CN101974121A - Chemical amplified high-resolution silicon-containing I-ray ultraviolet photoresist and forming resin thereof - Google Patents

Chemical amplified high-resolution silicon-containing I-ray ultraviolet photoresist and forming resin thereof Download PDF

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CN101974121A
CN101974121A CN 201010294204 CN201010294204A CN101974121A CN 101974121 A CN101974121 A CN 101974121A CN 201010294204 CN201010294204 CN 201010294204 CN 201010294204 A CN201010294204 A CN 201010294204A CN 101974121 A CN101974121 A CN 101974121A
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formula
ester
forming resin
acid
methyl
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冉瑞成
沈吉
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KUNSHAN SD PHOTOELECTRIC MATERIAL Co Ltd
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KUNSHAN SD PHOTOELECTRIC MATERIAL Co Ltd
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Abstract

The invention discloses a silicon-containing copolymer forming resin which is prepared by carrying out copolymerization reaction on a comonomer in a solvent in the presence of radical initiator, and is characterized in that the molecular weight of the forming resin is 4000-100000; the molecular weight distribution is 1.4-2.8; and the comonomer mainly comprises the following components by weight percent: 40-90% of substituted phenylethylene, 0.5-20% of silicon-containing acrylic ester coupling agent and 5-60% of acidsensitivity-containing basic group monomer. In the invention, the silicon-containing acrylic ester coupling agent which can be copolymerized with the forming resin is introduced in a forming resin formula by taking poly (p-hydroxystyrene) as a base to carry out copolymerization, so as to prepare into the new forming resin. Under the action of the silicon-containing acrylic ester coupling agent unit, the new forming resin increases the adhesive property between the photoresist and a silicon wafer, and simultaneously improves the anti-corrosion performance.

Description

Chemical amplification type high resolving power siliceous I-line ultraviolet photoresist and film-forming resin thereof
Technical field
The present invention relates to a kind of ultraviolet photoresist, particularly a kind of silicon-containing copolymer film-forming resin and utilize this film-forming resin formulated to be used for I-line (365nm) UV-light be the chemical amplification type positivity ultraviolet photolithographic glue composition of exposure light source.
Background technology
Photoresist material is the key function material that carries out photo-etching technological process in the large-scale integrated circuit industry.Wherein film-forming resin is again the important component part of photoresist material, and its chemistry and physicals directly influence the result of use of photoresist material in large-scale integrated circuit industry.
Traditional ultraviolet (UV) exposure light source is a high voltage mercury lamp, and its optical wavelength is between 600～300nm, and its main spectrum comprises g-line (436nm), h-line (405nm) and I-line (365nm).Being inversely proportional at photoetching process intermediate-resolution and exposure wavelength, (R=k λ/NA), promptly the short more resolving power of exposure wavelength is high more.Therefore, I-line photoresist material can obtain higher resolving power in the photoetching process of uv-exposure.Traditional ultraviolet photoresist is to be membrane-forming agent with the phenolic aldehyde urea formaldehyde, and formulated in suitable solvent based on the photosensitizers of DNQ (diazo naphthoquinone), its resolving power is generally about 2.0～1.0 microns.In order to improve the resolving power of ultraviolet photoresist, people have done a large amount of improvement to resol resin and photosensitizers, and its resolving power can reach 0.8～0.5 mu m range, but prior art again can't further break through the resolving power of photoresist material.
Summary of the invention
The invention provides the siliceous I-line of a kind of high resolving power ultraviolet photolithographic glue composition, purpose is to make the resolving power of I-line (354nm) ultraviolet photoresist can reach the 0.35-0.25 mu m range.
For achieving the above object, first kind of technical scheme that the present invention adopts is: a kind of silicon-containing copolymer film-forming resin, by comonomer under the condition that radical initiator exists, carrying out copolymerization in the solvent is prepared from, the molecular weight of described film-forming resin is 4000～100000, and molecular weight distribution is 1.4～2.8; Described comonomer is mainly the compound of following quality percentage composition:
Substituted phenylethylene 40%～90%;
Acrylate containing silicone class coupling agent 0.5%～20%;
Contain acid-sensitive group monomer 5%～60%;
Described substituted phenylethylene is at least a compound that meets chemical general formula (I):
Figure BSA00000286387200021
In the formula, R 1Be H, ethanoyl or propionyl; M=1 or 2;
The chemical general formula of described acrylate containing silicone class coupling agent is shown in (II) formula:
Figure BSA00000286387200022
In the formula: R 2Be H or CH 3R 3Be that carbonatoms is 1～20 alkyl; R 4Be that carbonatoms is 1～20 alkyl; R 5Be that OH, carbonatoms are that 1～20 alkyl or carbonatoms are 1～20 alkoxyl group; N=1～8;
Described contain acid-sensitive group monomer be meet chemical general formula (III) formula and (IV) at least a compound:
Figure BSA00000286387200023
In the formula: R 6Be H, CH 3Or CF 3R 7Be
Figure BSA00000286387200024
Figure BSA00000286387200025
Perhaps
Figure BSA00000286387200026
Wherein, R xBe methyl or ethyl;
Figure BSA00000286387200027
In the formula: R 8Be:
Figure BSA00000286387200028
Perhaps
Figure BSA00000286387200029
R wherein yBe methyl or ethyl.
For achieving the above object, second kind of technical scheme that the present invention adopts is: mainly be made up of the material of following mass parts:
The I-linear light causes 10 parts of acid;
1～3 part of film-forming resin;
60～120 parts of solvents;
Described solvent is at least a in 1-Methoxy-2-propyl acetate, propylene glycol list Acetic Ester, dihydroxypropane single-ether, 1-Methoxy-2-propyl acetate, tirethylene glycol methyl ether, tirethylene glycol ether, N-BUTYL ACETATE, acetic acid peopentyl ester, ethyl lactate, methyl ethyl ketone and the methyl iso-butyl ketone (MIBK).
Related content in the technique scheme is explained as follows:
1, in the such scheme, also comprise the quality percentage composition in the described comonomer and be 1%～40% meet chemical general formula (V) and (VI) at least a compound;
Figure BSA00000286387200031
In the formula: R wBe that H, carbonatoms are that 1～20 alkyl or carbonatoms are 1～20 alkoxyl group; R zBe H, carbonatoms be 1～20 alkyl, carbonatoms be 1～20 alkoxyl group,
Figure BSA00000286387200032
Perhaps HO (CH 2) 2O-;
Figure BSA00000286387200033
In the formula: R 9Be H or CH 3, R 10Be H,
Figure BSA00000286387200034
Carbonatoms is that 1～20 alkyl or carbonatoms are 1～20 alkoxyl group.
2, in the such scheme, described substituted phenylethylene is para hydroxybenzene ethene, to acetoxy-styrene, rare, the acetoxy-styrene, 3 of a hydroxybenzene second, 4-dihydroxy-benzene ethene, 3,4-diacetoxy vinylbenzene, 3,5-dihydroxy-benzene ethene and 3, at least a in the 5-diacetoxy vinylbenzene.
3, in the such scheme, described to meet chemical general formula (III) formula compound be tert-butyl acrylate, the methacrylic tert-butyl acrylate, the vinylformic acid tert-pentyl ester, the methacrylic acid tert-pentyl ester, vinylformic acid-1-methyl ring pentyl ester, methacrylic acid-1-methyl ring pentyl ester, vinylformic acid-1-methyl cyclohexane ester, methacrylic acid-1-methyl cyclohexane ester, vinylformic acid-1-ethyl ring pentyl ester, methacrylic acid-1-ethyl ring pentyl ester, vinylformic acid-1-ethyl cyclohexyl, methacrylic acid-1-ethyl cyclohexyl, vinylformic acid-2-methyl adamantane alcohol ester, methacrylic acid-2-methyl adamantane alcohol ester, acrylic acid-2-ethyl diamantane alcohol ester, methacrylic acid-2-ethyl diamantane alcohol ester, vinylformic acid-2-butyrolactone base ester, methacrylic acid-2-butyrolactone base ester, vinylformic acid-2-caprolactone base ester or methacrylic acid-2-caprolactone base ester.
4, in the such scheme, described chemical general formula (IV) the formula compound that meets is to tert.-butoxy vinylbenzene, to uncle's amyl phenyl ether ethene, to tertiary butyl carbonic ether vinylbenzene or to the different phenetole ethene of 1-ethoxy.
5, in the such scheme, it is described that to meet chemical general formula (V) formula compound be vinylbenzene, to t-butyl styrene, to tert.-amylbenzene ethene, to phenetole ethene, 3,5-dimethoxy styrene, 3,5-diethoxy vinylbenzene, to phenoxy group vinylbenzene or to 2-hydroxy ethoxy vinylbenzene.
6, in the such scheme, it is at least a compound that meets among structural formula (VII) and general formula (VIII), (X), (XI), (XII), (XIII), (XIV) that described I-linear light causes acid:
Figure BSA00000286387200041
In the formula, o=1～2;
Figure BSA00000286387200051
In the formula, p=1～2;
In the formula, R 11For-C 3H 7,-C 8H 17,
Figure BSA00000286387200053
Perhaps
Figure BSA00000286387200054
Figure BSA00000286387200055
In the formula, R 11For-CF 3,-C 4F 9Perhaps
Figure BSA00000286387200056
Figure BSA00000286387200057
In the formula, R 13For-CF 3,-C 6F 5Perhaps
Figure BSA00000286387200058
Figure BSA00000286387200059
In the formula, R 14For
Figure BSA00000286387200061
Perhaps
Figure BSA00000286387200062
7, in the such scheme, the listed I-linear light of structural formula and general formula causes acid three classes: imide sulfonic acid esters, fragrant oxime sulfonates class and trichloromethyl melamine class.The imide sulfonic acid esters is as phenyl imide benzene sulfonate, phenyl imide tosylate, phenyl imide napsylate, naphthalimide benzene sulfonate, naphthalimide trifluoromethane sulfonic acid ester etc.
8, in the such scheme, about polyreaction
(1), above-mentioned copolymerization can carry out in the mixture of all kinds of SOLVENTS or solvent, these solvents comprise methyl alcohol, ethanol, dioxane, acetone, tetrahydrofuran (THF), toluene, benzene, dimethylbenzene, methylene dichloride, chloroform, trichloromethane, ethylene dichloride, trichloroethane etc.
(2), these copolymerizations can carry out in the presence of various radical initiators, comprise azo initiators such as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), and the radical initiator of various superoxide, as tert-butyl hydroperoxide pivalate, tertbutyl peroxide, phenylformic acid hydrogen peroxide, benzoyl peroxides etc., initiator amount are 0.3%～15% of total monomer weight.
(3), the adding of radical initiator can be adopted dual mode: first kind is after each comonomer is dissolved in solvent, is heated to polymerization temperature earlier, adds initiator then and carries out polyreaction.Second kind is after each comonomer is dissolved in solvent, adds earlier initiator, and then is warmed to polymerization temperature and carries out polyreaction.Described initiator can disposablely add in this dual mode, also can gradation add.The temperature of polyreaction: the temperature of polyreaction is controlled at 40～150 ℃ of scopes according to the solvent that uses is different with initiator.Polymerization reaction time is also according to be controlled at 4～28 hour different with initiator of solvent of using.
9, in the such scheme, the aftertreatment of polyreaction:
(1), purification process
After polyreaction was finished, unreacted residual monomer and part organic impurity thereof can be removed after extracting with heptane, hexane, hexanaphthene, pentane, sherwood oil, ether equal solvent.
(2), separate solid multipolymer
Multipolymer can be in organic or inorganic solvents such as the mixture of mixture, Virahol and the water thereof of mixture, ethanol and the water thereof of pure water, methyl alcohol, first alcohol and water, heptane, hexane, hexanaphthene, pentane, sherwood oil, ether precipitate and separate, the yield of vacuum-drying rear copolymer is 60%～90%.
(3), the reaction of polymkeric substance
Some multipolymer also can be obtained through suitable chemical reaction by the specific polymkeric substance of forming except can directly being formed by their corresponding monomer copolymerization.Can obtain via polyreaction by monomer para hydroxybenzene ethene as poly(4-hydroxystyrene), also can remove deacetylate and obtain poly(4-hydroxystyrene) through hydrolysis reaction acetoxy-styrene by poly-.Hydrolysis reaction can carry out in the presence of an acidic catalyst, also can carry out in the presence of basic catalyst.As sulfuric acid, hydrochloric acid, ammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methylate, sodium ethylates etc. can be as the catalyzer of hydrolysis reaction.
And for example, gather, outside can obtaining by the monomer whose direct polymerization, also can and obtain by poly(4-hydroxystyrene) and tert-Butyl dicarbonate (DBDC) reaction to tertiary butyl carbonic ether vinylbenzene.Reality is used the sort of method, should decide according to processing requirement and pricing.
Because the technique scheme utilization, the present invention compared with prior art has following advantage and effect:
The present invention has introduced the siliceous esters of acrylic acid coupling agent of copolymerization with it in the film-forming resin prescription based on poly(4-hydroxystyrene), carry out copolymerization and be prepared into the new film-forming resin of a class.This new film-forming resin is because the unitary effect of acrylate containing silicone class coupling agent has increased the adhesive property between photoresist material and the silicon chip.Simultaneously, also improved anti-etching performance.Furtherly, because the existence of acrylate containing silicone class coupling agent unit in film-forming resin, photoresist material glued membrane on its silicon chip is in photoetching process, in the non-exposed area, Si-OR group in the coupling agent will reduce the solvability of glued membrane in developing solution, exposure region causes under the strong acid effect of acid formation at the I linear light, the Si-OR group is decomposed to form Si-OH and increases the solvability of glued membrane in alkaline-based developer in the coupling agent, and so just increased exposure region and non-exposed area contrast gradient, and form litho pattern more clearly.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one～12: a kind of chemical amplification type high resolving power siliceous I-line ultraviolet photoresist and film-forming resin thereof
One, the comonomer of silicon-containing copolymer film-forming resin is as follows
(1), substituted phenylethylene
Embodiment one: to acetoxy-styrene
Embodiment two: to acetoxy-styrene
Embodiment three: para hydroxybenzene ethene
Embodiment four: to acetoxy-styrene
Embodiment five: para hydroxybenzene ethene
Embodiment six: a hydroxy styrenes
Embodiment seven: 3,5-dihydroxy-benzene ethene, a hydroxybenzene second are rare
Embodiment eight: 3,5-diacetoxy vinylbenzene
Embodiment nine: 3,4-diacetoxy vinylbenzene, para hydroxybenzene ethene
Embodiment ten: an acetoxy-styrene
Embodiment 11: 3, and 4-dihydroxy-benzene ethene, a hydroxy styrenes
Embodiment 12: 3, and 5-dipropyl acetoxystyrene
(2), acrylate containing silicone class coupling agent
Embodiment one: the KH-570 silane coupling agent
Embodiment two: methacrylic acid ethyl trimethoxy silane ester
Embodiment three: the KH-570 silane coupling agent
Embodiment four: vinylformic acid ethyl trimethoxy silane ester
Embodiment five: methacrylic acid propyl group dimethoxy-ethyl silicon ester
Embodiment six: vinylformic acid propyl group dimethoxy-ethyl silicon ester
Embodiment seven: methacrylic acid ethyl diethoxy silane ester
Embodiment eight: methacrylic acid methyl Trimethoxy silane ester
Embodiment nine: vinylformic acid ethyl diamyl TMOS ester
Embodiment ten: methacrylic acid methyl diethoxy silane ester
Embodiment 11: vinylformic acid methyl dipropoxy silicon ester
Embodiment 12: methacrylic acid methylmethane TMOS ester
(3), contain acid-sensitive group monomer
Embodiment one: to tert.-butoxy vinylbenzene
Embodiment two: vinylformic acid-1-methyl ring pentyl ester
Embodiment three: the methacrylic tert-butyl acrylate
Embodiment four: vinylformic acid-1-ethyl cyclohexyl
Embodiment five: methacrylic acid-2-ethyl diamantane ester
Embodiment six: to tertiary butyl carbonic ether vinylbenzene
Embodiment seven: to tert.-butoxy vinylbenzene, to uncle's amyl phenyl ether ethene
Embodiment eight: methacrylic acid-1-methyl ring pentyl ester, tert-butyl acrylate
Embodiment nine: vinylformic acid-2-butyrolactone base ester, to uncle's amyl phenyl ether ethene
Embodiment ten: vinylformic acid-2-caprolactone base ester
Embodiment 11: to uncle's amyl phenyl ether ethene
Embodiment 12: methacrylic acid-1-ethyl ring pentyl ester, tert-butyl acrylate
(4), meet chemical general formula (V) and (VI) in compound
Embodiment one: isobornyl methacrylate
Embodiment two: vinylbenzene
Embodiment three: vinylbenzene
Embodiment four: to phenetole ethene
Embodiment five:
Embodiment six: vinylformic acid diamantane alcohol ester, methacrylic acid diamantane alcohol ester
Embodiment seven: the methacrylic acid cholesterol ester
Embodiment eight: 3,5-dimethoxy styrene, 3,5-dioxy base vinylbenzene
Embodiment nine:
Embodiment ten: methacrylic acid benzyl ester, vinylbenzene
Embodiment 11: 3, and 5-diethoxy vinylbenzene, to phenoxy group vinylbenzene
Embodiment 12:
Two, the preparation method of the silicon-containing copolymer film-forming resin of embodiment one～five is as follows
(1) comonomer
To acetoxy-styrene 113.4 grams 65.4%;
Methacrylic acid iso-borneol fat 15.8 grams 9.1%;
To tert.-butoxy vinylbenzene 35.2 grams 20.3%;
Methacrylic acid propyl trimethoxy silicane ester (KH570) 9 grams 5.2%.
The preparation method is: be equipped with electric mixer at one, condenser, thermometer, temperature regulator, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, adding is to acetoxy-styrene 113.4 grams, isobornyl methacrylate 15.8 grams, to tert.-butoxy vinylbenzene 35.2 grams, methacrylic acid propyl trimethoxy silicane ester (KH570) 9 grams, tetrahydrofuran (THF) (solvent) 400 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of Diisopropyl azodicarboxylate (AIBN) 12 grams in 100 gram tetrahydrofuran (THF)s, continue the reaction backflow after 8～28 hours, add 6.5 gram sodium methylates (98%) and 200 gram tetrahydrofuran (THF)s, back flow reaction 8 hours, and steam about 100 milliliters and steam thing, be cooled to room temperature then.Remove by filter ion exchange resin.Extract three times with heptane, polymers soln precipitates in pure water, gets polymer solids, molecular weight 12500, yield 80% after the vacuum-drying.
(2) comonomer
To acetoxy-styrene 97.2 grams 61.3%;
Vinylbenzene 20.8 grams 13.1%;
Vinylformic acid 1-methyl ring pentyl ester 33.6 grams 21.2%;
Methacrylic acid ethyl trimethoxy silane ester 7 grams 4.4%.
The preparation method is: be equipped with electric mixer at one, condenser, thermometer, temperature regulator, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, adding is to acetoxy-styrene 97.2 grams, vinylbenzene 20.8 grams, vinylformic acid-1-methyl ring pentyl ester 33.6 grams, methacrylic acid ethyl trimethoxy silane ester 7 grams, tetrahydrofuran (THF) 400 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of Diisopropyl azodicarboxylate (AIBN) 11 grams in 100 gram tetrahydrofuran (THF)s, continue the reaction backflow after 8～18 hours, add 5.0 sodium ethylates, add 200 gram tetrahydrofuran (THF)s after 15 minutes, back flow reaction 8 hours, and steam about 200 milliliters and steam thing, be cooled to room temperature then.Extract three times with heptane, polymers soln precipitates in pure water, gets polymer solids, molecular weight 13100, yield 82% after the vacuum-drying.
(3) comonomer
Para hydroxybenzene ethene 96.0 grams 64.1%;
Vinylbenzene 20.8 grams 13.8%;
Methacrylic tert-butyl acrylate 26.0 grams 17.4%;
Methacrylic acid propyl trimethoxy silicane ester (KH570) 7.0 grams 4.7%.
The preparation method is: be equipped with electric mixer at one, condenser, thermometer, temperature regulator, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, add para hydroxybenzene ethene 96.0 grams, vinylbenzene 20.8 grams, methacrylic tert-butyl acrylate 26.0 grams, methacrylic acid propyl trimethoxy silicane ester (KH570) 7.0 grams, tetrahydrofuran (THF) 400 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of Diisopropyl azodicarboxylate (AIBN) 9.5 grams in 100 gram tetrahydrofuran (THF)s, continue the reaction backflow after 6～24 hours, be cooled to room temperature then.Extract three times with heptane, polymers soln precipitates in pure water, gets polymer solids, molecular weight 17300, yield 85% after the vacuum-drying.
(4) comonomer
To acetoxy-styrene 105.3 grams 57.4%;
To phenetole ethene 29.6 grams 16.1%;
Vinylformic acid 1-ethyl cyclohexyl 41.7 grams 22.7%;
Methacrylic acid ethyl trimethoxy silane ester 7 grams 3.8%.
The preparation method is: be equipped with electric mixer at one, condenser, thermometer, temperature regulator, in the 1000ml there-necked flask of heating jacket and nitrogen inlet, adding is to acetoxy-styrene 105.3 grams, to phenetole ethene 29.6 grams, vinylformic acid-1-ethyl cyclohexyl 41.7 grams, methacrylic acid ethyl trimethoxy silane ester 7 grams, methyl alcohol 300 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of tert-butyl hydroperoxide pivalate 29 grams in 100 gram methyl alcohol, continue the reaction backflow after 8～18 hours, add 3.2 gram sodium ethylates, add 200 gram methyl alcohol after 15 minutes, back flow reaction 8 hours, and steam about 200 milliliters and steam thing, be cooled to room temperature then.Extract three times with heptane, polymers soln precipitates in pure water, gets polymer solids, molecular weight 9800, yield 82% after the vacuum-drying.
(5) comonomer
Para hydroxybenzene ethene 84.6 grams 51%;
Methacrylic acid 2-ethyl diamantane ester 70.8 grams 42.7%;
Methacrylic acid propyl group dimethoxy-ethyl silicon ester 10.5 grams 6.3%.
The preparation method is: in a 1000ml there-necked flask that is equipped with electric mixer, condenser, thermometer, temperature regulator, heating jacket and nitrogen inlet, add para hydroxybenzene ethene 84.6 grams, methacrylic acid-2-ethyl diamantane ester 70.8 grams, methacrylic acid propyl group dimethoxy-ethyl silicon ester 10.5 grams, tetrahydrofuran (THF) 500 grams, under agitation logical nitrogen 10 minutes, be heated to 60～70 ℃ then, add the solution of Diisopropyl azodicarboxylate (AIBN) 9.8 grams in 100 gram tetrahydrofuran (THF)s, continue the reaction backflow after 4～18 hours, be cooled to room temperature then.Extract three times with heptane, polymers soln precipitates in pure water, gets polymer solids, molecular weight 10850, yield 81% after the vacuum-drying.
Three, the quality percentage composition of the comonomer of the silicon-containing copolymer film-forming resin of embodiment six～12 such as following table 1, copolymerization process is same as embodiment one～five.
Table 1
Monomer 1/% Monomer 2/% Monomer 3/% Monomer 4/%
Embodiment six 45 13 39 3
Embodiment seven 87 3 5 5
Embodiment eight 67 18 7 8
Embodiment nine 35 10 55
Embodiment ten 40 20 5 35
Embodiment 11 70 15 12 3
Embodiment 12 60 15 25
In the last table, monomer 1 is a substituted phenylethylene; Monomer 2 is acrylate containing silicone class coupling agents; Monomer 3 is to contain acid-sensitive group monomer; Monomer 4 be meet chemical general formula (V) and (VI) in compound.When certain monomer was mixture, its blending ratio was 1: 1.
Four, it is as follows that the I-linear light causes acid
Embodiment one: 1,8-naphthalene two formyl trifluoromethyl sulfimides
Embodiment two:
Figure BSA00000286387200121
Embodiment three: the naphthalimide benzene sulfonate
Embodiment four:
Embodiment five: phenyl imide napsylate
Embodiment six:
Figure BSA00000286387200123
Embodiment seven: phenyl imide tosylate
Embodiment eight:
Figure BSA00000286387200124
Embodiment nine:
Figure BSA00000286387200125
Embodiment ten:
Figure BSA00000286387200126
Embodiment 11: phenyl imide benzene sulfonate
Embodiment 12:
Figure BSA00000286387200131
Five, solvent
Embodiment one: 1-Methoxy-2-propyl acetate
Embodiment two: the tirethylene glycol methyl ether
Embodiment three: dihydroxypropane single-ether
Embodiment four: the acetic acid peopentyl ester
Embodiment five: 1-Methoxy-2-propyl acetate, N-BUTYL ACETATE, ethyl lactate
Embodiment six: 1-Methoxy-2-propyl acetate, N-BUTYL ACETATE
Embodiment seven: N-BUTYL ACETATE
Embodiment eight: methyl ethyl ketone
Embodiment nine: the tirethylene glycol methyl ether
Embodiment ten: N-BUTYL ACETATE
Embodiment 11: the tirethylene glycol ether
Embodiment 12: ethyl lactate
Six, the siliceous I-line of chemical amplification type high resolving power ultraviolet photoresist preparation method is as follows
In clean 250 new ml polypropylene Plastic Bottles, the multipolymer that adds preparation among the 17.0 gram embodiment one, 0.68 restrain 1,8-naphthalene two formyl trifluoromethyl sulfimides (NITf), 100 gram electronic grade propylene glycol monomethyl ether acetic ester (PGMEA) solvents, and 0.1 the gram n-Butyl Amine 99,0.12 the gram tensio-active agent.This mixture is fixed on the mechnical oscillator, and concussion reflection at room temperature 10～24 hours is fully dissolved it.Strainer with 0.5 micron pore size filters one time, and the strainer with 0.1 micron pore size filters one time then.
Lithography experiments method and result: the photoresist material of above-mentioned preparation is 6 "～8 " on the silicon chip with 2000～6000 rev/mins speed rotation film forming, on 120 ℃ of hot plates, toasted for 90 seconds, use ASMALI-line (365nm) step-by-step exposure machine (NA=0.60) to go up exposure then.Exposure intensity 60～180mJ/cm 2Toasted for 90 seconds on 110 ℃ of hot plates the exposure back, developed for 60 seconds oven dry back submicroscopy lithographic results at last again in 2.38%TMAH developing solution (23 ℃).The result proves that this photoresist material resolving power can reach 0.35～0.25 μ m, and has good photoetching process operation allowed band.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.

Claims (8)

1. silicon-containing copolymer film-forming resin, by comonomer under the condition that radical initiator exists, carry out copolymerization in the solvent and be prepared from, it is characterized in that: the molecular weight of described film-forming resin is 4000～100000, and molecular weight distribution is 1.4～2.8; Described comonomer is mainly the compound of following quality percentage composition:
Substituted phenylethylene 40%～90%;
Acrylate containing silicone class coupling agent 0.5%～20%;
Contain acid-sensitive group monomer 5%～60%;
Described substituted phenylethylene is at least a compound that meets chemical general formula (I):
Figure FSA00000286387100011
In the formula, R 1Be H, ethanoyl or propionyl; M=1 or 2;
The chemical general formula of described acrylate containing silicone class coupling agent is shown in (II) formula:
In the formula: R 2Be H or CH 3R 3Be that carbonatoms is 1～20 alkyl; R 4Be that carbonatoms is 1～20 alkyl; R 5Be that OH, carbonatoms are that 1～20 alkyl or carbonatoms are 1～20 alkoxyl group; N=1～8;
Described contain acid-sensitive group monomer be meet chemical general formula (III) formula and (IV) at least a compound:
In the formula: R 6Be H, CH 3Or CF 3R 7Be
Figure FSA00000286387100014
Figure FSA00000286387100015
Perhaps Wherein, R xBe methyl or ethyl;
Figure FSA00000286387100021
In the formula: R 8Be:
Figure FSA00000286387100022
Perhaps
Figure FSA00000286387100023
R wherein yBe methyl or ethyl.
2. silicon-containing copolymer film-forming resin according to claim 1 is characterized in that: also comprise the quality percentage composition in the described comonomer and be 1%～40% meet chemical general formula (V) and (VI) at least a compound;
Figure FSA00000286387100024
In the formula: R wBe that H, carbonatoms are that 1～20 alkyl or carbonatoms are 1～20 alkoxyl group; R zBe H, carbonatoms be 1～20 alkyl, carbonatoms be 1～20 alkoxyl group,
Figure FSA00000286387100025
Perhaps HO (CH 2) 2O-;
Figure FSA00000286387100026
In the formula: R 9Be H or CH 3, R 10Be H,
Figure FSA00000286387100027
Carbonatoms is that 1～20 alkyl or carbonatoms are 1～20 hydroxyalkyl.
3. silicon-containing copolymer film-forming resin according to claim 1, it is characterized in that: described substituted phenylethylene is para hydroxybenzene ethene, to acetoxy-styrene, rare, the acetoxy-styrene, 3 of a hydroxybenzene second, 4-dihydroxy-benzene ethene, 3,4-diacetoxy vinylbenzene, 3,5-dihydroxy-benzene ethene and 3, at least a in the 5-diacetoxy vinylbenzene.
4. silicon-containing copolymer film-forming resin according to claim 1 is characterized in that: described to meet chemical general formula (III) formula compound be tert-butyl acrylate, the methacrylic tert-butyl acrylate, the vinylformic acid tert-pentyl ester, the methacrylic acid tert-pentyl ester, vinylformic acid-1-methyl ring pentyl ester, methacrylic acid-1-methyl ring pentyl ester, vinylformic acid-1-methyl cyclohexane ester, methacrylic acid-1-methyl cyclohexane ester, vinylformic acid-1-ethyl ring pentyl ester, methacrylic acid-1-ethyl ring pentyl ester, vinylformic acid-1-ethyl cyclohexyl, methacrylic acid-1-ethyl cyclohexyl, vinylformic acid-2-methyl adamantane alcohol ester, methacrylic acid-2-methyl adamantane alcohol ester, acrylic acid-2-ethyl diamantane alcohol ester, methacrylic acid-2-ethyl diamantane alcohol ester, vinylformic acid-2-butyrolactone base ester, methacrylic acid-2-butyrolactone base ester, vinylformic acid-2-caprolactone base ester or methacrylic acid-2-caprolactone base ester.
5. silicon-containing copolymer film-forming resin according to claim 1 is characterized in that: described chemical general formula (IV) the formula compound that meets is to tert.-butoxy vinylbenzene, to uncle's amyl phenyl ether ethene, to tertiary butyl carbonic ether vinylbenzene or to the different phenetole ethene of 1-ethoxy.
6. silicon-containing copolymer film-forming resin according to claim 2, it is characterized in that: described to meet chemical general formula (V) formula compound be vinylbenzene, to t-butyl styrene, to tert.-amylbenzene ethene, to phenetole ethene, 3,5-dimethoxy styrene, 3,5-diethoxy vinylbenzene, to phenoxy group vinylbenzene or to 2-hydroxy ethoxy vinylbenzene.
7. the siliceous I-line of chemical amplification type high resolving power ultraviolet photoresist is characterized in that: mainly be made up of the material of following mass parts:
The I-linear light causes 10 parts of acid;
1～3 part of film-forming resin;
60～120 parts of solvents;
Described film-forming resin is as described in arbitrary claim in the claim 1～6;
Described solvent is at least a in 1-Methoxy-2-propyl acetate, propylene glycol list Acetic Ester, dihydroxypropane single-ether, 1-Methoxy-2-propyl acetate, tirethylene glycol methyl ether, tirethylene glycol ether, N-BUTYL ACETATE, acetic acid peopentyl ester, ethyl lactate, methyl ethyl ketone and the methyl iso-butyl ketone (MIBK).
8. the siliceous I-line of chemical amplification type high resolving power according to claim 7 ultraviolet photoresist is characterized in that: it is at least a compound that meets among structural formula (VII) and general formula (VIII), (X), (XI), (XII), (XIII), (XIV) that described I-linear light causes acid:
Figure FSA00000286387100041
In the formula, o=1～2;
Figure FSA00000286387100042
In the formula, p=1～2;
Figure FSA00000286387100043
In the formula, R 11For-C 3H 7,-C 8H 17,
Figure FSA00000286387100044
Perhaps
Figure FSA00000286387100045
Figure FSA00000286387100046
In the formula, R 11For-CF 3,-C 4F 9Perhaps
Figure FSA00000286387100051
In the formula, R 13For-CF 3,-C 6F 5Perhaps
Figure FSA00000286387100052
Figure FSA00000286387100053
In the formula, R 14For
Figure FSA00000286387100054
Perhaps
Figure FSA00000286387100055
CN 201010294204 2010-09-28 2010-09-28 Chemical amplified high-resolution silicon-containing I-ray ultraviolet photoresist and forming resin thereof Pending CN101974121A (en)

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CN112558409A (en) * 2019-09-25 2021-03-26 常州强力先端电子材料有限公司 Sulfonyl imide photoacid generator capable of generating acid at I line
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