CN117143285A - Photoresist based on metallocene compound and preparation method and application thereof - Google Patents
Photoresist based on metallocene compound and preparation method and application thereof Download PDFInfo
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- CN117143285A CN117143285A CN202210574010.0A CN202210574010A CN117143285A CN 117143285 A CN117143285 A CN 117143285A CN 202210574010 A CN202210574010 A CN 202210574010A CN 117143285 A CN117143285 A CN 117143285A
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000001875 compounds Chemical class 0.000 title abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 71
- 239000000203 mixture Substances 0.000 claims abstract description 58
- 239000000178 monomer Substances 0.000 claims abstract description 56
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 150000007530 organic bases Chemical class 0.000 claims description 40
- 239000003960 organic solvent Substances 0.000 claims description 39
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000206 photolithography Methods 0.000 claims description 9
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229940116333 ethyl lactate Drugs 0.000 claims description 6
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical group CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 238000000059 patterning Methods 0.000 claims 1
- 238000001900 extreme ultraviolet lithography Methods 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract description 5
- 230000036211 photosensitivity Effects 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- 235000012431 wafers Nutrition 0.000 description 8
- 238000011161 development Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 238000001459 lithography Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WNEODWDFDXWOLU-QHCPKHFHSA-N 3-[3-(hydroxymethyl)-4-[1-methyl-5-[[5-[(2s)-2-methyl-4-(oxetan-3-yl)piperazin-1-yl]pyridin-2-yl]amino]-6-oxopyridin-3-yl]pyridin-2-yl]-7,7-dimethyl-1,2,6,8-tetrahydrocyclopenta[3,4]pyrrolo[3,5-b]pyrazin-4-one Chemical compound C([C@@H](N(CC1)C=2C=NC(NC=3C(N(C)C=C(C=3)C=3C(=C(N4C(C5=CC=6CC(C)(C)CC=6N5CC4)=O)N=CC=3)CO)=O)=CC=2)C)N1C1COC1 WNEODWDFDXWOLU-QHCPKHFHSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
-
- 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
Abstract
The invention discloses a photoresist based on a metallocene compound, a preparation method and application thereof. The photoresist composition provided by the invention comprises the following components: the polymer is prepared from a monomer A and a monomer B shown below through polymerization reaction. The photoresist can be used for EUV lithography, has the characteristics of high resolution, high sensitivity and high photosensitivity, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of photoresist, and particularly relates to a photoresist based on a metallocene compound, and a preparation method and application thereof.
Background
With the continuous development of modern semiconductor technology and the wide application of the technology in the fields of electronic equipment, communication equipment information security, entertainment equipment and the like, the technology becomes the most active technical field in the world today, and the technology is widely penetrated into various aspects of our work and life. The fabrication of integrated circuits is a core field of the semiconductor industry, and each time the integrated circuits are updated, the development history of the photolithography technique is the development history of the integrated circuits, and the level of the photolithography technique determines the fabrication level of the integrated circuits.
The principle of photoetching is that a layer of photoresist with high photosensitivity is covered on the surface of a silicon wafer, and then light rays (ultraviolet light, deep ultraviolet light and extreme ultraviolet light are generally used for irradiating the surface of the silicon wafer through a mask, and the photoresist irradiated by the light rays can react. Thereafter the irradiated/non-irradiated photoresist is washed away with a specific solvent, and the transfer of the circuit pattern from the mask to the silicon wafer is achieved. Photolithography has undergone a revolution in the contact/proximity, equi-magnification projection, reduction step projection, scanning step projection exposure modes, full spectrum exposure at exposure wavelengths from 300 to 450nm, to 436nm G-line, 365nm I-line, 248nm KrF laser, to the most widely used 193nm ArF laser, to the 13.5nm extreme ultraviolet, electron beam and X-ray currently being widely studied, with fabrication nodes from 0.5mm, 0.1mm, 90nm to 30nm, and even lower. Extreme ultraviolet lithography differs from conventional optical lithography by having an extremely short wavelength. However, most of the elements have strong absorption to the euv light, so that the conventional long wavelength photoresist is not suitable for the euv lithography, and thus a new euv photoresist system needs to be developed. Photolithography is one of the most critical technologies in integrated circuit fabrication, and the successful application of each generation of photolithography greatly promotes the development of integrated circuits, so that the integrated circuits have higher integration level and lower cost. Photolithography is a process that exposes a photoresist material coated on a surface of a semiconductor substrate to transfer fine geometric patterns on a mask to the semiconductor substrate. The resolution of the lithographic patterns is higher and higher, i.e., the integrated circuit integration is higher and the critical dimensions are smaller and smaller.
Currently, the semiconductor industry is in agreement that extreme ultraviolet lithography (Extreme Ultraviolet, EUV,13.5 nm) is the next generation of lithography with great potential. The final resolution will be limited only by the material properties of the photoresist at very short wavelengths. The EUV lithography can be used to generate a circuit diagram with higher resolution, thereby greatly improving the integration density of an integrated circuit and the performance of electronic devices. Research into photoresist and photolithography processes suitable for EUV lithography is a hotspot and difficulty in lithography research.
EUV photoresists must have low absorbance, high transparency, high etch resistance, high resolution, high sensitivity, low exposure dose, high environmental stability, low outgassing, and low line edge roughness. The development of EUV photoresists has been limited by three factors: resolution, line edge roughness, and photosensitivity, which are generally in a relationship to one another. In early lithography, polymeric photoresists were most widely used, and thus polymeric photoresist systems were first applied to EUV lithography. The industry is in need of developing EUV photoresists that improve resolution.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defect of few types of EUV photoresist, thereby providing a photoresist composition based on a metallocene compound, and a preparation method and application thereof. The photoresist provided by the invention can be applied to extreme ultraviolet lithography, has the characteristics of high resolution, high sensitivity and high photosensitivity, and has wide application prospect.
The invention provides a polymer, which is prepared by the following method: in a solvent, the polymer is obtained by polymerization of a monomer A and a monomer B;
50-60 parts of monomer A by weight and 10-17.5 parts of monomer B by weight;
in the polymerization reaction, the part by weight of the monomer A is preferably 51.5 to 55 parts, more preferably 55 parts.
In the polymerization reaction, the part by weight of the monomer B is preferably 12.5 to 17.5 parts, more preferably 14 to 17.5 parts, still more preferably 14 parts.
The polymerization may be carried out in a protective gas, for example in a nitrogen atmosphere.
In the polymerization reaction, the solvent may be a reaction solvent conventional in the art, preferably an ester solvent, and more preferably propylene glycol methyl ether acetate.
The polymerization temperature may be a reaction temperature conventional in the art, preferably in the range of 60 to 80 ℃, for example 70 ℃.
The polymerization time may be a reaction time conventional in the art, for example, 8 hours.
The polymerization reaction preferably comprises the following steps: mixing the monomer A, the monomer B and propylene glycol methyl ether acetate in nitrogen atmosphere to obtain a mixture; slowly dripping the mixture into propylene glycol methyl ether acetate, and reacting for 3 hours at 70 ℃; after the reaction solution was cooled to room temperature, the reaction solution was mixed with methanol to obtain the polymer.
The weight average molecular weight of the polymer is preferably 5000 to 9000, more preferably 5500 to 7900, most preferably 6000.
The molecular weight dispersion index (weight average molecular weight/number average molecular weight) of the polymer is preferably 1.0 to 2.0, more preferably 1.5 to 2.0, and most preferably 1.5.
The polymer is preferably obtained by polymerization of 51.5 to 55 parts by weight of monomer A and 12.5 to 17.5 parts by weight of monomer B.
The polymer is preferably a polymer obtained by polymerizing the monomer a and the monomer B in parts by weight of any one of the following groups;
polymer 1:55 parts of the monomer A and 14 parts of the monomer B;
polymer 2:51.5 parts of the monomer A and 17.5 parts of the monomer B;
polymer 3:55 parts of the monomer A and 12.5 parts of the monomer B;
polymer 4:51.5 parts of the monomer A and 10 parts of the monomer B;
polymer 5:57.5 parts of the monomer A and 10 parts of the monomer B;
polymer 6:50 parts of the monomer A and 17.5 parts of the monomer B;
polymer 7:55 parts of the monomer A and 10 parts of the monomer B.
The invention also provides a photoresist composition, which comprises the following components: the polymer, photoacid generator, organic solvent and organic base.
In the photoresist composition, the parts by weight of the polymer may be conventional in the art, for example, 75 to 95 parts, preferably 85 parts.
In the photoresist composition, the parts by weight of the photoacid generator may be conventional in the art, for example, 1 to 10 parts, preferably 7 parts.
In the photoresist composition, the parts by weight of the organic solvent may be parts conventional in the art, for example, 1000 to 2000 parts, preferably 1500 parts.
In the photoresist composition, the organic base may be present in parts by weight as is conventional in the art, preferably 0.2 to 1 part, more preferably 0.5 part.
In the photoresist composition, the photoacid generator may be a photoacid generator conventional in the photoresist field, for example
In the photoresist composition, the organic solvent may be an organic solvent conventional in the photoresist field, preferably an ester solvent such as ethyl lactate.
In the photoresist composition, the organic base may be an organic base conventional in the photoresist field, preferably an organic weak base such as trioctylamine.
In a specific embodiment, the parts by weight of the polymer in the photoresist composition is 75-95 parts, and the polymer is one or more of the polymers 1-7;
the photoacid generator is 1-10 parts by weight
The organic solvent is 1000-2000 parts by weight of ethyl lactate;
the organic base is trioctylamine with the weight of 0.2-1 part.
In a specific embodiment, the photoresist composition consists of the following components: the polymer, the photoacid generator, the organic solvent, and the organic base;
wherein the polymer refers to the type and content of the polymer; the photoacid generator refers to the type and content of the photoacid generator; the organic solvent refers to the kind and content of the organic solvent; the organic base refers to the kind and content of the organic base.
The photoresist composition preferably consists of any one of the following groups of polymers, photoacid generators, organic solvents and organic bases in parts by weight;
photoresist composition 1:85 parts of the polymer 1, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 2:75 parts of the polymer 1, 1 part of the photoacid generator, 1000 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 3:80 parts of the polymer 1, 3 parts of the photoacid generator, 1200 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 4:90 parts of the polymer 1, 5 parts of the photoacid generator, 1600 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 5:95 parts of the polymer 1, 10 parts of the photoacid generator, 2000 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 6:85 parts of the polymer 2, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 7:85 parts of the polymer 3, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 8:85 parts of the polymer 4, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 9:85 parts of the polymer 5, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 10:85 parts of the polymer 6, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 11:85 parts of the polymer 7, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
in the photoresist compositions 1 to 11, the photoacid generator isThe organic solvent is ethyl lactate, and the organic base is trioctylamine.
The invention also provides a preparation method of the photoresist composition, which comprises the following steps: and uniformly mixing the components of the photoresist composition.
After the mixing, a filtering step can be further included. The filtration may be carried out in a manner conventional in the art, preferably by filtration using an ultra-high molecular weight polyethylene membrane. The pore diameter of the ultra-high molecular weight polyethylene film is preferably 0.1 μm.
The invention also provides a method for forming patterns by using the photoetching technology, which comprises the following steps:
step 1: coating the photoresist composition on the surface of a substrate, and baking to obtain a photoresist layer;
step 2: and (3) exposing, baking and developing the photoresist layer obtained in the step (1) to obtain a photoresist pattern.
In step 1, the substrate may be a substrate conventional in the art, preferably a wafer, such as an 8 inch wafer.
In step 1, the coating method may be a conventional method in the art, preferably spin coating with a spin coater.
In step 1, when spin coating using a spin coater is selected, the number of coater revolutions is preferably 2000 to 3000 revolutions per minute, for example 2500 revolutions per minute.
The thickness of the photoresist layer in step 1 may be conventional in the art, preferably 40-60nm, for example 50nm.
In step 1, the baking temperature may be a baking temperature conventional in the art, preferably 70-90 ℃, for example 80 ℃.
In step 1, the baking time may be a baking time conventional in the art, preferably 50 to 70 seconds, for example 60 seconds.
In step 2, the baking temperature may be a baking temperature conventional in the art, preferably 120-140 ℃, for example 130 ℃.
In step 2, the baking time may be a baking time conventional in the art, preferably 50 to 70 seconds, for example 60 seconds.
In step 2, the development may be performed as is conventional in the art, and the developer typically used is an aqueous solution of tetramethylammonium hydroxide, for example, an aqueous solution of tetramethylammonium hydroxide having a mass fraction of 2.38%.
The above preferred conditions can be arbitrarily combined on the basis of not deviating from the common knowledge in the art, and thus, each preferred embodiment of the present invention can be obtained.
The resin is self-made, and other used reagents and raw materials are commercially available.
The invention has the positive progress effects that: the photoresist provided by the invention has high resolution, good photosensitivity and low line edge roughness. Therefore, the EUV photoresist composition of the invention has better performance.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Preparation of polymers examples 1-7 and comparative examples 1-6
Monomer a and monomer B were dissolved in 70g of propylene glycol methyl ether acetate solvent by mass in table 1 under nitrogen protection, and this mixture was added dropwise to 30g of propylene glycol methyl ether acetate over 5 hours while stirring at 70 ℃, stirring was continued at 70 ℃ for 3 hours after the completion of the addition, the reaction solution was cooled to room temperature and added dropwise to 1000g of methanol. The precipitated solids were collected by filtration and dried in vacuo at 40 ℃ for 24 hours to obtain polymer in powder solid form and comparative polymer;
the monomer A and the monomer B are metallocene compounds shown in the following formula,
TABLE 1
Preparation of Photoresist compositions examples 1-11 and comparative examples 1-6
According to the combination and content shown in Table 2, the components are uniformly mixed, and an ultra-high molecular weight polyethylene film with the thickness of 0.1 mu m is adopted for filtration, so that the photoresist of the metallocene compound is obtained; wherein the photoacid generator isThe organic solvent is ethyl lactate; the organic base is trioctylamine.
TABLE 2
Effect examples
EUV exposure and inspection
Preparing and exposing a photoresist film: the prepared photoresist was coated on an 8-inch wafer at 2500RPM using a spin coater, and heated at 80 ℃ for 60 seconds on a hot plate to obtain a photoresist film. The average film thickness was measured at 25 points by an optical film thickness measuring system F50 (Filmetrics) and 50nm. Extreme ultraviolet exposure was performed on an upper sea light source interference reticle stage (BL 08U 1B) and then baked at 130℃for 60 seconds. Finally, the resultant film was developed in a 2.38wt% aqueous solution of tetramethylammonium hydroxide (TMAH), thereby obtaining a pattern.
LER assay: LER of the 50-nm LS pattern was measured under FE-SEM (Hitachi SU 9000).
LWR assay: LWR of the 50-nm LS pattern was measured under CD-SEM (HITACHI, CD-SEM, CG 5000).
Sensitivity detection: an Eth value was used as a sensitivity index. Stepped 25-point exposures (e.g., 0.5 mJ/cm) of different energies were performed on 8 inch wafers 2 ，1mJ/cm 2 ，1.5mJ/cm 2 ...), post-baking (PEB), developing, and measuring the film thickness thereof, the film thickness thereof being recorded as Eth just reaching 0nm.
And (3) detecting the resolution: under the conditions given the above sensitivity, the limit resolution (minimum limit width when separating and resolving lines and spaces) at the exposure dose (dose of electron beam irradiation) is taken as the LS resolution.
TABLE 3 Table 3
EB exposure and detection
Preparing and exposing a photoresist film: the photoresist was coated on an 8-inch wafer using a spin coater at 2500RPM, and heated at 80 ℃ for 60 seconds on a hot plate to obtain a photoresist film. The average film thickness was measured at 25 points by an optical film thickness measuring system F50 (Filmetrics) and 50nm. The photoresist was exposed to an electron beam using an EB writing system Elionix ELS-G100 (Elionix, acceleration voltage 100 KeV) and baked at 130 ℃ for 60 seconds. Finally, the resultant film was developed in a 2.38wt% aqueous solution of tetramethylammonium hydroxide (TMAH), thereby obtaining a pattern.
Eop: the optimal exposure (Eop) is defined as the exposure dose that provides 1:1 resolution at the top and bottom of a 50-nm 1:1 line-and-space (LS) pattern.
LER assay: LER of the 50-nm LS pattern was measured under FE-SEM (Hitachi SU 9000).
LWR assay: LWR of the 50-nm LS pattern was measured under CD-SEM (HITACHI, CD-SEM, CG 5000).
And (3) detecting the resolution: under the conditions given above Eop, the limit resolution (minimum limit width when separating and resolving lines and spaces) at the exposure dose (dose of electron beam irradiation) was taken as LS resolution.
TABLE 4 Table 4
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Claims (10)
1. A polymer, characterized in that it is prepared by the following process: in a solvent, the polymer is obtained by polymerization of a monomer A and a monomer B;
50-60 parts of monomer A by weight and 10-17.5 parts of monomer B by weight;
2. the polymer of claim 1, wherein the polymer satisfies one or more of the following conditions;
(1) The part by weight of the monomer A is 51.5-55 parts, preferably 55 parts;
(2) The part by weight of the monomer B is 12.5-17.5 parts, preferably 14-17.5 parts, and more preferably 14 parts;
(3) The polymerization is carried out in a protective gas, such as nitrogen;
(4) The solvent is an ester solvent, and is more preferably propylene glycol methyl ether acetate;
(5) The temperature of the polymerization reaction is 60-80 ℃, for example 70 ℃;
(6) The polymerization time is 8 hours;
(7) The weight average molecular weight of the polymer is 5000-9000, preferably 5500-7900, further preferably 6000;
(8) The molecular weight dispersion index of the polymer is 1.0 to 2.0, preferably 1.5 to 2.0, and more preferably 1.5.
3. The polymer of claim 2, wherein the polymerization reaction comprises the steps of: mixing the monomer A, the monomer B and propylene glycol methyl ether acetate in nitrogen atmosphere to obtain a mixture; slowly dripping the mixture into propylene glycol methyl ether acetate, and reacting for 3 hours at 70 ℃; after the reaction solution was cooled to room temperature, the reaction solution was mixed with methanol to obtain the polymer.
4. A polymer according to any one of claims 1 to 3, which is a polymer obtained by polymerisation of monomer a and monomer B in parts by weight of any one of the following groups;
polymer 1:55 parts of the monomer A and 14 parts of the monomer B;
polymer 2:51.5 parts of the monomer A and 17.5 parts of the monomer B;
polymer 3:55 parts of the monomer A and 12.5 parts of the monomer B;
polymer 4:51.5 parts of the monomer A and 10 parts of the monomer B;
polymer 5:57.5 parts of the monomer A and 10 parts of the monomer B;
polymer 6:50 parts of the monomer A and 17.5 parts of the monomer B;
polymer 7:55 parts of the monomer A and 10 parts of the monomer B.
5. A photoresist composition comprising the following components: the polymer of any one of claims 1-4, photoacid generator, organic solvent, and organic base.
6. The photoresist composition of claim 5, wherein the photoresist composition meets one or more of the following conditions;
(1) The polymer is 75-95 parts by weight, preferably 85 parts by weight;
(2) In the photoresist composition, the photo-acid generator is 1-10 parts by weight, preferably 7 parts by weight;
(3) In the photoresist composition, the organic solvent is 1000-2000 parts by weight, preferably 1500 parts by weight;
(4) In the photoresist composition, the organic base is 0.2-1 part, preferably 0.5 part, by weight;
(5) The photoacid generator is
(6) The organic solvent is an ester solvent such as ethyl lactate;
(7) The organic base is a weak organic base, such as trioctylamine.
7. The photoresist composition of claim 5 or 6, consisting of: the polymer, the photoacid generator, the organic solvent, and the organic base.
8. The photoresist composition according to claim 5 or 6, which consists of any one of the following group of polymers, photoacid generator, organic solvent and organic base in parts by weight;
photoresist composition 1:85 parts of the polymer 1, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 2:75 parts of the polymer 1, 1 part of the photoacid generator, 1000 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 3:80 parts of the polymer 1, 3 parts of the photoacid generator, 1200 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 4:90 parts of the polymer 1, 5 parts of the photoacid generator, 1600 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 5:95 parts of the polymer 1, 10 parts of the photoacid generator, 2000 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 6:85 parts of the polymer 2, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 7:85 parts of the polymer 3, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 8:85 parts of the polymer 4, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 9:85 parts of the polymer 5, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 10:85 parts of the polymer 6, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 11:85 parts of the polymer 7, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
in the photoresist compositions 1 to 11, the photoacid generator isThe organic solvent is ethyl lactate, and the organic base is trioctylamine.
9. A method of preparing a photoresist composition according to any one of claims 5 to 8, comprising the steps of: and uniformly mixing the components of the photoresist composition.
10. A method of patterning by photolithography, the method comprising the steps of:
step 1: coating the photoresist composition according to any one of claims 5-8 on the surface of a substrate, and baking to obtain a photoresist layer;
step 2: and (3) exposing, baking and developing the photoresist layer obtained in the step (1) to obtain a photoresist pattern.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202210574010.0A CN117143285A (en) | 2022-05-24 | 2022-05-24 | Photoresist based on metallocene compound and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210574010.0A CN117143285A (en) | 2022-05-24 | 2022-05-24 | Photoresist based on metallocene compound and preparation method and application thereof |
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| CN117143285A true CN117143285A (en) | 2023-12-01 |
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| CN202210574010.0A Pending CN117143285A (en) | 2022-05-24 | 2022-05-24 | Photoresist based on metallocene compound and preparation method and application thereof |
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| CN (1) | CN117143285A (en) |
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