CN115873165A - Resin and preparation method of 193nm dry-process photoresist containing same - Google Patents
Resin and preparation method of 193nm dry-process photoresist containing same Download PDFInfo
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- CN115873165A CN115873165A CN202111146206.1A CN202111146206A CN115873165A CN 115873165 A CN115873165 A CN 115873165A CN 202111146206 A CN202111146206 A CN 202111146206A CN 115873165 A CN115873165 A CN 115873165A
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Abstract
The invention discloses a resin and a preparation method of 193nm dry-process photoresist containing the resin. The resin is a copolymer obtained by polymerizing a monomer represented by a formula (A), a monomer represented by a formula (B), a monomer represented by a formula (C) and a monomer represented by a formula (D); wherein, the weight portion of the monomer shown in the formula (A) is 42.5 to 49.5 portions, the weight portion of the monomer shown in the formula (B) is 1 to 7.5 portions, the weight portion of the monomer shown in the formula (C) is 0.25 to 2.5 portions, and the weight portion of the monomer shown in the formula (D) is 0.25 to 2.5 portions. The photoresist containing the resin prepared by the preparation method has at least the following advantagesPotential: excellent photosensitivity, good depth of focus and good line width uniformity.
Description
Technical Field
The invention relates to a resin and a preparation method of 193nm dry-process photoresist containing the resin.
Background
The photolithography technique is a fine processing technique for transferring a pattern designed on a mask plate to a pattern on a substrate by using the chemical sensitivity of a photolithography material (particularly a photoresist) under the action of visible light, ultraviolet rays, electron beams and the like through the processes of exposure, development, etching and the like. The main components of the photoresist material (referred to as photoresist), also called Photo resist, are resin, photo Acid Generator (PAG), and corresponding additives and solvents. The photoacid generator is a photosensitive compound, which decomposes under irradiation of light to generate an acid, which causes decomposition or crosslinking of the acid-sensitive resin, thereby increasing the dissolution contrast between the irradiated portion and the non-irradiated portion in a developer, and can be used in the field of fine patterning technology.
Three important parameters of the photoresist include resolution, sensitivity, line width roughness, which determine the process window of the photoresist during chip fabrication. With the increasing performance of semiconductor chips, the integration level of integrated circuits is increased exponentially, and the patterns in the integrated circuits are continuously reduced. In order to make patterns with smaller dimensions, the performance indexes of the three photoresists must be improved. The use of a short wavelength light source in a photolithography process can improve the resolution of the photoresist according to the rayleigh equation. The light source wavelength of the photolithography process is developed from 365nm (I-line) to 248nm (KrF), 193nm (ArF), and 13nm (EUV). In order to improve the sensitivity of the photoresist, the current KrF, arF and EUV photoresists are mainly made of chemically amplified photosensitive resin. Thus, photosensitizers (photoacid generators) compatible with chemically amplified photopolymer resins are widely used in high-end photoresists.
With the development of the photolithography process, the process complexity is increased to 193nm dry exposure process, and the requirements on the resist (i.e. photoresist) are increased. Development of resists 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 above problems in the prior art, the present invention is directed to a resin and a method for preparing 193nm dry photoresist containing the same, wherein the photoresist containing the resin prepared by the preparation method of the present invention has at least the following advantages: excellent photosensitivity, good depth of focus (DOF) and good line width uniformity (CDU).
The invention provides a preparation method of resin, which comprises the following steps: carrying out polymerization reaction on 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) in an organic solvent to obtain the resin;
wherein, the weight portion of the monomer shown in the formula (A) is 42.5 to 49.5 portions, the weight portion of the monomer shown in the formula (B) is 1 to 7.5 portions, the weight portion of the monomer shown in the formula (C) is 0.25 to 2.5 portions, and the weight portion of the monomer shown in the formula (D) is 0.25 to 2.5 portions;
wherein R is 1 Is C 1 -C 10 Alkyl radical, R 2 Is H or methyl.
In one embodiment of the present invention, R 1 Can be C 1 -C 4 Alkyl groups, such as methyl.
In one embodiment of the present invention, R 2 May be a methyl group.
In one embodiment of the present invention, in the method for preparing the resin, the monomer represented by the formula (a) may be
In one embodiment of the present invention, in the method for preparing the resin, the weight part of the monomer represented by the formula (a) may be 42.5 to 46.
In one embodiment of the present invention, in the method for preparing the resin, the weight part of the monomer represented by the formula (B) may be 2.5 to 4.
In one embodiment of the present invention, in the method for preparing the resin, 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, in the method for preparing the resin, the weight part of the monomer represented by the formula (D) may be 0.5 to 1.25.
In a certain aspect of the present invention, in the method for preparing the resin, the weight average molecular weight (Mw) of the resin may be 5000 to 10000.
In one aspect of the present invention, in the method for preparing the resin, the resin may have a molecular weight distribution coefficient of 1.0 to 2.0, for example, 1.5 to 2.0. The molecular weight distribution coefficient refers to a ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight of the resin.
In a certain aspect of the present invention, in the method for preparing the resin, the resin may be selected from any one of the following resins 1 to 8:
resin 1: the weight portion of the monomer shown in the formula (A) is 42.5 parts, the weight portion of the monomer shown in the formula (B) is 5 parts, the weight portion of the monomer shown in the formula (C) is 1.25 parts, and the weight portion 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 monomer represented by the formula (A) comprises 45 parts by weight, the monomer represented by the formula (B) comprises 4 parts by weight, the monomer represented by the formula (C) comprises 0.25 part by weight, and the monomer represented by the formula (D) comprises 0.75 part by weight;
resin 4: the weight portion of the monomer shown in the formula (A) is 45 portions, the weight portion of the monomer shown in the formula (B) is 2.5 portions, the weight portion of the monomer shown in the formula (C) is 1.25 portions, and the weight portion of the monomer shown in the formula (D) is 1.25 portions;
resin 5: the weight portion of the monomer shown in the formula (A) is 42.5 parts, the weight portion of the monomer shown in the formula (B) is 4 parts, the weight portion of the monomer shown in the formula (C) is 1.75 parts, and the weight portion of the monomer shown in the formula (D) is 1.75 parts;
resin 6: the weight portion of the monomer shown in the formula (A) is 49.5 parts, the weight portion of the monomer shown in the formula (B) is 1 part, the weight portion of the monomer shown in the formula (C) is 0.75 part, and the weight portion of the monomer shown in the formula (D) is 0.75 part;
resin 7: the weight portion of the monomer shown in the formula (A) is 42.5 parts, the weight portion of the monomer shown in the formula (B) is 7.5 parts, the weight portion of the monomer shown in the formula (C) is 1.5 parts, and the weight portion of the monomer shown in the formula (D) is 1 part;
resin 8: the monomer represented by the formula (A) is 46 parts by weight, the monomer represented by the formula (B) is 2.5 parts by weight, the monomer represented by the formula (C) is 0.75 part by weight, and the monomer represented by the formula (D) is 0.75 part by weight.
In the resin 1, the weight average molecular weight of the resin may be 6800; the resin may have a molecular weight distribution coefficient of 1.4.
In the resin 2, the weight average molecular weight of the resin may be 7300; the resin may have a molecular weight distribution coefficient of 1.1.
In the resin 3, the weight average molecular weight of the resin may be 9800; the resin may have a molecular weight distribution coefficient of 2.
In the resin 4, the weight average molecular weight of the resin may be 7100. The resin may have a molecular weight distribution coefficient of 1.2.
In the resin 5, the weight average molecular weight of the resin may be 6400. The resin may have a molecular weight distribution coefficient of 1.7.
In the resin 6, the weight average molecular weight of the resin may be 6300. The resin may have a molecular weight distribution coefficient of 1.5.
In the resin 7, the weight average molecular weight of the resin may be 7200. The resin may have a molecular weight distribution coefficient of 1.7.
In the resin 8, the weight average molecular weight of the resin may be 7600. The resin may have a molecular weight distribution coefficient of 1.1.
In one embodiment of the present invention, in the method for preparing the resin, the organic solvent is 50 to 300 parts by weight, for example, 100 parts by weight.
In an embodiment of the present invention, in the method for preparing the resin, the organic solvent may be one or more of propylene glycol methyl ether acetate, propylene glycol diacetate, methylene bisacrylamide, N-methylpyrrolidone, ethyl 3-ethoxypropionate, cyclohexanone, and dichloromethane, for example, propylene Glycol Methyl Ether Acetate (PGMEA).
In a certain embodiment of the present invention, in the method for preparing 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 preparing 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), 2-azobis (methyl 2-methylpropionate), benzoyl peroxide, and lauroyl peroxide.
When the polymerization is initiated by means of heat, the polymerization temperature is preferably from 50 to 150 deg.C, more preferably from 60 to 90 deg.C, for example 70 deg.C, in the polymerization.
In one embodiment of the present invention, the polymerization time in the method for preparing the resin may be a time conventional in the art, such as 6 to 12 hours, and further such as 8 hours.
In one embodiment of the present invention, the method for preparing the resin further comprises a post-treatment step after the polymerization reaction, such as one or more of cooling, precipitation and drying.
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 following steps: the solution of the monomer represented by the formula (a), the monomer represented by the formula (B), the monomer represented by the formula (C), and the monomer represented by the formula (D) and a part of the organic solvent as described above is 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. The adding mode is dropwise adding. The addition time is from 1 to 8 hours, for example 5 hours.
The invention provides a resin prepared by the preparation method of the resin.
The invention provides a preparation method of a photoresist composition, which comprises the following steps: uniformly mixing the resin, the photoacid generator and the solvent; wherein the resin is prepared by the preparation method of the resin.
In one embodiment of the present invention, in the method for preparing the photoresist composition, the photoacid generator may be any of known photoacid generators conventionally used in photoresists, especially chemically amplified photoresist compositions. The photoacid generator can be any compound capable of generating an acid upon exposure to high energy radiation, such as one or more of a sulfonium salt, an iodonium salt, a sulfonyldiazomethane, an N-sulfonyloxyimide, and an oxime-O-sulfonate ester, for the purpose of fine tuning the performance of the photolithography. 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 method for preparing the photoresist composition, the photoacid generator may have a structure represented by formula (I):
x+ Y-
(I)，
wherein X + Any one of the following structures:
Y - any one of the structures selected from:
in a certain aspect of the present invention, in the method for preparing a photoresist composition, the photoacid generator may be selected from any one of the following structures:
in one embodiment of the present invention, in the method for preparing the photoresist composition, the solvent may be any known solvent conventionally used in photoresists, especially chemically amplified photoresist compositions. The solvent may be one or more of a ketone-based solvent (e.g., cyclohexanone and/or methyl-2-n-amyl ketone), an alcohol-based solvent (e.g., one or more of monohydric alcohol-based solvents (e.g., 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol), and/or a glycol-based solvent (e.g., diacetone alcohol)), an ether-based 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-based 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 mono-t-butyl ether acetate, γ -butyrolactone).
In a certain embodiment of the present invention, in the method for preparing the photoresist composition, the solvent may be one or more of ketone solvents, ether solvents and ester solvents, for example, one or more of cyclohexanone, ethylene glycol monoethyl ether and γ -butyrolactone.
In one embodiment of the present invention, the photoresist composition may further include an additive, which may be any known additive conventionally used in photoresist, especially chemically amplified photoresist compositions, such as a quencher and/or a surfactant.
In a certain aspect of the present invention, in the method for producing a photoresist composition, the quencher is a compound capable of suppressing a diffusion rate when an acid generated from the photoacid generator diffuses through the resist film, and may be, for example, one or more of an amine-containing compound, a sulfonate, and a carboxylate. The amine compounds can be primary, secondary, and tertiary amine compounds, such as amine compounds having hydroxyl, ether, ester, lactone, cyano, or sulfonate groups. The protected amine compounds are effective, particularly when the resist composition includes a base labile component.
In one embodiment of the present invention, in the method for preparing the photoresist composition, the quencher may be
In one embodiment of the present invention, in the method for preparing the photoresist composition, 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 embodiment of the present invention, the surfactant may be one or more of FC-4430 (available from 3M), S-381 (available from AGC Seimi chemical), E1004 (available from Air Products), KH-20 and KH-30 (available from Asahi Glass), such as KH-20 and/or KH-30, in the process for preparing the photoresist composition.
In the preparation method of the photoresist composition, the content of each component is the conventional content in the photoresist in the field, and the invention is preferably as follows.
In one embodiment of the present invention, in the method for preparing the photoresist composition, the resin may be present in an amount of 75 to 95 parts by weight (e.g., 75, 85, 90, 95 parts by weight).
In one embodiment of the present invention, in the method for preparing the photoresist composition, the photoacid generator may be present in an amount of 1 to 10 parts (e.g., 1,3, 5, 7, 10 parts) by weight.
In one embodiment of the present invention, in the method for preparing the photoresist composition, the solvent may be used in an amount of 1000 to 2000 parts by weight (e.g., 1000, 1200, 1500, 1600, 2000).
In one embodiment of the present invention, in the method for preparing the photoresist composition, the weight part of the quencher may be 0.5 to 3 parts (e.g., 0.5, 0.8, 1.5, 2, 3) by weight part.
In one embodiment of the present invention, in the method for preparing the photoresist composition, the surfactant may be present in an amount of 0.1 to 0.2 parts by weight.
In a certain aspect of the present invention, in the method for preparing the photoresist composition, the photoresist composition may be composed of: 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.
In a certain aspect of the present invention, in the method for preparing the photoresist composition, the photoresist composition may be selected from any one of the following combinations 1 to 23:
in one embodiment of the present invention, the method for preparing the photoresist composition may further comprise a filtering step after the mixing. The filtration may be performed in a manner conventional in the art, and preferably filtration using a filter is used. The filter membrane pore size of the filter is preferably 0.2 μm.
The invention provides a photoresist composition, which is prepared by the preparation method of the photoresist composition.
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 base material, and baking to form a photoresist layer;
s2: exposing the photoresist layer formed in the step S1;
s3: baking the photoresist layer exposed in the step S2;
s4: and developing the photoresist layer baked in the step S3.
In S1, the substrate can be a substrate used in integrated circuit fabrication (e.g., si, siO) 2 One or more of SiN, siON, tiN, WSi, BPSG, SOG, and organic antireflection film), or a base material for mask circuit fabrication (e.g., cr, crO, crON, moSi) 2 And SiO 2 One or more of the above).
In S1, the coating manner may be a conventional coating manner used in the art for forming a photolithographic pattern, such as spin coating.
In S1, the baking temperature may be a conventional baking temperature used in the art for forming a photolithographic pattern, such as 120-250 ℃, and further such as 130 ℃.
In S1, the baking time may be a conventional baking time used in the art for forming a photolithographic pattern, such as 1-10 minutes, and further such as 1 minute.
In S1, the photoresist layer may have a thickness of 0.05 to 2 μm, for example, 300nm.
In S2, the exposure may be performed using conventional procedures used in the art for forming photolithographic patterns, such as high-energy radiation (e.g., krF excimer laser, arF excimer laser, or EUV), wherein the exposure dose may be in the range of 1-200mJ/cm 2 (e.g., 10-100mJ/cm 2 ) Or electron beam exposure, wherein the exposure dose can be 0.1-100 μ C/cm 2 (e.g., 0.5-50. Mu.C/cm) 2 )。
In S2, the exposure may be performed by a conventional photolithography method or a dry photolithography method.
In S2, in the case of dry lithography, a protective film insoluble in water may be formed on the resist film. When a water-insoluble protective film used for dry photolithography is used to prevent any component from leaching out of a photoresist layer and improve water slipperiness (water slippage) at the film surface, it is generally classified into two types. The first type is an organic solvent strippable protective film, which must be stripped prior to alkaline development using an organic solvent in which the resist film is insoluble. The second type is an alkali-soluble protective film that 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 1,1,1,3,3,3-hexafluoro-2-propanol residues, which are 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 that is insoluble in water and soluble in an alkaline developer may be soluble 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 baking temperature may be a conventional baking temperature used in the art for forming a photolithographic pattern, such as 60-150 ℃, such as 80-140 ℃, and further such as 115 ℃.
In S3, the baking time may be a conventional baking time used in the art for forming a photolithographic pattern, such as 1-3 minutes, and further such as 1 minute.
In S3, the baking may further include a cooling step, for example, cooling to 10 to 30 ℃, preferably 23 ℃.
In S4, the developing method may be a conventional developing method used in the art for forming a photolithographic pattern, such as one or more of immersion, spin-on immersion, and spraying.
In S4, the developing developer may be a conventional developer used in the art for forming a photolithographic pattern, such as an aqueous alkaline solution and/or an organic solvent.
The aqueous alkaline solution may be an aqueous alkaline solution of a developer, such as an aqueous 0.1 to 5 weight percent, preferably 2 to 3 weight percent, tetramethylammonium hydroxide (TMAH) solution.
The organic solvent may be one or more of 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isoamyl acetate, butenyl acetate, phenyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, benzyl acetate, methyl phenylacetate, benzyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, and 2-phenylethyl acetate.
In S4, the developing temperature may be a conventional developing temperature used in the art for forming a photolithographic pattern, for example, 10 to 30 ℃, preferably 23 ℃.
In S4, the developing time may be a conventional developing time used in the art for forming a photolithographic pattern, such as 0.1 to 3 minutes, such as 0.5 to 2 minutes, and further such as 1 minute.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
In the present invention, dry lithography, also commonly referred to in the art as dry lithography, is a 193nm exposure lithography method that is distinguished from 193nm (ArF) immersion exposure lithography.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the photoresist containing the resin prepared by the preparation method of the invention has 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 the following examples, which are not intended to limit the invention thereto. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
Preparation of the resin
A solution was prepared by dissolving the following monomer A, monomer B, monomer C, monomer D in the following weight parts (g) of Table 1 in 70g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) under a nitrogen atmosphere. The solution was added dropwise over 5 hours to 30g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) under a nitrogen atmosphere while stirring at 70 ℃. After 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 a polymer in the form of a powder solid.
TABLE 1
Examples 1 to 23, comparative examples 1 to 23: preparation of photoresists
The resins, photoacid generators, and quenchers prepared as described above were dissolved in an organic solvent according to the formulations shown in table 2, and photoresists of examples 1 to 23 and comparative examples 1 to 23 were prepared as solutions by filtration through a filter having a pore size of 0.2 μm, wherein
The polymers used in Table 2 were R-1 to R-8 and CR-1 to CR-8 obtained as described in Table 1 above.
The photoacid generator used in table 2 has the following structure:
the quenchers used in table 2 have 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 either KH-30 or KH-20 (Asahi Glass Co., ltd.).
TABLE 2
Application and effects embodiments
ArF Dry lithography patterning test (hole Pattern test)
1. Hole pattern formation:
the photoresist was spin coated on a silicon wafer covered with an anti-reflective coating (ARC 29A, nissan chemical co., ltd., thickness 78 nm) and heat treated at 130 ℃ for 60 seconds to form a 300nm thick photoresist film. Exposing in an ArF excimer laser stepper (Nikon Corp., NA = 0.68) at an exposure of 45mJ/cm 2 Heat-treated at 115 ℃ for 60 seconds, cooled to 23 ℃ and at 23 ℃ at 2.38% tetramethylammonium hydroxide in water for 60 seconds, thereby forming a hole pattern with a pitch of 100 nm.
2. Evaluation of photosensitivity:
the hole pattern formed above was observed under TD-SEM (CG-4000, high-Technologies Corp.). The optimum dose (Eop) is to provide an exposure dose (mJ/cm) with a hole diameter of 50nm at a pitch of 100nm 2 ) And used as an index of photosensitivity.
3. Evaluation depth of focus (DOF) margin:
the pore size at the optimal dose was measured under TD-SEM (CG-4000) from which the DOF margin providing a size of 50nm + -5 nm was determined. Larger values indicate smaller changes in pattern size as the DOF changes and thus the DOF margin is better.
4. Evaluation of CDU:
the hole pattern formed above was observed under TD-SEM (CG-4000) and the diameter of 125 holes was measured. From this, a triple value (3 σ) of the standard deviation (σ) was calculated and recorded as CDU. A smaller value of 3 σ indicates a smaller deviation of the pores.
5. Evaluation of PPD:
immediately after PEB (no retardation, PPD =0 h), the wafer was immersion developed for 30 seconds in suspension to form a hole pattern having a diameter of 50nm and a pitch of 100 nm. In another run, the wafer was held for 6 hours (PPD =6 h) after the PEB and then developed similarly to form a pattern.
The hole patterns at PPD =0h and 6h were observed under TD-SEM (CG-4000) and the diameter of 125 holes was measured. The average thereof was taken as the pore size (CD), and the CDU was calculated by the same method as above. The difference between CD at PPD 0h and CD at PPD 6h was taken as the CD shrinkage due to PPD (. DELTA.PPD CD).
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
As can be seen from table 3 above, the photoresist composition within the scope of the present invention showed improvement in DOF and CDU and reduction in CD shrinkage due to PPD (small CD change) compared to the photoresist composition of the comparative example.
Claims (10)
1. A method for preparing a resin, comprising the steps of: carrying out polymerization reaction on 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) in an organic solvent to obtain the resin;
wherein, the weight portion of the monomer shown in the formula (A) is 42.5 to 49.5 portions, the weight portion of the monomer shown in the formula (B) is 1 to 7.5 portions, the weight portion of the monomer shown in the formula (C) is 0.25 to 2.5 portions, and the weight portion of the monomer shown in the formula (D) is 0.25 to 2.5 portions;
wherein R is 1 Is C 1 -C 10 Alkyl radical, R 2 Is H or methyl.
2. The method of claim 1, wherein R is 1 Is C 1 -C 4 Alkyl groups such as methyl;
and/or, R 2 Is a methyl group.
3. The method for producing a 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 42.5-46;
and/or, the weight portion of the monomer shown in the formula (B) is 2.5-4;
and/or, the weight portion of the monomer shown in the formula (C) is 0.5-1.25;
and/or, the weight portion 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 from 1.0 to 2.0, such as from 1.5 to 2.0.
4. The method for producing a resin according to claim 1, wherein the resin is selected from any one of the following resins 1 to 8:
resin 1: the monomer shown in the formula (A) is 42.5 parts by weight, the monomer shown in the formula (B) is 5 parts by weight, the monomer shown in the formula (C) is 1.25 parts by weight, and the monomer shown in the formula (D) is 1.25 parts by weight;
resin 2: the monomer represented by the formula (A) comprises 45 parts by weight, the monomer represented by the formula (B) comprises 4 parts by weight, the monomer represented by the formula (C) comprises 0.5 part by weight, and the monomer represented by the formula (D) comprises 0.5 part by weight;
resin 3: the monomer represented by the formula (A) comprises 45 parts by weight, the monomer represented by the formula (B) comprises 4 parts by weight, the monomer represented by the formula (C) comprises 0.25 part by weight, and the monomer represented by the formula (D) comprises 0.75 part by weight;
resin 4: the monomer represented by the formula (A) comprises 45 parts by weight, the monomer represented by the formula (B) comprises 2.5 parts by weight, the monomer represented by the formula (C) comprises 1.25 parts by weight, and the monomer represented by the formula (D) comprises 1.25 parts by weight;
resin 5: the monomer shown in the formula (A) is 42.5 parts by weight, the monomer shown in the formula (B) is 4 parts by weight, the monomer shown in the formula (C) is 1.75 parts by weight, and the monomer shown in the formula (D) is 1.75 parts by weight;
resin 6: the weight portion of the monomer shown in the formula (A) is 49.5 parts, the weight portion of the monomer shown in the formula (B) is 1 part, the weight portion of the monomer shown in the formula (C) is 0.75 part, and the weight portion of the monomer shown in the formula (D) is 0.75 part;
resin 7: the monomer represented by the formula (A) is 42.5 parts by weight, the monomer represented by the formula (B) is 7.5 parts by weight, the monomer represented by the formula (C) is 1.5 parts by weight, and the monomer represented by the formula (D) is 1 part by weight;
resin 8: the weight portion of the monomer shown in the formula (A) is 46 parts, the weight portion of the monomer shown in the formula (B) is 2.5 parts, the weight portion of the monomer shown in the formula (C) is 0.75 part, and the weight portion of the monomer shown in the formula (D) is 0.75 part.
5. The method for producing a resin according to any one of claims 1 to 4,
the organic solvent is 50-300 parts by weight, such as 100 parts by weight;
and/or the organic solvent is one or more of propylene glycol methyl ether acetate, propylene glycol diacetate, methylene bisacrylamide, N-methyl pyrrolidone, ethyl 3-ethoxypropionate and cyclohexanone and dichloromethane, such as propylene glycol methyl ether acetate;
and/or, the polymerization reaction is carried out under an inert gas, which can be nitrogen;
and/or the polymerization is initiated by means of a free-radical initiator or by means of heat; 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 heat, the polymerization temperature is preferably from 50 to 150 ℃, more preferably from 60 to 90 ℃, for example 70 ℃;
and/or the time of the polymerization reaction is 6 to 12 hours, such as 8 hours;
and/or, the polymerization reaction further comprises a post-treatment step: one or more of cooling, precipitating, and drying; the solvent used in the precipitation may be an alcohol solvent, such as methanol; the drying may be vacuum drying, for example, vacuum drying at 40 ℃ for 24 hours.
6. The method of preparing a resin according to claim 5, comprising the steps of: adding the solution of the monomer shown in the formula (A), the monomer shown in the formula (B), the monomer shown in the formula (C), 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; the adding mode is dripping; the addition time is 1 to 8 hours, for example 5 hours.
7. A method of preparing a photoresist composition, comprising the steps of: uniformly mixing the resin, the photoacid generator and the solvent; wherein the resin is obtained by the method for preparing the resin according to any one of claims 1 to 6;
preferably, the photoresist composition further comprises an additive.
8. The method of claim 7, wherein the photoacid generator has a structure of formula (I):
X+Y-
(I)，
wherein X + Any one of the structures selected from:
Y - any one of the following structures:
and/or the solvent is one or more of ketone solvent, ether solvent, ester solvent and alcohol solvent;
and/or the additive is a quencher and/or a surfactant.
9. The method of preparing a photoresist composition of claim 8, wherein the photoacid generator is selected from any of the following structures:
and/or the solvent is one or more of cyclohexanone, ethylene glycol monoethyl ether and gamma-butyrolactone;
and/or the quenching agent 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 part of the resin is 75-95 parts;
and/or, the parts by weight of the photoacid generator is 1-10 parts;
and/or, the weight portion of the solvent is 1000-2000;
and/or, the weight part of the quenching agent is 0.5-3 parts;
and/or, the weight part of the surfactant is 0.1-0.2 part by weight.
10. The method of claim 7, further comprising a filtration step after the mixing, wherein the filtration is performed by a filter, and the filter membrane pore size of the filter is preferably 0.2 μm.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050158656A1 (en) * | 2004-01-21 | 2005-07-21 | Sumitomo Chemical Company, Limited | Chemical amplification type positive resist composition |
| JP2007302821A (en) * | 2006-05-12 | 2007-11-22 | Asahi Glass Co Ltd | Fluorine-containing copolymer, method for producing the same and resist composition containing the same |
| CN103193696A (en) * | 2013-04-18 | 2013-07-10 | 北京大学 | Mesogen-jacketed polymer monomers of norbornene imide system and polymers of polymer monomers |
| CN103980417A (en) * | 2014-04-24 | 2014-08-13 | 东南大学 | Novel dendritic polymers positive photoresist resin, preparation method and application thereof |
| CN107383344A (en) * | 2017-06-16 | 2017-11-24 | 上海科技大学 | It is a kind of can functionalization high polymer material and preparation method thereof |
| WO2018205896A1 (en) * | 2017-05-12 | 2018-11-15 | 湖北固润科技股份有限公司 | Poly(p-hydroxystyrene)-based oxetane resin, and synthesis and use thereof |
| US20200218154A1 (en) * | 2019-01-08 | 2020-07-09 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| US20200249571A1 (en) * | 2019-02-05 | 2020-08-06 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| CN111635341A (en) * | 2020-06-16 | 2020-09-08 | 徐州博康信息化学品有限公司 | Trifluoro sulfonamide octahydro-pentalene photoresist resin monomer and preparation method thereof |
-
2021
- 2021-09-28 CN CN202111146206.1A patent/CN115873165A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050158656A1 (en) * | 2004-01-21 | 2005-07-21 | Sumitomo Chemical Company, Limited | Chemical amplification type positive resist composition |
| JP2007302821A (en) * | 2006-05-12 | 2007-11-22 | Asahi Glass Co Ltd | Fluorine-containing copolymer, method for producing the same and resist composition containing the same |
| CN103193696A (en) * | 2013-04-18 | 2013-07-10 | 北京大学 | Mesogen-jacketed polymer monomers of norbornene imide system and polymers of polymer monomers |
| CN103980417A (en) * | 2014-04-24 | 2014-08-13 | 东南大学 | Novel dendritic polymers positive photoresist resin, preparation method and application thereof |
| WO2018205896A1 (en) * | 2017-05-12 | 2018-11-15 | 湖北固润科技股份有限公司 | Poly(p-hydroxystyrene)-based oxetane resin, and synthesis and use thereof |
| CN107383344A (en) * | 2017-06-16 | 2017-11-24 | 上海科技大学 | It is a kind of can functionalization high polymer material and preparation method thereof |
| US20200218154A1 (en) * | 2019-01-08 | 2020-07-09 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| US20200249571A1 (en) * | 2019-02-05 | 2020-08-06 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| CN111635341A (en) * | 2020-06-16 | 2020-09-08 | 徐州博康信息化学品有限公司 | Trifluoro sulfonamide octahydro-pentalene photoresist resin monomer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| YOKO TAKEBE等: "Development of new resist materials for 193-nm dry and immersion lithography", 《MICROELECTRONIC ENGINEERING》, vol. 83, no. 4, pages 1091 - 1093 * |
| 李虎: "光刻胶用成膜树脂的合成及性能研究", 《中国博士学位论文全文数据库 工程科技I辑》, no. 1, pages 016 - 40 * |
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