CN115963694A - Application of photoresist in ArF dry method photoetching - Google Patents
Application of photoresist in ArF dry method photoetching Download PDFInfo
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- CN115963694A CN115963694A CN202111189001.1A CN202111189001A CN115963694A CN 115963694 A CN115963694 A CN 115963694A CN 202111189001 A CN202111189001 A CN 202111189001A CN 115963694 A CN115963694 A CN 115963694A
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Abstract
The invention discloses an application of a photoresist in ArF dry method photoetching. The photoresist composition in the application is prepared from the following raw materials in parts by weight: 75-95 parts of resin, 1.0-10 parts of photoacid generator, 1000-2000 parts of solvent, 0.5-3.0 parts of quencher and surfactant. The photoresist containing the resin has the advantages of high resolution, high sensitivity and low line width roughness.
Description
Technical Field
The invention relates to an application of a photoresist in ArF dry method photoetching.
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 photoresist material (specifically referred to as photoresist), also called photoresist, is the most critical functional chemical material involved in the photolithography technology, and its main components are resin, photo Acid Generator (PAG), and corresponding additives and solvents. The photo-acid generator is a light-sensitive compound, which is decomposed under illumination to generate acid, and the generated acid can make acid-sensitive resin generate decomposition or cross-linking reaction, so that the dissolution contrast of the illuminated part and the non-illuminated part in a developing solution is increased, and the photo-acid generator can be used in the technical field of pattern micro-machining.
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 mainly adopt chemically amplified photosensitive resin. Thus, photosensitizers (photoacid generators) compatible with chemically amplified photopolymer resins are widely used in high-end photoresists.
As the development of photolithography technology progresses, the process complexity increases to 193nm technology, and higher requirements are put on the resist (i.e. photoresist). Developing a photoresist capable of improving resolution, sensitivity and line width roughness becomes a problem to be solved urgently in the industry.
Disclosure of Invention
The invention aims to overcome the defects of high resolution, sensitivity or line width roughness and the like in ArF dry etching in the technology, and provides the application of the photoresist in the ArF dry etching. The photoresist containing the resin has the advantages of high resolution, high sensitivity and low line width roughness.
The invention provides an application of a photoresist composition in ArF dry method photoetching;
the photoresist composition is prepared from the following raw materials in parts by weight: 75 to 95 parts (e.g., 85 parts or 90 parts) of a resin, 1.0 to 10 parts (e.g., 3 parts, 5 parts or 7 parts) of a photoacid generator, 1000 to 2000 parts (e.g., 1200 parts, 1600 parts or 1500 parts) of a solvent, 0.5 to 3.0 parts (e.g., 0.8 parts or 1.5 parts) of a quencher and a surfactant;
the resin is obtained by polymerizing the following monomers in parts by weight: 40-50 parts of monomer A, 0.5-5 parts of monomer B, 0.25-2.5 parts of monomer C and 0.25-2.5 parts of monomer D;
wherein R is 1 Is C 1-10 Alkyl groups of (a);
R 2 is H or C 1-10 Alkyl groups of (a);
R 3 is C 1-10 Alkyl groups of (a);
R 4 is C 2-4 Alkenyl of (a);
R 5 and R 6 Independently is H or C 1-5 The alkyl group of (1).
In some embodiments, R 1 In (b), the C 1-10 Alkyl of (A) is C 1-5 Preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, for example methyl.
In some embodiments, R 2 In (b), the C 1-10 Alkyl of (A) is C 1-5 Preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, for example methyl.
In some embodiments, R 3 In (b), the C 1-10 Alkyl of (A) is C 1-5 The alkyl group of (b) is preferably a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl group, for example a methyl group.
In some of the arrangements, the first and second sets of sensors are,R 4 in (b), the C 2-4 Alkenyl of (A) is C 2-3 The alkenyl group of (b) is preferably an ethenyl group or an isopropenyl group, e.g., an isopropenyl group.
In some embodiments, R 5 In (b), the C 1-5 The alkyl group of (b) is preferably a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl group, for example a methyl group.
In some embodiments, R 2 Is C 1-10 Alkyl group of (1).
In some embodiments, R 5 And R 6 Independently is C 1-10 Alkyl group of (1).
In some embodiments, the monomer D isIn some embodiments, the resin has a weight average molecular weight (Mw) of 5000 to 10000, e.g., 5544 to 9568 (e.g., 6518, 6639, 6736, 7355, 7518, or 9131).
In some embodiments, the resin has a molecular weight distribution coefficient (Mw/Mn) of 1.0 to 2.0 (e.g., 1.1, 1.3, 1.4, 1.6, or 1.7), such as 1.5 to 2.0.
The molecular weight distribution coefficient refers to the ratio of the weight average molecular weight to the number average molecular weight of the resin.
In some embodiments, the portion of monomer A is from 42.5 to 45.
In some embodiments, the portion of monomer B is from 2.5 to 5 parts (e.g., 3 parts).
In some embodiments, the fraction of monomer C is from 0.5 to 1.25 parts (e.g., 0.75).
In some embodiments, the portion of monomer D is from 0.5 to 1.25 parts (e.g., 0.75 or 1.0).
the part of the monomer B is 2.5-5 parts;
In some embodiments, the resin is any one of resins 1 to 8 obtained by polymerizing the following monomers in parts by weight:
resin 1:42.5 parts of monomer A, 5 parts of monomer B, 1.25 parts of monomer C and 1.25 parts of monomer D; the weight average molecular weight is 7518, the molecular weight distribution coefficient is 1.1;
resin 2:45 parts of monomer A, 3 parts of monomer B, 0.5 part of monomer C and 0.5 part of monomer D; the weight average molecular weight is 7355, and the molecular weight distribution coefficient is 1.3;
resin 3:45 parts of monomer A, 3 parts of monomer B, 0.25 part of monomer C and 0.75 part of monomer D; the weight average molecular weight is 5544, and the molecular weight distribution coefficient is 1.1;
resin 4:45 parts of monomer A, 2.5 parts of monomer B, 1.25 parts of monomer C and 1.25 parts of monomer D; the weight average molecular weight is 6639, and the molecular weight distribution coefficient is 1.4;
resin 5:42.5 parts of monomer A, 3 parts of monomer B, 1.75 parts of monomer C and 1.75 parts of monomer D; the weight average molecular weight is 6518, and the molecular weight distribution coefficient is 1;
resin 6:50 parts of monomer A, 1 part of monomer B, 0.75 part of monomer C and 0.75 part of monomer D; the weight average molecular weight is 9568, the molecular weight distribution coefficient is 1.7;
resin 7:40 parts of monomer A, 5 parts of monomer B, 1.5 parts of monomer C and 1 part of monomer D; the weight-average molecular weight is 9131, and the molecular weight distribution coefficient is 1.6;
resin 8:46 parts of monomer A, 2.5 parts of monomer B, 0.75 part of monomer C and 0.75 part of monomer D; the weight average molecular weight is 6736, the molecular weight distribution coefficient is 2;
In the photoresist composition, the resin is preferably the resin 1.
In the photoresist composition, the photoacid generator may be a photoacid generator conventional in the art, and preferably a compound having the formula (I):
X + Y -
(I),
In the photoresist composition, the solvent may be any known solvent conventionally used in photoresists, especially chemically amplified photoresist compositions. The solvent is preferably one or more of a ketone solvent (e.g., cyclohexanone and/or methyl-2-n-amyl ketone), 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), a glycol 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 mono-t-butyl ether acetate, γ -butyrolactone);
more preferably one or more of ketone solvents, ether solvents and ester solvents, for example one or more of cyclohexanone, ethylene glycol monoethyl ether and gamma-butyrolactone.
In the photoresist composition, the quencher may be a quencher conventional in the art, preferably one or more of amine-containing compounds (e.g., primary, secondary and tertiary amine compounds, specifically amine compounds having hydroxyl, ether, ester, lactone, cyano or sulfonate ester groups), sulfonates and carboxylates, more preferably sulfonates, further preferably compounds of formula Q1 and/or compounds of formula Q2 as follows, more preferably compounds of Q1;
protection with amine-containing compounds is effective, particularly when the photoresist composition also includes a base labile component.
The amount of the surfactant in the photoresist composition may be that which is conventional in the art for such photoresists, and is preferably 0.1 to 0.2 parts, for example 0.15 parts, by weight.
In the photoresist composition, the surfactant may be a surfactant conventional in the art (a surfactant insoluble or substantially insoluble in water and soluble in an alkaline developer, and/or a surfactant insoluble or substantially insoluble in water and an alkaline developer), preferably one or more of FC-4430 (from 3M), S-381 (from AGC Seimi chemical), E1004 (from Air Products), KH-20 and KH-30 (from Asahi Glass), more preferably KH-20 and/or KH-30, preferably KH-30.
In some embodiments, the photoresist composition comprises: the photo-acid generator is One or more of;
the solvent is one or more of cyclohexanone (S1), ethylene glycol monoethyl ether (S2) and gamma-butyrolactone (S3);
The surfactant is KH-20 and/or KH-30;
preferably, the resin is the resin 1;
The surfactant is KH-30.
In some embodiments, the photoresist composition is prepared from the following raw materials in parts by weight: a resin as described above (including the kind and part of the resin), a photoacid generator as described above (including the kind and part of the photoacid generator), a solvent as described above (including the kind and part of the solvent), a quencher as described above (including the kind and part of the quencher), and a surfactant as described above (including the kind and part of the surfactant).
In some embodiments, the photoresist composition is any one of the following photoresist compositions prepared from the following raw materials in parts by weight:
photoresist composition 1:85 parts of resin 1, 7 parts of compound shown as a formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 2:75 parts of the resin 1, 1 part of the compound shown as the formula X1Y1, 1000 parts of cyclohexanone (S1), 0.5 part of the compound shown as the formula Q1 and 0.1 part of KH-30;
photoresist composition 3:80 parts of resin 1, 3 parts of compound shown as a formula X1Y1, 1200 parts of cyclohexanone (S1), 0.8 part of compound shown as a formula Q1 and 0.12 part of KH-30;
photoresist composition 4:90 parts of resin 1, 5 parts of compound shown as a formula X1Y1, 1600 parts of cyclohexanone (S1), 1.5 parts of compound shown as a formula Q1 and 0.16 part of KH-30;
photoresist composition 5:95 parts of the resin 1, 10 parts of the compound shown in the formula X1Y1, 2000 parts of cyclohexanone, 3 parts of the compound shown in the formula Q1 and 0.2 part of KH-30;
photoresist composition 6:85 parts of resin 1, 7 parts of compound shown as a formula X1Y3, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 7:85 parts of resin 1, 7 parts of compound shown as a formula X2Y5, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 8:85 parts of resin 1, 7 parts of compound shown as a formula X3Y6, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 9:85 parts of resin 1, 7 parts of compound shown as a formula X4Y4, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 10:85 parts of resin 1, 7 parts of compound shown as a formula X5Y8, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 11:85 parts of resin 1, 7 parts of compound shown as a formula X1Y8, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 12:85 parts of resin 1, 7 parts of compound shown as a formula X2Y7, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 13:85 parts of the resin 1, 7 parts of the compound shown as the formula X1Y1, 1500 parts of ethylene glycol monoethyl ether (S2), 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 14:85 parts of the resin 1, 7 parts of the compound shown as the formula X1Y1, 1500 parts of gamma-butyrolactone (S3), 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 15:85 parts of resin 1, 7 parts of compound shown as a formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q2 and 0.15 part of KH-30;
photoresist composition 16:85 parts of the resin 1, 7 parts of the compound shown as the formula X1Y1, 1500 parts of gamma-butyrolactone (S3), 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-20;
photoresist composition 17:85 parts of resin 2, 7 parts of compound shown as a formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 18:85 parts of resin 3, 7 parts of compound shown as a formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 19:85 parts of the resin 4, 7 parts of the compound shown as the formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 20:85 parts of resin 5, 7 parts of compound shown as a formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 21:85 parts of resin 6, 7 parts of compound shown as a formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 22:85 parts of the resin 7, 7 parts of the compound shown as the formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 23:85 parts of resin 8, 7 parts of compound shown as a formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30.
The ArF dry lithography preferably includes the steps of:
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 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 for integrated circuit manufacturing (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 method may be a conventional coating method 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, for example, 60 to 200 ℃.
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, 100nm.
In S2, the exposure is performed under conventional operations used in the art for forming a lithographic pattern, such as high-energy radiation (e.g., krF excimer laser), arF excimer laser (e.g., exposure in ArF excimer laser stepper (Nikon corp., NA = 0.68), or EUV), wherein the dose of the exposure may be 1-200mJ/cm 2 (e.g., 10-100mJ/cm 2 ) (ii) a Further, for example, electron beam exposure is used, wherein the exposure dose may be 0.1 to 100. Mu.C/cm 2 (e.g., 0.5-50. Mu.C/cm) 2 ) (ii) a Exposure is also accomplished, for example, by an immersion lithography method in which a liquid having a refractive index of at least 1.0 (e.g., water) is provided between the projection lens and the photoresist layer.
In S3, the baking temperature may be a conventional baking temperature used in the art for forming a photolithographic pattern, such as 60-150 deg.C, such as 90-100 deg.C, and further such as 95 deg.C.
In S3, the baking time may be a conventional baking time used in the art for forming a photolithographic pattern, such as 1-5 minutes, and further such as 1 minute.
In S4, the developing method may be a conventional developing method used in the art for forming a photolithographic pattern, and is preferably one or more of dipping, spin immersion, and spraying, for example, spin immersion.
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 concentration of the alkaline aqueous solution may be 0.1 to 5wt%, preferably 2 to 3wt% of tetramethylammonium hydroxide (TMAH) aqueous solution.
The organic solvent is preferably 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, isopentyl 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, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, benzyl acetate, methyl phenylacetate, benzyl formate, ethyl 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, preferably 10 to 30 ℃, for example, room temperature.
In S4, the developing time may be a conventional developing time used in the art for forming a photolithographic pattern, for example, 0.1 to 3 minutes, for example, 0.5 to 2 minutes.
Any desired step may be added to the pattern forming method. For example, after the photoresist layer is formed, a step of rinsing with pure water (post-soaking) may be introduced to extract an acid generator or the like from the film surface or wash off particles. After exposure, a step of rinsing (after soaking) may be introduced to remove any water remaining on the film after exposure.
The invention also provides a preparation method of the resin, which comprises the following steps: polymerizing 40-50 parts by weight of monomer A, 0.5-5 parts by weight of monomer B, 0.25-2.5 parts by weight of monomer C and 0.25-2.5 parts by weight of monomer D in an organic solvent to obtain the resin;
R 1 、R 2 、R 3 、R 4 、R 5 and R 6 The definitions of (A) and (B) are the same as described above;
the parts of the monomer A, the parts of the monomer B, the parts of the monomer C and the parts of the monomer D are the same as those described above.
The conditions and operations of the polymerization reaction may be those conventional in the art for such reactions, with the following conditions and operations being particularly preferred in the present invention:
in the polymerization reaction, the weight ratio of the total weight of the monomer a, the monomer B, the monomer C and the monomer D to the organic solvent is preferably 0.40 to 1.2, for example 0.47.
In the polymerization reaction, the organic solvent is preferably one or more of an aromatic hydrocarbon solvent (e.g., toluene or benzene), an ether solvent (e.g., tetrahydrofuran (THF), diethyl ether or dioxane), methyl Ethyl Ketone (MEK), propylene Glycol Monomethyl Ether Acetate (PGMEA) and γ -butyrolactone, for example, propylene glycol monomethyl ether acetate.
The polymerization is preferably initiated in the presence of a free-radical initiator or by means of heat, for example by means of heat.
When the polymerization is initiated in the presence of a free radical initiator, the free radical initiator is preferably one or more of 2,2 '-Azobisisobutyronitrile (AIBN), 2,2' -azobis (2,4-dimethylvaleronitrile), 2,2-azobis (methyl 2-methylpropionate), benzoyl peroxide and lauroyl peroxide.
When the polymerization is initiated by heating, the polymerization temperature is preferably 50 to 150 ℃, more preferably 60 to 100 ℃, for example 70 ℃ in the polymerization.
In the polymerization, the time of the polymerization is preferably 2 to 6 hours, for example, 3 hours.
Preferably, the polymerization reaction comprises the following steps:
step 1: mixing the monomer A, the monomer B, the monomer C, the monomer D and propylene glycol monomethyl ether acetate to obtain a mixture;
the weight ratio of the total weight of monomer a, monomer B, monomer C, and monomer D to the propylene glycol monomethyl ether acetate is from 0.6;
step 2: carrying out polymerization reaction on the mixture obtained in the step 1 in propylene glycol monomethyl ether acetate to obtain the resin;
the weight ratio of the mixture to the propylene glycol monomethyl ether acetate is 3:1-5:1 (e.g., 4:1); the polymerization temperature is 60 to 100 deg.C (e.g., 70 deg.C).
In step 2, the mixture obtained in step 1 is preferably added dropwise (at a rate of 20 to 40 g/hr, for example, 30 g/hr) to propylene glycol monomethyl ether acetate to carry out polymerization.
In the polymerization reaction, any known chain transfer agent (e.g., dodecanethiol or 2-mercaptoethanol) may be added for the purpose of controlling the molecular weight. The amount of the chain transfer agent added is preferably 0.01 to 10mol% (the amount of the chain transfer agent may be based on the total moles of the monomers to be polymerized).
After the polymerization reaction is finished, the post-treatment of the polymerization reaction is preferably as follows: cooling, precipitation of solid (e.g. addition of methanol to precipitate solid), filtration and drying (e.g. vacuum drying at 40 ℃ for 24 hours).
The invention also provides a resin prepared by the preparation method of the resin.
The invention also provides a photoresist composition, which is prepared from the following raw materials in parts by weight: 75 to 95 parts (e.g., 85 parts or 90 parts) of a resin, 1.0 to 10 parts (e.g., 3 parts, 5 parts or 7 parts) of a photoacid generator, 1000 to 2000 parts (e.g., 1200 parts, 1600 parts or 1500 parts) of a solvent, 0.5 to 3.0 parts (e.g., 0.8 parts or 1.5 parts) of a quencher and a surfactant;
the resin, the photoacid generator, the solvent, the quencher and the surfactant are as described above (including species and parts).
The invention provides a preparation method of the photoresist composition, which comprises the following steps: and (3) uniformly mixing all the components in the photoresist composition.
In the method for preparing the photoresist composition, after the mixing, a filtering step can be further included. 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 above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
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 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 scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples, the operation temperature is not specifically limited, and all of the operations are carried out at room temperature. The room temperature means 10-30 ℃.
Examples 1-8 and comparative examples 1-8 resins 1-8 and comparative resins 1-8 preparation
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 to 30g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) over 5 hours 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 resins 1 to 8 and comparative resins 1 to 8 as powder solids.
TABLE 1
Preparation of photoresists 1-23 of examples 9-32 and comparative photoresists 1-23
The materials for photoresists 1-23 of the invention and comparative photoresists are listed in table 2.
According to the formulation shown in Table 3, solid components were added to the liquid components and stirred uniformly, and the photoresists of examples 1 to 23 and comparative examples 1 to 23 were prepared in the form of solutions by filtering through a filter having a pore size of 0.2. Mu.m.
TABLE 2
TABLE 3
Application and effects embodiments
ArF Dry 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 on a hot plate at 200 ℃ for 60 seconds to form a photoresist layer 100nm thick.
Exposure was performed in an ArF excimer laser stepper (Nikon corp., NA = 0.68). The photoresist layer was baked (PEB) at a temperature of 95 ℃ for 60 seconds. After PEB, the developer in table 4 was injected from the developing nozzle while the wafer was spun at 30rpm for 3 seconds, which was followed by static immersion development for 27 seconds. Hole patterns with a pitch of 100nm were formed.
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 exposure doses with 50nm hole diameters (mJ/cm) at a pitch of 100nm 2 ) And is 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 better DOF margins.
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 which 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 delay, PPD =0 h), the wafer was development immersed in the developer for 30 seconds to form a hole pattern having a diameter of 50nm and a pitch of 100nm. In another run, the wafer was held for 6 hours after PEB (PPD =6 h) 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 value 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 PPD6h was taken as the CD shrinkage due to PPD (. DELTA.PPD CD).
The effects of photoresists P1-P23 prepared from examples 9-32 and photoresists CP1-CP23 prepared from comparative photoresists 9-23 are shown in Table 4.
The developers used in Table 4 were n-butyl acetate (D1), 2-heptanone (D2) and methyl benzoate (D3).
TABLE 4
As can be seen from the above table, the photoresist composition within the scope of the present invention shows improved DOF and CDU and reduced CD shrinkage (less CD change) due to PPD, as compared to the photoresist composition of the comparative example. Particularly, the photoresist containing the resin 1 of the present invention has a significantly reduced amount of CD shrinkage as compared with the photoresist containing the resins 2 to 8.
Claims (10)
1. An application of a photoresist composition in ArF dry method photoetching;
the photoresist composition is prepared from the following raw materials in parts by weight: 75-95 parts of resin, 1.0-10 parts of photoacid generator, 1000-2000 parts of solvent, 0.5-3.0 parts of quencher and surfactant;
the resin is obtained by polymerizing the following monomers in parts by weight: 40-50 parts of monomer A, 0.5-5 parts of monomer B, 0.25-2.5 parts of monomer C and 0.25-2.5 parts of monomer D;
wherein R is 1 Is C 1-10 Alkyl groups of (a);
R 2 is H or C 1-10 Alkyl groups of (a);
R 3 is C 1-10 Alkyl groups of (a);
R 4 is C 2-4 Alkenyl of (a);
R 5 and R 6 Independently is H or C 1-5 Alkyl group of (1).
2. Use according to claim 1, wherein the resin satisfies one or more of the following conditions:
(1)R 1 in (b), the C 1-10 Alkyl of (A) is C 1-5 Preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, for example methyl;
(2)R 2 in (b), the C 1-10 Alkyl of (A) is C 1-5 Preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, for example methyl;
(3)R 3 in (b), the C 1-10 Alkyl of (A) is C 1-5 Preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, for example methyl;
(4)R 4 in (b), the C 2-4 Alkenyl of (A) is C 2-3 Alkenyl of (a), preferably vinyl or isopropenyl, for example isopropenyl;
(5)R 5 in (b), the C 1-5 The alkyl group of (b) is preferably a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl group, for example a methyl group.
3. Use according to claim 1, wherein the resin satisfies one or more of the following conditions:
(4) The part of the monomer A is 42.5-45;
(5) The part of the monomer B is 2.5-5 parts, such as 3 parts;
(6) The portion of the monomer C is 0.5 to 1.25 portions, such as 0.75 portion;
(7) The portion of the monomer D is 0.5 to 1.25, for example 0.75 or 1.0;
(8) The weight average molecular weight of the resin is 5000-10000, such as 5544-9568;
(9) The resin has a molecular weight distribution coefficient of 1.0 to 2.0, for example 1.5 to 2.0.
5. The use according to claim 1, wherein the resin is any one of resins 1 to 8 obtained by polymerizing the following monomers in parts by weight:
resin 1:42.5 parts of monomer A, 5 parts of monomer B, 1.25 parts of monomer C and 1.25 parts of monomer D; the weight average molecular weight is 7518, the molecular weight distribution coefficient is 1.1;
resin 2:45 parts of monomer A, 3 parts of monomer B, 0.5 part of monomer C and 0.5 part of monomer D; the weight average molecular weight is 7355, and the molecular weight distribution coefficient is 1.3;
resin 3:45 parts of monomer A, 3 parts of monomer B, 0.25 part of monomer C and 0.75 part of monomer D; the weight average molecular weight is 5544, and the molecular weight distribution coefficient is 1.1;
resin 4:45 parts of monomer A, 2.5 parts of monomer B, 1.25 parts of monomer C and 1.25 parts of monomer D; the weight average molecular weight is 6639, and the molecular weight distribution coefficient is 1.4;
resin 5:42.5 parts of monomer A, 3 parts of monomer B, 1.75 parts of monomer C and 1.75 parts of monomer D; the weight average molecular weight is 6518, and the molecular weight distribution coefficient is 1;
resin 6:50 parts of monomer A, 1 part of monomer B, 0.75 part of monomer C and 0.75 part of monomer D; the weight average molecular weight is 9568, the molecular weight distribution coefficient is 1.7;
resin 7:40 parts of monomer A, 5 parts of monomer B, 1.5 parts of monomer C and 1 part of monomer D; the weight-average molecular weight is 9131, and the molecular weight distribution coefficient is 1.6;
resin 8:46 parts of monomer A, 2.5 parts of monomer B, 0.75 part of monomer C and 0.75 part of monomer D; the weight average molecular weight is 6736, the molecular weight distribution coefficient is 2;
6. Use according to any one of claims 1 to 5, wherein the resin is prepared by: and carrying out polymerization reaction on the monomer A, the monomer B, the monomer C and the monomer D in an organic solvent to obtain the resin.
7. Use according to claim 6, wherein the resin satisfies one or more of the following conditions:
(1) The weight ratio of the total weight of said monomer a, said monomer B, said monomer C and said monomer D to said organic solvent is preferably from 0.40;
(2) In the polymerization reaction, the organic solvent is one or more of aromatic hydrocarbon solvents, ether solvents, methyl ethyl ketone, propylene glycol monomethyl ether acetate and gamma-butyrolactone, such as propylene glycol monomethyl ether acetate;
(3) The polymerization reaction is initiated in the presence of a free radical initiator or by means of heating; when the polymerization is initiated by heating, the polymerization temperature is preferably 50 to 150 deg.C, more preferably 60 to 100 deg.C, for example 70 deg.C.
8. The use of claim 1, wherein the photoresist composition satisfies one or more of the following conditions:
(1) The photoresist composition, wherein the resin is the resin 1 according to claim 6;
(2) In the photoresist composition, the photoacid generator is a compound having the formula (I):
X + Y -
(Ⅰ),
(3) In the photoresist composition, the solvent is one or more of a ketone solvent, a monohydric alcohol solvent, a dihydric alcohol solvent, an ether solvent and an ester solvent, and is further preferably one or more of cyclohexanone, ethylene glycol monoethyl ether and gamma-butyrolactone;
(4) In the photoresist composition, the quencher is one or more of amine-containing compound, sulfonate and carboxylate, preferably sulfonate, further preferably the compound of formula Q1 and/or the compound of formula Q2, and further more preferably the compound of formula Q1;
(5) In the photoresist composition, the surfactant is 0.1-0.2 part, such as 0.15 part by weight;
(6) The surfactant is one or more of FC-4430, S-381, E1004, KH-20 and KH-30, preferably KH-20 and/or KH-30, more preferably KH-30.
9. The use of claim 8, wherein the photoresist composition is a solution of scheme 1 or scheme 2:
scheme 1:
the solvent is one or more of cyclohexanone, ethylene glycol monoethyl ether and gamma-butyrolactone;
The surfactant is KH-20 and/or KH-30;
preferably, the resin is the resin 1;
The surfactant is KH-30;
scheme 2:
the photoresist composition is prepared from the following raw materials: said resin, said photoacid generator, said solvent, said quencher, and said surfactant;
wherein, the kinds and parts of the resin, the kinds and parts of the photoacid generator, the solvents, the quenchers and the surfactants are as defined in claim 8;
preferably, the photoresist composition is any one prepared from the following components in parts by weight:
photoresist composition 1:85 parts of resin 1, 7 parts of the compound shown as the formula X1Y1, 1500 parts of cyclohexanone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 2:75 parts of resin 1, 1 part of the compound shown as the formula X1Y1, 1000 parts of cyclohexanone, 0.5 part of the compound shown as the formula Q1 and 0.1 part of KH-30;
photoresist composition 3:80 parts of resin 1, 3 parts of the compound shown as the formula X1Y1, 1200 parts of cyclohexanone, 0.8 part of the compound shown as the formula Q1 and 0.12 part of KH-30;
photoresist composition 4:90 parts of resin 1, 5 parts of the compound shown as the formula X1Y1, 1600 parts of cyclohexanone, 1.5 parts of the compound shown as the formula Q1 and 0.16 part of KH-30;
photoresist composition 5:95 parts of resin 1, 10 parts of the compound shown in the formula X1Y1, 2000 parts of cyclohexanone, 3 parts of the compound shown in the formula Q1 and 0.2 part of KH-30;
photoresist composition 6:85 parts of resin 1, 7 parts of the compound shown as the formula X1Y3, 1500 parts of cyclohexanone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 7:85 parts of resin 1, 7 parts of the compound shown as the formula X2Y5, 1500 parts of cyclohexanone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 8:85 parts of resin 1, 7 parts of the compound shown as the formula X3Y6, 1500 parts of cyclohexanone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 9:85 parts of resin 1, 7 parts of the compound shown as the formula X4Y4, 1500 parts of cyclohexanone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 10:85 parts of resin 1, 7 parts of the compound shown as the formula X5Y8, 1500 parts of cyclohexanone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 11:85 parts of resin 1, 7 parts of the compound shown as the formula X1Y8, 1500 parts of cyclohexanone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 12:85 parts of resin 1, 7 parts of the compound shown as the formula X2Y7, 1500 parts of cyclohexanone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 13:85 parts of resin 1, 7 parts of the compound shown as the formula X1Y1, 1500 parts of ethylene glycol monoethyl ether, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 14:85 parts of resin 1, 7 parts of the compound shown as the formula X1Y1, 1500 parts of gamma-butyrolactone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 15:85 parts of resin 1, 7 parts of the compound shown as the formula X1Y1, 1500 parts of cyclohexanone, 2 parts of the compound shown as the formula Q2 and 0.15 part of KH-30;
photoresist composition 16:85 parts of resin 1, 7 parts of the compound shown as the formula X1Y1, 1500 parts of gamma-butyrolactone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-20;
photoresist composition 17:85 parts of resin 2, 7 parts of the compound shown as the formula X1Y1, 1500 parts of cyclohexanone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 18:85 parts of resin 3, 7 parts of the compound shown as the formula X1Y1, 1500 parts of cyclohexanone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 19:85 parts of resin 4, 7 parts of the compound shown as the formula X1Y1, 1500 parts of cyclohexanone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 20:85 parts of resin 5, 7 parts of the compound shown as the formula X1Y1, 1500 parts of cyclohexanone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 21:85 parts of resin 6, 7 parts of the compound shown as the formula X1Y1, 1500 parts of cyclohexanone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 22:85 parts of resin 7, 7 parts of the compound shown as the formula X1Y1, 1500 parts of cyclohexanone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
photoresist composition 23:85 parts of resin 8, 7 parts of the compound shown as the formula X1Y1, 1500 parts of cyclohexanone, 2 parts of the compound shown as the formula Q1 and 0.15 part of KH-30;
wherein said resin 1, said resin 2, said resin 3, said resin 4, said resin 5, said resin 6, said resin 7, and said resin 8 are as defined in claim 5.
10. The use according to claim 1, wherein the ArF dry lithography comprises the steps of:
s1: coating the photoresist composition on the surface of a base material, and baking to form a photoresist layer; the baking temperature is preferably 60-200 ℃; the baking time is preferably 1-10 minutes; the thickness of the photoresist layer is preferably 0.05-2 μm, for example 100nm;
s2: exposing the photoresist layer formed in the step S1; the exposure mode is preferably ArF excimer laser;
s3: baking the photoresist layer exposed in the step S2; the baking temperature is preferably 60-150 ℃, such as 90-100 ℃, and such as 95 ℃; the baking time is preferably 1-10 minutes;
s4: developing the photoresist layer baked in the step S3; the developer of the development is an aqueous alkaline solution and/or an organic solvent, such as an aqueous solution of 2 to 3wt% tetramethylammonium hydroxide.
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