CN114181342A - 193nm BARC resin and preparation method thereof - Google Patents
193nm BARC resin and preparation method thereof Download PDFInfo
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- CN114181342A CN114181342A CN202111628384.8A CN202111628384A CN114181342A CN 114181342 A CN114181342 A CN 114181342A CN 202111628384 A CN202111628384 A CN 202111628384A CN 114181342 A CN114181342 A CN 114181342A
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- 239000011347 resin Substances 0.000 title claims abstract description 59
- 229920005989 resin Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 75
- 239000000178 monomer Substances 0.000 claims abstract description 74
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000009835 boiling Methods 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 18
- 230000000977 initiatory effect Effects 0.000 claims abstract description 17
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 69
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 7
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- 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 5
- NFEGKOIJMCGIKN-UHFFFAOYSA-N 3-(2-methylbutan-2-ylperoxymethyl)heptane Chemical compound CCCCC(CC)COOC(C)(C)CC NFEGKOIJMCGIKN-UHFFFAOYSA-N 0.000 claims description 3
- 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
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 22
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 4
- 238000001259 photo etching Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 238000003756 stirring Methods 0.000 description 27
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 22
- 125000004093 cyano group Chemical group *C#N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 10
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 238000010526 radical polymerization reaction Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 4
- 239000006117 anti-reflective coating Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
- C08F212/24—Phenols or alcohols
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2400/00—Characteristics for processes of polymerization
- C08F2400/02—Control or adjustment of polymerization parameters
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Emergency Medicine (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention is suitable for the technical field of photoresist, and provides 193nm BARC resin and a preparation method thereof, wherein the method comprises the following steps: uniformly mixing a styrene monomer and an acrylic monomer in a solvent to obtain a monomer mixed solution; based on the boiling point of the solvent, adding an initiator into the monomer mixed solution and carrying out polymerization reaction for 20-30h at the initiation temperature of the initiator to obtain a reaction solution; wherein the initiator comprises a main initiator with a 10h half-life temperature and a secondary initiator with the initiation temperature; and precipitating the reaction solution by using a precipitator to obtain 193nm BARC resin. The 193nm BARC resin prepared by the invention solves the technical problem that the molecular weight and the molecular weight distribution of the main resin in the bottom anti-reflection coating cannot be finely adjusted, and can obviously eliminate the standing wave effect, the swing effect and the notch effect in the photoetching process and greatly improve the resolution of photoresist after being applied to the bottom anti-reflection coating.
Description
Technical Field
The invention belongs to the technical field of photoresist, and particularly relates to 193nm BARC resin and a preparation method thereof.
Background
With the continuous improvement of the technical nodes of integrated circuit processing, the characteristic size of the integrated circuit is correspondingly reduced, and the image resolution is gradually improved. However, as the wavelength is reduced during processing, the standing wave effect, the wobbling effect, and the notching effect in the photolithography process affect the processing more, which in turn affects the resolution of the photoresist.
At present, a Bottom Anti-Reflection Coating (BARC) is added between the Si substrate and the photoresist to improve the absorption and refraction of light in the Coating, thereby eliminating the standing wave effect, the wiggle effect, the notch effect, and the like. However, in order to achieve the effect of eliminating the standing wave effect, the wobbling effect and the notch effect in the bottom anti-reflective coating, the molecular weight and the molecular weight distribution of the host resin in the bottom anti-reflective coating are generally controlled.
It is known that the larger the molecular weight of the resin, the higher the viscosity of the resin and the greater the film thickness, but too large results in problems such as the film being too stable to be developed or insufficient development, while too small results in problems such as the film being too thin and excessive development. Further, the molecular weight distribution index shows the property that the narrower the film, the more uniform the film, the higher the resolution, but the solubility may be poor, while the too wide molecular weight distribution may cause the problems of film unevenness, film stability, and the like.
In the prior art, when a main body resin is prepared, the molecular weight and the molecular weight distribution of the main body resin are usually regulated and controlled according to the type and the dosage of an initiator, however, the method cannot realize the fine adjustment of the molecular weight and the molecular weight distribution of the main body resin, so that the standing wave effect of a bottom anti-reflection coating is eliminated, the swinging effect and the notch effect are poor, and the resolution of a photoresist is low.
Disclosure of Invention
The embodiment of the invention provides 193nm BARC resin and a preparation method thereof, aiming at solving the technical problem that the molecular weight and the molecular weight distribution of main resin in a bottom anti-reflection coating cannot be finely adjusted.
The embodiment of the invention is realized in such a way that the method for preparing the 193nm BARC resin comprises the following steps:
uniformly mixing a styrene monomer and an acrylic monomer in a solvent to obtain a monomer mixed solution;
based on the boiling point of the solvent, adding an initiator into the monomer mixed solution and carrying out polymerization reaction for 20-30h at the initiation temperature of the initiator to obtain a reaction solution; wherein the initiator comprises a main initiator with a 10h half-life temperature and a secondary initiator with the initiation temperature;
and precipitating the reaction solution by using a precipitator to obtain 193nm BARC resin.
Preferably, in the preparation method of the 193nm BARC resin, the styrene monomer is one or more of p-hydroxystyrene and styrene.
More preferably, in the method for preparing 193nm BARC resin, the styrene monomer comprises p-hydroxystyrene and styrene, and the mass ratio of the p-hydroxystyrene to the styrene is (1-10): (1-10).
Preferably, in the preparation method of the 193nm BARC resin, the solvent is one or more of ethyl acetate, tetrahydrofuran, butanone and propylene glycol methyl ether acetate.
Preferably, in the method for preparing 193nm barc resin, the main initiator and the sub-initiator are low-temperature azo initiators or high-temperature peroxide initiators.
More preferably, in the method for preparing 193nm barc resin, the low-temperature azo initiator is one or more of azobiscyanovaleric acid, azobisisovaleronitrile, azobisisobutyronitrile and azobiscyclohexylcarbonitrile.
More preferably, in the preparation method of the 193nm BARC resin, the high-temperature peroxide initiator is one or more of benzoyl peroxide and tert-amyl 2-ethylhexyl peroxide.
Preferably, in the preparation method of the 193nm BARC resin, the initiator is 1-10% of the total mass of the monomers.
More preferably, in the 193nm BARC resin preparing method, the main initiator accounts for 2-4% of the total mass of the monomers, and the sub-initiator accounts for 0.1-1% of the total mass of the monomers.
The embodiment of the invention also provides 193nm BARC resin which is applied to photoresist and is prepared by the preparation method of the 193nm BARC resin.
The embodiment of the invention provides 193nm BARC resin and a preparation method thereof, wherein the method comprises the following steps: uniformly mixing a styrene monomer and an acrylic monomer in a solvent to obtain a monomer mixed solution; based on the boiling point of the solvent, adding an initiator into the monomer mixed solution and carrying out polymerization reaction for 20-30h at the initiation temperature of the initiator to obtain a reaction solution; wherein the initiator comprises a main initiator with a 10h half-life temperature and a secondary initiator with the initiation temperature; and precipitating the reaction solution by using a precipitator to obtain 193nm BARC resin. In the preparation process of the 193nm BARC resin, polymerization of the BARC resin is realized by adopting a main initiator with a half-life temperature of 10h and a side initiator with the initiation temperature according to the boiling point of a solvent for dissolving a polymerization monomer, so that the technical problem that the molecular weight and the molecular weight distribution of the main resin in a bottom anti-reflection coating cannot be finely adjusted is solved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides 193nm BARC resin and a preparation method thereof, in the process of preparing the 193nm BARC resin, an initiator with proper half-life temperature is selected according to points with similar solvent boiling point temperature, and when the temperature of the initiator is lower than the solvent boiling point temperature, a trace amount of high-temperature initiator is added; on the contrary, when the main initiator is higher than the boiling point of the solvent, a trace amount of low-temperature initiator is added, so that the initiator temperature of the initiator is suitable for the boiling point temperature of the solvent to reach the optimal initiation temperature, the technical problem that the molecular weight and the molecular weight distribution of the main resin in the bottom anti-reflection coating cannot be finely adjusted is solved, after the low-temperature initiator is applied to the bottom anti-reflection coating, the standing wave effect, the swing effect and the notch effect in the photoetching process can be obviously eliminated, and the resolution ratio of the photoresist is greatly improved.
In one embodiment, the styrene monomer is one or more of p-hydroxystyrene and styrene. Wherein the styrene monomer is prepared from the p-hydroxystyrene and the styrene in a mass ratio of (1-10): (1-10) mixing.
In one embodiment, the solvent is one or more of ethyl acetate, tetrahydrofuran, butanone, and propylene glycol methyl ether acetate.
In one embodiment, the main initiator and the secondary initiator are low-temperature azo initiators or high-temperature peroxide initiators.
Preferably, the low-temperature azo initiator is one or more of azodicyano valeric acid, azodiisovaleronitrile, azodiisobutyronitrile and azodicyclohexyl formonitrile; the high-temperature peroxide initiator is one or more of benzoyl peroxide and tert-amyl 2-ethylhexyl peroxide.
In one embodiment, the initiator is 1-10% of the total mass of the monomers; wherein the main initiator accounts for 2-4% of the total mass of the monomers, and the auxiliary initiator accounts for 0.1-1% of the total mass of the monomers.
The following examples illustrate bottom antireflective coating compositions of embodiments of the present invention by way of a number of specific examples.
Example one
A method for preparing 193nm BARC resin comprises the following steps:
s1, placing 5 parts by weight of p-hydroxystyrene, 3 parts by weight of styrene and 2 parts by weight of hydroxypropyl methacrylate into a four-neck flask containing ethyl acetate, and stirring until the monomers are uniformly mixed, wherein the total using amount of the ethyl acetate for dissolving the monomers is 4 times of the total mass of the monomers;
s2, after the monomer is dissolved, adding azodicyclohexyl carbonitrile, stirring until the azodicyclohexyl carbonitrile is dissolved, wherein the using amount of the azodicyclohexyl carbonitrile is 3% of the total mass of the monomer, and then adding azodiisoheptanonitrile, wherein the using amount of the azodiisoheptanonitrile is 0.1% of the total mass of the monomer;
s3, placing the four-neck flask containing the reaction liquid into an oil bath kettle with a magnetic stirrer, installing the four-neck flask, starting condensed water after a condenser pipe and a nitrogen interface, introducing nitrogen, starting stirring, raising the temperature to the boiling temperature of the solvent, about 77 ℃, recording the temperature and carrying out free radical polymerization reaction for 24 hours after the boiling phenomenon occurs;
s4, cooling the reaction solution, and carrying out precipitation treatment by using n-hexane;
s5, solid-liquid separation, drying, weighing and GPC measurement.
Example two
A method for preparing 193nm BARC resin comprises the following steps:
s1, placing 5 parts by weight of p-hydroxystyrene, 3 parts by weight of styrene and 2 parts by weight of hydroxypropyl methacrylate into a four-neck flask containing ethyl acetate, and stirring until the monomers are uniformly mixed, wherein the total using amount of the ethyl acetate for dissolving the monomers is 4 times of the total mass of the monomers;
s2, after the monomer is dissolved, adding azodicyclohexyl carbonitrile, stirring until the azodicyclohexyl carbonitrile is dissolved, wherein the using amount of the azodicyclohexyl carbonitrile is 3% of the total mass of the monomer, and then adding azodiisoheptanonitrile, wherein the using amount of the azodiisoheptanonitrile is 0.5% of the total mass of the monomer;
s3, placing the four-neck flask containing the reaction liquid into an oil bath kettle with a magnetic stirrer, installing the four-neck flask, starting condensed water after a condenser pipe and a nitrogen interface, introducing nitrogen, starting stirring, raising the temperature to the boiling temperature of the solvent, about 77 ℃, recording the temperature and carrying out free radical polymerization reaction for 24 hours after the boiling phenomenon occurs;
s4, cooling the reaction solution, and carrying out precipitation treatment by using n-hexane;
s5, solid-liquid separation, drying, weighing and GPC measurement.
EXAMPLE III
A method for preparing 193nm BARC resin comprises the following steps:
s1, placing 5 parts by weight of p-hydroxystyrene, 3 parts by weight of styrene and 2 parts by weight of hydroxypropyl methacrylate into a four-neck flask containing ethyl acetate, and stirring until the monomers are uniformly mixed, wherein the total using amount of the ethyl acetate for dissolving the monomers is 4 times of the total mass of the monomers;
s2, after the monomer is dissolved, adding azodicyclohexyl carbonitrile, stirring until the azodicyclohexyl carbonitrile is dissolved, wherein the using amount of the azodicyclohexyl carbonitrile is 3% of the total mass of the monomer, and then adding azodiisoheptanonitrile, wherein the using amount of the azodiisoheptanonitrile is 1% of the total mass of the monomer;
s3, placing the four-neck flask containing the reaction liquid into an oil bath kettle with a magnetic stirrer, installing the four-neck flask, starting condensed water after a condenser pipe and a nitrogen interface, introducing nitrogen, starting stirring, raising the temperature to the boiling temperature of the solvent, about 77 ℃, recording the temperature and carrying out free radical polymerization reaction for 24 hours after the boiling phenomenon occurs;
s4, cooling the reaction solution, and carrying out precipitation treatment by using n-hexane;
s5, solid-liquid separation, drying, weighing and GPC measurement.
Example four
A method for preparing 193nm BARC resin comprises the following steps:
s1, placing 5 parts by weight of p-hydroxystyrene, 3 parts by weight of styrene and 2 parts by weight of hydroxypropyl methacrylate into a four-neck flask containing ethyl acetate, and stirring until the monomers are uniformly mixed, wherein the total using amount of the ethyl acetate for dissolving the monomers is 4 times of the total mass of the monomers;
s2, after the monomer is dissolved, adding azodicyclohexyl carbonitrile, stirring until the azodicyclohexyl carbonitrile is dissolved, wherein the using amount of the azodicyclohexyl carbonitrile is 3% of the total mass of the monomer, and then adding azodiisovaleronitrile, wherein the using amount of the azodiisovaleronitrile is 0.1% of the total mass of the monomer;
s3, placing the four-neck flask containing the reaction liquid into an oil bath kettle with a magnetic stirrer, installing the four-neck flask, starting condensed water after a condenser pipe and a nitrogen interface, introducing nitrogen, starting stirring, raising the temperature to the boiling temperature of the solvent, about 77 ℃, recording the temperature and carrying out free radical polymerization reaction for 24 hours after the boiling phenomenon occurs;
s4, cooling the reaction solution, and carrying out precipitation treatment by using n-hexane;
s5, solid-liquid separation, drying, weighing and GPC measurement.
EXAMPLE five
A method for preparing 193nm BARC resin comprises the following steps:
s1, placing 5 parts by weight of p-hydroxystyrene, 3 parts by weight of styrene and 2 parts by weight of hydroxypropyl methacrylate into a four-neck flask containing ethyl acetate, and stirring until the monomers are uniformly mixed, wherein the total using amount of the ethyl acetate for dissolving the monomers is 4 times of the total mass of the monomers;
s2, after the monomer is dissolved, adding azodicyclohexyl carbonitrile, stirring until the azodicyclohexyl carbonitrile is dissolved, wherein the using amount of the azodicyclohexyl carbonitrile is 3% of the total mass of the monomer, and then adding azodiisovaleronitrile, wherein the using amount of the azodiisovaleronitrile is 0.5% of the total mass of the monomer;
s3, placing the four-neck flask containing the reaction liquid into an oil bath kettle with a magnetic stirrer, installing the four-neck flask, starting condensed water after a condenser pipe and a nitrogen interface, introducing nitrogen, starting stirring, raising the temperature to the boiling temperature of the solvent, about 77 ℃, recording the temperature and carrying out free radical polymerization reaction for 24 hours after the boiling phenomenon occurs;
s4, cooling the reaction solution, and carrying out precipitation treatment by using n-hexane;
s5, solid-liquid separation, drying, weighing and GPC measurement.
EXAMPLE six
A method for preparing 193nm BARC resin comprises the following steps:
s1, placing 5 parts by weight of p-hydroxystyrene, 3 parts by weight of styrene and 2 parts by weight of hydroxypropyl methacrylate into a four-neck flask containing ethyl acetate, and stirring until the monomers are uniformly mixed, wherein the total using amount of the ethyl acetate for dissolving the monomers is 4 times of the total mass of the monomers;
s2, after the monomer is dissolved, adding azodicyclohexyl carbonitrile, stirring until the azodicyclohexyl carbonitrile is dissolved, wherein the using amount of the azodicyclohexyl carbonitrile is 3% of the total mass of the monomer, and then adding azodiisovaleronitrile, wherein the using amount of the azodiisovaleronitrile is 1% of the total mass of the monomer;
s3, placing the four-neck flask containing the reaction liquid into an oil bath kettle with a magnetic stirrer, installing the four-neck flask, starting condensed water after a condenser pipe and a nitrogen interface, introducing nitrogen, starting stirring, raising the temperature to the boiling temperature of the solvent, about 77 ℃, recording the temperature and carrying out free radical polymerization reaction for 24 hours after the boiling phenomenon occurs;
s4, cooling the reaction solution, and carrying out precipitation treatment by using n-hexane;
s5, solid-liquid separation, drying, weighing and GPC measurement.
Comparative example 1
A method for preparing 193nm BARC resin comprises the following steps:
s1, placing 5 parts by weight of p-hydroxystyrene, 3 parts by weight of styrene and 2 parts by weight of hydroxypropyl methacrylate into a four-neck flask containing ethyl acetate, and stirring until the monomers are uniformly mixed, wherein the total using amount of the ethyl acetate for dissolving the monomers is 4 times of the total mass of the monomers.
S2, after the monomer is dissolved, adding the azodicyclohexyl formonitrile, and stirring until the azodicyclohexyl formonitrile is dissolved, wherein the using amount of the azodicyclohexyl formonitrile is 3% of the total mass of the monomer;
s3, placing the four-neck flask containing the reaction liquid into an oil bath kettle with a magnetic stirrer, installing the four-neck flask, starting condensed water after a condenser pipe and a nitrogen interface, introducing nitrogen, starting stirring, raising the temperature to the boiling temperature of the solvent, about 77 ℃, recording the temperature and carrying out free radical polymerization reaction for 24 hours after the boiling phenomenon occurs;
s4, cooling the reaction solution, and carrying out precipitation treatment by using n-hexane;
s5, solid-liquid separation, drying, weighing and GPC measurement.
Comparative example No. two
A method for preparing 193nm BARC resin comprises the following steps:
s1, placing 5 parts by weight of p-hydroxystyrene, 3 parts by weight of styrene and 2 parts by weight of hydroxypropyl methacrylate into a four-neck flask containing ethyl acetate, and stirring until the monomers are uniformly mixed, wherein the total using amount of the ethyl acetate for dissolving the monomers is 4 times of the total mass of the monomers;
s2, after the monomers are dissolved, adding the azobisisovaleronitrile, and stirring until the use amount of the dissolved azobisisovaleronitrile is 3% of the total mass of the monomers;
s3, placing the four-neck flask containing the reaction liquid into an oil bath kettle with a magnetic stirrer, installing the four-neck flask, starting condensed water after a condenser pipe and a nitrogen interface, introducing nitrogen, starting stirring, raising the temperature to the boiling temperature of the solvent, about 77 ℃, recording the temperature and carrying out free radical polymerization reaction for 24 hours after the boiling phenomenon occurs;
s4, cooling the reaction solution, and carrying out precipitation treatment by using n-hexane;
s5, solid-liquid separation, drying, weighing and GPC measurement.
Comparative example No. three
A method for preparing 193nm BARC resin comprises the following steps:
s1, placing 5 parts by weight of p-hydroxystyrene, 3 parts by weight of styrene and 2 parts by weight of hydroxypropyl methacrylate into a four-neck flask containing ethyl acetate, and stirring until the monomers are uniformly mixed, wherein the total using amount of the ethyl acetate for dissolving the monomers is 4 times of the total mass of the monomers;
s2, after the monomer is dissolved, adding the azobisisoheptonitrile, and stirring until the usage amount of the dissolved azobisisoheptonitrile is 3% of the total mass of the monomer;
s3, placing the four-neck flask containing the reaction liquid into an oil bath kettle with a magnetic stirrer, installing the four-neck flask, starting condensed water after a condenser pipe and a nitrogen interface, introducing nitrogen, starting stirring, raising the temperature to the boiling temperature of the solvent, about 77 ℃, recording the temperature and carrying out free radical polymerization reaction for 24 hours after the boiling phenomenon occurs;
s4, cooling the reaction solution, and carrying out precipitation treatment by using n-hexane;
s5, solid-liquid separation, drying, weighing and GPC measurement.
Test example
The Mw, PDI and yield results for the 193nm barc resins prepared in the above examples one-six, and comparative examples one-third are shown in table 1:
TABLE 1 test results
| Mw | PDI | Yield of | |
| Example one | 9013 | 1.65 | 51％ |
| Example two | 14555 | 1.32 | 56％ |
| EXAMPLE III | 12343 | 1.41 | 60％ |
| Example four | 26134 | 1.5 | 68％ |
| EXAMPLE five | 28431 | 1.43 | 78％ |
| EXAMPLE six | 27111 | 1.56 | 76％ |
| Comparative example 1 | 25144 | 1.77 | 66％ |
| Comparative example No. two | 15489 | 1.65 | 74％ |
| Comparative example No. three | 5471 | 1.89 | 50％ |
As can be seen from Table 1, in comparative examples one to three, the same reaction conditions, polymer molecular weight and molecular weight distribution were varied because of the different initiators added, and it can be seen from comparative examples one to three that the solvent used was ethyl acetate, the boiling temperature was about 77 ℃ and the 10h half-life temperature of the selected initiator was about 77 ℃ most suitable but generally not so matched, and among the initiators in comparative examples one to three, the optimum initiation temperature for azobiscyclohexylcarbonitrile was 88 ℃, the optimum initiation temperature for azobisisovaleronitrile was 67 ℃ and the optimum initiation temperature for azobisisoheptonitrile was 51 ℃. Also, as shown in Table 1, the high temperature initiator may continue to decompose due to its slow decomposition rate, which is beneficial for chain growth, but may not react sufficiently to end, and some small chain polymers appear, which results in broadening of the molecular weight distribution, while the initiator with the lower initiation temperature decomposes too fast, which results in excessive polymerization of the small chains and also a broad molecular weight distribution.
In the preparation method of the 193nm BARC resin, provided by the embodiment of the invention, a high-temperature initiator is used as a main initiator, so that the chain length of a polymer can be prolonged, a low-temperature initiator is added, and the initiator efficiency of a mixed initiator can be matched with the polymerization temperature. Also, as can be seen from table 1, using azobisisovaleronitrile as a secondary initiator, the initiation effect more closely matches the reaction temperature of ethyl acetate, and thus the molecular weight distribution can be reduced while the chain is extended. If too much of the secondary initiator is added, the effect of the secondary initiator may be more pronounced, leading to an initiation effect of the low-temperature initiator, i.e. a reduction in the molecular weight and a broadening of the molecular weight distribution. This phenomenon is more pronounced because the initiation temperature of azobisisoheptonitrile is 51 ℃. Thus, it can be determined that: however, the combination of different kinds of initiators can change the molecular weight and molecular weight distribution of the polymer, and can be adjusted according to the requirements of the photoresist performance.
In summary, in the method for preparing 193nm BARC resin according to the present invention, the molecular weight and molecular weight distribution of the resin can be changed by using different combinations of initiators, and the molecular weight and molecular weight distribution can be adjusted by changing the combination of the types and the amounts of the initiators according to the requirements.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method for preparing 193nm BARC resin is characterized by comprising the following steps:
uniformly mixing a styrene monomer and an acrylic monomer in a solvent to obtain a monomer mixed solution;
based on the boiling point of the solvent, adding an initiator into the monomer mixed solution and carrying out polymerization reaction for 20-30h at the initiation temperature of the initiator to obtain a reaction solution; wherein the initiator comprises a main initiator with a 10h half-life temperature and a secondary initiator with the initiation temperature;
and precipitating the reaction solution by using a precipitator to obtain 193nm BARC resin.
2. The method for preparing 193nm BARC resin according to claim 1, wherein the styrenic monomer is one or more of p-hydroxystyrene and styrene.
3. The method for preparing 193nm BARC resin of claim 2, wherein the styrene monomer comprises p-hydroxystyrene and styrene, and the mass ratio of p-hydroxystyrene to styrene is (1-10): (1-10).
4. The method for preparing 193nm BARC resin of claim 1, wherein the solvent is one or more of ethyl acetate, tetrahydrofuran, methyl ethyl ketone, and propylene glycol methyl ether acetate.
5. The method for preparing 193nm BARC resin of claim 1, wherein the main initiator and the sub-initiator are low temperature azo type initiators or high temperature peroxide type initiators.
6. The method for preparing 193nm BARC resin of claim 5, wherein the low temperature azo initiator is one or more of azobiscyanovaleric acid, azobisisovaleronitrile, azobisisobutyronitrile, and azobiscyclohexylcarbonitrile.
7. The method for preparing 193nm BARC resin of claim 5, wherein the high temperature peroxide initiator is one or more of benzoyl peroxide and tert-amyl 2-ethylhexyl peroxide.
8. The method for preparing 193nm BARC resin according to claim 1, wherein the initiator is 1-10% of the total mass of the monomers.
9. The method of claim 8, wherein the main initiator is 2-4% of the total mass of the monomers, and the sub-initiator is 0.1-1% of the total mass of the monomers.
10. A 193nm barc resin applied to a photoresist, which is characterized by being prepared by the preparation method of the 193nm barc resin as claimed in any one of claims 1-9.
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| US20030087188A1 (en) * | 2001-10-26 | 2003-05-08 | Hynix Semiconductor Inc. | Organic anti-reflective coating material and preparation thereof |
| US20080114139A1 (en) * | 2004-04-30 | 2008-05-15 | Maruzen Petrochemical Co., Ltd. | Copolymer For Semiconductor Lithography And Producing Method Thereof, And Composition |
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| CN1373143A (en) * | 2001-03-07 | 2002-10-09 | 海力士半导体有限公司 | Organic antireflective coating polymer, antireflective paint composition contg. said polymer, and process for preparing same |
| US20030087188A1 (en) * | 2001-10-26 | 2003-05-08 | Hynix Semiconductor Inc. | Organic anti-reflective coating material and preparation thereof |
| US20080114139A1 (en) * | 2004-04-30 | 2008-05-15 | Maruzen Petrochemical Co., Ltd. | Copolymer For Semiconductor Lithography And Producing Method Thereof, And Composition |
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