JP6237279B2 - Thin film transistor substrate having protective film and method for manufacturing the same - Google Patents

Description

  The present invention relates to a thin film transistor substrate having a protective film and a method for manufacturing the same.

In recent years, thin film transistors using an oxide semiconductor typified by amorphous InGaZnO have been actively developed for high-resolution displays. Oxide semiconductor, as compared with amorphous silicon thin film transistor used in liquid crystal displays, the electron mobility is large, because it exhibits excellent electrical properties, such as large ON / OFF ratio, Ya driving element of an organic EL Di scan play It is expected as a power-saving element. In the development for displays, it is particularly important to maintain device operation stability as a transistor and uniformity over a large area substrate. An extremely important element for device operation stability is an insulating film that protects the oxide semiconductor layer from the external atmosphere. However, as such an insulating film, a protective insulating film that has been used for a conventional thin film transistor using amorphous silicon is mainly used (Patent Documents 1 and 2), and an oxide semiconductor has essentially. The physical properties may not be fully utilized. This is considered to be one of the factors that limit the performance of a thin film transistor using an oxide semiconductor.

The protective film in the oxide semiconductor must suppress entry of moisture, hydrogen, oxygen, and the like. The intrusion of these impurities significantly changes the conductivity of the oxide semiconductor and hinders operation stability such as threshold fluctuation. From this point of view, conventional protective insulating films are mainly single layer or multiple layers of SiOx, SiNx, SiONx, etc. using chemical vapor deposition (CVD) or physical vapor deposition (PVD) such as sputtering. Applied in layers. In the manufacturing process such as CVD for forming these inorganic films having a high barrier property, there is a possibility that an oxide semiconductor which is an underlayer of a thin film transistor using an oxide semiconductor is damaged. Specifically, as a conventional protective film formed by using a vacuum deposition apparatus, there are a SiO ₂ film and a SiN film, but these films are formed by decomposing a source gas by plasma or the like. In the manufacturing process, ion species generated by plasma may damage the surface of the oxide semiconductor and deteriorate film characteristics. Further, when manufacturing an oxide semiconductor element, there is a concern that the oxide semiconductor may be further deteriorated by various chemical solutions or processes such as dry etching. Therefore, a protective film such as an etch stopper is also applied as protection from the process (Patent Document 3).

  Further, when a film forming method using such a gas as a raw material is used, it is difficult to form a uniform protective film when a large-screen display is produced. Therefore, in order to eliminate such a point, it has been proposed to form a protective film by a coating method.

JP 2013-211410 A JP 2013-207247 A JP 2012-235105 A JP 2013-89971 A

Juan Paolo Bermundo, Yasuaki Ishikawa, Haruka Yamazaki, Toshiaki Nonaka, Yukiharu Uraoka, "Effect of polysilsesquioxane passivation layer on the dark and illuminated negative bias stress of amorphous InGaZnO thin-film transistors", Lecture at the 60th JSAP Spring Meeting Proceedings, March 29, 2013, 29p-F1-5 Juan Paolo Bermundo, Yasuaki Ishikawa, Haruka Yamazaki, Toshiaki Nonaka, Yukiharu Uraoka, "Effect of reactive ion etching and post-annealing conditions on the characteristics and reliability of a-InGaZnO thin-film transistors with polysilsesquioxane based passivation layer", The 13th International Meeting on Information Display (IMID) Proceedings, August 26, 2013, p. 431 (P2-30)

  However, the solution for forming a protective film used in such a coating method so far mainly contains a polyimide resin or an acrylic resin, and the film formed using the solution may be annealed at a high temperature. In many cases, sufficient performance cannot be exhibited because of the inability to do so, leaving room for improvement. Also, a coating-type protective film using a siloxane resin has been proposed (Patent Document 4). Although this document shows the transistor characteristics at the initial stage of a semiconductor element equipped with the protective film, the driving stability has been proposed. Is not sufficiently disclosed, and there is room for improvement. In addition, using siloxane resin as a coating-type protective film, the oxide semiconductor element deteriorated when the protective film is processed by dry etching is annealed in an oxygen atmosphere at 300 ° C. for 2 hours to restore the semiconductor element characteristics. And the method of manufacturing a reliable element is proposed (nonpatent literature 1 and 2). However, the method of processing the protective film by dry etching and the long-term annealing of the semiconductor element at a high temperature are expensive and there is room for further improvement from the viewpoint of production efficiency.

  The inventors of the present invention have studied a method for solving the above-mentioned problems, and from a photosensitive siloxane composition containing at least two types of polysiloxanes having different alkali dissolution rates, a photosensitive agent, and a solvent, a simple method. Thus, it was found that a thin film transistor substrate having a protective film can be formed. Furthermore, it was found that a thin film transistor substrate having such a protective film can suppress deterioration of the thin film transistor and can impart high driving stability to the thin film transistor substrate with relatively gentle annealing. The present invention has been made based on such knowledge.

  Therefore, an object of the present invention is to provide a thin film transistor substrate having a protective film, which can provide high driving stability.

  Another object of the present invention is a method of manufacturing a thin film transistor substrate having a protective film. The protective film can be processed by exposure and development. Further, annealing of the thin film transistor substrate provides high driving stability to the thin film transistor. It is to provide a production method that can be applied.

According to one aspect of the invention,
A thin film transistor;
A thin film transistor substrate comprising a protective film made of a cured product of a photosensitive siloxane composition covering the thin film transistor,
The thin film transistor has a semiconductor layer made of an oxide semiconductor,
The photosensitive siloxane composition is
At least two types of polysiloxanes having different alkali dissolution rates;
A photosensitizer,
A thin film transistor substrate comprising a solvent is provided.

According to a preferred embodiment of the present invention,
The polysiloxane is
A polysiloxane obtained by hydrolysis and condensation of a silane compound represented by the following formula (1) and a silane compound represented by the following formula (2) in the presence of a basic catalyst, wherein the film after prebaking is A polysiloxane (I) that is soluble in a 5 wt% tetramethylammonium hydroxide aqueous solution and has a dissolution rate of 1000 kg / sec or less;
RSi (OR ¹ ) ₃ (1)
Si (OR ¹ ) ₄ (2)
Wherein R is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a linear, branched or cyclic group having 1 to 20 carbon atoms in which at least one methylene may be substituted with oxygen. An alkyl group, or an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms in which at least one hydrogen may be substituted with fluorine, and R ¹ represents an alkyl group having 1 to 5 carbon atoms. .)
A polysiloxane obtained by hydrolyzing and condensing at least the silane compound of the general formula (1) in the presence of an acidic or basic catalyst, and the pre-baked film has a 2.38 wt% tetramethylammonium hydroxide aqueous solution. There is provided the above-mentioned thin film transistor substrate which is formed from a photosensitive siloxane composition comprising polysiloxane (II) which is soluble in water and has a dissolution rate of 100 Å / second or more.

According to another aspect of the present invention, in the method of manufacturing the thin film transistor substrate,
At least two types of polysiloxanes having different alkali dissolution rates;
A photosensitizer,
Preparing a photosensitive siloxane composition containing a solvent;
Applying the photosensitive siloxane composition to a thin film transistor and drying the solvent to form a protective film precursor layer;
Exposing the protective film precursor layer;
Developing the exposed protective film precursor layer;
A step of heat-curing the developed protective film precursor layer to form a protective film;
And a step of annealing the thin film transistor including the heat-cured protective film at least once.

  ADVANTAGE OF THE INVENTION According to this invention, the thin-film transistor substrate provided with the protective film which shows high stability with respect to voltage stress, light stress, and light and voltage stress can be provided. In the conventional coating type protective film, it is very difficult to give the thin film transistor high stability against stress. Further, according to the present invention, a thin film transistor capable of stable operation more easily is realized. Moreover, since a vacuum device or the like is not necessary, productivity can be greatly improved.

It is a schematic diagram which shows the one aspect | mode (Example 1) of the thin-film transistor substrate which comprises the protective film by this invention. It is a schematic diagram which shows another one aspect | mode of the thin-film transistor substrate which comprises the protective film by this invention. It is a schematic diagram which shows another one aspect | mode of the thin-film transistor substrate which comprises the protective film by this invention. 3 is a graph showing transfer characteristics of a thin film transistor substrate according to the present invention. 6 is a graph showing performance recovery by annealing of a thin film transistor substrate according to Comparative Example 2. 10 is a graph showing transfer characteristics of a thin film transistor substrate according to Comparative Example 2. 6 is a graph showing performance recovery by annealing of a thin film transistor substrate according to Reference Example 1. 5 is a graph showing transfer characteristics of a thin film transistor substrate according to Reference Example 1. 6 is a graph showing performance recovery by annealing of a thin film transistor substrate according to Reference Example 2.

  Embodiments of the present invention will be described in detail with reference to the accompanying drawings.

  First, FIG. 1 shows one mode of a thin film transistor substrate 1 having a protective film formed by the manufacturing method according to the present invention. In FIG. 1, a gate insulating layer 3 is formed on a gate layer 2, and a metal oxide semiconductor layer 4 is formed thereon. Further, a source electrode 5 and a drain electrode 6 are formed on both ends of the metal oxide semiconductor layer 4 so as to be in contact with the gate insulating layer 3. Although not shown, an etch stopper may be formed on the metal oxide semiconductor layer 4. The protective film 7 is formed so as to cover the metal oxide semiconductor layer 4, the source electrode 5, and the drain electrode 6. As another embodiment, for example, a thin film transistor substrate (FIG. 2) having a structure in which a source electrode 5 and a drain electrode 6 are formed in contact with the oxide semiconductor layer 4 through a contact hole 9 on the protective film 7. Alternatively, the same can be applied to a thin film transistor substrate having a top gate structure. Note that the structure shown here is merely an example, and a thin film transistor substrate having a structure other than that shown here can be manufactured by the manufacturing method according to the present invention.

  FIG. 3 shows one mode of the thin film transistor substrate in which the pixel electrode 8 is formed on the protective film 7. The pixel electrode 8 and the drain electrode 6 are in contact with each other through a contact hole 9 formed in the protective film.

[Thin film transistor substrate having a protective film]
The thin film transistor substrate according to the present invention includes a thin film transistor and a protective film made of a cured product of a siloxane composition that covers the thin film transistor. The thin film transistor substrate according to the present invention may include a plurality of protective films, and may have a second protective film on the protective film covering the thin film transistor. In this specification, a thin film transistor refers to all elements constituting a thin film transistor substrate, such as a substrate having an electrode, an electric circuit, a semiconductor layer, an insulating layer, and the like on a surface. Examples of the wiring arranged on the substrate include gate wiring, data wiring, and via wiring for connecting two or more types of wiring layers. As the semiconductor layer, an amorphous silicon semiconductor, a polycrystalline silicon semiconductor, and an oxide semiconductor are generally used. The thin film transistor substrate provided with the protective film according to the present invention is preferable in that high protective properties can be obtained particularly by an oxide semiconductor and an annealing process. Conventionally, in order to enable high temperature annealing, inorganic films such as silicon oxide film and silicon nitride formed by PE-CVD method have been applied as a protective film, but in order to form contact holes in these inorganic films. Reactive ion etching or the like was necessary for the above. However, since reactive ion etching significantly accelerates deterioration to an oxide semiconductor, it was necessary to increase the annealing temperature described later in order to restore the performance of the semiconductor after processing. In the present invention, the protective film can suppress deterioration of the semiconductor and can impart high driving stability to the thin film transistor by relatively gradual annealing.

  The protective film in the thin film transistor substrate according to the present invention is formed from a photosensitive siloxane composition containing at least two types of polysiloxanes having different alkali dissolution rates, a photosensitive agent, and a solvent. By using such a photosensitive siloxane composition, it is possible to process a protective film by exposure and development, and it is not necessary to perform pattern processing by dry etching or the like, so that the damage to the thin film transistor performance is relatively small, and the annealing time Has the advantage of being short. Such a photosensitive siloxane composition will be described in detail below.

[Photosensitive siloxane composition]
The photosensitive siloxane composition is classified into a positive photosensitive siloxane composition and a negative photosensitive siloxane composition depending on the type of the photosensitive agent. The preferred positive photosensitive siloxane composition used for forming the protective film in the thin film transistor substrate according to the present invention is at least two polysiloxanes (I) and (II) having different alkali dissolution rates, and a diazonaphthoquinone derivative as a photosensitive agent. As well as a solvent. Such a positive photosensitive siloxane composition forms a positive photosensitive layer that is removed by development when the exposed portion becomes soluble in an alkaline developer. On the other hand, the preferred negative photosensitive siloxane composition used for forming the protective film in the thin film transistor substrate according to the present invention is at least two types of polysiloxanes (I) and (II) having different alkali dissolution rates, and an acid or base by light. It is characterized by comprising a curing aid capable of generating water, and a solvent. Such a negative photosensitive siloxane composition forms a negative photosensitive layer that remains after development when the exposed portion becomes insoluble in an alkaline developer.

<Polysiloxane>
Polysiloxane refers to a polymer having a Si—O—Si bond (siloxane bond) as the main chain. In the present specification, polysiloxane includes a silsesquioxane polymer represented by the general formula (RSiO _1.5 ) _n .

In the present invention, as the polysiloxane contained in the photosensitive siloxane composition used for forming the protective film, it is preferable to use at least two types of polysiloxanes having different alkali dissolution rates. As such polysiloxanes having different alkali dissolution rates, the following polysiloxanes (I) and (II) are preferably used. The polysiloxane (I) is a polysiloxane obtained by hydrolysis and condensation of a silane compound represented by the following formula (1) and a silane compound represented by the following formula (2) in the presence of a basic catalyst. . The pre-baked film of polysiloxane (I) is soluble in a 5 wt% TMAH solution, and the dissolution rate is 1000 Å / sec or less, preferably 10 to 700 Å / sec. When the solubility is 10 kg / second or more, the possibility that an insoluble matter remains after development is extremely low, which is preferable for preventing disconnection and the like.
RSi (OR ¹ ) ₃ (1)
Si (OR ¹ ) ₄ (2)
Wherein R is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a linear, branched or cyclic group having 1 to 20 carbon atoms in which at least one methylene may be substituted with oxygen. An alkyl group, or an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms in which at least one hydrogen may be substituted with fluorine, and R ¹ represents an alkyl group having 1 to 5 carbon atoms. .)

  The polysiloxane (II) is a polysiloxane obtained by hydrolyzing and condensing at least a silane compound of the general formula (1) in the presence of an acidic or basic catalyst. The pre-baked film of polysiloxane (II) is soluble in a 2.38 wt% TMAH aqueous solution, and the dissolution rate is 100 Å / second or more, preferably 100 to 15,000 Å / second. The dissolution rate of polysiloxane (II) can be selected in the range of 100 Å / second to 15,000 Å / second depending on the thickness of the target protective film. More preferably, it is 100 Å / second to 10,000 Å / second. By setting it to 15,000 K / sec or less, the difference in dissolution rate with polysiloxane (I) is not too large, and uniform development can be performed.

  Polysiloxane (I) is difficult to cause a “pattern” dripping at the time of heat-curing after development, but cannot be used alone because its alkali solubility is extremely small. In addition, even if the polysiloxane (I) or the polysiloxane (II) is used alone and the alkali solubility is adjusted, the photosensitive siloxane composition used for forming the protective film in the present invention shows Therefore, it is preferable to use a combination of polysiloxanes (I) and (II). In addition, when the dissolution rate difference is large, it is preferable to use a plurality of polysiloxanes (II) having different dissolution rates.

  The content of the silane compound of the general formula (2) in the polysiloxane (I) and the polysiloxane (II) can be appropriately set according to the use, but in each polysiloxane compound, 3 mol% to It is preferably 40 mol%, and more preferably 5 mol% to 30 mol%, from the viewpoint of controlling the hardness of the film and the thermal stability of the pattern. By making this content 3 mol% or more, the pattern stability at high temperature becomes better, and by making it 40 mol or less, the reaction activity is suppressed, and the stability during storage becomes better.

<Measurement and calculation method of alkali dissolution rate (ADR)>
The dissolution rate of the polysiloxanes (I) and (II) in the TMAH aqueous solution is measured and calculated as follows.

  First, polysiloxane is dissolved in propylene glycol monomethyl ether acetate (PGMEA) so as to be about 35% by weight. This solution is spin-coated on a silicon wafer so as to have a dry film thickness of about 2 μm, and then the solvent is further removed by heating on a hot plate at 100 ° C. for 60 seconds. The film thickness of the coating film is measured with a spectroscopic ellipsometer (Woollam). Next, the silicon wafer having this film was immersed in a 5% TMAH aqueous solution for polysiloxane (I) and a 2.38% TMAH aqueous solution for polysiloxane (II) at room temperature (25 ° C.), and the film disappeared. Measure the time to complete. The dissolution rate is determined by dividing the initial film thickness by the time until the film disappears. When the dissolution rate is remarkably slow, the film thickness is measured after being immersed for a certain time, the amount of change in film thickness before and after the immersion is divided by the immersion time, and the dissolution rate is calculated.

  In both the polysiloxane (I) and (II) polymers, the weight average molecular weight in terms of polystyrene is generally 700 to 10,000, preferably 1,000 to 4,000. If the molecular weight is within the above range, it is preferable to adjust the molecular weight to be within the above range, since it is possible to prevent the occurrence of development residuals and obtain sufficient resolution and good sensitivity.

  The mixing ratio of the polysiloxane (I) and (II) can be adjusted at an arbitrary ratio depending on the film thickness of the interlayer insulating film, the sensitivity of the photosensitive composition, the resolution, etc. The content of 20% by weight or more is preferable because it has an effect of preventing “pattern” dripping during heat curing. Here, “pattern” is a pattern that is deformed when the pattern is heated. For example, a pattern whose cross section is rectangular and whose ridgeline is clear is a rectangle whose ridgeline portion is rounded or near vertical after heating. A phenomenon that the side of the shape is inclined.

<Photosensitive agent>
In the present invention, the photosensitive siloxane composition for forming a pattern by light contains various photosensitive agents as its components. Examples of the photosensitive agent used in the positive photosensitive siloxane composition include diazonaphthoquinone derivatives. The photosensitive agent used in the negative photosensitive siloxane composition decomposes when irradiated with light and promotes condensation of silanol groups. And a curing aid to be used. Hereinafter, each photosensitive agent will be described.

<Diazonaphthoquinone derivative>
The diazonaphthoquinone derivative in the present invention is a compound in which naphthoquinone diazide sulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group, and the structure is not particularly limited, but is preferably an ester compound with a compound having one or more phenolic hydroxyl groups. Preferably there is. As naphthoquinone diazide sulfonic acid, 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid can be used. Since 4-naphthoquinonediazide sulfonic acid ester compound has absorption in the i-line (wavelength 365 nm) region, it is suitable for i-line exposure. Moreover, since 5-naphthoquinone diazide sulfonic acid ester compound has absorption in a wide range of wavelengths, it is suitable for exposure in a wide range of wavelengths. It is preferable to select a 4-naphthoquinone diazide sulfonic acid ester compound or a 5-naphthoquinone diazide sulfonic acid ester compound depending on the wavelength to be exposed. A 4-naphthoquinone diazide sulfonic acid ester compound and a 5-naphthoquinone diazide sulfonic acid ester compound may be mixed and used.

Although it does not specifically limit as a compound which has a phenolic hydroxyl group, For example, the following compounds are mentioned (a brand name, the Honshu Chemical Industry Co., Ltd. product).

  The amount of diazonaphthoquinone derivative added varies depending on the esterification rate of naphthoquinone diazide sulfonic acid, the physical properties of the polysiloxane used, the required sensitivity, and the dissolution contrast between the exposed and unexposed areas. The interlayer insulating film is preferably 3 to 20 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the polysiloxane mixture. When the addition amount of the diazonaphthoquinone derivative is 3 parts by weight or more, the dissolution contrast between the exposed part and the unexposed part is increased, and the photosensitivity is good. Further, in order to obtain a better dissolution contrast, 5 parts by weight or more is preferable. On the other hand, when the addition amount of the diazonaphthoquinone derivative is 20 parts by weight or less, the colorless transparency of the cured film is improved.

<Curing aid>
As the curing aid used in the present invention, there is one that decomposes when irradiated with light and promotes condensation of silanol groups. Examples thereof include a photoacid generator that releases an acid that is an active substance for photocuring the composition, a photobase generator that releases a base, and the like. Here, examples of light include visible light, ultraviolet light, and infrared light. In particular, those that generate an acid or a base by ultraviolet rays used in the production of thin film transistors are preferred.

  The amount of curing aid added varies depending on the type of active substance generated by the decomposition of the curing aid, the amount generated, the required sensitivity, and the dissolution contrast between the exposed and unexposed areas. Preferably it is 0.001-10 weight part with respect to 100 weight part, More preferably, it is 0.01-5 weight part. When the addition amount is 0.001 part by weight or more, the dissolution contrast between the exposed part and the unexposed part becomes high, and the effect of addition becomes good. On the other hand, if the addition amount of the curing aid is 10 parts by weight or less, cracks in the formed film are suppressed, and coloring due to decomposition of the curing aid is also suppressed, so that the colorless transparency of the film is improved.

Examples of the photoacid generator include diazomethane compounds, diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, ammonium salts, phosphonium salts, sulfonimide compounds and the like. The structure of these photoacid generators can be represented by general formula (A).
R ⁺ X ⁻ (A)
Here, R ⁺ represents an organic ion selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an acyl group, and an alkoxyl group modified with hydrogen, a carbon atom or other hetero atom, such as diphenyliodonium ion, triphenyl Represents a sulfonium ion.

Further, X ⁻ is preferably any counter ion represented by the following general formula.
SbY ₆ ⁻
AsY ₆ ⁻
R ^a _p PY _6-p ^-
R ^a _q BY _4-q ⁻
R ^a _q GaY _4-q ⁻
R ^a SO ₃ ⁻
(R ^a SO ₂ ) ₃ C ⁻
(R ^a SO ₂ ) ₂ N ⁻
R ^b COO ⁻
SCN ^-
(Wherein Y is a halogen atom, and R ^a is an alkyl group having 1 to 20 carbon atoms or aryl having 6 to 20 carbon atoms substituted with a substituent selected from fluorine, nitro group, and cyano group) R ^b is hydrogen or an alkyl group having 1 to 8 carbon atoms, p is a number from 0 to 6, and q is a number from 0 to 4.)

Specific counter ions include BF ₄ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ⁻ , PF ₆ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ^−. , SbF ₆ ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ⁻ , SCN ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ SO ₂ ) ₂ N ^-, formate ions, acetate ions, trifluoromethanesulfonate ions, consisting nonafluorobutanesulfonate ion, methanesulfonate ion, butane sulfonic acid ion, benzenesulfonic acid ion, p- toluenesulfonate ion, and a sulfonate ion Those selected from the group can be mentioned.

Among the photoacid generators used in the present invention, those that generate sulfonic acids or boric acids are particularly preferable. For example, tricumyliodonium tetrakis (pentafluorophenyl) boric acid (PHOTINITITOR 2074 (trade name) manufactured by Rhodia), Examples thereof include diphenyliodonium tetra (perfluorophenyl) borate, a cation part composed of a sulfonium ion, and an anion part composed of a pentafluoroborate ion. In addition, triphenylsulfonium trifluoromethanesulfonic acid, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetra (perfluorophenyl) boric acid, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenic acid, 1- (4-n-butoxynaphthalene- 1-yl) tetrahydrothiophenium trifluoromethanesulfonic acid, 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonic acid, diphenyliodonium trifluoromethanesulfonic acid, diphenyliodonium hexafluoroarsenic acid, etc. Can be mentioned. Furthermore, a photoacid generator represented by the following formula can also be used.
In the formula, each A independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylcarbonyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. 20 is a substituent selected from an arylcarbonyl group, a hydroxyl group and an amino group, p is independently an integer of 0 to 5, and B ⁻ is a fluorinated alkyl sulfonate group or a fluorinated aryl sulfonate. Groups, fluorinated alkyl borate groups, alkyl sulfonate groups, aryl sulfonate groups and the like. A compound obtained by exchanging the cation and anion shown in these formulas with each other, or a photoacid generator combining the cation or anion shown in these formulas with the above-mentioned various cations or anions can also be used. . For example, a combination of any of the sulfonium ions represented by the formula and a tetra (perfluorophenyl) borate ion, a combination of any of the iodonium ions represented by the formula and a tetra (perfluorophenyl) borate ion Those can also be used as photoacid generators.

  Examples of the photobase generator include a polysubstituted amide compound having an amide group, a lactam, an imide compound, or a compound containing the structure.

  Examples of the thermal base generator include N- (2-nitrobenzyloxycarbonyl) imidazole, N- (3-nitrobenzyloxycarbonyl) imidazole, N- (4-nitrobenzyloxycarbonyl) imidazole, N- (5 -Methyl-2-nitrobenzyloxycarbonyl) imidazole, imidazole derivatives such as N- (4-chloro-2-nitrobenzyloxycarbonyl) imidazole, 1,8-diazabicyclo (5,4,0) undecene-7, third Secondary amines, quaternary ammonium salts, and mixtures thereof. These base generators can be used alone or as a mixture, like the acid generator.

<Solvent>
Examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether. Diethylene glycol dialkyl ethers such as methyl cellosolve acetate, ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, propylene glycol such as PGMEA, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Ruki ether acetates, benzene, toluene, aromatic hydrocarbons such as xylene, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and the like ketones such as cyclohexanone. These solvents are used alone or in combination of two or more. The mixing ratio of the solvent varies depending on the coating method and the film thickness requirement after coating. For example, in the case of spray coating, it becomes 90% by weight or more based on the total weight of polysiloxane and optional components, but it is usually 50% for slit coating of a large glass substrate used in the production of displays. % Or more, preferably 60% by weight or more, usually 90% by weight or less, preferably 85% by weight or less.

<Optional component>
Moreover, the photosensitive siloxane composition by this invention may contain the other arbitrary components as needed. Examples of such components include surfactants.

  Among these, it is preferable to use a surfactant in order to improve applicability. Examples of the surfactant that can be used in the photosensitive siloxane composition of the present invention include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether and polyoxyethylene cetyl ether, and polyoxyethylene fatty acids. Diesters, polyoxy fatty acid monoesters, polyoxyethylene polyoxypropylene block polymers, acetylene alcohol, acetylene glycol, acetylene alcohol polyethoxylates, acetylene glycol derivatives such as acetylene glycol polyethoxylates, fluorine-containing surfactants such as Fluorado (Product name, manufactured by Sumitomo 3M Co., Ltd.), Megafuck (Product name, manufactured by DIC Corporation), Sulfron (Product name, Asahi Glass Co., Ltd.) Ltd.), or organosiloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the acetylene glycol include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4, 7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyne-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,5 -Dimethyl-2,5-hexanediol etc. are mentioned.

  As anionic surfactants, alkyl diphenyl ether disulfonic acid ammonium salt or organic amine salt, alkyl diphenyl ether sulfonic acid ammonium salt or organic amine salt, alkylbenzene sulfonic acid ammonium salt or organic amine salt, polyoxyethylene alkyl ether sulfuric acid And ammonium salts of alkylsulfuric acid, organic amine salts of alkylsulfuric acid, and the like.

  Further, examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauric acid amidopropyl hydroxysulfone betaine, and the like.

  These surfactants can be used alone or in admixture of two or more, and the blending ratio is usually 50 to 10,000 ppm, preferably 100 to 5, based on the total weight of the photosensitive siloxane composition. 000 ppm.

[Method for Manufacturing Thin Film Transistor Having Protective Film]
A thin film transistor substrate having a protective film (cured film) is obtained by applying the photosensitive siloxane composition to the thin film transistor and heating. At that time, a pattern such as a contact hole is formed by performing exposure and development through a desired mask.

  As a method for manufacturing a thin film transistor substrate having an oxide semiconductor layer, a bottom-gate TFT illustrated in FIG. 1 will be described as an example. The gate electrode 2 is patterned on a substrate made of glass or the like. As the gate electrode material, a material such as molybdenum, aluminum and an aluminum alloy, copper and a copper alloy, or titanium is formed as a single layer or two or more kinds of laminated films. A gate insulating film 3 is formed on the gate electrode. As the gate insulating film, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or the like is generally formed by a PE-CVD method. The thickness of the gate insulating film is usually 100 to 300 nm. The oxide semiconductor layer 4 on the gate insulating film is formed by a sputtering method in which a sputtering target having the same composition as the oxide semiconductor is formed by DC sputtering or RF sputtering, a precursor solution such as a metal alkoxide, a metal organic acid salt, or a chloride, There is a liquid phase method in which an oxide semiconductor layer is formed by applying and baking a dispersion of oxide semiconductor nanoparticles. After patterning the oxide semiconductor layer 4, the source / drain electrodes 5 and 6 are patterned. As the source / drain electrode material, a material such as molybdenum, aluminum and aluminum alloy, copper and copper alloy, and titanium is formed as a single layer or two or more kinds of laminated films.

  In the method for manufacturing a thin film transistor substrate having a protective film, a photosensitive siloxane composition is applied onto the thin film transistor having the oxide semiconductor layer, dried by prebaking or the like, and then exposed to an aqueous tetramethylammonium hydroxide solution (generally, 2. 38% aqueous solution is used to form a pattern such as a contact hole, and then the applied photosensitive siloxane composition (protective film precursor layer) is cured to form the protective film 7. Further, an ITO film is formed on the protective film by sputtering, for example, and patterned to form the element of FIG. Further, an inorganic film can be formed on the protective film by CVD or PVD, or an organic material can be provided for the purpose of the protective film or planarization by a coating method.

  Each step of the production method according to the present invention will be described below.

<Process for preparing photosensitive siloxane composition>
In the method of manufacturing a thin film transistor substrate having a protective film according to the present invention, a photosensitive siloxane composition containing at least two types of polysiloxanes having different alkali dissolution rates, a photosensitive agent, and a solvent is prepared. The details of each component of the photosensitive siloxane composition are as described above.

<Application process>
The coating process in the present invention is performed by coating the photosensitive siloxane composition on the surface of the thin film transistor. This coating process is a general coating method, that is, as a conventional photosensitive composition coating method such as dip coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, slit coating, etc. This can be done by any known method. The protective film precursor layer can be made to have a desired film thickness by applying it once or twice or more as necessary.

<Pre-baking process>
After forming the protective film precursor layer, it is preferable to pre-bake (heat treatment) the layer in order to further dry the layer and reduce the residual solvent. The pre-baking step is generally performed at a temperature of 70 to 150 ° C., preferably 90 to 130 ° C., for 10 to 180 seconds, preferably 30 to 90 seconds when using a hot plate, and 1 to 5 minutes when using a clean oven. be able to. It is preferable that a solvent removal step by spin or vacuum is included before pre-baking.

<Exposure process>
After forming the protective film precursor layer, the surface is irradiated with light. As the light source used for the light irradiation, any one conventionally used in the pattern forming method can be used. Examples of such light sources include high pressure mercury lamps, low pressure mercury lamps, metal halide, xenon lamps, laser diodes, LEDs, and the like. As irradiation light, ultraviolet rays such as g-line, h-line and i-line are usually used. Except for ultrafine processing such as a semiconductor, it is common to use light (high pressure mercury lamp) of 360 to 430 nm for patterning of several μm to several tens of μm. In particular, in the case of a liquid crystal display device, light of 430 nm is often used. The energy of the irradiation light, depending on the thickness of the light source and the protective film precursor layer, generally in the case of a positive diazonaphthoquinone derivative, 20~2000mJ / cm ^2, preferably a 50~1000mJ / cm ^2. If the irradiation light energy is lower than 20 mJ / cm ² , sufficient resolution may not be obtained. Conversely, if the irradiation light energy is higher than 2000 mJ / cm ² , overexposure may occur and halation may occur. In the case of a negative type, it is 1 to 500 mJ / cm ² , preferably 10 to 100 mJ / cm ² . When the irradiation light energy is lower than 1 mJ / cm ² , film slippage is large. On the other hand, when the irradiation light energy is higher than 500 mJ / cm ² , overexposure occurs and resolution may not be obtained.

  A general photomask can be used to irradiate light in a pattern. Such a photomask can be arbitrarily selected from known ones. The environment at the time of irradiation is not particularly limited, but generally an ambient atmosphere (in the air) or a nitrogen atmosphere may be used. In addition, when a film is formed on the entire surface of the substrate, light irradiation may be performed on the entire surface of the substrate. In the present invention, the pattern film includes the case where a film is formed on the entire surface of the substrate.

<Post-exposure heating process>
After the exposure, since the reaction between the polymers in the film is promoted by the reaction initiator generated at the exposed portion, post-exposure baking can be performed as necessary. This heat treatment is not performed in order to completely cure the protective film precursor layer, so that only a desired pattern remains on the substrate after development, and other portions can be removed by development. Is what you do.

<Development process>
After the exposure, after the post-exposure heating as necessary, the protective film precursor layer is developed. As a developing solution used at the time of development, any developing solution used for developing a known photosensitive siloxane composition can be used. In the present invention, an aqueous tetramethylammonium hydroxide (TMAH) solution is used to specify the dissolution rate of polysiloxane, but the developer used for forming a cured film is not limited thereto. Preferred developers include tetraalkylammonium hydroxide, choline, alkali metal hydroxide, alkali metal metasilicate (hydrate), alkali metal phosphate (hydrate), ammonia, alkylamine, alkanolamine, complex Examples include an alkaline developer that is an aqueous solution of an alkaline compound such as a cyclic amine, and a particularly preferred alkaline developer is an aqueous TMAH solution. These alkaline developers may further contain a water-soluble organic solvent such as methanol and ethanol, or a surfactant, if necessary. The developing method can be arbitrarily selected from conventionally known methods. Specific examples include immersion (dip) in a developer, paddle, shower, slit, cap coat, and spray. By this development, a pattern can be obtained. After development with a developer, it is preferably washed with water. In the manufacturing method according to the present invention, as shown in FIG. 3, the drain electrode 6 and the transparent electrode (pixel electrode 8) formed on the protective film 7 are electrically connected through the contact hole 9 formed by development. It can also be made.

<Post-development irradiation process>
When a positive composition is used and the protective film to be formed is used as a transparent film, it is preferable to perform light irradiation called bleaching exposure. By performing bleaching exposure, the unreacted diazonaphthoquinone derivative remaining in the film is photodegraded, and the light transparency of the film is further improved. As a bleaching exposure method, a high-pressure mercury lamp, a low-pressure mercury lamp, or the like is used, and the entire surface is exposed to about 100 to 2,000 mJ / cm ² (wavelength 365 nm exposure amount conversion) depending on the film thickness. Further, in the case of a negative type, the subsequent heat curing can be performed more easily by activating the curing aid in the residual film after development by light irradiation. The entire surface is exposed to about 100 to 2,000 mJ / cm ² (wavelength 365 nm exposure amount conversion) depending on the film thickness.

<Heat curing (firing) step>
The firing temperature at the time of curing the protective film precursor layer can be arbitrarily selected as long as the protective film is cured. However, if the firing temperature is too low, the reaction may not proceed sufficiently and may not be cured sufficiently. For this reason, it is preferable that a calcination temperature is 200 degreeC or more, and 250 degreeC or more is more preferable. Moreover, when the temperature is excessively high, the production cost is increased, and the polymer may be decomposed. 400 degrees C or less is more preferable. Moreover, although baking time is not specifically limited, Generally it is 10 minutes or more, Preferably it is 20 minutes or more. Firing is performed in an inert gas or in the air.

<Annealing process>
Further, after the thin film transistor including the protective film is formed, the thin film transistor is annealed. In particular, an element using an oxide semiconductor has a thin film transistor performance deteriorated due to film formation by PVD or CVD, pattern processing of dry etching or wet etching, a resist peeling process, and the like. Is desirable. By performing annealing at 250 ° C. or higher after the formation of the protective film in the present invention, the performance of the thin film transistor once lowered during processing is recovered. In particular, in the present invention, a thin film transistor having a greatly deteriorated oxide semiconductor layer is characterized in that significant performance recovery occurs by annealing in the presence of oxygen. Depending on the degree of deterioration of the oxide semiconductor, the performance recovery of the thin film transistor and the reliability of the device can be improved by increasing the annealing temperature or extending the annealing time. The annealing temperature is 250 ° C. or higher and 450 ° C. or lower, preferably 300 ° C. or higher and 400 ° C. or lower. The annealing time is 30 minutes or more, preferably 60 minutes or more, but more preferably 60 minutes or more and less than 120 minutes from the viewpoint of cost and production efficiency. Annealing is preferably performed in the presence of oxygen. In the case of a thin film transistor substrate provided with a protective film formed of a conventional organic coating film, annealing at such a high temperature could not be performed, so that a significant performance recovery by annealing could not be achieved. However, the annealing in the presence of oxygen is preferably performed at 400 ° C. or lower in consideration of the influence of coloring of the electrode and the oxidation of the protective film of the present invention. Further, since the protective film formed by the photosensitive siloxane composition in the present invention has photosensitivity, it is not necessary to perform pattern processing by dry etching or the like, so that the damage to the thin film transistor performance is relatively small and the annealing time is short. There is an advantage of being short.

  The present invention will be specifically described below with reference to examples.

Synthesis Example 1 (Synthesis of polysiloxane (I))
A 2 L flask equipped with a stirrer, a thermometer, and a condenser tube was charged with 36.5 g of 25 wt% tetramethylammonium hydroxide (TMAH) aqueous solution, 300 ml of isopropyl alcohol (IPA), and 1.5 g of water. A mixed solution of 44.6 g of phenyltrimethoxysilane, 34.1 g of methyltrimethoxysilane, and 3.8 g of tetramethoxysilane was prepared. The mixed solution was added dropwise at 60 ° C., stirred at the same temperature for 3 hours, and neutralized by adding a 10% aqueous HCl solution. 200 ml of toluene and 300 ml of water are added to the neutralized solution, and the mixture is separated into two layers. The resulting organic layer is concentrated under reduced pressure to remove the solvent, and propylene glycol is added to the concentrate to a solid content concentration of 40% by weight. Monomethyl ether acetate (PGMEA) was added and adjusted. The molecular weight (polystyrene conversion) of the obtained polysiloxane (I) was weight average molecular weight (Mw) = 1420. The obtained resin solution was applied to a silicon wafer so that the film thickness after pre-baking was 2 μm, and the dissolution rate in a 5% TMAH aqueous solution was measured. The result was 950 kg / sec.

Synthesis Example 2 (Synthesis of polysiloxane (II))
A 2 L flask equipped with a stirrer, a thermometer, and a condenser tube was charged with 36.5 g of 25 wt% TMAH aqueous solution, 800 ml of IPA, and 2.0 g of water, and then 39.7 g of phenyltrimethoxysilane and methyltrimethoxysilane in a dropping funnel. A mixed solution of 34.1 g and tetramethoxysilane 7.6 g was prepared. The mixed solution was added dropwise at 10 ° C. and stirred at the same temperature for 24 hours, and then neutralized by adding a 10% HCl aqueous solution. To the neutralized solution, 400 ml of toluene and 100 ml of water were added, and the mixture was separated into two layers. The resulting organic layer was concentrated under reduced pressure to remove the solvent, and PGMEA was added to the concentrate to a solid concentration of 40% by weight. The addition was adjusted. The molecular weight (polystyrene conversion) of the obtained polysiloxane (II) was Mw = 2,200. The obtained resin solution was applied onto a silicon wafer so that the film thickness after pre-baking was 2 μm, and the dissolution rate in a 2.38% TMAH aqueous solution was measured.

Positive photosensitive siloxane composition A
After mixing at a ratio of polysiloxane (I) :( II) = (80 wt%) :( 20 wt%), the polysiloxane mixture was adjusted to a 35% PGMEA solution, and 4-4 ′-(1- ( 4- (1- (4-hydroxyphenol) -1-methylethyl) phenyl) ethylidene) bisphenol diazonaphthoquinone 2.0 mol modified product (hereinafter abbreviated as “PAC”) is 12% by weight based on polysiloxane. Added. Moreover, 0.3% by weight of KF-53 manufactured by Shin-Etsu Chemical Co., Ltd. as a surfactant was added to the polysiloxane to obtain a photosensitive siloxane composition A.

Example 1 (Thin Film Transistor Substrate Comprising a Protective Film According to the Present Invention)
A 100 nm silicon oxide film was placed as a gate insulating film on an n-doped silicon wafer. Amorphous InGaZnO was formed on the gate insulating film by RF sputtering (70 nm). After the patterning of the amorphous InGaZnO film, the source / drain electrodes were patterned. Molybdenum was used as the source / drain electrode material. Thereafter, the thin film transistor was annealed at 300 ° C. for 1 hour. Next, a positive photosensitive siloxane composition A was applied as a protective film by a spin coating method. After pre-baking at 100 ° C. for 90 seconds, contact holes were formed by exposure and development.

  Subsequently, it was cured in a nitrogen atmosphere at 250 ° C. for 60 minutes to form a protective film. The thin film transistor provided with the protective film was annealed. Annealing was performed at 250 ° C. in an oxygen atmosphere for 1 hour. The protective film thickness was 400 nm. FIG. 4 shows transfer characteristics of a thin film transistor including the protective film after annealing. Good transfer characteristics of the thin film transistor were obtained, whose characteristics hardly changed in response to positive voltage applied stress.

Comparative Example 1 (Thin Film Transistor Substrate with a Protective Film Containing Photosensitive Agent and One Type of Polysiloxane)
Polysiloxane (II) was adjusted to a 35% PGMEA solution and 4-4 ′-(1- (4- (1- (4-hydroxyphenol) -1-methylethyl) phenyl) ethylidene) bisphenol diazonaphthoquinone 2 0.0 mol modified product (hereinafter abbreviated as “PAC”) was added in an amount of 12% by weight based on polysiloxane (II). Moreover, 0.3% by weight of KF-53 manufactured by Shin-Etsu Chemical Co., Ltd. as a surfactant was added to the polysiloxane to obtain a photosensitive siloxane composition B. As in Example 1, photosensitive siloxane composition B was applied as a protective film by spin coating. After pre-baking at 100 ° C. for 90 seconds, contact holes were formed by exposure and development. Next, when cured in a nitrogen atmosphere at 250 ° C. for 60 minutes, the contact hole formed by development disappeared due to heat flow, and the transistor characteristics could not be measured.

Comparative Example 2 (Thin film transistor substrate having no protective film)
On the gate electrode, a 100 nm silicon oxide film was placed as a gate insulating film. Amorphous InGaZnO was formed on the gate insulating film by an RF sputtering method. After patterning the amorphous InGaZnO film, the source / drain electrodes were patterned. Molybdenum was used as the source / drain electrode material. A protective film was not provided, and a thin film transistor without the protective film was annealed. Annealing was performed at 300 ° C. for 2 hours. As shown in FIG. 5, performance recovery by annealing was insufficient. FIG. 6 shows transfer characteristics of the thin film transistor. The characteristics changed greatly with positive voltage applied stress, and the transfer characteristics of unstable thin film transistors were obtained.

Reference Example 1 (Thin film transistor substrate having a protective film containing one kind of polysiloxane)
Methylphenylsilsesquioxane (methyl group: phenyl group = 60 mol: 40 mol) was synthesized in the presence of a basic catalyst. The molecular weight (polystyrene conversion) was Mw = 1,800. It was hardly dissolved in 5% TMAH aqueous solution, and the dissolution rate was almost 0 kg / second. The obtained polymer was adjusted to a 35% PGMEA solution, and 0.3% by weight of KF-53 manufactured by Shin-Etsu Chemical Co., Ltd. was added as a surfactant to the polysiloxane to obtain a siloxane composition C. After applying the siloxane composition C onto the amorphous InGaZnO prepared in the same manner as in Example 1 by spin coating, pre-baking and curing (at 300 ° C. for 1 hour in nitrogen) at 100 ° C. for 90 seconds to form a protective film Formed. After forming the contact hole by dry etching, the thin film transistor was annealed at 300 ° C. for 1 hour in an oxygen atmosphere. FIG. 7 shows the transfer characteristics of the thin film transistor. The characteristic deterioration was observed by dry etching after the protective film was applied. Moreover, the characteristics close to the initial characteristics were shown by annealing. When the characteristic change due to the stress application was verified, a large characteristic change was confirmed as shown in FIG.

Reference Example 2 (Thin Film Transistor Substrate with a Protective Film Containing Acrylic Material)
A composition composed of an acrylic resin composed of a polymer of 2-hydroxyethyl methacrylate and a vinyl group-containing silane monomer (Shin-Etsu Chemical KBM-5103) and methylphenylsilsesquioxane synthesized in Comparative Example 3 was prepared. The acrylic resin was added in an amount of 30% by weight to 100% by weight of methylphenylsilsesquioxane. As in the example, a 35% solution was prepared by adding a surfactant. In the same manner as in Comparative Example 3, a protective film was formed on amorphous InGaZnO, a contact hole was formed by dry etching, and annealing of the thin film transistor was performed at 300 ° C. for 1 hour in an oxygen atmosphere. FIG. 9 shows transfer characteristics before and after annealing of the thin film transistor. Even after annealing, good transistor characteristics such as a high current flowing in the negative voltage region could not be obtained.

DESCRIPTION OF SYMBOLS 1 Thin-film transistor substrate provided with protective film 2 Gate layer 3 Gate insulating layer 4 Metal oxide semiconductor layer 5 Source electrode 6 Drain electrode 7 Protective film 8 Pixel electrode 9 Contact hole

Claims (8)

A thin film transistor having a semiconductor layer made of an oxide semiconductor ;
A method for producing a thin film transistor substrate comprising a protective film made of a cured product of a photosensitive siloxane composition that covers the thin film transistor,
At least two types of polysiloxanes having different alkali dissolution rates;
A photosensitizer,
With solvent
Preparing a photosensitive siloxane composition containing
Applying the photosensitive siloxane composition to a thin film transistor and drying the solvent to form a protective film precursor layer;
Exposing the protective film precursor layer;
Developing the exposed protective film precursor layer;
A step of heat-curing the developed protective film precursor layer to form a protective film;
Annealing the thin film transistor comprising the heat-cured protective film at least once;
A production method comprising: The polysiloxane is
A polysiloxane obtained by hydrolysis and condensation of a silane compound represented by the following formula (1) and a silane compound represented by the following formula (2) in the presence of a basic catalyst, wherein the film after prebaking is A polysiloxane (I) that is soluble in a 5 wt% tetramethylammonium hydroxide aqueous solution and has a dissolution rate of 1000 kg / sec or less;
RSi (OR ¹ ) ₃ (1)
Si (OR ¹ ) ₄ (2)
Wherein R is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a linear, branched or cyclic group having 1 to 20 carbon atoms in which at least one methylene may be substituted with oxygen. An alkyl group, or an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms in which at least one hydrogen may be substituted with fluorine, and R ¹ represents an alkyl group having 1 to 5 carbon atoms. .)
A polysiloxane obtained by hydrolyzing and condensing at least the silane compound of the general formula (1) in the presence of an acidic or basic catalyst, and the pre-baked film has a 2.38 wt% tetramethylammonium hydroxide aqueous solution. A polysiloxane (II) that is soluble in water and has a dissolution rate of 100 kg / second or more;
The manufacturing method of Claim 1 which comprises these. The production method according to claim 1 or 2, wherein the photosensitive siloxane composition is a positive photosensitive siloxane composition containing at least two types of polysiloxanes having different alkali dissolution rates, a diazonaphthoquinone derivative, and a solvent. The photosensitive siloxane composition is a negative photosensitive siloxane composition containing at least two types of polysiloxanes having different alkali dissolution rates, a curing aid capable of generating an acid or a base by light, and a solvent. The manufacturing method of Claim 1 or 2. The content of the silane compound of the general formula (2) in the polysiloxane (I) and the polysiloxane (II) is 3 mol% to 40 mol% in each polysiloxane compound. The manufacturing method as described in any one of these. The manufacturing method as described in any one of Claims 1-5 which has a 2nd protective film on the said protective film. The said annealing is performed at 250 degreeC or more and 450 degrees C or less, The manufacturing method as described in any one of Claims 1-6 characterized by the above-mentioned. The said annealing is performed at the temperature of 250 degreeC or more and 400 degrees C or less under oxygen atmosphere, The manufacturing method as described in any one of Claims 1-6 characterized by the above-mentioned.