JP6306278B2 - Semiconductor element, semiconductor substrate, radiation-sensitive resin composition, protective film, and display element - Google Patents

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

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JP6306278B2
JP6306278B2 JP2012088397A JP2012088397A JP6306278B2 JP 6306278 B2 JP6306278 B2 JP 6306278B2 JP 2012088397 A JP2012088397 A JP 2012088397A JP 2012088397 A JP2012088397 A JP 2012088397A JP 6306278 B2 JP6306278 B2 JP 6306278B2
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group
compound
semiconductor
semiconductor layer
protective film
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JP2013219173A (en
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大吾 一戸
大吾 一戸
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Jsr株式会社
Jsr株式会社
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L29/00Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof; Multistep manufacturing processes therefor
    • H01L29/66Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76Unipolar devices, e.g. field effect transistors
    • H01L29/772Field effect transistors
    • H01L29/78Field effect transistors with field effect produced by an insulated gate
    • H01L29/786Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/78606Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L27/00Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
    • H01L27/12Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1248Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition or shape of the interlayer dielectric specially adapted to the circuit arrangement
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L29/00Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof; Multistep manufacturing processes therefor
    • H01L29/40Electrodes ; Multistep manufacturing processes therefor
    • H01L29/41Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions
    • H01L29/417Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions carrying the current to be rectified, amplified or switched
    • H01L29/41725Source or drain electrodes for field effect devices
    • H01L29/41733Source or drain electrodes for field effect devices for thin film transistors with insulated gate
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L29/00Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof; Multistep manufacturing processes therefor
    • H01L29/66Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76Unipolar devices, e.g. field effect transistors
    • H01L29/772Field effect transistors
    • H01L29/78Field effect transistors with field effect produced by an insulated gate
    • H01L29/786Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/78651Silicon transistors
    • H01L29/7866Non-monocrystalline silicon transistors
    • H01L29/78672Polycrystalline or microcrystalline silicon transistor
    • H01L29/78678Polycrystalline or microcrystalline silicon transistor with inverted-type structure, e.g. with bottom gate
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L29/00Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof; Multistep manufacturing processes therefor
    • H01L29/66Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76Unipolar devices, e.g. field effect transistors
    • H01L29/772Field effect transistors
    • H01L29/78Field effect transistors with field effect produced by an insulated gate
    • H01L29/786Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/7869Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate

Description

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

  A liquid crystal display element which is a display element is configured by sandwiching liquid crystal between a pair of substrates. An alignment film is provided on the surface of each substrate so as to control the alignment of the liquid crystal. Then, an orientation change is caused in the liquid crystal by applying an electric field between the substrates. In the liquid crystal display element, light is partially transmitted or shielded according to the change in the orientation of the liquid crystal. A liquid crystal display element can display an image using such characteristics. The liquid crystal display element has an advantage that it can be made thinner and lighter than a conventional CRT display element.

  The liquid crystal display elements at the beginning of development were used as display elements for calculators and clocks centered on character displays and the like. After that, the simple matrix method was developed, and the dot matrix display became easy. Subsequently, an active matrix liquid crystal display element was developed by developing a thin film transistor (TFT) which is a semiconductor element. And it has become possible to realize good image quality with excellent contrast ratio and response performance, and has also overcome problems such as high definition, colorization, and viewing angle expansion, so it can also be used for desktop computer monitors, etc. It came to be able to. Recently, a wider viewing angle, faster response of liquid crystal, improved display quality, and the like have been realized, and it has come to be used as a thin display element for television.

  In recent years, liquid crystal display elements are required to have higher performance, for example, a large screen for providing a large television, a flexible display using a flexible substrate, and the like. For this reason, high performance is also required for TFTs which are the main constituent elements of liquid crystal display elements.

  Conventionally, TFTs, which are semiconductor elements, have been frequently used in which amorphous silicon or polycrystalline silicon is used for a semiconductor layer. Recently, a TFT having a new structure has been studied so that it can be formed at a lower temperature, can be formed on a flexible substrate such as a resin substrate, and the desired mobility can be obtained. .

  For example, Patent Document 1 discloses a TFT technology that uses a transparent oxide semiconductor for a semiconductor layer. In the TFT described in Patent Document 1, IGZO (indium gallium zinc oxide) is used for the semiconductor layer. Then, the TFT can be formed at a low temperature, and the TFT is formed on a resin substrate having poor heat resistance, so that a flexible active matrix liquid crystal display element can be provided.

JP 2006-165529 A

  However, a semiconductor using an oxide semiconductor for the semiconductor layer has a problem with light resistance. Specifically, in the case of a semiconductor layer using an oxide semiconductor, the semiconductor layer may have absorption in an ultraviolet region or the like. For this reason, in semiconductor elements using the same, the resistance at the time of OFF decreases when light is irradiated from the outside, and a sufficient ON / OFF ratio may not be obtained when used as a switching element of a display element. . Therefore, when the semiconductor element is used for a liquid crystal display element, there is a problem that the characteristics deteriorate due to the influence of light from the outside.

  Such a problem of deterioration of characteristics due to light irradiation is a problem even in a semiconductor element using conventional amorphous silicon or the like as a semiconductor layer, although the degree of weight is different. Therefore, there is a demand for a technique for improving light resistance in a semiconductor element, particularly in a semiconductor element used for a display element such as a liquid crystal display element.

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

  Another object of the present invention is to provide a semiconductor substrate having a semiconductor element with reduced deterioration in characteristics due to the influence of light and suitable for forming a display element.

  Moreover, the objective of this invention is providing the radiation sensitive resin composition used for formation of the protective film of the semiconductor element which reduced the characteristic fall by the influence of light.

  An object of the present invention is to provide a protective film for a semiconductor element in which a deterioration in characteristics due to the influence of light is reduced.

  Furthermore, the objective of this invention is providing the display element which has a semiconductor element which reduced the characteristic fall by the influence of light.

A first aspect of the present invention is a semiconductor element having a semiconductor layer and an electrode provided on the first surface of the semiconductor layer,
A protective film is disposed between the semiconductor layer and the electrode,
The protective film includes a resin and at least one of a quinonediazide compound and an indenecarboxylic acid.

  In the first aspect of the present invention, the resin is preferably one kind selected from an acrylic resin having a carboxyl group, a polyimide resin, a polysiloxane, and a novolac resin.

In the first aspect of the present invention, the protective film is provided with a through hole,
The first surface of the semiconductor layer and the electrode are preferably connected to each other through the through hole.

In the first aspect of the present invention, a gate electrode provided on the second surface of the semiconductor layer via a gate insulating film;
It is preferable to form a bottom gate type semiconductor element having a source electrode and a drain electrode provided on the first surface.

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

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

  In the first aspect of the present invention, the semiconductor layer is preferably composed of silicon (Si).

A second aspect of the present invention includes a substrate,
A plurality of gate wirings and a plurality of data wirings arranged on the substrate;
A semiconductor element having a semiconductor layer and an electrode provided on the first surface of the semiconductor layer is disposed in a matrix pixel formed at the intersection of the plurality of gate lines and the plurality of data lines. ,
Having a protective film between the semiconductor layer and the electrode;
The protective film relates to a semiconductor substrate comprising a resin and at least one of a quinonediazide compound and an indenecarboxylic acid.

  In the second aspect of the present invention, the resin is preferably one kind selected from an acrylic resin having a carboxyl group, a polyimide resin, a polysiloxane, and a novolac resin.

In the second aspect of the present invention, the protective film is provided with a through hole,
The first surface of the semiconductor layer and the electrode are preferably connected to each other through the through hole.

In a second aspect of the present invention, a gate electrode provided on the second surface of the semiconductor layer via a gate insulating film;
It is preferable to form a bottom gate type semiconductor element having a source electrode and a drain electrode provided on the first surface.

  In the second aspect of the present invention, the semiconductor layer is formed using an oxide including at least one of indium (In), zinc (Zn), and tin (Sn). It is preferable.

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

  In the second aspect of the present invention, the semiconductor layer is preferably configured using silicon (Si).

  According to a third aspect of the present invention, there is provided a radiation-sensitive resin composition used for forming a protective film for a semiconductor device according to the first aspect of the present invention, comprising a resin and a quinonediazide compound. The present invention relates to a radiation resin composition.

  4th aspect of this invention is related with the protective film formed from the radiation sensitive resin composition of 3rd aspect of this invention.

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

  According to the first aspect of the present invention, it is possible to obtain a semiconductor element with reduced characteristic deterioration due to the influence of light.

  According to the second aspect of the present invention, it is possible to obtain a semiconductor substrate having a semiconductor element with reduced characteristic deterioration due to the influence of light and suitable for forming a display element.

  According to the 3rd aspect of this invention, the radiation sensitive resin composition used for formation of the protective film of the semiconductor element which reduced the characteristic fall by the influence of light is obtained.

  According to the fourth aspect of the present invention, it is possible to obtain a protective film for a semiconductor element with reduced characteristic deterioration due to the influence of light.

  According to the fifth aspect of the present invention, it is possible to obtain a liquid crystal display element having a semiconductor element with reduced characteristic deterioration due to the influence of light.

It is sectional drawing which illustrates the structure of the semiconductor element of this embodiment typically. It is a top view which illustrates typically the principal part structure of the semiconductor substrate of this embodiment. It is sectional drawing which illustrates typically the principal part structure of the liquid crystal display element of this embodiment.

Below, the semiconductor element of embodiment of this invention is demonstrated. Next, a semiconductor substrate configured using the semiconductor element and a liquid crystal display element as a display element having the semiconductor element will be described.
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 the semiconductor device of this embodiment.

FIG. 1 shows an example in which the semiconductor element 1 of this embodiment is provided on one surface of a substrate 10.
The semiconductor element 1 has a semiconductor layer 2 and an electrode provided on the first surface, which is the upper surface of the semiconductor layer 2 in FIG. The electrode includes a source electrode 3 and a drain electrode 4.

  The semiconductor element 1 has a protective film 5 disposed between a semiconductor layer 2 and a source electrode 3 and a drain electrode 4. As will be described in detail later, the protective film 5 is made of resin. Therefore, the protective film 5 is provided with a through hole 6, and the electrical connection between the first surface of the semiconductor layer 2 and the source electrode 3 and the electrical connection between the first surface of the semiconductor layer 2 and the drain electrode 4. Each connection is configured to be made through a corresponding through hole 6.

  A semiconductor element 1 in FIG. 1 has a gate electrode 11 on a second surface, which is a lower surface in FIG. 1, of a semiconductor layer 2 via a gate insulating film 12. That is, in the semiconductor element 1, the gate electrode 11 is disposed on the substrate 10, and the gate insulating film 12 is formed on the gate electrode 11. The semiconductor layer 2 is disposed on the gate electrode 11 via the gate insulating film 12 and has a source electrode 3 and a drain electrode 4 connected to the semiconductor layer 2. The semiconductor element 1 constitutes a bottom gate type semiconductor element.

  The semiconductor device according to the embodiment of the present invention is not limited to the bottom gate type shown in FIG. A gate electrode is provided on the first surface side, which is the upper surface of the semiconductor layer, via a gate insulating film, and a source electrode and a drain electrode connected to the first surface are arranged on the first surface to be a top gate type. It is also possible.

  In the semiconductor device 1 shown in FIG. 1, the gate electrode 11 can be formed by forming a metal thin film on the substrate 10 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.

  Examples of the material for the metal thin film constituting the gate electrode 11 include metals such as Al, Mo, Cr, Ta, Ti, Au, and Ag, and alloys such as Al—Nd and APC (Ag / Pd / Cu) alloys. I can give you. As the metal thin film, a laminated film such as a laminated film of Al (aluminum) and Mo (molybdenum) can be used.

Examples of the material of the metal oxide conductive film constituting the gate electrode 11 include metal oxide conductive materials such as tin oxide, zinc oxide, indium oxide, ITO (Indium Tin Oxide), and zinc indium oxide (IZO). Mention may be made of membranes.
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 11 is preferably 10 nm to 1000 nm.

The gate insulating film 12 disposed so as to cover the gate electrode 11 can be formed by forming an oxide film or a nitride film by sputtering, CVD, vapor deposition, or the like. The gate insulating film 12 can be formed from, for example, a metal oxide such as SiO 2 or a metal nitride such as SiN. It can also be composed of an organic material such as a polymer material. The film thickness of the gate insulating film 12 is preferably 10 nm to 10 μm. In particular, when an inorganic material such as a metal oxide is used, 10 nm to 1000 nm is preferable, and when an organic material is used, 50 nm to 10 μm is preferable.

After the source electrode 3 and the drain electrode 4 connected to the semiconductor layer 2 are formed by using a method such as a sputtering method, a CVD method, or a vapor deposition method in addition to a printing method or a coating method, a conductive film constituting the electrodes, It can be formed by patterning using a photolithography method or the like. Examples of the constituent material of the source electrode 3 and the drain electrode 4 include metals such as Al, Mo, Cr, Ta, Ti, Au, and Ag, alloys such as Al—Nd and APC, tin oxide, zinc oxide, and indium oxide. , ITO, indium zinc oxide (IZO), AZO (aluminum doped zinc oxide), and conductive metal oxides such as GZO (gallium doped zinc oxide), conductive organic compounds such as polyaniline, polythiophene, and polypyrrole Can be mentioned.
The thicknesses of the source electrode 3 and the drain electrode 4 are preferably 10 nm to 1000 nm.

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

  Moreover, the semiconductor layer 2 of the semiconductor element 1 of this embodiment can be formed using an oxide. Examples of the oxide applicable to the semiconductor layer 2 of the present embodiment include a single crystal oxide, a polycrystalline oxide, an amorphous oxide, and a mixture thereof. Examples of the polycrystalline oxide include zinc oxide (ZnO).

  As an amorphous oxide applicable to the semiconductor layer 2, an amorphous oxide including at least one element of indium (In), zinc (Zn), and tin (Sn) can be given.

  Specific examples of the amorphous oxide applicable to the semiconductor layer 2 include Sn—In—Zn oxide, In—Ga—Zn oxide (IGZO: indium gallium zinc oxide), and In—Zn—Ga—Mg oxide. Zn-Sn 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 2 using an amorphous oxide is formed using IGZO or ZTO, the semiconductor layer is formed by sputtering or vapor deposition using an IGZO target or ZTO target, and a photolithography method is used. Then, patterning is performed by a resist process and an etching process. The thickness of the semiconductor layer 2 using the amorphous oxide is preferably 1 nm to 1000 nm.
By using the oxides exemplified above, the semiconductor layer 2 having high mobility can be formed at a low temperature, and the semiconductor element 1 of this embodiment can be provided.

As oxides particularly preferable for forming the semiconductor layer 2 of the semiconductor element 1 of the present embodiment, zinc oxide (ZnO), indium gallium zinc oxide (IGZO), zinc tin oxide (ZTO), and indium zinc oxide ( ZIO).
By using these oxides, the semiconductor element 1 has the semiconductor layer 2 having excellent mobility formed at a lower temperature, and can exhibit a high ON / OFF ratio.

  In the semiconductor element 1 of this embodiment, a protective film 5 is disposed between the semiconductor layer 2 and the source electrode 3 and the drain electrode 4. The protective film 5 of this embodiment is an insulating organic film made of a resin formed from a radiation-sensitive resin composition containing a resin and a quinonediazide compound, which will be described in detail later.

The protective film 5 is necessary to apply the radiation sensitive resin composition of the present embodiment on the substrate 10 on which the gate electrode 11, the gate insulating film 12, the semiconductor layer 2, and the like are formed, and to form the through holes 6. After patterning, it is formed by heat curing. The formed protective film 5 can contain a quinonediazide compound, and in that case, excellent light shielding properties can be realized.
Therefore, the semiconductor element 1 of the present embodiment having the protective film 5 between the semiconductor layer 2 and the source electrode 3 and the drain electrode 4 can shield the semiconductor layer 2 due to the effect of the protective film 5. And the semiconductor element 1 of this embodiment can reduce the deterioration of the characteristic by the influence of light by the light-shielding effect of the protective film 5.

At this time, as described above, as an element configured using a semiconductor element, for example, there is a liquid crystal display element. In the case of a liquid crystal display element, a semiconductor substrate having a TFT as a semiconductor element and a color having a color filter. Manufactured with the liquid crystal sandwiched between the filter substrate. In general, a backlight unit is disposed on the semiconductor substrate side to enable image display with a high contrast ratio.
Therefore, the semiconductor substrate side of the liquid crystal display element needs to easily transmit light from the backlight unit (transparency), and it is usually not preferable to provide a protective film having a light shielding property.

  However, the semiconductor element 1 of the present embodiment can suitably control the balance between transparency and light shielding required for a liquid crystal display element or the like by using the protective film 5 containing a quinonediazide compound.

When exposed to light, the quinonediazide compound has a characteristic called photobleaching property that changes the molecular structure to become indenecarboxylic acid and changes the light absorption performance of the molecule.
Therefore, the semiconductor element 1 of the present embodiment can be made transparent simply by irradiating the protective film 5 with light when a problem occurs in the transparency after the protective film 5 is formed. Therefore, the protective film 5 contains at least one of a quinonediazide compound and an indenecarboxylic acid together with the resin.

  As described above, in the semiconductor element 1 of this embodiment, the protective film 5 exhibits a specific effect and is a very important component. Then, formation of the protective film 5 of the semiconductor element 1 of this embodiment is demonstrated in detail next. In particular, the radiation-sensitive resin composition used for forming the protective film 5 will be described in detail.

<Radiation sensitive resin composition>
In the semiconductor element of this embodiment, the radiation-sensitive resin composition of this embodiment used for the production of a protective film as a constituent member thereof contains a resin and a quinonediazide compound as essential components. The resin is preferably a resin having alkali developability. By having such a composition, the film formed from the radiation-sensitive resin composition of the present embodiment can have both excellent patterning properties and light shielding properties after formation. And the radiation sensitive resin composition of this embodiment can contain the hardening accelerator which accelerates | stimulates hardening of the film | membrane formed, and also contains other arbitrary components, unless the effect of this invention is impaired. can do.

  The resin contained in the radiation-sensitive resin composition of the present embodiment is preferably one kind selected from an acrylic resin having a carboxyl group, a polyimide resin, a polysiloxane, and a novolac resin. Each of the acrylic resin having a carboxyl group, the polyimide resin, the polysiloxane, and the novolac resin, which is preferable as the resin, will be described in more detail below.

[Acrylic resin having carboxyl group]
The acrylic resin having a carboxyl group, which is preferable as a resin, preferably includes a structural unit having a carboxyl group and a structural unit having a polymerizable group. In that case, it is not particularly limited as long as it includes a structural unit having a carboxyl group and a structural unit having a polymerizable group and has alkali developability.
The structural unit having a polymerizable group is preferably at least one structural unit selected from the group consisting of a structural unit having an epoxy group and a structural unit having a (meth) acryloyloxy group. When the acrylic resin having a carboxyl group contains the specific structural unit, a cured film having excellent surface curability and deep part curability can be formed, and the protective film of this embodiment can be formed.

  The structural unit having a (meth) acryloyloxy group is, for example, a method of reacting an epoxy group in a copolymer with (meth) acrylic acid, a (meth) acrylic acid ester having an epoxy group in a carboxyl group in the copolymer By a method of reacting (meth) acrylic acid ester having an isocyanate group with a hydroxyl group in a copolymer, a method of reacting (meth) acrylic acid hydroxy ester at an acid anhydride site in the copolymer, etc. Can be formed. Among these, a method of reacting a carboxyl group in the copolymer with a (meth) acrylic ester having an epoxy group is preferable.

  The acrylic resin containing a structural unit having a carboxyl group and a structural unit having an epoxy group as a polymerizable group is at least one selected from the group consisting of (A1) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter referred to as “a”). It can be synthesized by copolymerizing “(A1) compound”) and (A2) an epoxy group-containing unsaturated compound (hereinafter also referred to as “(A2) compound”). In this case, the acrylic resin having a carboxyl group is a structural unit formed from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a structural unit formed from an epoxy group-containing unsaturated compound. It becomes a copolymer containing.

  The acrylic resin having a carboxyl group is, for example, copolymerizing a compound (A1) that gives a carboxyl group-containing structural unit and a compound (A2) that gives an epoxy group-containing structural unit in the presence of a polymerization initiator in a solvent. Can be manufactured. Further, (A3) a hydroxyl group-containing unsaturated compound that gives a hydroxyl group-containing structural unit (hereinafter also referred to as “(A3) compound”) may be further added to form a copolymer. Further, in the production of an acrylic resin having a carboxyl group, together with the (A1) compound, the (A2) compound and the (A3) compound, the (A4) compound (derived from the above (A1), (A2) and (A3) compounds) An unsaturated compound that gives structural units other than the structural unit to be added) can be further added to form a copolymer. Hereinafter, each compound will be described in detail.

[(A1) Compound]
Examples of the compound (A1) include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids.

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

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

  As an anhydride of unsaturated dicarboxylic acid, the anhydride of the compound illustrated as said dicarboxylic acid etc. are mentioned, for example.

Among these (A1) compounds, acrylic acid, methacrylic acid, and maleic anhydride are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an alkaline aqueous solution, and availability.
These (A1) compounds may be used alone or in combination of two or more.

  The use ratio of the compound (A1) is preferably 5% by mass to 30% by mass based on the sum of the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound as necessary). 10 mass%-25 mass% are more preferable. (A1) By making the usage-amount of a compound into 5 mass%-30 mass%, while optimizing the solubility with respect to the alkaline aqueous solution of the acrylic resin which has a carboxyl group, the insulating film excellent in radiation sensitivity is obtained.

[(A2) Compound]
The compound (A2) is an epoxy group-containing unsaturated compound having radical polymerizability. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) or an oxetanyl group (1,3-epoxy structure).

  Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, and 6,7 acrylic acid. Epoxy heptyl, methacrylic acid 6,7-epoxy heptyl, α-ethylacrylic acid-6,7-epoxy heptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, methacrylic acid 3 , 4-epoxycyclohexylmethyl and the like. Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, methacrylate 4-Epoxycyclohexyl, 3,4-epoxycyclohexyl acrylate, and the like are preferable from the viewpoint of improving the copolymerization reactivity and the solvent resistance of the insulating film and the like.

As an unsaturated compound having an oxetanyl group, for example,
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2 -Acrylic esters such as phenyloxetane;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2 -Methacrylic acid esters such as phenyloxetane and 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane.

  Of these (A2) compounds, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferable. These (A2) compounds may be used alone or in combination of two or more.

  The proportion of the compound (A2) used is preferably 5% by mass to 60% by mass based on the sum of the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound as necessary). 10 mass%-50 mass% are more preferable. (A2) By making the usage-amount of a compound into 5 mass%-60 mass%, the protective film of this Embodiment which has the outstanding sclerosis | hardenability etc. can be formed.

[(A3) Compound]
Examples of the compound (A3) include (meth) acrylic acid ester having a hydroxyl group, (meth) acrylic acid ester having a phenolic hydroxyl group, and hydroxystyrene.
Examples of the acrylic acid ester having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate.

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

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

  As hydroxystyrene, o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene are preferable. These (A3) compounds may be used alone or in admixture of two or more.

  The proportion of the compound (A3) used is preferably 1% by mass to 30% by mass based on the sum of the compound (A1), the compound (A2) and the compound (A3) (optional (A4) compound if necessary). 5 mass%-25 mass% are more preferable.

[(A4) Compound]
(A4) A compound will not be restrict | limited especially if it is unsaturated compounds other than said (A1) compound, (A2) compound, and (A3) compound. Examples of (A4) compounds include methacrylic acid chain alkyl esters, methacrylic acid cyclic alkyl esters, acrylic acid chain alkyl esters, acrylic acid cyclic alkyl esters, methacrylic acid aryl esters, acrylic acid aryl esters, and unsaturated dicarboxylic acid diesters. , Maleimide compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, and other unsaturated compounds.

Examples of the chain alkyl ester of methacrylic acid include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n methacrylate. -Lauryl, tridecyl methacrylate, n-stearyl methacrylate and the like.
Examples of the cyclic alkyl ester of methacrylic acid include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 2,6 ] decane-8-yl methacrylate, and tricyclomethacrylate [5.2. 1.0 2,6 ] decan-8-yloxyethyl, isobornyl methacrylate and the like.

  Examples of the acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-acrylate. -Lauryl, tridecyl acrylate, n-stearyl acrylate and the like.

Examples of the acrylic acid cyclic alkyl ester include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl acrylate, and tricyclo [5.2 acrylate]. 1.0 2,6 ] decan-8-yloxyethyl, isobornyl acrylate, and the like.

  Examples of the methacrylic acid aryl ester include phenyl methacrylate and benzyl methacrylate.

  Examples of the acrylic acid aryl ester include phenyl acrylate and benzyl acrylate.

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

  Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.
Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

  Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.

  Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among these (A4) compounds, methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid aryl ester, maleimide compound, tetrahydrofuran skeleton, unsaturated aromatic compound, and acrylic acid cyclic alkyl ester are preferable. Of these, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate, p -Methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and tetrahydrofurfuryl methacrylate are preferred from the viewpoints of copolymerization reactivity and solubility in an aqueous alkali solution.

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

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

[Polyimide resin]
A polyimide resin preferable as a resin used in the radiation-sensitive resin composition of the present embodiment includes at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group in the structural unit of the polymer. It has a polyimide resin. By having these alkali-soluble groups in the structural unit, the occurrence of scum in the exposed portion can be suppressed during alkali development. In addition, it is preferable to have a fluorine atom in the structural unit because water repellency is imparted to the interface of the film and the penetration of the interface is suppressed when developing with an alkaline aqueous solution. The fluorine atom content in the polyimide resin is preferably 10% by mass or more in order to sufficiently obtain the effect of preventing the penetration of the interface, and is preferably 20% by mass or less from the viewpoint of solubility in an alkaline aqueous solution.

  A polyimide resin preferable as a resin used in the radiation-sensitive resin composition of the present embodiment is not particularly limited, but preferably has a structural unit represented by the following formula (I-1).

In the above formula (I-1), R 1 represents a tetravalent to 14-valent organic group, and R 2 represents a divalent to 12-valent organic group.
R 3 and R 4 represent a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a thiol group, and may be the same or different. a and b represent the integer of 0-10.

In the above formula (I-1), R 1 represents a tetracarboxylic dianhydride residue, which is a tetravalent to 14-valent organic group. Among these, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

  As tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ) Ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) Methane dianhydride Bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis {4- (3 , 4-dicarboxyphenoxy) phenyl} fluorene dianhydride or an acid dianhydride having the structure shown below is preferred. Two or more of these may be used.

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

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

  Specific examples of the diamine include 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4 , 4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,4'-diamino Diphenylsulfide, 4,4′-diaminodiphenylsulfide, m-phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene or A diamine having the structure shown below is preferred. Two or more of these may be used.

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

In order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with R 1 or R 2 as long as the heat resistance is not lowered. Specific examples of the diamine component include those obtained by copolymerizing bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like at 1 mol% to 10 mol%.

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

By adjusting the amount of the alkali-soluble group of R 3 and R 4, the dissolution rate with respect to the aqueous alkali solution is changed, so that a radiation-sensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment.

In the case where both R 3 and R 4 are phenolic hydroxyl groups, in order to make the dissolution rate in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution more suitable, It is preferable to contain 2 mol to 4 mol of phenolic hydroxyl group in 1 kg of (a). By setting the amount of phenolic hydroxyl group within this range, a radiation-sensitive resin composition with higher sensitivity and contrast can be obtained.

  Moreover, it is preferable that the polyimide which has a structural unit represented by the said formula (I-1) has an alkali-soluble group in the principal chain terminal. Such polyimide has high alkali solubility. Specific examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Introduction of an alkali-soluble group at the end of the main chain can be carried out by imparting an alkali-soluble group to the end capping agent. As the terminal capping agent, monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound and the like can be used.

  Monoamines used as end capping agents include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy. -4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4 -Aminobenzoic acid, 4-aminosalicylic acid, 5-amino Salicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4 -Aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like are preferable. Two or more of these may be used.

  Examples of acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds used as end-capping agents include phthalic anhydride, maleic anhydride, nadic acid anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic acid Acid anhydrides such as acid anhydrides, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1 -Hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, etc. Mo Carboxylic acids and monoacid chloride compounds in which these carboxyl groups are acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7- A monoacid chloride compound in which only one carboxyl group of dicarboxylic acids such as dicarboxynaphthalene and 2,6-dicarboxynaphthalene is acid chloride, monoacid chloride compound and N-hydroxybenzotriazole or N-hydroxy-5-norbornene- Active ester compounds obtained by reaction with 2,3-dicarboximide are preferred. Two or more of these may be used.

  The introduction ratio of the monoamine used for the terminal blocking agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 60 mol% or less, particularly preferably 50, based on the total amine component. It is less than mol%. The introduction ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound used as the end-capping agent is preferably 0.1 mol% or more, particularly preferably 5 mol%, relative to the diamine component. Or more, preferably 100 mol% or less, particularly preferably 90 mol% or less. A plurality of different end groups may be introduced by reacting a plurality of end-capping agents.

  In the polyimide having the structural unit represented by the above formula (I-1), the number of repeating structural units is preferably 3 or more, more preferably 5 or more, and preferably 200 or less, more preferably 100 or less. Within this range, the photosensitive resin composition of the present invention can be used in a thick film.

  In this embodiment, a preferable polyimide resin may be composed only of the structural unit represented by the above formula (I-1), or may be a copolymer or a mixture with other structural units. Good. In that case, it is preferable to contain the structural unit represented by general formula (I-1) 10 mass% or more of the whole polyimide resin. If it is 10 mass% or more, the shrinkage | contraction at the time of thermosetting can be suppressed, and it is suitable for preparation of a thick film. The type and amount of the structural unit used for copolymerization or mixing are preferably selected within a range that does not impair the heat resistance of the polyimide obtained by the final heat treatment. Examples include benzoxazole, benzimidazole, and benzothiazole. These structural units are preferably 70% by mass or less in the polyimide resin.

  In the present embodiment, for example, a preferable polyimide resin can be synthesized by using a method in which a polyimide precursor is obtained using a known method and is imidized using a known imidization reaction method. As a known synthesis method of the polyimide precursor, a part of the diamine is replaced with a monoamine which is a terminal blocking agent, or a part of the acid dianhydride is a monocarboxylic acid or an acid anhydride which is a terminal blocking agent. It can be obtained by reacting an amine component and an acid component in place of a monoacid chloride compound or a monoactive ester compound. For example, a method of reacting a tetracarboxylic dianhydride and a diamine compound (partially substituted with a monoamine) at a low temperature, a tetracarboxylic dianhydride (partially an acid anhydride, a monoacid chloride compound, or a mono A method of reacting an active ester compound) with a diamine compound, a diester obtained by tetracarboxylic dianhydride and an alcohol, and then reacting in the presence of a diamine (partially substituted with a monoamine) and a condensing agent, tetra There is a method in which a diester is obtained from carboxylic dianhydride and alcohol, and then the remaining dicarboxylic acid is converted to acid chloride and reacted with diamine (partially substituted with monoamine).

Moreover, the imidation ratio of a polyimide resin can be easily calculated | required with the following method, for example. First, measuring the infrared absorption spectrum of the polymer, absorption peaks of an imide structure caused by a polyimide (1780 cm around -1, 1377 cm around -1) to confirm the presence of. Next, the polymer was heat-treated at 350 ° C. for 1 hour, the infrared absorption spectrum was measured, and the peak intensity around 1377 cm −1 was compared to calculate the content of imide groups in the polymer before heat treatment. Find the rate.

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

  Moreover, the terminal blocker introduce | transduced into the preferable polyimide resin in this embodiment can be easily detected with the following method. For example, by dissolving a polyimide having an end capping agent dissolved in an acidic solution and decomposing it into an amine component and an acid anhydride component, which are constituent units of the polyimide, and measuring this by gas chromatography (GC) or NMR The end capping agent used in the present invention can be easily detected. Apart from this, the polymer component into which the end-capping agent has been introduced can also be easily detected by directly measuring it with a pyrolysis gas chromatograph (PGC), an infrared spectrum and a 13C-NMR spectrum.

[Polysiloxane]
A preferred polysiloxane as a resin used in the radiation sensitive resin composition of the present embodiment is a polysiloxane having a radical reactive functional group. When the polysiloxane is a polysiloxane having a radical reactive functional group, the polysiloxane is not particularly limited as long as it has a radical reactive functional group in the main chain or side chain of a polymer having a siloxane bond. In that case, the polysiloxane can be cured by radical polymerization, and cure shrinkage can be minimized. Examples of the radical reactive functional group include unsaturated organic groups such as vinyl group, α-methylvinyl group, acryloyl group, methacryloyl group, and styryl group. Among these, those having an acryloyl group or a methacryloyl group are preferable because the curing reaction proceeds smoothly.

  In the present embodiment, the preferred polysiloxane is preferably a hydrolysis condensate of a hydrolyzable silane compound. The hydrolyzable silane compound constituting the polysiloxane includes (s1) a hydrolyzable silane compound represented by the following formula (S-1) (hereinafter also referred to as (s1) compound), and (s2) the following formula (S -2) and a hydrolyzable silane compound (hereinafter also referred to as (s2) compound).

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

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

  In the present invention, the “hydrolyzable silane compound” is usually hydrolyzed by heating in the temperature range of room temperature (about 25 ° C.) to about 100 ° C. in the presence of a catalyst and excess water. It refers to a compound having a group capable of forming a silanol group or a group capable of forming a siloxane condensate. In the hydrolysis reaction of the hydrolyzable silane compound represented by the above formula (S-1) and (S-2), some hydrolyzable groups are not hydrolyzed in the polysiloxane to be formed. It may remain in the state. Here, the “hydrolyzable group” means a group capable of forming a silanol group by hydrolysis as described above or a group capable of forming a siloxane condensate. In addition, in the radiation-sensitive resin composition, some hydrolyzable silane compounds are in a state in which some or all of the hydrolyzable groups in the molecule are not hydrolyzed and other hydrolyzable silane compounds. It may remain in the monomer state without condensing with. The “hydrolysis condensate” means a hydrolysis condensate obtained by condensing some silanol groups of a hydrolyzed silane compound. Hereinafter, the (s1) compound and the (s2) compound will be described in detail.

[(S1) Compound]
In the above formula (S-1), R 11 is an alkyl group having 1 to 6 carbon atoms. R 12 is an organic group containing a radical reactive functional group. p is an integer of 1 to 3. However, if R 11 and R 12 is plural, R 11 and R 12 are each, independently.
Examples of the alkyl group having 1 to 6 carbon atoms that is R 11 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a butyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of easy hydrolysis. As said p, 1 or 2 is preferable from a viewpoint of progress of a hydrolysis condensation reaction, and 1 is more preferable.

Examples of the organic group having a radical reactive functional group include a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with the above radical reactive functional group, A 6-12 aryl group, a C7-12 aralkyl group, etc. are mentioned. When a plurality of R 12 are present in the same molecule, these are independent of each other. Further, the organic group represented by R 12 may have a hetero atom. Examples of such an organic group include an ether group, an ester group, and a sulfide group.

  Examples of the compound (s1) in the case of p = 1 include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, o-styryltrimethoxysilane, o-styryltriethoxysilane, and m-styryltrimethoxysilane. M-styryltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methacryloxytrimethoxysilane, methacryloxytriethoxysilane, methacryloxytripropoxysilane, Acryloxytrimethoxysilane, acryloxytriethoxysilane, acryloxytripropoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, -Methacryloxyethyl tripropoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acryloxyethyltri Ethoxysilane, 2-acryloxyethyltripropoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane Trifluoro-butyl trimethoxy silane, 3-trialkoxysilane compounds such as (trimethoxysilyl) propyl succinic anhydride and the like.

  Examples of the compound (s1) in the case of p = 2 include vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, phenyltri And dialkoxysilane compounds such as fluoropropyldimethoxysilane.

  Examples of the compound (s1) in the case of p = 3 include allyldimethylmethoxysilane, allyldimethylethoxysilane, divinylmethylmethoxysilane, divinylmethylethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, and 3-acryloxypropyldimethyl. Methoxysilane, 3-methacryloxypropyldiphenylmethoxysilane, 3-acryloxypropyldiphenylmethoxysilane, 3,3′-dimethacryloxypropyldimethoxysilane, 3,3′-diaacryloxypropyldimethoxysilane, 3,3 ′, Monoalkoxysilane compounds such as 3 ″ -trimethacryloxypropylmethoxysilane, 3,3 ′, 3 ″ -triacryloxypropylmethoxysilane, dimethyltrifluoropropylmethoxysilane, etc. It is below.

  Among these (s1) compounds, scratch resistance and the like can be achieved at a high level, and condensation reactivity is increased. Therefore, vinyltrimethoxysilane, p-styryltriethoxysilane, 3-methacryloxypropyltrimethoxysilane. 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, and 3- (trimethoxysilyl) propyl succinic anhydride are preferable.

[(S2) Compound]
In the above formula (S-2), R 13 is an alkyl group having 1 to 6 carbon atoms. R 14 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, an epoxy group, an amino group, or an isocyanate group. n is an integer of 0-20. q is an integer of 0-3. However, if R 13 and R 14 is each one, the plurality of R 13 and R 14 are each, independently.

Examples of the alkyl group having 1 to 6 carbon atoms as R 13 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a butyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of easy hydrolysis. As said q, 1 or 2 is preferable from a viewpoint of progress of a hydrolysis condensation reaction, and 1 is more preferable.

When R 14 described above is an alkyl group having 1 to 20 carbon atoms, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a sec-butyl group. Group, tert-butyl group, n-pentyl group, 3-methylbutyl group, 2-methylbutyl group, 1-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl Group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2- Dimethylbutyl, 1,1-dimethylbutyl, n-heptyl, 5-methylhexyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methyl Tylhexyl group, 4,4-dimethylpentyl group, 3,4-dimethylpentyl group, 2,4-dimethylpentyl group, 1,4-dimethylpentyl group, 3,3-dimethylpentyl group, 2,3-dimethylpentyl group 1,3-dimethylpentyl group, 2,2-dimethylpentyl group, 1,2-dimethylpentyl group, 1,1-dimethylpentyl group, 2,3,3-trimethylbutyl group, 1,3,3-trimethyl Butyl group, 1,2,3-trimethylbutyl group, n-octyl group, 6-methylheptyl group, 5-methylheptyl group, 4-methylheptyl group, 3-methylheptyl group, 2-methylheptyl group, 1- Methylheptyl group, 2-ethylhexyl group, n-nonanyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n Heptadecyl, n- hexadecyl group, n- heptadecyl group, n- octadecyl, n- nonadecyl group and the like. Preferably it is a C1-C10 alkyl group, More preferably, it is a C1-C3 alkyl group.

  As the compound (s2) in the case of q = 0, for example, as a silane compound substituted with four hydrolyzable groups, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetra-n-propoxysilane, tetra -I-propoxysilane etc. are mentioned.

  As the compound (s2) in the case of q = 1, as a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, for example, methyltrimethoxysilane, methyltriethoxysilane, Methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, naphthyl Trimethoxysilane, phenyltriethoxysilane, naphthyltriethoxysilane, aminotrimethoxysilane, aminotriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy, γ-glycidoxypropyltrimethoxysilane 3 isocyanoacetate trimethoxysilane, 3-isocyanoacetate triethoxysilane o- tolyl trimethoxysilane, m- tolyl trimethoxysilane p- tolyl trimethoxysilane, and the like.

  As the compound (s2) in the case of q = 2, examples of the silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups include dimethyldimethoxysilane, diphenyldimethoxysilane, and ditolyl. Examples include dimethoxysilane and dibutyldimethoxysilane.

  As the compound (s2) in the case of q = 3, examples of the silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group include trimethylmethoxysilane, triphenylmethoxysilane, Examples include tolylmethoxysilane and tributylmethoxysilane.

  Of these (s2) compounds, a silane compound substituted with four hydrolyzable groups, a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups is preferred. More preferred are silane compounds substituted with one non-hydrolyzable group and three hydrolyzable groups. Particularly preferred hydrolyzable silane compounds include, for example, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, ethyltrisilane. Methoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, naphthyltrimethoxysilane, γ-aminopropyltrimethoxysilane and γ-isocyanate And propyltrimethoxysilane. Such hydrolyzable silane compounds may be used alone or in combination of two or more.

  Regarding the mixing ratio of the (s1) compound and the (s2) compound, it is desirable that the (s1) compound exceeds 5 mol%. When the compound (s1) is 5 mol% or less, the exposure sensitivity when forming a protective film as a cured film is low, and the scratch resistance and the like of the resulting protective film tend to be reduced.

[Hydrolytic condensation of (s1) compound and (s2) compound]
The conditions for hydrolyzing and condensing the compound (s1) and the compound (s2) include hydrolyzing at least a part of the compound (s1) and the compound (s2) to convert a hydrolyzable group into a silanol group and condensing the compound. Although it will not specifically limit as long as it raise | generates reaction, As an example, it can implement as follows.

  As water used for the hydrolysis condensation reaction, it is preferable to use 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, more preferably 0.3 mol to 2 mol, with respect to 1 mol of the total amount of hydrolyzable groups of the (s1) compound and (s2) compound. Particularly preferred is 0.5 to 1.5 mol. By using such an amount of water, the reaction rate of the hydrolysis condensation can be optimized.

  Examples of the solvent used for hydrolysis condensation include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers. Examples include propionates, aromatic hydrocarbons, ketones, and other esters. These solvents can be used alone or in combination of two or more.

  Of these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and butyl methoxyacetate are preferred. Particularly, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate. , Propylene glycol monomethyl ether and butyl methoxyacetate are preferred.

  The hydrolysis condensation reaction 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, acidic ion exchange resin, various Lewis acids, etc.), base Catalysts (for example, ammonia, primary amines, secondary amines, tertiary amines, nitrogen-containing compounds such as pyridine; basic ion exchange resins; hydroxides such as sodium hydroxide; carbonates such as potassium carbonate; Carboxylic acid salts such as sodium acetate; various Lewis bases) or alkoxides (for example, zirconium alkoxide, titanium alkoxide, aluminum alkoxide, etc.) are used in the presence of a catalyst. For example, tri-i-propoxyaluminum can be used as the aluminum alkoxide. The amount of the catalyst to be used is preferably 0.2 mol or less, more preferably 0.00001 mol to 0.001 mol per mol of the hydrolyzable silane compound monomer from the viewpoint of promoting the hydrolysis condensation reaction. 1 mole.

  The polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) by GPC (gel permeation chromatography) of the above-mentioned hydrolysis-condensation product is preferably 500 to 10,000, more preferably 1000 to 5000. By making Mw 500 or more, the film formability of the radiation sensitive resin composition of the present embodiment can be improved. On the other hand, by setting Mw to 10,000 or less, it is possible to prevent the developability of the radiation-sensitive resin composition from decreasing.

  The number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) by GPC of the above-mentioned hydrolysis-condensation product is preferably 300 to 5000, and more preferably 500 to 3000. By making Mn of polysiloxane into the said range, the cure reactivity at the time of hardening of the coating film of the radiation sensitive resin composition of this embodiment can be improved.

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

[Novolac resin]
A novolak resin preferable as a resin used in the radiation-sensitive resin composition of the present embodiment can be obtained by polycondensing phenols with aldehydes such as formalin by a known method.

  Examples of phenols for obtaining a preferred novolak resin in the present embodiment include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, and 2,5-dimethylphenol. 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, , 4,5-trimethylphenol, methylene bisphenol, methylene bis p-cresol, resorcin, catechol, 2-methyl resorcin, 4-methyl resorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichloro Phenol, m-methoxy Enol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol and the like can be mentioned. Two or more of these may be used.

  In the present embodiment, examples of aldehydes for obtaining a preferred novolak resin include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like in addition to formalin. Two or more of these may be used.

  The preferred weight average molecular weight of the novolak resin that is a resin used in the radiation-sensitive resin composition of the present embodiment is 2000 to 50000, more preferably 3000 to 40000 in terms of polystyrene by GPC (gel permeation chromatography).

[Quinonediazide compound]
The radiation sensitive resin composition of this embodiment contains a quinonediazide compound as an essential component together with the resin described above. Thereby, the radiation sensitive resin composition of this embodiment can be used as a positive type radiation sensitive resin composition. And the light-shielding property of the protective film after formation can be provided. Furthermore, the transparency of the formed protective film can be adjusted by the photo bleaching performance.

  A quinonediazide compound is a quinonediazide compound that generates a carboxylic acid upon irradiation with radiation. As the quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

  Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei.

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

  Examples of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2, Examples include 3,4,2′-tetrahydroxy-4′-methylbenzophenone and 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone.

  Examples of pentahydroxybenzophenone include 2,3,4,2 ', 6'-pentahydroxybenzophenone.

  Examples of hexahydroxybenzophenone include 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone, and the like.

  Examples of the (polyhydroxyphenyl) alkane include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p- Hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl) -4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol, bis (2,5- Dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobi Nden -5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl -7,2 ', 4'-trihydroxy flavan like.

  Examples of other mother nuclei include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- {3- (1- [ 4-hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] -3- [1- {3- (1- [4-hydroxyphenyl] -1-methylethyl)- 4,6-dihydroxyphenyl} -1-methylethyl] benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene, and the like.

  Among these mother nuclei, 2,3,4,4′-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane, 4,4 ′-[1- {4- (1- [ 4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol is preferably used.

  As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. Examples of 1,2-naphthoquinonediazide sulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, and the like. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferred.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazide sulfonic acid halide, preferably 30 mol% to the number of OH groups in the phenolic compound or alcoholic compound. 1,2-naphthoquinonediazide sulfonic acid halide corresponding to 85 mol%, more preferably 50 mol% to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Examples of the quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, such as 2,3,4-triaminobenzophenone-1,2-naphtho. Quinonediazide-4-sulfonic acid amide and the like are also preferably used.

  These quinonediazide compounds can be used alone or in combination of two or more. The use ratio of the quinonediazide compound in the radiation-sensitive resin composition of the present embodiment is preferably 5 parts by mass to 100 parts by mass, and more preferably 10 parts by mass to 50 parts by mass with respect to 100 parts by mass of the resin. By setting the use ratio of the quinonediazide compound in the above range, the difference in solubility between the irradiated portion and the unirradiated portion with respect to the alkaline aqueous solution serving as the developer can be increased, and the patterning performance can be improved. Moreover, the solvent resistance of the protective film obtained using this radiation sensitive resin composition can also be made favorable.

[Other ingredients]
The radiation-sensitive resin composition of the present embodiment contains a resin and a quinonediazide compound as essential components, and can contain a curing accelerator, a thermal acid generator, and other optional components.

  The curing accelerator is a compound that functions to promote curing of a film formed by the radiation-sensitive resin composition of the present embodiment.

  The thermal acid generator is a compound capable of releasing an acidic active substance that acts as a catalyst when the resin is cured by applying heat.

  The radiation-sensitive resin composition of the present embodiment includes other optional components such as a surfactant, a storage stabilizer, an adhesion aid, and a heat resistance improver as necessary, as long as the effects of the present invention are not impaired. Can be contained. Each of these optional components may be used alone or in combination of two or more.

<Method for preparing radiation-sensitive resin composition>
The radiation sensitive resin composition of the present embodiment is prepared by uniformly mixing a resin and a quinonediazide compound. Moreover, when it contains a hardening accelerator, a thermal acid generator, or other optional components added as necessary, it is prepared by uniformly mixing the resin and the quinonediazide compound with these components. This radiation-sensitive resin composition is preferably used in the form of a solution after being dissolved in an appropriate solvent. A solvent can be used individually or in mixture of 2 or more types.

  As a solvent used for the preparation of the radiation sensitive resin composition of the present embodiment, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used. Examples of such solvents include alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol mono Examples include alkyl ether propionates, ketones, esters and the like.

  Although the content of the solvent is not particularly limited, the total concentration of each component excluding the solvent of the radiation-sensitive resin composition is 5% by mass from the viewpoints of applicability and stability of the resulting radiation-sensitive resin composition. The amount of ˜50% by mass is preferable, and the amount of 10% by mass to 40% by mass is more preferable. When preparing a solution of a radiation sensitive resin composition, actually, a solid content concentration (a component other than the solvent in the composition solution) corresponding to a desired film thickness value or the like is set in the above concentration range. The

  The solution composition thus prepared is preferably used for forming the protective film of the present embodiment after being filtered using a Millipore filter having a pore diameter of about 0.5 μm.

<Method for forming protective film>
The protective film of the semiconductor element of this embodiment is formed by applying the radiation-sensitive resin composition of this embodiment on a substrate on which a gate electrode, a gate insulating film, a semiconductor layer, and the like are formed, and forming a through hole, etc. After necessary patterning, it is formed by heat curing. The formed protective film preferably includes a quinonediazide compound, and in that case, has a light shielding property.
Below, the formation method of a protective film is demonstrated in detail.

  In the formation of the protective film of the semiconductor element of this embodiment, first, a coating film of the radiation-sensitive resin composition of this embodiment is formed on the substrate. On this substrate, a gate electrode, a gate insulating film, a semiconductor layer, and the like are formed according to a known method. For example, the semiconductor layer or the like is formed by repeating semiconductor film formation and etching by photolithography on a substrate in accordance with the method described in Patent Document 1 above.

  In the said board | substrate, after apply | coating the radiation sensitive resin composition of this embodiment to the surface in which the semiconductor layer etc. were formed, a prebaking is performed and a solvent is evaporated and a coating film is formed.

  Examples of the coating method of the radiation sensitive resin composition include a spray method, a roll coating method, a spin coating method (sometimes called a spin coating method or a spinner method), and a slit coating method (slit die coating method). An appropriate method such as a bar coating method or an ink jet coating method can be employed. Of these, the spin coating method or the slit coating method is preferable because a film having a uniform thickness can be formed.

  The pre-baking conditions described above vary depending on the type of each component constituting the radiation-sensitive resin composition, the blending ratio, etc., but it is preferably performed at a temperature of 70 ° C. to 120 ° C., and the time is such as a hot plate or an oven. Although it differs depending on the heating device, it is about 1 to 15 minutes.

  Next, radiation is applied to at least a part of the coating film formed as described above. At this time, in order to irradiate only a part of the coating film, for example, it is performed through a photomask having a pattern corresponding to formation of a desired through hole and formation of a desired shape.

  Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 200 nm to 550 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable.

Radiation dose (exposure amount), the intensity at the wavelength 365nm of the radiation emitted as a value measured by a luminometer (OAI model 356, Optical Associates Ltd. Inc.), be 10J / m 2 ~10000J / m 2 can be preferably 100J / m 2 ~5000J / m 2 , 200J / m 2 ~3000J / m 2 is more preferable.

  Next, the coating film after irradiation is developed to remove unnecessary portions, and a coating film in which through holes having a predetermined shape are formed is obtained.

  Examples of the developer used for development include inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, choline, An aqueous solution of an alkaline compound such as 8-diazabicyclo- [5.4.0] -7-undecene and 1,5-diazabicyclo- [4.3.0] -5-nonene can be used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol can be added to the aqueous solution of the alkaline compound described above. Furthermore, the surfactant can be used alone or in combination with the addition of the above-mentioned water-soluble organic solvent.

  The developing method may be any of a liquid filling method, a dipping method, a shower method, a spraying method, etc., and the developing time can be 5 seconds to 300 seconds at room temperature, preferably 10 seconds to 180 seconds at room temperature. is there. Subsequent to the development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern is obtained by air drying with compressed air or compressed nitrogen.

  Next, the coating film on which through holes having a predetermined shape are formed is cured (also referred to as post-baking) by an appropriate heating device such as a hot plate or an oven. Thereby, the protective film of this embodiment as a cured film is obtained. The thickness of the protective insulating film is preferably 10 nm to 1000 nm. As described above, the protective film is formed with a through hole arranged at a desired position.

  According to the radiation sensitive resin composition of the present embodiment, the curing temperature is preferably 100 ° C. to 250 ° C., and the curing temperature may be 200 ° C. or less due to the effect of the added curing accelerator or the like. Is possible. For example, the curing time is preferably 5 to 30 minutes on a hot plate, and preferably 30 to 180 minutes in an oven.

  After forming the protective film of this embodiment, the semiconductor element of this embodiment can be manufactured by forming a source electrode and a drain electrode on the protective film according to a known method. The source electrode and the drain electrode are formed according to a known method by forming a conductive film constituting the electrodes using a printing method, a coating method, a sputtering method, a CVD method, a vapor deposition method, or the like, and then a photolithography method. It can be formed by patterning using the like.

Embodiment 2. FIG.
<Semiconductor substrate>
FIG. 2 is a plan view schematically illustrating the main structure of the semiconductor substrate of the present embodiment.

  As shown in FIG. 2, on the semiconductor substrate 21 of the present embodiment, data wirings 23 and gate wirings 24 are arranged on the substrate 22 in a matrix. The semiconductor element 1 of the present embodiment described above is disposed in the vicinity of the intersection of the data line 23 and the gate line 24, and the source electrode (not shown in FIG. 2) of the semiconductor element 1 is connected to the data line 23 and the gate The electrode 11 is connected to the gate wiring 24. Thus, each pixel partitioned on the semiconductor substrate 21 is configured. The semiconductor substrate 21 of this embodiment is suitable for the configuration of a display element such as a liquid crystal display element.

  Examples of the material of the substrate 22 include glass substrates such as soda lime glass and non-alkali glass, or resin substrates such as silicon, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, aromatic polyamide, polyamideimide, and polyimide. Etc. In addition, these substrates may be subjected to pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition or the like, if desired.

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

  In the semiconductor substrate 21 of the present embodiment, when the scanning signal is supplied to the gate wiring 24, the semiconductor element 1 is turned on. A video signal from the data wiring 23 is supplied to the pixel electrode 25 through the semiconductor element 1 that is turned on. Here, the gate lines 24 are juxtaposed in the vertical direction in FIG. 2, and the data lines 23 are juxtaposed in the left-right direction in FIG. A pixel electrode 25 having a desired shape is arranged in a region (pixel) surrounded by a pair of adjacent gate wirings 24 and a pair of adjacent data wirings 23. The pixel electrode 25 shown in FIG. 2 has a solid plate shape. However, as will be described later, when the display element of the present embodiment is an IPS mode or FFS mode liquid crystal display element, a comb tooth shape or the like is used. Is possible.

Embodiment 3. FIG.
<Liquid crystal display element>
FIG. 3 is a cross-sectional view schematically illustrating the main structure of the liquid crystal display element of the present embodiment.

  A liquid crystal display element 100 shown in FIG. 3 which is a display element is an active matrix type TN (twisted nematic) mode color liquid crystal display element configured using the semiconductor substrate 21 of the present embodiment described above.

  The liquid crystal display element 100 has a structure in which the semiconductor substrate 21 including the semiconductor element 1 described above and the color filter substrate 30 on which the color filter 40 is formed face each other via a nematic phase liquid crystal 43 that is 90 ° twist aligned. .

  As shown in FIG. 3, in the semiconductor substrate 21, the semiconductor element 1 of this embodiment and a transparent pixel electrode (not shown in FIG. 3) made of ITO are provided on the side of the transparent substrate 22 in contact with the liquid crystal 43. The pixels are arranged in a matrix form. An alignment film 42 that controls the alignment of the liquid crystal 43 is provided on the surface of the semiconductor substrate 21 that is in contact with the liquid crystal 43.

  In the color filter substrate 30, the colored pattern 36 and the like are arranged on the side of the transparent substrate 45 in contact with the liquid crystal 43 to constitute the color filter 40. The color filter 40 includes red, green, and blue coloring patterns 36 provided in the pixel region, and a black matrix 37 that surrounds them. The color filter substrate 30 has a protective layer 38 on the colored pattern 36 of the color filter 40. The color filter substrate 30 has a transparent common electrode 41 made of ITO and an alignment film 42 for controlling the alignment of the liquid crystal 43 on the protective layer 38.

  As described above, the alignment film 42 for controlling the alignment of the liquid crystal 43 is provided on each of the semiconductor substrate 21 and the color filter substrate 30. If necessary, the alignment film 42 is subjected to, for example, an alignment process such as a rubbing process or a photo-alignment process by polarized light irradiation, so that the liquid crystal 43 sandwiched between the semiconductor substrate 21 and the color filter substrate 30 has a uniform alignment. Realize.

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

  In FIG. 3, reference numeral 47 denotes backlight light emitted toward the liquid crystal 43 from a backlight unit (not shown). As the backlight unit, for example, a structure in which a fluorescent tube such as a cold cathode fluorescent lamp (CCFL) and a scattering plate are combined can be used. A backlight unit using a white LED as a light source can also be used. As the white LED, for example, a white LED that obtains white light by mixing a red LED, a green LED, and a blue LED, and a white light that is obtained by mixing a blue LED, a red LED, and a green phosphor to emit white light. A white LED that obtains white light by mixing white LEDs, a blue LED, a red light emitting phosphor, and a green light emitting phosphor to obtain white light by mixing colors, a white LED that obtains white light by mixing colors with a YAG phosphor, A combination of a blue LED, an orange light emitting phosphor, and a green light emitting phosphor to obtain white light by mixing colors, a white LED, an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor And white LEDs that obtain white light by color mixing.

  In the liquid crystal display element 100 of the present embodiment, in addition to the above-described TN mode, STN (Super Twisted Nematic) mode, IPS (In-Plane Switching) mode, FFS (Fringe Field Switching) mode, VA (Vertical Alignment) mode or A liquid crystal mode such as an OCB (Optically Compensated Birefringence) mode can be set.

  The semiconductor element of the semiconductor substrate of the liquid crystal display element of the present embodiment has the protective film of the present embodiment between the semiconductor layer and the source electrode and the drain electrode. It is. Therefore, the semiconductor element of the liquid crystal display element of this embodiment can reduce deterioration of characteristics due to the influence of light. As a result, the liquid crystal display element of the present embodiment can suppress display quality degradation due to the influence of light.

  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.

<Preparation of radiation-sensitive resin composition>
Synthesis example 1
[Synthesis of Resin (α-I)]
A flask equipped with a condenser and a stirrer was charged with 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether. Subsequently, 13 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of α-methyl-p-hydroxystyrene, 10 parts by weight of styrene, 12 parts by weight of tetrahydrofurfuryl methacrylate, 15 parts by weight of N-cyclohexylmaleimide and n- After charging 10 parts by mass of lauryl methacrylate and substituting with nitrogen, the temperature of the solution was raised to 70 ° C. while gently stirring, and polymerization was carried out while maintaining this temperature for 5 hours, whereby a resin (α- A solution containing I) was obtained. The Mw of the resin (α-I) as a copolymer was 8000.

Synthesis example 2
[Synthesis of Resin (α-II)]
Under a dry nitrogen stream, 29.30 g (0.08 mol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane (Central Glass), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 1 .24 g (0.005 mol), 3.27 g (0.03 mol) of 3-aminophenol (Tokyo Chemical Industry Co., Ltd.) as an end-capping agent is N-methyl-2-pyrrolidone (hereinafter referred to as NMP). Dissolved in 80 g. Bis (3,4-dicarboxyphenyl) ether dianhydride (Manac) 31.2 g (0.1 mol) was added together with 20 g of NMP and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. I let you. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropically distilling water with xylene. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried for 20 hours in a vacuum dryer at 80 ° C. to obtain a resin (α-II) as a polymer having a structure represented by the following formula.

Synthesis example 3
[Synthesis of Resin (α-III)]
In a vessel equipped with a stirrer, 20 parts by mass of propylene glycol monomethyl ether was charged, followed by 70 parts by mass of methyltrimethoxysilane and 30 parts by mass of tolyltrimethoxysilane, and heated until the solution temperature reached 60 ° C. . After the solution temperature reached 60 ° C., 0.15 parts by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 4 hours. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, a resin (α-III) was obtained as a siloxane polymer which is a hydrolysis-condensation product. The Mw of the resin (α-III) which is a siloxane polymer was 5000.

Example 1
[Preparation of radiation-sensitive resin composition (β-I)]
A solution containing the resin (α-I) of Synthesis Example 1 was added in an amount corresponding to 100 parts by mass (solid content) of the copolymer, and 4,4 ′-[1- {4- (1- [ 4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol (1.0 mol) 30 parts by mass, and 2 parts by mass of benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate as a thermal acid generator, After dissolving in diethylene glycol ethyl methyl ether, the mixture was filtered through a membrane filter having a diameter of 0.2 μm to prepare a radiation sensitive resin composition (β-I).

Example 2
[Preparation of radiation-sensitive resin composition (β-II)]
2 g of novolak resin (trade name, XPS-4958G, m-cresol / p-cresol ratio = 55/45 (weight ratio), Gunei Chemical Industry Co., Ltd.) was added to 8 g of the resin (α-II) of Synthesis Example 2. . Further, 2.4 g of a compound represented by the following formula (β1) and 0.6 g of a compound represented by the following formula (β2) are added as a thermally crosslinkable compound that undergoes a crosslinking reaction by heat, and 2 g of a quinonediazide compound (β3) is added. Then, γ-butyrolactone was added and dissolved as a solvent, followed by filtration through a membrane filter having a diameter of 0.2 μm to prepare a radiation sensitive resin composition (β-II).

Example 3
[Preparation of radiation-sensitive resin composition (β-III)]
4,4 ′-[1- {as a quinonediazide compound was added to the solution containing siloxane polymer resin (α-III) obtained in Synthesis Example 3 (amount corresponding to 100 parts by mass (solid content) of siloxane polymer). Condensation of 4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol (1.0 mol) with 1,2-naphthoquinonediazide-5-sulfonic acid chloride (3.0 mol) 12 parts by mass of a product and 0.1 part by mass of a fluorosurfactant (FTX-218, manufactured by Neos) as a surfactant are added, and propylene glycol monomethyl ether is added so that the solid content concentration is 25% by mass. A radiation sensitive resin composition (β-III) was prepared.

<Formation and evaluation of protective film>
Example 4
[Protective film formed from radiation-sensitive resin composition (β-I)]
After applying the radiation sensitive resin composition (β-I) prepared in Example 1 on a non-alkali glass substrate with a spinner, a coating film was formed by pre-baking on a hot plate at 90 ° C. for 2 minutes. Next, the obtained coating film was irradiated with radiation at an exposure amount of 700 J / m 2 using a high-pressure mercury lamp, and developed with a 0.4 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 60 seconds. Next, a protective film was formed by post-baking in an oven at a curing temperature of 230 ° C. and a curing time of 30 minutes.

Example 5
[Protective film formed from radiation-sensitive resin composition (β-II)]
After applying the radiation sensitive resin composition (β-II) prepared in Example 2 on a non-alkali glass substrate with a spinner, a coating film was formed by prebaking on a hot plate at 90 ° C. for 2 minutes. Next, the obtained coating film was irradiated with radiation at an exposure amount of 1000 J / m 2 using a high-pressure mercury lamp, and developed with a 0.4 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 150 seconds. Next, a protective film was formed by post-baking in an oven at a curing temperature of 230 ° C. and a curing time of 30 minutes.

Example 6
[Protective film formed from radiation-sensitive resin composition (β-III)]
The radiation-sensitive resin composition (β-III) prepared in Example 3 was applied on an alkali-free glass substrate with a spinner, and then pre-baked on a hot plate at 100 ° C. for 2 minutes to form a coating film. Next, the obtained coating film was irradiated with radiation at an exposure amount of 800 J / m 2 using a high-pressure mercury lamp, and developed with a 0.4 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds. Next, a protective film was formed by post-baking in an oven at a curing temperature of 230 ° C. and a curing time of 30 minutes.

Example 7
[Evaluation of heat resistance]
About the protective film by the formation method of Example 4, it heated at 230 degreeC for 20 minute (s) further in oven, and measured the film thickness before and behind this heating with the stylus type film thickness measuring machine (alpha step IQ, KLA Tencor). . And the remaining film rate (film thickness after a process / film thickness before a process x100) was computed, and this remaining film rate was made into heat resistance. The residual film ratio was 99%, and the heat resistance was judged to be good.

  Similarly, the protective film by the forming method of Example 5 was further heated in an oven at 230 ° C. for 20 minutes, and the film thickness before and after this heating was measured with a stylus-type film thickness measuring machine (Alphastep IQ, KLA Tencor). It was measured. And the remaining film rate (film thickness after a process / film thickness before a process x100) was computed, and this remaining film rate was made into heat resistance. The residual film ratio was 99%, and the heat resistance was judged to be good.

  Similarly, the protective film by the forming method of Example 6 was further heated in an oven at 230 ° C. for 20 minutes, and the film thickness before and after this heating was measured with a stylus-type film thickness measuring machine (Alphastep IQ, KLA Tencor). It was measured. And the remaining film rate (film thickness after a process / film thickness before a process x100) was computed, and this remaining film rate was made into heat resistance. The residual film ratio was 99%, and the heat resistance was judged to be good.

Example 8
[Evaluation of light resistance]
About the protective film by the formation method of Example 4, further using a UV irradiation apparatus (UVX-02516S1JS01, Ushio Inc.), irradiating with 800,000 J / m 2 of ultraviolet light at an illuminance of 130 mW, the film reduction amount after irradiation I investigated. The amount of film loss was 2% or less, and light resistance was judged to be good.

Similarly, about the protective film by the formation method of Example 5, further using a UV irradiation apparatus (UVX-02516S1JS01, Ushio Inc.), irradiated with ultraviolet light of 800000 J / m 2 at an illuminance of 130 mW, and after irradiation The amount of film loss was examined. The amount of film loss was 2% or less, and light resistance was judged to be good.

Similarly, about the protective film by the formation method of Example 6, further using a UV irradiation apparatus (UVX-02516S1JS01, Ushio), irradiated with 80000 J / m 2 of ultraviolet light at an illuminance of 130 mW, and after irradiation The amount of film loss was examined. The amount of film loss was 2% or less, and light resistance was judged to be good.

<Manufacture of liquid crystal display elements>
Example 9
Using the radiation sensitive resin composition (β-I) obtained in Example 1, a gate electrode and a gate insulating film are formed according to a known method, and a semiconductor layer made of indium gallium zinc oxide (IGZO) is formed thereon. It apply | coated with the slit die coater on the board | substrate with which was arrange | positioned. The semiconductor layer on this substrate is formed according to a known method by referring to the method described in Japanese Patent Application Laid-Open No. 2007-115902, forming a semiconductor film, and repeating etching by a photolithography method. is there.

Next, a protective film having a through hole was formed by patterning on the semiconductor layer on the substrate by the formation method of Example 4.
Thereafter, according to a known method, on the protective film having a through hole, an electrode such as a source electrode and a drain electrode is formed, wiring such as a data wiring and a gate wiring is formed, and then a pixel electrode is patterned and formed. A semiconductor substrate was manufactured. This semiconductor substrate has the same structure as the semiconductor substrate 21 shown in FIG. Therefore, the semiconductor element having the same structure as the semiconductor element 1 shown in FIG. 1 is provided.

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

Next, a photoalignment film was formed on each of the obtained semiconductor substrate and color filter substrate using a liquid crystal aligning agent containing a radiation-sensitive polymer having a photoalignable group. As a method for forming a photo-alignment film, a liquid crystal aligning agent A-1 described in Example 6 of International Publication (WO) 2009/025386 pamphlet is used as a liquid crystal aligning agent including a radiation-sensitive polymer having a photo-aligning group. Is applied onto each substrate by a spinner. Next, after pre-baking for 1 minute on an 80 ° C. hot plate, it was heated at 180 ° C. for 1 hour in an oven in which the inside was replaced with nitrogen to form a coating film having a thickness of 80 nm. Next, the surface of the coating film was irradiated with polarized ultraviolet rays 200 J / m 2 containing a 313 nm emission line from a direction inclined by 40 ° with respect to the direction perpendicular to the substrate surface using a Hg-Xe lamp and a Grand Taylor prism, A semiconductor substrate having a photo-alignment film and a color filter substrate were manufactured.

  A liquid crystal layer was sandwiched between the obtained semiconductor substrate with a photo-alignment film and a color filter substrate to produce a color liquid crystal display element. As the liquid crystal layer, a layer made of nematic liquid crystal and aligned almost in parallel with a very small inclination with respect to the substrate surface was used. This liquid crystal display element has the same structure as the liquid crystal display element 100 shown in FIG. And even if light, such as an ultraviolet-ray, was irradiated, the operating characteristic was not deteriorated and the excellent display characteristic was shown.

Example 10
Using the radiation-sensitive resin composition (β-II) obtained in Example 2, a protective film having through holes was formed by patterning on the semiconductor layer on the substrate by the formation method of Example 5. A color liquid crystal display element was manufactured in the same manner as in Example 9 described above. This liquid crystal display element has the same structure as the liquid crystal display element 100 shown in FIG. And even if light, such as an ultraviolet-ray, was irradiated, the operating characteristic was not deteriorated and the excellent display characteristic was shown.

Example 11
Using the radiation-sensitive resin composition (β-III) obtained in Example 3, a protective film having a through hole was formed by patterning on the semiconductor layer on the substrate by the formation method of Example 6. A color liquid crystal display element was manufactured in the same manner as in Example 9 described above. This liquid crystal display element has the same structure as the liquid crystal display element 100 shown in FIG. And even if light, such as an ultraviolet-ray, was irradiated, the operating characteristic was not deteriorated and the excellent display characteristic was shown.

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

  The semiconductor element of the present invention can be produced by low-temperature heat treatment by forming the protective film using the radiation-sensitive resin composition of the present invention, and has excellent mobility characteristics and light resistance. Therefore, it is suitable for formation on a substrate having a heat resistance problem such as a resin substrate, and is suitable for providing a light-weight liquid crystal display element having flexibility. Moreover, since it is excellent in light resistance, it is suitable for outdoor use. Therefore, the semiconductor element, the semiconductor substrate and the display element of the present invention are suitable not only for large liquid crystal TV applications but also for display elements of portable information equipment.

DESCRIPTION OF SYMBOLS 1 Semiconductor element 2 Semiconductor layer 3 Source electrode 4 Drain electrode 5 Protective film 6 Through hole 10, 22, 45 Substrate 11 Gate electrode 12 Gate insulating film 21 Semiconductor substrate 23 Data wiring 24 Gate wiring 25 Pixel electrode 30 Color filter substrate 36 Coloring pattern 37 Black matrix 38 Protective layer 40 Color filter 41 Common electrode 42 Alignment film 43 Liquid crystal 44 Polarizing plate 46 Sealing material 47 Backlight 100 Liquid crystal display element

Claims (5)

  1. A substrate,
    A plurality of gate wirings and a plurality of data wirings disposed on the substrate;
    A semiconductor layer and a source electrode and a drain electrode provided in contact with the first surface of the semiconductor layer in a matrix pixel formed at an intersection of the plurality of gate wirings and the plurality of data wirings. A semiconductor element having
    The semiconductor layer is formed using an oxide including at least one of indium (In), zinc (Zn), and tin (Sn),
    Having a protective film between the semiconductor layer and the source and drain electrodes;
    The protective film is Resin, Quinonediazide compounds and indenecarboxylic acids
    A semiconductor substrate comprising:
  2. 2. The semiconductor substrate according to claim 1 , wherein the resin is one selected from an acrylic resin having a carboxyl group, a polyimide resin, a polysiloxane, and a novolac resin.
  3. The protective film is provided with a through hole,
    The connection between the electrode and the first surface of the semiconductor layer, the semiconductor substrate according to claim 1 or 2, characterized in that it is configured to be performed through the through hole.
  4. A gate electrode provided on the second surface of the semiconductor layer via a gate insulating film;
    A source electrode and a drain electrode provided on the first surface;
    A semiconductor substrate according to any one of claims 1 to 3 , wherein a bottom gate type semiconductor element is configured.
  5. The semiconductor layer is formed using at least one of zinc oxide (ZnO), indium gallium zinc oxide (IGZO), zinc tin oxide (ZTO), and indium zinc oxide (IZO). The semiconductor substrate according to any one of claims 1 to 4 .
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