CN117126324A - Resin and 193nm immersed photoresist containing same - Google Patents

Resin and 193nm immersed photoresist containing same Download PDF

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Publication number
CN117126324A
CN117126324A CN202111305909.4A CN202111305909A CN117126324A CN 117126324 A CN117126324 A CN 117126324A CN 202111305909 A CN202111305909 A CN 202111305909A CN 117126324 A CN117126324 A CN 117126324A
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formula
monomer shown
weight part
resin
parts
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王溯
方书农
徐森
林逸鸣
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Shanghai Xinke Micro Material Technology Co Ltd
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Shanghai Xinke Micro Material Technology Co Ltd
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Priority to CN202111305909.4A priority Critical patent/CN117126324A/en
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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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a resin and 193nm immersion photoresist containing the same. The resin is a copolymer obtained by polymerizing a monomer shown in a formula (A), a monomer shown in a formula (B), a monomer shown in a formula (C) and a monomer shown in a formula (D); the weight part of the monomer shown in the formula (A) is 42.5-47.5 parts, the weight part of the monomer shown in the formula (B) is 1-7.5 parts, the weight part of the monomer shown in the formula (C) is 0.25-2.5 parts, and the weight part of the monomer shown in the formula (D) is 0.25-2.5 parts. Photoresists comprising resins of the invention have at least the following advantages: excellent photosensitivity, good depth of focus (DOF) and good line width uniformity (CDU).

Description

Resin and 193nm immersed photoresist containing same
Technical Field
The invention relates to a resin and 193nm immersion photoresist containing the same.
Background
The photolithography technique refers to a pattern micromachining technique for transferring a pattern designed on a mask plate onto a substrate through exposure, development, etching and other technological processes by utilizing chemical sensitivity of a photolithography material (particularly photoresist) under the actions of visible light, ultraviolet rays, electron beams and the like. Photolithography materials (particularly photoresists), also known as photoresists, are the most critical functional chemical materials involved in photolithography, the main components of which are resins, photoacid generators (Photo Acid Generator, PAG), and corresponding additives and solvents. The photoacid generator is a photosensitive compound which is decomposed under illumination to generate acid, and the generated acid can lead acid-sensitive resin to generate decomposition or crosslinking reaction, so that the dissolution contrast of an illumination part and a non-illumination part in a developing solution is increased, and the photoacid generator can be used in the technical field of pattern micromachining.
Three important parameters of photoresist include resolution, sensitivity, line width roughness, which determine the process window of the photoresist at the time of chip fabrication. With the continuous improvement of the performance of semiconductor chips, the integration level of integrated circuits increases exponentially, and the patterns in the integrated circuits continue to shrink. In order to make smaller sized patterns, the performance index of the above three photoresists must be improved. The use of a short wavelength light source in the photolithography process may increase the resolution of the photoresist according to the rayleigh equation. The light source wavelength of the photolithography process has evolved from 365nm (I-line) to 248nm (KrF), 193nm (ArF), 13nm (EUV). In order to improve the sensitivity of the photoresist, the currently mainstream KrF, arF, EUV photoresist adopts a chemically amplified photosensitive resin. Thus, photosensitizers (photoacid generators) compatible with chemically amplified photoprotective resins are widely used in high-end photoresists.
As photolithography processes evolve, to 193nm immersion exposure processes, the complexity of the process increases, placing higher and higher demands on resist (i.e., photoresist). Development of a resist capable of improving resolution, sensitivity and line width roughness becomes a problem to be solved urgently in the industry.
Disclosure of Invention
In view of the foregoing problems with the prior art, the present invention is directed to a resin and 193nm immersion photoresist comprising the same, the photoresist comprising the resin of the present invention having at least the following advantages: excellent photosensitivity, good depth of focus (DOF) and good line width uniformity (CDU).
The invention provides a resin, which is a copolymer obtained by polymerizing a monomer shown in a formula (A), a monomer shown in a formula (B), a monomer shown in a formula (C) and a monomer shown in a formula (D);
wherein, the weight part of the monomer shown in the formula (A) is 42.5-47.5 parts, the weight part of the monomer shown in the formula (B) is 1-7.5 parts, the weight part of the monomer shown in the formula (C) is 0.25-2.5 parts, and the weight part of the monomer shown in the formula (D) is 0.25-2.5 parts;
wherein R is 1 Is C 1 -C 10 Alkyl, R 2 Is H or methyl.
In one embodiment of the invention, R 1 May be C 1 -C 4 Alkyl groups such as methyl.
In one embodiment of the invention, R 2 May be methyl.
In one embodiment of the present invention, the monomer represented by the formula (A) may be
In one embodiment of the present invention, the weight part of the monomer represented by the formula (a) may be 42.5 to 45.
In one embodiment of the present invention, the weight part of the monomer represented by the formula (B) may be 2.5 to 4.
In one embodiment of the present invention, the weight part of the monomer represented by the formula (C) may be 0.5 to 1.25.
In one embodiment of the present invention, the weight part of the monomer represented by the formula (D) may be 0.5 to 1.25.
In one embodiment of the invention, the weight average molecular weight (Mw) of the resin may be in the range 1000 to 500000, preferably 3000 to 100000, for example 5000 to 10000.
In one embodiment of the invention, the molecular weight distribution coefficient of the resin may be 1.0 to 2.0, for example, 1.5 to 2.0. The molecular weight distribution coefficient refers to the ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight of the resin.
In one aspect of the present invention, the resin may be selected from any one of the following resins 1 to 8:
resin 1: the weight part of the monomer shown in the formula (A) is 42.5 parts, the weight part of the monomer shown in the formula (B) is 5 parts, the weight part of the monomer shown in the formula (C) is 1.25 parts, and the weight part of the monomer shown in the formula (D) is 1.25 parts;
resin 2: the weight part of the monomer shown in the formula (A) is 45 parts, the weight part of the monomer shown in the formula (B) is 4 parts, the weight part of the monomer shown in the formula (C) is 0.5 part, and the weight part of the monomer shown in the formula (D) is 0.5 part;
resin 3: the weight part of the monomer shown in the formula (A) is 45 parts, the weight part of the monomer shown in the formula (B) is 4 parts, the weight part of the monomer shown in the formula (C) is 0.25 part, and the weight part of the monomer shown in the formula (D) is 0.75 part;
resin 4: the weight part of the monomer shown in the formula (A) is 45 parts, the weight part of the monomer shown in the formula (B) is 2.5 parts, the weight part of the monomer shown in the formula (C) is 1.25 parts, and the weight part of the monomer shown in the formula (D) is 1.25 parts;
resin 5: the weight part of the monomer shown in the formula (A) is 42.5 parts, the weight part of the monomer shown in the formula (B) is 4 parts, the weight part of the monomer shown in the formula (C) is 1.75 parts, and the weight part of the monomer shown in the formula (D) is 1.75 parts;
resin 6: the weight part of the monomer shown in the formula (A) is 47.5 parts, the weight part of the monomer shown in the formula (B) is 1 part, the weight part of the monomer shown in the formula (C) is 0.75 part, and the weight part of the monomer shown in the formula (D) is 0.75 part;
resin 7: the weight part of the monomer shown in the formula (A) is 42.5 parts, the weight part of the monomer shown in the formula (B) is 7.5 parts, the weight part of the monomer shown in the formula (C) is 1.5 parts, and the weight part of the monomer shown in the formula (D) is 1 part;
resin 8: the weight part of the monomer shown in the formula (A) is 46 parts, the weight part of the monomer shown in the formula (B) is 2.5 parts, the weight part of the monomer shown in the formula (C) is 0.75 part, and the weight part of the monomer shown in the formula (D) is 0.75 part.
In the resin 1, the weight average molecular weight of the resin may be 9500; the molecular weight distribution coefficient of the resin may be 1.
In the resin 2, the weight average molecular weight of the resin may be 7400; the molecular weight distribution coefficient of the resin may be 1.2.
In the resin 3, the weight average molecular weight of the resin may be 6000; the molecular weight distribution coefficient of the resin may be 1.8.
In the resin 4, the weight average molecular weight of the resin may be 6600. The molecular weight distribution coefficient of the resin may be 1.
In the resin 5, the weight average molecular weight of the resin may be 7500. The molecular weight distribution coefficient of the resin may be 1.6.
In the resin 6, the weight average molecular weight of the resin may be 6900. The molecular weight distribution coefficient of the resin may be 1.7.
In the resin 7, the weight average molecular weight of the resin may be 8300. The molecular weight distribution coefficient of the resin may be 1.9.
In the resin 8, the weight average molecular weight of the resin may be 8400. The molecular weight distribution coefficient of the resin may be 1.1.
In one embodiment of the present invention, the resin may be prepared by a preparation method comprising the steps of: the above-mentioned monomer represented by the formula (A), monomer represented by the formula (B), monomer represented by the formula (C) and monomer represented by the formula (D) are polymerized in an organic solvent to obtain the resin.
In one embodiment of the present invention, the resin is prepared by using 50 to 300 parts by weight, for example 100 parts by weight, of the organic solvent.
In an embodiment of the present invention, the organic solvent may be one or more of propylene glycol methyl ether acetate, propylene glycol diacetate, methylenebisacrylamide, N-methylpyrrolidone, ethyl 3-ethoxypropionate, cyclohexanone, and methylene chloride, for example Propylene Glycol Methyl Ether Acetate (PGMEA).
In one embodiment of the present invention, in the method for producing the resin, the polymerization reaction may be performed under an inert gas (e.g., nitrogen).
In one embodiment of the present invention, in the method for producing the resin, the polymerization reaction may be initiated by a radical initiator or by heating.
When the polymerization reaction is initiated by a radical initiator, the radical initiator is preferably one or more of 2,2 '-Azobisisobutyronitrile (AIBN), 2' -azobis (2, 4-dimethylvaleronitrile), methyl 2, 2-azobis (2-methylpropionate), benzoyl peroxide and lauroyl peroxide.
When the polymerization is initiated by heating, the polymerization temperature in the polymerization is preferably 50 to 150 ℃, more preferably 60 to 100 ℃, for example 70 ℃.
In one embodiment of the present invention, the polymerization time may be a time conventional in the art, for example, 2 to 12 hours, and further, for example, 8 hours.
In one embodiment of the present invention, the method for preparing the resin further comprises a post-treatment step, such as one or more of cooling, precipitation and drying, after the polymerization reaction.
The solvent used in the precipitation may be an alcohol solvent such as methanol.
Wherein the drying may be vacuum drying (e.g., vacuum drying at 40 ℃ for 24 hours).
In one embodiment of the present invention, the method for preparing the resin comprises the steps of: the monomer represented by the formula (A), the monomer represented by the formula (B), the monomer represented by the formula (C), and the solution of the formula (D) and a part of the organic solvent as described above are added to the remaining organic solvent.
Preferably, the mass ratio of the part of the organic solvent to the rest of the organic solvent is 1:1 to 5:1, for example 7:3. The adding mode is dripping. The time of addition is 1 to 8 hours, for example 5 hours.
The present invention provides a photoresist composition comprising a resin as described above, a photoacid generator, and a solvent.
In one aspect of the invention, the photoacid generator in the photoresist composition may be any of the known photoacid generators conventionally used in photoresists, particularly chemically amplified photoresist compositions. For the purpose of fine tuning the lithographic performance, the photoacid generator may be any compound capable of generating an acid upon exposure to high energy radiation, such as one or more of sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxy imides and oxime-O-sulfonates. Among them, examples of the acid generated by the photoacid generator include strong acids such as sulfonic acid, bis (perfluoroalkanesulfonyl) imide, and tris (perfluoromethanesulfonyl) methane anion (methide), and weak acids such as carboxylic acid.
In one embodiment of the present invention, in the photoresist composition, the photoacid generator may have a structure represented by formula (I):
X+ Y-
(I)，
wherein X is + Selected from any one of the following structures:
Y - selected from any one of the following structures:
in one aspect of the present invention, in the photoresist composition, the photoacid generator may be selected from any one of the following structures:
in one embodiment of the present invention, the solvent may be any known solvent conventionally used in photoresists, particularly chemically amplified photoresist compositions, in the preparation process of the photoresist composition. The solvent may be one or more of a ketone solvent (e.g., cyclohexanone and/or methyl-2-n-amyl ketone), an alcohol solvent (e.g., a monohydric alcohol solvent (e.g., one or more of 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol), and/or a dihydric alcohol solvent (e.g., diacetone alcohol)), an ether solvent (e.g., one or more of propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether), and an ester solvent (e.g., one or more of Propylene Glycol Monomethyl Ether Acetate (PGMEA), propylene glycol monoethyl ether acetate, methyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol monobutyl ether acetate, gamma-butyrolactone).
In an aspect of the present invention, the solvent in the photoresist composition may be one or more of a ketone solvent, an ether solvent, and an ester solvent, for example, one or more of cyclohexanone, ethylene glycol monoethyl ether, and γ -butyrolactone.
In one aspect of the invention, the photoresist composition may further comprise additives, which may be any of the well known additives conventionally used in photoresists, particularly chemically amplified photoresist compositions, such as quenchers and/or surfactants.
In an aspect of the present invention, in the photoresist composition, the quencher is a compound capable of inhibiting a diffusion rate when an acid generated from a photoacid generator diffuses through the resist film, and may be, for example, one or more of an amine-containing compound, a sulfonate salt, and a carboxylate salt. The amine compounds may be primary, secondary and tertiary amine compounds, for example amine compounds having hydroxyl, ether, ester, lactone, cyano or sulfonate groups. The protected amine compound is effective especially when the resist composition includes an alkali labile component.
In one embodiment of the present invention, the quencher may be
And/or +.>
In one aspect of the invention, the surfactant may be a surfactant that is insoluble or substantially insoluble in water and soluble in an alkaline developer, and/or a surfactant that is insoluble or substantially insoluble in water and an alkaline developer.
In one aspect of the invention, the surfactant may be one or more of FC-4430 (available from 3M), S-381 (available from AGC SeimiChemical), E1004 (available from Air Products), KH-20, and KH-30 (available from Asahi Glass), such as KH-20 and/or KH-30.
The contents of the components in the photoresist composition are conventional contents in the photoresist in the art, and the present invention is preferably as follows.
In one embodiment of the present invention, the resin may be present in an amount of 75 to 95 parts by weight (e.g., 75, 85, 90, 95) in the photoresist composition.
In one embodiment of the present invention, the weight part of the photoacid generator in the photoresist composition may be 1 to 10 parts (e.g., 1,3, 5, 7, 10).
In one embodiment of the present invention, the weight portion of the solvent in the photoresist composition may be 1000 to 2000 parts (e.g., 1000, 1200, 1500, 1600, 2000) by weight.
In one embodiment of the present invention, the quencher may be present in an amount of 0.5 to 3 parts by weight (e.g., 0.5, 0.8, 1.5, 2, 3) in the photoresist composition.
In one embodiment of the present invention, the weight part of the surfactant in the photoresist composition may be 0.1 to 0.2 part by weight.
In one aspect of the invention, the photoresist composition may be composed of the following components: a resin as described above, a photoacid generator as described above, a solvent as described above, a quencher as described above and a surfactant as described above.
The invention provides a preparation method of the photoresist composition, which comprises the following steps: and uniformly mixing the components in the photoresist composition.
In the preparation method 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 a filter. The pore size of the filter membrane of the filter is preferably 0.2 μm.
The invention provides a method for forming a photoetching pattern, which comprises the following steps:
s1: coating the photoresist composition on the surface of a substrate, and baking to form a photoresist layer;
s2: exposing the photoresist layer formed in the step S1;
s3: baking the photoresist layer after the exposure of the S2;
s4: and (3) developing the photoresist layer after the S3 baking.
In S1, the substrate may be a substrate for integrated circuit fabrication (e.g., si, siO 2 One or more of SiN, siON, tiN, WSi, BPSG, SOG and organic anti-reflective films), or substrates for mask circuit fabrication (e.g., cr, crO,CrON、MoSi 2 And SiO 2 One or more of the following).
In S1, the coating may be a conventional coating method used in the art for forming a photolithography pattern, such as spin coating.
In S1, the temperature of the baking may be a conventional baking temperature used in the art to form a lithographic pattern, e.g. 60-250 ℃, and further e.g. 200 ℃.
In S1, the baking time may be a conventional baking time used in the art to form a photolithographic pattern, for example, 1 to 10 minutes, and further, for example, 1 minute.
In S1, the photoresist layer may have a thickness of 0.05-2 μm, for example 100nm.
In S2, the exposure may be performed using conventional procedures used in the art for forming lithographic patterns, such as high energy radiation (e.g., krF excimer laser, arF excimer laser, or EUV), where the exposure dose may be 1-200mJ/cm 2 (e.g., 10-100 mJ/cm) 2 ) Or electron beam exposure, wherein the exposure dose can be 0.1-100 μC/cm 2 (e.g., 0.5-50. Mu.C/cm) 2 )。
In S2, in the case of immersion lithography, a water-insoluble protective film may be formed on the resist film. Water insoluble protective films used in immersion lithography are generally classified into two types when they are used to prevent any component from leaching out of the photoresist layer and to improve water slip (water slip) at the film surface. The first type is an organic solvent peelable protective film, which must be peeled off with an organic solvent in which the resist film is insoluble before alkaline development. The second type is an alkali-soluble protective film which is soluble in an alkali developer so that it can be removed simultaneously with the removal of the dissolved region of the resist film. The second type of protective film preferably comprises a polymer having 1, 3-hexafluoro-2-propanol residues, which is insoluble in water and soluble in an alkaline developer, as a base material in an alcohol solvent of at least 4 carbon atoms, an ether solvent of 8 to 12 carbon atoms, or a mixture thereof. Alternatively, the aforementioned surfactant, which is insoluble in water and soluble in an alkaline developer, may be dissolved in an alcohol solvent of at least 4 carbon atoms, an ether solvent of 8 to 12 carbon atoms, or a mixture thereof to form a material from which the second type of protective film is formed.
In S3, the temperature of the baking may be a conventional baking temperature used in the art to form a photolithographic pattern, for example, 60-150 ℃, for example, 80-140 ℃ (90 ℃, 95 ℃, 100 ℃).
In S3, the baking time may be a conventional baking time used in the art to form a photolithographic pattern, for example, 1 to 3 minutes, and further, for example, 1 minute.
In S4, the developing means may be conventional developing means used in the art for forming a lithographic pattern, such as one or more of dipping, spin-coating immersion and spraying.
In S4, the developed developer may be a conventional developer used in the art for forming a photolithography pattern, such as an alkaline aqueous solution and/or an organic solvent.
The aqueous alkaline solution may be an aqueous alkaline solution of the developer, for example, 0.1 to 5% by weight, preferably 2 to 3% by weight, of an aqueous solution of tetramethylammonium hydroxide (TMAH).
The organic solvent may be one or more of 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutylketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, butenyl acetate, phenyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, benzyl acetate, methyl phenylacetate, benzyl formate, phenyl ethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate and 2-phenylethyl acetate, for example, one or more of 2-heptanone or more of n-butyl acetate and methyl benzoate.
In S4, the temperature of the development may be a conventional development temperature used in the art to form a lithographic pattern, for example 10 to 30 ℃, preferably 23 ℃.
In S4, the development time may be a conventional development time used in the art to form a lithographic pattern, for example, 0.1 to 3 minutes, for example, 0.5 to 2 minutes, and for example, 1 minute.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that: photoresists comprising resins of the invention have at least the following advantages: excellent photosensitivity, good depth of focus (DOF) and good line width uniformity (CDU).
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.
In the following examples, the specific operating temperatures are not limited, and all refer to being conducted under room temperature conditions. Room temperature is 10-30 ℃.
Preparation of the resin
A solution was prepared by dissolving the following monomers A, B, C, and D in 70g Propylene Glycol Monomethyl Ether Acetate (PGMEA) in parts by weight (g) of Table 1 under a nitrogen atmosphere. The solution was added dropwise to 30g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) over 5 hours under a nitrogen atmosphere while stirring at 70 ℃. After the completion of the dropwise addition, stirring was continued at 70℃for 3 hours. The reaction solution was cooled to room temperature and added dropwise to 1000g of methanol. The solid thus precipitated was collected by filtration and dried under vacuum at 40 ℃ for 24 hours to obtain the polymer as a powder solid.
TABLE 1
Examples 1 to 23, comparative examples 1 to 23: preparation of photoresists
The resins, photoacid generator, and quencher thus prepared were dissolved in an organic solvent according to the formulation shown in Table 2, and the photoresists of examples 1 to 23 and comparative examples 1 to 23 in the form of solutions were prepared by filtration through a filter having a pore size of 0.2. Mu.m, wherein
The polymers used in Table 2 are the obtained R-1 to R-8 and CR-1 to CR-8 prepared in Table 1 above.
The photoacid generator used in table 2 has the following structure:
the quencher used in table 2 has the following structure:
the organic solvents used in Table 2 were cyclohexanone (S-1), ethylene glycol monoethyl ether (S-2) and gamma-butyrolactone (S-3), which contained 0.01 wt% of surfactant KH-30 or KH-20 (Asahi Glass Co., ltd.).
TABLE 2
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Application and Effect examples ArF immersion lithography patterning test (hole Pattern test)
1. Hole pattern formation:
on a substrate (silicon wafer), a spin-on carbon film ODL-70 (carbon content: 65wt%, shin-Etsu Chemical Co., ltd.) was deposited to a thickness of 200nm and a spin-on hard mask SHB-A940 (silicon content: 43 wt%; shin-Etsu Chemical Co., ltd.) containing silicon was deposited thereon to a thickness of 35 nm. Then, a photoresist composition was spin-coated thereon, and then baked at 200 ℃ for 60 seconds on a hot plate to form a 100nm thick photoresist film.
Using an ArF excimer laser immersion scanner NS resin-S610C (Nikon corp., NA1.30, σ0.9/0.72, 35 ° cross-polar opening, azimuthal polarized illumination), the photoresist film was exposed through a 6% halftone phase shift mask at varying doses using immersion lithography. The photoresist film was baked (PEB) at a temperature of 95 ℃ for 60 seconds. After PEB, developer was injected from the developing nozzle while the wafer was rotated at 30rpm for 3 seconds, followed by static spin-on immersion development for 27 seconds. A hole pattern with a pitch of 100nm was formed.
2. Evaluating photosensitivity:
the hole pattern formed above was observed under a TD-SEM (CG-4000,Hitachi High-Technologies Corp.). The optimum dose (Eop) was a dose (mJ/cm) for providing exposure with a 50nm hole diameter at a pitch of 100nm 2 ) And is used as an index of photosensitivity.
3. Depth of focus (DOF) limit was evaluated:
pore size at the optimum dose was measured under TD-SEM (CG-4000) from which the DOF margin providing a size of 50 nm.+ -. 5nm was determined. The larger value indicates that the smaller the change in pattern size with DOF change and thus the better DOF margin.
4. Evaluation of CDU:
the hole pattern formed above was observed under TD-SEM (CG-4000) and the diameters of 125 holes were measured. From which a triple value (3σ) of the standard deviation (σ) was calculated and recorded as CDU. Smaller 3 sigma values indicate smaller deviations of the holes.
5. Evaluation of PPD:
immediately after PEB (no delay, ppd=0h) the wafer was developed in a cantilever immersion for 30 seconds to form a hole pattern with a diameter of 50nm and a pitch of 100nm. In another run, the wafer was held 6 hours after PEB (ppd=6h) and then developed as such to form a pattern.
The pore pattern at ppd=0h and 6h was observed under TD-SEM (CG-4000) and the diameter of 125 pores was measured. The average value thereof was taken as a pore size (CD), and the CDU was calculated by the same method as above. The difference between the CD at PPD 0h and the CD at PPD 6h was taken as the CD shrinkage due to PPD (ΔPPDCD).
The effects of the photoresists P-1 to P-23 prepared in examples 1 to 23 and the photoresists CP-1 to CP-23 prepared in comparative examples 1 to 23 are shown in Table 3.
The developers used in Table 3 were n-butyl acetate (D-1), 2-heptanone (D-2) and methyl benzoate (D-3).
TABLE 3 Table 3
As can be seen from table 3 above, photoresist compositions within the scope of the present invention show DOF and CDU improvements and reduced CD shrinkage (small CD change) due to PPD as compared to the photoresist composition of the comparative example.

Claims (10)

1. A resin, characterized in that the resin is a copolymer obtained by polymerizing a monomer represented by formula (a), a monomer represented by formula (B), a monomer represented by formula (C), and a monomer represented by formula (D);
wherein, the weight part of the monomer shown in the formula (A) is 42.5-47.5 parts, the weight part of the monomer shown in the formula (B) is 1-7.5 parts, the weight part of the monomer shown in the formula (C) is 0.25-2.5 parts, and the weight part of the monomer shown in the formula (D) is 0.25-2.5 parts;
wherein R is 1 Is C 1 -C 10 Alkyl, R 2 Is H or methyl.
2. The resin of claim 1 wherein R 1 Is C 1 -C 4 Alkyl groups such as methyl;
and/or R 2 Is methyl.
3. The resin according to claim 1, wherein the monomer represented by the formula (A) is
And/or, the weight portion of the monomer shown in the formula (A) is 42.5-45;
and/or, the weight part of the monomer shown in the formula (B) is 2.5-4;
and/or, the weight part of the monomer shown in the formula (C) is 0.5-1.25;
and/or, the weight part of the monomer shown in the formula (D) is 0.5-1.25;
and/or the weight average molecular weight of the resin is 5000-10000;
and/or the resin has a molecular weight distribution coefficient of 1.0 to 2.0, for example 1.5 to 2.0.
4. The resin of claim 1, wherein the resin is selected from any one of the following resins 1-8:
resin 1: the weight part of the monomer shown in the formula (A) is 42.5 parts, the weight part of the monomer shown in the formula (B) is 5 parts, the weight part of the monomer shown in the formula (C) is 1.25 parts, and the weight part of the monomer shown in the formula (D) is 1.25 parts;
resin 2: the weight part of the monomer shown in the formula (A) is 45 parts, the weight part of the monomer shown in the formula (B) is 4 parts, the weight part of the monomer shown in the formula (C) is 0.5 part, and the weight part of the monomer shown in the formula (D) is 0.5 part;
resin 3: the weight part of the monomer shown in the formula (A) is 45 parts, the weight part of the monomer shown in the formula (B) is 4 parts, the weight part of the monomer shown in the formula (C) is 0.25 part, and the weight part of the monomer shown in the formula (D) is 0.75 part;
resin 4: the weight part of the monomer shown in the formula (A) is 45 parts, the weight part of the monomer shown in the formula (B) is 2.5 parts, the weight part of the monomer shown in the formula (C) is 1.25 parts, and the weight part of the monomer shown in the formula (D) is 1.25 parts;
resin 5: the weight part of the monomer shown in the formula (A) is 42.5 parts, the weight part of the monomer shown in the formula (B) is 4 parts, the weight part of the monomer shown in the formula (C) is 1.75 parts, and the weight part of the monomer shown in the formula (D) is 1.75 parts;
resin 6: the weight part of the monomer shown in the formula (A) is 47.5 parts, the weight part of the monomer shown in the formula (B) is 1 part, the weight part of the monomer shown in the formula (C) is 0.75 part, and the weight part of the monomer shown in the formula (D) is 0.75 part;
resin 7: the weight part of the monomer shown in the formula (A) is 42.5 parts, the weight part of the monomer shown in the formula (B) is 7.5 parts, the weight part of the monomer shown in the formula (C) is 1.5 parts, and the weight part of the monomer shown in the formula (D) is 1 part;
resin 8: the weight part of the monomer shown in the formula (A) is 46 parts, the weight part of the monomer shown in the formula (B) is 2.5 parts, the weight part of the monomer shown in the formula (C) is 0.75 part, and the weight part of the monomer shown in the formula (D) is 0.75 part.
5. The resin according to any one of claims 1 to 4, wherein the resin is prepared by a preparation method comprising the steps of: and (3) polymerizing the monomer shown in the formula (A), the monomer shown in the formula (B), the monomer shown in the formula (C) and the monomer shown in the formula (D) in an organic solvent to obtain the resin.
6. The resin according to claim 5, wherein the resin is prepared by a process wherein the organic solvent is present in an amount of 50 to 300 parts by weight, for example 100 parts by weight;
and/or, in the preparation method of the resin, the organic solvent is one or more of propylene glycol methyl ether acetate, propylene glycol diacetate, methylene bisacrylamide, N-methylpyrrolidone, ethyl 3-ethoxypropionate, cyclohexanone and methylene dichloride, such as propylene glycol methyl ether acetate;
and/or, in the method for producing a resin, the polymerization reaction is performed under an inert gas, which may be nitrogen;
and/or, in the method for preparing the resin, the polymerization reaction is initiated by a free radical initiator or by heating; when the polymerization reaction is initiated by a radical initiator, the radical initiator is preferably one or more of 2,2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), 2-azobis (methyl 2-methylpropionate), benzoyl peroxide and lauroyl peroxide; when the polymerization is initiated by means of heating, the temperature of the polymerization is preferably 50-150 ℃, more preferably 60-100 ℃, for example 70 ℃;
and/or, in the method for producing the resin, the polymerization reaction time is 2 to 12 hours, for example, 8 hours;
and/or, in the preparation method of the resin, the post-treatment step is further included after the polymerization reaction: one or more of cooling, precipitating and drying; the solvent used in the precipitation may be an alcoholic solvent, such as methanol; the drying may be vacuum drying, for example, vacuum drying at 40 ℃ for 24 hours.
7. The resin of claim 5, wherein the method of preparing the resin comprises the steps of: adding the monomer shown in the formula (A), the monomer shown in the formula (B), the monomer shown in the formula (C) and the solution of the formula (D) and part of the organic solvent into the rest of the organic solvent;
preferably, the mass ratio of the part of the organic solvent to the rest of the organic solvent is 1:1 to 5:1, for example 7:3; the adding mode is dripping; the time of addition is 1 to 8 hours, for example 5 hours.
8. A photoresist composition comprising the resin of any one of claims 1 to 7, a photoacid generator, and a solvent;
preferably, the photoresist composition further comprises an additive.
9. The photoresist composition of claim 8, wherein the photoacid generator has a structure of formula (I):
X+Y-
(I)，
wherein X is + Selected from any one of the following structures:
y-is selected from any one of the following structures:
and/or the solvent is one or more of ketone solvents, ether solvents, ester solvents and alcohol solvents;
and/or the additive is a quencher and/or a surfactant.
10. The photoresist composition of claim 9, wherein the photoacid generator is selected from any one of the following structures:
and/or the solvent is one or more of cyclohexanone, ethylene glycol monoethyl ether and gamma-butyrolactone;
and/or the quencher is
And/or the surfactant is one or more of FC-4430, S-381, E1004, KH-20, and KH-30, such as KH-20 and/or KH-30;
and/or, the weight portion of the resin is 75-95 portions;
and/or, the weight part of the photoacid generator is 1-10 parts;
and/or, the weight portion of the solvent is 1000-2000 portions;
and/or, the weight portion of the quenching agent is 0.5-3 portions;
and/or, the weight portion of the surfactant is 0.1-0.2 portion based on the weight portion.
CN202111305909.4A 2021-11-05 2021-11-05 Resin and 193nm immersed photoresist containing same Pending CN117126324A (en)

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CN202111305909.4A CN117126324A (en) 2021-11-05 2021-11-05 Resin and 193nm immersed photoresist containing same

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Application Number Priority Date Filing Date Title
CN202111305909.4A CN117126324A (en) 2021-11-05 2021-11-05 Resin and 193nm immersed photoresist containing same

Publications (1)

Publication Number Publication Date
CN117126324A true CN117126324A (en) 2023-11-28

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Country Link
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