CN104403048B - Film-forming resin and its positivity immersion exposure 193nm photoresists containing sesquiterpene lactone - Google Patents
Film-forming resin and its positivity immersion exposure 193nm photoresists containing sesquiterpene lactone Download PDFInfo
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- CN104403048B CN104403048B CN201410684078.XA CN201410684078A CN104403048B CN 104403048 B CN104403048 B CN 104403048B CN 201410684078 A CN201410684078 A CN 201410684078A CN 104403048 B CN104403048 B CN 104403048B
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- China
- Prior art keywords
- film
- forming resin
- sesquiterpene lactone
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- grams
- Prior art date
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- 239000011347 resin Substances 0.000 title claims abstract description 37
- 229920005989 resin Polymers 0.000 title claims abstract description 37
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- 229930009674 sesquiterpene lactone Natural products 0.000 title claims abstract description 34
- 150000002107 sesquiterpene lactone derivatives Chemical class 0.000 title claims abstract description 33
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 29
- 238000007654 immersion Methods 0.000 title claims abstract description 15
- -1 Acrylic ester compound Chemical class 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229930014626 natural product Natural products 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 5
- 239000000470 constituent Substances 0.000 claims abstract description 3
- 239000003999 initiator Substances 0.000 claims description 21
- 150000002148 esters Chemical class 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 150000003254 radicals Chemical class 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
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- 229940116333 ethyl lactate Drugs 0.000 claims description 3
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 claims description 3
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- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
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- FIXANHZJVHLQBJ-UHFFFAOYSA-N benzoic acid hydrogen peroxide Chemical compound C(C1=CC=CC=C1)(=O)O.OO FIXANHZJVHLQBJ-UHFFFAOYSA-N 0.000 claims description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
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- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims 2
- ZOMBFBVBZZRKOR-UHFFFAOYSA-N CC(C(=O)O)(C)C.C(C)(C)(C)OO Chemical compound CC(C(=O)O)(C)C.C(C)(C)(C)OO ZOMBFBVBZZRKOR-UHFFFAOYSA-N 0.000 claims 1
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- 125000003118 aryl group Chemical group 0.000 claims 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 claims 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N propylene glycol methyl ether Substances COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229930004725 sesquiterpene Natural products 0.000 description 1
- 150000004354 sesquiterpene derivatives Chemical class 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Landscapes
- Materials For Photolithography (AREA)
Abstract
The present invention discloses a kind of film-forming resin containing sesquiterpene lactone and its positivity immersion exposure 193nm photoresists;The film-forming resin is by containing sesquiterpene lactone(Methyl)Acrylate monomer and related comonomer carry out free radicals copolymerization reaction and are prepared in a solvent, it is characterised in that:The molecular weight of the film-forming resin is 4,000~5,000,000, and molecular weight distribution is 1.4~2.4;The comonomer is mainly the compound of following masses percentage composition:The component units 10%~60% of the sesquiterpene lactone containing natural products;Monomer containing acid-labile group 5%~40%;Monomer 2% ~ 40% with hydrophobic performance group;Other performance adjusts constituent monomers 1% ~ 20%;The unit containing sesquiterpene lactone refers to meet chemical general formula(Ⅱ)At least one sesquiterpene lactone alcohol(Methyl)Acrylic ester compound.Immersion exposure 193nm positive photoresists disclosed by the invention not only have good resolution ratio, can also increase the adhesion property between photoresist and silicon chip, also improve the heat resistance and etch resistance energy of photoresist.
Description
Technical field
Match somebody with somebody the present invention relates to a kind of film-forming resin of lactone copolymers containing natural sesquiterpene and using this film-forming resin
What system formed is used for ArF laser(193nm)For the deep ultraviolet of exposure light source(DUV)Immersion exposure positivity chemical amplification type light
Photoresist composition.
Background technology
Photoresist is the key function material that photoetching process is carried out in large scale integrated circuit industry.The nineties in last century opens
Begin grow up with ArF laser(193nm)For the deep ultraviolet of exposure light source(DUV)Wave band exposure technology is widely used in making
Make in large scale integrated circuit, its resolution ratio is up to 0.13~0.10 micrometer range.But with the rapid hair of semiconductor industry
Exhibition, the continuous diminution of device size, as the extension of ArF (193nm) Photolithography Technology, 193nm immersion lithography process with filtered air is
Through as higher resolution is reached, breaking through the 45nm even generally acknowledged selection of 32nm technology nodes.Due to the raising and leaching of resolution ratio
Do not have the particular/special requirement of photoetching process, used in immersion 193nm(193i)Technique in photoresist also have its special performance requirement,
As glued membrane cannot swelling set in water;Prevent glue intermediate ion from spreading in water and pollute exposure circle's matter and exposure machine it is expensive
Camera lens etc..There are following technical problem in actual process at present:(1)The adhesiveness of photoresist and base material silicon chip is weak;(2)Photoetching
The heat resistance and etch resistant poor performance of glue.
On the other hand, it is well known that China's natural products aboundresources, turpentine oil, rosin, by leaf-alcohol, terpene and sequiterpene
And its lactone etc. derives from a wealth of sources, yield is huge.It is as high in all contained in the trees such as pine tree, cypress, eucalyptus and many herbaceous plant
The compound such as turpentine oil, rosin, sequiterpene and its lactone.How national conditions are combined, by the compound from natural products, application
The photoresist field into integrated circuit industry, and above-mentioned technical problem can be overcome at the same time, existing photoresist is solved to exposure machine mirror
Head harmful effect, becomes the direction of those skilled in the art's effort.
The content of the invention
First purpose of the invention is to provide a kind of film-forming resin containing sesquiterpene lactone, this contains sesquiterpene lactone film-forming resin
The adhesive property between photoresist and silicon chip can be increased, due to the increase of the carbon atom density of film-forming resin, will also improve photoetching
The heat resistance of glue, improves its etch resistance energy.
Second object of the present invention is to provide a kind of leaching being configured to using the above-mentioned film-forming resin containing sesquiterpene lactone
Do not have formula to expose 193nm positive photoresists.
To reach above-mentioned first goal of the invention, the technical solution adopted by the present invention is:It is a kind of containing sesquiterpene lactone into
Film resin, it is characterised in that:Under the conditions of the film-forming resin is as existing for comonomer in radical initiator, in a solvent into
Row copolyreaction is prepared;It is characterized in that:The molecular weight of the film-forming resin is 4,000~5,000,000, molecular weight point
Cloth is 1.4~2.4;The comonomer is mainly the compound of following masses percentage composition:
The component units 10%~60% of the sequiterpene containing natural products;
Monomer containing acid-labile group 5%~40%;
Monomer 2% ~ 40% with hydrophobic performance group;
Other performance adjusts constituent monomers 1% ~ 20%;
The unit containing sesquiterpene lactone refers to meet chemical general formula()At least one sesquiterpene lactone alcohol(Methyl)
Acrylic ester compound:
(II);
Chemical general formula()The common sesquiterpene lactone alcohol of middle R bases(R-OH)As shown in table 1:
Table 1
The monomer containing acid-labile group is to meet chemical general formula()At least one of formula compound:
();
Chemical general formula()R in formula3For can leaving group, R3Structural formula is for example following(IV)Shown in:
(IV);
Wherein Y=- CH3Or-CH2CH3;
The monomer with hydrophobic performance group is to meet chemical general formula(V)At least one of formula compound:
(V);
Wherein Rf is fluorine-containing organic group, as follows:
Wherein Rf is containing silsesquioxane(Silsesquioxane)Group:
Above-mentioned technical proposal is described as follows:
1. in such scheme, the initiator is azo initiator, the radical initiator of peroxide;The azo
Initiator is that two isobutyl of azo is fine or azo is fine two different heptan, and the radical initiator of the peroxide is special for tert-butyl hydroperoxide
Valerate, tert-butyl hydroperoxide, benzoic acid hydrogen peroxide or benzoyl peroxide etc.;The initiator amount is described common
The 0.3%~15% of polycondensation monomer gross weight;The addition of radical initiator can use two ways:The first is single in each copolymerization
After body is dissolved in solvent, polymerization temperature is first to heat to, initiator is then added and carries out polymerisation.Second is in each comonomer
After being dissolved in solvent, initiator is first added, polymerization temperature is then warmed to again and carries out polymerisation.The initiator is in both sides
It can disposably add, can also add by several times in formula.The temperature of polymerisation is controlled according to the solvent used is different with initiator
System is in 40~150 DEG C of scopes.Polymerization reaction time is controlled when 4~28 is small also according to the solvent used is different with initiator.
2. in such scheme, the most common method of combined polymerization is with the monomer containing sesquiterpene lactone and other monomers
Combined polymerization, copolymerization monomer species and content are determined by their functions in the copolymer;
Such as copolymer as shown below is the unit containing acid-labile group by unit containing sesquiterpene lactone (A)(B)And hydrophobicity
What energy unit (C) was formed:
3. it is above-mentioned to there is copolymerization individually or in their mixture to be carried out in various solvents in such scheme, this
A little solvents include methanol, ethanol, dioxane, acetone, tetrahydrofuran, toluene, benzene, dimethylbenzene, dichloromethane, chloroform, trichlorine
Methane, dichloroethanes, trichloroethanes etc..
4. in such scheme, the post processing on polymerisation:
(1), purification process
After the completion of polymerisation, unreacted residual monomer and its part organic impurities can use heptane, hexane, hexamethylene,
Removed after pentane, petroleum ether, the extraction of ether equal solvent.
(2), separation solid copolymer
Copolymer can be in mixture, isopropanol and its water of pure water, methanol, the mixture of first alcohol and water, ethanol and its water
Mixture, heptane, hexane, hexamethylene, pentane, petroleum ether, precipitate separation, vacuum drying in the organic or inorganic solvent such as ether
The yield of rear copolymer is 60%~90%.
To reach above-mentioned second goal of the invention, the technical solution adopted by the present invention is:It is a kind of to contain sequiterpene using above-mentioned
Immersion 193nm positive photoresists made of the film-forming resin of lactone, it is characterised in that:Mainly by the compound of following mass parts
Composition:
Film-forming resin containing sesquiterpene lactone 10~35;
Photic sour 0.5~8;
Additive 0.5 ~ 30;
Solvent 70~90;
The photic acid is to meet chemical general formula()Or()One of sulfosalt, or meet chemical general formula
()One of diaryl group iodized salt;
();
In formula:R16、R17、R18It is alkyl that H, carbon number are 1~20 independently of one another or carbon number is 1~20
Alkoxy;Q=0~12;
();
In formula:R19It is the alkyl that H, carbon number are 1~20 or the alkoxy that carbon number is 1~20;R=0~12;
(IX);
In formula:R20、R21It is the alkyl that H, carbon number are 1~20 or the alkane that carbon number is 1~20 independently of one another
Epoxide;S=0~12;
The solvent is propylene glycol methyl ether acetate, propane diols list Acetic Ester, dihydroxypropane single-ether, propylene glycol monomethyl ether acetic acid
Ester, tirethylene glycol methyl ether, tirethylene glycol ether, butyl acetate, acetic acid peopentyl ester, ethyl lactate, methyl ethyl ketone and first
At least one of base isobutyl ketone;
The additive includes surface waterproofer, organic base, levelling agent;The surface waterproofer is selected from fluorine-containing or siliceous
Polymer;The organic base is selected from following compounds tripropyl amine (TPA), tri-n-butylamine, triisobutylamine, trioctylamine, triethanolamine, three ethoxies
At least one of ethylethanolamine, trimethoxy methoxy ethyl amine, tetramethylammonium hydroxide.The levelling agent be selected from it is fluorine-containing or
Siliceous surfactant.
Above-mentioned technical proposal is further described below:
It is 1. described to meet chemical general formula in such scheme()Or()Sulfosalt be:Triphenyl sulfosalt, three
P-methylphenyl sulfosalt, three couples of tert-butyl-phenyl sulfosalts, three(3,5- 3,5-dimethylphenyls)Sulfosalt, three(3,5- di-t-butyls
Phenyl)Sulfosalt, its coordination anion are:Trifluoromethane sulfonic acid, perfluoro butyl sulfonic acid, p-methylphenyl sulfonic acid, naphthalene sulfonic acids.
It is 2. described to meet chemical general formula in such scheme()Diaryl group iodized salt:Diphenyl iodnium, two pairs of first
Phenyl salt compounded of iodine, two pairs of tert-butyl-phenyl salt compounded of iodine, its coordination anion are:Trifluoromethane sulfonic acid, perfluoro butyl sulfonic acid, to first
Phenylbenzimidazole sulfonic acid, naphthalene sulfonic acids, camphorsulfonic acid.
Since above-mentioned technical proposal is used, the present invention has following advantages and effect:
1st, film-forming resin and its positivity immersion exposure 193nm photoresists of the invention containing sesquiterpene lactone, set in film forming
The polymerisable monomer of the sesquiterpene lactone containing natural products is introduced in fat and forms a kind of brand-new film-forming resin.It is this it is new into
Film resin can increase the adhesive property between photoresist and silicon chip;Due to the increase of the carbon atom density of film-forming resin, also will
The heat resistance of photoresist is improved, improves its etch resistance energy.Secondly, by the use of natural products as electronic product raw material, not only
Cost is low, environmentally protective, and itself is polycyclic aliphatic alkane, also with alloisomerism and optical activity, to improve photoetching
Colloidality can impart new development space, open the new gate of a fan.
2nd, film-forming resin and its positivity immersion exposure 193nm photoresists of the invention containing sesquiterpene lactone, in its exposure
During decomposition, since the molecular weight of its catabolite sesquiterpene lactone alkene or sesquiterpene lactone alcohol is very big, boiling point is very high, so as to avoid
Form gas overflowing and influence litho pattern and the photoetching machine lens of damage costliness.
Specific embodiment
With reference to embodiment, the invention will be further described:
Embodiment one:A kind of film-forming resin containing sesquiterpene lactone, by copolymerized monomers and its content, draws in free radical
Under the conditions of sending out existing for agent, it is prepared by heating progress copolyreaction:
3.70 grams of methacrylic acid -1- methyl cyclopentanes alcohol ester;
2.20 grams of methacrylic acid hexafluoro isopropyl alkyl ester;
6.38 grams of the short Docetaxel A esters of methacrylic acid.
At one equipped with electric mixer, condenser, thermometer, temperature controller, heating mantle and nitrogen inlet
In 100ml there-necked flasks, 3.70 grams of methacrylic acid -1- methyl cyclopentanes alcohol ester, methacrylic acid hexafluoro isopropyl alkyl ester are added
2.20 grams, 6.38 grams of the short Docetaxel A esters of methacrylic acid, 60 grams of tetrahydrofuran leads to nitrogen 10 minutes under agitation, then heats
Fine (the AIBN of two isobutyl of azo is added dropwise in 60~70 DEG C, 20 minutes)0.71 gram is made solution in 10 grams of tetrahydrofurans and then adds
Enter in reaction system, the reaction was continued reflux 24 it is small when after, be subsequently cooled to room temperature.With heptane extraction three times, polymer solution exists
Precipitated in pure water, polymer solids, yield 72% are obtained after vacuum drying.
Embodiment two:A kind of film-forming resin containing sesquiterpene lactone, by copolymerized monomers and its content, draws in free radical
Under the conditions of sending out existing for agent, it is prepared by heating progress copolyreaction:
4.50 grams of methacrylic acid -1- methyl cyclopentanes alcohol ester
Methacrylic acid is to 3.52 grams of hexafluoro t-butylcyclohexane diol monoester;
6.48 grams of the short Docetaxel A esters of methacrylic acid.
At one equipped with electric mixer, condenser, thermometer, temperature controller, heating mantle and nitrogen inlet
In 100ml there-necked flasks, 4.50 grams of methacrylic acid -1- methyl cyclopentanes alcohol ester is added, methacrylic acid is to hexafluoro tert-butyl group ring
3.52 grams of hexane diol monoesters, 6.48 grams of the short Docetaxel ester of methacrylic acid, 60 grams of tetrahydrofuran, leads to nitrogen 10 and divides under agitation
Clock, is then heated to 65~70 DEG C, and it is fine to add two isobutyl of azo(AIBN)0.73 gram in 10 grams of tetrahydrofurans solution to be made right
Afterwards add reaction system in, the reaction was continued reflux 8~24 it is small when after, be subsequently cooled to room temperature.With heptane extraction three times, polymer
Solution precipitates in pure water, and polymer solids, yield 70% are obtained after vacuum drying.
Embodiment three:A kind of film-forming resin containing sesquiterpene lactone, by copolymerized monomers and its content, draws in free radical
Under the conditions of sending out existing for agent, it is prepared by heating progress copolyreaction:
2.55 grams of methacrylic acid -2- butyrolactone alcohol ester;
1.81 grams of methacrylic acid hexafluoro isobutyl hydroxyl isobornyl thiocyanoacetate;
6.38 grams of the short Docetaxel A esters of methacrylic acid;
At one equipped with electric mixer, condenser, thermometer, temperature controller, heating mantle and nitrogen inlet
In 100ml there-necked flasks, 2.55 grams of methacrylic acid -2- butyrolactone alcohol ester, methacrylic acid hexafluoro isobutyl hydroxyl isoborneol are added
1.81 grams of ester, 6.38 grams of the short Docetaxel A esters of methacrylic acid, 60 grams of tetrahydrofuran lead to nitrogen 10 minutes under agitation, Ran Houjia
It is fine to add two isobutyl of azo to 60~70 DEG C for heat(AIBN)0.59 gram solution is made in 10 grams of tetrahydrofurans and then adds reaction
In system, the reaction was continued reflux 18 it is small when after, be subsequently cooled to room temperature.With heptane extraction three times, polymer solution is in pure water
Precipitation, obtains polymer solids, yield 71% after vacuum drying.
Example IV:The copolymer film-forming resin of a kind of sequiterpene containing natural products, by copolymerized monomers in free radical
Copolyreaction is carried out under the conditions of initiator is existing to be prepared:
3.40 grams of methacrylic acid -2- butyrolactone alcohol ester;
2.36 grams of methacrylic acid hexafluoroisopropanol ester;
6.38 grams of the short Docetaxel A esters of methacrylic acid;
At one equipped with electric mixer, condenser, thermometer, temperature controller, heating mantle and nitrogen inlet
In 100ml there-necked flasks, 3.40 grams of addition methacrylic acid -2- butyrolactone alcohol ester, 2.36 grams of methacrylic acid hexafluoroisopropanol ester,
6.38 grams of the short Docetaxel A esters of methacrylic acid, 60 grams of tetrahydrofuran, leads to nitrogen 10 minutes under agitation, is then heated to 70 DEG C, and 20
Fine (the AIBN of two isobutyl of azo is added dropwise in minute)0.61 gram is made solution in 10 grams of tetrahydrofurans and then adds in reaction system,
After when reflux 24 that the reaction was continued is small, room temperature is subsequently cooled to.With heptane extraction three times, polymer solution precipitates in pure water, very
Polymer solids, yield 72% are obtained after sky is dry.
Embodiment five:The copolymer film-forming resin of a kind of sesquiterpene lactone containing natural products, by comonomer in free radical
It is polymerized in the presence of initiator, its equation is as follows:
3.40 grams of methacrylic acid -2- butyrolactone alcohol ester;
2.94 grams of methacrylic acid -5- hydroxyl neoheptane -2- alcohol esters;
6.38 grams of the short Docetaxel A esters of methacrylic acid
At one equipped with electric mixer, condenser, thermometer, temperature controller, heating mantle and nitrogen inlet
In 100ml there-necked flasks, 3.40 grams of methacrylic acid -2- butyrolactone alcohol ester, methacrylic acid -5- hydroxyl neoheptane -2- alcohol are added
2.94 grams of ester, 6.38 grams of the short Docetaxel A esters of methacrylic acid, 60 grams of tetrahydrofuran lead to nitrogen 10 minutes, then heat under agitation
To 60 ~ 70 DEG C, it is fine to add two isobutyl of azo(AIBN)0.63 gram of solution in 10 grams of THF, when reflux 8~24 that the reaction was continued is small
Afterwards, it is subsequently cooled to room temperature.Polymer solution precipitates in pure water, and polymer solids, yield 72% are obtained after vacuum drying.
Embodiment six:A kind of copolymer film-forming resin of sequiterpene containing natural products, is triggered by comonomer in free radical
It is polymerized in the presence of agent, reaction equation is as follows:
2.45 grams of methacrylic acid propylsilsesquioxane ester
3.40 grams of methacrylic acid -2- butyrolactone alcohol ester
6.38 grams of the short Docetaxel A esters of methacrylic acid
At one equipped with electric mixer, condenser, thermometer, temperature controller, heating mantle and nitrogen inlet
In 100ml there-necked flasks, 2.45 grams of methacrylic acid -1- cyclohexyls alcohol ester, methacrylic acid propylsilsesquioxane ester are added
3.40 grams, 6.38 grams of the short Docetaxel A esters of methacrylic acid, 60 grams of tetrahydrofuran leads to nitrogen 10 minutes under agitation, is then heated to
60 ~ 70 DEG C, it is fine to add two isobutyl of azo(AIBN)0.55 gram of solution in 10 grams of THF, the reaction was continued reflux 24 it is small when after, so
Postcooling is to room temperature.Polymer solution precipitates in pure water, and polymer solids, yield 64% are obtained after vacuum drying.
Embodiment seven:A kind of sequiterpene containing natural products and tert-butyl acrylate copolymer film-forming resin, by being copolymerized
Monomer is polymerized in the presence of a free-radical initiator, and reaction equation is as follows:
4.41 grams of methacrylic acid -2- methyl adamantanes alcohol ester
1.74 grams of methacrylic acid 3- hydroxyl hexafluoro dissidents alcohol ester
6.78 grams of chloranthalactone alcohol methacrylate
At one equipped with electric mixer, condenser, thermometer, temperature controller, heating mantle and nitrogen inlet
In 100ml there-necked flasks, 4.41 grams of methacrylic acid -2- methyl adamantanes alcohol ester, methacrylic acid 3- hydroxyl hexafluoro dissidents are added
1.74 grams of alcohol ester, 6.78 grams of chloranthalactone alcohol methacrylate, 60 grams of tetrahydrofuran lead to nitrogen 10 minutes under agitation,
60 ~ 70 DEG C are then heated to, it is fine to add two isobutyl of azo(AIBN)0.54 gram of solution in 10 grams of THF, reflux 8 that the reaction was continued
~24 it is small when after, be subsequently cooled to room temperature.Polymer solution precipitates in pure water, and polymer solids, yield are obtained after vacuum drying
68%。
The copolymer film-forming resin deep ultraviolet 193nm of eight~embodiment of embodiment 12, the sesquiterpene lactone containing natural products
Immersion positive photoresist is prepared:
(1)Photic acid:Embodiment eight:Triphenyl trifluoromethyl sulfosalt, coordination anion are perfluoro butyl sulfonic acid;Implement
Example nine:Triphenyl sulfosalt, coordination anion are perfluoro butyl sulfonic acid;Embodiment ten:Three p-methylphenyl sulfosalts, coordination it is cloudy from
Son is naphthalene sulfonic acids;Embodiment 11:Two pairs of tert-butyl-phenyl salt compounded of iodine, coordination anion are trifluoromethane sulfonic acid;Embodiment ten
Two:Three pairs of tert-butyl-phenyl sulfosalts, coordination anion are trifluoromethane sulfonic acid.
(2)Solvent:Embodiment eight:Propylene glycol methyl ether acetate;Embodiment nine:Acetic acid peopentyl ester;Embodiment ten:Methyl second
Base ketone;Embodiment 11:Dihydroxypropane single-ether, propylene glycol methyl ether acetate;Embodiment 12:Butyl acetate, ethyl lactate.
(3)Organic base:Embodiment eight:Triisobutylamine;Embodiment nine:Trimethoxy methoxy ethyl amine;Embodiment ten:Three
Monoethanolamine;Embodiment 11:Triisobutylamine;Embodiment 12:Tripropyl amine (TPA).
(4)The collocation method of the photoresist of embodiment eight:
A kind of preparation method of the deep ultraviolet 193nm immersion positive photoresists of the sesquiterpene lactone containing natural products:One
In a clean 100 milliliters of new Polypropylene bottles, the copolymer prepared, 0.32 gram of triphen are added in 7.60 grams of embodiments one
Base trifluoromethyl sulfosalt, 100 grams of electronic grade propylene glycol methyl ether acetates(PGMEA)Solvent, and 0.2 gram of n-butylamine,
0.12 gram of surfactant.This mixture is fixed on a mechnical oscillator, when concussion 10~24 is small at room temperature, fills it
Divide dissolving.Filtered 2 times with the filter of 0.2 micron pore size, then filtered one time with the filter of 0.05 micron pore size.
Lithography experiments method and result:The photoresist of above-mentioned preparation is on 12 " silicon chips with 2000~6000 revs/min
Speed rotation forms a film, and toasts on 120 DEG C of hot plates 90 seconds, is then exposed with 193nm immersion exposures technique.Exposure intensity 10-
50 mJ/cm2.Toasted 90 seconds on 110 DEG C of hot plates after exposure, finally again in 2.38% TMAH developer solutions(23℃)Middle development
60 seconds, electron microscopy lithographic results are used after drying.As a result this photoresist resolution ratio is proved up to 0.10~0.08 μm,
And with good photoetching process operation allowed band.
(5)The formula of nine~embodiment of embodiment 12 such as following table, collocation method with embodiment eight, adopt successively by film-forming resin
It is expressed as below with the copolymer prepared in embodiment.The resolution ratio of gained photoresist and anti-etching performance evaluation result such as table 2 below:
Table 2
Film-forming resin | Photic acid | Solvent | Resolution ratio | It is 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:(1)When photoresist is assessed, since technological requirement is different, resolution ratio is all in the range of 0.13um -0.10um
Well;
(2)In dry etching assessment, in the case where setting process conditions, Liu Mo Shuai≤80% is +++;Liu Mo Shuai≤60% is
++;Liu Mo Shuai≤40% for+;Liu Mo Shuai≤30% is unqualified.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should be covered by the protection scope of the present invention.
Claims (5)
- A kind of 1. film-forming resin containing sesquiterpene lactone, it is characterised in that:The film-forming resin is drawn by comonomer in free radical Under the conditions of sending out existing for agent, copolyreaction is carried out in a solvent and is prepared;It is characterized in that:The molecular weight of the film-forming resin For 4,000~5,000,000, molecular weight distribution is 1.4~2.4;The comonomer is mainly following masses percentage composition Compound:The component units 10%~60% of the sequiterpene containing natural products;Monomer containing acid-labile group 5%~40%;Monomer 2% ~ 40% with hydrophobic performance group;Other performance adjusts constituent monomers 1% ~ 20%;The component units of the sequiterpene containing natural products refer to meet chemical general formula (II)At least one sesquiterpene lactone alcohol 's(Methyl)Acrylic ester compound:(II);Chemical general formula(II)The common sesquiterpene lactone alcohol of middle R bases(R-OH)It is as follows:;The monomer containing acid-labile group is to meet chemical general formula(III)At least one of formula compound:(III);Chemical general formula(III)R in formula3For can leaving group, R3Structural formula is for example following(IV)Shown in:(IV);Wherein Y=- CH3Or-CH2CH3;The monomer with hydrophobic performance group is to meet chemical general formula(V)At least one of formula compound:(V);Wherein Rf is organic fluoride-containing group, as follows:Wherein Rf either contains silsesquioxane(Silsesquioxane)Group, it is as follows:。
- 2. the film-forming resin according to claim 1 containing sesquiterpene lactone, it is characterised in that:The initiator draws for azo Send out agent, the radical initiator of peroxide;The azo initiator is azodiisobutyronitrile or azobisisoheptonitrile, described The radical initiator of peroxide for tert-butyl hydroperoxide pivalate, tert-butyl hydroperoxide, benzoic acid hydrogen peroxide or Person's benzoyl peroxide;The initiator amount is the 0.3%~15% of the comonomer gross weight.
- 3. the positivity immersion that a kind of film-forming resin containing sesquiterpene lactone using described in claims 1 or 2 is configured to exposes Light 193nm photoresists, it is characterised in that:Mainly it is made of the compound of following mass parts:Film-forming resin containing sesquiterpene lactone 10~35;Photic sour 0.5~8;Additive 0.5 ~ 30;Solvent 70~90;The photic acid is to meet chemical general formula()Or()One of sulfosalt, or meet chemical general formula()Two One of aryl salt;();In formula:R16、R17、R18It is the alkyl that H, carbon number are 1~20 or the alkane that carbon number is 1~20 independently of one another Epoxide;Q=0~12;();In formula:R19It is the alkyl that H, carbon number are 1~20 or the alkoxy that carbon number is 1~20;R=0~12;(IX);In formula:R20、R21It is the alkyl that H, carbon number are 1~20 or the alkoxy that carbon number is 1~20 independently of one another; S=0~12;The solvent is propylene glycol methyl ether acetate, propane diols list Acetic Ester, dihydroxypropane single-ether, tirethylene glycol methyl ether, two At least one in condensed ethandiol ether, butyl acetate, acetic acid peopentyl ester, ethyl lactate, methyl ethyl ketone and methyl iso-butyl ketone (MIBK) Kind;The additive includes surface waterproofer, organic base, levelling agent;The surface waterproofer is selected from fluorine-containing or siliceous polymerization Thing;The organic base is selected from following compounds tripropyl amine (TPA), tri-n-butylamine, triisobutylamine, trioctylamine, triethanolamine, triethoxy second At least one of hydramine, trimethoxy methoxy ethyl amine, tetramethylammonium hydroxide;The levelling agent is selected from fluorine-containing or siliceous Surfactant.
- 4. positivity immersion exposure 193nm photoresists according to claim 3, it is characterised in that:The chemistry that meets leads to Formula()Or()Sulfosalt be:Triphenyl sulfosalt, three p-methylphenyl sulfosalts, three pairs of tert-butyl-phenyl sulfosalts, its Coordination anion is:Trifluoromethane sulfonic acid, perfluoro butyl sulfonic acid.
- 5. positivity immersion exposure 193nm photoresists according to claim 3, it is characterised in that:The chemistry that meets leads to Formula()Diaryl group iodized salt:Diphenyl iodnium, di-p-tolyl salt compounded of iodine, two pairs of tert-butyl-phenyl salt compounded of iodine, it is matched somebody with somebody Complex anion is:Trifluoromethane sulfonic acid, perfluoro butyl sulfonic acid.
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