CN104403048A - Sesquiterpene-lactone-containing film-forming resin and positive immersion type exposure 193nm photoresist adopting same - Google Patents
Sesquiterpene-lactone-containing film-forming resin and positive immersion type exposure 193nm photoresist adopting same Download PDFInfo
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Abstract
The invention discloses sesquiterpene-lactone-containing film-forming resin and positive immersion type exposure 193nm photoresist adopting the same. The film-forming resin is prepared by performing free radical copolymerization reaction on a sesquiterpene-lactone-containing (methyl) acrylate monomer and a relevant comonomer in a solvent and is characterized in that the molecular weight of the film-forming resin is 4,000-5,000,000, and the molecular weight distribution is 1.4-2.4; the comonomer mainly comprises the following components in percentage by mass; 10-60 percent of a constitutional unit containing a natural product sesquiterpene lactone, 5-40 percent of an acid-labile-group-containing monomer, 2-40 percent of a monomer with a hydrophobic property group and 1-20 percent of other performance adjustment constitutional monomers; the sesquiterpene-lactone-containing (methyl) acrylate monomer is at least one sesquiterpene-lactone-containing (methyl) acrylate type compound meting a chemical general formula (II). The positive immersion type exposure 193nm photoresist disclosed by the invention is high in resolution, and the adhesion property between the photoresist and a silicon sheet is also enhanced; meanwhile, the heat resistance and the etching resistance of the photoresist are also improved.
Description
Technical field
The present invention relates to a kind of film-forming resin containing natural sesquiterpene lactone copolymers and utilize this film-forming resin formulated for deep ultraviolet (DUV) the immersion exposure positivity chemical amplification type photoetching compositions that is exposure light source with ArF laser (193nm).
Background technology
Photoresist material is the key function material carrying out photoetching process in large-scale integrated circuit industry.What start the nineties in last century to grow up is exposure light source with ArF laser (193nm) deep ultraviolet (DUV) wave band exposure technology is widely used in manufacturing in large-scale integrated circuit, and its resolving power can reach 0.13 ~ 0.10 micrometer range.But along with developing rapidly of semiconductor industry, constantly reducing of device size, as the extension of ArF (193nm) Photolithography Technology, 193nm immersion lithography process with filtered air has become and has reached more high resolving power, breaks through the 45nm even generally acknowledged selection of 32nm technology node.Due to the raising of resolving power and the particular requirement of immersion lithography process, be used in immersion 193nm(193i) technique in photoresist material also have its special performance requriements, as glued membrane can not in water swelling set; Prevent glue intermediate ion from spreading in water and pollute the camera lens etc. of costliness of exposure circle's matter and exposure machine.Following technical problem is there is at present: the adhesivity of (1) photoresist material and base material silicon chip is weak in actual process; (2) thermotolerance of photoresist material and etch resistant poor performance.
On the other hand, as everyone knows, China's natural product aboundresources, turps, rosin, by leaf-alcohol, terpene and the wide material sources such as sesquiterpene and lactone thereof, output is huge.As pine tree, cypress, all contains the compounds such as high turps, rosin, sesquiterpene and lactone thereof in the trees such as eucalyptus and many herbaceous plant.How in conjunction with national conditions, by the compound from natural product, be applied to photoresist material field in integrated circuit industry, and above-mentioned technical problem can be overcome simultaneously, solve existing photoresist material to the detrimentally affect of exposure machine camera lens, become the direction that those skilled in the art make great efforts.
Summary of the invention
The present invention's first object is to provide a kind of containing sesquiterpene lactones film-forming resin, this can increase the adhesive property between photoresist material and silicon chip containing sesquiterpene lactones film-forming resin, due to the increase of the carbon atom density of film-forming resin, also by improving the resistance toheat of photoresist material, improve its anti-etching performance.
Second object of the present invention is to provide a kind of immersion exposure 193nm positive photoresist applied the above-mentioned film-forming resin containing sesquiterpene lactones and be mixed with.
For reaching above-mentioned first goal of the invention, the technical solution used in the present invention is: a kind of film-forming resin containing sesquiterpene lactones, it is characterized in that: described film-forming resin by comonomer, is carried out copolyreaction in a solvent and is prepared under radical initiator existent condition; It is characterized in that: the molecular weight of described film-forming resin is 4,000 ~ 5,000,000, molecular weight distribution is 1.4 ~ 2.4; Described comonomer is mainly the compound of following masses percentage composition:
Containing the component units 10% ~ 60% of natural product sesquiterpene;
Containing acid-labile group monomer 5% ~ 40%;
There is the monomer 2% ~ 40% of hydrophobic performance group;
Other property regulation constituent monomers 1% ~ 20%;
Described containing sesquiterpene lactones unit refer to meet chemical general formula (
) (methyl) acrylic ester compound of at least one sesquiterpene lactones alcohol:
（II）；
Chemical general formula (
) in the common sesquiterpene lactones alcohol (R-OH) of R base as shown in table 1:
Table 1
Described containing acid-labile group monomer be meet chemical general formula (
) at least one compound in formula:
（
）；
Chemical general formula (
) R in formula
3for can leavings group, R
3structural formula is as shown in following (IV):
（IV）；
Wherein Y=-CH
3or-CH
2cH
3;
The described monomer with hydrophobic performance group meets at least one compound in chemical general formula (V) formula:
（V）；
Wherein Rf is fluorine-containing organic group, as follows:
Wherein Rf or the group for containing silsesquioxane (Silsesquioxane):
Technique scheme is described as follows:
1., in such scheme, described initiator is the radical initiator of azo initiator, superoxide; Described azo initiator is that azo two isobutyl is fine or azo two is fine for different heptan, and the radical initiator of described superoxide is tert-butyl hydroperoxide pivalate, tertbutyl peroxide, phenylformic acid hydrogen peroxide or benzoyl peroxide etc.; Described initiator amount is 0.3% ~ 15% of described comonomer gross weight; Adding of radical initiator can be adopted in two ways: the first is after each comonomer is dissolved in solvent, is first heated to polymerization temperature, then adds initiator and carries out polyreaction.The second is after each comonomer is dissolved in solvent, first adds initiator, and then is warmed to polymerization temperature and carries out polyreaction.Described initiator can disposablely add in these two kinds of modes, also can gradation add.The temperature of polyreaction controls 40 ~ 150 DEG C of scopes according to the solvent used is different with initiator.Polymerization reaction time also controls at 4 ~ 28 hours according to the solvent used is different with initiator.
2. in such scheme, the most frequently used method of described copolymerization is with containing the monomer of sesquiterpene lactones and other monomer copolymerizable, and copolymerization monomer contamination is by they function decisions in the copolymer;
Such as multipolymer shown below is by containing sesquiterpene lactones unit (A), forms containing acid-labile group unit (B) and hydrophobic performance unit (C):
3. in such scheme, above-mentioned have copolymerization can carry out separately or in their mixture at all kinds of SOLVENTS, and these solvents comprise methyl alcohol, ethanol, dioxane, acetone, tetrahydrofuran (THF), toluene, benzene, dimethylbenzene, methylene dichloride, chloroform, trichloromethane, ethylene dichloride, trichloroethane etc.
4. in such scheme, the aftertreatment about polyreaction:
(1), purification process
After polyreaction completes, removing after unreacted residual monomer and part organic impurity thereof can use heptane, hexane, hexanaphthene, pentane, sherwood oil, ether equal solvent to extract.
(2), separate solid multipolymer
Multipolymer can in the organic or inorganic solvent such as mixture, heptane, hexane, hexanaphthene, pentane, sherwood oil, ether of the mixture of the mixture of pure water, methyl alcohol, first alcohol and water, ethanol and water thereof, Virahol and water thereof precipitate and separate, the yield of vacuum-drying rear copolymer is 60% ~ 90%.
For reaching above-mentioned second goal of the invention, the technical solution used in the present invention is: a kind of immersion 193nm positive photoresist applied the above-mentioned film-forming resin containing sesquiterpene lactones and make, is characterized in that: the compound primarily of following mass parts forms:
Containing sesquiterpene lactones film-forming resin 10 ~ 35;
Photic sour 0.5 ~ 8;
Additive 0.5 ~ 30;
Solvent 70 ~ 90;
Described photic acid be meet chemical general formula (
) or (
) one of sulfosalt, or meet chemical general formula (
) one of diaryl group iodized salt;
（
）；
In formula: R
16, R
17, R
18h independently of one another, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20; Q=0 ~ 12;
（
）；
In formula: R
19h, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20; R=0 ~ 12;
（IX）；
In formula: R
20, R
21h independently of one another, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20; S=0 ~ 12;
Described solvent is at least one 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 methyl iso-butyl ketone (MIBK);
Described additive comprises surface waterproofer, organic bases, flow agent; Described surface waterproofer is selected from fluorine-containing or siliceous polymkeric substance; Described organic bases is selected from least one in following compounds tripropyl amine, Tributylamine, tri-isobutylamine, trioctylamine, trolamine, triethoxy thanomin, trimethoxy methoxy ethyl amine, Tetramethylammonium hydroxide.Described flow agent is selected from fluorine-containing or siliceous tensio-active agent.
Technique scheme further illustrates as follows:
1. in such scheme, described in meet chemical general formula (
) or (
) sulfosalt be: triphenyl sulfosalt, three p-methylphenyl sulfosalts, the three pairs of tert-butyl-phenyl sulfosalts, three (3,5-3,5-dimethylphenyl) sulfosalt, three (3,5-di-tert-butyl-phenyl) sulfosalt, its coordination anion is: trifluoromethane sulfonic acid, perfluoro butyl sulfonic acid, p-methylphenyl sulfonic acid, naphthene sulfonic acid.
2. in such scheme, described in meet chemical general formula (
) diaryl group iodized salt: diphenyl iodnium, di-p-tolyl salt compounded of iodine, two pairs of tert-butyl-phenyl salt compounded of iodine, its coordination anion is: trifluoromethane sulfonic acid, perfluoro butyl sulfonic acid, p-methylphenyl sulfonic acid, naphthene sulfonic acid, camphorsulfonic acid.
Because technique scheme is used, the present invention has following advantages and effect:
1, the present invention contains film-forming resin and the positivity immersion exposure 193nm photoresist material thereof of sesquiterpene lactones, introduces containing the polymerisable monomer of natural product sesquiterpene lactones and form the brand-new film-forming resin of a class in film-forming resin.This new film-forming resin can increase the adhesive property between photoresist material and silicon chip; Due to the increase of the carbon atom density of film-forming resin, also by improving the resistance toheat of photoresist material, improve its anti-etching performance.Secondly, utilize natural product as electronic product raw material, not only cost is low, environmental protection, and itself is polycyclic aliphatic alkane, also has stereoisomerism and optical activity, imparting new development space, opening the gate that a fan is new for improving photoresist material performance.
2, the present invention contains film-forming resin and the positivity immersion exposure 193nm photoresist material thereof of sesquiterpene lactones, when its exposure is decomposed, because the molecular weight of its degradation production sesquiterpene lactones alkene or sesquiterpene lactones alcohol is very large, boiling point is very high, thus avoids the formation of gas overflowing and affect litho pattern and damage expensive photoetching machine lens.
Specific embodiments
Below in conjunction with embodiment, the invention will be further described:
Embodiment one: a kind of film-forming resin containing sesquiterpene lactones, by copolymerized monomers and content thereof, under radical initiator existent condition, carry out copolyreaction by heating and be prepared from:
Methacrylic acid-1-methylcyclopentane alcohol ester 3.70 grams;
Methacrylic acid hexafluoro isopropyl alkane ester 2.20 grams;
Methacrylic acid short Docetaxel A ester 6.38 grams.
Electric mixer is equipped with at one, condenser, thermometer, temperature regulator, in the 100ml there-necked flask of heating jacket and nitrogen inlet, add methacrylic acid-1-methylcyclopentane alcohol ester 3.70 grams, methacrylic acid hexafluoro isopropyl alkane ester 2.20 grams, methacrylic acid short Docetaxel A ester 6.38 grams, tetrahydrofuran (THF) 60 grams, under agitation logical nitrogen 10 minutes, then 60 ~ 70 DEG C are heated to, drip azo two isobutyl fine (AIBN) 0.71 gram in 20 minutes to make solution at 10 grams of tetrahydrofuran (THF)s and then add in reaction system, continue reaction backflow after 24 hours, then room temperature is cooled to.Extract three times with heptane, polymers soln precipitates in pure water, obtains polymer solids, yield 72% after vacuum-drying.
Embodiment two: a kind of film-forming resin containing sesquiterpene lactones, by copolymerized monomers and content thereof, under radical initiator existent condition, carry out copolyreaction by heating and be prepared from:
Methacrylic acid-1-methylcyclopentane alcohol ester 4.50 grams
Methacrylic acid is to hexafluoro t-butylcyclohexane diol monoester 3.52 grams;
Methacrylic acid short Docetaxel A ester 6.48 grams.
Electric mixer is equipped with at one, condenser, thermometer, temperature regulator, in the 100ml there-necked flask of heating jacket and nitrogen inlet, add methacrylic acid-1-methylcyclopentane alcohol ester 4.50 grams, methacrylic acid is to hexafluoro t-butylcyclohexane diol monoester 3.52 grams, the short Docetaxel ester of methacrylic acid 6.48 grams, tetrahydrofuran (THF) 60 grams, under agitation logical nitrogen 10 minutes, then 65 ~ 70 DEG C are heated to, add azo two isobutyl fine (AIBN) 0.73 gram in 10 grams of tetrahydrofuran (THF)s, to make solution then add in reaction system, continue reaction backflow after 8 ~ 24 hours, then room temperature is cooled to.Extract three times with heptane, polymers soln precipitates in pure water, obtains polymer solids, yield 70% after vacuum-drying.
Embodiment three: a kind of film-forming resin containing sesquiterpene lactones, by copolymerized monomers and content thereof, under radical initiator existent condition, carry out copolyreaction by heating and be prepared from:
Methacrylic acid-2-butyrolactone alcohol ester 2.55 grams;
Methacrylic acid hexafluoro isobutyl hydroxyl isobornyl thiocyanoacetate 1.81 grams;
Methacrylic acid short Docetaxel A ester 6.38 grams;
Electric mixer is equipped with at one, condenser, thermometer, temperature regulator, in the 100ml there-necked flask of heating jacket and nitrogen inlet, add methacrylic acid-2-butyrolactone alcohol ester 2.55 grams, methacrylic acid hexafluoro isobutyl hydroxyl isobornyl thiocyanoacetate 1.81 grams, methacrylic acid short Docetaxel A ester 6.38 grams, tetrahydrofuran (THF) 60 grams, under agitation logical nitrogen 10 minutes, then 60 ~ 70 DEG C are heated to, add azo two isobutyl fine (AIBN) 0.59 gram in 10 grams of tetrahydrofuran (THF)s, to make solution then add in reaction system, continue reaction backflow after 18 hours, then room temperature is cooled to.Extract three times with heptane, polymers soln precipitates in pure water, obtains polymer solids, yield 71% after vacuum-drying.
Embodiment four: a kind of multipolymer film-forming resin containing natural product sesquiterpene, under radical initiator existent condition, carry out copolyreaction by copolymerized monomers and be prepared from:
Methacrylic acid-2-butyrolactone alcohol ester 3.40 grams;
Methacrylic acid hexafluoroisopropanol ester 2.36 grams;
Methacrylic acid short Docetaxel A ester 6.38 grams;
Electric mixer is equipped with at one, condenser, thermometer, temperature regulator, in the 100ml there-necked flask of heating jacket and nitrogen inlet, add methacrylic acid-2-butyrolactone alcohol ester 3.40 grams, methacrylic acid hexafluoroisopropanol ester 2.36 grams, methacrylic acid short Docetaxel A ester 6.38 grams, tetrahydrofuran (THF) 60 grams, under agitation logical nitrogen 10 minutes, then 70 DEG C are heated to, drip azo two isobutyl fine (AIBN) 0.61 gram in 20 minutes to make solution at 10 grams of tetrahydrofuran (THF)s and then add in reaction system, continue reaction backflow after 24 hours, then room temperature is cooled to.Extract three times with heptane, polymers soln precipitates in pure water, obtains polymer solids, yield 72% after vacuum-drying.
Embodiment five: a kind of multipolymer film-forming resin containing natural product sesquiterpene lactones, be polymerized in the presence of a free-radical initiator by comonomer, its equation is as follows:
Methacrylic acid-2-butyrolactone alcohol ester 3.40 grams;
Methacrylic acid-5-hydroxyl neoheptane-2-alcohol ester 2.94 grams;
Methacrylic acid short Docetaxel A ester 6.38 grams
Be equipped with in the 100ml there-necked flask of electric mixer, condenser, thermometer, temperature regulator, heating jacket and nitrogen inlet at one, add methacrylic acid-2-butyrolactone alcohol ester 3.40 grams, methacrylic acid-5-hydroxyl neoheptane-2-alcohol ester 2.94 grams, methacrylic acid short Docetaxel A ester 6.38 grams, tetrahydrofuran (THF) 60 grams, under agitation logical nitrogen 10 minutes, then 60 ~ 70 DEG C are heated to, add azo two isobutyl fine (AIBN) 0.63 gram of solution in 10 grams of THF, continue reaction backflow after 8 ~ 24 hours, be then cooled to room temperature.Polymers soln precipitates in pure water, obtains polymer solids, yield 72% after vacuum-drying.
Embodiment six: a kind of multipolymer film-forming resin containing natural product sesquiterpene, be polymerized in the presence of a free-radical initiator by comonomer, reaction equation is as follows:
Methacrylic acid propylsilsesquioxane ester 2.45 grams
Methacrylic acid-2-butyrolactone alcohol ester 3.40 grams
Methacrylic acid short Docetaxel A ester 6.38 grams
Be equipped with in the 100ml there-necked flask of electric mixer, condenser, thermometer, temperature regulator, heating jacket and nitrogen inlet at one, add methacrylic acid-1-cyclohexyl alcohol ester 2.45 grams, methacrylic acid propylsilsesquioxane ester 3.40 grams, methacrylic acid short Docetaxel A ester 6.38 grams, tetrahydrofuran (THF) 60 grams, under agitation logical nitrogen 10 minutes, then 60 ~ 70 DEG C are heated to, add azo two isobutyl fine (AIBN) 0.55 gram of solution in 10 grams of THF, continue reaction backflow after 24 hours, be then cooled to room temperature.Polymers soln precipitates in pure water, obtains polymer solids, yield 64% after vacuum-drying.
Embodiment seven: a kind of containing natural product sesquiterpene with the multipolymer film-forming resin of tert-butyl acrylate, be polymerized in the presence of a free-radical initiator by comonomer, reaction equation is as follows:
Methacrylic acid-2-methyl adamantane alcohol ester 4.41 grams
Methacrylic acid 3-hydroxyl hexafluoro dissident alcohol ester 1.74 grams
Chloranthalactone alcohol methacrylic ester 6.78 grams
Be equipped with in the 100ml there-necked flask of electric mixer, condenser, thermometer, temperature regulator, heating jacket and nitrogen inlet at one, add methacrylic acid-2-methyl adamantane alcohol ester 4.41 grams, methacrylic acid 3-hydroxyl hexafluoro dissident alcohol ester 1.74 grams, chloranthalactone alcohol methacrylic ester 6.78 grams, tetrahydrofuran (THF) 60 grams, under agitation logical nitrogen 10 minutes, then 60 ~ 70 DEG C are heated to, add azo two isobutyl fine (AIBN) 0.54 gram of solution in 10 grams of THF, continue reaction backflow after 8 ~ 24 hours, be then cooled to room temperature.Polymers soln precipitates in pure water, obtains polymer solids, yield 68% after vacuum-drying.
Embodiment eight ~ embodiment 12, to prepare containing the multipolymer film-forming resin deep ultraviolet 193nm immersion positive photoresist of natural product sesquiterpene lactones:
(1) photic acid: embodiment eight: triphenyl trifluoromethyl sulfosalt, coordination anion is perfluoro butyl sulfonic acid; Embodiment nine: triphenyl sulfosalt, coordination anion is perfluoro butyl sulfonic acid; Embodiment ten: three p-methylphenyl sulfosalt, coordination anion is naphthene sulfonic acid; Embodiment 11: two pairs of tert-butyl-phenyl salt compounded of iodine, coordination anion is trifluoromethane sulfonic acid; Embodiment 12: three pairs of tert-butyl-phenyl sulfosalts, coordination anion is trifluoromethane sulfonic acid.
(2) solvent: embodiment eight: 1-Methoxy-2-propyl acetate; Embodiment nine: acetic acid peopentyl ester; Embodiment ten: methyl ethyl ketone; Embodiment 11: dihydroxypropane single-ether, 1-Methoxy-2-propyl acetate; Embodiment 12: N-BUTYL ACETATE, ethyl lactate.
(3) organic bases: embodiment eight: tri-isobutylamine; Embodiment nine: trimethoxy methoxy ethyl amine; Embodiment ten: trolamine; Embodiment 11: tri-isobutylamine; Embodiment 12: tripropyl amine.
(4) collocation method of the photoresist material of embodiment eight:
A kind of compound method of the deep ultraviolet 193nm immersion positive photoresist containing natural product sesquiterpene lactones: in clean 100 new ml polypropylene Plastic Bottles, add the multipolymer of preparation in 7.60 grams of embodiments one, 0.32 gram of triphenyl trifluoromethyl sulfosalt, 100 grams of electronic grade propylene glycol methyl ether acetate (PGMEA) solvents, and 0.2 gram of n-Butyl Amine 99,0.12 gram of tensio-active agent.This mixture is fixed on a mechnical oscillator, at room temperature shakes 10 ~ 24 hours, makes it fully dissolve.With the metre filter 2 times of 0.2 micron pore size, then use the metre filter one time of 0.05 micron pore size.
Lithography experiments method and result: the photoresist material of above-mentioned preparation is 12 " silicon chip rotates film forming with the speed of 2000 ~ 6000 revs/min, 120 DEG C of hot plates toasted for 90 seconds, then with the exposure of 193nm immersion exposure technique.Exposure intensity 10-50 mJ/cm
2.On 110 DEG C of hot plates, toasted for 90 seconds after exposure, finally developed for 60 seconds in 2.38% TMAH developing solution (23 DEG C) again, after drying, uses submicroscopy lithographic results.Result proves that this photoresist material resolving power can reach 0.10 ~ 0.08 μm, and has good photoetching process operation allowed band.
(5) formula of embodiment nine ~ embodiment 12 is as following table, and collocation method is with embodiment eight, and film-forming resin adopts the multipolymer prepared in embodiment to represent as follows successively.The resolving power of gained photoresist material and anti-etching performance evaluation result are as following table 2:
Table 2
| Film-forming resin | Photic acid | Solvent | Resolving power | Anti-etching | |
| Embodiment eight | (example one) 7.60 | 0.320 | 100 | Well | ++ |
| Embodiment nine | (example two) 7.80 | 0.312 | 112 | Well | +++ |
| Embodiment ten | (example three) 7.51 | 0.305 | 102 | Well | +++ |
| Embodiment 11 | (example four) 7.65 | 0.344 | 103 | Well | ++ |
| Embodiment 12 | (example seven) 7.85 | 0.353 | 112 | Well | +++ |
Note: during the assessment of (1) photoresist material, because processing requirement is different, resolving power is all good in 0.13um-0.10um scope;
(2) in dry etching assessment, under setting processing condition, Liu Mo Shuais≤80% be +++; Liu Mo Shuais≤60% be ++; Liu Mo Shuais≤40% for+; Liu Mo Shuais≤30% for defective.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (4)
1., containing a film-forming resin for sesquiterpene lactones, it is characterized in that: described film-forming resin by comonomer, is carried out copolyreaction in a solvent and is prepared under radical initiator existent condition; It is characterized in that: the molecular weight of described film-forming resin is 4,000 ~ 5,000,000, molecular weight distribution is 1.4 ~ 2.4; Described comonomer is mainly the compound of following masses percentage composition:
Containing the component units 10% ~ 60% of natural product sesquiterpene;
Containing acid-labile group monomer 5% ~ 40%;
There is the monomer 2% ~ 40% of hydrophobic performance group;
Other property regulation constituent monomers 1% ~ 20%;
Described containing sesquiterpene lactones unit refer to meet chemical general formula (
) (methyl) acrylic ester compound of at least one sesquiterpene lactones alcohol:
（II）；
Chemical general formula (
) in the common sesquiterpene lactones alcohol (R-OH) of R base as shown in table 1:
Table 1
Described containing acid-labile group monomer be meet chemical general formula (
) at least one compound in formula:
（
）；
Chemical general formula (
) R in formula
3for can leavings group, R
3structural formula is as shown in following (IV):
（IV）；
Wherein Y=-CH
3or-CH
2cH
3;
The described monomer with hydrophobic performance group meets at least one compound in chemical general formula (V) formula:
（V）；
Wherein Rf is organic fluoride-containing group, as follows:
Wherein Rf or the group containing silsesquioxane (Silsesquioxane), as follows:
Film-forming resin containing sesquiterpene lactones according to claim 1, is characterized in that: described initiator is the radical initiator of azo initiator, superoxide; Described azo initiator is that azo two isobutyl is fine or azo two is fine for different heptan, and the radical initiator of described superoxide is tert-butyl hydroperoxide pivalate, tertbutyl peroxide, phenylformic acid hydrogen peroxide or benzoyl peroxide etc.; Described initiator amount is 0.3% ~ 15% of described comonomer gross weight.
2. application rights requires the positivity immersion exposure 193nm photoresist material be mixed with containing the film-forming resin of sesquiterpene lactones described in 1 or 2, it is characterized in that: the compound primarily of following mass parts forms:
Containing sesquiterpene lactones film-forming resin 10 ~ 35;
Photic sour 0.5 ~ 8;
Additive 0.5 ~ 30;
Solvent 70 ~ 90;
Described photic acid be meet chemical general formula (
) or (
) one of sulfosalt, or meet chemical general formula (
) one of diaryl group iodized salt;
（
）；
In formula: R
16, R
17, R
18h independently of one another, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20; Q=0 ~ 12;
（
）；
In formula: R
19h, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20; R=0 ~ 12;
（IX）；
In formula: R
20, R
21h independently of one another, carbonatoms be 1 ~ 20 alkyl or carbonatoms be the alkoxyl group of 1 ~ 20; S=0 ~ 12;
Described solvent is at least one 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 methyl iso-butyl ketone (MIBK);
Described additive comprises surface waterproofer, organic bases, flow agent; Described surface waterproofer is selected from fluorine-containing or siliceous polymkeric substance; Described organic bases is selected from least one in following compounds tripropyl amine, Tributylamine, tri-isobutylamine, trioctylamine, trolamine, triethoxy thanomin, trimethoxy methoxy ethyl amine, Tetramethylammonium hydroxide; Described flow agent is selected from fluorine-containing or siliceous tensio-active agent.
3. positivity immersion exposure 193nm photoresist material according to claim 3, is characterized in that: described in meet chemical general formula (
) or (
) sulfosalt be: triphenyl sulfosalt, three p-methylphenyl sulfosalts, the three pairs of tert-butyl-phenyl sulfosalts, three (3,5-3,5-dimethylphenyl) sulfosalt, three (3,5-di-tert-butyl-phenyl) sulfosalt, its coordination anion is: trifluoromethane sulfonic acid, perfluoro butyl sulfonic acid, p-methylphenyl sulfonic acid, naphthene sulfonic acid.
4. positivity immersion exposure 193nm photoresist material according to claim 3, is characterized in that: described in meet chemical general formula (
) diaryl group iodized salt: diphenyl iodnium, di-p-tolyl salt compounded of iodine, two pairs of tert-butyl-phenyl salt compounded of iodine, its coordination anion is: trifluoromethane sulfonic acid, perfluoro butyl sulfonic acid, p-methylphenyl sulfonic acid, naphthene sulfonic acid, camphorsulfonic acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410684078.XA CN104403048B (en) | 2014-11-25 | 2014-11-25 | Film-forming resin and its positivity immersion exposure 193nm photoresists containing sesquiterpene lactone |
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|---|---|---|---|
| CN201410684078.XA CN104403048B (en) | 2014-11-25 | 2014-11-25 | Film-forming resin and its positivity immersion exposure 193nm photoresists containing sesquiterpene lactone |
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| Publication Number | Publication Date |
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| CN104403048A true CN104403048A (en) | 2015-03-11 |
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| CN109071576A (en) * | 2016-05-03 | 2018-12-21 | 美国陶氏有机硅公司 | Silsesquioxane resins and oxa- amine composition |
| CN112521552A (en) * | 2018-12-13 | 2021-03-19 | 儒芯微电子材料（上海）有限公司 | Polymer resin, preparation method thereof and metal stripping adhesive composition |
| WO2023165101A1 (en) * | 2022-03-03 | 2023-09-07 | 甘肃华隆芯材料科技有限公司 | Polymer resin for 193 nm water immersion lithography, water-resistant coating composition, water-resistant coating, and preparation method therefor |
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| JPH11202495A (en) * | 1998-01-13 | 1999-07-30 | Toshiba Corp | Photosensitive composition, pattern forming method using the same and production of semiconductor device |
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| CN112521552A (en) * | 2018-12-13 | 2021-03-19 | 儒芯微电子材料（上海）有限公司 | Polymer resin, preparation method thereof and metal stripping adhesive composition |
| CN112521552B (en) * | 2018-12-13 | 2022-03-11 | 儒芯微电子材料（上海）有限公司 | Polymer resin, preparation method thereof and metal stripping adhesive composition |
| WO2023165101A1 (en) * | 2022-03-03 | 2023-09-07 | 甘肃华隆芯材料科技有限公司 | Polymer resin for 193 nm water immersion lithography, water-resistant coating composition, water-resistant coating, and preparation method therefor |
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| CN104403048B (en) | 2018-05-08 |
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