CN101799627A - Positive type photosensitive organic compound - Google Patents
Positive type photosensitive organic compound Download PDFInfo
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Abstract
The present invention relates to positive type photosensitive organic compound.Photosensitive polymer combination, it contains following compositions (A), (B) and (C), composition (B) and (C) be set at (B) 5～50 mass parts and (C) 1～40 mass parts respectively with respect to the composition of composition (A) 100 mass parts.Composition (A) be contain by the dimethyl ester monomer derived constitute unit (a1), by aromatic vinyl monomer derive constitute unit (a2), by α, the multipolymer of the formation unit (a3) of beta-unsaturated carboxylic acid monomer derived and the formation unit (a4) of deriving by (methyl) acrylate monomer.Composition (B) is the emulsion with diazonium quinonyl.Composition (C) is the hardening agent with 2 above epoxy radicals.
Description
Technical field
The present invention relates to photosensitive polymer combination, particularly the photosensitive polymer combination of eurymeric.And then at length, relate to and to form the photosensitive polymer combination of pattern film by using photoetching technique, and then relate to having and use the interlayer dielectric that this photosensitive polymer combination forms or the flat-panel monitor (FPD) or the semiconductor device of planarization film.
Background technology
Be in the wide spectrum of representative with the manufacturing of SIC (semiconductor integrated circuit) such as LSI, the manufacturing of FPD display surface, the manufacturing of thermal head circuit substrates such as (サ one マ Le ヘ Star De) etc., for the formation or the microfabrication of carrying out fine element, use photoetching technique all the time.In this photoetching technique, used photosensitive polymer combination in order to form resist pattern (レ ジ ス ト パ タ one Application).In recent years, as the new purposes of these photosensitive polymer combinations, the interlayer dielectric of SIC (semiconductor integrated circuit) or FPD etc. or the formation technology of planarization film are subjected to attracting attention of people.Especially, become more meticulous or be the cripeturaization of manufacturing process of the semiconductor element of representative with TFT etc. for the height of FPD display surface, the expectation in market is strong.
For the height of realizing this FPD display surface becomes more meticulous, it is important suppressing to transmit loss in circuit, and wherein the interlayer dielectric with fine pattern of low dielectric property excellence or planarization film are must material.In addition, for the cripeturaization of semiconductor element manufacturing process, in order to protect source electrode or gate electrode, people's expectation will utilize the inorganic interlayer dielectric of the SiNx that vacuum vapour deposition forms etc. to replace to organic interlayer dielectric that can form by the wet type handling ease.Therefore, for organic interlayer dielectric, the insulativity equal with SiNx is necessary, needs the interlayer dielectric of specific inductive capacity in the low dielectric property below 3.0.In order to obtain above-mentioned interlayer dielectric or planarization film with low dielectric property, the effect of the alkali soluble resin in the photosensitive polymer combination is very big, about being used for the photosensitive polymer combination of this purposes, is carrying out a large amount of research.
For example patent documentation 1 discloses the alkali soluble resin that cooperates as in the photosensitive polymer combination that interlayer dielectric or planarization film are used, the free-radical polymerised compound that has used unsaturated carboxylic acid and had epoxy radicals, photosensitive polymer combination has good development and can form high-resolution pattern film thus.But, general known to formation unit contained in the above-mentioned alkali soluble resin is made of (methyl) acryloyl group, thereby can not obtain having the photosensitive polymer combination of fully low dielectric property.
Patent documentation 2 discloses the alkali soluble resin that cooperates as in the photosensitive polymer combination that interlayer dielectric or planarization film are used, use contains phenylethylene, (methyl) acrylic acid and hydroxyalkyl acrylate as the multipolymer that constitutes the unit, and the low dielectric property of photosensitive polymer combination becomes good thus.But, the present application people notices that the hydrophobicity of resin increases when volume in resin imports phenylethylene, though therefore can keep residual film ratio when developing than the highland, but there is the development residue to become many, can not obtains having the problem of the photosensitive polymer combination of abundant development.
In addition; patent documentation 3 discloses in order to form diaphragm, RGB pixel, black matrix or the sept that color filter is used; contain the negative light-sensitive resin combination of multifunctional (methyl) acrylate compounds of alkali soluble resin, optical polymerism with dimethyl ester and Photoepolymerizationinitiater initiater by use, can obtain good development.But the present application people notices the specific inductive capacity height owing to optical polymerism multifunctional (methyl) acrylate contained in this negative light-sensitive resin combination, therefore has to obtain the having problem of fully hanging down the photosensitive polymer combination of dielectric property.
In view of this truth, for the photosensitive polymer combination that in the interlayer dielectric of FPD or semiconductor device etc. or planarization film, uses, people require it can keep high residual film ratio, residue does not simultaneously develop, development is good, and can form the high-resolution pattern film of low dielectric property excellence.
The prior art document
Patent documentation
Patent documentation 1 Japanese kokai publication hei 7-248629 communique (the 2nd page, the 3rd page and the 4th page)
Patent documentation 2 TOHKEMY 2004-4233 communiques (the 2nd page, the 4th page and the 34th page)
Patent documentation 3 TOHKEMY 2007-137947 communiques (the 2nd page, the 3rd page and the 5th page)
Summary of the invention
First purpose of the present invention is to provide photosensitive polymer combination, it is in the developing procedure that forms pattern film, can keep high residual film ratio, residue does not simultaneously develop, even behind high-temperature baking, also do not damage the rerum natura of filming of flatness, light transmission, solvent resistance etc., can form the high-resolution pattern film of low dielectric property excellence.
Second purpose of the present invention is to provide has the planarization film that the photosensitive polymer combination that utilizes above-mentioned excellence forms or the FPD or the semiconductor device of interlayer dielectric.
The 3rd purpose of the present invention is to provide FPD or semiconductor device, it has the photosensitive polymer combination that utilizes above-mentioned excellence, organic interlayer dielectric that available wet type processing (ウ エ Star ト プ ロ セ ス) forms easily, rather than form the inorganic interlayer dielectric of SiNx etc.
Photosensitive polymer combination of the present invention contains the composition (A) shown in following, (B) and (C), and composition (B) and composition (C) are respectively (B) 5～50 mass parts and (C) 1～40 mass parts with respect to composition (A) 100 mass parts.
Composition (A) is to comprise to constitute unit (a1) with following formula (1) expression by the dimethyl ester monomer derived, constitute unit (a2) with following formula (2) expression by what aromatic vinyl monomer was derived, with following formula (3) expression by α, the formation unit (a3) of beta-unsaturated carboxylic acid monomer derived and with the multipolymer of the formation unit (a4) of deriving by (methyl) acrylate monomer of following formula (4) expression, wherein, the total amount that constitutes unit (a1) and formation unit (a2) is 40～85 quality % in this composition (A), and the mass ratio (a4)/(a3) that constitutes unit (a3) and formation unit (a4) is 0.2～7.0.
(in the formula, R
1And R
2Be respectively that carbon number is that 3～8 branched alkyl, carbon number are 4～12 naphthenic base or replace the side chain naphthenic base)
(in the formula, R
3Be hydrogen atom or methyl, R
4Be that carbon number is 6～12 aromatic hydrocarbyl)
(the R in the formula
5Be hydrogen atom, methyl or ethyloic)
(the R in the formula
6Be hydrogen atom or methyl, R
7Be that carbon number is that 6～12 aromatic hydrocarbyl, carbon number are that 1～12 alkyl, carbon number are that 1～12 branched alkyl, carbon number are that 2～12 hydroxy alkyl or the carbon number that constitutes main ring are 5～12 ester ring type alkyl)
Composition (B) makes phenoloid and diazonium naphtoquinone compounds with hydroxyl carry out the emulsion that esterification obtained, had the diazonium quinonyl.
Composition (C) is the hardening agent with 2 above epoxy radicals.
The photosensitive polymer combination that the flat-panel monitor of the 2nd invention has the 1st invention solidifies the layer that forms.
The photosensitive polymer combination that the semiconductor device of the 3rd invention has the 1st invention solidifies the layer that forms.
The present invention can bring into play following effect.
Photosensitive polymer combination according to the 1st invention, in the developing procedure of the formation pattern film that uses photoetching technique, can keep high residual film ratio, residue does not simultaneously develop, even behind the high-temperature baking of back baking etc., also do not damage the rerum natura of filming of flatness, light transmission, solvent resistance etc., can form the high-resolution pattern film of low dielectric property excellence.By using this photosensitive polymer combination, can provide FPD and semiconductor device with excellent specific property.
Embodiment
Below, be described in detail for embodiments of the present invention.
The photosensitive polymer combination of present embodiment contains composition (A), (B) and (C), and composition (B) and composition (C) be with respect to composition (A) 100 mass parts, and to be set in (B) respectively be 5～50 mass parts and (C) be 1～40 mass parts.
Composition (A): following illustrated specific multipolymer.
Composition (B): emulsion with diazonium quinonyl.
Composition (C): hardening agent with 2 above epoxy radicals.
Below describe successively for each composition.
＜composition (A): multipolymer 〉
The multipolymer of composition (A) is to comprise to constitute unit (a1) with following formula (1) expression by the dimethyl ester monomer derived, constitute unit (a2) with following formula (2) expression by what aromatic vinyl monomer was derived, with following formula (3) expression by α, the formation unit (a3) of beta-unsaturated carboxylic acid monomer derived and with the multipolymer of the formation unit (a4) of deriving by (methyl) acrylate monomer of following formula (4) expression, wherein, the total amount that constitutes unit (a1) and formation unit (a2) is 40～85 quality % in this composition (A), and the mass ratio (a4)/(a3) that constitutes unit (a3) and formation unit (a4) is 0.2～7.0.
(in the formula, R
1And R
2Be respectively that carbon number is that 3～8 branched alkyl, carbon number are 4～12 naphthenic base or replace the side chain naphthenic base)
(in the formula, R
3Be hydrogen atom or methyl, R
4Be that carbon number is 6～12 aromatic hydrocarbyl)
(the R in the formula
5Be hydrogen atom, methyl or ethyloic)
(the R in the formula
6Be hydrogen atom or methyl, R
7Be that carbon number is that 6～12 aromatic hydrocarbyl, carbon number are that 1～12 alkyl, carbon number are that 1～12 branched alkyl, carbon number are that 2～12 hydroxy alkyl or the carbon number that constitutes main ring are 5～12 ester ring type alkyl)
Derived by the monomer (respectively constituting the unit monomer) of following formula (5)～(8) expression respectively in the formation unit of following formula (1)～(4) expression.
(in the formula, R
1And R
2Respectively with formula (1) in identical.The monomer of formula (5) is referred to as the dimethyl ester monomer.)
(in the formula, R
3And R
4With identical in the formula (2).The monomer of formula (6) is referred to as aromatic vinyl monomer.)
(the R in the formula
5With identical in the formula (3).The monomer of formula (7) is referred to as α, the beta-unsaturated carboxylic acid monomer.)
(the R in the formula
6, R
7With identical in the formula (4).The monomer of formula (8) is referred to as (methyl) acrylate monomer.)
[by the dimethyl ester monomer derived constitute unit (a1)]
For by the dimethyl ester monomer derived constitute unit (a1), do not have methylene in the part that becomes backbone structure, (the COOR in the formula (1) of bonding substituting group on the carbon of main chain
1, COOR
2), the polymkeric substance that is made of dimethyl ester has the backbone structure of rigidity thus.Owing to be the backbone structure of rigidity, therefore can suppress the strand thermal motion of main chain, can suppress the loss of thermal energy in specific frequency zone, can obtain good low dielectric property.
R in the following formula (1)
1And R
2Be respectively that carbon number is that 3～8 branched alkyl, carbon number are 4～12 naphthenic base or replace the side chain naphthenic base.R
1And R
2Preferably carbon number is that 3～6 branched alkyl, carbon number are 6～10 naphthenic base or replace the side chain naphthenic base.Be more preferably carbon number and be 3～5 branched alkyl or carbon number and be 6～8 naphthenic base.
When the carbon number of branched alkyl surpassed 8, polymerism descended sometimes, produced unfavorable condition.In addition, when naphthenic base or the carbon number that replaces the side chain naphthenic base surpass 12, the development problem fully that becomes is inadequately arranged.R in the following formula (1)
1And R
2Identical substituting group can be, also different substituting groups can be.Consider preferred R from the angle that is easy to obtain
1And R
2Identical.
[constituting unit (a2)] by what aromatic vinyl monomer was derived
When the aromatic vinyl monomer that constitutes unit (a2) of deriving can increase polymerization with the copolyreaction of the dimethyl ester monomer that constitutes unit (a1) of deriving.The dimethyl ester monomer is the strong monomer of electronics acceptance (Electricity is subjected to capacitive), and is therefore low with the copolyreaction of this monomer with polarity of (methyl) acrylate or vinyl cyanide, but higher with the copolymerization of the monomer of electron donability.Derive and constitute the aromatic vinyl monomer of unit (a2), with dimethyl ester monomer, α, this the copolymerization of any monomer of beta-unsaturated carboxylic acid monomer and (methyl) acrylate monomer is all good, therefore the unit that respectively constitutes by the different monomer derived of copolymerization successfully can be incorporated in the polymkeric substance when polyreaction, can access is not having the inequality that distributes, the multipolymer with even character aspect the copolymerization composition.
R in the following formula (2)
3Be hydrogen atom or methyl, R
4Be that carbon number is 6～12 aromatic hydrocarbyl.R
3Be preferably hydrogen atom, R
4Be that carbon number is 6～10 aromatic hydrocarbyl.Work as R
4Carbon number surpass at 12 o'clock, the development of photosensitive polymer combination becomes insufficient.
[total amount (a1)+(a2)]
Above-mentionedly be preferably 45～80 quality % by the constituting unit (a1) and in composition (A), be 40～85 quality % of dimethyl ester monomer derived by the total amount that constitutes unit (a2) that aromatic vinyl monomer is derived, and then preferred 50～75 quality %.When (a1) and total amount (a2) are lower than 40 quality %, lack with by α, the copolymerization of the formation unit (a3) of beta-unsaturated carboxylic acid monomer derived and the formation unit (a4) of deriving by (methyl) acrylate monomer, and, cause to obtain having the photosensitive polymer combination of fully low dielectric property because the segment of rigidity tails off in the multipolymer.On the other hand, when being higher than 85 quality %,, cause the development of photosensitive polymer combination to become insufficient, on pattern, produce the development residue because the hydrophobicity of multipolymer uprises.
(a1) and preferred group (a2) are proportional in (a1)+(a2) total amount of composition (A) is preferably (a1) in mole fraction (モ Le branch rate): (a2)=80: 20～10: 90, and then be preferably 70: 30～15: 85.Be higher than 80 moles of % as (a1), when (a2) is lower than 20 moles of %, the polymerism of (a1) descends in polyreaction, existing problems aspect copolymerization.On the other hand, be higher than 90 moles of % as (a2), when (a1) is lower than 10 moles of %, the unit that constitutes of being derived by aromatic vinyl monomer in the composition (A) becomes many, so the hydrophobicity of multipolymer increases, have the development of photosensitive polymer combination become inadequate may.
[by α, the formation unit (a3) of beta-unsaturated carboxylic acid monomer derived]
By α, the formation unit (a3) of beta-unsaturated carboxylic acid monomer derived is the deliquescent composition that helps in developing procedure in developer solution.R in the following formula (3)
5Be hydrogen atom, methyl or ethyloic.Preferably hydrogen atom or methyl when the formation unit that uses beyond above-mentioned, have the problem that can not obtain constituting with other copolymerization of unit.
By by this α, the content of the formation unit (a3) of beta-unsaturated carboxylic acid monomer derived can be regulated the acid number of the multipolymer of composition (A).Regulate to constitute the ratio of unit (a3), so that the scope of acid number is preferably 50～200mgKOH/g, 70～150mgKOH/g more preferably.When this acid number is too low, there is the dissolubility in developer solution to become inadequate possible, when acid number is too high, the possibility of the residual film ratio decline when developing is arranged on the other hand.
[the formation unit (a4) of deriving by (methyl) acrylate monomer]
The formation unit (a4) of being derived by (methyl) acrylate monomer is to help the adjusting of development property, the residual film ratio when particularly developing or the composition of resolution.R in the following formula (4)
6Be hydrogen atom or methyl, R
7Be that carbon number is that 6～12 aromatic hydrocarbyl, carbon number are that 1～12 alkyl, carbon number are that 1～12 branched alkyl, carbon number are that 2～12 hydroxy alkyl or the carbon number that constitutes main ring are 5～12 ester ring type alkyl.The carbon number of above-mentioned formation main ring is a bridging alkyl etc. in the side chain, ring of 5～12 the ester ring type alkyl side chain that also can contain additional structure, for example cyclic olefinic bond, alkyl, volution.R
6Be preferably methyl, R
7Preferably carbon number is that 1～6 alkyl or branched alkyl, carbon number are that 6～10 aromatic hydrocarbyl, carbon number are 2～4 hydroxy alkyl or cyclohexyl, two cyclopentyl (ジ シ Network ロ ペ Application タ ニ Le base).Work as R
7Carbon number surpass at 12 o'clock, polymerism descends, and unfavorable condition is arranged.In order to regulate development, these (methyl) acrylate monomers that constitute unit (a4) of deriving can only use a kind, perhaps will be used in combination more than 2 kinds.
[mass ratio (a4)/(a3)]
By α, the formation unit (a3) of beta-unsaturated carboxylic acid monomer derived is 0.2～7.0 with the mass ratio (a4)/(a3) of the formation unit (a4) of being derived by (methyl) acrylate monomer, is preferably 0.3～6.0, more preferably 0.6～4.0.When the value of mass ratio (a4)/(a3) was hanged down than 0.2, by α, it is many that the formation unit of beta-unsaturated carboxylic acid monomer derived becomes in the multipolymer, and the residual film ratio during development reduces.On the other hand, when the value of mass ratio (a4)/(a3) was higher than 7.0, the formation unit of being derived by (methyl) acrylate monomer became many, and it is insufficient that development becomes, and the generation of residue or the decline of resolution cause developing.
The polymerization that is used to obtain the multipolymer of composition (A) can be used general known solvent with solvent.The object lesson of this solvent can be enumerated the ethylene glycol monoalkyl ether class of glycol monoethyl ether, ethylene glycol monoethyl ether etc.; The ethylene glycol monoalkyl ether acetate class of ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate etc.; The diglycol dialkyl ether of diethylene glycol dimethyl ether, diethyl carbitol, diglycol methyl ethyl ether etc.; The propylene-glycol monoalky lether class of propylene glycol monomethyl ether, dihydroxypropane single-ether etc.; The propylene-glycol monoalky lether acetate esters of propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate etc.; The lactic acid ester of methyl lactate, ethyl lactate etc.; The aromatic hydrocarbons of toluene, dimethylbenzene etc.; The ketone of methyl ethyl ketone, 2-heptanone, cyclohexanone etc.; The amide-type of N,N-dimethylacetamide, N-Methyl pyrrolidone etc.; The lactone of gamma-butyrolacton etc. etc.These polymer solvents can use separately, perhaps use mixing more than 2 kinds.
The polymerization initiator that uses for the multipolymer that obtains composition (A) can use general known material as radical polymerization initiator.As its object lesson, can use azo is that polymerization initiator, the azo that does not have cyano group are polymerization initiator or organic peroxide and hydrogen peroxide etc.When using superoxide, also this superoxide and reductive agent can be made up and use as the oxidation-reduction type polymerization initiator as radical polymerization initiator.
Weight-average molecular weight when being adjusted in the multipolymer that obtains composition (A) can be used molecular weight regulator.Molecular weight regulator can be enumerated for example thio-alcohol of n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan, mercaptoacetic acid, mercaptopropionic acid etc.; Xanthate (the キ サ Application ト ゲ Application) class of curing dimethyl yellow ortho esters (ジ メ チ Le キ サ Application ト ゲ Application ジ ス Le Off イ De), dithiodiisopropyl xanthate (ジ イ ソ プ ロ ピ Le キ サ Application ト ゲ Application ジ ス Le Off イ De) etc.; Terpinolene, α-Jia Jibenyixierjuwu etc.
The weight-average molecular weight of the multipolymer of composition (A) is preferably 5,000～60, and 000, more preferably 5,000～30,000, and then preferred 8,000～25,000.When weight-average molecular weight less than 5,000 o'clock, when baking back being arranged to take place that pattern flows (パ タ one Application Off ロ one), the resolution of pattern film becomes inadequate may, when surpassing 60,000 o'clock, the dissolubility of shortage for developer solution arranged, can not obtain the possibility of satisfied development.
＜composition (B): emulsion〉with diazonium quinonyl
Emulsion for composition (B) with diazonium quinonyl, when in utilizing photolithographic exposure process, exposing by photomask, the photoisomerization reaction that has the emulsion of diazonium quinonyl at exposed portion, generate carboxyl thus, after developing procedure in it is dissolved for developer solution.On the other hand, unexposed portion has the dissolving power of forbidding for developer solution, thereby can form film.That is, the emulsion with diazonium quinonyl is exposed by photomask, thus after developing procedure in can make its dissolubility difference for developer solution, therefore can obtain pattern film.
The emulsion with diazonium quinonyl of composition (B) can obtain by making phenoloid with hydroxyl and diazonium naphtoquinone compounds carry out esterification.The diazonium naphtoquinone compounds can use with 1,2-diazo naphthoquinone-5-sulfonic acid chloride, 1, and 2-diazo naphthoquinone-4-sulfonic acid chloride etc. is the diazo naphthoquinone sulfonic acid chloride of representative or the such diazonium quinone sulfonic acid halide of diazonium benzoquinones sulfonic acid chloride.
Esterification is carried out as following, promptly, in the presence of base catalyst, for example NaOH, sodium carbonate, sodium bicarbonate, triethylamine etc., phenoloid with hydroxyl and diazonium quinone sulfonic acid halide are being generally under the temperature about-20～60 ℃ react.Esterification yield can have the amount of phenoloid of hydroxyl and the amount of diazonium naphtoquinone compounds forms suitable value by adjusting.In this esterification, can obtain the esterification number potpourri different separately with the esterification position.Therefore, esterification yield can be represented with the mean value of these potpourris.In addition, these reaction product can be used a kind separately, also can will also use more than 2 kinds.
Esterification yield with emulsion of diazonium quinonyl is preferably 20～95 moles of %, more preferably 35～90 moles of %.When esterification yield when 20 moles of % are following, having causes the possibility that sensitivity descends, when when 95 moles of % are above, emulsion is for the compatibility variation of multipolymer, has pattern film to be separated and the possibility of gonorrhoea takes place.
Can be used for having phenoloid in the emulsion of diazonium quinonyl and preferably use the compound of following formula (9) or (10) expression with hydroxyl.
(in the formula, R
8, R
9, R
10And R
11Represent that respectively hydrogen atom or carbon number are 1～2 alkyl, R
12And R
13Represent that respectively carbon number is 1～2 alkyl.)
(in the formula, R
14, R
15, R
16, R
17, R
18, R
19And R
20Represent that respectively hydrogen atom, carbon number are 1～4 alkyl or following formula (11),
R in the formula
21Expression hydrogen atom or carbon number are 1～4 alkyl, and m and n are respectively 0～2 integers, and a, b, c, d, e, f, g and h satisfy a+b≤5, c+d≤5, e+f≤5, integer g+h≤5,0～5, and i is 0～2 integer.)
Can enumerate for example following compound as the phenoloid shown in the following formula (9).
In addition, phenoloid shown in the following formula (10) can be enumerated orthoresol, metacresol, paracresol, 2, the 4-xylenols, 2, the 5-xylenols, 2, the 6-xylenols, bisphenol-A, B, C, E, F and G, 4,4 '; 4 "-methine trisphenol, 2, two [(2-hydroxy-5-methyl base phenyl) the methyl]-4-methylphenols of 6-, 4,4 '-[1-[4-[1-(4-hydroxy phenyl)-1-Methylethyl] phenyl] ethylidene] bis-phenol, 4,4 '-[1-[4-[2-(4-hydroxy phenyl)-2-propyl group] phenyl] ethylidene] bis-phenol, 4,4 '; 4 "-ethylidine trisphenol, two (4-hydroxy phenyl) methyl of 4-[]-the 2-thanatol, 4,4 '-[(2-hydroxy phenyl) methylene] two [2,3-xylenol], 4,4 '-[(3-hydroxy phenyl) methylene] two [2,6-xylenol], 4,4 '-[(4-hydroxy phenyl) methylene] two [2,6-xylenol], 2,2 '-[(2-hydroxy phenyl) methylene] two [3,5-xylenol], 2,2 '-[(4-hydroxy phenyl) methylene] two [3,5-xylenol], 4,4 '-[(3, the 4-dihydroxy phenyl) methylene] two [2,3,6-pseudocuminol], two (3-cyclohexyl-4-hydroxyl-6-aminomethyl phenyl) methyl of 4-[]-1, the 2-benzenediol, 4,6-two [(3,5-dimethyl-4-hydroxy phenyl) methyl]-1,2, the 3-benzenetriol, 4,4 '-[(2-hydroxy phenyl) methylene] two [3-methylphenols], 4,4 '; 4 "-(3-methyl isophthalic acid-propyl group-3-time base) trisphenol, 4,4 '; 4 "; 4 " '-(1,4-benzene two methines) four phenol, 2,4,6-three [(3,5-dimethyl-4-hydroxy phenyl) methyl]-1, the 3-benzenediol, 2,4,6-three [(3,5-dimethyl-2-hydroxy phenyl) methyl]-1, the 3-benzenediol, 4,4 '-[1-[4-[1-[4-hydroxyl-3, two [(hydroxy-3-methyl phenyl) methyl] phenyl of 5-]-1-Methylethyl] phenyl] ethylidene] two [2, two (hydroxy-3-methyl phenyl) methyl of 6-] phenol etc.In these compounds, preferred 4,4 '; 4 "-methine trisphenol, 2, two [(2-hydroxy-5-methyl base phenyl) the methyl]-4-methylphenols, 4 of 6-, 4 '-[1-[4-[1-(4-hydroxy phenyl)-1-Methylethyl] phenyl] ethylidene] bis-phenol, 4,4 '-[1-[4-[2-(4-hydroxy phenyl)-2-propyl group] phenyl] ethylidene] bis-phenol, 4,4 ', 4 "-the ethylidine trisphenol etc.
In these phenoloids, especially preferably use the compound of following formula (15) or following formula (16) expression with general formula (10) expression.
The composition of the emulsion with diazonium quinonyl in the photosensitive polymer combination, composition (B) is 5～50 mass parts with respect to copolymer 1 00 mass parts of composition (A), is preferably 7～45 mass parts, and then preferred 10～40 mass parts.When this composition is lower than 5 mass parts, the possibility that causes that susceptibility descends or the development residue produces is arranged, when being higher than 50 mass parts, emulsion is for the compatibility variation of multipolymer, the possibility that has pattern film to be separated.
＜composition (C): hardening agent〉with 2 above epoxy radicals
The hardening agent that uses in the photosensitive polymer combination of the present invention has the epoxy radicals more than 2.This hardening agent can be when high-temperature baking and the carboxyl generation heat curing of multipolymer side chain reaction, forms cross linking membrane.The object lesson of this hardening agent can use bisphenol-type epoxy resin, cresols or phenol novolac epoxy resins, naphthalene type epoxy resin, alicyclic epoxy resin, the diglycidyl ether type epoxy, glycidyl ester type epoxy resin, glycidyl group amine type epoxy resin, hetero ring type epoxy resin, silicone-type epoxy resin, fluorenes type epoxy resin, four hydroxyphenyl ethane type epoxy resin, DPP (amyl phthalate) type epoxy resin, three hydroxyphenyl methane type epoxy resin, the aromatics polyglycidyl ether of bicyclopentadiene phenol-type epoxy resin (ジ シ Network ロ ペ Application タ ジ エ Application Off エ ノ one Le type エ Port キ シ Trees fat) etc. can also use the aromatic proton hydride of above-mentioned epoxy resin in addition.Hardening agent is not limited to these macromolecular epoxy resin, also can be the low epoxy compound that divides subsystem.Preferably enumerate cresols phenolic resin varnish type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin etc.The preferred especially bisphenol-type epoxy resin with 2 above epoxy radicals that uses can be realized good curable, high light transmittance and solvent resistance thus.These epoxy resin can only use a kind, or will be used in combination more than 2 kinds.
The composition of the hardening agent of composition in the photosensitive polymer combination (C) is 1～40 mass parts with respect to copolymer 1 00 mass parts of composition (A), is preferably 5～35 mass parts, and then preferred 10～30 mass parts.When this composition when 1 mass parts is following, the solvent patience of pattern film (cured film) is insufficient, when when 40 mass parts are above, the compatibility variation of hardening agent for multipolymer is arranged, and produces being separated and the possibility of gonorrhoea taking place of pattern film.
＜other adding ingredient 〉
In photosensitive polymer combination, the adding ingredient that can add solvent, curing accelerator, contrast (コ Application ト ラ ス ト) improving agent, compatilizer, adaptation raising auxiliary agent, surfactant etc. uses.
(solvent)
The object lesson of solvent can be enumerated the ethylene glycol monoalkyl ether class of glycol monoethyl ether, ethylene glycol monoethyl ether etc.; The ethylene glycol monoalkyl ether acetate class of ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate etc.; The diglycol dialkyl ether of diethylene glycol dimethyl ether, diethyl carbitol, diglycol methyl ethyl ether etc.; The propylene-glycol monoalky lether class of propylene glycol monomethyl ether, dihydroxypropane single-ether etc.; The propylene-glycol monoalky lether acetate esters of propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate etc.; The lactic acid ester of methyl lactate, ethyl lactate etc.; The aromatic hydrocarbons of toluene, dimethylbenzene etc.; The ketone of methyl ethyl ketone, 2-heptanone, cyclohexanone etc.; The amide-type of N,N-dimethylacetamide, N-Methyl pyrrolidone etc.; The lactone of gamma-butyrolacton etc. etc.These polymer solvents can use separately, perhaps use mixing more than 2 kinds.
(curing accelerator)
Curing accelerator can promote the cross-linking reaction of carboxyl of the multipolymer side chain of the hardening agent of mentioned component (C) and composition (A).Curing accelerator can be enumerated for example SI-60L, SI-80L, SI-100L, SI-110L[are above is made by three new chemical industry (strain)] etc. the aromatics sulfonium salt; U-CATSA102, U-CAT SA106, U-CAT SA506, U-CAT SA603, U-CAT 5002[are above by サ Application ア プ ロ (strain) system] etc. diazabicyclo undecylene salt; Make by サ Application ア プ ロ (strain) more than U-CAT 5003, U-CAT 18X, the CPI-210s[].And then the curing accelerator of imidazoles system can be enumerated キ ユ ア ゾ one Le 1B2PZ[four countries and changes into industry (strain) system].
In addition, also can use light alkali propellant of producing alkali by irradiates light etc.The condition of this light alkali propellant when regulating bleaching process can produce the alkali of amine etc. when rayed, after back baking operation in can be used as the crosslinking accelerator use.Therefore by contain these curing accelerators in photosensitive polymer combination, the reaction velocity of epoxy radicals and carboxyl accelerates, and in the high-temperature baking of back baking etc., can suppress the hot sagging of pattern film, obtains high-resolution pattern film.
The composition of curing accelerator is preferably 0.1～15 mass parts, more preferably the 1-10 mass parts with respect to hardening agent 100 mass parts of composition (C).
(contrast improving agent)
In order to improve contrast, can in photosensitive polymer combination, cooperate the phenoloid shown in following formula (9) or (10) with hydroxyl.Phenoloid with hydroxyl is low molecule, and therefore being suitable as common dissolution accelerator in photosensitive polymer combination is used to regulate dissolution velocity, or is used for the raising of susceptibility of photosensitive polymer combination or the adjusting of susceptibility.The adjusting of these dissolution velocities or susceptibility can be undertaken by the addition of regulating phenoloid, when increasing dissolution velocity and susceptibility, as long as increase addition, during opposite in addition situation as long as the minimizing addition.By using these phenoloids, compare with obsolete situation, in the resinous principle that the dissolving with emulsion generation azo coupling is inhibited, contain low molecular compound, the difference (increase contrast) of the dissolution velocity of exposed portion and unexposed portion can be increased thus, resolution can be improved.
Phenoloid with hydroxyl is following formula (12), (13), (14), (15) or (16) preferably, usually with respect to copolymer 1 00 mass parts, use with the amount of 1～20 mass parts.
(compatilizer)
In order to improve the compatibility of composition (A), (B), (C), can in photosensitive polymer combination, further cooperate parts shown in the following formula (17), 2 above carboxyls by the higher alcohol esterification the polycarboxylate compound.
(R
23OCO)
p——R
22——(COOH)
q …(17)
Here, R
22Be can be by the alkyl of hydroxyl, halogen, amino or sulfonic group replacement, R
23Be alkyl, p and q are respectively the integer more than 1.R
22Preferably stable hydrocarbon, unsaturated hydrocarbon or aromatic hydrocarbon, preferred especially unsaturated hydrocarbon.R
23Carbon number limit especially, be preferably 3～16, more preferably 5～12.And then R
23Can be the alkyl of straight chain or the alkyl of side chain.In addition, p is preferably 1～2, and q is preferably 1～3, when p is 2 when above, and R separately
23Can be identical, also can be different.
The content of polycarboxylate compound is 0.01～10 mass parts with respect to copolymer 1 00 mass parts of composition (A), is preferably 0.5～5 mass parts.When the content of polycarboxylate compound than 10 mass parts for a long time, the possibility that has the thermotolerance of the tunicle of formation to worsen.
(adaptation improves auxiliary agent and surfactant)
In photosensitive polymer combination, can further cooperate adaptation to increase auxiliary agent and surfactant etc. as required.Adaptation increases the example of auxiliary agent can enumerate alkyl imidazoline, butyric acid, alkyl acid, polycarboxylated styrene, polyvinyl methyl ether, tert-butyl phenol Novolac (t-Block チ Le ノ ボ ラ Star Network), epoxy silane, epoxy polymer, silane coupling agent etc.The example of surfactant can be enumerated nonionic surfactant, for example polyethylene glycols and its derivant, be polypropylene glycol or polyoxyethylene lauryl ether, contains surfactant, for example Off ロ ラ one De [trade name, Sumitomo 3M (strain) system], メ ガ Off ア Star Network [trade name, big Japanese イ Application キ chemical industry (strain) system], ス Le Off ロ Application [trade name, rising sun ガ ラ ス (strain) system] or organosiloxane surfactant, for example KP341[trade name, SHIN-ETSU HANTOTAI's chemical industry (strain) system of fluorine].
The modulation method of＜photosensitive polymer combination 〉
When modulation photosensitive polymer combination or its dilution, each composition that with mentioned component (A), (B) and (C) is representative can be cooperated together, also can be dissolved in each composition in the solvent after cooperation one by one.In addition, restriction especially of addition sequence during cooperation or operating condition.For example whole compositions can be dissolved in simultaneously and come resin composition modulation in the solvent, also can as required each composition suitably be made in advance the solution more than 2 kinds, in use (during coating) these solution mixed modulate photosensitive polymer combination.
＜flat-panel monitor and semiconductor device 〉
Flat-panel monitor and semiconductor device have above-mentioned photosensitive polymer combination are solidified the layer that forms, are planarization film or interlayer dielectric.When forming planarization film and interlayer dielectric, usually with the solution coat of photosensitive polymer combination on substrate, carry out preceding baking, form film (photoresist film) of photosensitive polymer combination.At this moment, the substrate of photosensitive resin coating composition can be that glass, siloxane etc. are used for FPD at present or are used for known any substrates such as substrate that semiconductor device forms.Substrate can be naked substrate, also can form oxide film, nitride film, metal film etc., and then also can be the substrate that has formed circuit pattern or semiconductor device etc.In addition, the temperature of preceding baking is generally 40～140 ℃, and the time is about 0～15 minute.Secondly, after the mask by regulation carries out pattern exposure on the photoresist film, use alkaline developer to carry out development treatment, carry out drip washing as required and handle, form the film of photosensitive polymer combination.The film of Xing Chenging carries out back baking formation pattern film after by blanket exposure like this.Exposure during blanket exposure is generally 600mJ/cm
2More than get final product.In addition, back baking temperature is generally 150～250 ℃, and preferred 180～230 ℃, the back baking time is generally 30～90 minutes.
The pattern film that the usability photosensitive resin composition forms can be used as the planarization film of FPD of semiconductor device or liquid crystal indicator, plasma scope etc. or interlayer dielectric and waits and utilize.Here, planarization film and interlayer dielectric are not fully independently, and the pattern film that is formed by photosensitive polymer combination can be used as the planarization film utilization, also can be used as the interlayer dielectric utilization.In semiconductor device etc., this film both can be used as interlayer dielectric, also can be used as planarization film performance function.
In the formation of above-mentioned pattern film, as the coating process of photosensitive polymer combination or its dilution, can use arbitrary method such as spin-coating method, rolling method, land coat (ラ Application De コ one ト) method, spray-on process, curtain coating rubbing method, dip coated method, slot coated method.In addition, as the radiant rays that in exposure, uses, can enumerate far ultraviolet, X ray, electron beam of for example ultraviolet ray, KrF excimer laser or the ArF excimer laser etc. of g line, h line, i line etc. etc.
Development method is so long as oar formula development method (パ ド ル Now is as method), immersion development method, shake the method that immersion development method, fountain development method etc. use at present and get final product when the development photoresist.Developer can use the aqueous solution that quaternary ammoniums such as organic amine, tetramethylammonium hydroxide such as inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, ammonia, ethylamine, propyl group amine, diethylamide, DEAE diethylaminoethanol, triethylamine etc. is adjusted to normal concentration.
Embodiment
Below, enumerate embodiment and comparative example and be described more specifically above-mentioned embodiment.And " part " and " % " short of explanation especially is quality criteria.Following assay method and the evaluation method of using in expression each embodiment and each comparative example.
＜acid number 〉
Acid number (mgKOH/g) is according to JIS K0070:1992 " test method of the acid number of chemicals, saponification number, esterification number, iodine number, hydroxyl value and unsaponifiables ", with a certain amount of resin dissolves in tetrahydrofuran (THF) solution, as indicator, utilize potassium hydroxide/ethanolic solution titration to measure with phenolphthalein.
＜weight-average molecular weight 〉
Weight-average molecular weight (Mw) is tried to achieve as following, promptly, use eastern ソ one (strain) system gel permeation chromatography device HLC-8220GPC and clear and electrician's (strain) system pillar SHODEX K801, with THF as eluent, utilize the RI detecting device to measure, the typical curve that uses the polystyrene standards by the known molecular amount to obtain converts.
[synthesizing of synthesis example 1, copolymer A-1]
Ethyl lactate (EL) 540.0g that in the 4 neck flasks of the 1000mL with thermometer, stirring machine and condenser pipe, packs into, carry out the nitrogen displacement after, in oil bath, heat up, be 90 ℃ until the liquid temperature.
In addition, after dripping following such liquid (dropping composition) by tap funnel with 2 hours average rates, under uniform temp, kept 8 hours, obtain copolymer A-1, described liquid is with fumaric acid two (4-tert-butylcyclohexyl) ester (DcHtBF) 71.1g, methacrylic acid (MAA) 38.4g, styrene (St) 18.9g, 2-hydroxyethyl methacrylate (HEMA) 71.6g, 2,2 '-azoisobutyronitrile [azo is the pure pharmaceutical worker's industry of polymerization initiator and light (strain) system] 10.0g and EL60.0g evenly mix in advance and liquid.
[synthesis example 2～9]
Except adding kind and amount, dropping and polymerization temperature that change list 1 is recorded and narrated, other uses the method synthetic copolymer A-2～A-9 same with synthesis example 1.
The meaning of the ellipsis in the table 1 is as described below.
DcHtBF: two (4-tert-butylcyclohexyl) esters of fumaric acid
DcHF: fumaric acid two cyclohexyls
DiPF: fumaric acid diisopropyl ester
DsBF: fumaric acid di-secondary butyl ester
DtBF: fumaric acid di tert butyl carbonate
DsAF: fumaric acid di-secondary pentyl ester
St: styrene
α MeSt: α-Jia Jibenyixi
MAA: methacrylic acid
AA: acrylic acid
HEMA: methacrylic acid-2-hydroxy methacrylate
HPMA: methacrylic acid hydroxyl propyl ester
MMA: methyl methacrylate
CHMA: cyclohexyl methacrylate
Hex-O: the peroxidating system polymerization initiator " パ one ヘ キ シ Le Le O " of uncle's hexyl peroxidating-2 ethyl hexanoic acid ester, day oil (strain) system
Bu-O: the peroxidating system polymerization initiator " パ one Block チ Le O " of tert-butyl hydroperoxide-2 ethyl hexanoic acid ester, day oil (strain) system
AIBN:2,2 '-azoisobutyronitrile [azo is the pure pharmaceutical worker's industry of polymerization initiator and light (strain) system]
PGMEA: propylene glycol methyl ether acetate
EL: ethyl lactate
＜embodiment 1 〉
In propylene glycol methyl ether acetate 75.2g and ethyl lactate 0.2g, copolymer A-1 100g that dissolving synthesis example 1 obtains, the compound and 1 of following formula (15) expression, the carboxylate 6.25g of 2-diazo naphthoquinone-5-sulfonic acid chloride, and then the dissolving phenoloid 1.25g of formula (15) expression, テ Network モ ア VG3101L[(strain) プ リ Application テ Star Network system] 5g, U-CAT SA102[サ Application ア プ ロ (strain) system] 0.1g, in order to prevent the actinoid gauffer on the resist film when the rotary coating, so-called streak, further adding fluorine is surfactant, the メ ガ Off ア Star Network big Japanese イ Application キ chemical industry of R-08[(strain) system] 0.01g, stir the filtrator filtration of back, make the dilution of photosensitive polymer combination with 0.2 μ m.
(formation of Thinfilm pattern)
The dilution of this photosensitive polymer combination is carried out rotary coating on 4 inches silicon chips (シ リ コ Application ウ エ Ha one), after 90 seconds, obtain the thick film of 4.2 μ m 100 ℃ of bakings with heating plate.Utilizing キ ヤ ノ Application (strain) system g+h+i line mask aligner (PLA-501F) on this film is that 1: 1 the various live widths and the test pattern of contact hole (コ Application タ Network ト ホ one Le) expose with optimum exposure to lines and interval width, 23 ℃ of developments of carrying out 60 seconds, form lines and interval width thus and be 1: 1 Xian Tiao ﹠amp with 0.4 quality % tetramethyl ammonium hydroxide aqueous solution; Intermittent pattern and contact hole pattern.After this film carried out blanket exposure with PLA-501F, by in baking oven in 220 ℃ of heating 60 minutes, carry out back baking processing, obtaining thickness is the film that has pattern (pattern film) of 3.0 μ m.
(evaluation of development)
In the pattern of above-mentioned making, utilize SEM to observe the sectional hole patterns of 10 μ m.When in whole of hole portion, observing residue note do *, only note is made △ when the near interface of hole and substrate is observed residue, note work zero is not estimated development when all observing residue in whole of hole portion.It the results are shown in table 2.
(evaluation of specific inductive capacity)
Except PLA-501F of no use exposed to test pattern, other carried out and above-mentioned same operation, can on 4 inches silicon chips, obtain thus not having pattern, thickness is the film of 3.0 μ m.On this film, form electrode, calculate specific inductive capacity by the static capacity of under the condition of room temperature, 10kHz, using peace rattan electric (strain) system LCR meter (AG-4311) to obtain.It the results are shown in table 2.
(evaluation of transmissivity)
Except using the quartz glass substrate of long 70mm, wide 70mm size, and beyond test pattern not being exposed, other carries out and above-mentioned same operation, obtains not having the film of pattern thus on glass substrate.Use ultraviolet-visible spectrophotometer CARY4E (バ リ ア Application society system), the optical wavelength of measuring the glass substrate with this film is the transmissivity of 400nm.It the results are shown in table 2.
(evaluation of solvent resistance)
Will be by operating the glass substrate that obtains equally in Remover100[AZ エ レ Network ト ロ ニ Star Network マ テ リ ア Le ズ (strain) system with the evaluation of transmissivity] in 80 ℃ of dippings after 1 minute, carry out pure water drip washing, 200 ℃ of baking processing again of carrying out 15 minutes.Transmission rate variance after transmissivity before solvent impregnated and the baking processing again is evaluated as zero less than 3% the time, when the transmission rate variance be 3% be evaluated as when above *.It the results are shown in table 2.
＜embodiment 2 〉
The copolymer A-2 that obtains in using synthesis example 2, other and embodiment 1 carry out same operation, modulate the dilution of photosensitive polymer combination thus.For this photosensitive polymer combination, estimate rerum natura similarly to Example 1, they the results are shown in table 2.
＜embodiment 3～18 〉
For the cooperation shown in table 2 and the table 3, carry out operation similarly to Example 1, modulate the dilution of the photosensitive polymer combination of embodiment 3～18 thus.For these photosensitive polymer combinations, estimate rerum natura similarly to Example 1, they the results are shown in table 2 and table 3.
＜comparative example 1 and 2 〉
For the cooperation shown in the table 3, carry out operation similarly to Example 1, modulate the dilution of the photosensitive polymer combination of comparative example 1,2 thus.For these photosensitive polymer combinations, estimate rerum natura similarly to Example 1, these the results are shown in table 3.
Can confirm according to the result shown in table 2 and the table 3, for embodiment 1～18, in the developing procedure that forms pattern film, residue does not develop, even behind high-temperature baking, do not damage the rerum natura of filming, development and the low dielectric property excellence of light transmission, solvent resistance etc. yet.And, for embodiment 1～18, can fully keep the residual film ratio of pattern film, the flatness of pattern film is also good in addition.
On the other hand, according to the result shown in the table 3, the multipolymer of composition in the comparative example 1 (A) does not contain formation unit (a1), thereby the development deterioration.In comparative example 2, do not contain in the multipolymer and constitute unit (a1) and (a2) so specific inductive capacity deterioration.
Claims (3)
1. photosensitive polymer combination, it contains composition (A), (B) and (C), it is characterized in that, composition (A) is to comprise to constitute unit (a1) with following formula (1) expression by the dimethyl ester monomer derived, constitute unit (a2) with following formula (2) expression by what aromatic vinyl monomer was derived, with following formula (3) expression by α, the formation unit (a3) of beta-unsaturated carboxylic acid monomer derived and with the multipolymer of the formation unit (a4) of deriving by (methyl) acrylate monomer of following formula (4) expression, the total amount that constitutes unit (a1) and formation unit (a2) is 40～85 quality % in this composition (A), the mass ratio (a4)/(a3) that constitutes unit (a3) and formation unit (a4) is 0.2～7.0
(in the formula, R
1And R
2Be respectively that carbon number is that 3～8 branched alkyl, carbon number are 4～12 naphthenic base or replace the side chain naphthenic base)
(in the formula, R
3Be hydrogen atom or methyl, R
4Be that carbon number is 6～12 aromatic hydrocarbyl)
(the R in the formula
5Be hydrogen atom, methyl or ethyloic)
(the R in the formula
6Be hydrogen atom or methyl, R
7Be that carbon number is that 6～12 aromatic hydrocarbyl, carbon number are that 1～12 alkyl, carbon number are that 1～12 branched alkyl, carbon number are that 2～12 hydroxy alkyl or the carbon number that constitutes main ring are 5～12 ester ring type alkyl),
Composition (B) makes phenoloid and diazonium naphtoquinone compounds with hydroxyl carry out the emulsion that esterification obtained, had the diazonium quinonyl,
Composition (C) is the hardening agent with 2 above epoxy radicals,
Composition (B) and composition (C) are respectively that (B) is 5～50 mass parts and (C) is 1～40 mass parts with respect to composition (A) 100 mass parts.
2. flat-panel monitor, it has the described photosensitive polymer combination of claim 1 is solidified the layer that obtains.
3. semiconductor device, it has the photosensitive polymer combination that claim 1 is described and solidifies the layer that obtains.
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| KR101312603B1 (en) | 2013-09-30 |
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| JP2010181827A (en) | 2010-08-19 |
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