide) and indium zinc oxide (IZO) are used. Can be mentioned.
Examples of the material for the organic conductive film include conductive organic compounds such as polyaniline, polythiophene, and polypyrrole, or a mixture thereof.
The thickness of the gate electrode 4 is preferably 10 nm to 1000 nm.

  The gate insulating film 5 disposed so as to cover the gate electrode 4 is formed of a cured film formed by patterning using the radiation-sensitive resin composition of the embodiment of the present invention. This cured film is formed using the radiation-sensitive resin composition of the embodiment of the present invention, is insulating, and has transparency, heat-resistant transparency, adhesion to the substrate and gate electrode, low water absorption, crack resistance, etc. Excellent characteristics. The film thickness of the gate insulating film 5 made of this cured film is preferably 50 nm to 10 μm. The cured film of the embodiment of the present invention used for forming the gate insulating film 5 of the TFT 3 and the radiation sensitive resin composition of the embodiment of the present invention used for forming the same will be described in detail later.

  For the first source-drain electrode 7 and the second source-drain electrode 8 connected to the semiconductor layer 6, a conductive film constituting these electrodes is formed by a sputtering method, a CVD method, an evaporation method in addition to a printing method or a coating method. After forming using a method such as a method, patterning using a photolithography method or the like can be performed. Examples of the material constituting the first source-drain electrode 7 and the second source-drain electrode 8 include metals such as Al, Cu, Mo, Cr, Ta, Ti, Au, W, and Ag, and alloys of these metals. And alloys such as Al-Nd and APC. Also, conductive metal oxides such as tin oxide, zinc oxide, indium oxide, ITO, indium zinc oxide (IZO), AZO (aluminum doped zinc oxide) and GZO (gallium doped zinc oxide), polyaniline, polythiophene and polypyro Examples thereof include conductive organic compounds such as As the conductive film constituting these electrodes, a laminated film made of layers of different materials such as a laminated film of Ti and Al can be used.

  The thicknesses of the first source-drain electrode 7 and the second source-drain electrode 8 are preferably 10 nm to 1000 nm.

The semiconductor layer 6 is made of, for example, silicon (such as amorphous a-Si (amorphous-silicon)) or p-Si (polysilicon) obtained by crystallizing a-Si by excimer laser or solid phase growth. It can be formed by using Si) material.
When a-Si is used for the semiconductor layer 6, the thickness of the semiconductor layer 6 is preferably 30 nm to 500 nm. In addition, an n + Si layer (not shown) for forming an ohmic contact is formed with a thickness of 10 nm to 150 nm between the semiconductor layer 6 and the first source-drain electrode 7 or the second source-drain electrode 8. It is preferable.

  The semiconductor layer 6 of the TFT 3 can be formed using an oxide. Examples of the oxide applicable to the semiconductor layer 6 include a single crystal oxide, a polycrystalline oxide, an amorphous oxide, and a mixture thereof. Examples of the polycrystalline oxide include zinc oxide (ZnO).

  Examples of the amorphous oxide applicable to the semiconductor layer 6 include an amorphous oxide including at least one element of indium (In), zinc (Zn), and tin (Sn).

  Specific examples of amorphous oxides applicable to the semiconductor layer 6 include Sn—In—Zn oxide, In—Ga—Zn oxide (IGZO: indium gallium zinc oxide), and In—Zn—Ga—Mg oxide. Zn-Sn oxide (ZTO: zinc tin oxide), In oxide, Ga oxide, In-Sn oxide, In-Ga oxide, In-Zn oxide (IZO: indium zinc oxide), Zn-Ga An oxide, a Sn—In—Zn oxide, and the like can be given. In the above case, the composition ratio of the constituent materials is not necessarily 1: 1, and a composition ratio that realizes desired characteristics can be selected.

  For example, when the semiconductor layer 6 using an amorphous oxide is formed using IGZO or ZTO, a film is formed by sputtering or vapor deposition using an IGZO target or ZTO target, and a photolithography method or the like. Is formed by patterning using a resist process and an etching process. The thickness of the semiconductor layer 6 using an amorphous oxide is preferably 1 nm to 1000 nm.

  By using the oxides exemplified above, the semiconductor layer 6 with high mobility can be formed at a low temperature, and the TFT 3 with excellent performance can be provided.

Examples of oxides particularly preferable for forming the semiconductor layer 6 of the TFT 3 include zinc oxide (ZnO), indium gallium zinc oxide (IGZO), zinc tin oxide (ZTO), and indium zinc oxide (ZIO). it can.
By using these oxides, the TFT 3 has the semiconductor layer 6 having excellent mobility formed at a lower temperature and can exhibit a high ON / OFF ratio.

In the semiconductor layer 6 of the TFT 3, a SiO 2 having a thickness of, for example, 5 nm to 80 nm is formed in a channel region where the first source-drain electrode 7 and the second source-drain electrode 8 are not formed on the upper surface of the semiconductor layer 6. _A protective layer (not shown) of ₂ can be provided. This protective layer is sometimes referred to as an etching stop layer or a stop layer. Such a protective layer is a particularly preferable component when the above-described oxide is used for the semiconductor layer 6.

An inorganic insulating film 19 can be provided on the TFT 3 so as to cover the TFT 3. The inorganic insulating film 19 can be formed by using, for example, an inorganic oxide such as SiO ₂ or an inorganic nitride such as SiN alone or in a laminated manner. The inorganic insulating film 19 is provided to protect the semiconductor layer 6 and prevent it from being influenced by humidity, for example. The TFT 3 according to this embodiment may have a structure in which the inorganic insulating film 19 is not provided. In that case, an interlayer insulating film made of an organic material provided between a pixel electrode or the like (not shown) and the TFT 3 can have the function of the inorganic insulating film 19.

  Further, as described above, the TFT 3 shown in FIG. 1 has a bottom gate structure, but the semiconductor element of the present embodiment is not limited to the bottom gate structure, and is a TFT having a positive stagger structure (top gate structure). It is also possible. In that case, the TFT which is the semiconductor element of this embodiment has a semiconductor layer on a substrate and a pair of first source-drain electrode and second source-drain electrode connected to the semiconductor layer, respectively. The gate electrode is superimposed on the semiconductor layer with a gate insulating film interposed therebetween. At this time, the gate insulating film is the same as the gate insulating film 5 of the TFT 3 described above. A semiconductor layer using p-Si can be preferably applied. In the semiconductor layer using p-Si, a source region and a drain region are preferably formed by doping impurities such as phosphorus (P) or boron (B) and sandwiching a channel region of the semiconductor layer. In addition, it is preferable to form an LDD (Lightly Doped Drain) layer between the channel region of the semiconductor layer and the source and drain regions.

  The TFT 3 of FIG. 1 having the above structure is an example of a semiconductor device according to an embodiment of the present invention, and includes a coating-type gate insulating film 5 having an advantage in film formation and cost. That is, the TFT 3 can be formed by coating, can be patterned with high resolution, is insulative, and has various properties such as transparency, heat-resistant transparency, adhesion to the substrate and gate electrode, low water absorption, and crack resistance. The gate insulating film 5 having excellent characteristics is provided. As a result, the productivity of the TFT 3 can be improved, and as a result, the productivity of a display device using the TFT 3 can be improved. The TFT 3 can provide an excellent display quality display element.

Embodiment 2. FIG.
<Radiation sensitive resin composition>
The radiation sensitive resin composition of this embodiment is a radiation sensitive resin composition comprising [A] a siloxane compound and [B] a photopolymerization initiator. And it can contain [C] inorganic oxide particle, [D] solvent, and other arbitrary components as needed. The radiation sensitive resin composition of this embodiment can be used suitably for formation of the gate insulating film of a semiconductor element which is embodiment of this invention mentioned above. Hereinafter, the component contained in the radiation sensitive resin composition of this embodiment is demonstrated.

[A] Siloxane Compound The [A] siloxane compound that is the [A] component of the radiation-sensitive resin composition of the present embodiment is a polymer of a compound having a siloxane bond, and is particularly limited as long as it is such a polymer. Is not to be done. This [A] siloxane compound often undergoes hydrolytic condensation in the process of forming a cured product.

  [A] The siloxane compound is preferably a hydrolytic condensate of a hydrolyzable silane compound represented by the following formula (1).

（式（１）中、Ｒ^１は、それぞれ独立に、炭素数１〜６のアルキル基を示し、Ｒ^２は、それぞれ独立に、水素原子、炭素数１〜２０のアルキル基、炭素数６〜１４のアリール基、（メタ）アクリロイルオキシ基、エポキシ基、３，４−エポキシシクロヘキシル基またはメルカプト基を示す。ｎは１〜３の整数を示し、ｐは０〜６の整数を示す。）

(In the formula (1), ^{R 1} each independently represent an alkyl group having 1 to 6 carbon atoms, ^{R 2} are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms 14 represents an aryl group, a (meth) acryloyloxy group, an epoxy group, a 3,4-epoxycyclohexyl group or a mercapto group, n represents an integer of 1 to 3, and p represents an integer of 0 to 6.

The hydrolyzable silane compound in the present invention is usually hydrolyzed and silanol by heating in the temperature range of room temperature (about 25 ° C.) to about 100 ° C. in the presence of non-catalyst and excess water. It refers to a compound having a “hydrolyzable functional group” that can form a group and can be further condensed by heating to form a siloxane compound that is a hydrolysis condensate. In this case, the “non-hydrolyzable group” refers to a group that does not undergo hydrolysis or condensation under the hydrolysis conditions as described above and exists stably. In the hydrolyzable silane compound represented by the above formula (1), the hydrolyzable group is —OR ¹ , and the non-hydrolyzable group is — (CH ₂ ) _P —R ² .

  In the hydrolysis reaction of the hydrolyzable silane compound represented by the above formula (1), some hydrolyzable groups may remain in an unhydrolyzed state. In addition, in the hydrolysis condensate of the hydrolyzable silane compound, some hydrolyzable groups may remain in an unhydrolyzed state, and some silanol groups of the hydrolyzed silane compound are not condensed. It may remain in the state.

  The hydrolyzable silane compound represented by the above formula (1) will be described in more detail.

The group represented by R ¹ in the formula (1), in view of easiness of hydrolysis, preferably an alkyl group having 1 to 6 carbon atoms, a methyl group or an ethyl group is particularly preferred. Further, as long as it can be handled stably, R ¹ may be in the form of hydrogen, that is, a silanol group hydrolyzed in advance.

R ^{2 in the} above formula (1) is an unsubstituted alkyl group having 1 to 20 carbon atoms, or an alkyl group substituted with one or more vinyl group, (meth) acryloyl group or epoxy group, or a substituent group having 6 to 20 carbon atoms. An aryl group which may have, an aralkyl group which may have a substituent having 7 to 20 carbon atoms, a (meth) acryloyloxy group, an epoxy group, a 3,4-epoxycyclohexyl group or a mercapto group It is done. These may be linear, branched, or cyclic, and may be a combination thereof when a plurality of R ² are present in the same molecule. R ² may contain a structural unit having a hetero atom. Examples of such a structural unit include ether, ester, sulfide, carbonyl, carboxyl, dicarboxylic anhydride, amide and the like.

  Moreover, although n in the said Formula (1) is an integer of 1-3, More preferably, it is an integer of 1-2, Especially preferably, it is 1. When n is an integer of 1 to 2, the hydrolysis / condensation reaction proceeds more easily, and as a result, the generation rate of [A] siloxane compound and the curing reaction of the obtained siloxane compound are further increased. Become. Therefore, in the film formation using the radiation sensitive resin composition of the present embodiment, the melt flow resistance in the heating step after development, the film hardness after film formation, and the low water absorption can be improved.

  As the hydrolyzable silane compound represented by the above formula (1), a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, two non-hydrolyzable groups, and A silane compound substituted with two hydrolyzable groups, a silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group, or a mixture thereof may be mentioned.

As a specific example of the hydrolyzable silane compound represented by the above formula (1),
As a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, hydrotrimethoxysilane, hydrotriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxy Silane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane , Phenyltrimethoxysilane, phenyltriethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Lan, vinyltri-n-propoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, γ-glycidoxy Propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, 3-trimethoxysilylpropyl succinate Acid anhydrides, 3-triethoxysilylpropyl succinic anhydride, 2-trimethoxysilylethyl succinic anhydride, 2-triethoxysilylethyl succinic anhydride, etc .;
As silane compounds substituted with two non-hydrolyzable groups and two hydrolyzable groups, dihydrodimethoxysilane, dihydrodiethoxysilane, hydromethyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyl Dimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane and the like;
As a silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group, trihydromethoxysilane, trihydroethoxysilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, tributylmethoxysilane, trimethyl Examples thereof include methoxysilane, trimethylethoxysilane, and tributylethoxysilane.

  Among these hydrolyzable silane compounds represented by the above formula (1), a silane compound (n = 1) substituted with one non-hydrolyzable group and three hydrolyzable groups is hydrolyzed. Particularly preferred from the viewpoints of decomposition reactivity and condensation reactivity. Specific examples of this preferred hydrolyzable silane compound include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethyl. Examples include methoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltriethoxysilane. Such hydrolyzable silane compounds may be used singly or in combination of two or more.

Moreover, when obtaining a siloxane compound by hydrolysis condensation, hydrolyzable silane compounds other than the hydrolyzable silane compound represented by the formula (1) can be used in combination. Examples of hydrolyzable silane compounds other than the above formula (1) include silane compounds substituted with four hydrolyzable groups; tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxy Silane, tetra-n-propoxysilane, tetra-i-propoxysilane and other compounds having a plurality of hydrolyzable silane moieties in one molecule; tris (3-trimethoxysilylpropyl) isocyanurate, etc. Examples of the siloxane compound include: siloxane oligomers, siloxane polymers, modified silicone oils, silica particles, and the like, and chlorosilane compounds; chlorotrimethylsilane, chlorotriethylsilane, and the like.
Other than silane compounds, compounds having hydrolyzability and condensation reactivity, hydrolyzable titanium compounds, hydrolyzable aluminum compounds, hydrolyzable zinc compounds, and the like can also be used in combination.

  The conditions for hydrolyzing and condensing the hydrolyzable silane compound represented by the above formula (1) are hydrolyzable by hydrolyzing at least a part of the hydrolyzable silane compound represented by the above formula (1). Although it does not specifically limit as long as it converts a group into a silanol group and causes a condensation reaction, it can implement as follows as an example.

The water used for hydrolysis / condensation of the hydrolyzable silane compound represented by the above formula (1) is preferably water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment or distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. The amount of water used is preferably 0.1 mol to 3 mol with respect to 1 mol of the total amount of hydrolyzable groups (—OR ¹ ) of the hydrolyzable silane compound represented by the above formula (1). The amount is preferably 0.3 mol to 2 mol, more preferably 0.5 mol to 1.5 mol. By using such an amount of water, the hydrolysis / condensation reaction rate can be optimized.

  Although it does not specifically limit as a solvent which can be used for hydrolysis and condensation of the hydrolysable silane compound represented by the said Formula (1), For example, a C1-C15 linear, branched Chain or cyclic alkyl alcohol, ketones having 3 to 20 carbon atoms, tetrahydrofuran, benzene, toluene, xylene, ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propionic acid Examples include esters. Among these solvents, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate or methyl 3-methoxypropionate is particularly preferable.

The hydrolysis / condensation reaction of the hydrolyzable silane compound represented by the above formula (1) is preferably an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid). , Phosphoric acid, maleic anhydride, methanesulfonic acid, toluenesulfonic acid, acidic ion exchange resin, various Lewis acids), base catalysts (eg, ammonia, primary amines, secondary amines, tertiary amines, pyridine, Nitrogen-containing compounds such as quaternary ammonium hydroxide; basic ion exchange resins; hydroxides such as sodium hydroxide and potassium hydroxide; carbonates such as sodium carbonate and potassium carbonate; carboxylates such as sodium acetate and potassium acetate Various Lewis bases) or metal alkoxides (eg, zirconium alkoxides, titanium alkoxides, It is carried out in the presence of a mini Umm alkoxide), and the like of the catalyst. For example, tetra-i-propoxyaluminum can be used as the aluminum alkoxide. The amount of the catalyst to be used is preferably 10 ⁻⁶ mol to 0.2 mol, more preferably 0.8 mol, relative to 1 mol of the monomer of the hydrolyzable silane compound from the viewpoint of promoting the hydrolysis / condensation reaction. It is 00001 mol to 0.1 mol.

  The reaction temperature and reaction time in the hydrolysis / condensation of the hydrolyzable silane compound represented by the above formula (1) are appropriately set. For example, the following conditions can be adopted. The reaction temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 150 ° C. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 hour to 12 hours. By setting such reaction temperature and reaction time, hydrolysis / condensation reaction can be most efficiently performed. In this hydrolysis / condensation, the reaction may be carried out in one step by adding a hydrolyzable silane compound, a solvent, water and a catalyst to the reaction system at one time. Alternatively, the hydrolyzable silane compound, solvent, water In addition, the hydrolysis and condensation reaction may be performed in multiple stages by adding any one of the catalyst and an arbitrarily selected mixture or an arbitrarily selected mixture into the reaction system in several times. After the hydrolysis / condensation reaction, water and the produced alcohol can be removed from the reaction system by adding a dehydrating agent and then subjecting it to evaporation. By completely removing the solvent and water, or by adding an arbitrary solvent, the siloxane compound obtained by hydrolysis condensation can be handled as a solution.

  The hydrolytic condensate of the hydrolyzable silane compound represented by the above formula (1), that is, the molecular weight of the siloxane compound is a number average in terms of polystyrene using GPC (gel permeation chromatography) using tetrahydrofuran as the mobile phase. It can be measured as molecular weight or weight average molecular weight. And it is preferable to make the weight average molecular weight of a hydrolysis-condensation product into the value within the range of 500-20000, it is more preferable to set it as the value within the range of 600-10000, and the value within the range of 600-5000, More preferably.

  By making the value of the weight average molecular weight of the hydrolyzed condensate to be 500 or more, the film formability of the coating film is improved in the radiation sensitive resin composition of this embodiment containing the [A] siloxane compound composed of them. can do. On the other hand, the radiation sensitive fall of the radiation sensitive resin composition of this embodiment can be prevented by making the value of the weight average molecular weight of a hydrolysis condensate into 20000 or less.

[B] Photopolymerization initiator [B] The photopolymerization initiator, which is the [B] component of the radiation-sensitive resin composition of the present embodiment, condenses the above-mentioned [A] siloxane compound by irradiation with radiation. It is defined as a compound that generates an active species that acts upon curing reaction. [B] Examples of the radiation applied to generate the above-mentioned active species from the photopolymerization initiator include visible light, ultraviolet light, far ultraviolet light, X-rays, and charged particle beams as described above. . Among these radiations, it is preferable to use ultraviolet rays because they have a constant energy level, can achieve a high curing rate, and the irradiation device is relatively inexpensive and small.

  The radiation-sensitive resin composition of the embodiment of the present invention can exhibit a negative patterning property by containing [B] a photopolymerization initiator.

  And it is preferable that the radiation sensitive resin composition of embodiment of this invention uses an oxime ester photoinitiator and an acyl phosphine oxide type photoinitiator as a [B] photoinitiator.

  More specifically, it is preferable to use at least one selected from the group of photopolymerization initiators represented by the following formula (2) and the following formula (4). The compound represented by the following formula (2) is an oxime ester photopolymerization initiator, and the compound represented by the following formula (4) is an acylphosphine oxide photopolymerization initiator.

（式（２）中、Ｒ^１１およびＲ^１２は、それぞれ独立に、水素原子、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基、炭素数７〜３０のアリールアルキル基または炭素数２〜２０の複素環基を示す。Ｘは、酸素原子、硫黄原子またはセレン原子である。Ｒ^１３およびＲ^１４は、それぞれ独立に、水素原子、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基、炭素数７〜３０のアリールアルキル基、炭素数２〜２０の複素環基、炭素数１〜１２のフルオロアルキル基、ハロゲンまたは下記式（３）で示される基を示す。ａは１〜５の整数を示し、ｂは１〜４の整数を示す。）

(In Formula (2), R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or carbon. Represents a heterocyclic group having a number of 2 to 20. X represents an oxygen atom, a sulfur atom or a selenium atom, and R ¹³ and R ¹⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number. A 6-30 aryl group, a C7-30 arylalkyl group, a C2-C20 heterocyclic group, a C1-C12 fluoroalkyl group, a halogen or a group represented by the following formula (3) A represents an integer of 1 to 5, and b represents an integer of 1 to 4.)

（式（３）中、Ｒ^１５は、それぞれ独立に、水素原子、炭素数１〜１２のアルキル基、フェニル基またはトリル基を示す。ｋは１〜６の整数を示す。Ｒ^１６は、水素原子またはアシル基を示す。Ｒ^１７は単結合、−Ｏ−、−Ｓ−、−ＮＲ^１８−、−ＮＲ^１８ＣＯ−、−ＳＯ_２−、−ＣＯ−、−ＣＳ−、−ＯＣＯ−または−ＣＯＯ−である。Ｒ^１８は、水素原子または炭素数１〜６のアルキル基を示す。＊は結合位置を示す。）

(In Formula (3), R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group. K represents an integer of 1 to 6. R ¹⁶ represents hydrogen. R ¹⁷ represents a single bond, —O—, —S—, —NR ¹⁸ —, —NR ¹⁸ CO—, —SO ₂ —, —CO—, —CS—, —OCO— or —. COO-- R ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, * represents a bonding position.)

（式（４）中、Ｒ^１９およびＲ^２０は、それぞれ独立に、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、ハロゲンまたは水酸基を示す。ｍは１または２を示し、ｃおよびｄはそれぞれ独立に０〜５の整数を示す。）

(In Formula (4), R ¹⁹ and R ²⁰ each independently represent an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen or a hydroxyl group. M represents 1 or 2, c and d each independently represents an integer of 0 to 5.)

  These [B] photopolymerization initiators mentioned as preferred are photopolymerization initiators having photobleaching properties. Photobleaching is the loss of photoactivation ability of photosensitive substances induced by light. In these photopolymerization initiators, decomposition proceeds with light irradiation, and the wavelength range effective for photoactivation. Absorption capacity in That is, these photopolymerization initiators are decomposed by light irradiation to generate active species, and the transmittance at an effective wavelength is improved. Further, the improvement in the transmittance of the effective wavelength due to the decomposition leads to the improvement in the transmittance of the effective wavelength even when the photopolymerization initiator remaining in the coating film is thermally decomposed by the heat treatment.

  The effective wavelength of the [B] photopolymerization initiator of the radiation-sensitive resin composition according to the embodiment of the present invention is a wavelength region of 250 nm to 400 nm. The coating film containing [B] photopolymerization initiator formed from the radiation-sensitive resin composition of the embodiment of the present invention and having photobleaching properties is 250 nm to 400 nm after light irradiation and after heat treatment. The transmittance of is improved. Therefore, the radiation-sensitive resin composition of the present embodiment is used for forming a gate insulating film of a TFT that requires high visible light transmission, that is, transparency in a liquid crystal display element or an organic EL element, as well as an interlayer insulating film, etc. It can be suitably used for forming.

  That is, the radiation sensitive resin composition of the embodiment of the present invention has a high resolution patterning property and can form a cured film having excellent transparency. And the radiation sensitive resin composition of embodiment of this invention is suitable for provision of the gate insulating film of semiconductor elements, such as TFT, for example, can provide the display element of the outstanding display quality.

  Hereinafter, the photopolymerization initiator represented by the above formula (2) and the above formula (4) will be described in more detail.

In the photopolymerization initiator represented by the above formula (2), as described above, R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms. , An arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms.

Then, the photopolymerization initiator of the above formula ^(2), as the ^{R 11,} preferably an alkyl group having 1 to 12 carbon atoms. R ¹² is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a trifluoromethyl group.

  In the photopolymerization initiator represented by the above formula (2), X is particularly preferably a sulfur atom.

In the photopolymerization initiator represented by the above formula (2), R ¹³ and R ¹⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 7 to 7 carbon atoms. 30 arylalkyl groups, heterocyclic groups having 2 to 20 carbon atoms, fluoroalkyl groups having 1 to 12 carbon atoms, halogen, or a group represented by the above formula (3). a shows the integer of 1-5, b shows the integer of 1-4.

Then, ^{R 15} in the formula (3) each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a tolyl group. k shows the integer of 1-6. R ¹⁶ represents a hydrogen atom or an acyl group. R ¹⁷ is a single bond, —O—, —S—, —NR ¹⁸ —, —NR ¹⁸ CO—, —SO ₂ —, —CO—, —CS—, —OCO— or —COO—. R ¹⁸ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. * Indicates binding position

Examples of the acyl group represented by R ¹⁶ in the above formula (3) include formyl group, acetyl group, propionyl group, butyroyl group, isobutyroyl group, valeroyl group, isovaroyl group, hexanoyl group, octanoyl group, benzoyl group, toluoyl group, cyclohexanecarbonyl Group, trifluoroacetyl group and the like are preferable, and acetyl group, benzoyl group and trifluoroacetyl group are particularly preferable.

In the photopolymerization initiator represented by the above formula (4), as described above, R ¹⁹ and R ²⁰ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, halogen or A hydroxyl group is shown. m represents 1 or 2, and c and d each independently represent an integer of 0 to 5.

In the photopolymerization initiator represented by the above formula (4), R ¹⁹ and R ²⁰ are methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n- A heptyl group, n-octyl group, n-dodecyl group, a methoxy group, an ethoxy group, a chlorine atom, and a fluorine atom are mentioned, Among these, a methyl group and an ethyl group are preferable.

  Specific examples of the photopolymerization initiator represented by the above formula (2) include the following compounds (2-1) to (2-13).

  Specific examples of the photopolymerization initiator represented by the above formula (4) include the following compounds (4-1) to (4-9).

[C] Inorganic oxide particles The radiation-sensitive resin composition of the present embodiment contains [C] inorganic oxide particles as an optional component in addition to the [A] siloxane compound and [B] photopolymerization initiator. be able to.

  The [C] inorganic oxide particles that are the [C] component of the radiation-sensitive resin composition of the present embodiment are contained in the radiation-sensitive resin composition, and the electrical insulation of the resulting cured product is maintained. At the same time, it is possible to control the dielectric constant, which is a dielectric characteristic. For example, the relative dielectric constant of the cured film of this embodiment formed using the radiation-sensitive resin composition of this embodiment is set to a desired value as a gate insulating film of a semiconductor element, for example, nitriding conventionally used It can be controlled to a lower relative dielectric constant for the purpose of approaching 7-8, which is the relative dielectric constant of silicon, or to reduce parasitic capacitance. As a result, the semiconductor element of the embodiment of the present invention forms a cured film from the radiation-sensitive resin composition of the present embodiment and uses it as a gate insulating film, thereby increasing the wiring delay while ensuring short circuit prevention capability. Can be prevented. The inorganic oxide particles can also be used for the purpose of controlling the refractive index of the cured film, controlling the transparency of the cured film, suppressing cracks by alleviating curing shrinkage, and improving the surface hardness of the cured film. .

  The [C] inorganic oxide particles that are the [C] component of the radiation sensitive resin composition of the present embodiment are silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium, and hafnium. Inorganic oxide particles that are oxides containing at least one element selected from the group consisting of:

Among these groups, oxide particles of silicon, zirconium, titanium or zinc are preferable, silica particles which are silicon oxide particles, oxide particles of zirconium or titanium, and barium titanate (BaTiO ₃ ) described later are particularly preferable. . These can be used alone or in combination of two or more. [C] The inorganic oxide particles may be composite oxide particles of the above-described elements. Examples of the composite oxide particles include barium titanate and strontium titanate. Moreover, ATO (antimoy-tin oxide), ITO (indium-tin oxide), IZO (indium-zinc oxide), etc. can also be used in the range which does not impair the electrical insulation of hardened | cured material. As these inorganic oxide particles, commercially available ones such as Nanotech (registered trademark) manufactured by CI Kasei Co., Ltd. can be used.

  [C] The shape of the inorganic oxide particles is not particularly limited, and may be spherical or amorphous, and may be hollow particles, porous particles, core-shell particles, or the like. Further, the volume average particle diameter of the [C] inorganic oxide particles determined by the dynamic light scattering method is preferably 5 nm to 200 nm, more preferably 5 nm to 100 nm, and particularly preferably 10 nm to 80 nm. [C] If the volume average particle diameter of the inorganic oxide particles is less than 5 nm, the hardness of the cured film obtained using the radiation-sensitive resin composition may be reduced, or the intended relative dielectric constant may not be exhibited. Yes, if it exceeds 200 nm, the haze of the cured film may increase and the transmittance may decrease, and the smoothness of the cured film may deteriorate.

  [C] Although it does not specifically limit as a compounding quantity of an inorganic oxide particle, 1 mass part-500 mass parts are preferable with respect to 100 mass parts of the above-mentioned [A] siloxane compounds, and 5 mass parts-300 mass parts are. More preferred. [C] If the blending amount of the inorganic oxide particles is less than 1 part by mass, the relative dielectric constant of the obtained cured film cannot be controlled within a desired range. On the other hand, when the blending amount of [C] inorganic oxide particles exceeds 500 parts by mass, applicability and film curability may decrease, and the resulting cured film may have high haze.

  [C] When preparing the radiation-sensitive resin composition of this embodiment, [C] inorganic oxide particles are used as powders as [A] siloxane compound, [B] photopolymerization initiator, and [D] solvent described later. And [C] inorganic oxide particles may be mixed in advance with a solvent as a component [D] described later, and treated as a dispersion of [C] inorganic oxide particles. . Furthermore, you may handle by adding the dispersing agent as a below-mentioned [D] component to the dispersion liquid of [C] inorganic oxide particle. In addition, when the [C] inorganic oxide particles are mixed with other components, it is preferable to perform a dispersion treatment in order to prevent aggregation of the [C] inorganic oxide particles and to control the particle size to be uniform.

  The dispersion treatment may be performed by using various bead mills such as a paint shaker, an SC mill, an annular mill, a pin mill, and the like until the decrease in particle size is not observed. The duration is preferably several hours. In this dispersion, it is preferable to use dispersed beads such as glass beads and zirconia beads. The bead diameter is not particularly limited, but is preferably 0.05 mm to 0.5 mm, more preferably 0.08 mm to 0.5 mm, and still more preferably 0.08 mm to 0.2 mm.

  [C] The inorganic oxide particles may be controlled to have a uniform particle size by dispersing the aggregated coarse particles as described above, or the sol-gel reaction in the gas phase or in the liquid phase. Thus, the [C] inorganic oxide particles or the dispersion of [C] inorganic oxide particles having a controlled particle size may be directly produced.

[D] Solvent and other optional components In addition to [A] siloxane compound and [B] photopolymerization initiator, the radiation-sensitive resin composition of the present embodiment includes [C] inorganic oxide particles as optional components. In addition, [D] a solvent and other optional components can be contained.

  When the radiation-sensitive resin composition of the present embodiment contains [C] inorganic oxide particles, it further uniformly contains [C] inside the radiation-sensitive resin composition by further containing a dispersant as the [D] component. Inorganic oxide particles can be dispersed, and coating properties can be improved. The radiation-sensitive resin composition of the present embodiment can be controlled so that the adhesion of a cured film obtained by using the radiation-sensitive resin composition to a substrate or the like is increased and the relative dielectric constant becomes a desired value uniformly. it can.

  [D] Examples of the dispersant include nonionic dispersants, cationic dispersants, anionic dispersants, and the like.

  [D] Nonionic dispersants suitable for the dispersant include polyoxyethylene alkyl phosphate ester, amide amine salt of high molecular weight polycarboxylic acid, ethylenediamine propylene oxide-ethylene oxide condensate, polyoxyethylene alkyl ether, polyoxyethylene Alkyl phenol ethers, alkyl glucosides, polyoxyethylene fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or fatty acid alkanolamides are preferred.

  As said polyoxyethylene alkyl phosphate ester, the compound represented by following formula (5) is preferable.

（式（５）中、Ｒ^３は、各々独立に、Ｃ_ｑＨ_２ｑ＋１−ＣＨ_２Ｏ−（ＣＨ_２ＣＨ_２Ｏ）_ｑ’−ＣＨ_２ＣＨ_２Ｏ−である。そのｑは１２〜１６の整数である。そのｑ’は８〜１０の整数である。そのＬは１〜３の整数である。）

(In the formula (5), ^{R 3} are each _{independently, C q H 2q + 1 -CH} 2 O- (CH 2 CH 2 O) q '-CH 2 CH 2 is O-. Its q is 12-16 The q ′ is an integer of 8 to 10. The L is an integer of 1 to 3.)

  As a commercial item of the dispersant represented by the above formula (5), PLAAD ED151 manufactured by Enomoto Kasei Co., Ltd. and the like can be mentioned. According to the above polyoxyethylene alkyl phosphate ester, the uniform dispersibility of the inorganic oxide particles can be further improved.

  As the above-mentioned amidoamine salt of high molecular weight polycarboxylic acid, those represented by the following formula (6) are preferable.

（式（６）中、ｒおよびｓは、ゲルパーミエーションクロマトグラフィーにより求められたポリスチレン換算数平均分子量が、１００００〜４００００となるように選択される数である。）

(In formula (6), r and s are numbers selected such that the polystyrene-equivalent number average molecular weight determined by gel permeation chromatography is 10,000 to 40,000.)

  As a commercial item of the dispersant represented by the above formula (6), PLAAD ED211 manufactured by Enomoto Kasei Co., Ltd. and the like can be mentioned. The uniform dispersibility of the inorganic oxide particles can be further improved by the above amide amine salt of high molecular weight polycarboxylic acid.

  As the above-mentioned ethylenediaminepropylene oxide-ethylene oxide condensate, one represented by the following formula (7) is preferable.

（式（７）中、ｔおよびｕは、ゲルパーミエーションクロマトグラフィーにより求められたポリスチレン換算数平均分子量が１０００〜３００００となるように選択される数である。）

(In formula (7), t and u are numbers selected so that the polystyrene-equivalent number average molecular weight determined by gel permeation chromatography is 1000 to 30000.)

  Examples of commercially available dispersants represented by the above formula (7) include Adeka Pluronic TR-701, TR-702, and TR-704 manufactured by ADEKA Corporation. Even with the above ethylenediaminepropylene oxide-ethylene oxide condensate, the uniform dispersibility of the inorganic oxide particles can be further improved.

  As said polyoxyethylene alkyl ether, what is represented by following formula (8) is preferable.

（式（８）中、Ｒ^４は炭素数１〜２０のアルキル基である。ｖは１０〜３００の整数である。）

(In the formula (8), ^{R 4} is .v an alkyl group having 1 to 20 carbon atoms is an integer of 10 to 300.)

In the polyoxyethylene alkyl ether represented by the above formula (8), R ⁴ is particularly preferably an alkyl group having 1 to 12 carbon atoms.
As a commercial item of the dispersing agent represented by the above formula (8), Adeka (trademark) TN / SO / UA series manufactured by ADEKA Corporation and the like can be mentioned.

  As the above-mentioned polyoxyethylene alkylphenol ether, a compound represented by the following formula (9) is preferable.

（式（９）中、Ｒ^５は炭素数１〜１２のアルキル基である。ｗは１０〜３００の整数である。）

(In the formula (9), ^{R 5} is .w an alkyl group having 1 to 12 carbon atoms is an integer of 10 to 300.)

  Examples of commercially available dispersants represented by the above formula (9) include ADEKA Adecatol (registered trademark) SP / PC series.

  As said alkyl glucoside, what is represented by following formula (10) is preferable.

（式（１０）中、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９およびＲ^１０は、それぞれ独立して、水素または炭素数１〜１２のアルキル基である。）

(In formula (10), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms.)

  As said polyoxyethylene fatty acid ester, what is represented by following formula (11) is preferable.

（式（１１）中、Ｒ^２１は、炭素数１〜２０のアルキル基である。Ｒ^２２は、水素または炭素数２〜１３のアシル基である。ｙは１０〜３００の整数である。）

(In Formula (11), R ²¹ is an alkyl group having 1 to 20 carbon atoms. R ²² is hydrogen or an acyl group having 2 to 13 carbon atoms. Y is an integer of 10 to 300.)

In the polyoxyethylene fatty acid ester represented by the above formula (11), R ²¹ is particularly preferably an alkyl group having 1 to 12 carbon atoms.

  Examples of commercially available dispersants represented by the above formula (11) include Adeka Estor (registered trademark) OEG series, Adeka Estor (registered trademark) TL series manufactured by ADEKA Corporation.

  As said sucrose fatty acid ester, what is represented by following formula (12) is preferable.

（式（１２）中、Ｒ^２３、Ｒ^２４、Ｒ^２５、Ｒ^２６、Ｒ^２７、Ｒ^２８、Ｒ^２９およびＲ^３０はそれぞれ独立して、水素または炭素数２〜１３のアシル基である。）

(In formula (12), R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ are each independently hydrogen or an acyl group having 2 to 13 carbon atoms.)

  As said sorbitan fatty acid ester, what is represented by following formula (13) is preferable.

（式（１３）中、Ｒ^３１は、−（ＣＨ^２ＣＨ^２Ｏ）_ｚ１−Ｈで表される基である。ｚ１は、１０〜３００の整数である。）

(In formula (13), R ³¹ is a group represented by — (CH ² CH ² O) _z1 —H. Z1 is an integer of 10 to 300.)

  As a commercial item of the dispersing agent represented by the above formula (13), Adeka Estor (registered trademark) S series manufactured by ADEKA Corporation and the like can be mentioned.

  As polyoxyethylene sorbitan fatty acid ester, what is represented by following formula (14) is preferable.

（式（１４）中、Ｒ^３２、Ｒ^３３およびＲ^３４は、それぞれ独立して、水素または−（ＣＨ_２ＣＨ_２Ｏ）_ｚ２−Ｈで表される基である。ｚ２は、１０〜３００の整数である。）

(In the formula ^{(14), R 32, R} 33 and ^{R 34} are each independently hydrogen or _{- (CH 2 CH 2 O)} .z2 a group represented by z2 -H is 10 to 300 (It is an integer.)

  As fatty acid alkanolamide, what is represented by following formula (15) is preferable.

（式（１５）中、Ｒ^３５は、炭素数１〜２０のアルキル基である。）

(In the formula (15), R ³⁵ is an alkyl group having 1 to 20 carbon atoms.)

In the fatty acid alkanolamide represented by the above formula (15), R ³⁵ is particularly preferably an alkyl group having 1 to 12 carbon atoms.

  Examples of commercially available dispersants represented by the above formula (15) include ADEKA's Adekatol (registered trademark) series and the like.

  In the radiation sensitive resin composition of the present embodiment, the blending amount of the dispersant as the component [D] is not particularly limited, but when [C] inorganic oxide particles are contained, [C] inorganic oxide 0.1 mass part-100 mass parts are preferable with respect to 100 mass parts of particle | grains, and 10 mass parts-60 mass parts are more preferable. When the blending amount of the dispersant as the component [D] is less than 0.1 parts by mass, the dispersibility of the [C] inorganic oxide particles is lowered, and thereby the coating property and storage stability of the radiation-sensitive resin composition As a result, the patterning property may decrease. On the other hand, when the blending amount exceeds 100 parts by mass, the radiation sensitive property may be deteriorated in the radiation sensitive resin composition of the present embodiment. Moreover, when there are too many dispersing agents, there exists a possibility that the adhesiveness to the board | substrate etc. of the hardened | cured material obtained using the radiation sensitive resin composition of this embodiment may fall, and heat resistant transparency may be impaired. .

  The dispersant as the [D] component may be added when preparing the radiation-sensitive resin composition, and the dispersant and the [C] inorganic oxide particles are added in advance as an arbitrary solvent as the [D] component. The dispersion may be mixed in the mixture and treated as a dispersion of [C] inorganic oxide particles.

  As the [D] solvent and other optional components of the radiation-sensitive resin composition of the present embodiment, a solvent, a surfactant, and the like can be contained in addition to the dispersant. Hereinafter, the solvent and the surfactant, which are the [D] solvent and other optional components of the radiation-sensitive resin composition of the present embodiment, will be described.

  The solvent which is [D] component adjusts the radiation sensitive resin composition of this embodiment to desired solid content concentration, [A] siloxane compound, [B] photoinitiator, and [D] component In the case where the other optional components are uniformly and stably dissolved, or when [C] inorganic oxide particles are contained, the [C] inorganic oxide particles can be uniformly and stably dispersed in the radiation-sensitive resin composition. it can. Moreover, the applicability | paintability and film formability at the time of apply | coating the radiation sensitive resin composition of this embodiment to a board | substrate can be improved. That is, the solvent which is [D] component will not be specifically limited if it has the above functions.

  [D] Solvents include alcohols such as methanol, ethanol, isopropyl alcohol, butanol and octanol; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3- Esters such as methyl methoxypropionate and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether and diethylene glycol monomethyl ether; dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. Amides; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; benzene, toluene Xylene, it can be used aromatic hydrocarbons such as ethylbenzene. The solvent for obtaining the [A] siloxane compound by hydrolysis / condensation of the hydrolyzable silane compound described above can also be used as the [D] component. [D] A solvent can be used 1 type or in mixture of 2 or more types.

  The surfactant as the component [D] can be added to improve the coating property of the radiation-sensitive resin composition of the present embodiment, reduce coating unevenness, and improve the developability of the radiation irradiated part. Examples of preferable surfactants include fluorine-based surfactants and silicone-based surfactants.

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether and 1,1,2,2-tetrafluorooctylhexyl. Ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1, Fluoroethers such as 1,2,2-tetrafluorobutyl) ether and hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether; sodium perfluorododecyl sulfonate; 1,1 , 2, 2, 8, 8, 9, 9, 10, 10-decafluorododecane, 1, 1, 2, 2, 3, 3 Fluoroalkanes such as hexafluorodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides; fluoroalkylpolyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxy Rates: Fluorine alkyl esters and the like can be mentioned.

  Commercially available products of these fluorosurfactants include Ftop (registered trademark) EF301, 303, and 352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFac (registered trademark) F171, 172, and 173 (DIC Corporation). Manufactured), FLORARD FC430, 431 (manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710, Surflon (registered trademark) S-382, SC-101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.) )), FTX-218 (manufactured by Neos Co., Ltd.), and the like.

  As an example of the above-mentioned silicone type surfactant, it is a commercial name, SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH8400 FLUID (manufactured by Toray Dow Corning Silicone Co., Ltd.), organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.).

  The amount of the surfactant used is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass of the [A] siloxane compound. . By making the compounding quantity of surfactant into 0.01 mass part-10 mass parts, the applicability | paintability of the radiation sensitive resin composition of this embodiment can be optimized.

The radiation sensitive resin composition of this embodiment can contain a various additive further as a [D] component as needed. Examples of the additive include a radiation-sensitive acid generator such as triphenylsulfonium salt and tetrahydrothiophenium salt; a radiation-sensitive base generator such as 2-nitrobenzylcyclohexyl carbamate and O-carbamoylhydroxyamide; -Antioxidants such as thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol; 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5 UV absorbers such as chlorobenzotriazole and alkoxybenzophenones; various monofunctional or polyfunctional (meth) acrylate compounds; various hydrolyzable silane compounds represented by silane coupling agents; formula (2) and formula Other photoinitiators other than the photoinitiator represented by (4) can be mentioned.
The content of these additives can be appropriately selected within a range that does not impair the object of the present invention.

<Preparation of radiation-sensitive resin composition>
The radiation sensitive resin composition of this embodiment is prepared by mixing the above-described [A] siloxane compound and [B] photopolymerization initiator at a predetermined ratio. Moreover, when the radiation sensitive resin composition of this embodiment contains [C] inorganic oxide particle, [D] solvent, and other arbitrary components as needed, [C] inorganic oxide particle, [D] It is prepared by mixing a solvent and other optional components at a predetermined ratio. [A] The siloxane compound may be dissolved in a solvent in advance and handled as a solution of the [A] siloxane compound. [B] The photopolymerization initiator is dissolved in a solvent in advance and [B] the photopolymerization initiator. The [C] inorganic oxide particles may be handled as a dispersion of [C] inorganic oxide particles as described above, and the other optional components as the [D] component are pre-solvents. It may be dissolved in [D] and treated as a solution of other optional components. The solvent used in these cases can be the same as the solvent [D] described above. Moreover, when it contains [C] inorganic oxide particle | grains, as above-mentioned, you may perform a dispersion process as needed.

Embodiment 3. FIG.
<Curing film and gate insulating film>
The cured film of this embodiment is formed using the radiation sensitive resin composition of this embodiment mentioned above. Below, the cured film of this embodiment and the method of forming it are demonstrated. The cured film of this embodiment can be suitably used, for example, as the gate insulating film of the semiconductor element of the embodiment of the present invention described above, that is, the gate insulating film of the embodiment of the present invention.
The method for forming a cured film according to this embodiment includes the following steps.

(1) The process of forming the coating film of the radiation sensitive resin composition of embodiment of this invention on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) Step of developing the coating film irradiated with radiation in step (2) (developing step), and (4) Step of heating the coating film developed in step (3) (heating step)

It is preferable that the formation method of the cured film of this embodiment includes a process (1)-a process (4) in this order, and before and after each process of a process (1)-a process (4) as needed. Other steps may be included.
Next, each process of the above-mentioned process (1)-process (4) is demonstrated in detail.

(1) The process of forming the coating film of a radiation sensitive resin composition on a board | substrate In the above-mentioned process (1), after apply | coating the radiation sensitive resin composition of embodiment of this invention mentioned above on a board | substrate, Preferably, the solvent is removed by heating (pre-baking) the coated surface to form a coating film.

  Examples of the substrate that can be used include glass, quartz, silicon, and resin. Specific examples of the resin include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opened polymer of cyclic olefin, and a hydrogenated product thereof.

  When the cured film of the present embodiment is used as the gate insulating film of the semiconductor element of the present embodiment described above, the substrate is a gate electrode (scanning signal line) on the substrate made of the glass or resin described above. It can be set as the board | substrate with which this was formed. In that case, the above-mentioned step (1) is a step of forming a coating film on a substrate having a gate electrode using the radiation-sensitive resin composition of the embodiment of the present invention.

  The application method of the radiation sensitive resin composition is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method or the like is adopted. can do. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable. Prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but can be preferably about 70 to 120 ° C. for 1 to 10 minutes.

(2) Step of irradiating at least a part of the coating film In the above-described step (2), at least a part of the coating film on the substrate formed in the step (1) is irradiated with radiation, that is, exposed. In this case, when exposing a part of the coating film, for example, the exposure is performed through a photomask having a predetermined pattern. When the cured film of this embodiment is used as the gate insulating film of the semiconductor element of this embodiment described above, the pattern of the photomask corresponds to the pattern of the gate insulating film.

  As radiation used for exposure, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used, for example. Among these radiations, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation including ultraviolet light of 365 nm is particularly preferable.

The exposure amount in this step is preferably 10 mJ / cm ^{2 to} 1000 mJ / cm ² , more preferably 20 mJ, as a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.). / Cm ^{2 to} 600 mJ / cm ² .
In the case of the negative type by exposure, [B] active species such as radicals, acids, bases, etc. are generated from the photopolymerization initiator or the like, so that unsaturated bonds existing in the coating are bonded to each other, siloxane A siloxane bond is generated by a condensation reaction of a compound or the like, so that the exposed portion is insoluble in the developer.

(3) Development process In the above-mentioned process (3), an unnecessary part (in the case of a negative type, a non-irradiated part) is removed by developing the coating film after the exposure in the process (2). A predetermined pattern is formed. The developer used in the development step is preferably an aqueous solution of an alkali (basic compound). Examples of alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide Etc.

  In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to such an alkaline aqueous solution. The concentration of alkali in the aqueous alkali solution is preferably 0.05% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. As a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the radiation sensitive resin composition, but is preferably about 10 seconds to 180 seconds. Following such development processing, for example, after washing with running water for 30 seconds to 90 seconds, a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

(4) Heating step In the step (4) described above, the [A] siloxane compound of the radiation sensitive resin composition is obtained by heating the patterned film at a relatively high temperature using a heating device such as a hot plate or oven. The condensation reaction can be promoted to obtain a cured film. The cured film patterned in the predetermined shape can be used as a gate insulating film of the semiconductor element of this embodiment.

  The heating temperature in this step is, for example, 150 ° C to 350 ° C. The heating time varies depending on the type of heating device, but for example, when performing the heating process on a hot plate, it may be 5 minutes to 30 minutes, and when performing the heating process in an oven, it may be 30 minutes to 90 minutes. it can. Moreover, the step baking method etc. which perform a heating process 2 times or more can also be used. In this manner, a desired patterned cured film can be formed on the surface of the substrate. When a cured film is formed over the gate electrode and used as a gate insulating film, heating may be performed in an inert gas atmosphere such as nitrogen or argon in order to prevent the gate electrode from being deteriorated in this step.

  The formed cured film of the present embodiment is made of resin and is insulative. And the cured film of this embodiment is formed using the radiation sensitive resin composition of this embodiment, can be patterned, and has high visible light permeability. And the cured film of this embodiment is excellent in heat resistance, As a result, it is excellent in heat-resistant transparency. Further, in the cured film of this embodiment, the relative dielectric constant, which is a dielectric property, is controlled to a desired value.

  Therefore, as described above, the cured film of the present embodiment is used as a gate insulating film, and can provide a semiconductor element. That is, the gate insulating film of the embodiment of the present invention can be the one using the cured film of the embodiment of the present invention formed using the radiation-sensitive resin composition of the embodiment of the present invention. In other words, the gate insulating film of the semiconductor element according to the embodiment of the present invention uses the radiation-sensitive resin composition according to the embodiment of the present invention in the same manner as the cured film according to the present embodiment. It can be formed according to the forming method.

  Therefore, the gate insulating film of the semiconductor element of this embodiment has heat resistance and high visible light transmittance, and is excellent in heat-resistant transparency. Further, the relative dielectric constant of the gate insulating film of this embodiment is controlled to a desired value.

  About the formation method of the gate insulating film of this embodiment, since it consists of the cured film of embodiment of this invention as mentioned above, formation of the cured film of embodiment of this invention mentioned above It becomes the same as the method.

  That is, the cured film of the embodiment of the present invention is formed on the substrate on which the gate electrode (scanning signal line) is formed on the same substrate as that described above, which is made of glass, resin, or the like. It becomes an insulating film and constitutes a semiconductor element. Therefore, the method for forming a gate insulating film according to the embodiment of the present invention preferably includes the following steps (1) to (4) similar to those described above in this order.

(1) The process of forming a coating film on the board | substrate which has a gate electrode using the radiation sensitive resin composition of embodiment of this invention,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) Step of developing the coating film irradiated with radiation in step (2) (developing step), and (4) Step of heating the coating film developed in step (3) (heating step)

  And each of process (1)-process (4) for forming the gate insulating film of this embodiment respond | corresponds to process (1)-process (4) of the formation method of the cured film of this embodiment mentioned above. It is the same as each of the above. In the step (1) for forming the gate insulating film, the gate electrode (scanning signal line) is formed on the substrate made of the above glass, resin, or the like as the substrate in the method for forming the cured film. Corresponds to the case where things are used. Therefore, the description which overlaps about each of the above process (1) -process (4) is abbreviate | omitted.

Embodiment 4 FIG.
<Display device>
As an example of the display device according to the present embodiment, an example of the organic EL display device according to the present embodiment will be described with reference to the drawings.

  FIG. 2 is a cross-sectional view schematically illustrating the structure of the main part of the organic EL display device of this embodiment.

  The organic EL display device 1 of the present embodiment is an active matrix organic EL display device having a plurality of pixels formed in a matrix. The organic EL display device 1 may be either a top emission type or a bottom emission type. The organic EL display device 1 has the TFT 3 which is the semiconductor element of the embodiment of the present invention shown in FIG. Therefore, in the organic EL display device 1 of the present embodiment shown in FIG. 2, the same reference numerals are given to the same components as those of the TFT 3 of FIG.

  As for the substrate 2 of the organic EL display device 1, when the organic EL display device 1 is a bottom emission type, the substrate 2 is required to be transparent. As an example of the material of the substrate 2, PET (polyethylene terephthalate) or Transparent resins such as PEN (polyethylene naphthalate) and PI (polyimide), and glass such as non-alkali glass are used. On the other hand, when the organic EL display device 1 is a top emission type, the substrate 2 does not need to be transparent, so that an arbitrary insulator can be used as the material of the substrate 2. Similarly to the bottom emission type, a glass material such as alkali-free glass can be used.

  As described above, the TFT 3 includes a gate electrode 4 that forms part of a scanning signal line (not shown) on the substrate 2, a gate insulating film 5 that covers the gate electrode 4, and a gate insulating film on the gate electrode 4. 5, a first source-drain electrode 7 that forms part of a video signal line (not shown) and is connected to the semiconductor layer 6, and a second source that is connected to the semiconductor layer 6. And a source-drain electrode 8.

  The TFT 3 is a semiconductor element having a structure in which the semiconductor layer 6 and the gate electrode 4 overlap with each other with the gate insulating film 5 interposed therebetween. The TFT 3 has a bottom gate structure in which the gate electrode 4, the gate insulating film 5, and the semiconductor layer 6 are stacked in this order on the substrate 2.

  In the organic EL display device 1, the first insulating film 10 is disposed on the inorganic insulating film 19 so as to cover the TFT 3 on the substrate 2. The first insulating film 10 has a function of flattening unevenness caused by the TFT 3 formed on the substrate 2. The first insulating film 10 can be an insulating film formed using a radiation-sensitive resin composition. That is, the first insulating film 10 can be an organic film formed using an organic material. The first insulating film 10 preferably has an excellent function as a planarizing film, and is preferably formed thick from this viewpoint. For example, the first insulating film 10 can be formed with a film thickness of 1 μm to 6 μm. The first insulating film 10 can be formed in accordance with a known method by performing patterning by exposure and development after application and curing.

  On the first insulating film 10, an anode 11 serving as a pixel electrode is disposed. The anode 11 is made of a conductive material. The material of the anode 11 is preferably selected from materials having different characteristics depending on whether the organic EL display device 1 is a bottom emission type or a top emission type. In the case of the bottom emission type, since the anode 11 is required to be transparent, the material of the anode 11 is selected from ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), tin oxide, and the like. On the other hand, when the organic EL display device 1 is a top emission type, the anode 11 is required to have light reflectivity. As the material of the anode 11, APC alloy (silver, palladium, copper alloy) or ARA (silver, rubidium) is used. , Gold alloy), MoCr (molybdenum and chromium alloy), NiCr (nickel and chromium alloy), and the like are selected. The thickness of the anode 11 is preferably 100 nm to 500 nm.

  Since the anode 11 disposed on the first insulating film 10 is connected to the second source-drain electrode 8, a through hole 12 that penetrates the first insulating film 10 is formed in the first insulating film 10. Has been. The through hole 12 is formed so as to also penetrate the inorganic insulating film 19 under the first insulating film 10. As described above, the first insulating film 10 can be formed using a radiation-sensitive resin composition. Therefore, according to the above-described forming method, the first insulating film 10 having a through hole having a desired shape is formed by irradiating the coating film of the radiation-sensitive resin composition with radiation, and then the first insulating film 10 is formed. By performing dry etching on the inorganic insulating film 19 as a mask, the through hole 12 can be completed. In the case where the inorganic insulating film 19 is not disposed on the TFT 3, a through hole formed by irradiating the first insulating film 10 with radiation constitutes the through hole 12. As a result, the anode 11 covers at least a part of the first insulating film 10 and is applied to the TFT 3 through the through hole 12 provided in the first insulating film 10 so as to penetrate the first insulating film 10. It can be connected to the second source-drain electrode 8 to be connected.

  In the organic EL display device 1, a second insulating film 13 is formed on the anode 11 on the first insulating film 10 and serves as a partition that defines the arrangement region of the organic light emitting layer 14. Similar to the first insulating film 10 described above, the second insulating film 13 can be formed using a radiation-sensitive resin composition. That is, using a radiation-sensitive resin composition, the coating film can be patterned according to the same formation method as described above to form a cured film. The second insulating film 13 can have, for example, a lattice shape in plan view. In an area defined by the second insulating film 13, an organic light emitting layer 14 that emits electroluminescence is disposed. In the organic EL display device 1, the second insulating film 13 serves as a barrier that surrounds the periphery of the organic light emitting layer 14 and partitions each of a plurality of adjacent pixels.

  In the organic EL display device 1, the height of the second insulating film 13 (the distance between the upper surface of the second insulating film 13 and the upper surface of the anode 11 in the region where the organic light emitting layer 14 is disposed) is 0.1 μm to 2 μm. It is preferable that it is 0.8 micrometer-1.2 micrometers. When the height of the second insulating film 13 is 2 μm or more, the second insulating film 13 may collide with the sealing substrate 20 above the second insulating film 13. Further, when the height of the second insulating film 13 is 0.1 μm or less, an ink-like luminescent material composition is applied to the region defined by the second insulating film 13 by an ink jet method. Sometimes, the luminescent material composition may leak from the second insulating film 13.

  As described above, the second insulating film 13 of the organic EL display device 1 is formed as a cured film by using a radiation-sensitive resin composition and patterning the coating film according to the above-described forming method. be able to. That is, the second insulating film 13 can be configured to include a resin. The second insulating film 13 defines a region to which the ink-like luminescent material composition containing an organic luminescent material is applied when the ink-like luminescent material composition is applied by an ink-jet method. Is preferably low. When the wettability of the second insulating film 13 is controlled to be particularly low, the second insulating film 13 can be subjected to plasma treatment with fluorine gas, and radiation sensitivity for forming the second insulating film 13 is also possible. A liquid repellent may be contained in the functional resin composition. Since plasma treatment may adversely affect other components of the organic EL display device 1, it may be preferable to include a liquid repellent in the radiation-sensitive resin composition forming the second insulating film 13.

  In the organic EL display device 1 of the embodiment of the present invention, the radiation-sensitive resin composition of the embodiment of the present invention described above is used as the radiation-sensitive resin composition for forming the first insulating film 10. Can be used. Moreover, the radiation sensitive resin composition of embodiment of this invention mentioned above can be used for the radiation sensitive resin composition which forms the 2nd insulating film 13. FIG.

  An organic light emitting layer 14 that emits light by applying an electric field is disposed in a region defined by the second insulating film 13. The organic light emitting layer 14 is a layer containing an organic light emitting material that emits electroluminescence.

The organic light emitting material contained in the organic light emitting layer 14 may be a low molecular weight organic light emitting material or a polymer organic light emitting material. For example, a material obtained by doping quinacridone or coumarin into a base material base such as Alq ₃ or BeBq ₃ can be used. Moreover, when using the coating method of the organic luminescent material by the inkjet method, it is preferable that it is a polymeric organic luminescent material suitable for it. Examples of the polymer organic light emitting material include polyphenylene vinylene and derivatives thereof, polyacetylene and derivatives thereof, polyphenylene and derivatives thereof, polyparaphenylene ethylene and derivatives thereof, poly 3 -Hexylthiophene (Poly 3-hexyl thiophene (P3HT)) and its derivatives, polyfluorene (Poly fluorene (PF)) and its derivatives, etc. can be selected and used.

  The organic light emitting layer 14 is disposed on the anode 11 in a region defined by the second insulating film 13. The thickness of the organic light emitting layer 14 is preferably 50 nm to 100 nm. Here, the thickness of the organic light emitting layer 14 means the distance from the bottom surface of the organic light emitting layer 14 on the anode 11 to the top surface of the organic light emitting layer 14 on the anode 11.

  A hole injection layer and / or an intermediate layer may be disposed between the anode 11 and the organic light emitting layer 14. When the hole injection layer and the intermediate layer are disposed between the anode 11 and the organic light emitting layer 14, the hole injection layer is disposed on the anode 11, the intermediate layer is disposed on the hole injection layer, and An organic light emitting layer 14 is disposed on the intermediate layer. Further, the hole injection layer and the intermediate layer may be omitted as long as holes can be efficiently transported from the anode 11 to the organic light emitting layer 14.

  In the organic EL display device 1, a cathode 15 is formed so as to cover the organic light emitting layer 14 and the second insulating film 13 for pixel division. The cathode 15 is formed so as to cover a plurality of pixels in common, and forms a common electrode of the organic EL display device 1.

The organic EL display device 1 of the present embodiment has a cathode 15 on the organic light emitting layer 14, and the cathode 15 is made of a conductive member. The material used for forming the cathode 15 differs depending on whether the organic EL display device 1 is a bottom emission type or a top emission type. In the case of the top emission type, the cathode 15 is preferably an ITO electrode or an IZO electrode that constitutes a visible light transmissive electrode. On the other hand, when the organic EL display device 1 is a bottom emission type, the cathode 15 does not have to be visible light transmissive. In this case, the constituent material of the cathode 15 is not particularly limited as long as it is conductive. For example, barium (Ba), barium oxide (BaO), aluminum (Al), and an alloy containing Al can be selected. is there.
In addition, between the cathode 15 and the organic light emitting layer 14, the electron injection layer which consists of barium (Ba), lithium fluoride (LiF), etc. may be arrange | positioned, for example.

  A passivation film 16 can be provided on the cathode 15. The passivation film 16 can be formed by using a metal nitride such as SiN or aluminum nitride (AlN) alone or by laminating them. Due to the action of the passivation film 16, the intrusion of moisture and oxygen into the organic EL display device 1 can be suppressed.

  The main surface of the substrate 2 thus configured on which the organic light emitting layer 14 is disposed uses a sealing agent (not shown) applied in the vicinity of the outer peripheral end portion, and the sealing substrate via the sealing layer 17. It is preferable to seal with 20. The sealing layer 17 can be a layer of an inert gas such as dried nitrogen gas or a layer of a filler material such as an adhesive. As the sealing substrate 20, a glass substrate such as non-alkali glass can be used.

  In the organic EL display device 1 of the present embodiment having the above-described structure, the gate insulating film 5 of the TFT 3 as a constituent element is formed using the radiation-sensitive resin composition of the present embodiment having patterning properties. . The gate insulating film 5 of the TFT 3 becomes the gate insulating film of the embodiment of the present invention described above. That is, the gate insulating film 5 is controlled to have heat resistance and transparency, heat resistance transparency, and desired dielectric characteristics.

  Therefore, the organic EL display device 1 according to the present embodiment controls the dielectric characteristics and insulates the TFT 3 by the coating type gate insulating film according to the present embodiment using the radiation-sensitive resin composition according to the present embodiment. Is realized. That is, the organic EL display device 1 of the present embodiment does not use a vacuum process that requires a large-scale device in forming the gate insulating film 5 when forming the TFT 3. And the organic EL display device 1 of this embodiment implement | achieves high productivity with the outstanding display quality.

  Hereinafter, although an embodiment of the present invention is explained in full detail based on an example, the present invention is not limitedly interpreted by this example.

  The number average molecular weight (Mn) and weight average molecular weight (Mw) of the siloxane compound obtained from the following synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.

Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 (manufactured by Showa Denko KK) Mobile phase: Tetrahydrofuran

Further, the solid content concentration of the solution containing the siloxane compound obtained from the following synthesis example is the mass of the residue after measuring a solution containing a certain amount of the siloxane compound and heating it on a hot plate at 175 ° C. for 60 minutes. Was measured and determined by the following formula.
(Solid content concentration (mass%)) = (mass of residue after heating) / (mass of solution containing siloxane compound before heating) × 100

[A] Synthesis of Siloxane Compound [Synthesis Example 1] Synthesis of Siloxane Compound (A-1) In a vessel equipped with a stirrer, 80 parts by mass of propylene glycol monomethyl ether was charged, and subsequently hydrolyzable silane compounds were added in total. 100 parts by mass (methyltrimethoxysilane (MTMS) 45 mol%, dimethoxydimethylsilane (DMDMS) 30 mol%, 3-methacryloxypropyltrimethoxysilane (MPTMS) 25 mol%) is added, and the solution temperature becomes 60 ° C. Until heated. After the solution temperature reached 60 ° C., 0.5 parts by mass of formic acid and 25 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 3 hours. After cooling to 45 ° C., 28 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation and concentration were performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thereafter, propylene glycol monomethyl ether was added and diluted so that the solid content concentration was 35% by mass to obtain a solution containing the siloxane compound (A-1). The weight average molecular weight (Mw) of the obtained siloxane compound (A-1) was 1810, and the molecular weight distribution dispersity (Mw / Mn) was 1.6.

[Synthesis Example 2] Synthesis of siloxane compound (A-2) As hydrolyzable silane compound, MTMS was 25 mol%, DMDMS was 30 mol%, MPTMS was 45 mol%, except that 100 parts by mass was used in total. In the same manner as in Synthesis Example 1, a solution containing the siloxane compound (A-2) was obtained. The weight average molecular weight (Mw) of the obtained siloxane compound (A-2) was 1720, and the molecular weight distribution dispersity (Mw / Mn) was 1.6.

[Synthesis Example 3] Synthesis of Siloxane Compound (A-3) As a hydrolyzable silane compound, MTMS was 25 mol%, phenyltrimethoxysilane (PTMS) was 50 mol%, and MPTMS was 25 mol%, for a total of 100 parts by mass. And a solution containing the siloxane compound (A-3) was obtained in the same manner as in Synthesis Example 1 except that 0.75 part by mass of formic acid was used. The weight average molecular weight (Mw) of the obtained siloxane compound (A-3) was 1360, and the molecular weight distribution dispersity (Mw / Mn) was 1.5.

[Synthesis Example 4] Synthesis of Siloxane Compound (A-4) As hydrolyzable silane compound, 35 mass% of MTMS, 50 mol% of DMDMS, 15 mol% of MPTMS, and 100 parts by mass in total were used. In the same manner as in Synthesis Example 1, a solution containing the siloxane compound (A-4) was obtained. The weight average molecular weight (Mw) of the obtained siloxane compound (A-4) was 1420, and the molecular weight distribution dispersity (Mw / Mn) was 1.5.

[Synthesis Example 5] Synthesis of Siloxane Compound (A-5) As a hydrolyzable silane compound, 45 mol% of MTMS, 30 mol% of DMDMS, and 25 mol% of 3-acryloxypropyltrimethoxysilane (APTMS) were combined. A solution containing the siloxane compound (A-5) was obtained in the same manner as in Synthesis Example 1 except that 100 parts by mass was used. The weight average molecular weight (Mw) of the obtained siloxane compound (A-5) was 1780, and the molecular weight distribution dispersity (Mw / Mn) was 1.6.

[Synthesis Example 6] Synthesis of Siloxane Compound (A-6) As a hydrolyzable silane compound, 45 mol% of MTMS, 30 mol% of DMDMS, and 25 mol% of 3-methacryloxypropyltriethoxysilane (MPTES), total A solution containing the siloxane compound (A-6) was obtained in the same manner as in Synthesis Example 1 except that 100 parts by mass was used. The weight average molecular weight (Mw) of the obtained siloxane compound (A-6) was 1540, and the molecular weight distribution dispersity (Mw / Mn) was 1.6.

[Synthesis Example 7] Synthesis of Siloxane Compound (A-7) As a hydrolyzable silane compound, MTMS is 45 mol%, DMDMS is 30 mol%, and styryltrimethoxysilane (StTMS) is 25 mol%, for a total of 100 parts by mass. A solution containing the siloxane compound (A-7) was obtained in the same manner as in Synthesis Example 1 except that was used. The resulting siloxane compound (A-7) had a weight average molecular weight (Mw) of 1610 and a molecular weight distribution dispersity (Mw / Mn) of 1.6.

[Synthesis Example 8] Synthesis of Siloxane Compound (A-8) As a hydrolyzable silane compound, MTMS was 45 mol%, DMDMS was 30 mol%, and vinyltrimethoxysilane (VTMS) was 25 mol%, for a total of 100 parts by mass. A solution containing the siloxane compound (A-8) was obtained in the same manner as in Synthesis Example 1 except that was used. The resulting siloxane compound (A-8) had a weight average molecular weight (Mw) of 1850 and a molecular weight distribution dispersity (Mw / Mn) of 1.7.

[Synthesis Example 9] Synthesis of Siloxane Compound (A-9) As a hydrolyzable silane compound, tetraethoxysilane (TEOS) was 30 mol%, DMDMS was 45 mol%, MPTMS was 25 mol%, and 100 parts by mass in total. Except having used, it carried out similarly to the synthesis example 1, and obtained the solution containing a siloxane compound (A-9). The weight average molecular weight (Mw) of the obtained siloxane compound (A-9) was 2230, and the molecular weight distribution dispersity (Mw / Mn) was 2.0.

Synthesis Example 10 Synthesis of Siloxane Compound (A-10) As a hydrolyzable silane compound, MTMS was 40 mol%, DMDMS was 30 mol%, MPTMS was 25 mol%, 3-trimethoxysilylpropyl succinic anhydride ( A solution containing the siloxane compound (A-10) was obtained in the same manner as in Synthesis Example 1, except that 5 mol% of SAPTMS) and 100 parts by mass in total were used. The weight average molecular weight (Mw) of the obtained siloxane compound (A-10) was 1700, and the molecular weight distribution dispersity (Mw / Mn) was 1.6.

[Comparative Synthesis Example 1] Synthesis of Siloxane Compound (a-1) A total of 100 parts by mass of hydrolyzable silane compound (45 mol% of MTMS, 30 mol% of DMDMS, 25 mol% of MPTMS) was mixed, It used for subsequent evaluation as it was, without carrying out decomposition condensation reaction. The solid content was obtained by adding propylene glycol monomethyl ether such that the theoretical weight when the hydrolyzable silane compound was completely hydrolyzed and condensed was regarded as the solid content weight, and the solid content concentration was 35% by mass. This mixture was used as a solution containing the siloxane compound (a-1).

[Comparative Synthesis Example 2] Synthesis of Siloxane Compound (a-2) Except that 100 parts by mass of TEOS and 0.3 part by mass of formic acid were used as the hydrolyzable silane compound, in the same manner as in Synthesis Example 1, A solution containing the siloxane compound (a-2) was obtained. The weight average molecular weight (Mw) of the obtained siloxane compound (a-2) was 2660, and the molecular weight distribution dispersity (Mw / Mn) was 2.3.

[Example 1]
<Preparation of radiation-sensitive resin composition>
In the solution containing the siloxane compound (A-1) obtained in Synthesis Example 1 (an amount corresponding to 50 parts by mass (solid content) of the compound (A-1)), [B] : 4 parts by mass of the compound (2-13) described above was added, and [C] a dispersion of silica particles (C-1) as inorganic oxide particles (trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) Is added in an amount corresponding to 50 parts by mass (solid content), and propylene glycol monomethyl ether is added as a component [D] so that the solid content concentration of the prepared radiation-sensitive resin composition is 25% by mass. Resin composition (PA-1) was prepared.
Similarly, according to the composition of Table 1, the radiation sensitive resin compositions (PA-2) to (PA-15) corresponding to Examples 2 to 15 and the radiation sensitive resin compositions corresponding to Comparative Examples 1 to 4 were used. Products (Pa-1) to (Pa-4) were prepared.
Details of each component used in Examples and Comparative Examples are shown below.

[B] Photopolymerization initiator B-1: Compound (2-13) described above (trade name: IRGACURE (registered trademark) OXE 01, manufactured by BASF)
B-2: Compound (2-1) described above
B-3: Compound (4-6) described above (trade name: IRGACURE (registered trademark) 819, manufactured by BASF)
B-4: Compound (4-1) described above (trade name: LUCIRIN (registered trademark) TPO, manufactured by BASF)
b-1: Oxime ester photoinitiator (trade name: IRGACURE (registered trademark) OXE 02, manufactured by BASF)
b-2: Acetophenone photopolymerization initiator (trade name: IRGACURE (registered trademark) 369, manufactured by BASF)
[C] As inorganic oxide particles,
C-1: Dispersion of silica particles (trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd.)
C-2: Dispersion liquid of zirconia particles (trade name: ID191, manufactured by Teika Co., Ltd.)
C-3: Dispersion liquid of titania particles (trade name: TS-103, manufactured by Teika Co., Ltd.)

<Formation of cured film>
Using the above-mentioned radiation-sensitive resin composition (PA-1), applying onto a glass substrate and a glass substrate with a Ti film using a spinner, pre-baking on a hot plate at 100 ° C. for 2 minutes to form a coating film did. Next, using a TOPCON exposure machine TME-400PRJ, line / space pattern of 10 μm width / 30 μm width, hole pattern of 30 μm diameter, exposed area of 1 cm square or more, and unexposed area of 1 cm square or more Through a negative photomask having a partial layout, the exposure gap (interval between the substrate with the coating film and the photomask) was set to 50 μm, and the coating film was exposed to ultraviolet rays at an exposure amount of 100 mJ / cm ² . Subsequently, the coated substrate was immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution, developed at 25 ° C. for 60 seconds, washed with pure water for 1 minute, blown off water droplets, and air-dried. Further, a cured film having a thickness of 1.5 μm was formed by heating in an oven at 230 ° C. for 30 minutes and then in an oven at 350 ° C. for 30 minutes.

  Similarly, radiation-sensitive resin compositions (PA-2) to (PA-15) corresponding to Examples 2 to 15 and radiation-sensitive resin compositions (Pa-1) corresponding to Comparative Examples 1 to 4 Also for-(Pa-4), a cured film having a thickness of 1.5 μm was formed on the glass substrate and the substrate with the Ti film.

  In addition, since the radiation sensitive resin composition (PA-12) of Example 12 and the radiation sensitive resin composition (Pa-3) of Comparative Example 3 were expected to have high solubility in an alkali developer, curing was performed. In forming the film, development was performed using a 0.4 mass% tetramethylammonium hydroxide aqueous solution instead of development using a 2.38 mass% tetramethylammonium hydroxide aqueous solution in order to suppress pattern peeling. It was.

<Physical property evaluation>
Using the cured film formed according to the above method, the transparency, heat-resistant transparency, adhesion to the substrate, crack resistance and pattern resolution were evaluated according to the method described below. The evaluation results are summarized in Table 1.

(1) Evaluation of transparency About a cured film having a film thickness of 1.5 μm formed on a glass substrate with an area of 1 cm square or more, an ultraviolet-visible spectrophotometer (V-670 manufactured by JASCO Corporation) was used. The light transmittance (%) for each wavelength was measured in the wavelength range of 400 to 800 nm using only the measured value as a reference. Based on the light transmittance (%) for each wavelength, each value of XYZ in the CIE color system was calculated under the conditions of a D65 light source and a 2-degree visual field. Based on the calculated XYZ values, YI values (Yellowness Index, yellowness) in ASTM E313 standard were calculated. The criteria for determining transparency were as follows.
If the light transmittance (%) at a wavelength of 400 nm was 95% or more and the YI value was 1.0 or less, the transparency was determined to be good. When any one of the criteria was not satisfied, the transparency was determined to be poor.

(2) Evaluation of heat-resistant transparency The glass substrate with a cured film whose light transmittance and YI value were measured in the above "(1) Evaluation of transparency" was additionally heated in an oven at 350 ° C for 30 minutes. Thereafter, the same part as the part where the light transmittance was measured in the above “(1) Transparency evaluation” was again measured by the method of “(1) Transparency evaluation”. ) And YI value was calculated. The criteria for determining transparency were as follows.
When the light transmittance (%) at a wavelength of 400 nm was 95% or more and the YI value was 1.0 or less, the heat-resistant transparency was determined to be good. When any one of the criteria was not satisfied, the heat-resistant transparency was determined to be poor.

(3) Evaluation of Adhesiveness to Substrate Regarding a cured film having a film thickness of 1.5 μm formed on each of a glass substrate and a glass substrate with a Ti film with an area of 1 cm square or more, “8.5 of JIS K5400-1990. The “3 adhesive cross-cut tape method” was performed to determine the number of cross-cuts remaining in 100 cross-cuts. The adhesion to the glass substrate with the Ti film corresponds to the adhesion of the gate electrode to the metal. The criteria for determining adhesion were as follows.
Adhesion was determined to be good if 80 or more of 100 grids remained on both the glass substrate and the glass substrate with the Ti film. If any one of the criteria was not satisfied, the adhesion was determined to be poor.

(4) Evaluation of crack resistance A cured film pattern having a film thickness of 1.5 μm was formed on each of the glass substrate and the glass substrate with the Ti film, and left at 23 ° C. for 24 hours. Then, it was confirmed with an optical microscope whether or not cracks were generated. The crack resistance on the glass substrate with the Ti film corresponds to the crack resistance on the metal of the gate electrode. The criteria for determining crack resistance were as follows, based on the observation of a cured film in the range of 1 mm square with an optical microscope.
○: No cracks are found.
X: Cracks are found or there are innumerable cracks on the entire surface of the film.
And if both a glass substrate and the glass substrate with Ti film were "(circle)", it determined with crack resistance being favorable. If either one was “x”, the crack resistance was judged to be poor.

(5) Evaluation of pattern resolution A cured film pattern having a thickness of 1.5 μm was formed on each of the glass substrate and the glass substrate with the Ti film. The pattern resolution on the glass substrate with the Ti film corresponds to the pattern resolution on the metal of the gate electrode. The determination criteria for pattern resolution were as follows: 10 μm width / 30 μm width line / space pattern and 30 μm diameter hole pattern.
○: The above-mentioned pattern can be resolved and there is no peeling of the pattern.
X: There is a part where the above-mentioned pattern cannot be resolved, or there is pattern peeling.
When both the glass substrate and the glass substrate with the Ti film were “◯”, the pattern resolution was determined to be good. If either one is “x”, the pattern resolution is determined to be poor.

  Similarly formed radiation sensitive resin compositions (PA-2) to (PA-15) corresponding to Examples 2 to 15 and radiation sensitive resin compositions corresponding to Comparative Examples 1 to 4 For the cured films of the products (Pa-1) to (Pa-4), the transparency, heat-resistant transparency, adhesion to the substrate, crack resistance, and pattern resolution were evaluated according to the above methods. The evaluation results are summarized in Table 1.

  As shown in Table 1, the cured films formed using the radiation-sensitive resin compositions of Examples 1 to 15 were transparent, heat-resistant transparency, crack resistance, and pattern resolution when compared with Comparative Examples. All of these showed good evaluation results. On the other hand, Comparative Examples 1 and 2 had poor heat-resistant transparency. In Comparative Example 3, there was much pattern peeling, and a cured film that could be used for evaluation of transparency, heat-resistant transparency, adhesion, and crack resistance could not be produced. In Comparative Example 4, since the crack resistance was poor and fine cracks were formed on the entire surface of the cured film, a cured film that could be used for evaluation of transparency, heat-resistant transparency, and adhesion could not be produced.

  From this result, the cured film formed using the radiation sensitive resin compositions of Examples 1 to 15 is a gate insulating film of a semiconductor element such as a TFT, which is included in an active matrix organic EL display device or a liquid crystal display device. It was found to be suitable for use in

  The radiation-sensitive resin composition of the present invention is suitable for forming a gate insulating film of a semiconductor element included in a display device such as a liquid crystal display device and an organic EL display device. Conventionally, as the gate insulating film of the semiconductor element of this display device, inorganic films such as silicon oxide and silicon nitride have been widely used. However, the gate insulating film formed from the radiation-sensitive resin composition of the present invention is not limited to these. Instead, a simpler gate insulating film can be formed.

  In addition, the semiconductor element of the present invention has a gate insulating film made of a cured film using the radiation-sensitive resin composition of the present invention, and has excellent productivity and high reliability. Therefore, the semiconductor element of the present invention is suitable for uses such as a display device of a portable information device such as a large-sized liquid crystal television or a smartphone.

1 Organic EL display device 2 Substrate 3 TFT
DESCRIPTION OF SYMBOLS 4 Gate electrode 5 Gate insulating film 6 Semiconductor layer 7 1st source-drain electrode 8 2nd source-drain electrode 10 1st insulating film 11 Anode 12 Through hole 13 2nd insulating film 14 Organic light emitting layer 15 Cathode 16 Passivation film 17 Sealing layer 19 Inorganic insulating film 20 Sealing substrate

Claims (8)

A gate insulating film disposed between the semiconductor layer and the gate electrode of a semiconductor element having a semiconductor layer and a gate electrode,
[A] A siloxane compound obtained by hydrolytic condensation of a silane compound represented by the following formula (1), and [B] selected from the group of photopolymerization initiators represented by the following formula (2) and the following formula (4) A gate insulating film formed using a radiation-sensitive resin composition containing at least one selected from the above.

(In the formula (1), ^{R 1} each independently represent an alkyl group having 1 to 6 carbon atoms, ^{R 2} are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms 14 represents an aryl group, a (meth) acryloyloxy group, an epoxy group, a 3,4-epoxycyclohexyl group or a mercapto group, n represents an integer of 1 to 3, and p represents an integer of 0 to 6.

(In Formula (2), R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or carbon. Represents a heterocyclic group having a number of 2 to 20. X represents an oxygen atom, a sulfur atom or a selenium atom, and R ¹³ and R ¹⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number. A 6-30 aryl group, a C7-30 arylalkyl group, a C2-C20 heterocyclic group, a C1-C12 fluoroalkyl group, a halogen or a group represented by the following formula (3) A represents an integer of 1 to 5, and b represents an integer of 1 to 4.)

(In Formula (3), R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group. K represents an integer of 1 to 6. R ¹⁶ represents hydrogen. R ¹⁷ represents a single bond, —O—, —S—, —NR ¹⁸ —, —NR ¹⁸ CO—, —SO ₂ —, —CO—, —CS—, —OCO— or —. COO-- R ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, * represents a bonding position.)

(In Formula (4), R ¹⁹ and R ²⁰ each independently represent an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen or a hydroxyl group. M represents 1 or 2, c and d each independently represents an integer of 0 to 5.) [A] A siloxane compound obtained by hydrolytic condensation of a silane compound represented by the following formula (1), and [B] selected from the group of photopolymerization initiators represented by the following formula (2) and the following formula (4) Including at least one selected from
A radiation-sensitive resin composition used for forming the gate insulating film of a semiconductor element having a semiconductor layer, a gate electrode, and a gate insulating film disposed between the semiconductor layer and the gate electrode object.

(In the formula (1), ^{R 1} each independently represent an alkyl group having 1 to 6 carbon atoms, ^{R 2} are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms 14 represents an aryl group, a (meth) acryloyloxy group, an epoxy group, a 3,4-epoxycyclohexyl group or a mercapto group, n represents an integer of 1 to 3, and p represents an integer of 0 to 6.

(In Formula (2), R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or carbon. R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms. An alkyl group, a heterocyclic group having 2 to 20 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, a halogen, or a group represented by the following formula (3): a represents an integer of 1 to 5; Represents an integer of ~ 4.)

(In Formula (3), R ¹⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group. K represents an integer of 1 to 6. R ¹⁶ represents hydrogen. R ¹⁷ represents a single bond, —O—, —S—, —NR ¹⁸ —, —NR ¹⁸ CO—, —SO ₂ —, —CO—, —CS—, —OCO— or —. COO-- R ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, * represents a bonding position.)

(In Formula (4), R ¹⁹ and R ²⁰ each independently represent an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen or a hydroxyl group. M represents 1 or 2, c and d each independently represents an integer of 0 to 5.)   And [C] inorganic oxide particles that are oxides containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium, and hafnium. The radiation sensitive resin composition of Claim 2 characterized by the above-mentioned. A cured film formed using the radiation-sensitive resin composition according to claim 2 or 3,
A cured film used for a gate insulating film of a semiconductor element having a semiconductor layer, a gate electrode, and a gate insulating film disposed between the semiconductor layer and the gate electrode. (1) The process of forming a coating film on the board | substrate which has a gate electrode using the radiation sensitive resin composition of Claim 2 or 3.
(2) A step of irradiating at least a part of the coating film with radiation,
(3) A step of developing the coating film irradiated with the radiation; and (4) a step of heating the developed coating film.   A semiconductor element comprising a gate insulating film formed using the radiation-sensitive resin composition according to claim 2.   A semiconductor element comprising a bottom gate structure, wherein a gate electrode, the gate insulating film according to claim 1, and a semiconductor layer are arranged in this order on a substrate. A display device comprising the semiconductor element according to claim 6.

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