CN116003681B - Polymer for 193nm water immersion type photoresist top layer coating, preparation method thereof and top layer coating composition - Google Patents
Polymer for 193nm water immersion type photoresist top layer coating, preparation method thereof and top layer coating composition Download PDFInfo
- Publication number
- CN116003681B CN116003681B CN202211642487.4A CN202211642487A CN116003681B CN 116003681 B CN116003681 B CN 116003681B CN 202211642487 A CN202211642487 A CN 202211642487A CN 116003681 B CN116003681 B CN 116003681B
- Authority
- CN
- China
- Prior art keywords
- polymer
- monomer
- reaction
- water
- water immersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 30
- 238000007654 immersion Methods 0.000 title claims abstract description 25
- 238000000576 coating method Methods 0.000 title claims abstract description 13
- 239000011248 coating agent Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000008199 coating composition Substances 0.000 title abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 150000003254 radicals Chemical class 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 8
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- FXYPBSKJSOBFAC-UHFFFAOYSA-N tert-butyl $l^{1}-oxidanylformate Chemical compound CC(C)(C)OC([O])=O FXYPBSKJSOBFAC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- -1 hexafluorotertiary butyl structure Chemical group 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000002386 leaching Methods 0.000 description 7
- FPOSNZIGNWKAGA-UHFFFAOYSA-N 2-(trifluoromethylsulfonylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNS(=O)(=O)C(F)(F)F FPOSNZIGNWKAGA-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000000671 immersion lithography Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SXKLNBJCHYEPDL-UHFFFAOYSA-N n,n-difluorosulfamoyl fluoride Chemical group FN(F)S(F)(=O)=O SXKLNBJCHYEPDL-UHFFFAOYSA-N 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Abstract
The invention relates to the technical field of photoresist, in particular to a polymer for 193nm water immersion type photoresist top layer coating, a preparation method thereof and a top layer coating composition, wherein the polymer has the following general formula:x, y and z are mass fractions of polymer repeating units, x is selected from 80-94%, y is selected from 5-15%, z is selected from 1-10%, polymer molecular weight is selected from 2000-10000Da, and molecular weight dispersion coefficient is selected from 1.0-3.0. The preparation method comprises the following steps: mixing a monomer A, a monomer B, a monomer C and a free radical initiator, dissolving in an electronic grade reaction solvent to prepare a mixed solution, dripping the mixed solution into the electronic grade reaction solvent, controlling the reaction temperature and the reaction time, dripping the reaction system into water after the reaction is finished, and granulating to obtain the polymer. The top coat composition formulated with the polymer has a higher contact angle.
Description
Technical Field
The invention relates to a polymer for a 193nm water immersion type photoresist top layer coating, a preparation method thereof and a top layer coating composition, and belongs to the technical field of photoresists.
Background
The photolithography technique refers to a pattern micromachining technique in which a resist chemically changes under light of a specific wavelength or an electron beam, and a pattern designed on a mask plate is transferred onto a substrate through processes such as exposure, development, etching, and the like.
The resolution of the photoresist can be improved by using a short wavelength light source in the photolithography process, which has been developed from 365nm (I-line) to 248nm (KrF), 193nm (ArF), 13.5nm (EUV).
In 193nm immersion lithography, pure water is considered the preferred immersion medium because pure water can bring the Numerical Aperture (NA) value of an optical lens up to 1.35. However, in the lithographic process, direct contact of the photoresist with water can cause leaching of the photoacid generator component into the immersion fluid, causing defects in the photoresist pattern, and such leaching can cause contamination of the optical lens and change in the effective refractive index and transmittance properties of the immersion fluid. Thus 193nm lithography, using pure water as the immersion fluid, requires the use of a topcoat composition over the photoresist as a barrier to the immersion fluid and photoresist layer. Such barrier layers also face various challenges such as global defects caused by microbridge, top layer coating refractive index, thickness, acidity, interactions with underlying photoresist, and immersion time, which can result in variations in photolithography process window, critical dimension, and topography.
To overcome the above drawbacks, improving the properties of top coating compositions, it is desirable to design polymers for top coatings that have high receding contact angles.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a polymer for 193nm water immersion type photoresist top layer coating, a preparation method thereof and a top layer coating composition, and the top layer coating composition prepared by the polymer has a higher contact angle.
The technical scheme for solving the technical problems is as follows: a polymer for 193nm water immersion photoresist topcoat, said polymer having the formula:
x, y and z are mass fractions of polymer repeating units, x is selected from 80-94%, y is selected from 5-15%, z is selected from 1-10%, polymer molecular weight is selected from 2000-10000Da, and molecular weight dispersion coefficient is selected from 1.0-3.0.
Based on the technical scheme, the invention can also be improved as follows:
preferably, x in the polymer repeat unit is selected from 85-90%; y is selected from 5-10%; z is selected from 1-5%.
Preferably, the polymer molecular weight is selected from 4000-7000Da; the PDI is selected from 1.0-1.8.
The invention also discloses a preparation method of the polymer for the 193nm water immersion type photoresist top layer coating, which comprises the following steps: mixing a monomer A, a monomer B, a monomer C and a free radical initiator, dissolving the mixture in an electronic grade reaction solvent to prepare a mixed solution, dripping the mixed solution into the electronic grade reaction solvent, controlling the reaction temperature and the reaction time, dripping the reaction system into water after the reaction is finished, and granulating to obtain the polymer;
the monomer A is methacrylic acid-2-trifluoromethanesulfonyl amino ethyl ester, the monomer B is 2-acrylamide-2-methyl-1-propane sulfonic acid, and the monomer C is 2- ((tert-butyloxycarbonyl) oxygen) -1, 1-trifluoro-6-methyl-2- (trifluoromethyl) heptane-4-yl methacrylate.
Further, according to the mass fraction, the monomer A is 80-94% of the total mass of the monomers, the monomer B is 5-15% of the total mass of the monomers, and the monomer C is 1-10% of the total mass of the monomers.
Preferably, the monomer A accounts for 85-90% of the total mass of the monomers, the monomer B accounts for 5-10% of the total mass of the monomers, and the monomer C accounts for 1-5% of the total mass of the monomers.
Further, the free radical initiator is selected from any one of azobisisobutyronitrile, benzoyl peroxide, azobisisoheptonitrile and dimethyl azobisisobutyrate. The free radical initiator is used in an amount of 1 to 15% of the total mass of the monomers (the sum of the masses of monomer A, monomer B and monomer C).
Preferably, the free radical initiator is azobisisobutyronitrile. Preferably, the free radical initiator is used in an amount of 5 to 10% of the total mass of the monomers.
Further, the electronic grade reaction solvent is selected from any one of propylene glycol methyl ether, propylene glycol methyl ether acetate, methyl isobutyl methanol, dipropylene glycol methyl ether and isopropanol.
Preferably, the electronic grade reaction solvent is methyl isobutyl carbinol.
Further, the reaction temperature is 40-100 ℃ and the reaction time is 2-10 hours.
Preferably, the reaction temperature is 70-90 ℃ and the reaction time is 2-5 hours.
The invention also discloses a top layer coating composition, which comprises a polymer, a photoacid generator and an electronic grade solvent, wherein the polymer is the polymer for the 193nm water immersion type photoresist top layer coating.
The beneficial effects of the invention are as follows:
(1) The polymer structure has high transparency at 193nm, and the trifluoro sulfonamide group enhances the dissolution rate of the polymer in a developer, reduces the overall defect rate caused by micro bridging, maintains a high dynamic contact angle and has little leaching of a photoacid generator;
(2) The polymer structure has acid-unstable tert-butyl oxycarbonyl groups, which is helpful for the developability during the development process and the removal of the top coating;
(3) The polymer structure has a hexafluorotertiary butyl structure, so that the contact angle with water is increased;
(4) The polymer structure related by the invention has a strong acid sulfonic acid group, and can be used for adjusting the special contour of the photoresist and controlling the top deletion of the photoresist;
(5) The preparation method is simple and convenient.
Drawings
FIG. 1 shows Polymer B 1 H-NMR spectrum.
Detailed Description
The following describes the present invention in detail. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, so that the invention is not limited to the specific embodiments disclosed.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Monomer a (2-trifluoromethanesulfonyl aminoethyl methacrylate), monomer B (2-acrylamido-2-methyl-1-propanesulfonic acid), monomer C (2- ((tert-butyloxycarbonyl) oxy) -1, 1-trifluoro-6-methyl-2- (trifluoromethyl) heptan-4-yl methacrylate) are all known compounds and can be purchased commercially.
Example 1
27g of monomer A (methacrylic acid-2-trifluoromethanesulfonyl amino ethyl ester), 1.5g of monomer B (2-acrylamide-2-methyl-1-propane sulfonic acid), 1.5g of monomer C (2- ((tert-butyloxycarbonyl) oxy) -1, 1-trifluoro-6-methyl-2- (trifluoromethyl) heptane-4-yl methacrylate) and 4.0g of azodiisobutyronitrile are dissolved in 100g of electronic grade dipropylene glycol methyl ether to prepare a mixed solution, the mixed solution is pumped into 70g of electronic grade dipropylene glycol methyl ether by a metering pump, the reaction temperature is controlled to be 60-70 ℃, the reaction is kept for 8 hours, the reaction is completed, the system is cooled to room temperature, the system is slowly dripped into 1000g of water, white solid is precipitated, and the Polymer A16.5 g is obtained after filtration and drying, the yield is 55 percent, mw=3285 Da and PDI=1.38.
Example 2
27g of monomer A (2-trifluoromethanesulfonyl amino ethyl methacrylate), 2.0g of monomer B (2-acrylamide-2-methyl-1-propane sulfonic acid), 1.0g of monomer C (2- ((tert-butyloxycarbonyl) oxy) -1, 1-trifluoro-6-methyl-2- (trifluoromethyl) heptane-4-yl methacrylate) and 2.5g of azobisisobutyronitrile were dissolved in 100g of electronic grade methyl isobutyl carbinol to prepare a mixed solution, the mixed solution was pumped into 70g of electronic grade methyl isobutyl carbinol by a metering pump, the reaction temperature was controlled to 80-90 ℃, the reaction was kept for 4 hours, the reaction was completed, the system was cooled to room temperature, the system was slowly dropped into 1000g of water, a white solid was precipitated, and the Polymer B19.5 g was obtained by filtration and drying, the yield was 65%, mw=4885 Da, and PDI=1.59.
The nuclear magnetism detection is as follows: 1 H-NMR(400MHz，(CD 3 ) 2 CO), δ=0.903-2.112 (not to O, N, CF) 3 Connected CH, CH 2 、CH 3 ) Delta= 3.644-4.131 (and O, N, CF 3 Connected CH, CH 2 )，δ
= 7.317-8.255 (and O, N, CF 3 Attached active hydrogen), as shown in figure 1.
Example 3
27g of monomer A (methacrylic acid-2-trifluoromethanesulfonyl amino ethyl ester), 5.0g of monomer B (2-acrylamide-2-methyl-1-propane sulfonic acid), 1.5g of monomer C (2- ((tert-butyloxycarbonyl) oxy) -1, 1-trifluoro-6-methyl-2- (trifluoromethyl) heptane-4-yl methacrylate) and 2.0g of azo-diisoheptonitrile are dissolved in 100g of electronic grade propylene glycol methyl ether to prepare a mixed solution, the mixed solution is pumped into 100g of electronic grade propylene glycol methyl ether by a metering pump, the reaction temperature is controlled to be 40-50 ℃, the reaction is kept for 10 hours, the reaction is completed, the system is cooled to room temperature, the system is slowly dripped into 1000g of water, white solid is separated out, the Polymer C20.8 g is obtained after filtration and drying, the yield is 62%, mw=6562 Da, and PDI=1.72.
Example 4
27g of monomer A (2-trifluoromethanesulfonyl amino ethyl methacrylate), 1.5g of monomer B (2-acrylamide-2-methyl-1-propane sulfonic acid), 3.2g of monomer C (2- ((tert-butyloxycarbonyl) oxy) -1, 1-trifluoro-6-methyl-2- (trifluoromethyl) heptane-4-yl methacrylate) and 1.5g of dimethyl azodiisobutyrate were dissolved in 100g of electronic grade propylene glycol methyl ether acetate to prepare a mixed solution, the mixed solution was pumped into 100g of electronic grade propylene glycol methyl ether acetate by a metering pump, the reaction temperature was controlled to 70-80 ℃, the reaction was kept for 2 hours, the reaction was completed, the system was cooled to room temperature, slowly dropped into 1000g of water to precipitate a white solid, and the Polymer D17.7 g was obtained by filtration and drying, the yield was 54%, mw=7824 Da, and PDI=1.79.
Example 5
27g of monomer A (2-trifluoromethanesulfonyl amino ethyl methacrylate), 3.0g of monomer B (2-acrylamide-2-methyl-1-propane sulfonic acid), 3.0g of monomer C (2- ((tert-butyloxycarbonyl) oxy) -1, 1-trifluoro-6-methyl-2- (trifluoromethyl) heptane-4-yl methacrylate) and 1.5g of benzoyl peroxide are dissolved in 100g of electronic grade isopropanol to prepare a mixed solution, the mixed solution is pumped into 50g of electronic grade isopropanol by a metering pump, the reaction temperature is controlled to be 50-60 ℃, the reaction is kept for 6 hours, the system is cooled to room temperature after the reaction, the system is slowly dripped into 1000g of water, white solid is precipitated, the Polymer E21.8 g is obtained after filtration and drying, the yield is 61%, mw=9927 Da, and PDI=1.94.
Example 6
27g of monomer A (2-trifluoromethanesulfonyl amino ethyl methacrylate), 1.5g of monomer B (2-acrylamide-2-methyl-1-propane sulfonic acid), 0.3g of monomer C (2- ((tert-butyloxycarbonyl) oxy) -1, 1-trifluoro-6-methyl-2- (trifluoromethyl) heptane-4-yl methacrylate) and 4.3g of azobisisobutyronitrile were dissolved in 100g of electronic grade methyl isobutyl carbinol to prepare a mixed solution, the mixed solution was pumped into 60g of electronic grade methyl isobutyl carbinol by a metering pump, the reaction temperature was controlled to 70-80 ℃, the reaction was kept for 6 hours, the reaction was completed, the system was cooled to room temperature, the system was slowly dropped into 1000g of water, a white solid was precipitated, and the Polymer F15.2 g was obtained by filtration and drying, the yield 52.78%, mw=3035 Da, and PDI=1.31.
Example 7
27G of monomer A (2-trifluoromethanesulfonyl amino ethyl methacrylate), 3.4G of monomer B (2-acrylamide-2-methyl-1-propane sulfonic acid), 3.3G of monomer C (2- ((tert-butyloxycarbonyl) oxy) -1, 1-trifluoro-6-methyl-2- (trifluoromethyl) heptane-4-yl methacrylate) and 0.4G of azobisisoheptonitrile were dissolved in 100G of electronic grade propylene glycol methyl ether acetate to prepare a mixed solution, the mixed solution was pumped into 60G of electronic grade propylene glycol methyl ether acetate by a metering pump, the reaction temperature was controlled to be 90-100 ℃, the reaction was kept for 3 hours, the reaction was completed, the system was cooled to room temperature, the mixture was slowly dropped into 1000G of water, a white solid was precipitated, and the Polymer G17.3G was obtained by filtration and drying, the yield was 51.33%, mw=9647 Da, and PDI=1.93.
Top coat composition formulation
The polymer prepared in the above example and photoacid generator (4-tert-butylphenyl diphenyl thio-nonafluorobutanesulfonate) and electronic grade solvent methyl isobutyl carbinol are prepared into 193nm water immersion type photoresist top layer coating composition with certain solid content, and the formula of the top layer coating composition is shown in table 1:
table 1 top coat composition formulation
Wherein the structural formula of the Polymer X is as follows:
top coat composition performance test
The top coating composition was spin coated on 6 inch silicon wafers at rotation speeds of 0rpm/10s, 200rpm/2s, 0rpm/2s, 1500rpm/30s, baked at 90 ℃ for 1 minute on a hot plate after spin coating, then placed on a cold plate for cooling, and tested for n value (refractive index), k value (light absorption coefficient), static contact angle, dynamic contact angle, leaching of photoacid generator in water. The test instrument is as follows:
n value, k value: ellipsometer (brand/model U.S. Woollam/RC 2)
Static contact angle, dynamic contact angle: contact angle measuring instrument (brand/model German Kelu upper/DSA 25S)
Leaching the photoacid generator in water: HPLC-MS (brand/model Agilent 1260/6420)
The test results are shown in Table 2:
TABLE 2 results of Top coating composition Performance test
Table 2 shows that compositions 1-14 formulated with the polymers of the present invention are all transparent at 193nm (k values of 0), and have very low leaching of photoacid generator in water due to the hydrophobic t-butyl structure. In particular, the static contact angle and the (advancing) dynamic contact angle of the composition 3 and the composition 4 prepared from the polymer B with water are both larger than 90 degrees, the leaching of the photoacid generator in water is smaller than 1ppb, the pollution of the photoacid generator to a lens during 193nm water immersion type photoresist exposure can be obviously reduced, the shape and the critical dimension of a pattern are improved, and the photoresist has good application prospect. The compositions 15, 16 prepared from polymer X, however, do not contain a hydrophobic tertiary butyl structure, but contain hydrophilic hydroxyl groups, which reduces the contact angle with water.
The technical features of the above-described embodiments may be arbitrarily combined, and in order to simplify the description, all possible combinations of the technical features in the above-described embodiments are not exhaustive, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims.
Claims (10)
1. A polymer for 193nm water immersion photoresist topcoat, said polymer having the formula:
x, y and z are mass fractions of polymer repeating units, x is selected from 80-94%, y is selected from 5-15%, z is selected from 1-10%, polymer molecular weight is selected from 2000-10000Da, and molecular weight dispersion coefficient is selected from 1.0-3.0.
2. A polymer for 193nm water immersion photoresist topcoat as claimed in claim 1 wherein x in the polymer repeat unit is selected from 85-90%; y is selected from 5-10%; z is selected from 1-5%.
3. A polymer for 193nm water immersion photoresist topcoat as claimed in claim 1, wherein the polymer molecular weight is selected from 4000-7000Da; the PDI is selected from 1.0-1.8.
4. A method for preparing a polymer for 193nm water immersion photoresist top coat according to any one of claims 1-3, wherein the preparation method comprises: mixing a monomer A, a monomer B, a monomer C and a free radical initiator, dissolving the mixture in an electronic grade reaction solvent to prepare a mixed solution, dripping the mixed solution into the electronic grade reaction solvent, controlling the reaction temperature and the reaction time, dripping the reaction system into water after the reaction is finished, and granulating to obtain the polymer;
the monomer A is methacrylic acid-2-trifluoromethanesulfonyl amino ethyl ester, the monomer B is 2-acrylamide-2-methyl-1-propane sulfonic acid, and the monomer C is 2- ((tert-butyloxycarbonyl) oxygen) -1, 1-trifluoro-6-methyl-2- (trifluoromethyl) heptane-4-yl methacrylate.
5. The method for preparing a polymer for 193nm water immersion type photoresist top layer coating according to claim 4, wherein the monomer A is 80-94% of the total mass of the monomers, the monomer B is 5-15% of the total mass of the monomers, and the monomer C is 1-10% of the total mass of the monomers.
6. The method for preparing a polymer for 193nm water immersion photoresist top coating according to claim 4, wherein the monomer A is 85-90% of the total mass of the monomers, the monomer B is 5-10% of the total mass of the monomers, and the monomer C is 1-5% of the total mass of the monomers.
7. The method of preparing a polymer for 193nm water immersion photoresist top coating according to claim 4, wherein said free radical initiator is selected from any of azobisisobutyronitrile, benzoyl peroxide, azobisisoheptonitrile and dimethyl azobisisobutyrate.
8. The method of claim 4, wherein the electron-grade reaction solvent is selected from the group consisting of propylene glycol methyl ether, propylene glycol methyl ether acetate, methyl isobutyl carbinol, dipropylene glycol methyl ether, and isopropyl alcohol.
9. The method of claim 4, wherein the reaction temperature is 40-100deg.C and the reaction time is 2-10 hours.
10. A topcoat composition comprising a polymer, a photoacid generator, and an electronic grade solvent, wherein the polymer is a polymer for 193nm water-immersion photoresist topcoat as defined in any one of claims 1 to 3, or wherein the polymer is a polymer prepared by a process for preparing a polymer for 193nm water-immersion photoresist topcoat as defined in any one of claims 4 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211642487.4A CN116003681B (en) | 2022-12-20 | 2022-12-20 | Polymer for 193nm water immersion type photoresist top layer coating, preparation method thereof and top layer coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211642487.4A CN116003681B (en) | 2022-12-20 | 2022-12-20 | Polymer for 193nm water immersion type photoresist top layer coating, preparation method thereof and top layer coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116003681A CN116003681A (en) | 2023-04-25 |
| CN116003681B true CN116003681B (en) | 2024-01-30 |
Family
ID=86026030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211642487.4A Active CN116003681B (en) | 2022-12-20 | 2022-12-20 | Polymer for 193nm water immersion type photoresist top layer coating, preparation method thereof and top layer coating composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116003681B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013040320A (en) * | 2011-01-26 | 2013-02-28 | Sumitomo Chemical Co Ltd | Resin, resist composition, and method for manufacturing resist pattern |
| CN105255246A (en) * | 2013-12-30 | 2016-01-20 | 罗门哈斯电子材料有限公司 | Topcoat compositions and photolithographic methods |
| CN114153124A (en) * | 2021-12-29 | 2022-03-08 | 中节能万润股份有限公司 | Composition for top coating of ArF immersion photoresist and preparation method thereof |
| CN114262416A (en) * | 2022-03-03 | 2022-04-01 | 甘肃华隆芯材料科技有限公司 | Polymer resin for 193nm water immersion lithography, water-resistant coating composition, water-resistant coating and preparation method thereof |
| CN114349898A (en) * | 2022-01-27 | 2022-04-15 | 苏州润邦半导体材料科技有限公司 | Polymer for 193nm immersed photoresist top coating, preparation method and application |
| CN114637165A (en) * | 2022-03-23 | 2022-06-17 | 中节能万润股份有限公司 | Composition for top coating of photoresist and preparation method of polymer of composition |
-
2022
- 2022-12-20 CN CN202211642487.4A patent/CN116003681B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013040320A (en) * | 2011-01-26 | 2013-02-28 | Sumitomo Chemical Co Ltd | Resin, resist composition, and method for manufacturing resist pattern |
| CN105255246A (en) * | 2013-12-30 | 2016-01-20 | 罗门哈斯电子材料有限公司 | Topcoat compositions and photolithographic methods |
| CN114153124A (en) * | 2021-12-29 | 2022-03-08 | 中节能万润股份有限公司 | Composition for top coating of ArF immersion photoresist and preparation method thereof |
| CN114349898A (en) * | 2022-01-27 | 2022-04-15 | 苏州润邦半导体材料科技有限公司 | Polymer for 193nm immersed photoresist top coating, preparation method and application |
| CN114262416A (en) * | 2022-03-03 | 2022-04-01 | 甘肃华隆芯材料科技有限公司 | Polymer resin for 193nm water immersion lithography, water-resistant coating composition, water-resistant coating and preparation method thereof |
| CN114637165A (en) * | 2022-03-23 | 2022-06-17 | 中节能万润股份有限公司 | Composition for top coating of photoresist and preparation method of polymer of composition |
Non-Patent Citations (1)
| Title |
|---|
| Exploring Acidic Functionalities in the Desigh and Development of High Performance 193nm Photoresist Polymers;P. R. Varanasi等;J. Photopol. Sci. Technol.;第20卷(第4期);481-491 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116003681A (en) | 2023-04-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4368266B2 (en) | Resist protective film forming material and resist pattern forming method using the same | |
| TWI334421B (en) | ||
| JP5301070B2 (en) | Resist protective film forming material for immersion exposure process, and resist pattern forming method using the protective film | |
| JP4434762B2 (en) | Resist composition | |
| JP2006227632A (en) | Immersion lithography process-use resist protection film forming material, composite film and resist pattern forming method | |
| JPWO2004074937A1 (en) | Resist protective film forming material for immersion exposure process, composite film, and resist pattern forming method | |
| WO2005085954A1 (en) | Positive resist composition for immersion exposure and method for forming resist pattern | |
| EP1840655A1 (en) | Material for forming resist protection films and method for resist pattern formation with the same | |
| JP2005250511A (en) | Material for forming resist protective film for liquid immersion exposure process, resist film having protective film made of the material for forming protective film, and method for forming resist pattern by using the protective film | |
| CN114349898B (en) | Polymer for 193nm immersed photoresist top layer coating, preparation method and application | |
| JP4368267B2 (en) | Resist protective film forming material and resist pattern forming method using the same | |
| WO2006070694A1 (en) | Acrylic copolymer | |
| CN114153124A (en) | Composition for top coating of ArF immersion photoresist and preparation method thereof | |
| JP6262416B2 (en) | Lithographic polymer solution manufacturing method, resist composition manufacturing method, and pattern-formed substrate manufacturing method | |
| CN116003681B (en) | Polymer for 193nm water immersion type photoresist top layer coating, preparation method thereof and top layer coating composition | |
| KR20050103789A (en) | Top anti-reflective coating polymer, its preparation method and top anti-reflective coating composition comprising the same | |
| CN117447885B (en) | Photoresist top layer coating polymer, preparation method, composition and application | |
| CN117304394B (en) | Polymer for photoresist top layer coating, preparation method and application | |
| JP4851140B2 (en) | (Meth) acrylic acid ester, polymer, resist composition, and method for producing substrate on which pattern is formed | |
| JP6369103B2 (en) | Lithographic polymer manufacturing method, resist composition manufacturing method, and pattern-formed substrate manufacturing method | |
| CN100352870C (en) | Organic anti-reflective coating polymer, its preparation method and organic anti-reflective coating composition comprising the same | |
| JP5793825B2 (en) | Lithographic polymer manufacturing method, resist composition manufacturing method, and substrate manufacturing method | |
| JP5507601B2 (en) | Resist pattern forming method | |
| JP5539304B2 (en) | Positive resist composition | |
| KR20230103978A (en) | Photoresist topcoat compositions and pattern formation methods |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |