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WO2013080884A1 - Composition de siloxane photosensible de type négatif - Google Patents

Composition de siloxane photosensible de type négatif Download PDF

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Publication number
WO2013080884A1
WO2013080884A1 PCT/JP2012/080299 JP2012080299W WO2013080884A1 WO 2013080884 A1 WO2013080884 A1 WO 2013080884A1 JP 2012080299 W JP2012080299 W JP 2012080299W WO 2013080884 A1 WO2013080884 A1 WO 2013080884A1
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WIPO (PCT)
Prior art keywords
polysiloxane
group
negative photosensitive
film
pattern
Prior art date
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Ceased
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PCT/JP2012/080299
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English (en)
Japanese (ja)
Inventor
大志 横山
恵 高橋
崇司 福家
裕治 田代
泰明 田中
吉田　尚史
野中　敏章
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Merck Performance Materials IP Japan GK
EMD Performance Materials Corp
Original Assignee
AZ Electronic Materials IP Japan Co Ltd
AZ Electronic Materials USA Corp
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Application filed by AZ Electronic Materials IP Japan Co Ltd, AZ Electronic Materials USA Corp filed Critical AZ Electronic Materials IP Japan Co Ltd
Priority to JP2013547125A priority Critical patent/JP6173918B2/ja
Priority to KR1020147017766A priority patent/KR101992594B1/ko
Priority to CN201280058463.2A priority patent/CN103959168B/zh
Publication of WO2013080884A1 publication Critical patent/WO2013080884A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds

Definitions

  • the present invention relates to a negative photosensitive siloxane composition.
  • the present invention also relates to a method for producing a cured film using the same, a cured film formed therefrom, and an element having the cured film.
  • a transparent flattening film is formed on a thin film transistor (hereinafter also referred to as TFT) element, and a pixel electrode is formed on the flattening film, thereby increasing the aperture ratio of the display device.
  • TFT thin film transistor
  • a method is known (see Patent Document 1).
  • the structure of an organic electroluminescent element (hereinafter, also referred to as an organic EL element) is a TFT which is formed by depositing a light emitting layer on a transparent pixel electrode formed on a substrate and taking out light emission from the substrate side (bottom emission).
  • the aperture ratio is the same as that of a liquid crystal display by adopting a method (top emission) in which light emitted from the transparent pixel electrode on the planarizing film coated on the element and the light emitting layer thereon is extracted to the opposite side of the TFT element.
  • a method for improving this has been proposed (see Patent Document 2).
  • a negative photosensitive material mainly composed of a polysiloxane compound and a curing aid is known.
  • a polysiloxane compound is obtained by polymerizing a silane compound having a bifunctional functional group, for example, a dialkyl dialkoxysilane in the presence of a catalyst.
  • degassing may occur during the film forming process.
  • the gas generated here is a decomposition product derived from an organic group generated at a high temperature and often has an adverse effect on the light emission efficiency and life of the organic EL device, and thus is not an optimal material for use.
  • the decomposed product may increase the dielectric constant, and the parasitic capacitance due to the insulating film increases, resulting in increased power consumption, resulting in a delay in the liquid crystal element drive signal, resulting in higher image quality. May give problems. Even with an insulating material having a high dielectric constant, the capacitance can be reduced by increasing the film thickness, for example, but it is generally difficult to form a uniform thick film and the amount of material used is also increased. It is not preferable (see Patent Document 3).
  • the present invention has been made on the basis of the circumstances as described above, has high resolution, high heat resistance, and high transparency, does not contain an organic group that can be a polymerization site such as an acrylic group, and depends on the reaction system.
  • Another object of the present invention is to provide a planarized film for a TFT substrate, a cured film such as an interlayer insulating film formed from the above negative photosensitive siloxane composition, a solid-state imaging device including the cured film, and an antireflection coating.
  • An object of the present invention is to provide optical elements and semiconductor elements such as films, antireflection plates, optical filters, high-intensity light emitting diodes, touch panels, solar cells, and optical waveguides.
  • the negative photosensitive siloxane composition according to the present invention comprises (I) (Ia) hydrolyzing a silane compound (ia) selected from the group consisting of trialkoxysilane and tetraalkoxysilane in the presence of a basic catalyst.
  • the dissolution rate in a 38% by weight tetramethylammonium hydroxide aqueous solution is 150 kg / Polysiloxane mixture comprising polysiloxane with a higher, It comprises (II) a curing aid capable of generating an acid or base by heat or radiation, and (III) a solvent.
  • the method for producing a cured film according to the present invention comprises applying the negative photosensitive siloxane composition to a substrate to form a coating film, exposing the coating film, and heating.
  • the cured film according to the present invention is characterized in that it is formed from the above-mentioned negative photosensitive siloxane composition.
  • the element according to the present invention is characterized by comprising the above-mentioned cured film.
  • the negative photosensitive siloxane composition of the present invention has high sensitivity and high resolution, and the obtained cured film is excellent in heat resistance, chemical resistance, environmental resistance, transparency, and remaining film ratio, and is due to thermal sag. There is no reduction in resolution.
  • it since it has excellent flatness and electrical insulation characteristics, it is a flattening film for thin film transistor (TFT) substrates used for display backplanes such as liquid crystal display elements and organic EL display elements, and an interlayer insulating film for semiconductor elements.
  • TFT thin film transistor
  • Various film forming materials such as insulating films and transparent protective films in solid-state imaging devices, antireflection films, antireflection plates, optical filters, high-intensity light-emitting diodes, touch panels, solar cells, and optical elements such as optical waveguides Can be suitably used.
  • FIG. 2 is an optical microscope photograph of contact hole patterns of 3, 5, and 10 ⁇ m obtained in Example 3 after baking and curing at 250 ° C.
  • FIG. It is a photograph of the optical microscope of the contact hole pattern of 3, 5, and 10 micrometers after baking hardening at 250 degreeC obtained by the comparative example 1.
  • FIG. It is a photograph of the optical microscope which shows the state of thermal sag which is a deformation
  • Negative photosensitive polysiloxane composition is a mixture of polysiloxane having a specific dissolution rate with respect to tetramethylammonium hydroxide aqueous solution (hereinafter referred to as TMAH aqueous solution), heat or It contains a curing aid capable of generating an acid or a base by radiation, and a solvent.
  • TMAH aqueous solution tetramethylammonium hydroxide aqueous solution
  • the polysiloxane mixture used in the present invention contains two kinds of polysiloxanes (Ia) and (Ib) described later.
  • the dissolution rate of the film formed by this composition needs to be appropriate.
  • a negative pattern can be formed by exposure-development if the dissolution rate of the formed film in a 2.38% TMAH aqueous solution is 50 kg / second or more.
  • TMAH aqueous solution is 50 kg / second or more.
  • the curing of the film is progressed by adding many curing aids, the pattern shape obtained will be deformed and the remaining film rate will decrease Decrease in transmittance may occur.
  • the polysiloxane synthesized using a base catalyst starts to cure quickly when a temperature of 150 ° C. or higher is applied, and can maintain a beautiful shape without causing thermal sag after firing. It became clear by examination of those.
  • the present inventors have found that the above-described problems can be solved simultaneously by using such a polysiloxane mixture containing a specific polysiloxane.
  • the ga-type photosensitive polysiloxane composition used in the present invention comprises at least two types of polysiloxanes.
  • the first polysiloxane is: (Ia) A polysiloxane obtained by hydrolyzing and condensing a silane compound (ia) selected from the group consisting of trialkoxysilane and tetraalkoxysilane in the presence of a basic catalyst, and a film after pre-baking Is a polysiloxane that is soluble in a 5% by weight tetramethylammonium hydroxide aqueous solution and has a dissolution rate of 3,000 kg / sec or less, preferably 2,000 k / sec or less, and 2.38% by itself. Those that are hardly soluble in an aqueous TMAH solution.
  • This first polysiloxane is obtained by hydrolyzing and condensing a silane compound (ia) selected from the group consisting of trialkoxysilane and tetraalkoxysilane in the presence of a basic catalyst.
  • any compound can be used as the silane compound (ia) selected from the group consisting of trialkoxysilane and tetraalkoxysilane used as a raw material.
  • a compound represented by the following general formula (i) should be used.
  • R 1 n Si (OR 2 ) 4-n (i) (Wherein R 1 is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms in which arbitrary methylene may be replaced with oxygen, or arbitrary hydrogen in 6 to 20 carbon atoms with fluorine. And n is 0 or 1, and R 2 represents an alkyl group having 1 to 5 carbon atoms.)
  • R 1 for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2, Examples include 2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, cyclohexyl group, phenyl group, tolyl group, and naphthyl group.
  • a compound in which R 1 is a methyl group is preferable because raw materials are easily available, film hardness after curing is high, and chemical resistance is high.
  • a phenyl group is preferred because it increases the solubility of the polysiloxane in a solvent and the cured film is less likely to crack.
  • examples of R 2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • a plurality of R 2 are included, but each R 2 may be the same or different.
  • trialkoxysilane compound represented by the general formula (i) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, and the like.
  • tetraalkoxysilane compound represented by the general formula (i) include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like. Among these, tetramethoxysilane, Tetraethoxysilane and the like are preferable because of their high reactivity.
  • the silane compound (ia) used for the production of polysiloxane (Ia) may be used alone or in combination of two or more.
  • thermal sag tends to be reduced. This is presumably because the crosslink density of the polysiloxane increases.
  • a sensitivity may fall.
  • the blending ratio is 0.1 to 40 mol% with respect to the total number of moles of trialkoxysilane and tetraalkoxysilane.
  • the thermal sagging increases, but such characteristics can also be used effectively.
  • an insulating film is formed to cover an element or the like provided on the surface of the substrate, it can be advantageously used that the thermal sag is large.
  • the polysiloxane (Ia) used in the present invention is produced by hydrolyzing and condensing the above silane compound in the presence of a basic catalyst.
  • a silane compound or a mixture of silane compounds is dropped into a reaction solvent consisting of an organic solvent, a basic catalyst, and water to cause hydrolysis and condensation reactions, and if necessary, purification or concentration by neutralization or washing is performed. After performing, it can manufacture by substituting the reaction solvent with the desired organic solvent as needed.
  • organic solvent used as the reaction solvent examples include hydrocarbon solvents such as hexane, toluene, xylene and benzene, ether solvents such as diethyl ether and tetrahydrofuran, ester solvents such as ethyl acetate and propylene glycol monomethyl ethyl acetate, Examples include alcohol solvents such as methanol, ethanol, isopropanol, butanol, 1,3-dipropanol, and ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. These organic solvents may be used alone or in combination. Can be used. Further, the amount of the organic solvent used is generally 0.1 to 10 times by weight, preferably 0.5 to 2 times by weight of the mixed solution of the silane compound.
  • the reaction temperature for carrying out the hydrolysis and condensation reaction is generally 0 to 200 ° C, preferably 10 to 60 ° C. At this time, the temperature of the dropping silane compound and the temperature of the reaction solvent may be the same or different.
  • the reaction time varies depending on the type of silane compound, but is usually from several tens of minutes to several tens of hours, preferably 30 minutes or more.
  • Various conditions in the hydrolysis and condensation reaction are set to the intended application by setting the amount of basic catalyst, reaction temperature, reaction time, etc., taking into account the reaction scale, reaction vessel size, shape, etc. Suitable physical properties can be obtained.
  • Examples of the basic catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, an organic base such as alkoxysilane having an amino group, Examples thereof include inorganic bases such as sodium hydroxide and potassium hydroxide, anion exchange resins, and quaternary ammonium salts such as tetrabutylammonium hydroxide, tetraethylammonium hydroxide, and tetramethylammonium hydroxide.
  • the amount of catalyst is preferably 0.0001 to 10 moles per mole of the silane compound mixture.
  • the degree of hydrolysis can be adjusted by the amount of water added to the reaction solvent. In general, it is desirable to react water at a ratio of 0.01 to 10 moles, preferably 0.1 to 5 moles, with respect to the hydrolyzable alkoxy group of the silane compound. If the amount of water added is less than the above range, the degree of hydrolysis will be low and it will be difficult to form a film of the composition, which is not preferable. On the other hand, if too much, gelation will occur and storage stability will be poor. Absent.
  • the water used is preferably ion exchange water or distilled water.
  • the reaction solution may be neutral or weakly acidic using an acidic compound as a neutralizing agent.
  • acidic compounds include inorganic acids such as phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, or hydrofluoric acid, acetic acid, trifluoroacetic acid, formic acid, lactic acid, acrylic acid, oxalic acid, maleic acid, succinic acid, or citric acid
  • organic acids such as sulfonic acid such as p-toluenesulfonic acid or methanesulfonic acid.
  • it can also neutralize using a cation exchange resin.
  • the amount of the neutralizing agent is appropriately selected according to the pH of the reaction solution after the reaction, but is preferably 0.5 to 1.5 mole times, more preferably 1 to 1 with respect to the basic catalyst. .1 mole times. Moreover, when using a cation exchange resin, it is preferable that the number of the ionic groups contained in a cation exchange resin be in the said range.
  • the neutralized reaction solution can be washed and purified as necessary.
  • the washing method is not particularly limited.
  • at least polysiloxane (Ia) is obtained by adding a hydrophobic organic solvent and water as necessary to the reaction solution after neutralization, stirring, and bringing the polysiloxane into contact with the organic solvent. Is dissolved in the hydrophobic organic solvent phase.
  • a compound that dissolves polysiloxane (Ia) and is immiscible with water is used as the hydrophobic organic solvent.
  • “Immiscible with water” means that water and a hydrophobic organic solvent are sufficiently mixed and then allowed to stand to separate into an aqueous phase and an organic phase.
  • Preferred hydrophobic organic solvents include ether solvents such as diethyl ether, ester solvents such as ethyl acetate, alcohol solvents such as butanol, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic solvents such as toluene and xylene.
  • a solvent etc. are mentioned.
  • the hydrophobic organic solvent used for washing may be the same as or different from the organic solvent used as the reaction solvent, or a mixture of two or more types may be used. By such washing, most of the basic catalyst used in the reaction process, the neutralizing agent, the salt generated by the neutralization, and the alcohol and water that are by-products of the reaction are contained in the aqueous layer. Virtually eliminated. The number of washings can be changed according to need.
  • the temperature at the time of washing is not particularly limited, but is preferably 0 ° C. to 70 ° C., more preferably 10 ° C. to 60 ° C.
  • the temperature at which the aqueous phase and the organic phase are separated is also not particularly limited, but is preferably 0 ° C. to 70 ° C., and more preferably 10 ° C. to 60 ° C. from the viewpoint of shortening the liquid separation time.
  • the application property and storage stability of the composition may be improved.
  • the reaction solution after washing can be passed through to the composition according to the present invention as it is, but if necessary, the concentration can be changed by removing the solvent and residual by-products such as alcohol and water by concentration. Further, the solvent can be replaced with another solvent. When carrying out the concentration, it can be carried out under normal pressure (atmospheric pressure) or reduced pressure, and the degree of concentration can be arbitrarily changed by controlling the amount of distillation.
  • the temperature at the time of concentration is generally 30 to 150 ° C., preferably 40 to 100 ° C.
  • the solvent can be replaced by adding a desired solvent at appropriate times and further concentrating so as to obtain a target solvent composition.
  • the polysiloxane (Ia) used for the siloxane resin composition of the present invention can be produced by the above method.
  • the second polysiloxane is: (Ib) A polysiloxane obtained by hydrolyzing and condensing a silane compound (ib) selected from the group consisting of trialkoxysilane and tetraalkoxysilane in the presence of an acidic catalyst or a basic catalyst,
  • the latter film is a polysiloxane that is soluble in an aqueous 2.38 wt% tetramethylammonium hydroxide solution and has a dissolution rate of 150 ⁇ / second or more, preferably 500 ⁇ / second or more.
  • the polysiloxane (Ib) is produced by hydrolyzing and condensing a silane compound (ib) selected from the group consisting of trialkoxysilane and tetraalkoxysilane in the presence of an acidic or basic catalyst.
  • the same method as the production method of polysiloxane (Ia) can be used.
  • the reaction catalyst an acidic catalyst can be used in addition to the basic catalyst.
  • conditions such as the amount of reaction solvent, particularly the amount of water added, the reaction time, and the reaction temperature are appropriately prepared.
  • the silane compound (ib) may be the same as or different from the silane compound (ia) used as a raw material for the polysiloxane (Ia).
  • thermal sag tends to be reduced.
  • the compounding ratio of tetraalkoxysilane as the raw material for the second polysiloxane (Ib) is preferably low. . This is because precipitation of the silane compound occurs or sensitivity of the formed film is reduced when the compounding ratio of the tetraalkoxysilane is high as a whole. For this reason, the compounding ratio of tetraalkoxysilane is 1 to 40 mol% with respect to the total number of moles of silane compounds (ia) and (ib), which are raw materials of polysiloxanes (Ia) and (Ib). Preferably, it is 1 to 20 mol%.
  • an acidic catalyst can be used as a catalyst for the production of polysiloxane (Ib).
  • the acidic catalyst examples include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid, and anhydrides thereof.
  • the addition amount of the catalyst is preferably 0.0001 to 10 mol times with respect to the mixture of silane compounds, although it depends on the strength of the acid.
  • the reaction solution may be neutralized after completion of the reaction in the same manner as when a basic catalyst is used.
  • a basic compound is used as a neutralizing agent.
  • Examples of basic compounds used for neutralization include organic compounds such as triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, or diethanolamine.
  • Examples include bases, inorganic bases such as sodium hydroxide or potassium hydroxide, and quaternary ammonium salts such as tetrabutylammonium hydroxide, tetraethylammonium hydroxide, and tetramethylammonium hydroxide.
  • An anion exchange resin can also be used.
  • the amount of the neutralizing agent may be the same as that when a basic catalyst is used. Although it is appropriately selected according to the pH of the reaction solution after the reaction, it is preferably 0.5 to 1.5 mol times, more preferably 1 to 1.1 mol times with respect to the acidic catalyst.
  • the polysiloxane (Ib) used in the siloxane resin composition of the present invention can be produced.
  • the dissolution rate of the polysiloxane (Ib) in the 2.38% TMAH aqueous solution needs to be 150 kg / second or more, and preferably 500 kg / second or more as described later.
  • the dissolution rate of the polysiloxane (Ib) in the 2.38% TMAH aqueous solution is less than 150 kg / sec
  • the dissolution rate of the mixture of the polysiloxane (Ia) and (Ib) in the 2.38% TMAH aqueous solution is 50 to 3
  • the content of the polysiloxane (Ia) is small, it is difficult to prevent thermal sag of the pattern. become.
  • the polysiloxane mixture (I) used in the present invention comprises the above polysiloxane (Ia) and polysiloxane (Ib). These blending ratios are not particularly limited, but the weight ratio of polysiloxane (Ia) / polysiloxane (Ib) contained in the polysiloxane mixture (I) is preferably 1/99 to 80/20, and 20/80 More preferably, it is ⁇ 50 / 50.
  • composition according to the present invention it is not essential to use a basic catalyst that is considered to be effective in improving thermal sag prevention and to use tetraalkoxysilane as a raw material in the production of polysiloxane (Ib).
  • a basic catalyst that is considered to be effective in improving thermal sag prevention and to use tetraalkoxysilane as a raw material in the production of polysiloxane (Ib).
  • the effects of the present invention can be obtained, and it may be preferable from the viewpoint of residue and sensitivity.
  • the effects of the present invention can be achieved without using tetraalkoxysilane as the raw material for polysiloxane (Ib).
  • the weight average molecular weight (Mw) of the polysiloxane mixture (I) is preferably 5,000 or less, and more preferably 1,000 to 4,000. If the weight average molecular weight is less than 1,000, the effect of preventing thermal sag is small. On the other hand, if it exceeds 5,000, sufficient resolution cannot be obtained due to undissolved residue during development, and the sensitivity is also lowered.
  • the weight average molecular weight means that measured by gel permeation chromatography (GPC) using polystyrene as a standard.
  • the dissolution rate of polysiloxane (Ia) in 5% TMAH aqueous solution is 3,000 kg / sec or less and the dissolution rate of polysiloxane (Ib) in 2.38% TMAH aqueous solution is 150 kg / sec or more, it remains undissolved and sensitivity decreases.
  • the polysiloxane mixture (I) can be dissolved in 2.38% TMAH aqueous solution. The speed can also be set as appropriate.
  • the dissolution rate of the polysiloxane mixture (I) can be adjusted by changing the mixing ratio of the polysiloxanes (Ia) and (Ib), and varies depending on the type and amount of the photosensitive agent contained in the negative photosensitive siloxane composition. For example, when the film thickness is 0.1 to 10 ⁇ m (1,000 to 100,000 mm), the dissolution rate in the 2.38% TMAH aqueous solution is preferably 50 to 3,000 mm / sec.
  • polysiloxanes (Ia) and (Ib) each have a specific dissolution rate in a TMAH aqueous solution.
  • the dissolution rate of the polysiloxane in the TMAH aqueous solution is measured as follows. Polysiloxane is diluted with propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) to 35% by weight and dissolved with stirring with a stirrer at room temperature for 1 hour. In a clean room with a temperature of 23.0 ⁇ 0.5 ° C.
  • PGMEA propylene glycol monomethyl ether acetate
  • the prepared polysiloxane solution is pipetted onto a 4 inch, 525 ⁇ m thick silicon wafer and the center of a 1 cc silicon wafer. And then spin-coated to a thickness of 2 ⁇ 0.1 ⁇ m, and then heated on a hot plate at 100 ° C. for 90 seconds to remove the solvent.
  • the film thickness of the coating film is measured with a spectroscopic ellipsometer (manufactured by JA Woollam).
  • the silicon wafer having this film was gently immersed in a 6-inch diameter glass petri dish containing 100 ml of a TMAH aqueous solution having a predetermined concentration adjusted to 23.0 ⁇ 0.1 ° C., and then left to stand. The time until the film disappeared was measured. The dissolution rate is determined by dividing by the time until the film in the portion 10 mm inside from the edge of the wafer disappears. If the dissolution rate is extremely slow, the wafer is immersed in a TMAH aqueous solution for a certain period of time and then heated on a hot plate at 200 ° C. for 5 minutes to remove moisture taken into the film during the dissolution rate measurement. Thickness is measured, and the dissolution rate is calculated by dividing the amount of change in film thickness before and after immersion by the immersion time. The above measurement method is performed 5 times, and the average of the obtained values is taken as the dissolution rate of polysiloxane.
  • the negative photosensitive polysiloxane composition according to the present invention comprises a curing aid.
  • the curing aid includes a curing aid that generates an acid or a base by radiation and a curing aid that generates an acid or a base by heat.
  • the curing aid can improve the resolution by strengthening the shape of the pattern or increasing the contrast of development.
  • Curing aids used in the present invention include photoacid generators that release an acid that is an active substance that decomposes when irradiated with radiation to photocure the composition, photobase generators that release bases, and heat. Examples thereof include a thermal acid generator that releases an acid, which is an active substance that decomposes and thermally cures the composition, and a thermal base generator that releases a base.
  • the radiation include visible light, ultraviolet rays, infrared rays, X-rays, electron beams, ⁇ rays, and ⁇ rays.
  • 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, and the required sensitivity and dissolution contrast between the exposed and unexposed areas.
  • the amount is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight. If the addition amount is less than 0.001 part by weight, the dissolution contrast between the exposed part and the unexposed part is too low, and the additive effect may not be obtained. On the other hand, if the addition amount of the curing aid is more than 10 parts by weight, cracks may occur in the formed coating, or coloring due to decomposition of the curing aid may become prominent, resulting in a decrease in the colorless transparency of the coating.
  • thermal decomposition may cause deterioration of the electrical insulation of the cured product or outgassing, which may cause a problem in the subsequent process.
  • the resistance of the coating to a photoresist stripping solution containing monoethanolamine or the like as a main ingredient may be reduced.
  • photoacid generator examples 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 + 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.
  • X ⁇ is preferably any counter ion represented by the following general formula.
  • R a is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms substituted with a substituent selected from fluorine, a nitro group, and a cyano group
  • R b is hydrogen or an alkyl group having 1 to 8 carbon atoms
  • p is a number from 0 to 6
  • 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 Selected from the group consisting of N ⁇ , formate ion, acetate ion, trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, methanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and sulfonic acid ion Is mentioned.
  • those that generate sulfonic acids are particularly preferable.
  • triphenylsulfonium trifluoromethanesulfonic acid triphenylsulfonium camphorsulfonic acid
  • thermal acid generator examples include various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids and salts thereof such as citric acid, acetic acid, and maleic acid, and various aromatic carboxylic acids such as benzoic acid and phthalic acid.
  • thermal acid generators used in the present invention a salt composed of an organic acid and an organic base is preferable, and a salt composed of a sulfonic acid and an organic base is more preferable.
  • Preferred thermal acid generators containing sulfonic acid include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, and the like. These acid generators can be used alone or in combination.
  • photobase generator examples include polysubstituted amide compounds having an amide group, lactams, imide compounds, and those containing the structure.
  • thermal base generator examples 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.
  • the negative photosensitive siloxane composition according to the present invention comprises a solvent.
  • the solvent is not particularly limited as long as it can uniformly dissolve or disperse the polysiloxane mixture (I), the curing aid, and the additive added as necessary.
  • Examples of the solvent that can be used in the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, Propylene glycol alkyl ether acetates such as propylene glycol monopropyl ether acetate, aromatic hydrocarbons such as benzene, toluene, xylene, ketones such as methyl
  • propylene glycol alkyl ether acetates and esters from the viewpoints of easy availability, easy handling, and polymer solubility.
  • These solvents are used singly or in combination of two or more, and the amount used varies depending on the coating method and the requirements of the film thickness after coating.
  • the solvent content of the negative photosensitive siloxane composition can be arbitrarily adjusted according to the method of applying the composition. For example, when the composition is applied by spray coating, the proportion of the solvent in the negative photosensitive siloxane composition can be 90% by weight or more. In the slit coating used for coating a large substrate, it is usually 60% by weight or more, preferably 70% by weight or more. The characteristics of the negative photosensitive siloxane composition of the present invention do not vary greatly depending on the amount of the solvent.
  • the negative photosensitive siloxane composition according to the present invention may contain other additives as required.
  • additives include a developer dissolution accelerator, a scum remover, an adhesion enhancer, a polymerization inhibitor, an antifoaming agent, a surfactant, and a sensitizer.
  • the developer dissolution accelerator or scum remover adjusts the solubility of the coating film to be formed in the developer, and has a function of preventing scum from remaining on the substrate after development.
  • crown ether can be used.
  • a crown ether having the simplest structure is represented by the general formula (—CH 2 —CH 2 —O—) n . Of these, those in which n is 4 to 7 are preferred in the present invention. Crown ethers are sometimes called x-crown-y-ethers, where x is the total number of atoms constituting the ring and y is the number of oxygen atoms contained therein.
  • Specific examples of more preferred crown ethers include 21-crown-7 ether, 18-crown-6-ether, 15-crown-5-ether, 12-crown-4-ether, dibenzo-21-crown-7-ether, Dibenzo-18-crown-6-ether, dibenzo-15-crown-5-ether, dibenzo-12-crown-4-ether, dicyclohexyl-21-crown-7-ether, dicyclohexyl-18-crown-6-ether, Dicyclohexyl-15-crown-5-ether, and dicyclohexyl-12-crown-4-ether.
  • the amount added is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the polysiloxane mixture (I).
  • the adhesion enhancer has an effect of preventing a pattern from being peeled off by stress applied after firing when a cured film is formed using the negative photosensitive siloxane composition according to the present invention.
  • imidazoles and silane coupling agents are preferable.
  • imidazoles 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, 2 -Aminoimidazole is preferred, and 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, and imidazole are particularly preferably used.
  • silane coupling agents are preferably used, and examples include epoxy silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, and the like.
  • the addition amount is preferably 0.05 to 15 parts
  • a silane coupling agent a silane compound having an acid group, a siloxane compound, or the like can be used.
  • the acid group include a carboxyl group, an acid anhydride group, and a phenolic hydroxyl group.
  • a monobasic acid group such as a carboxyl group or a phenolic hydroxyl group is contained, it is preferable that a single silicon-containing compound has a plurality of acid groups.
  • silane coupling agents include the following general formula (B): X n Si (OR 3 ) 4-n (B) Or a polymer having the same as a polymerization unit. At this time, a plurality of polymer units having different X or R 3 can be used in combination.
  • R 3 includes a hydrocarbon group, for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • a hydrocarbon group for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • R 3 includes a hydrocarbon group, for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • X includes those having acid groups such as thiol, phosphonium, borate, carboxyl, phenol, peroxide, nitro, cyano, sulfo, and alcohol groups, and those acid groups represented by acetyl, aryl, amyl, benzyl, methoxymethyl, Examples thereof include those protected with mesyl, tolyl, trimethoxysilyl, triethoxysilyl, triisopropylsilyl, or a trityl group, and acid anhydride groups.
  • a compound represented by the following general formula (B-1) (X-12-967C (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)) and a corresponding structure having a silicon-containing polymer such as silicone.
  • the polymer contained in the terminal or side chain of is preferred.
  • a compound in which an acid group such as thiol, phosphonium, borate, carboxyl, phenol, peroxide, nitro, cyano, or sulfo group is added to the terminal portion of dimethyl silicone is also preferable.
  • Examples of such a compound include compounds represented by the following general formulas (B-2) and (B-3) (X-22-2290AS and X-22-1821 (both trade names, manufactured by Shin-Etsu Chemical Co., Ltd.)).
  • the silane coupling agent contains a silicone structure
  • the compatibility with the polysiloxane contained in the composition will be poor, the solubility in the developer will not be improved, and reactive groups will remain in the film.
  • the weight average molecular weight of a silicon containing compound is 5000 or less, and it is more preferable that it is 4,000 or less.
  • the polymer corresponding to (B-1) is preferably a relatively small polymer having a weight average molecular weight of 1,000 or less, but in the case of a polymer containing a silicone structure in other repeating units, The weight average molecular weight is preferably 1,000 or more. Further, when a silane compound having an acid group, a siloxane compound or the like is used as a silane coupling agent, the addition amount is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the polysiloxane mixture (I). .
  • nitrone derivatives and nitroxide radical derivatives such as hydroquinone derivatives such as hydroquinone, methylhydroquinone and butylhydroquinone can be added. These can be used singly or in combination.
  • the addition amount is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polysiloxane mixture (I).
  • an alcohol C 1 ⁇ 18
  • higher fatty acids such as oleic acid and stearic acid
  • higher fatty acid esters such as glycerol monolaurate
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • dimethyl silicone oils dimethyl silicone oils
  • alkyl-modified silicone oils silicone compounds such as fluorosilicone oils, and organosiloxane surfactants described in detail below.
  • the amount of addition is preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the total amount of the polysiloxane mixture (I).
  • the negative photosensitive siloxane composition of the present invention may contain a surfactant as necessary.
  • the surfactant is added for the purpose of improving coating properties, developability and the like.
  • examples of the surfactant that can be used in the present invention include nonionic surfactants, anionic surfactants, and amphoteric surfactants.
  • nonionic surfactant examples 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.
  • Acetylene glycol derivatives such as diesters, polyoxy fatty acid monoesters, polyoxyethylene polyoxypropylene block polymers, acetylene alcohol, acetylene glycol, polyethoxylates of acetylene alcohol, polyethoxylates of acetylene glycol, fluorine-containing surfactants such as Fluorado (Trade name, manufactured by Sumitomo 3M Limited), Megafuck (trade name, manufactured by DIC Corporation), Sulfron (trade name, Asahi Glass Co., Ltd.) Company Ltd.), or organosiloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Fluorado Trade name, manufactured by Sumitomo 3M Limited
  • Megafuck trade name, manufactured by DIC Corporation
  • Sulfron trade name, Asahi Glass Co., Ltd.
  • organosiloxane surfactants such as KP341 (trade name, manufactured
  • acetylene glycol examples 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 and the like.
  • Anionic surfactants include 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 sulfate. And ammonium salts and organic amine salts of alkyl sulfates.
  • amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauric acid amidopropyl hydroxysulfone betaine, and the like.
  • surfactants can be used alone or in admixture of two or more, and the blending amount thereof is usually 50 to 2,000 ppm, preferably 100 to 2,000, based on the negative photosensitive siloxane composition of the present invention. 1,000 ppm.
  • a sensitizer can be added to the negative photosensitive siloxane composition of the present invention as necessary.
  • Sensitizers preferably used in the negative photosensitive siloxane composition of the present invention include coumarins, ketocoumarins and their derivatives, thiopyrylium salts, acetophenones, etc., specifically p-bis (o-methylstyryl) benzene.
  • the amount added is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the polysiloxane mixture (I).
  • each R 31 independently represents a substituent selected from the group consisting of an alkyl group, an aralkyl group, an allyl group, a hydroxyalkyl group, an alkoxyalkyl group, a glycidyl group, and a halogenated alkyl group
  • Each of R 32 independently represents a substituent selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, a hydroxyl group, an amino group, and a carboalkoxy group
  • k is an integer independently selected from 0, 1 to 4.
  • Such a sensitizer having an anthracene skeleton is also disclosed in Patent Document 5 or 6 or the like.
  • the addition amount is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the polysiloxane mixture (I).
  • a stabilizer can be added to the negative photosensitive siloxane composition according to the present invention as necessary.
  • the stabilizer can be arbitrarily selected from those generally used, but in the composition according to the present invention, an aromatic amine is preferable because of its high stabilizing effect.
  • aromatic amines pyridine derivatives are preferred, and those having relatively bulky substituents at the 2-position and the 6-position are particularly preferred. Specific examples include the following.
  • a method for forming a cured film according to the present invention comprises applying the above-described negative polysiloxane photosensitive composition to the surface of a substrate and curing it by heating.
  • the method for forming the cured film will be described in the order of steps as follows.
  • the negative photosensitive polysiloxane composition described above is applied to a substrate.
  • Formation of the coating film of the photosensitive polysiloxane composition in this invention can be performed by the arbitrary methods conventionally known as a coating method of the photosensitive composition. Specifically, it can be arbitrarily selected from dip coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, slit coating, and the like.
  • coats a composition suitable base materials, such as a silicon substrate, a glass substrate, and a resin film, can be used. Various semiconductor elements etc. may be formed in these base materials as needed.
  • the substrate is a film, gravure coating can also be used. If desired, a drying step can be separately provided after the coating. Further, if necessary, the coating process can be repeated once or twice or more to obtain a desired coating film thickness.
  • Pre-bake process After forming a coating film by applying a negative photosensitive siloxane composition, the coating film is dried and the residual solvent in the coating film is reduced.
  • Pre-baking preheating treatment
  • the pre-baking step is generally carried out at a temperature of 50 to 150 ° C., preferably 90 to 120 ° C., for 10 to 300 seconds when using a hot plate, preferably 30 to 120 seconds, and for 1 to 30 minutes when using a clean oven. be able to.
  • the coating film surface is irradiated with light.
  • 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.
  • irradiation light ultraviolet rays such as g-line, h-line and i-line are usually used. Except for ultrafine processing such as semiconductors, light of 360 to 430 nm (high pressure mercury lamp) is generally used for patterning of several ⁇ m to several tens of ⁇ m.
  • the energy of the irradiation light is generally 10 to 2000 mJ / cm 2 , preferably 20 to 1000 mJ / cm 2 , although it depends on the light source and the film thickness of the coating film. If the irradiation light energy is lower than 10 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.
  • 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.
  • an ambient atmosphere in the air
  • a nitrogen atmosphere may be used.
  • the pattern film includes the case where a film is formed on the entire surface of the substrate.
  • post-exposure baking can be performed as necessary in order to promote the interpolymer reaction in the film by the reaction initiator generated at the exposure site. This heat treatment is not performed in order to completely cure the coating film, but is performed so that only a desired pattern remains on the substrate after development and other portions can be removed by development. is there.
  • the heating temperature should not be excessively high because it is not desirable for the acid in the exposed areas generated by light irradiation to diffuse to the unexposed areas.
  • the range of the heating temperature after exposure is preferably 40 ° C. to 150 ° C., more preferably 60 ° C. to 120 ° C.
  • Stepwise heating can be applied as needed to control the cure rate of the composition.
  • the atmosphere during heating is not particularly limited, but can be selected from an inert gas such as nitrogen, a vacuum, a reduced pressure, and an oxygen gas for the purpose of controlling the curing rate of the composition. .
  • the heating time is preferably a certain value or more in order to maintain higher uniformity of temperature history in the wafer surface, and is preferably not excessively long in order to suppress the diffusion of the generated acid. From such a viewpoint, the heating time is preferably 20 seconds to 500 seconds, and more preferably 40 seconds to 300 seconds.
  • the coating film is developed.
  • a developing solution used in the development any developing solution that has been conventionally used for developing a known photosensitive siloxane composition can be used.
  • a TMAH aqueous 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.
  • a particularly preferred alkaline developer is an aqueous tetramethylammonium hydroxide 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. A pattern can be obtained by this development. After development with a developer, washing is preferably performed.
  • the obtained pattern film is cured by heating.
  • the heating apparatus used for the heating process the same apparatus as used for the post-exposure heating described above can be used.
  • the heating temperature in this heating step is not particularly limited as long as the coating film can be cured, and is usually 150 to 400 ° C., preferably 200 to 350 ° C. Below 150 ° C., unreacted silanol groups may remain. If silanol groups remain, the cured film may not exhibit sufficient chemical resistance or the dielectric constant of the cured film may increase. From such a viewpoint, the heating temperature is preferably 150 ° C. or higher.
  • the heating time is not particularly limited, and is generally 10 minutes to 24 hours, preferably 30 minutes to 3 hours. The heating time is a time after the temperature of the pattern film reaches a desired heating temperature. Usually, it takes about several minutes to several hours for the pattern film to reach a desired temperature from the temperature before heating.
  • the cured film thus obtained can achieve excellent heat resistance, transparency, relative dielectric constant, and the like.
  • the heat resistance is 400 ° C. or higher
  • the light transmittance of the effect film is 95% or higher
  • the relative dielectric constant is 4 or lower, preferably 3.3 or lower.
  • it has light transmittance and relative dielectric constant characteristics that are not found in acrylic materials that have been used in the past, such as flat panel display (FPD) and other flattening films of various elements as described above, low-temperature polysilicon It can be suitably used in various fields as an interlayer insulating film for use, a buffer coat film for IC chips, a transparent protective film, and the like.
  • a spin coater MS-A100 type (trade name, manufactured by Mikasa Co., Ltd.) was used for coating the composition, and the thickness of the formed film was a film thickness meter VM-1200 type (trade name, manufactured by Dainippon Screen Mfg. Co., Ltd.). ).
  • the mixed solution was added dropwise to the reaction solvent using a dropping funnel at 10 ° C., stirred for 2 hours while maintaining at 10 ° C., and neutralized by adding 10% HCl aqueous solution.
  • 200 ml of toluene and 300 ml of water were added and shaken, and then separated into two layers.
  • the solvent was removed by concentrating the obtained organic layer under reduced pressure, and PGMEA was added to the concentrate to adjust the solid concentration to 40% by weight to prepare a solution containing polysiloxane Ia-1.
  • the obtained polysiloxane Ia-1 had an average weight molecular weight (polystyrene conversion) of 2,180.
  • the obtained polysiloxane solution was applied to a silicon wafer, and the dissolution rate in a 5% TMAH aqueous solution was measured under the above-mentioned conditions.
  • Example 1 negative photosensitive siloxane composition
  • the polysiloxane mixture was adjusted to a 35 wt% PGMEA solution.
  • the dissolution rate of this polysiloxane mixture in a 2.38% TMAH aqueous solution after pre-baking was measured, it was 105 kg / sec.
  • a photoacid generator A1 (acid releasing type) composed of triphenylsulfonium cation and sulfonate anion and capable of functioning by irradiation with g-line or i-line is added to polysiloxane.
  • KF-53 trade name, manufactured by Shin-Etsu Chemical Co., Ltd.
  • a surfactant was added in an amount of 0.3% by weight based on the polysiloxane to obtain a negative photosensitive siloxane composition.
  • This photosensitive siloxane composition was applied on a silicon wafer by spin coating, and after application, pre-baked on a hot plate at 100 ° C. for 90 seconds to adjust the film thickness to 2 ⁇ m.
  • the film was allowed to stand for development for 60 seconds with a 38% TMAH aqueous solution and rinsed with pure water for 30 seconds.
  • the 10 ⁇ m line and space (L / S) pattern and the contact hole (C / H) pattern were left without any residue.
  • baking and curing were performed at 250 ° C., and when confirmed with an optical microscope, a 10 ⁇ m pattern was retained.
  • the dielectric constant was measured by a mercury probe method using Solid State Measurements 495.
  • the relative dielectric constant was calculated from the saturation capacitance obtained by performing CV measurement at a measurement frequency of 100 KHz using a mercury probe type capacitance measuring device 495 (manufactured by Solid State Instrument).
  • the measurement sample was prepared by applying the photosensitive siloxane composition on a silicon wafer by spin coating, pre-baking on a hot plate at 100 ° C.
  • Example 2 negative photosensitive siloxane composition
  • the dissolution rate of the siloxane mixture was evaluated.
  • a negative photosensitive siloxane composition was prepared in the same manner as in Example 1. When this composition was applied to a substrate in the same manner as in Example 1 and exposed to 220 mJ / cm 2 to form a pattern, the 8 ⁇ m line-and-space pattern and the contact hole pattern could be left without any residue. confirmed. After pattern formation, baking and curing were performed at 250 ° C., and when confirmed with an optical microscope, a cylindrical 8 ⁇ m pattern was retained.
  • Example 3 negative photosensitive siloxane composition
  • the dissolution rate of the siloxane mixture was evaluated.
  • a negative photosensitive siloxane composition was prepared in the same manner as in Example 1. This composition was applied to a substrate in the same manner as in Example 1 and exposed to 65 mJ / cm 2 to form a pattern. When a pattern of 3 and 10 ⁇ m line and space pattern and a contact hole pattern of 3 ⁇ m, 5 ⁇ m, and 10 ⁇ m was formed. In all cases, it was confirmed that there was no residue. After pattern formation, baking and curing were performed at 250 ° C., and the appearance of each pattern was observed with an optical microscope. FIG. 1 shows an optical micrograph of the contact hole. As is clear from FIG. 1, the contact hole patterns of any size were held in a good shape.
  • Example 4 negative photosensitive siloxane composition
  • the dissolution rate of the siloxane mixture was evaluated.
  • a negative photosensitive siloxane composition was prepared in the same manner as in Example 1. When this composition was applied to a substrate in the same manner as in Example 1 and exposed to 160 mJ / cm 2 to form a pattern, it was found that the 6 ⁇ m line and space pattern and the contact hole pattern were left without any residue. confirmed. After pattern formation, baking and curing were performed at 250 ° C., and when confirmed with an optical microscope, a 6 ⁇ m pattern was well maintained.
  • Example 5 negative photosensitive siloxane composition
  • the dissolution rate of the siloxane mixture was evaluated.
  • a negative photosensitive siloxane composition was prepared in the same manner as in Example 1. When this composition was applied to the substrate in the same manner as in Example 1 and exposed to 160 mJ / cm 2 to form a pattern, it was confirmed that the 6 ⁇ m line and space pattern and the contact hole pattern were left without any residue. It was done. After pattern formation, baking and curing were performed at 250 ° C., and when confirmed with an optical microscope, a 6 ⁇ m pattern was well maintained.
  • Example 6 negative photosensitive siloxane composition
  • the dissolution rate of the siloxane mixture was evaluated.
  • a negative photosensitive siloxane composition was prepared in the same manner as in Example 1. When this composition was applied to the substrate in the same manner as in Example 1 and exposed to 105 mJ / cm 2 to form a pattern, it was confirmed that the 6 ⁇ m line and space pattern and the contact hole pattern were left without any residue. It was done. After pattern formation, baking and curing were performed at 250 ° C., and when confirmed with an optical microscope, a good shape was maintained with rounded corners, and a 6 ⁇ m pattern was maintained.
  • Example 7 negative photosensitive siloxane composition
  • the dissolution rate of the siloxane mixture was evaluated.
  • a negative photosensitive siloxane composition was prepared in the same manner as in Example 1. When this composition was applied to a substrate in the same manner as in Example 1 and exposed to 105 mJ / cm 2 to form a pattern, it was found that the 6 ⁇ m line and space pattern and the contact hole pattern were left without any residue. confirmed. After pattern formation, baking and curing were performed at 250 ° C., and when confirmed with an optical microscope, a good shape was maintained with rounded corners, and a 6 ⁇ m pattern was maintained.
  • Example 8 negative photosensitive siloxane composition
  • the dissolution rate of the siloxane mixture was evaluated.
  • a negative photosensitive siloxane composition was prepared in the same manner as in Example 1. When this composition was applied to the substrate in the same manner as in Example 1 and exposed to 110 mJ / cm 2 to form a pattern, it was found that the 6 ⁇ m line and space pattern and the contact hole pattern were left without any residue. confirmed. After pattern formation, baking and curing were performed at 250 ° C., and when confirmed with an optical microscope, a good shape was maintained with rounded corners, and a 6 ⁇ m pattern was maintained.
  • Example 9 negative photosensitive siloxane composition
  • the dissolution rate of the siloxane mixture was evaluated.
  • NCB-101 (B1, base releasing type) manufactured by Midori Chemical Co., Ltd. as a photobase generator and Anthracure UVS-1331 (as a sensitizer) based on the total weight of the polysiloxane.
  • Negative photosensitive siloxane composition with 0.01% by weight of trade name, manufactured by Kawasaki Kasei Kogyo Co., Ltd. and 0.3% by weight of KF-53 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a surfactant.
  • KF-53 trade name, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 10 negative photosensitive siloxane composition
  • the dissolution rate of the siloxane mixture was evaluated.
  • a negative photosensitive siloxane composition was prepared in the same manner as in Example 1.
  • a 0.5 ⁇ m film was formed from this composition in the same manner as in Example 1, and was exposed to 109 mJ / cm 2 to form a pattern.
  • the 4 ⁇ m line and space pattern and the contact hole pattern were free of residues and the like. It was confirmed that it was missing.
  • baking and curing were performed at 250 ° C., and when confirmed with an optical microscope, a pattern of 4 ⁇ m was well maintained.
  • Example 11 negative photosensitive siloxane composition
  • the dissolution rate of the siloxane mixture was evaluated.
  • a negative photosensitive siloxane composition was prepared in the same manner as in Example 1.
  • a 0.2 ⁇ m film was formed on this composition in the same manner as in Example 1 and exposed to 60 mJ / cm 2 to form a pattern, a 3 ⁇ m line-and-space pattern and contact hole) pattern was a residue, etc. It was confirmed that it was missing.
  • baking and curing were performed at 250 ° C., and when confirmed with an optical microscope, a 3 ⁇ m pattern was well maintained.
  • Example 12 negative photosensitive siloxane composition
  • the dissolution rate of the siloxane mixture was evaluated.
  • a negative photosensitive siloxane composition was prepared in the same manner as in Example 1.
  • a 5 ⁇ m film was formed by the same method as in Example 1 except that the curing temperature was changed to 110 ° C., and a pattern was formed by exposure at 165 mJ / cm 2. It was confirmed that the space pattern and contact hole pattern were missing without residue.
  • baking and curing were performed at 250 ° C., and when confirmed with an optical microscope, a pattern of 5 ⁇ m was well maintained.
  • a photoacid generator (A2, acid-releasing type) that can function by irradiation with g-line or i-line and having a cation part of a sulfonium salt and an anion part of borate is 2.0% with respect to polysiloxane. Weight percent was added. Further, KF-53 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a surfactant was added in an amount of 0.3% by weight based on the polysiloxane to obtain a negative photosensitive siloxane composition.
  • A2 acid-releasing type
  • This photosensitive siloxane composition was applied onto a silicon wafer by spin coating, and after application, pre-baked on a hot plate at 100 ° C. for 90 seconds to adjust the film thickness to 1.5 ⁇ m. 1.
  • the film was allowed to stand for development for 60 seconds with a 38% TMAH aqueous solution and rinsed with pure water for 30 seconds.
  • This photosensitive siloxane composition was applied onto a silicon wafer by spin coating, and after application, pre-baked on a hot plate at 100 ° C. for 90 seconds to adjust the film thickness to 1.0 ⁇ m. 1.
  • the film was allowed to stand for development for 60 seconds with a 38% TMAH aqueous solution and rinsed with pure water for 30 seconds.
  • composition was applied onto a substrate, cured at 100 ° C. to form a 1.0 ⁇ m film, and exposed to 50 mJ / cm 2 to form a pattern. A 3 ⁇ m line and space pattern and a contact hole pattern were formed. It was confirmed that was removed without residue. After pattern formation, baking and curing were performed at 350 ° C., and when confirmed with an optical microscope, a 3 ⁇ m pattern was well maintained.
  • Example 16 negative photosensitive siloxane composition
  • the polysiloxane mixture was adjusted to a 40% PGMEA solution.
  • the dissolution rate of this polysiloxane mixture in a 2.38% TMAH aqueous solution after pre-baking was measured, it was 3,000 kg / sec.
  • the same additive as in Example 13 was added to this siloxane mixture to obtain a negative photosensitive siloxane composition.
  • composition was applied onto a substrate, cured at 100 ° C. to form a 3.0 ⁇ m film, and exposed to 120 mJ / cm 2 to form a pattern. A 3 ⁇ m line and space pattern and a contact hole pattern were formed. It was confirmed that was removed without residue. After pattern formation, baking and curing were performed at 350 ° C., and when confirmed with an optical microscope, a 3 ⁇ m pattern was well maintained.
  • composition was applied onto a substrate, cured at 100 ° C. to form a 1.0 ⁇ m film, and exposed to 50 mJ / cm 2 to form a pattern. A 3 ⁇ m line and space pattern and a contact hole pattern were formed. It was confirmed that was removed without residue. After pattern formation, baking and curing were performed at 350 ° C., and when confirmed with an optical microscope, a 3 ⁇ m pattern was well maintained.
  • Example 18 negative photosensitive siloxane composition
  • the polysiloxane mixture was adjusted to a 20% PGMEA solution.
  • the dissolution rate of this polysiloxane mixture in a 2.38% TMAH aqueous solution after pre-baking was measured and found to be 1,220 kg / sec.
  • the same additive as in Example 13 was added to this siloxane mixture to obtain a negative photosensitive siloxane composition.
  • This composition was applied onto a substrate, cured at 100 ° C. to form a 1.0 ⁇ m film, and exposed at 35 mJ / cm 2 to form a pattern. A 10 ⁇ m line and space pattern and a contact hole pattern were formed. It was confirmed that was removed without residue. After pattern formation, baking and curing were performed at 350 ° C., and when confirmed with an optical microscope, a 10 ⁇ m pattern was retained although slight thermal sag was observed. Such a composition having a relatively large thermal sag is effective when used for an insulating film covering an element or the like drawn on a substrate.
  • EL ethyl lactate
  • composition was applied onto a substrate, cured at 100 ° C. to form a 2.0 ⁇ m film, and exposed at 55 mJ / cm 2 to form a pattern.
  • a 4 ⁇ m line and space pattern and a contact hole pattern were formed. It was confirmed that was removed without residue.
  • baking and curing were performed at 200 ° C., and when confirmed with an optical microscope, a pattern of 4 ⁇ m was well maintained.
  • Example 20 negative photosensitive siloxane composition
  • X-12-967C trade name, manufactured by Shin-Etsu Chemical Co., Ltd.
  • silane coupling agent was added to the composition of Example 13 in an amount of 1.0% by weight based on the total weight of the polysiloxane mixture.
  • a negative photosensitive siloxane composition was obtained.
  • the composition was applied onto a substrate, cured at 100 ° C. to form a 2.0 ⁇ m film, and exposed to 30 mJ / cm 2 to form a pattern. A 5 ⁇ m line and space pattern and a contact hole pattern were formed. It was confirmed that was removed without residue. After pattern formation, baking and curing were performed at 350 ° C., and when confirmed with an optical microscope, a pattern of 5 ⁇ m was well maintained. Moreover, when the sensitivity was evaluated about the formed film, it turned out that it is improving further with respect to Example 13. FIG.
  • Example 21 negative photosensitive siloxane composition
  • 2,6-di-tert-butyl-4-methylpyridine manufactured by Tokyo Chemical Industry Co., Ltd.
  • amine-based additive was added to the total weight of the polysiloxane mixture by 0.3.
  • weight percent addition a negative photosensitive siloxane composition was obtained.
  • This composition was applied on a substrate, cured at 100 ° C. to form a 2.0 ⁇ m film, and exposed at 35 mJ / cm 2 to form a pattern. A 5 ⁇ m line and space pattern and a contact hole pattern were formed. It was confirmed that was removed without residue. After pattern formation, baking and curing were performed at 350 ° C., and when confirmed with an optical microscope, a pattern of 5 ⁇ m was well maintained. Moreover, when the storage stability at 40 ° C. was evaluated, it was found that the storage stability was further improved with respect to Example 13.
  • Example 22 For the composition of Example 13, as a photoacid generator, a photoacid generator comprising an iodonium salt in the cation portion and a borate in the anion portion, and ANTRACURE UVS-1331 (trade name, Kawasaki Kasei Kogyo Co., Ltd.) as the sensitizer. 4.0% by weight and 0.5% by weight with respect to the total weight of the polysiloxane mixture, respectively, to obtain a negative photosensitive siloxane composition.
  • a photoacid generator comprising an iodonium salt in the cation portion and a borate in the anion portion, and ANTRACURE UVS-1331 (trade name, Kawasaki Kasei Kogyo Co., Ltd.) as the sensitizer. 4.0% by weight and 0.5% by weight with respect to the total weight of the polysiloxane mixture, respectively, to obtain a negative photosensitive siloxane composition.
  • a negative photosensitive siloxane composition was prepared in the same manner as in Example 1. This composition was applied to a substrate in the same manner as in Example 1 and exposed to 20 mJ / cm 2 to form a pattern. As a result, 3 ⁇ m and 10 ⁇ m line and space patterns and 3 ⁇ m, 5 ⁇ m, and 10 ⁇ m contact hole patterns were obtained. confirmed. After the pattern formation, it was baked and cured at 250 ° C. and confirmed with an optical microscope. FIG. 2 shows an optical micrograph of the contact hole pattern. As is apparent from FIG. 2, thermal sagging occurred in Comparative Example 1, and the shape of any contact hole pattern or line and space pattern was not maintained.
  • a negative photosensitive siloxane composition was prepared in the same manner as in Example 1. This composition was applied to the substrate in the same manner as in Example 1, exposed at an exposure amount of 500 mJ / cm 2 or more, and post-exposure reheating was baked on a hot plate at 100 ° C. for 90 seconds, and a 2.38% TMAH aqueous solution. For 60 seconds and then rinsed with pure water for 30 seconds. As a result, the pattern could not be drawn due to insufficient sensitivity.
  • a negative photosensitive siloxane composition was prepared in the same manner as in Example 1. This composition was applied to the substrate in the same manner as in Example 1, exposed at an exposure amount of 500 mJ / cm 2 or more, and post-exposure reheating was baked on a hot plate at 100 ° C. for 90 seconds, and a 2.38% TMAH aqueous solution. For 60 seconds and then rinsed with pure water for 30 seconds. As a result, the pattern could not be drawn due to insufficient sensitivity.
  • a negative photosensitive siloxane composition was prepared in the same manner as in Example 1. When this composition was applied to a substrate in the same manner as in Example 1 and exposed at 155 mJ / cm 2 to form a pattern, it was confirmed that a 6 ⁇ m line and space pattern and a contact hole pattern were formed. However, a lot of scum and residue remained.
  • a negative photosensitive siloxane composition was prepared in the same manner as in Example 1. When this composition was applied to a substrate in the same manner as in Example 1 and exposed to 150 mJ / cm 2 to form a pattern, it was confirmed that a 6 ⁇ m line and space pattern and a contact hole pattern were formed. However, a lot of scum and residue remained.
  • Example 9 a negative photosensitive siloxane composition was prepared.
  • this composition was applied to a substrate in the same manner as in Example 1 and exposed at 195 mJ / cm 2 to form a pattern, it was confirmed that a 6 ⁇ m line and space pattern and a contact hole pattern were formed. However, a lot of scum and residue remained.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Silicon Polymers (AREA)

Abstract

[Problème] L'invention a pour objectif de fournir une composition de siloxane photosensible qui présente une résolution élevée, une résistance élevée à la chaleur et un degré élevé de transparence, ne subit pas d'affaissement thermique qui peut se produire pendant le durcissement thermique sans avoir besoin d'augmenter le poids moléculaire d'un agent de réticulation ou d'un composé siloxane et possède des propriétés comprenant une sensibilité élevée et un taux de film résiduel élevé. [Solution] Pour ce faire, l'invention concerne une composition de polysiloxane photosensible de type négatif caractérisée en ce qu'elle comprend : (I) (Ia) un polysiloxane ayant une propriété telle qu'un film précuit de celui-ci est soluble dans une solution aqueuse à 5 % en poids d'hydroxyde de tétraméthylammonium avec une vitesse de dissolution inférieure ou égale à 3 000 Å/sec et (Ib) un mélange de polysiloxane contenant un polysiloxane et ayant une propriété telle que la vitesse de dissolution d'un film précuit de celui-ci dans une solution aqueuse à 2,38 % en poids d'hydroxyde de tétraméthylammonium est supérieure ou égale à 150 Å/sec; (II) une aide au durcissement; et (III) un solvant.
PCT/JP2012/080299 2011-11-29 2012-11-22 Composition de siloxane photosensible de type négatif Ceased WO2013080884A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104238271A (zh) * 2013-06-14 2014-12-24 Az电子材料（卢森堡）有限公司 能低温固化的负型感光性组合物
KR20140146008A (ko) * 2013-06-14 2014-12-24 에이제트 일렉트로닉 머티어리얼스 (룩셈부르크) 에스.에이.알.엘. 저온 경화 가능한 네거티브형 감광성 조성물
WO2015060155A1 (fr) * 2013-10-21 2015-04-30 Ａｚエレクトロニックマテリアルズマニュファクチャリング株式会社 Composition thermodurcissable ou photodurcissable contenant du silicium
CN111512230A (zh) * 2017-12-28 2020-08-07 默克专利有限公司 感光性硅氧烷组合物以及使用了其的图案形成方法
CN111978861A (zh) * 2020-09-01 2020-11-24 淮阴工学院 苯基聚硅氧烷超疏水涂料的制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018189738A (ja) * 2017-04-28 2018-11-29 メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ ポジ型感光性シロキサン組成物、およびそれを用いて形成した硬化膜
JP2018205598A (ja) * 2017-06-07 2018-12-27 メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ 感光性シロキサン組成物、およびそれを用いて形成した硬化膜
TWI701511B (zh) * 2019-01-16 2020-08-11 臺灣永光化學工業股份有限公司 負型感光性樹脂組成物及其用途

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0527441A (ja) * 1990-06-25 1993-02-05 Matsushita Electron Corp 光または放射線感応性組成物とパターン形成方法とホトマスクの製造方法および半導体装置の製造方法
JP2010043030A (ja) * 2008-08-13 2010-02-25 Az Electronic Materials Kk アルカリ可溶性シルセスキオキサン及び感光性組成物
JP2011095432A (ja) * 2009-10-28 2011-05-12 Jsr Corp 感放射線性組成物、保護膜、層間絶縁膜、及びそれらの形成方法
JP2011133679A (ja) * 2008-12-25 2011-07-07 Jsr Corp ネガ型感放射線性組成物、硬化パターン形成方法および硬化パターン
JP2012098453A (ja) * 2010-11-01 2012-05-24 Hitachi Chem Co Ltd 感光性樹脂組成物、パターンを有するシリカ系絶縁被膜の形成方法及びその方法により形成されるパターンを有するシリカ系絶縁被膜を備える電子部品

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4929707A (en) * 1988-02-16 1990-05-29 Mitsui Toatsu Chemicals, Inc. Polyurethane base lens resin, plastic lens comprising the resin and preparation method of the lens
JP3279313B2 (ja) * 1990-06-25 2002-04-30 松下電器産業株式会社 パターン形成方法と位相シフトマスクの製造方法および半導体装置の製造方法
JP2933879B2 (ja) 1995-08-11 1999-08-16 シャープ株式会社 透過型液晶表示装置およびその製造方法
JP2002220471A (ja) * 2001-01-29 2002-08-09 Jsr Corp ポリシロキサン
JP4687250B2 (ja) 2004-06-02 2011-05-25 東レ株式会社 感光性樹脂組成物
JP2006236839A (ja) 2005-02-25 2006-09-07 Mitsubishi Electric Corp 有機電界発光型表示装置
WO2006132351A1 (fr) * 2005-06-09 2006-12-14 Hitachi Chemical Company, Ltd. Procede de formation d'un film antireflection
JP4104621B2 (ja) 2005-09-12 2008-06-18 株式会社日立製作所 生体認証システム
CN101443414A (zh) * 2006-03-16 2009-05-27 Jsr株式会社 含氧化物微粒的聚硅氧烷组合物及其制备方法
JP4947300B2 (ja) * 2007-06-14 2012-06-06 Ｊｓｒ株式会社 感放射線性樹脂組成物、層間絶縁膜およびマイクロレンズならびにそれらの形成方法
JP2010039051A (ja) * 2008-08-01 2010-02-18 Sekisui Chem Co Ltd 感光性組成物及びパターン膜の製造方法
TW201030469A (en) * 2008-12-25 2010-08-16 Jsr Corp Negative-tone radiation-sensitive composition, cured pattern forming method, and cured pattern
US8911932B2 (en) * 2009-04-13 2014-12-16 Sam Xunyun Sun Photo-imageable hardmask with positive tone for microphotolithography
JP4918578B2 (ja) 2009-08-17 2012-04-18 ダウ・コーニング・コーポレイション ネガ型パターン形成用硬化性シリコーン組成物、及びこれを用いたパターン形成方法
KR20110046331A (ko) * 2009-10-28 2011-05-04 제이에스알 가부시끼가이샤 감방사선성 조성물, 보호막, 층간 절연막 및 그들의 형성 방법
JP5516869B2 (ja) 2010-03-13 2014-06-11 川崎化成工業株式会社 光カチオン重合増感剤組成物、光感応性酸発生剤組成物、光カチオン重合性組成物及び該光カチオン重合組成物を重合してなる重合物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0527441A (ja) * 1990-06-25 1993-02-05 Matsushita Electron Corp 光または放射線感応性組成物とパターン形成方法とホトマスクの製造方法および半導体装置の製造方法
JP2010043030A (ja) * 2008-08-13 2010-02-25 Az Electronic Materials Kk アルカリ可溶性シルセスキオキサン及び感光性組成物
JP2011133679A (ja) * 2008-12-25 2011-07-07 Jsr Corp ネガ型感放射線性組成物、硬化パターン形成方法および硬化パターン
JP2011095432A (ja) * 2009-10-28 2011-05-12 Jsr Corp 感放射線性組成物、保護膜、層間絶縁膜、及びそれらの形成方法
JP2012098453A (ja) * 2010-11-01 2012-05-24 Hitachi Chem Co Ltd 感光性樹脂組成物、パターンを有するシリカ系絶縁被膜の形成方法及びその方法により形成されるパターンを有するシリカ系絶縁被膜を備える電子部品

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104238271A (zh) * 2013-06-14 2014-12-24 Az电子材料（卢森堡）有限公司 能低温固化的负型感光性组合物
KR20140146008A (ko) * 2013-06-14 2014-12-24 에이제트 일렉트로닉 머티어리얼스 (룩셈부르크) 에스.에이.알.엘. 저온 경화 가능한 네거티브형 감광성 조성물
JP2015018226A (ja) * 2013-06-14 2015-01-29 Ａｚエレクトロニックマテリアルズマニュファクチャリング株式会社 低温硬化可能なネガ型感光性組成物
TWI611267B (zh) * 2013-06-14 2018-01-11 AZ ELECTRONIC MATERIALS (LUXEMBOURG) S. a. r. l. 可低溫硬化之負型感光性組成物、硬化膜及其製造方法
CN104238271B (zh) * 2013-06-14 2020-01-03 Az电子材料（卢森堡）有限公司 能低温固化的负型感光性组合物
KR102203303B1 (ko) * 2013-06-14 2021-01-18 에이제트 일렉트로닉 머티어리얼스 (룩셈부르크) 에스.에이.알.엘. 저온 경화 가능한 네거티브형 감광성 조성물
WO2015060155A1 (fr) * 2013-10-21 2015-04-30 Ａｚエレクトロニックマテリアルズマニュファクチャリング株式会社 Composition thermodurcissable ou photodurcissable contenant du silicium
JP2015108116A (ja) * 2013-10-21 2015-06-11 メルクパフォーマンスマテリアルズマニュファクチャリング合同会社 ケイ素含有熱または光硬化性組成物
US9817312B2 (en) 2013-10-21 2017-11-14 Az Electronic Materials (Luxembourg) S.À R.L. Silicon-containing heat- or photo-curable composition
CN111512230A (zh) * 2017-12-28 2020-08-07 默克专利有限公司 感光性硅氧烷组合物以及使用了其的图案形成方法
CN111978861A (zh) * 2020-09-01 2020-11-24 淮阴工学院 苯基聚硅氧烷超疏水涂料的制备方法

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KR101992594B1 (ko) 2019-06-25
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