JP2008034604A - PATTERN FILM MANUFACTURING METHOD, POSITIVE PHOTOSENSITIVE COMPOSITION, AND SEMICONDUCTOR DEVICE - Google Patents

Abstract

[PROBLEMS] To provide a pattern film manufacturing method capable of sufficiently dissolving a photosensitive composition in an exposed area in a developer and obtaining a pattern film having an excellent pattern shape, and a positive photosensitive composition used therefor. provide.
A step of preparing a positive photosensitive composition containing a silicon condensate (A) and a photooxidant (B) and insoluble in a developer before being irradiated with light, on a substrate, A step of forming a photosensitive composition layer 1 composed of a positive photosensitive composition, a photosensitive composition layer 1 is selectively exposed, and a silicon condensate (A) is formed by the action of a photooxidant (B) in the exposed portion. ) In which a hydrophilic group is introduced to make the photosensitive composition layer 1A in the exposed area soluble in the developer, and the photosensitive composition layer 1A in the exposed area is made soluble in the developer, and then photosensitive. A method for producing a pattern film, comprising: developing the composition layer 1A with a developer to obtain a pattern film 1C; and a photosensitive composition used for the method.
[Selection] Figure 1

Description

  The present invention relates to a method for producing a patterned film using a positive photosensitive composition having photosensitivity, and more specifically, by exposing the photosensitive composition, the photosensitive composition in an exposed portion is developed as a developing solution. The present invention relates to a method for producing a pattern film that is soluble in water, a positive photosensitive composition that can be used in the method for producing the pattern film, and a semiconductor device using the same.

  In manufacturing electronic devices such as semiconductors, a passivation film, a gate insulating film, and the like are formed by a fine pattern forming method. For forming these films, for example, a photosensitive resin composition containing an alkoxysilane condensate or the like is used.

  In Patent Document 1 below, as an example of a photosensitive resin composition used for pattern formation, (1) an alkali-soluble siloxane polymer, (2) a compound that generates a reaction accelerator by light, and (3) a solvent are mainly used. A photosensitive resin composition as a component is disclosed. In Patent Document 1, (1) an alkali-soluble siloxane polymer obtained by removing water and a catalyst from a reaction solution obtained by hydrolyzing and condensing alkoxysilane with water and a catalyst is used as the alkali-soluble siloxane polymer. Yes.

Further, Patent Document 1 discloses a pattern forming method in which the photosensitive resin composition is applied onto a substrate, dried, exposed through a mask, and subsequently developed. In the pattern forming method described in Patent Document 1, specifically, a photosensitive resin composition layer made of a photosensitive resin composition is formed, and the photosensitive resin composition layer is exposed through a mask. In the exposed portion, the crosslinking reaction of the alkoxysilane condensate was advanced to cure the photosensitive resin composition layer.
Japanese Patent Laid-Open No. 06-148895

  Conventionally, a photosensitive resin composition called a negative type as described in Patent Document 1 has been mainly used to form a fine pattern. That is, the photosensitive resin composition described in Patent Document 1, as described above, proceeds with the crosslinking reaction of the siloxane polymer in the exposed portion and is cured to form a pattern, which is not a positive type but a negative type. It was a photosensitive resin composition.

  However, in recent years, in order to form a fine pattern, development of a positive photosensitive resin composition instead of a negative photosensitive resin composition has been strongly demanded.

  When forming a fine pattern using a positive photosensitive resin composition, the photosensitive resin composition is exposed according to the pattern to be formed, as in the case of a negative photosensitive resin composition. Prior to exposure, the photosensitive resin composition is insoluble in the developer, but exposure exposes the photosensitive resin composition in the exposed area to the developer and forms a patterned latent image. Next, by developing with a developing solution, the photosensitive resin composition of an exposed part is removed, and the thin film pattern which consists of the photosensitive resin composition of an unexposed part is obtained.

  In the positive photosensitive resin composition, there has been a strong demand for ensuring that the photosensitive resin composition in the exposed area is particularly soluble. However, in the conventional positive photosensitive resin composition, the photosensitive resin composition tends to be dissolved in the developer even in the exposed area, and when this occurs, the photosensitive resin composition remains in the exposed area. It was apt. As a result, the formed thin film pattern tends to be inferior in pattern shape.

  An object of the present invention is to manufacture a pattern film that can sufficiently dissolve a photosensitive composition in an exposed portion in a developer and obtain a pattern film having an excellent pattern shape in view of the above-described state of the prior art. The present invention relates to a method, a positive photosensitive composition that can be used in the method for producing the pattern film, and a semiconductor device using the same.

  The method for producing a patterned film according to the present invention prepares a positive photosensitive composition containing a silicon condensate (A) and a photooxidant (B) and insoluble in a developer before being irradiated with light. A step of forming a photosensitive composition layer comprising a positive photosensitive composition on the substrate, and selectively exposing the photosensitive composition layer in accordance with the pattern to be formed, and a photo-oxidizing agent in the exposed portion. A step of introducing a hydrophilic group into the silicon condensate (A) by the action of (B) and making the photosensitive composition layer in the exposed area soluble in the developer; and exposing the photosensitive composition layer in the exposed area to the developer And then developing the photosensitive composition layer with a developer to obtain a pattern film.

  In a specific aspect of the method for producing a patterned film according to the present invention, the silicon condensate (A) is reacted at least in part by reacting a coupling monomer with the SiOH group of the silicon condensate (a) having a SiOH group. The silicon condensate in which the SiOH group is converted into a coupling group, and in the step of making it soluble in the developer, the coupling group of the silicon condensate (A) by the action of the photooxidant (B) in the exposed portion Are converted into SiOH groups, and the photosensitive composition layer in the exposed area is solubilized in the developer.

  The positive photosensitive composition according to the present invention is used in the method for producing a patterned film of the present invention, and at least partly reacts a coupling monomer with the SiOH group of the silicon condensate (a) having a SiOH group. It contains the silicon condensate (A) in which the SiOH group of the above is converted into a coupling group, and the photooxidant (B).

  In a specific aspect of the positive photosensitive composition according to the present invention, the coupling monomer is a silane compound represented by the following formula (1).

Si (X) p (R) 4-p (1)
In the above formula (1), X represents a hydrolyzable group, R represents a non-hydrolyzable organic group having 1 to 30 carbon atoms, and p represents 0 or 1. A plurality of R may be the same or different.

  In another specific aspect of the positive photosensitive composition according to the present invention, the silicon condensate (A) contains 50 to 200 equivalents of a coupling monomer with respect to 100 equivalents of SiOH groups of the silicon condensate (a). It is a reacted silicon condensate.

  In still another specific aspect of the positive photosensitive composition according to the present invention, photooxidation is performed at a rate of 5 to 20 equivalents with respect to a total of 100 equivalents of the SiOH group and the coupling group of the silicon condensate (A). Agent (B) is included.

  The semiconductor device according to the present invention comprises at least one film selected from the group consisting of a gate insulating film, a passivation film and an interlayer insulating film, and the film is a positive photosensitive composition constituted according to the present invention. It is set as the film | membrane formed using.

  In the method for producing a patterned film according to the present invention, a positive photosensitive composition containing a silicon condensate (A) and a photooxidant (B) and insoluble in a developer before being irradiated with light is used. The photosensitive composition layer is selectively exposed according to the pattern to be formed, and a hydrophilic group is introduced into the silicon condensate (A) by the action of the photo-oxidant (B) in the exposed area, thereby exposing the photosensitive area Since the composition layer is soluble in the developer, for example, when the photosensitive composition layer is selectively irradiated with light using a photomask, the photosensitive composition in the exposed portion becomes soluble in the developer. In the unexposed portion, the photooxidant (B) does not act, and the photosensitive composition can be left insoluble in the developer.

  Since the method for producing a patterned film according to the present invention further includes a step of developing the photosensitive composition layer with a developer to obtain a pattern film, the exposed portion is developed by development using a developer such as an acid or alkali. The photosensitive composition is removed, and a patterned film made of the photosensitive composition in the unexposed area can be obtained.

  The silicon condensate (A) is a silicon condensate in which at least a part of the SiOH group is converted to a hydrophobic group by reacting the coupling monomer with the SiOH group of the silicon condensate (a) having a SiOH group. When the coupling group of the silicon condensate (A) is converted into a SiOH group by the action of the photooxidant (B) in the exposed area, and the photosensitive composition layer in the exposed area is soluble in the developer. Since the coupling group of the silicon condensate (A) is effectively converted into a SiOH group, the hydrophilicity of the photosensitive composition in the exposed area is further enhanced by exposure. Therefore, when it develops after exposing, the pattern film excellent in pattern shape can be obtained.

  The positive photosensitive composition according to the present invention is obtained by reacting a coupling monomer with a SiOH group of a silicon condensate (a) having a SiOH group, thereby converting at least a part of the SiOH group into a coupling group. Since the condensate (A) and the photooxidant (B) are contained, when the positive photosensitive composition is selectively irradiated with light using, for example, a photomask, the photooxidant (B) is exposed at the exposed portion. By the action, the photosensitive composition can be made soluble in a developer or the like. On the other hand, since the photooxidant (B) does not act in the unexposed area, the photosensitive composition can be left insoluble in the developer. Therefore, if it develops after exposing, the photosensitive composition of an exposure part will be removed and a pattern film can be obtained.

  When the coupling monomer is a silane compound represented by the above formula (1), the coupling group of the silicon condensate (A) is more effectively converted by the SiOH group by exposure. The hydrophilicity of the photosensitive composition is further enhanced.

  When the silicon condensate (A) is a silicon condensate obtained by reacting 50 to 200 equivalents of a coupling monomer with respect to 100 equivalents of SiOH groups of the silicon condensate (a), a positive photosensitive composition Has sufficient hydrophobicity before light irradiation and has sufficient hydrophilicity after light irradiation. Therefore, a more excellent pattern film can be obtained depending on the pattern shape.

  When the photooxidant (B) is contained at a ratio of 5 to 20 equivalents with respect to a total of 100 equivalents of SiOH groups and coupling groups of the silicon condensate (A), the silicon condensate (A) is exposed by exposure. Are effectively converted to hydrophilic groups. Therefore, a more excellent pattern film can be obtained depending on the pattern shape.

  The semiconductor element according to the present invention includes at least one film selected from the group consisting of a gate insulating film, a passivation film, and an interlayer insulating film, and the film uses the positive photosensitive composition of the present invention. Since it is a formed film, the shape of the film is excellent.

  Details of the present invention will be described below.

  In order to achieve the above-mentioned problems, the inventors of the present invention have made extensive studies on a method for producing a pattern film using a positive photosensitive composition. As a result, the silicon condensate (A), the photooxidant (B), When the positive photosensitive composition containing the photo-sensitive composition is further irradiated with light, the photoconducting agent (B) acts on the exposed portion to cause hydrophilicity to the silicon condensate (A). It was found that by introducing a functional group, the photosensitive composition in the exposed area can be sufficiently dissolved in the developer, and a pattern film having an excellent pattern shape can be obtained, and the present invention has been made.

  In the method for producing a patterned film according to the present invention, a positive photosensitive composition containing a silicon condensate (A) and a photooxidant (B) and insoluble in a developer before being irradiated with light is used. .

  The silicon condensate (A) is not particularly limited as long as a hydrophilic group can be introduced by the action of the photo-oxidant (B). As the silicon condensate (A), a silicon condensate in which at least a part of the SiOH group is converted into a coupling group by reacting a coupling monomer with the SiOH group of the silicon condensate (a) having a SiOH group. It is preferable that

  The silicon condensate (a) for reacting the coupling monomer is not particularly limited as long as it has a SiOH group.

  The coupling monomer is used to convert the SiOH group of the silicon condensate (a) into a coupling group. That is, the coupling group means a group formed by reacting a SiOH group with a coupling monomer. Since the coupling group has hydrophobicity, the hydrophobicity of the silicon condensate (A) is increased, and the positive photosensitive composition is insoluble in the developer before being irradiated with light.

  The coupling monomer is not particularly limited, and examples thereof include inorganic salts such as silane compounds and lithium salts. When a silane compound is used as the coupling monomer, the SiOH group of the silicon condensate (A) can be converted into a silane coupling group.

  As the coupling monomer, a silane compound represented by the following formula (1) is preferably used.

Si (X) p (R) 4-p (1)
In the above formula (1), X represents a hydrolyzable group, R represents a non-hydrolyzable organic group having 1 to 30 carbon atoms, and p represents 0 or 1. A plurality of R may be the same or different.

  By using the silane compound represented by the above formula (1), the coupling group of the silicon condensate (A) can be more effectively converted into a SiOH group by exposure. Of the silane compounds represented by the above formula (1), diphenyldimethoxysilane, ditrifluoromethyldimethoxysilane, phenyltrichlorosilane, vinyltrimethoxysilane, vinyltrichlorosilane and the like are more preferably used.

  Although reaction of a silicon condensate (a) and a coupling monomer is not specifically limited, For example, it can carry out by mixing in a liquid.

  The silicon condensate (A) is preferably a silicon condensate obtained by reacting 50 to 200 equivalents of a coupling monomer with respect to 100 equivalents of SiOH groups of the silicon condensate (a). If the coupling monomer is less than 50 equivalents, the silicon condensate (A) has too many SiOH groups, and the positive photosensitive composition before exposure is easily dissolved in the developer. When the coupling monomer is more than 200 equivalents, it may be excessive to convert the SiOH group into a coupling group, and a residue may be generated in the pattern film due to the excessive coupling monomer.

The number of equivalents of SiOH groups in the silicon condensate (a) can be measured, for example, by quantification using ²⁹ SI NMR.

  In the method for producing a patterned film according to the present invention, a positive photosensitive composition further containing a photooxidant (B) in addition to the silicon condensate (A) is used.

  The photooxidant (B) is not particularly limited, but 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, t-butylperoxybenzoate, methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide. , Methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1, -bis ( t-butylperoxy) -3,3,5-trimethylcyclohexane, di-t-butylperoxy-2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylpero C) Cyclododecane, 2,2-bis (t-butylperoxy) butane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butyl) Peroxycyclohexyl) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α, α ′ -Bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2, 5-Dimethyl-2,5-bis (t-butylpero Ii) Hexin-3-isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n-propyl peroxide Dicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyacetate, t-butylperoxymaleic acid, t-butylperoxyisobutyrate, t-hexylperoxybenzoate, 2, 4-bis (trichloromethyl) -6- (p-methoxyphenylvinyl) -1,3,5-triazine and the like can be mentioned. These compounds can be used alone or in combination of two or more. Among them, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2,4-bis (trichloromethyl) -6- (p-methoxyphenylvinyl) -1,3,5-triazine Is preferably used.

  The positive photosensitive composition preferably contains the photooxidant (B) at a ratio of 5 to 20 equivalents with respect to 100 equivalents in total of the SiOH groups and coupling groups of the silicon condensate (A). When the photooxidant (B) is less than 5 equivalents, the coupling group of the silicon condensate (A) may not be sufficiently converted to a SiOH group. When the photooxidant (B) exceeds 20 equivalents, it is excessive for converting the coupling group of the silicon condensate (A) to a SiOH group, and a residue is generated in the pattern film due to the excess photooxidant (B). Sometimes.

  In addition to the silicon condensate (A) and the photooxidant (B), an appropriate solvent may be further added to the positive photosensitive composition. By adding a solvent, a positive photosensitive composition that can be easily applied can be provided.

  The solvent is not particularly limited as long as it can dissolve the silicon condensate (A), but is an aromatic hydrocarbon compound such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, diethylbenzene; cyclohexane, cyclohexene, dipentene, saturated or unsaturated hydrocarbon compounds such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, tetrahydronaphthalene, squalane; Diethyl ether, di-n-propyl ether, di-isopropyl ether, dibutyl ether, ethyl propyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol die Ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, Ethylene glycol methyl ethyl ether, tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, ethylcyclohexane, Tylcyclohexane, p-menthane, o-menthane, m-menthane; ethers such as dipropyl ether and dibutyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone , Ketones such as cycloheptanone; ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, butyl stearate And esters. These solvents may be used independently and 2 or more types may be used together.

  What is necessary is just to select the mixing | blending ratio of the said solvent suitably so that it may apply uniformly, for example, when a positive photosensitive composition is applied on a board | substrate and a photosensitive composition layer is formed. Preferably, the positive photosensitive composition has a solid concentration of 0.5 to 60% by weight, more preferably about 2 to 40% by weight.

  If necessary, other additives may be further added to the positive photosensitive composition. Such additives include fillers, pigments, dyes, leveling agents, antifoaming agents, antistatic agents, UV absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, plasticizers, plasticizers. Examples include accelerators and sagging inhibitors.

  In the method for producing a patterned film according to the present invention, the positive photosensitive composition is used. As shown in FIG. 1A, a photosensitive composition layer comprising the positive photosensitive composition is formed on a substrate. The process of forming 1 is performed. Next, the photosensitive composition layer 1 is selectively exposed using a photomask 3 or the like corresponding to the pattern, and hydrophilic groups are added to the silicon condensate (A) by the action of the photooxidant (B) in the exposed portion. Is introduced to make the photosensitive composition layer 1A in the exposed area soluble in the developer (FIG. 1 (b)). Furthermore, after making photosensitive composition layer 1A of an exposed part soluble in a developing solution, developing photosensitive composition layer 1A with a developing solution such as an alkaline aqueous solution to obtain a pattern film (FIG. 1 (c)) Is done.

  Here, the development includes the operation of immersing the photosensitive composition layer 1A in the exposed area and the photosensitive composition layer 1B in the unexposed area in a developer such as an alkaline aqueous solution, as well as the photosensitive composition layer 1A, Various operations for treating the photosensitive composition layers 1A and 1B with a developing solution, such as an operation of washing the surface of 1B with a developing solution or an operation of spraying the developing solution onto the surface of the photosensitive composition layers 1A and 1B, are included. Shall be. The developing solution is not limited to an alkaline aqueous solution, and an acidic aqueous solution or various solvents may be used. Examples of the solvent include the various solvents described above. Examples of the acidic aqueous solution include oxalic acid, formic acid, acetic acid and the like.

  Although the process of forming the said photosensitive composition layer is not specifically limited, For example, the method of providing the said positive photosensitive composition on the board | substrate 2 shown in FIG. 1, and forming the photosensitive composition layer 1 is mentioned. . As a specific method in this case, a general coating method can be used, for example, dip coating, roll coating, bar coating, brush coating, spray coating, spin coating, extrusion coating. Work, gravure coating, etc. can be used. As the substrate on which the positive photosensitive composition is applied, a silicon substrate, a glass substrate, a metal plate, a plastics plate, or the like is used depending on the application. The thickness of the photosensitive composition layer varies depending on the use, but 10 nm to 10 μm is a standard. When the photosensitive composition layer coated on the substrate uses a solvent to dissolve the photosensitivity, it is desirable to perform a heat treatment to dry the solvent. The heat treatment temperature is generally 40 ° C. to 200 ° C., and is appropriately selected according to the boiling point and vapor pressure of the solvent.

  A photosensitive composition layer is formed on a substrate, the photosensitive composition layer is covered with a photomask, and light is irradiated in a pattern. As a result, a hydrophilic group is introduced into the silicon condensate (A) by the action of the photooxidant (B), so that the photosensitive composition layer in the exposed portion becomes soluble in the developer, and a latent image having a necessary pattern shape. Can be formed. What is necessary is just to use the common thing marketed as a photomask.

  The silicon condensate (A) is a silicon condensate obtained by reacting a coupling monomer with a SiOH group of the silicon condensate (a) having a SiOH group to convert at least a part of the SiOH group into a coupling group. In some cases, the coupling group of the silicon condensate (A) is converted into a SiOH group by the action of the photooxidant (B) by exposure. By being converted to the SiOH group, the photosensitive composition layer in the exposed area becomes soluble in a developer such as an alkaline aqueous solution.

Although it does not specifically limit as a light source for irradiating light rays, such as an ultraviolet-ray and visible light, An ultrahigh pressure mercury lamp, a Deep UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer laser etc. can be used. These light sources are appropriately selected according to the photosensitive wavelength of the photooxidant (B) or sensitizer. The irradiation energy of light is generally in the range of 10 to 1000 mJ / cm ² , although it depends on the desired film thickness and the type of photooxidant (B) or sensitizer. When it is less than 10 mJ / cm ² , the silicon condensate (A) is not sufficiently exposed. Moreover, when larger than 1000 mJ / cm < ² >, there exists a possibility that exposure time may become long and the manufacturing efficiency per time of a pattern film | membrane may fall.

  In the photosensitive composition layer of the exposed portion irradiated with light in the pattern shape, a hydrophilic group is introduced into the silicon condensate (A) and becomes soluble in the developer. By developing the photosensitive composition layer after exposure using a developer, the photosensitive composition layer in the exposed portion is dissolved and removed in the developer, and the unexposed portion remains on the substrate. As a result, a pattern is formed. This pattern is called a positive pattern because the exposed portion is removed. In the method for producing a patterned film of the present invention, the photosensitive composition in the exposed area can be reliably removed by development, so that a good resolution can be obtained.

  As the developer, an explosion-proof facility is unnecessary, and the burden on the facility due to corrosion or the like is small, so an alkaline aqueous solution is preferably used. For example, alkaline aqueous solutions, such as tetramethylammonium hydroxide aqueous solution, sodium silicate aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, are mentioned. The time required for development depends on the thickness of the photosensitive composition layer and the type of solvent, but is preferably in the range of 10 seconds to 5 minutes because development can be efficiently performed and production efficiency is increased. After development, the pattern film is preferably washed with distilled water to remove the aqueous alkali solution remaining on the thin film.

  The positive photosensitive composition is suitably used for forming a pattern film in various apparatuses. Preferably, the positive photosensitive composition is used to form an insulating protective film of an electronic device. Are preferably used. By using a film pattern composed of the positive photosensitive composition as an insulating protective film of an electronic device, the shape stability of the obtained insulating protective film can be effectively increased. Examples of such an insulating protective film for an electronic device include a TFT protective film for protecting a thin film transistor (TFT) in a liquid crystal display element, and a protective film for protecting a filter in a color filter.

  The positive photosensitive composition is more preferably used for constituting an interlayer insulating film or a passivation film of a semiconductor element.

  FIG. 2 is a front cross-sectional view schematically showing a semiconductor device including a passivation film and an interlayer insulating film constituted by using the positive photosensitive composition according to the present invention.

  In the semiconductor element 11 shown in FIG. 2, a gate electrode 13 is provided at the center of the upper surface of the substrate 12. A gate insulating film 14 is formed on the upper surface of the substrate 12 so as to cover the gate electrode 13. A source electrode 15 and a drain electrode 16 are provided on the gate insulating film 14. A semiconductor layer 17 is formed on the gate insulating film 14 so as to cover part of the source electrode 15 and part of the drain electrode 16. Further, a passivation film 18 is formed so as to cover the portion of the source electrode 15 and the drain electrode 16 that are not covered with the semiconductor layer 17 and the semiconductor layer 17. In the semiconductor element 11, the gate insulating film 14 and the passivation film 18 are films configured by the pattern film manufacturing method according to the present invention using the positive photosensitive composition according to the present invention.

  The film comprised by the manufacturing method of the pattern film which concerns on this invention is used for various uses. Films formed by the pattern film manufacturing method according to the present invention are widely used as insulating protective films for various electronic devices such as TFT protective films for organic EL elements, interlayer protective films for IC chips, and insulating layers for sensors. Can be used.

  Hereinafter, the present invention will be clarified by giving examples and comparative examples of the present invention. In addition, this invention is not limited to a following example.

<< Silicon condensate (a1) >>
To a 100 ml flask equipped with a condenser, 5 g of phenyltriethoxysilane, 10 g of triethoxysilane, 0.5 g of oxalic acid, 5 ml of water and 50 ml of propylene glycol monomethyl ether acetate were added. The solution was stirred using a semicircular type mechanical stirrer and reacted at 70 ° C. for 6 hours with a mantle heater. Subsequently, the ethanol produced | generated by water and condensation reaction was removed using the evaporator. After completion of the reaction, the flask was left to reach room temperature to prepare a silicon condensate (a1) having a SiOH group. The weight average molecular weight (Mw) of the obtained silicon condensate (a1) was 4000.

<< Silicon condensate (a2) >>
To a 100 ml flask equipped with a condenser, 6 g of phenyltriethoxysilane, 9 g of triethoxysilane, 0.5 g of oxalic acid, 5 ml of water and 50 ml of propylene glycol monomethyl ether acetate were added. The solution was stirred using a semicircular type mechanical stirrer and reacted with a mantle heater at 30 ° C. for 6 hours. Subsequently, the ethanol produced | generated by water and condensation reaction was removed using the evaporator. After completion of the reaction, the flask was left to reach room temperature to prepare a silicon condensate (a2) having a SiOH group. The weight average molecular weight (Mw) of the obtained silicon condensate (a2) was 1000.

(Example 1)
(Preparation of photosensitive composition)
100 equivalents (14 parts by weight) of vinyltrichlorosilane as a coupling monomer (C1) is blended with 100 equivalents of SiOH groups of the silicon condensate (a1) (100 parts by weight of the silicon condensate (a1)) at 30 ° C. The silicon condensate (A1) in which the SiOH group of the silicon condensate (a1) was converted into a coupling group was obtained by mixing and reacting for 1 hour. Next, 5 equivalents (8 parts by weight) of 3,3′-4,4′-tetra (t-butylperoxycarbonyl) benzophenone as a photooxidant (B1) is blended in the silicon condensate (A1) and mixed. Then, it was dissolved in 500 parts by weight of tetrahydrofuran as a solvent to prepare a photosensitive composition.

[Formation of pattern film]
As a base material, a glass substrate having aluminum deposited on the surface layer was used, and the photosensitive composition was spin-coated on the glass substrate at a rotation speed of 1500 rpm. After coating, it was dried in a hot air oven at 80 ° C. to form a coating film.

Next, ultraviolet rays having a wavelength of 365 nm are applied to the coating film through a photomask having a predetermined pattern (USHIO Inc., Spot Cure SP-5), and the irradiation energy is 500 mJ / cm ² . It was irradiated for 5 seconds with an ultraviolet illuminance of 100 mW / cm ² .

  Thereafter, the coating film was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide and developed to form a pattern film.

(Example 2)
The blending ratio of 3,3′-4,4′-tetra (t-butylperoxycarbonyl) benzophenone as the photooxidant (B1) is changed from 5 equivalents (8 parts by weight) to 2 equivalents (3.2 parts by weight). A photosensitive composition was prepared in the same manner as in Example 1 except for the change, and a pattern film was formed.

(Example 3)
The blending ratio of 3,3′-4,4′-tetra (t-butylperoxycarbonyl) benzophenone as the photooxidant (B1) was changed from 5 equivalents (8 parts by weight) to 20 equivalents (32 parts by weight). Except for this, a photosensitive composition was prepared in the same manner as in Example 1 to form a pattern film.

Example 4
A photosensitive composition was prepared in the same manner as in Example 1 except that the blending ratio of vinyltrichlorosilane as the coupling monomer (C1) was changed from 100 equivalents (14 parts by weight) to 50 equivalents (7 parts by weight). Then, a pattern film was formed.

(Example 5)
A photosensitive composition was prepared in the same manner as in Example 1 except that the blending ratio of vinyltrichlorosilane as the coupling monomer (C1) was changed from 100 equivalents (14 parts by weight) to 200 equivalents (28 parts by weight). Then, a pattern film was formed.

(Example 6)
5 equivalents (8 parts by weight) of 3,3′-4,4′-tetra (t-butylperoxycarbonyl) benzophenone as the photooxidant (B1) and 2,4-bis ( A photosensitive composition was prepared in the same manner as in Example 1 except that trichloromethyl) -6- (p-methoxyphenylvinyl) -1,3,5-triazine was changed to 5 equivalents (5.5 parts by weight). A pattern film was formed.

(Example 7)
Except for changing 100 equivalents (14 parts by weight) of vinyltrichlorosilane as the coupling monomer (C1) to 100 equivalents (26 parts by weight) of ditrifluoromethyldimethoxysilane as the coupling monomer (C2). A photosensitive composition was prepared in the same manner as in Example 1 to form a pattern film.

(Example 8)
100 equivalents (27 parts by weight) of vinyltrichlorosilane as the coupling monomer (C1) is blended with 100 equivalents of SiOH groups (100 parts by weight of the silicon condensate (a2)) of the silicon condensate (a2) at 30 ° C. The silicon condensate (A2) in which the SiOH group of the silicon condensate (a2) was converted into a coupling group was obtained by mixing and reacting for 1 hour.

  Thereafter, 5 equivalents (16 parts by weight) of 3,3′-4,4′-tetra (t-butylperoxycarbonyl) benzophenone as a photooxidant (B1) is blended into the silicon condensate (A2) and mixed. Then, it was dissolved in 500 parts by weight of tetrahydrofuran as a solvent to prepare a photosensitive composition.

  A pattern film was formed in the same manner as in Example 1 except that this photosensitive composition was used.

Example 9
The blending ratio of 3,3′-4,4′-tetra (t-butylperoxycarbonyl) benzophenone as the photooxidant (B1) is changed from 5 equivalents (8 parts by weight) to 1 equivalent (1.6 parts by weight). A photosensitive composition was prepared in the same manner as in Example 1 except for the change, and a pattern film was formed.

(Example 10)
The blending ratio of 3,3′-4,4′-tetra (t-butylperoxycarbonyl) benzophenone as the photooxidant (B1) was changed from 5 equivalents (8 parts by weight) to 30 equivalents (48 parts by weight). Except for this, a photosensitive composition was prepared in the same manner as in Example 1 to form a pattern film.

(Example 11)
Photosensitive composition in the same manner as in Example 1 except that the mixing ratio of vinyltrichlorosilane as the coupling monomer (C1) was changed from 100 equivalents (14 parts by weight) to 30 equivalents (4.2 parts by weight). And a pattern film was formed.

Example 12
A photosensitive composition was prepared in the same manner as in Example 1 except that the blending ratio of vinyltrichlorosilane as the coupling monomer (C1) was changed from 100 equivalents (14 parts by weight) to 250 equivalents (35 parts by weight). Then, a pattern film was formed.

(Comparative Example 1)
100 parts by weight of the above silicon condensate (a1) was dissolved in 500 parts by weight of tetrahydrofuran as a solvent to prepare a photosensitive composition. A pattern film was formed in the same manner as in Example 1 except that this photosensitive composition was used.

(Comparative Example 2)
A photosensitive composition was prepared in the same manner as in Example 1 except that 3,3′-4,4′-tetra (t-butylperoxycarbonyl) benzophenone as the photooxidant (B1) was not blended. A pattern film was formed.

(Evaluation of Examples and Comparative Examples)
About the pattern film obtained as mentioned above, the patterning state was evaluated according to the following evaluation criteria.

[Evaluation criteria for patterning condition]
○: The photosensitive composition in the exposed area was completely dissolved in the developer to form a good pattern. Δ: The photosensitive composition in the exposed area was not completely dissolved in the developer and remained slightly. Formation of almost good pattern ×: The photosensitive composition in the exposed area was hardly dissolved in the developer, and no pattern was formed. The results are shown in Table 1 below.

(A)-(c) is sectional drawing of each process for demonstrating the manufacturing method of the pattern film | membrane which concerns on this invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a front cross-sectional view showing a semiconductor element including a passivation film and an interlayer insulating film configured using a positive photosensitive composition according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photosensitive composition layer 1A ... Photosensitive composition layer of exposed part 1B ... Photosensitive composition layer of unexposed part 1C ... Pattern film 2 ... Substrate 3 ... Photomask 11 ... Semiconductor element 12 ... Substrate 13 ... Gate electrode DESCRIPTION OF SYMBOLS 14 ... Gate insulating film 15 ... Source electrode 16 ... Drain electrode 17 ... Semiconductor layer 18 ... Passivation film

Claims (7)

A step of preparing a positive photosensitive composition containing a silicon condensate (A) and a photooxidant (B) and insoluble in a developer before irradiation with light;
Forming a photosensitive composition layer comprising the positive photosensitive composition on a substrate;
The photosensitive composition layer is selectively exposed according to the pattern to be formed, and a hydrophilic group is introduced into the silicon condensate (A) by the action of the photooxidant (B) in the exposed portion, Making the photosensitive composition layer soluble in a developer;
And a step of making the photosensitive composition layer of the exposed portion soluble in a developer and then developing the photosensitive composition layer with the developer to obtain a pattern film. . The silicon condensate (A) is a silicon condensate in which at least a part of the SiOH group is converted into a coupling group by reacting a coupling monomer with the SiOH group of the silicon condensate (a) having a SiOH group. A thing,
In the step of solubilizing in the developing solution, the coupling group of the silicon condensate (A) is converted into a SiOH group by the action of the photooxidant (B) in the exposed portion, and the photosensitive composition in the exposed portion The method for producing a patterned film according to claim 1, wherein the physical layer is made soluble in a developer. A positive photosensitive composition used in the method for producing a patterned film according to claim 1 or 2,
A silicon condensate (A) in which at least a part of the SiOH groups are converted into coupling groups by reacting a coupling monomer with the SiOH groups of the silicon condensate (a) having SiOH groups, and a photooxidant A positive photosensitive composition comprising (B). The positive photosensitive composition of Claim 3 whose said coupling monomer is a silane compound represented by following formula (1).
Si (X) p (R) 4-p (1)
In the above formula (1), X represents a hydrolyzable group, R represents a non-hydrolyzable organic group having 1 to 30 carbon atoms, and p represents 0 or 1. A plurality of R may be the same or different.   The silicon condensate (A) is a silicon condensate obtained by reacting 50 to 200 equivalents of the coupling monomer with respect to 100 equivalents of SiOH groups of the silicon condensate (a). The positive photosensitive composition as described.   The photo-oxidant (B) is contained in any one of claims 3 to 5 in a ratio of 5 to 20 equivalents with respect to a total of 100 equivalents of SiOH groups and coupling groups of the silicon condensate (A). The positive photosensitive composition as described.   It comprises at least one film selected from the group consisting of a gate insulating film, a passivation film, and an interlayer insulating film, and the film uses the positive photosensitive composition according to any one of claims 3 to 6. A semiconductor element, which is a formed film.

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