CN102156386A - Positive radiation-sensitive composition, interlayer insulating film and method for forming the same - Google Patents

Positive radiation-sensitive composition, interlayer insulating film and method for forming the same Download PDF

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CN102156386A
CN102156386A CN2010105998586A CN201010599858A CN102156386A CN 102156386 A CN102156386 A CN 102156386A CN 2010105998586 A CN2010105998586 A CN 2010105998586A CN 201010599858 A CN201010599858 A CN 201010599858A CN 102156386 A CN102156386 A CN 102156386A
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positive radiation
radiation line
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一户大吾
花村政晓
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JSR Corp
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    • 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
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    • G—PHYSICS
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    • 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
    • G03F7/022—Quinonediazides
    • G03F7/0223—Iminoquinonediazides; Para-quinonediazides
    • G—PHYSICS
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Abstract

The invention relates to a positive radiation-sensitive composition, an interlayer insulating film, and a method for forming the same. The object of the invention is to provide a polysiloxanes positive radiation-sensitive composition capable of forming a highly smooth interlayer insulating film without uneven coating. The positive radiation-sensitive composition contains (A) siloxane polymer, (B) quinone diazide compound, and (C) copolymer of polymeric unsaturated compounds containing (c1) compound represented by the following formula (1), (c2) compound represented by the following formula (2) and (c3) polymeric unsaturated compound of a group represented by the following formula (3). (1) CH2=CR1COO-C<alpha>H2<alpha>-C<beta>F2 <beta> +1; (2) CH2=CR2COO-(C<gamma>H2<gamma>) a-R3.

Description

Positive radiation line sensitive compositions, interlayer dielectric and forming method thereof
Technical field
The interlayer dielectric that the present invention relates to be suitable as the positive radiation line sensitive compositions of the material of the interlayer dielectric that is used to form liquid crystal display cells (LCD), organic EL display element display elements such as (OLED), forms by said composition and this interlayer dielectric form method.
Background technology
Generally for purpose interlayer dielectric is set in the display element based on insulation between the wiring that makes layeredly configuration.Be extensive use of radiation-ray sensitive composition as the formation material of interlayer dielectric, this be because said composition to obtain the process number of necessary pattern form few, and have enough planarizations, so preferred.
In addition, the interlayer dielectric of display element must form the pattern of the contact hole of wiring usefulness.Minus composition owing to be difficult to forms the contact hole in aperture that can actual service rating, so when forming the interlayer dielectric of display element, be extensive use of positive radiation line sensitive compositions (with reference to TOHKEMY 2001-354822 communique).
On the other hand, the composition as the radiation-ray sensitive composition that forms the interlayer dielectric use mainly uses acrylic resin.With respect to this, attempted having proposed using the thermotolerance and the transparency than the composition (with reference to TOHKEMY 2000-1648 communique, TOHKEMY 2006-178436 communique) of the more excellent polysiloxane-based material of acrylic resin as radiation-ray sensitive composition.
The display elements such as TFT type liquid crystal display cells that for example use interlayer dielectric as this display element form the operation manufacturing of liquid crystal orientation film thereon then through form ELD on interlayer dielectric.In this case, interlayer dielectric is exposed under the hot conditions in the formation operation of ELD, perhaps is exposed to form in the stripper against corrosion that electrode pattern uses, so tolerance at them must be arranged.In addition, interlayer dielectric is in the developing procedure of its manufacturing process, if development time is more excessive slightly than Best Times, then developer solution is penetrated between pattern and substrate, is easy to generate and peels off, so must strict control development time.In addition, in recent years, in the display device of display elements such as use TFT type liquid crystal display cells, has big pictureization, high brightnessization, high precision int, high-speed responseization, trend such as lightening, so low-k and high permeability to the interlayer dielectric of the high radioactive ray sensitivity of the radiation-ray sensitive composition that is used to form interlayer dielectric and formation are also increasing demanding performance at present.
Because the requirement of extensively popularizing and cutting down manufacturing cost of this big frame TV in recent years, the base plate glass size of using when manufacturing has the substrate of color filter also has the trend of maximization.Therefore, in the working procedure of coating of the radiation-ray sensitive composition when on substrate, forming interlayer dielectric, be difficult to adopt present widely used spin-coating method.Therefore, for large-size glass substrate is applied, can adopt the so-called slit coating method that applies from the nozzle ejection radiation-ray sensitive composition of slit-shaped to replace this spin-coating method.This slit coating method is compared with spin-coating method, also has the advantage of the amount that can reduce the needed radiation-ray sensitive composition of coating, the manufacturing cost that also helps to cut down display element.This slit coating method be by vacuum suction with the substrate driving fit to coating platform, will be inswept on certain orientation from the coating nozzle, forming on substrate films carries out.After formation is filmed, rise by making the supporting pin of ensconcing in the hole that vacuum suction uses, substrate is picked up from coating platform, is transported to next operation.In this a series of operation, might on filming, produce the irregular of fine concavo-convex formation that the hole that is used for vacuum suction causes, become the obstacle of realization as the desired height planarization of the character of interlayer dielectric.
In this case, the strong positive radiation line sensitive compositions of wishing to develop a kind of poly organo siloxane, said composition can form as general thermotolerance, the transparency, solvent resistance and the low-dielectric excellence that requires of interlayer dielectric, and have the cured film of not having the irregular height planarization (film thickness uniformity) of coating, and has very high radioactive ray sensitivity and big development nargin (being used to form the allowed band of the development time of good pattern).
[prior art document]
[patent documentation]
[patent documentation 1] TOHKEMY 2000-1648 communique
[patent documentation 2] TOHKEMY 2006-178436 communique
Summary of the invention
The present invention is based on the problems referred to above proposition, its purpose is to provide a kind of positive radiation line sensitive compositions of poly organo siloxane, said composition can form has excellent thermotolerance, the transparency, solvent resistance and low-dielectric, and have the interlayer dielectric that does not have the irregular height planarization (film thickness uniformity) of coating, and have very high radioactive ray sensitivity and big development nargin; And the method that forms that the interlayer dielectric that formed by said composition and this interlayer dielectric are provided.
The present invention who proposes in order to solve above-mentioned problem is a kind of positive radiation line sensitive compositions, and it contains:
[A] siloxane polymer,
[B] quinone di-azido compound, and
The multipolymer of polymerizable unsaturated compound that [C] comprises the compound shown in the compound shown in (c1) following formula (1), (c2) following formula (2) and (c3) have the polymerizable unsaturated compound of the group shown in the following formula (3).
CH 2＝CR 1COO-C αH 2α-C βF 2β+1 (1)
In the formula (1), R 1Be hydrogen atom or methyl, α is 0～6 integer, and β is 1～20 integer.
CH 2＝CR 2COO-(C γH 2γ-O) a-R 3 (2)
In the formula (2), R 2Be hydrogen atom or methyl, R 3Be that carbon number is 1～12 alkyl, γ is 2 or 3, and a is a number of repeat unit, and its number average value is 1～30.
Figure BSA00000397909500041
In the formula (3), R 4, R 5, R 6, R 7And R 8Be the group shown in alkyl, phenyl or the following formula (4) of carbon number 1～20 independently of one another, b is 0～3 integer.
Figure BSA00000397909500042
In the formula (4), R 9, R 10And R 11Be the alkyl or phenyl of carbon number 1～20 independently of one another, c is 0～3 integer.
The radiation-sensitive that this positive radiation line sensitive compositions has eurymeric, by except above-mentioned [A] and [B] composition, also contain multipolymer [C] composition that forms by monomer with ad hoc structure, can form the character that can harmonious satisfy thermotolerance, the transparency, solvent resistance and the so general requirement of low-dielectric well thus, have the interlayer dielectric that does not have the irregular height planarization (film thickness uniformity) of coating.In addition, this positive radiation line sensitive compositions has excellent radioactive ray sensitivity and development nargin.
In this positive radiation line sensitive compositions, [C] multipolymer is preferably except compound (c1), compound (c2) and compound (c3), also further comprises the multipolymer of polymerizable unsaturated compound of polymerizable unsaturated compound that (c4) has the alkyl of carbon number 1～8.Thus, can improve the compatibility of [C] multipolymer, further improve the film thickness uniformity of the interlayer dielectric that obtains other composition and solvent.
In this positive radiation line sensitive compositions, [C] multipolymer also further comprises (c5) has the polymerizable unsaturated compound of plural unsaturated link in a part the multipolymer of polymerizable unsaturated compound preferably except compound (c1), compound (c2), compound (c3) and compound (c4).Thus, the film thickness uniformity and the intensity of the interlayer dielectric that obtains can be improved, general character such as thermotolerance can also be improved.
In this positive radiation line sensitive resin composition, compound (c1) is the compound shown in the following formula (5), and compound (c2) is the compound shown in the following formula (6),
[C] multipolymer is preferably by compound (c1) 25～35 quality %, compound (c2) 20～30 quality %, compound (c3) 15～20 quality %, compound (c4) 25～35 quality %, and the multipolymer of the polymerizable unsaturated compound of compound (c5) 1～5 quality % formation.
CH 2＝CR 1COOC 2H 4C βF 2β+1 (5)
In the formula (5), R 1Identical with the definition in the above-mentioned formula (1).β is 1～8 integer.
CH 2＝CR 2COO(C 2H 4O) aR 3 (6)
In the formula (6), R 2And R 3Identical with the definition in the above-mentioned formula (2) respectively, the number average value of number of repeat unit a is 4～12.
This by using [C] multipolymer, play function as the high surfactant of the low performance of surface tension, even also can improve the surface smoothing of filming, thereby can further improve the film thickness uniformity of the interlayer dielectric of formation in the ratio of using it after a little while.
[A] siloxane polymer of this positive radiation line sensitive compositions is preferably the hydrolytic condensate of the water-disintegrable silane compound shown in the following formula (7).
(R 12) x-Si-(OR 13) 4-x (7)
In the formula (7), R 12Be that carbon number is 1～20 non-water-disintegrable organic group, R 13Be that carbon number is 1～4 alkyl, x is 0～3 integer.
In this positive radiation line sensitive compositions, by using the hydrolytic condensate of the water-disintegrable silane compound shown in the above-mentioned formula (7), can further improve radioactive ray sensitivity and development nargin as [A] siloxane polymer.
This positive radiation line sensitive compositions preferably further contains [D] thermonasty acid producing agent or thermonasty alkali produces agent.Produce agent by acid or the alkali that uses this thermonasty, further promote the condensation reaction of [A] composition in the heating process after positive radiation line sensitive compositions develops, can further improve the thermotolerance and the solvent resistance of the cured film that obtains.
This positive radiation line sensitive compositions preferably further contains [E] dewatering agent.So, by further containing dewatering agent, can improve the storage stability of this positive radiation line sensitive compositions.
In addition, display element of the present invention comprises with the formation method of interlayer dielectric:
(1) operation of filming of this positive radiation line sensitive compositions of formation on substrate,
(2) operation that at least a portion of filming of operation (1) formation is shone radioactive ray,
(3) will shine the operation that is coated with film development of radioactive ray in the operation (2), and
(4) operation of filming of heating development in operation (3).
In the method, use has the excellent radioactive ray sensitivity and the above-mentioned positive radiation line sensitive compositions of development nargin, by exposure, development, the heating that utilizes radiation-sensitive, form pattern, thereby can easily form display element interlayer dielectric with fine and exquisite pattern.In addition, the character of the general requirement of the interlayer dielectric of Xing Chenging like this, just all character of thermotolerance, the transparency, solvent resistance and low-dielectric is excellent well with harmony, has simultaneously and does not have the irregular height planarization of coating.
As above illustrate described, positive radiation line sensitive compositions of the present invention above-mentioned by containing [A], [B] and [C] composition, can form the character that can harmonious satisfy thermotolerance, the transparency, solvent resistance and the so general requirement of low-dielectric well, have the interlayer dielectric that does not have the irregular height planarization of coating simultaneously.In addition, this positive radiation line sensitive compositions shows excellent radioactive ray sensitivity and development nargin.
Embodiment
Positive radiation line sensitive compositions of the present invention contains the multipolymer that [A] siloxane polymer, [B] quinone di-azido compound and [C] are formed by the monomer with ad hoc structure, can at random contain other optional member ([D] thermonasty acid producing agent or thermonasty alkali produce agent etc.).
[A] composition: siloxane polymer,
The siloxane polymer of [A] composition is so long as have the polymkeric substance of siloxane bond, and just there is no particular limitation.Should pass through self condensation formation solidfied material by [A] composition.Produce agent in joining positive radiation line sensitive compositions the time as [D] the described later thermonasty acid producing agent of optional member or thermonasty alkali, by heating, produce acidic actives or alkaline active substance, it becomes catalyzer, further promotes the condensation of [A] composition self.
Be preferably the hydrolytic condensate of the water-disintegrable silane compound shown in the above-mentioned formula (7) as the siloxane polymer of [A] composition.In this please described in " water-disintegrable silane compound " typically refer to that have can be under the coexistence of catalyst-free, excessive water, by heating in the temperature range of room temperature (about 25 ℃)～about 100 ℃, hydrolysis generates the silane compound of the hydrolization group of silanol group, perhaps has the silane compound of the hydrolization group that can form the silicone condensation thing.With respect to this, described " non-hydrolization group " be meant and do not produce hydrolysis or condensation under this hydrolysising condition, stably the group of Cun Zaiing.
In the hydrolysis reaction of the water-disintegrable silane compound shown in the above-mentioned formula (7), a part of hydrolization group can be residual with unhydrolysed state.In addition, " hydrolytic condensate of water-disintegrable silane compound " described here is meant the hydrolytic condensate that reaction between the silanol group of a part of silane compound of hydrolysis, condensation form.
As above-mentioned R 12Shown in carbon number be 1～20 non-water-disintegrable organic group, can list carbon number and be 1～12 not replacement or be replaced more than one alkyl, carbon number by vinyl, (methyl) acryloyl group or epoxy radicals is that 6～12 aryl, carbon number are aralkyl of 7～12 etc.They can be straight chain shape, chain or ring-type, at same molecular memory at a plurality of R 12The time, can be their combination.In addition, R 12Can comprise and have heteroatomic structural unit.Can list for example ether, ester, thioether etc. as this structural unit.
As above-mentioned R 13Shown carbon number is the object lesson of 1～4 alkyl, can list methyl, ethyl, n-pro-pyl, isopropyl, butyl etc.These R 13In, from viewpoint, preferable methyl and the ethyl of the easiness of hydrolysis.In addition, subscript x is 0～3 integer, and more preferably 0～2 integer is preferably 0 or 1 especially, most preferably is 1.When x was 0～2 integer, hydrolysis, condensation reaction was easier carries out, and the speed of the curing reaction that causes as [A] composition self condensation consequently becomes bigger, and then can further improve the thermotolerance and the solvent resistance of the interlayer dielectric that obtains.
As the water-disintegrable silane compound shown in the above-mentioned formula (7), can list by the silane compound of four hydrolization groups replacements, by the silane compound of a non-hydrolization group and three hydrolization group replacements, by the silane compound of two non-hydrolization groups and two hydrolization group replacements, by three non-hydrolization groups and the silane compound of a hydrolization group replacement or their potpourri.
Object lesson as the water-disintegrable silane compound shown in this above-mentioned formula (7), be respectively,
Silane compound as being replaced by four hydrolization groups can list tetramethoxy-silicane, tetraethoxysilane, four butoxy silanes, tetraphenoxy-silicane alkane, benzyloxy-4 silane, four positive propoxy silane, tetraisopropoxysilan etc.;
As the silane compounds that replaced by a non-hydrolization group and three hydrolization groups, can list chlorotrimethoxysilane, methyltrimethoxy silane, methyl triethoxysilane, methyl three isopropoxy silane, methyl three butoxy silanes, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl three isopropoxy silane, ethyl three butoxy silanes, butyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three positive propoxy silane, the 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxysilane, 3-acryloxy propyl trimethoxy silicane, 3-acryloxy propyl-triethoxysilicane, γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl triethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc.;
As by two non-hydrolization groups and two silane compounds that hydrolization group replaces, can list dichloro-dimethoxy silane, dimethyldimethoxysil,ne, dimethoxydiphenylsilane, dibutyl dimethoxy silane etc.;
As by three non-hydrolization groups and the silane compound that hydrolization group replaces, can list three chloro methoxy silane, tributyl methoxy silane, trimethyl methoxy silane, trimethylethoxysilane, tributyl Ethoxysilane etc.
In the water-disintegrable silane compound shown in these above-mentioned formulas (7), preferably by the silane compound of 4 hydrolization groups replacements and by a non-hydrolization group and three silane compounds that hydrolization group replaces, especially preferably by a non-hydrolization group and three silane compounds that hydrolization group replaces.As the object lesson of preferred water-disintegrable silane compound, can list tetraethoxysilane, methyltrimethoxy silane, methyl triethoxysilane, methyl three isopropoxy silane, methyl three butoxy silanes, phenyltrimethoxysila,e, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl three isopropoxy silane, ethyl three butoxy silanes, butyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxysilane.This water-disintegrable silane compound can be used alone, and perhaps also can make up two or more uses.
Make the condition of the water-disintegrable silane compound hydrolysis shown in the above-mentioned formula (7), condensation so long as make at least a portion hydrolysis of the water-disintegrable silane compound shown in the above-mentioned formula (7), change hydrolization group into silanol group, the generation condensation reaction, just there is no particular limitation, can example of following enforcement.The water that uses in the hydrolysis of the water-disintegrable silane compound shown in the above-mentioned formula (7), the condensation preferably uses the refining water of methods such as anti-seepage membrane processing, ion-exchange treatment, distillation.By using this Purified Water, can suppress subsidiary reaction, improve the reactivity of hydrolysis.The consumption of water is with respect to the hydrolization group (OR that amounts to the water-disintegrable silane compound shown in the above-mentioned formula of 1mol (7) 13), be preferably 0.1～3mol, more preferably 0.3～2mol, the more preferably amount of 0.5～1.5mol.By using the water of this amount, can make the reaction velocity optimization of hydrolysis, condensation.
As the solvent that can use in the hydrolysis of the water-disintegrable silane compound shown in the above-mentioned formula (7), condensation, there is no particular limitation, can use the same solvent of solvent that uses in the preparation with positive radiation line sensitive compositions described later usually.As the preferred example of this solvent, can list ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene-glycol monoalky lether, propylene-glycol monoalky lether acetic acid esters, propionic acid ester.In these solvents, preferred especially diethylene glycol dimethyl ether, diethylene glycol ethyl-methyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol monomethyl ether or 3-methoxypropionic acid methyl esters.
The hydrolysis of the water-disintegrable silane compound shown in the above-mentioned formula (7), condensation reaction are preferably at acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetate, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acid-exchange resin, various lewis acid), base catalyst (for example, nitrogen-containing compounds such as ammonia, primary amine, secondary amine, tertiary amine, pyridine; Deacidite; Oxyhydroxide such as NaOH; Carbonate such as sal tartari; Carboxylates such as sodium acetate; Various lewis bases) or under the existence of alkoxide catalyzer such as (for example, alkoxide zirconium, alkyl dioxide, aluminum alkoxide) carry out.For example, can use tetraisopropoxide aluminium as aluminum alkoxide.As catalyst consumption,,, be preferably below the 0.2mol, more preferably 0.00001～0.1mol with respect to the monomer of the water-disintegrable silane compound of 1mol from promoting the viewpoint of hydrolysis, condensation reaction.
The hydrolysis of the water-disintegrable silane compound shown in the above-mentioned formula (7), the temperature of reaction in the condensation and reaction time can suitably be set.For example, can adopt following condition.Temperature of reaction is preferably 40～200 ℃, more preferably 50～150 ℃.Reaction time is preferably 30 minutes～and 24 hours, more preferably 1～12 hour.By choosing this temperature of reaction and reaction time, can be hydrolyzed most effectively, condensation reaction.In this hydrolysis, condensation, can be in reactive system the water-disintegrable silane compound of disposable interpolation, water and catalyzer, carry out one-step reaction; Perhaps also can divide and in reactive system, add water-disintegrable silane compound, water and catalyzer several times, carry out the hydrolysis and the condensation reaction of multistep.In addition, after hydrolysis, the condensation reaction, add dewatering agent,, remove the alcohol that anhydrates and generate from reactive system then by evaporation.The dewatering agent that uses in this stage, general because absorption or the excessive water of inclusion, dehydration can complete obiteration, perhaps removes by evaporation, so and be not counted in the category of dewatering agent of aftermentioned [E] composition that adds in the positive radiation line sensitive compositions.
The molecular weight of the hydrolytic condensate of the water-disintegrable silane compound shown in the above-mentioned formula (7) can be measured with the number-average molecular weight of polystyrene conversion by using the GPC (gel permeation chromatography) of tetrahydrofuran as mobile phase.And the number-average molecular weight of hydrolytic condensate is preferably 5.0 * 10 usually 2～1.0 * 10 4Scope in value, more preferably 1.0 * 10 3～5.0 * 10 3Value in the scope.The value of the number-average molecular weight by making hydrolytic condensate is 5.0 * 10 2More than, can improve the film forming of filming of positive radiation line sensitive compositions.On the other hand, the value of the number-average molecular weight by making hydrolytic condensate is 1.0 * 10 4Below, can prevent that the radiation-sensitive of radiation-ray sensitive composition is low.
[B] composition: quinone di-azido compound
[B] composition is the quinone di-azido compound that produces carboxylic acid by the irradiation radioactive ray.The positive radiation line sensitive compositions that contains this quinone di-azido compound has the positive radiation line sensitive natur of removing the exposed portion in the operation of radiating irradiation by developing procedure.Quinone di-azido compound as [B] composition preferably uses by making the compound with phenolic hydroxyl group and the naphthoquinones two nitrine sulfonic acid halides that constitute parent nucleus carry out the compound that esterification obtains.As the example of the compound with phenolic hydroxyl group, the ortho position and the contraposition that can list phenolic hydroxyl group are the compound of the substituent any situation shown in hydrogen or the following formula (8) independently of one another.
Figure BSA00000397909500121
In the formula, R 14, R 15And R 16Represent that independently of one another carbon number is any situation of the phenyl of 1～10 alkyl, carboxyl, phenyl, replacement.In addition, can be by R 14, R 15And R 16In two or three form ring.
In the substituting group shown in the above-mentioned formula (8), R 14, R 15, R 16Be carbon number when being 1～10 alkyl, this alkyl can be substituted, and also can not be substituted.As the example of this alkyl, can list methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the tert-butyl group, n-hexyl, cyclohexyl, n-heptyl, n-octyl, trifluoromethyl, 2-carboxy ethyl.Substituting group as the phenyl that replaces can list hydroxyl etc.In addition, as can be by R 14, R 15, R 16In two or three form the example of ring, can list cyclopentane ring, cyclohexane ring, diamantane ring, fluorenes ring.
As the example of compound, can list the group of the compound shown in following formula (9) and (10) with phenolic hydroxyl group.
Figure BSA00000397909500131
Figure BSA00000397909500141
As other example of the compound with phenolic hydroxyl group, can list 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] xenol, 1,1,1-three (p-hydroxybenzene) ethane etc.
As naphthoquinones two nitrine sulfonic acid halides, can use 4-naphthoquinones two nitrine sulfonic acid halides or 5-naphthoquinones two nitrine sulfonic acid halides.The ester compounds (naphthoquinones two triazo-compounds) that is obtained by 4-naphthoquinones two triazo-compounds is owing to have absorption in i line (wavelength 365nm) zone, so be fit to the i line exposing.In addition, the ester compounds (naphthoquinones two triazo-compounds) that is obtained by 5-naphthoquinones two triazo-compounds absorbs owing to the wavelength region may at wide region exists, so be fit to the wavelength exposure of wide region.Preferably select ester compounds that obtains by 4-naphthoquinones two nitrine sulfonic acid halides or the ester compounds that obtains by 5-naphthoquinones two nitrine sulfonic acid halides according to the wavelength of exposure.As particularly preferred quinone di-azido compound, can list 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] xenol (1.0mol) and 1, the condensation product of 2-naphthoquinones two nitrine-5-sulfonic acid chloride (2.0mol).
The molecular weight of quinone di-azido compound is preferably 300～1500, and more preferably 350～1200.By the molecular weight that makes quinone di-azido compound is more than 300, and that the transparency of the interlayer dielectric that forms can be kept is very high.On the other hand, be below 1500 by the molecular weight that makes quinone di-azido compound, the pattern that can suppress positive radiation line sensitive compositions forms the reduction of energy.
These [B] compositions can be used alone, or make up two or more uses.The consumption of [B] composition in the positive radiation line sensitive compositions is preferably 5～100 mass parts with respect to 100 mass parts [A] composition, more preferably 10～50 mass parts.By the consumption that makes [B] composition is 5～100 mass parts, can make the illuminated portion of radioactive ray and non-irradiated part very big to difference as the solubleness of the aqueous alkali of developer solution, form the functional of pattern, and the solvent resistance of the interlayer dielectric that obtains is also good.
[C] composition: the multipolymer that forms by monomer with ad hoc structure
[C] composition is the multipolymer that comprises at least from the structural unit of the polymerizable compound with above-mentioned ad hoc structure (c1), polymerizable compound (c2) and polymerizable compound (c3).In this positive radiation line sensitive compositions, multipolymer [C] plays the function as the high surfactant of the low performance of surface tension, even when less ratio is used this material, also can significantly improve the profile pattern of the interlayer dielectric of formation.
In this positive radiation line sensitive compositions, multipolymer [C] preferably further has the structural unit that has the polymerizable unsaturated compound that carbon number is 1～8 unsubstituted alkyl ester group (below, also abbreviate " polymerizable compound (c4) " as) from (c4); Has the structural unit that in a part, has the polymerizable unsaturated compound (below, also abbreviate " polymerizable compound (c5) " as) of plural unsaturated link from (c5) in addition and then more preferably; Especially preferably form by the composition that contains above-mentioned polymerizable compound (c1), polymerizable compound (c2), polymerizable compound (c3), polymerizable compound (c4) and polymerizable compound (c5).
Group-C in the above-mentioned formula (1) αH 2 α-be the alkylidene of methylene or alkyl methylene or a straight chain shape or a chain.Group-C αH 2 α-when being non-left-right symmetric, its closure is not limit.Group-C αH 2 α-carbon number α be preferably 2～4.As group-C αH 2 α-object lesson, for example can list 1,2-ethylidene, 1,2-propylidene, 1,3-propylidene, 1,4-butylidene etc.; Among them, preferred 1,2-ethylidene or 1, the 3-propylidene, preferred especially 1, the 2-ethylidene.
Group-C in the above-mentioned formula (1) βF 2 β+1It is the fluoro-alkyl of a straight chain shape or a chain.Group-C βF 2 β+1Carbon number β be 1～20, be preferably 1～12, more preferably 1～8, be preferably 2～8 especially.Group-C βF 2 β+1Be preferably the fluoro-alkyl of straight chain shape.
Be preferably the compound shown in the above-mentioned formula (5) as the polymerizable compound among the present invention (c1).As the object lesson of compound (c1), can list the following formula (c1-1) and (c1-8) compound etc. of expression respectively.
CH 2＝CHCOOC 2H 4C 8F 17 (c1-1)
CH 2＝C(CH 3)COOC 2H 4C 8F 17 (c1-2)
CH 2＝CHCOOC 2H 4C 6F 13 (c1-3)
CH 2＝C(CH 3)COOC 2H 4C 6F 13 (c1-4)
CH 2＝CH?CO?OC 2H 4C 4F 9 (c1-5)
CH 2＝C(CH 3)COOC 2H 4C 4F 9 (c1-6)
CH 2＝CHCOOC 2H 4C 2F 5 (c1-7)
CH 2＝C(CH 3)COOC 2H 4C 2F 5 (c1-8)
Group-C in the above-mentioned formula (2) γH 2 γ-be the alkylidene of a straight chain shape or a chain.Group-C γH 2 γ-when being non-left-right symmetric, its closure is not limit.As group-C γH 2 γ-object lesson, for example can list 1,2-ethylidene and 1, the 2-propylidene, preferred 1, the 2-ethylidene.
Compound (c2) uses with the potpourri of the different compound of the value of the number of repeat unit a in the above-mentioned formula (2).The number average value of a is 1～30, is preferably 2～20, is preferably 4～12 especially.In compound (c2), be respectively to be 2 o'clock at γ, (methyl) acrylic acid and reacting ethylene oxide are synthesized, be 3 o'clock at γ, make (methyl) acrylic acid and propylene oxide reaction synthetic.At this moment, with respect to 1mol (methyl) acrylic acid, the oxirane of importing or the molal quantity of epoxypropane are according to the value of a and different.This a value at compound (c2) can be by trying to achieve gel permeation chromatography the number-average molecular weight of polystyrene conversion, molal quantity from oxirane or epoxypropane with respect to the importing of 1mol (methyl) acrylic acid add calculates the value of above-mentioned number-average molecular weight of trying to achieve and tries to achieve.
Be fit to commodity in use as compound (c2).As the example of this commodity, can enumerate village's chemical industry (Co., Ltd.) is made in making new advances NK-エ ス テ Le M-40G, NK-エ ス テ Le M-90G, AM-90G; Block レ Application マ one PME-200, PME-400, PME-550 etc. that day oil (Co., Ltd.) is made.
There are a plurality of R respectively in above-claimed cpd (c3) in above-mentioned formula (3) 5And R 6The time, each R 5Can be identical, also can be different, each R 6Can be identical, also can be different.In addition, in above-mentioned formula (4), there are a plurality of R respectively 10And R 11The time, each R 10Can be identical, also can be different, each R 11Can be identical, also can be different.In addition, as compound (c3), preferably in above-mentioned formula (3), R 4, R 5And R 6Be respectively that carbon number is 1～20 alkyl or phenyl, and R 7And R 8It is respectively polymerizable unsaturated compound with the group shown in the above-mentioned formula (4).
Preferably can use the compound shown in the following formula (c3-1) as compound (c3).
Figure BSA00000397909500181
In the formula (c3-1), R SiBe the group shown in the above-mentioned formula (4), R 15Be hydrogen atom or methyl, d is 1～3 integer.
As the object lesson of compound (c3-1), can list following formula (c3-1-1), (c3-1-2) and (c3-1-3) compound of expression etc. respectively.
Figure BSA00000397909500182
In the formula (c3-1-1), Me is a methyl, and r, s and t are respectively 0～3 integers.
Figure BSA00000397909500191
In the formula (c3-1-2), definition similarly in Me and r, s and t and the above-mentioned formula (c3-1-1).
Figure BSA00000397909500192
In the formula (c3-1-3), definition similarly in Me and r, s and t and the above-mentioned formula (c3-1-1), Ph is a phenyl.
Can list as compound (c4) that for example to have carbon number be (methyl) alkyl acrylate of 1～8 unsubstituted alkyl ester group etc.As the object lesson of compound (c4), can list methacrylic acid n-butyl, methyl methacrylate, 2-ethylhexyl acrylate etc.
As compound (c5), for example can list 1,4-butylene glycol, the degree of polymerization are that 1～20 polyglycol, the degree of polymerization are the compound of the two terminal methyl group acroleic acid esterifications of polypropylene glycol of 1～20 etc.Be fit to commodity in use as compound (c5).As the example of this commodity, can enumerate village's chemical industry (Co., Ltd.) is made in making new advances NK-エ ス テ Le 1G, NK-エ ス テ Le 2G, NK-エ ス テ Le 3G, NK-エ ス テ Le 4G, NK-エ ス テ Le 9G, NK-エ ス テ Le 14G etc.
Multipolymer [C] is when having above-mentioned this structural unit from polymerizable compound (c1), polymerizable compound (c2) and polymerizable compound (c3), each polymerizable compound with respect to the usage ratio of the total amount of these polymerizable compounds is, polymerizable compound (c1) is 10～55 quality %, polymerizable compound (c2) is 10～50 quality %, and polymerizable compound (c3) is 5～45 quality %.
Multipolymer [C] is when the structural unit that further has from polymerizable compound (c4), each polymerizable compound with respect to the usage ratio of the total amount of these polymerizable compounds is, polymerizable compound (c1) is 20～50 quality %, polymerizable compound (c2) is 15～40 quality %, and polymerizable compound (c3) is that 10～30 quality %, polymerizable compound are 20～35 quality %.
Multipolymer [C] is when the structural unit that further has from polymerizable compound (c5), each polymerizable compound with respect to the usage ratio of the total amount of these polymerizable compounds is, polymerizable compound (c1) is 25～35 quality %, polymerizable compound (c2) is 20～30 quality %, polymerizable compound (c3) is that 15～20 quality %, polymerizable compound (c4) are 25～35 quality %, and polymerizable compound (c5) is 1～5 quality %.The compound (c1)～(c5) that is used to form multipolymer [C] can use separately respectively, also can mix multiple use.
The quality mean molecular weight (Mw) of multipolymer [C] is 5,000～25,000, be preferably 10,000～25,000, and be preferably 15,000～25,000 especially.The molecular weight distribution (Mw/Mn) (Mw is with respect to the ratio of number-average molecular weight Mn) of multipolymer [C] is preferably 1～10, and more preferably 2～4.
There is no particular limitation for the manufacture method of multipolymer [C], can pass through known method, for example based on polymerization mechanisms such as radical polymerization, cationic polymerization, anionic polymerizations, by manufacturings such as solution polymerization process, mass polymerization, emulsion polymerizations.In these manufacture methods and since solution in radical polymerization simple, industrial be preferred.
The polymerization initiator that uses during as manufacturing multipolymer [C] can list for example superoxide such as benzoyl peroxide, diacyl peroxide; 2,2 '-azo-compound such as azoisobutyronitrile, phenylazo triphenyl hexane etc.
The manufacturing of multipolymer [C] can be carried out under any situation in the presence of solvent or not, but from the operation aspect, preferably carries out in the presence of solvent.As above-mentioned solvent, for example can list alcohol, ketone, monocarboxylic Arrcostab, ether, propylene glycol and ester thereof, halogenated hydrocarbons, aromatic hydrocarbons, fluoridize inert fluid, other polar solvent etc.
Example as these solvents is:
As above-mentioned alcohol, can list for example ethanol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, the tert-butyl alcohol etc.;
As above-mentioned ketone, can list for example acetone, MEK, methyl isobutyl ketone, methylamino ketone etc.;
As above-mentioned monocarboxylic Arrcostab, can list for example methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, 2-oxo methyl propionate, ethyl 2-oxopropanoate, 2-oxo propyl propionate, 2-oxo butyl propionate, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester etc.;
As above-mentioned ether, can list for example methyl cellosolve, cellosolve, butyl cellosolve, the complete alcohol of butyl card, ethyl cellosolve acetate, tetrahydrofuran, diox etc.;
As above-mentioned propylene glycol and ester thereof, can list for example propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol single-butyl ether acetic acid esters etc.;
As above-mentioned halogenated hydrocarbons, for example can list 1,1,1-trichloroethanes, chloroform etc.;
As above-mentioned aromatic hydrocarbons, can list for example benzene,toluene,xylene etc.;
As the above-mentioned inert fluid of fluoridizing, can list for example PFO, perfluor tri-n-butyl amine etc.;
As above-mentioned other polar solvent, can list for example dimethyl formamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone etc.
These solvents can use a kind separately, two or more suitable mixing can be used.
When making multipolymer [C], as required, can further use chain-transferring agents such as lauryl mercaptan, 2 mercapto ethanol, ethyl thioacetate, thioacetic acid monooctyl ester.
The usage ratio of the multipolymer [C] in this positive radiation line sensitive compositions is with respect to 100 mass parts [A] composition, is preferably 0.01～3 mass parts, more preferably 0.05～2 mass parts.Has the interlayer dielectric that does not have the irregular height planarization of coating by using [C] composition with this ratio, can forming.
Other optional member
Positive radiation line sensitive compositions of the present invention is except above-mentioned [A]～[C] composition, in the scope of not damaging desirable effect, can contain [D] thermonasty acid producing agent or thermonasty alkali as required and produce other optional members such as agent, [E] dewatering agent.
Thermonasty acid producing agent of [D] composition or thermonasty alkali generation agent are defined as to be heated can emit the compound of acidic actives or alkaline active substance, the effect of the catalyzer when this acidic actives or alkaline active substance play as siloxane polymer (being preferably the hydrolytic condensate of the water-disintegrable silane compound shown in the above-mentioned formula (7)) self condensation that makes [A] composition, curing.The compound of this by using [D] composition can further improve the thermotolerance and the solvent resistance of the interlayer dielectric that obtains.In addition, thermonasty acid producing agent or alkali as [D] composition produce agent, can not emit acidic actives or alkaline active substance when being preferably prebake with the lower temperature (for example 70～120 ℃) in the formation operation of filming of positive radiation line sensitive compositions, when curing after the temperature (for example 120～250 ℃) that the ratio in the heating process after development is higher, emit the material of the character of acidic actives or alkaline active substance.
As [D] composition thermonasty acid producing agent, can list for example salt, sulfimine compounds etc. such as diphenyl iodnium, triphenyl sulfonium salt, sulfonium salt, benzothiazolium salt, ammonium salt, phosphonium salt, thiophane salt.
Example as diphenyl iodnium, can list diphenyl iodine tetrafluoroborate, diphenyl iodine hexafluorophosphate, diphenyl iodine hexafluoro arsenate, diphenyl iodine fluoroform sulphonate, diphenyl iodine trifluoroacetate, diphenyl iodo-tosilate, diphenyl iodine butyl three (2,6-difluoro-benzene base) borate, 4-methoxyphenyl-phenyl-iodide tetrafluoroborate, two (4-tert-butyl-phenyl) iodine tetrafluoroborate, two (4-tert-butyl-phenyl) iodine hexafluoro arsenate, two (4-tert-butyl-phenyl) iodine fluoroform sulphonate, two (4-tert-butyl-phenyl) iodine trifluoroacetate, two (4-tert-butyl-phenyl) iodo-tosilate, two (4-tert-butyl-phenyl) iodine camsilate etc.
Example as the triphenyl sulfonium salt, can list triphenylsulfonium fluoroform sulphonate, triphenylsulfonium camsilate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-tosilate, triphenylsulfonium butyl three (2,6-difluoro-benzene base) borate etc.
As the example of sulfonium salt, can list the benzyl sulfonium salt of alkyl sulfonium salt, benzyl sulfonium salt, dibenzyl sulfonium salt, replacement etc.
As these sulfonium salts, can list respectively:
As the alkyl sulfonium salt is for example 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro stibate, 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro arsenate, dimethyl-4-(benzyloxycarbonyloxy) phenyl sulfonium hexafluoro stibate, dimethyl-4-(benzoyl oxygen base) phenyl sulfonium hexafluoro stibate, dimethyl-4-(benzoyl oxygen base) phenyl sulfonium hexafluoro arsenate, dimethyl-3-chloro-4-acetoxyl group phenyl sulfonium hexafluoro stibate etc.;
As the benzyl sulfonium salt is for example benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro stibate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro phosphate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro stibate, benzyl-4-methoxybenzene ylmethyl sulfonium hexafluoro stibate, benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro stibate, benzyl-3-chloro-4-hydroxy phenyl methyl sulfonium hexafluoro arsenate, 4-methoxy-benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro phosphate etc.;
As the dibenzyl sulfonium salt is for example dibenzyl-4-hydroxy phenyl sulfonium hexafluoro stibate, dibenzyl-4-hydroxy phenyl sulfonium hexafluoro phosphate, 4-acetoxyl group phenyl dibenzyl sulfonium hexafluoro stibate, dibenzyl-4-methoxyphenyl sulfonium hexafluoro stibate, dibenzyl-3-chloro-4-hydroxy phenyl sulfonium hexafluoro arsenate, dibenzyl-3-methyl-4-hydroxyl-5-tert-butyl-phenyl sulfonium hexafluoro stibate, benzyl-4-methoxy-benzyl-4-hydroxy phenyl sulfonium hexafluoro phosphate etc.;
As the benzyl sulfonium salt that replaces be for example to chloro benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro stibate, to nitrobenzyl-4-hydroxy phenyl methyl sulfonium hexafluoro stibate, to chloro benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro phosphate, to nitrobenzyl-3-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro stibate, 3,5-dichloro-benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro stibate, adjacent chloro benzyl-3-chloro-4-hydroxy phenyl methyl sulfonium hexafluoro stibate etc.
As the example of benzothiazolium salt, can list 3-benzyl benzothiazole hexafluoro stibate, 3-benzyl benzothiazole hexafluoro phosphate, 3-benzyl benzothiazole tetrafluoroborate, 3-(to methoxy-benzyl) benzothiazole hexafluoro stibate, 3-benzyl-2-methyl-thio-benzothiazole hexafluoro stibate, 3-benzyl-5-chloro benzo thiazole hexafluoro stibate etc.
Example as thiophane salt, can list 1-(4-n-butoxy naphthalene-1-yl) thiophane three fluoro mesylates, the positive fourth sulfonate of 1-(4-n-butoxy naphthalene-1-yl) thiophane nine fluoro, 1-(4-n-butoxy naphthalene-1-yl) thiophane-1,1,2,2-tetrafluoro generation-2-(norbornane-2-yl) esilate, 1-(4-n-butoxy naphthalene-1-yl) thiophane-2-(5-tert-butoxycarbonyl oxygen base two ring [2.2.1] heptan-2-yl)-1,1,2, the 2-tetrafluoro is for esilate, 1-(4-n-butoxy naphthalene-1-yl) thiophane-2-(6-tert-butoxycarbonyl oxygen base two ring [2.2.1] heptan-2-yl)-1,1,2, the 2-tetrafluoro is for esilate, 1-(4,7-dibutoxy-1-naphthyl) thiophane fluoroform sulphonate etc.
Example as sulfimine compound, can list N-(trifluoromethyl sulfonyloxy) succinimide (trade name " SI-105 " (body ど り chemistry (Co., Ltd.) manufacturing)), N-(camphor sulfonyloxy) succinimide (trade name " SI-106 " (body ど り chemistry (Co., Ltd.) manufacturing)), N-(4-aminomethyl phenyl sulfonyloxy) succinimide (trade name " SI-101 " (body ど り chemistry (Co., Ltd.) manufacturing)), N-(2-trifluoromethyl sulfonyloxy) succinimide, N-(4-fluoro phenyl sulfonyloxy) succinimide, N-(trifluoromethyl sulfonyloxy) phthalimide, N-(camphor sulfonyloxy) phthalimide, N-(2-trifluoromethyl sulfonyloxy) phthalimide, N-(2-fluoro phenyl sulfonyloxy) phthalimide, N-(trifluoromethyl sulfonyloxy) diphenyl maleimide (trade name " PI-105 " (body ど り chemistry (Co., Ltd.) manufacturing)), N-(camphor sulfonyloxy) diphenyl maleimide, 4-(aminomethyl phenyl sulfonyloxy) diphenyl maleimide, N-(2-trifluoromethyl sulfonyloxy) diphenyl maleimide, N-(4-fluoro phenyl sulfonyloxy) diphenyl maleimide, N-(4-fluoro phenyl sulfonyloxy) diphenyl maleimide, N-(phenyl sulfonyloxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide (trade name " NDI-100 " (body ど り chemistry (Co., Ltd.) manufacturing)), N-(4-aminomethyl phenyl sulfonyloxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide (trade name " NDI-101 " (body ど り chemistry (Co., Ltd.) manufacturing)), N-(trifluoro-methanesulfonyl oxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide (trade name " NDI-105 " (body ど り chemistry (Co., Ltd.) manufacturing)), N-(nine fluoro fourth sulfonyloxies) two ring [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide (trade name " NDI-109 " (body ど り chemistry (Co., Ltd.) manufacturing)), N-(camphor sulfonyloxy) two ring [2.2.1] heptan-5-alkene-2, and 3-dicarboxyl acid imide (trade name " NDI-106 " (body ど り chemistry (Co., Ltd.) manufacturing));
N-(camphor sulfonyloxy)-7-oxabicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(trifluoromethyl sulfonyloxy)-7-oxabicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(4-aminomethyl phenyl sulfonyloxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(4-aminomethyl phenyl sulfonyloxy)-7-oxabicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-trifluoromethyl sulfonyloxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-trifluoromethyl sulfonyloxy)-7-oxabicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(4-fluoro phenyl sulfonyloxy) two ring [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(4-fluoro phenyl sulfonyloxy)-7-oxabicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(trifluoromethyl sulfonyloxy) two ring [2.2.1] heptane-5,6-oxo-2,3-dicarboxyl acid imide, N-(camphor sulfonyloxy) two ring [2.2.1] heptane-5,6-oxo-2,3-dicarboxyl acid imide, N-(4-aminomethyl phenyl sulfonyloxy) two ring [2.2.1] heptane-5,6-oxo-2,3-dicarboxyl acid imide, N-(2-trifluoromethyl sulfonyloxy) two ring [2.2.1] heptane-5,6-oxo-2,3-dicarboxyl acid imide, N-(4-fluoro phenyl sulfonyloxy) two ring [2.2.1] heptane-5,6-oxo-2,3-dicarboxyl acid imide, N-(trifluoromethyl sulfonyloxy) naphthyl dicarboxyl acid imide (trade name " NAI-105 " (body ど り chemistry (Co., Ltd.) manufacturing)), N-(camphor sulfonyloxy) naphthyl dicarboxyl acid imide (trade name " NAI-106 " (body ど り chemistry (Co., Ltd.) manufacturing)), N-(4-aminomethyl phenyl sulfonyloxy) naphthyl dicarboxyl acid imide (trade name " NAI-101 " (body ど り chemistry (Co., Ltd.) manufacturing)), N-(phenyl sulfonyloxy) naphthyl dicarboxyl acid imide (trade name " NAI-100 " (body ど り chemistry (Co., Ltd.) manufacturing)), N-(2-trifluoromethyl sulfonyloxy) naphthyl dicarboxyl acid imide, N-(4-fluoro phenyl sulfonyloxy) naphthyl dicarboxyl acid imide, N-(pentafluoroethyl group sulfonyloxy) naphthyl dicarboxyl acid imide, N-(seven fluoropropyl sulfonyloxies) naphthyl dicarboxyl acid imide, N-(nine fluoro butyl sulfonyloxies) naphthyl dicarboxyl acid imide (trade name " NAI-109 " (body ど り chemistry (Co., Ltd.) manufacturing)), N-(ethyl sulfonyloxy) naphthyl dicarboxyl acid imide, N-(sulfonyl propyl oxygen base) naphthyl dicarboxyl acid imide, N-(butyl sulfonyloxy) naphthyl dicarboxyl acid imide (trade name " NAI-1004 " (body ど り chemistry (Co., Ltd.) manufacturing)), N-(amyl group sulfonyloxy) naphthyl dicarboxyl acid imide, N-(hexyl sulfonyloxy) naphthyl dicarboxyl acid imide, N-(heptyl sulfonyloxy) naphthyl dicarboxyl acid imide, N-(octyl group sulfonyloxy) naphthyl dicarboxyl acid imide, N-(nonyl sulfonyloxy) naphthyl dicarboxyl acid imide etc.
In these thermonasty acid producing agents,, preferably use triphenyl sulfonium salt, sulfonium salt, benzothiazolium salt and thiophane salt from the thermotolerance and the solvent resistance aspect of the interlayer dielectric that improves gained.Among them, especially preferably use the triphenylsulfonium fluoroform sulphonate, the triphenylsulfonium camsilate, 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro arsenate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, dibenzyl-4-hydroxy phenyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, 3-benzyl benzothiazole hexafluoro antimonate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, 1-(4,7-dibutoxy-1-naphthyl) thiophane fluoroform sulphonate, N-(trifluoromethyl sulfonyloxy) naphthyl dicarboxyl acid imide.
Produce the example of agent as the thermonasty alkali of [D] composition; can list 2-nitrobenzyl cyclohexyl carbamate; [[(2; 6-dinitro benzyl) oxygen base] carbonyl] cyclo-hexylamine; N-(2-nitrobenzyl oxygen base carbonyl) pyrrolidine; two [[(2-nitrobenzyl) oxygen base] carbonyl] hexane-1, the 6-diamines; triphenylcarbinol; O-carbamyl hydroxy amide; O-carbamyl oxime; 4-(methyl thiobenzoyl)-1-methyl isophthalic acid-morpholino ethane; (4-morpholino benzoyl)-1-benzyl-1-dimethylaminopropanecompounds; 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone; hexamine cobalt (III) three (trityl group borate) etc.The thermonasty alkali of these [D] compositions produces in the agent, from the stable on heating viewpoint of the interlayer dielectric that improves gained, preferred especially 2-nitrobenzyl cyclohexyl carbamate and O-carbamyl hydroxy amide.
Thermonasty acid producing agent of [D] composition or thermonasty alkali generation agent can be used any one in acid or the alkali, can be used alone, and also can be use mixing two or more.Amount when using [D] composition with respect to 100 mass parts [A] composition, is preferably 0.1 mass parts～20 mass parts, more preferably 1 mass parts～10 mass parts.By the consumption that makes [D] composition is 0.1 mass parts～20 mass parts, the positive radiation line sensitive compositions of the thermotolerance of the interlayer dielectric that can obtain forming and solvent resistance excellence, and produce precipitate in the formation operation that can prevent to film, form easily and film.
The dewatering agent of [E] composition is defined as by chemical reaction and changes water into water material in addition, perhaps catches the material of water by physisorption or inclusion.Contain [E] dewatering agent by optional in this positive radiation line sensitive compositions, can reduce the moisture of invading from external environment condition.Therefore,, can reduce the moisture in the composition, thereby improve the storage stability of composition by using [E] dewatering agent.As this [E] dewatering agent, the preferred at least a compound that uses in the group that is selected from carboxylate, acetals (comprising ketals) and carboxylic acid anhydrides formation.
As the preferred example of carboxylate, can list original carboxylic acid ester, carboxylic acid silyl ester etc.As original carboxylic acid ester's object lesson, can list original acid A ester, ethyl orthoformate, orthoformic acid propyl ester, orthoformic acid butyl ester, ortho-acetic acid methyl esters, ethyl orthoacetate, ortho-acetic acid propyl ester, ortho-acetic acid butyl ester, former methyl propionate, former ethyl propionate base etc.In addition, among these original carboxylic acid esters, orthoformates such as preferred especially original acid A ester.As the object lesson of carboxylic acid silyl ester, can list acetate trimethyl silyl ester, acetate tributyl silyl ester, formic acid trimethyl silyl ester, oxalic acid trimethyl silyl ester etc.
As the preferred example of acetals, can list reactant, the ketenes silicyl acetals of reactant, ketone and the dibasic alcohol of ketone and alcohol.As the object lesson of ketone, can list dimethylacetal, diethyl acetal, dipropyl acetal etc. with the reactant of alcohol.
As the preferred example of carboxylic acid anhydrides, can list formic anhydride, acetic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoyl oxide, acetate benzoyl oxide etc.In these carboxylic acid anhydrides, aspect dehydrating effect, preferred acetic anhydride and succinic anhydride.
Combined amount when using [E] dewatering agent with respect to 100 mass parts [A] composition, is preferably 0.001～10 mass parts, and more preferably 0.01～5 mass parts is preferably 0.03～1 mass parts especially.By the consumption that makes [E] dewatering agent is 0.001～10 mass parts, can improve the storage stability of positive radiation line sensitive compositions.
Positive radiation line sensitive compositions
Multipolymer that the quinone di-azido compound of the siloxane polymer of positive radiation line sensitive compositions of the present invention by mixing above-mentioned [A] composition, [B] composition, the monomer by ad hoc structure of [C] composition form and the optional member (thermonasty acid producing agent of [D] composition or thermonasty alkali produce agent etc.) that contains as required prepare.Usually, preferably preparation under the state of dissolving or dispersion, use in suitable [F] solvent of positive radiation line sensitive compositions.For example, in solvent,, can prepare positive radiation line sensitive compositions by [A], [B] and [C] composition and optional member are mixed with the ratio of regulation.
As [F] solvent that can use in the preparation of this positive radiation line sensitive compositions, suitable use is dissolved each composition equably or is disperseed, and the solvent of each composition reaction of getting along well.As this solvent, for example can list alcohols, ethers, diethylene glycol alkyl ether, ethylene glycol alkyl ether acetate esters, propylene-glycol monoalky lether class, propylene-glycol monoalky lether acetate esters, propylene-glycol monoalky lether propionic acid ester, aromatic hydrocarbon based, ketone, ester class etc.
Can list respectively as these solvents:
As alcohols is for example phenmethylol, diacetone alcohol etc.;
As ethers is dialkyl ether such as tetrahydrofuran and Di Iso Propyl Ether, di-n-butyl ether, two n-pentyl ethers, diisoamyl ether, di-n-hexyl ether etc. for example;
As the diethylene glycol alkyl ether is for example diethylene glycol monomethyl ether, TC, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl-methyl ether etc.;
As ethylene glycol alkyl ether acetate esters is for example methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetic acid esters, ethylene glycol monomethyl ether acetate etc.;
As the propylene-glycol monoalky lether class is for example propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, propylene glycol single-butyl ether etc.;
As the propylene-glycol monoalky lether acetate esters is for example propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol list propyl ether acetic acid esters, propylene glycol single-butyl ether acetic acid esters etc.;
As the propylene-glycol monoalky lether propionic acid ester is for example propylene glycol monomethyl ether propionic ester, propylene glycol list ethylether propionic ester, propylene glycol list propyl ether propionic ester, propylene glycol single-butyl ether propionic ester etc.;
As aromatic hydrocarbon based be for example toluene, dimethylbenzene etc.;
As ketone is for example methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2 pentanone etc.;
As the ester class is methyl acetate for example, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, the 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, the glycolic acid butyl ester, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid propyl ester, 3-hydracrylic acid butyl ester, 2-hydroxy-3-methyl methyl butyrate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid propyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the ethoxyacetic acid propyl ester, the ethoxyacetic acid butyl ester, the propoxyl group methyl acetate, propoxyl group ethyl acetate, the propoxyl group propyl acetate, the propoxyl group butyl acetate, the butoxy acetic acid methyl esters, the butoxy acetic acid ethyl ester, the butoxy acetic acid propyl ester, the butoxy acetic acid butyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, 2-ethoxyl ethyl propionate etc.
In these solvents, from dissolubility or excellent dispersion, non-reacted with each composition, and the viewpoint that forms the easiness of filming is set out, ethers such as preferred dialkyl ether, the diethylene glycol alkyl ether, ethylene glycol alkyl ether acetate esters, the propylene-glycol monoalky lether class, the propylene-glycol monoalky lether acetate esters, ketone and ester class, preferred especially diethylene glycol diethyl ether, diethylene glycol ethyl-methyl ether, methylcellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, cyclohexanone, propyl acetate, isopropyl acetate, butyl acetate, the 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester.These solvents can be used alone or as a mixture.
In addition, in these solvents, ethers such as dialkyl ether such as preferred Di Iso Propyl Ether, di-n-butyl ether, two n-pentyl ethers, diisoamyl ether, di-n-hexyl ether, most preferably diisoamyl ether.By using this solvent, when on large-size glass substrate, being coated with radiation-ray sensitive composition, can shorten the drying process time by the slot coated method, can further improve coating (it is irregular to suppress coating) simultaneously.
Except above-mentioned solvent, as required, can also use together with high boiling solvents such as benzylisoeugenol, hexyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol single-butyl ether, acetonyl acetone, isophorone, caproic acid, capric acid, 1-octanol, 1 nonyl alcohol, benzylalcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetic acid esters, carbitol acetic acid esters.
When positive radiation line sensitive compositions is prepared with solution or dispersion liquid state, occupy the ratio of [F] solvent composition (total amount of [A], [B] and [C] composition and other optional member just) in addition in the solution, can set arbitrarily according to application target and desirable thickness etc., be preferably 5～50 quality %, more preferably 10～40 quality %, 15～35 quality % more preferably.
The formation of interlayer dielectric
Then, to using above-mentioned positive radiation line sensitive compositions, the method that forms interlayer dielectric on substrate describes.This method comprises the following operation of following order record.
(1) operation of filming of this positive radiation line sensitive compositions of formation on substrate,
(2) operation that at least a portion of filming of operation (1) formation is shone radioactive ray,
(3) will shine the operation that is coated with film development of radioactive ray in the operation (2), and
(4) operation of filming of heating development in operation (3).
(1) operation of filming of this positive radiation line sensitive compositions of formation on substrate
In the operation of above-mentioned (1), after the solution of this positive radiation line sensitive compositions or dispersed liquid coating are to the substrate, preferably remove and desolvate by heating (prebake) applicator surface, formation is filmed.As the example of operable substrate, can list glass, quartz, silicon, resin etc.As the object lesson of resin, can list the ring-opening polymerization polymer of polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, cyclic olefin and hydride thereof etc.
There is no particular limitation as the coating process of composition solution or dispersion liquid, can adopt for example suitable methods such as spray-on process, rolling method, method of spin coating (spin-coating method), slit die rubbing method, scraping article rubbing method.In these coating processes, preferred especially spin-coating method or slit die rubbing method.The condition of prebake is preferably being carried out about 1～10 minute under 70～120 ℃ according to the kind of each composition, blending ratio etc. and different.
(2) to the operation of at least a portion of filming irradiation radioactive ray
In the operation of above-mentioned (2), with at least a portion of the filming exposure that forms.In this case, when a part of filming is exposed, usually by having the photomask exposure of predetermined pattern.Radioactive ray as exposure is used can use for example luminous ray, ultraviolet ray, far ultraviolet, electron beam, X ray etc.In these radioactive ray, optimal wavelength especially preferably contains the ultraviolet radioactive ray of 365nm at the radioactive ray of the scope of 190～450nm.
Exposure in this operation is the value that obtains by the intensity under the wavelength 365nm of illuminometer (OAI model 356, OAI Optical Associates Inc. makes) mensuration radioactive ray, is preferably 500～6,000J/m 2, more preferably 1500～1,800J/m 2
(3) developing procedure
In the operation of above-mentioned (3),, remove unwanted part (illuminated portions of radioactive ray), form the pattern of regulation by the film development that is coated with after will exposing.As the developer solution that uses in the developing procedure, the aqueous solution of preferred bases (alkali compounds).As the example of alkali, can list inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, quaternary ammonium salts such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide etc.
In addition, in this aqueous alkali, can also add water-miscible organic solvent or surfactant uses such as methyl alcohol, ethanol in right amount.From obtaining the viewpoint of suitable development, the concentration of the alkali in the aqueous alkali is preferably more than the 0.1 quality %, below the 5 quality %.As developing method, can utilize the liquid method of containing, infusion process, shake suitable methods such as infusion process, shower method.Development time is preferably about 10～180 seconds according to the composition of positive radiation line sensitive compositions and different.After this development treatment, for example carry out flowing water washing in 30～90 seconds after, for example air-dry by pressurized air or compressed nitrogen, can form desirable pattern.
(4) heating process
In the operation of above-mentioned (4), use heating arrangements such as hot plate, baking oven, to forming the film heating of pattern, promotes self curing reaction of above-mentioned [A] composition and the curing reaction of [C] composition, can obtain solidfied material.Can think particularly that when thermonasty acid producing agent that uses [D] composition or thermonasty alkali generation agent produce acidic actives or alkaline active substance in heating process, it becomes catalyzer, further promotes the condensation reaction of [A] composition.Heating-up temperature in this operation for example is 120～250 ℃.When for example on hot plate carrying out heating process, carry out 5～30 minute according to the kind of firing equipment and different heat time heating time; When in baking oven, carrying out heating process, it is 30～90 minutes.Can also use the interim baking process that carries out twice above heating process etc.Like this, can be at the pattern-like film of substrate surface formation corresponding to needed interlayer dielectric.
Interlayer dielectric
The thickness of the interlayer dielectric of Xing Chenging is preferably 0.1～8 μ m like this, more preferably 0.1～6 μ m, more preferably 0.1～4 μ m.
The interlayer dielectric that is formed by positive radiation line sensitive compositions of the present invention is as following embodiment shows, can harmonious satisfy the character of thermotolerance, the transparency, solvent resistance and the so general requirement of low-dielectric well, have simultaneously and do not have the irregular height planarization of coating.Therefore, this interlayer dielectric is suitable as the purposes use of display element.
[embodiment]
The following stated synthesis example, embodiment are described more specifically the present invention, but the present invention is not subjected to the qualification of following examples.
The number-average molecular weight (Mn) of the hydrolytic condensate of the water-disintegrable silane compound of [A] composition that is obtained by each following synthesis example and the multipolymer of [C] composition and weight-average molecular weight (Mw) are measured by the gel permeation chromatography (GPC) of following manner.
Device: GPC-101 (clear and electrician (Co., Ltd.) makes)
Post: combination GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (clear and electrician (Co., Ltd.) makes) form
Mobile phase: tetrahydrofuran
The synthesis example of the hydrolytic condensate of the water-disintegrable silane compound of [A] composition
[synthesis example 1]
In the container of belt stirrer, add 25 mass parts propylene glycol monomethyl ether after, add 30 mass parts methyltrimethoxy silane, 23 mass parts phenyltrimethoxysila,e and 0.1 mass parts tetraisopropoxide aluminium, being heated to solution temperature is 60 ℃.After solution temperature reaches 60 ℃, add 18 mass parts ion exchange waters, be heated to 75 ℃, kept 3 hours.Then, add 28 mass parts original acid A esters, stirred 1 hour as dewatering agent.Then, making solution temperature is 40 ℃, and the limit keeps temperature, and the methyl alcohol of ion exchange water and hydrolytic condensation generation is removed in the limit evaporation.As above, obtain hydrolytic condensate (A-1).The solid component concentration of hydrolytic condensate (A-1) is 40.5 quality %, and the number-average molecular weight of the hydrolytic condensate of gained (Mn) is 1,500, and molecular weight distribution (Mw/Mn) is 2.
[synthesis example 2]
In the container of belt stirrer, add 25 mass parts propylene glycol monomethyl ether, then, add 22 mass parts methyltrimethoxy silane, 12 mass parts γ-glycidoxypropyltrimewasxysilane, 20 mass parts phenyltrimethoxysila,e and 0.1 mass parts tetraisopropoxide aluminium, method by same with synthesis example 1 obtains hydrolytic condensate (A-2).The solid component concentration of hydrolytic condensate (A-2) is 39.8 quality %, and the number-average molecular weight of the hydrolytic condensate of gained (Mn) is 1,600, and molecular weight distribution (Mw/Mn) is 2.
The multipolymer that the monomer by having ad hoc structure of [C] composition forms
[synthesis example 3]
Having stirring apparatus, in the glass flask of condenser and thermometer, add 28.4 mass parts as the compound shown in the above-mentioned formula (c1-1) of (c1) compound, 20.7 " the NK-エ ス テ Le M-90G " that mass parts is made as the Xin Zhong village chemistry (Co., Ltd.) of (c2) compound, 18.1 mass parts is as the compound shown in the following formula (c3-1-1-1) of (c3) compound, 5.9 mass parts methyl methacrylates and 23.5 mass parts 2-ethylhexyl acrylates as (c4) compound, 3.4 mass parts is as the compound 1 of (c5), the compound of two terminal methyl group acroleic acid esterifications of 4-butylene glycol and as 414 mass parts isopropyl alcohols of solvent, in nitrogen stream, under refluxing, add 0.7 mass parts as 2 of polymerization initiator, behind 2 '-azoisobutyronitrile and the lauryl mercaptan of 4 mass parts as chain-transferring agent, under 75 ℃, reflux and carried out copolymerization in 8 hours, obtain containing the solution of multipolymer (C-1).Afterwards, use evaporator, under the heating condition below 70 ℃, remove and desolvate, isolate multipolymer (C-1).The number-average molecular weight Mn of the multipolymer that obtains (C-1) is 2,800, and weight-average molecular weight Mw is 5,300, and molecular weight distribution (Mw/Mn) is 1.9.
Figure BSA00000397909500361
In the formula, Me is a methyl.
[synthesis example 4]
Except to make addition as the lauryl mercaptan of chain-transferring agent be 1 mass parts and above-mentioned synthesis example 3 similarly, obtain multipolymer (C-2).The number-average molecular weight Mn of the multipolymer that obtains (C-2) is 4,700, and weight-average molecular weight Mw is 11,000, and molecular weight distribution (Mw/Mn) is 2.3.
[synthesis example 5]
Except not using the lauryl mercaptan as chain-transferring agent, the temperature and time that makes copolymerization is respectively beyond 73 ℃ and 10 hours and above-mentioned synthesis example 3 similarly obtains multipolymer (C-3).The number-average molecular weight Mn of the multipolymer that obtains (C-3) is 5,600, and weight-average molecular weight Mw is 21,000, and molecular weight distribution (Mw/Mn) is 3.8.
[synthesis example 6]
Having stirring apparatus, in the glass flask of condenser and thermometer, add 31.8 mass parts as the compound shown in the above-mentioned formula (c1-3) of (c1) compound, 31.6 " the NK-エ ス テ Le M-90G " that mass parts is made as the Xin Zhong village chemistry (Co., Ltd.) of compound (c2), 29.0 mass parts is as compound and the 414 mass parts isopropyl alcohols shown in the following formula (c3-1-1-1) of (c3) compound, in nitrogen stream, under refluxing, add 0.7 mass parts as 2 of polymerization initiator, 2 '-azoisobutyronitrile (AIBN), behind the lauryl mercaptan of 4 mass parts as chain-transferring agent, under 75 ℃, reflux and carried out copolymerization in 8 hours, obtain containing the solution of multipolymer (C-4).Afterwards, use evaporator, under the heating condition below 70 ℃, remove and desolvate, isolate multipolymer (C-4).The number-average molecular weight Mn of the multipolymer that obtains (C-4) is 3,000, and weight-average molecular weight Mw is 6,000.And molecular weight distribution (Mw/Mn) is 2.0.
[synthesis example 7]
Having stirring apparatus, in the glass flask of condenser and thermometer, add 24.2 mass parts as the compound shown in the above-mentioned formula (c1-5) of (c1) compound, 20.7 " the NK-エ ス テ Le M-90G " that mass parts is made as the Xin Zhong village chemistry (Co., Ltd.) of compound (c2), 21.5 mass parts is as the compound shown in the following formula (c3-1-1-1) of (c3) compound, 29.4 mass parts is as the n-BMA and the 414 mass parts isopropyl alcohols of (c4) compound, in nitrogen stream, under refluxing, add 0.7 mass parts as 2 of polymerization initiator, 2 '-azoisobutyronitrile (AIBN), behind the lauryl mercaptan of 4 mass parts as chain-transferring agent, under 75 ℃, reflux and carried out copolymerization in 8 hours, obtain containing the solution of multipolymer (C-5).Afterwards, use evaporator, under the heating condition below 70 ℃, remove and desolvate, isolate multipolymer (C-5).The number-average molecular weight Mn of the multipolymer that obtains (C-5) is 2,600, and weight-average molecular weight Mw is 5,000.And molecular weight distribution (Mw/Mn) is 1.9.
The preparation of positive radiation line sensitive compositions
[embodiment 1]
In the solution that contains hydrolytic condensate (A-1) (amount that is equivalent to 100 mass parts hydrolytic condensate (A-1) (solid constituent)) that synthesis example 1 obtains, mix 30 mass parts as 4 of [B] composition, 4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] xenol (1.0mol) and 1, the condensation product (B-1) of 2-naphthoquinones two nitrine-5-sulfonic acid chloride (2.0mol), 0.50 the multipolymer (C-1) that the synthesis example 3 of mass parts conduct [C] composition obtains, add then as the diethylene glycol ethyl-methyl ether of solvent so that after solid component concentration is 25 quality %, membrane filter by bore 0.2 μ m filters, preparation positive radiation line sensitive compositions (S-1).
[embodiment 2～7 and comparative example 1～3]
Except each composition kind and amount such as table 1 the record and embodiment 1 similarly prepare positive radiation line sensitive compositions.In addition, comparative example 1 and 2 uses following surfactant to replace the multipolymer of [C] composition.
C-1 (comparative example 1): " SH-193 " that silicone based surfactant (East レ ダ ウ コ one ニ Application グ シ リ コ one Application (Co., Ltd.) is made)
C-2 (comparative example 2): fluorochemical surfactant (" Off タ one ジ エ Application ト 222F " that (Co., Ltd.) ネ オ ス makes)
Evaluation of physical property
Use the as above various positive radiation line sensitive compositions of preparation, following evaluation said composition and as filming or the various character of interlayer dielectric.
[ocular estimate of filming]
The model " TR632105-CL " of using slit die spreader (East capital ying chemical industry (Co., Ltd.) to make), the radiation-ray sensitive composition that as above prepares in the coating on glass of the formation chromium film of 550 * 650mm, the pressure that will reach is set at 100Pa, under vacuum, remove desolvate after, and then carry out 2 minutes prebake at 90 ℃, form filming of thickness 3.0 μ m.Under sodium vapor lamp, this outward appearance of filming by visual inspection.At this moment, with film integral produce vaporific irregular as " vaporific irregular ", will " sell irregular " from the irregular conduct near pin (プ ロ キ シ ピ Application) of prebake stove, study it and situation occurs.Do not find that nearly all these irregular situations are evaluated as " well ", the situation of any one that find on a small quantity that these are irregular is evaluated as " bad a little ", and the situation of clearly seeing is evaluated as " bad ".Evaluation result is represented in table 1.
[the radioactive ray sensitivity of radiation-ray sensitive composition is estimated]
At the coating hexamethyldisilazane on glass (HMDS) of the formation chromium film of 550 * 650mm, in 60 ℃ of heating 1 minute (HMDS processing).Use slit die formula spreader " TR632105-CL ", the radiation-ray sensitive composition that the coating on glass of the formation chromium film after this HMDS handles as above prepares, the pressure that will reach is set at 100Pa, under vacuum, remove desolvate after, and then carry out 2 minutes prebake at 90 ℃, form filming of thickness 3.0 μ m.Then, the MPA-600FA exposure machine that uses キ ヤ ノ Application (Co., Ltd.) to make, by line and the mask of space than the pattern of (10: 1) with 60 μ m, being variable to the exposure of filming, behind the irradiation radioactive ray, in the tetramethyl ammonium hydroxide aqueous solution of the concentration that table 1 is put down in writing, develop by containing the liquid method down at 25 ℃.Here, development time is to use the concentration of tetramethyl ammonium hydroxide when being the developer solution of 0.40 quality % is 80 seconds, is 50 seconds when using the developer solution of 2.38 quality %.Then, carry out flowing water washing in 1 minute, by dry, form pattern on the substrate of the formation chromium film after HMDS handles afterwards by ultrapure water.At this moment, research is dissolved necessary exposure with the line of 6 μ m and space fully than the space pattern of (1: 1).Should be worth and in table 1, represent as radioactive ray sensitivity.This value is 700J/m 2When following, think that sensitivity is good.
[evaluation of the development nargin of radiation-ray sensitive composition]
With the situation of above-mentioned [evaluation of the radioactive ray sensitivity of radiation-ray sensitive composition] similarly, the HMDS that forms the glass (4 inches chip glasses) of chromium film handles.Use spinner, the radiation-ray sensitive composition that the coating on glass of the formation chromium film after this HMD S handles as above prepares, the pressure that will reach is set at 100Pa, by vacuum drying remove desolvate after, and then carry out 2 minutes prebake at 90 ℃, form filming of thickness 3.0 μ m.Then, the MPA-600FA exposure machine that uses キ ヤ ノ Application (Co., Ltd.) to make, by line and the mask of space than the pattern of (1: 1) with 6 μ m, the exposure of the value of the radioactive ray sensitivity of research is exposed to above-mentioned filming in above-mentioned to be equivalent to [evaluation of the radioactive ray sensitivity of radiation-ray sensitive composition], then, using the tetramethyl ammonium hydroxide aqueous solution of the concentration of table 1 record, is variable with the development time, develops by containing the liquid method down at 25 ℃.Then, carry out flowing water washing in 1 minute, by dry, form pattern on the substrate of the formation chromium film after HMDS handles afterwards by ultrapure water.At this moment, with baseline wide be that the necessary development time of 6 μ m is an optimum development time, in table 1 expression.In addition, measure when this optimum development time further continues to develop, to the time that the line pattern of 6 μ m peels off, should the time as development nargin, expression in table 1.This value is more than 30 seconds the time, thinks that development nargin is good.
[evaluation of the solvent resistance of interlayer dielectric]
Use spinner, go up the as above radiation-ray sensitive composition of preparation of coating at the glass (4 inches chip glasses) that forms the chromium film, the pressure that will reach is set at 100Pa, under vacuum, remove desolvate after, and then carry out 2 minutes prebake at 90 ℃, formation is filmed.At this MPA-600FA exposer of filming and using キ ヤ ノ Application (Co., Ltd.) to make, be 9 with cumulative exposure, 000J/m 2Exposure then, in the cleaning baking oven, was heated 1 hour down at 220 ℃, in the formation cured film on glass that forms the chromium film.Measure the thickness (T1) of the cured film that obtains here.Then, the glass substrate that forms the formation chromium film of this cured film is controlled to be in 70 ℃ the dimethyl sulfoxide (DMSO) dipping in temperature measures the thickness (t1) of cured film once more after 20 minutes, calculate the Thickness Variation rate that dipping causes | t1-T1|/T1} * 100 (%).This result represents in table 1.This value is 5% when following, thinks that solvent resistance is good.
[the stable on heating evaluation of interlayer dielectric]
With the situation of above-mentioned [evaluation of the solvent resistance of interlayer dielectric] similarly, in the formation cured film on glass that forms the chromium film.Measure the thickness (T2) of the cured film that obtains here.Then, the glass substrate of formation chromium film that forms this cured film is appended heating after 1 hour in the cleaning baking oven, under 240 ℃, measures the thickness (t2) of cured film once more, calculate the Thickness Variation rate of appending heating and causing | t2-T2|/T2} * 100 (%).This result represents in table 1.This value is 5% when following, thinks that thermotolerance is good.
[evaluation of the transparency of interlayer dielectric]
Except the glass substrate (" NA35 " that NH テ Network ノ グ ラ ス (Co., Ltd.) company makes) that uses 550 * 650mm replaces forming the glass substrate of chromium film, with the situation of above-mentioned [evaluation of the solvent resistance of interlayer dielectric] similarly, on glass substrate, form cured film.The use spectrophotometer " 150-20 type ダ Block Le PVC one system ((the) Ri Li System of Co., Ltd. does manufacturing) ", with the glass substrate that do not have cured film as the reference side, under the wavelength of the scope of 400～800nm, measure the light penetration of the glass substrate of cured film with formation.The value of the minimum light penetration of this moment is represented in table 1.This value is 90% when above, thinks that the transparency is good.
[evaluation of the film thickness uniformity of interlayer dielectric (planarization)]
With above-mentioned [evaluation of the transparency of interlayer dielectric] similarly, on glass substrate, form cured film.This cured film is measured the thickness of 20 measuring point, calculate film thickness uniformity by following formula.
The homogeneity of thickness (%)=(maximal value-minimum value of the thickness of cured film) * 100/ ((mean value of 20 coating film thickness) * 2)
The film thickness uniformity of the cured film of so calculating is below 1%, thinks that film thickness uniformity is good.In addition, above-mentioned 20 measuring point is following definite.Just, from substrate (terminal area inside (450 * 550mm) the conduct mensuration zones of removing the scope of 5cm of 550 * 650mm) long limit and each of minor face, each determines 10 points (amount to 20 points) every 4cm ground respectively on the straight line of this regional long side direction and short side direction, with them as measuring point.
[evaluation of the relative dielectric constant of interlayer dielectric]
Pass through spin-coating method, on the SUS304 of the surface smoothing that grinds by sisal hemp moccasin (numb moccasin) system substrate, coating is the radiation-ray sensitive composition of preparation as above, the pressure that will reach is set at 100Pa, under vacuum, remove desolvate after, and then carry out 2 minutes prebake at 90 ℃, form filming of thickness 3.0 μ m.Film at this that obtains, the MPA-600FA exposer that uses キ ヤ ノ Application (Co., Ltd.) to make is 9 with cumulative exposure, 000J/m 2Exposure then, in the cleaning baking oven, was heated this substrate 1 hour down at 220 ℃, formed cured film on substrate.On this cured film, form the Pt/Pd electrode pattern by vapour deposition method, make the specific inductive capacity test sample.To having the substrate of this electrode pattern, HP 16451B electrode and the HP4284A プ レ シ ジ ヨ Application LCR instrument of using Yokogawa ヒ ユ one レ Star ト パ Star カ one De (Co., Ltd.) to make under the frequency of frequency 10kHz, are measured relative dielectric constant by the CV method.Measurement result is represented in table 1.This value is 3.9 when following, thinks that relative dielectric constant (low-dielectric) is good.
Figure BSA00000397909500431
Result as table 1 shows, can know that the positive radiation line sensitive compositions of positive radiation line sensitive compositions that contains [A], [B] and the embodiment 1～7 of [C] composition and the comparative example 1～3 that does not contain [C] composition compares, coating in the outward appearance of filming is not aspect the planarization of even interlayer dielectric, and is excellent more.In addition, the positive radiation line sensitive compositions of also knowing these embodiment can also form the interlayer dielectric of the character that fully satisfies thermotolerance, the transparency, solvent resistance and the so general requirement of low-dielectric when having high radioactive ray sensitivity and development nargin.
[industrial applicibility]
Positive radiation line sensitive compositions of the present invention has high radioactive ray sensitivity and development nargin as mentioned above, can form except having enough heat resistances, the transparency, solvent resistance and low-dielectric, also has the cured film of excellent planarization. Therefore, this positive radiation line sensitive compositions is suitable for forming the interlayer dielectric that display element is used.

Claims (10)

1. positive radiation line sensitive compositions, it comprises:
[A] siloxane polymer,
[B] quinone di-azido compound, and
The multipolymer of polymerizable unsaturated compound that [C] comprises the compound shown in the compound shown in (c1) following formula (1), (c2) following formula (2) and (c3) have the polymerizable unsaturated compound of the group shown in the following formula (3),
CH 2＝CR 1COO-C αH 2α-C βF 2β+1 (1)
In the formula (1), R 1Be hydrogen atom or methyl, α is 0～6 integer, and β is 1～20 integer,
CH 2＝CR 2COO-(C γH 2γ-O) a-R 3 (2)
In the formula (2), R 2Be hydrogen atom or methyl, R 3Be that carbon number is 1～12 alkyl, γ is 2 or 3, and a is a number of repeat unit, and its number average value is 1～30,
Figure FSA00000397909400011
In the formula (3), R 4, R 5, R 6, R 4And R 8Be the group shown in alkyl, phenyl or the following formula (4) of carbon number 1～20 independently of one another, b is 0～3 integer,
Figure FSA00000397909400012
In the formula (4), R 9, R 10And R 11Be the alkyl or phenyl of carbon number 1～20 independently of one another, c is 0～3 integer.
2. the positive radiation line sensitive compositions of putting down in writing according to claim 1, wherein [C] multipolymer is except compound (c1), compound (c2) and compound (c3), also further comprises the multipolymer of polymerism saturated compound of polymerizable unsaturated compound that (c4) has the alkyl of carbon number 1～8.
3. the positive radiation line sensitive compositions of putting down in writing according to claim 2, wherein [C] multipolymer is except compound (c1), compound (c2), compound (c3) and compound (c4), also further comprises (c5) has the polymerizable unsaturated compound of two above unsaturated links in a part the multipolymer of polymerizable unsaturated compound.
4. the positive radiation line sensitive compositions of putting down in writing according to claim 3, wherein:
Compound (c1) is the compound shown in the following formula (5),
Compound (c2) is the compound shown in the following formula (6),
[C] multipolymer is by compound (c1) 25～35 quality %, compound (c2) 20～30 quality %, compound (c3) 15～20 quality %, compound (c4) 25～35 quality %, and the multipolymer of the polymerizable unsaturated compound of compound (c5) 1～5 quality % formation
CH 2＝CR 1COOC 2H 4C βF 2β+1 (5)
In the formula (5), R 1Identical with the definition in the above-mentioned formula (1), β is 1～8 integer,
CH 2＝CR 2COO(C 2H 4O) aR 3 (6)
In the formula (6), R 2And R 3Identical with the definition in the above-mentioned formula (2) respectively, the number average value of number of repeat unit a is 4～12.
5. the positive radiation line sensitive compositions of putting down in writing according to claim 1, wherein [A] siloxane polymer is the hydrolytic condensate of the water-disintegrable silane compound shown in the following formula (7),
(R 12) x-Si-(OR 13) 4-x (7)
In the formula (7), R 12Be that carbon number is 1～20 non-water-disintegrable organic group, R 13Be that carbon number is 1～4 alkyl, x is 0～3 alkyl.
6. the positive radiation line sensitive compositions of putting down in writing according to claim 1, it further contains [D] thermonasty acid producing agent or thermonasty alkali produces agent.
7. the positive radiation line sensitive compositions of putting down in writing according to claim 1, it further contains [E] dewatering agent.
8. each positive radiation line sensitive compositions of being put down in writing according to claim 1～7, it is used to form the interlayer dielectric of display element.
9. a display element is with the formation method of interlayer dielectric, and this method comprises:
(1) operation of filming of the positive radiation line sensitive compositions that formation claim 8 is put down in writing on substrate,
(2) operation that at least a portion of filming of operation (1) formation is shone radioactive ray,
(3) will shine the operation that is coated with film development of radioactive ray in the operation (2), and
(4) operation of filming of heating development in operation (3).
10. the interlayer dielectric of the display element that forms of the positive radiation line sensitive compositions of putting down in writing by claim 8.
CN2010105998586A 2009-12-16 2010-12-14 Positive radiation-sensitive composition, interlayer insulating film and method for forming the same Pending CN102156386A (en)

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