CN113219789B - Star-shaped ArF photoresist film-forming resin, preparation method thereof and photoresist composition - Google Patents
Star-shaped ArF photoresist film-forming resin, preparation method thereof and photoresist composition Download PDFInfo
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- 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
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Abstract
The invention discloses a star ArF photoresist film-forming resin, a preparation method thereof and a photoresist composition, wherein the film-forming resin comprises a random polymer structure shown as the following formula I; wherein n, m, x, y and z are molar ratios of the monomers，0＜n≤0.3，0＜m≤0.8，0＜x≤0.2，0＜y≤0.3，n+m+x+y＝1；R 1 、R 2 、R 3 、R 4 And R 5 Is H, CH 3 Or CH 2 CH 3 . A photoresist composition comprises the film-forming resin and an organic solvent, wherein the film-forming resin accounts for 5-30%, and the balance is the organic solvent. The invention introduces the photoacid generator and the acid diffusion inhibitor into the film-forming resin simultaneously, and can well reduce the photoacid diffusion range, thereby improving the sensitivity and resolution of the photoresist.
Description
Technical Field
The invention belongs to the technical field of semiconductor photoresist microelectronic chemistry, and relates to star-shaped resin for photoresist, a preparation method thereof and a photoresist composition.
Background
Photoresist, also known as photoresist, refers to a resist film material whose solubility changes under the irradiation or radiation of ultraviolet light, electron beam, ion beam, X-ray, etc. The photoresist occupies a special position in the integrated circuit chip manufacturing process, and the higher the integration level of the integrated circuit, the higher the requirement on the photoresist.
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. At present, commercial photoresist materials independently developed in China mainly comprise phenolic resin, poly-p-hydroxystyrene and the like, and are mainly used for photoetching processes of G-lines (436 nm) and I-lines (365 nm). However, the wavelength of a light source used by the current international mainstream photoetching process is 193nm, and the photoresist material has the defects of low photosensitivity, low resolution of the obtained pattern, poor etching resistance, poor contrast of the obtained pattern and the like when being used for the 193nm process.
Therefore, how to design and develop a matching material (film-forming resin) meeting the requirements of the photoresist formulation is the focus of the current photoresist product formulation development. In addition, the screening and sizing of photoresist formulations is a more worldwide problem. How to make the whole photoresist formulation have good resolution and line roughness is always the direction of important research in the industry.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a film-forming resin for photoresist, a photoresist composition and a preparation method. And then the photoresist suitable for 193nm far ultraviolet exposure wavelength is prepared.
The technical scheme of the invention is as follows:
a star ArF photoresist film-forming resin comprising a random polymer structure as shown below:
wherein n, m, x, y and z are the molar ratio of the monomers, n is more than 0 and less than or equal to 0.3, m is more than 0 and less than or equal to 0.5, x is more than 0 and less than or equal to 0.2, y is more than 0 and less than or equal to 0.8, z is more than 0 and less than or equal to 0.1, n + m + x + y + z =1; r 1 、R 2 、R 3 、R 4 And R 5 Is H, CH 3 Or CH 2 CH 3 。
Preferably, the R is prepared by copolymerizing monomers I, II, III, IV and V, wherein the monomers I, II, III, IV and V are respectively as follows:
wherein R is 1 、R 2 、R 3 、R 4 And R 5 Is H, CH 3 Or CH 2 CH 3 。
Preferably, the method comprises the following steps:
(1) Under inert atmosphere, adding the monomers I, II, III and IV, an initiator, cuprous halide and a ligand into a solvent, and uniformly stirring; then, adding the monomer V, stirring uniformly, and reacting;
(2) After the reaction is finished, settling in methanol or ether, filtering, drying a filter cake, dissolving the filter cake in a solvent, precipitating again in methanol or ether, filtering, and drying the filter cake to obtain a crude product of the film-forming resin;
(4) Dissolving the crude product of the film-forming resin in an organic solvent containing Ethylene Diamine Tetraacetic Acid (EDTA), separating by column chromatography (multiple resin columns), removing copper ions, settling filtered solution in methanol or diethyl ether, filtering, and drying filter cakes to obtain the film-forming resin;
the initiator is as follows:
preferably, the weight ratio of the monomers I, II, III, IV and V in the step (1) is as follows: (10-30): (1-20): (1-20): (30-80): (0.001-10); the molar ratio of the initiator to the cuprous halide and the ligand is as follows: (1-5): (5-20): (5-20); the mass volume ratio of the total monomer amount to the solvent is 100: (20-2000) g/mL.
Preferably, the cuprous halide in the step (1) is one or two of cuprous bromide and cuprous chloride; the ligand is one or two of bipyridine and Pentamethyldiethylenetriamine (PMEDTA).
Preferably, the solvent in steps (1), (2) and (3) is one or more of dichloromethane, chloroform, tetrahydrofuran, toluene, acetone, dioxane, dichloroethane, trichloroethane, xylene and methyl ethyl ketone.
Preferably, the reaction temperature in the step (2) is 60-120 ℃, and the reaction time is 1-8 hours.
Preferably, the reaction temperature in the step (2) is 80-110 ℃, and the reaction time is 2-6 hours.
The photoresist composition comprises 5-30% of film-forming resin and organic solvent by mass percent, and the balance is organic solvent.
Preferably, the organic solvent is one or more of anisole, propylene glycol monoalkyl ether, toluene, chlorobenzene, benzene, carbon tetrachloride, chloroform, dichloromethane, hexane, butyl acetate, neopentyl acetate, ethyl lactate, propylene glycol alkyl ether acetate, ethyl acetate, butyl acetate, dimethylformamide, cyclopentanone, cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone.
Preferably, the film-forming resin, the acid diffusion inhibitor and the organic solvent are mixed according to the formula proportion and are vibrated for 12 to 96 hours in a dark place to be fully dissolved; the photoresist solution was then filtered through a 0.5 micron and below filter to obtain a photoresist composition.
Compared with the prior art, the invention has the following beneficial effects:
(1) Compared with a linear structure, the star structure has better film forming property and adhesiveness.
(2) The photoacid generator and the acid diffusion inhibitor are simultaneously introduced into the film-forming resin, the photoacid generator and the acid diffusion inhibitor can be well controlled to be uniformly distributed in a film of the film-forming resin, and the photoacid generator and the acid diffusion inhibitor in the film-forming resin can normally play a role, so that the photoacid diffusion range can be well reduced, and the sensitivity of the photoresist (less than or equal to 38 mJ/cm) is improved, namely the sensitivity of the photoresist (less than or equal to 38 mJ/cm) 2 ) And the resolution (less than or equal to 90 nm). In addition, the film forming ability and adhesion of the photoresist can be improved due to the introduction of each monomer.
Drawings
FIG. 1 is a photo-lithographic pattern of a photoresist of example 6 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
10g of cholate methacrylate (monomer 1, formula II), 20g of butyrolactone methacrylate (monomer 2, formula III), 10g of sulfonium methacrylate ester (monomer 3, formula IV), 60g of adamantyl methacrylate (monomer 4, formula V), 2mmol (1.45 g) of initiator (formula VII), 8mmol of CuBr, and 8mm in nitrogen gasAdding ol of PMEDTA and 200mL of dioxane into a 500mL reaction bottle, and fully stirring; then, 1g of dimethylethylamine-based methacrylate (monomer 5, formula VI) was added thereto and sufficiently stirred. The reaction was heated to 80 ℃ and held for 5 hours. Then cooled to room temperature, precipitated in ether, filtered and the filter cake dried. Dissolving the filter cake in tetrahydrofuran, precipitating in methanol, filtering, drying the filter cake, and repeating the process twice to obtain the crude product of the film-forming resin. Dissolving the crude product in tetrahydrofuran containing EDTA, passing through ion exchange resin column for 5 times, removing copper ions, precipitating, filtering, and drying the filter cake to obtain the film-forming resin. The weight average molecular weight M of the single chain of the star-shaped film-forming resin is measured by GPC w 8800, the star film-forming resin had a molecular weight distribution PDI of 1.50.
Example 2
30g of acrylic cholate (monomer 1, formula II), 10g of acrylic butyrolactone (monomer 2, formula III), 5g of sulfonium acrylate (monomer 3, formula IV), 55g of adamantyl acrylate (monomer 4, formula V), 4mmol (2.9 g) of an initiator (formula VI), 16mmol of CuBr, 16mmol of PMEDTA, and 200mL of dioxane were charged into a 500mL reaction flask and sufficiently stirred while being filled with nitrogen; then, 5g of dimethylethylamine-based methacrylate (monomer 5, formula VI) was added and stirred well. The reaction was heated to 110 ℃ for 3 hours. Then cooled to room temperature, precipitated in ether, filtered and the filter cake dried. Dissolving the filter cake in tetrahydrofuran, precipitating in methanol, filtering, drying the filter cake, and repeating the process twice to obtain a crude product of the film-forming resin. Dissolving the crude product in tetrahydrofuran containing EDTA, passing through ion exchange resin column for 5 times, removing copper ions, precipitating, filtering, and drying the filter cake to obtain the film-forming resin. The weight average molecular weight M of the single chain of the star-shaped film-forming resin is measured by GPC w 5500, and the molecular weight distribution PDI of the star-shaped film-forming resin is 1.65.
Example 3
Under a nitrogen-filled condition, 10g of methacrylic cholate (monomer 1, formula II), 10g of acrylic butyrolactone(monomer 2, formula III), 10g of sulfonium methacrylate (monomer 3, formula IV), 70g of adamantyl methacrylate (monomer 4, formula V), 3mmol (2.17 g) of initiator (formula VI), 12mmol of CuBr, 12mmol of PMEDTA and 200mL of methyl ethyl ketone were charged into a 500mL reaction flask and stirred well; then, 0.5g of dimethylethylamine methacrylate (monomer 5, formula VI) was added thereto and sufficiently stirred. The reaction was heated to 90 ℃ for 5 hours. Then cooled to room temperature, precipitated in ether, filtered and the filter cake dried. Dissolving the filter cake in tetrahydrofuran, precipitating in methanol, filtering, drying the filter cake, and repeating the process twice to obtain a crude product of the film-forming resin. Dissolving the crude product in tetrahydrofuran containing EDTA, passing through ion exchange resin column for 5 times, removing copper ions, precipitating, filtering, and drying the filter cake to obtain the film-forming resin. The weight average molecular weight M of the film-forming resin was measured by GPC w It was 5300 and had a molecular weight distribution PDI of 1.39.
Example 4
A positive chemical amplification type photoresist comprises the following components in percentage by weight:
the resin was the film forming resin of example 1; the solvent is propylene glycol monomethyl ether acetate.
The specific formula is prepared as follows:
25g of the film-forming resin and 75g of propylene glycol monomethyl ether acetate were put into a 100mL light-shielding glass bottle. The mixture was fully dissolved by shaking at room temperature for 12 hours. The photoresist solution was filtered through 0.5 micron, 0.2 micron and 0.02 micron filters in sequence. Finally, a photolithography experiment was performed.
Example 5
A positive chemical amplification type photoresist comprises the following formula:
the resin was the film-forming resin of example 2; the solvent is neopentyl acetate.
The specific formula is prepared as follows:
10g of the film-forming resin and 90g of neopentyl acetate were put into a 100mL light-shielding glass bottle. The mixture was fully dissolved by shaking at room temperature for 24 hours. The photoresist solution was filtered through 0.5 micron, 0.22 micron and 0.02 micron filters in sequence. Finally, a photolithography experiment was performed.
Example 6
A positive chemical amplification type photoresist comprises the following components in percentage by weight:
the resin was the film-forming resin of example 3; the solvent is propylene glycol monomethyl ether acetate.
The specific formula is prepared as follows:
20g of the acid-reactive and photoacid-generating film-forming resin, 80g of propylene glycol monomethyl ether acetate were added to a 200mL light-shielding glass bottle. The mixture was fully dissolved by shaking at room temperature for 12 hours. The photoresist solution was filtered through 0.5 micron, 0.2 micron and 0.02 micron filters in sequence. Finally, a photolithography experiment was performed.
Example 7
The photoresists prepared in examples 4 to 6 were used for the preparation of photolithographic films by the following specific operations: spin-coating the prepared photoresist on a 12-inch silicon plate, and baking at 90 ℃/120s to obtain a photoresist layer with the thickness of 75-80 nm. After obtaining the photoresist layer, using 193 photoetching machine to perform L/S pattern exposure, wherein the exposure energy range is 20-45mJ/cm 2 . After the completion of exposure, the resist film was exposed on a hot stage at 120 ℃/60s and then baked, and the exposed resist film layer was developed for 30s with an alkaline aqueous developer (2.38 mass% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution)), and then rinsed with ultrapure water to obtain a resist pattern. As can be seen from FIG. 1, the edges of the independent lines of the photoresist are uniform, and the phenomena of adhesion and back glue do not occur.
TABLE 1 Effect of the photoresists obtained in examples 4 to 6
| Product(s) | Resolution (nm) | Sensitivity (mJ/cm) 2 ) | Adhesion property | Film forming property |
| Example 4 | 80 | 28 | Good effect | Is good |
| Example 5 | 90 | 38 | Is good | In general |
| Example 6 | 85 | 30 | Good effect | Good effect |
Adhesion test: the characterization mode accepted in the industry is to prepare the resin into photoresist, and the prepared pattern is observed by a scanning electron microscope, the phenomena of stripping and glue falling are not seen, and the adhesion is proved to be good, if the phenomena of glue falling, stripping, line deformation and the like occur, the resin is proved to be invalid.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A star ArF photoresist film-forming resin is characterized by comprising a random polymer structure shown as follows:
wherein n, m, x, y and z are the molar ratio of the monomers, n is more than 0 and less than or equal to 0.3, m is more than 0 and less than or equal to 0.5, x is more than 0 and less than or equal to 0.2, y is more than 0 and less than or equal to 0.8, z is more than 0 and less than or equal to 0.1, n +, m +, x +, y +, z =1;
the R is prepared by copolymerizing monomers I, II, III, IV and V under the action of an initiator, wherein the monomers I, II, III, IV and V are respectively as follows:
wherein R is 1 、R 2 、R 3 、R 4 And R 5 Is H, CH 3 Or CH 2 CH 3 ；
The weight ratio of the monomers I, II, III, IV and V is as follows: (10-30): (1-20): (1-20): (30-80): (0.001-10);
the initiator is as follows:
2. a method of preparing a film-forming resin according to claim 1, comprising the steps of:
(1) Under inert atmosphere, adding the monomers I, II, III and IV, the initiator, cuprous halide and the ligand into a solvent, and uniformly stirring; then, adding the monomer V, uniformly stirring, and reacting;
(2) After the reaction is finished, settling in methanol or ether, filtering, drying a filter cake, dissolving the filter cake in a solvent, precipitating again in methanol or ether, filtering, and drying the filter cake to obtain a crude product of the film-forming resin;
(3) Dissolving the crude product of the film-forming resin in an organic solvent containing ethylene diamine tetraacetic acid, separating by column chromatography, removing copper ions, settling filtered solution in methanol or diethyl ether, filtering, and drying a filter cake to obtain the film-forming resin.
3. The preparation method according to claim 2, wherein the molar ratio of the initiator to the cuprous halide and the ligand in the step (1) is as follows: (1-5): (5-20): (5-20); the mass volume ratio of the total monomer amount to the solvent is 100: (20-2000) g/mL.
4. The production method according to claim 2 or 3, wherein the cuprous halide of step (1) is one or both of cuprous bromide and cuprous chloride; the ligand is one or two of bipyridine and pentamethyl diethylenetriamine;
the solvent in the steps (1), (2) and (3) is one or more than two of dichloromethane, chloroform, tetrahydrofuran, toluene, acetone, dioxane, dichloroethane, trichloroethane, xylene and methyl ethyl ketone.
5. The method according to claim 4, wherein the reaction temperature in the step (1) is 60 to 120 ℃ and the reaction time is 1 to 8 hours.
6. The method according to claim 5, wherein the reaction temperature in the step (1) is 80 to 110 ℃ and the reaction time is 2 to 6 hours.
7. A photoresist composition, which is characterized by comprising the film-forming resin of claim 1 and an organic solvent, wherein the film-forming resin accounts for 5-30% by mass, and the rest is the organic solvent.
8. The photoresist composition of claim 7, wherein the organic solvent is one or more of anisole, propylene glycol monoalkyl ether, toluene, chlorobenzene, benzene, carbon tetrachloride, chloroform, dichloromethane, hexane, butyl acetate, neopentyl acetate, ethyl lactate, propylene glycol alkyl ether acetate, ethyl acetate, butyl acetate, dimethylformamide, cyclopentanone, cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone.
9. The process for preparing the photoresist composition according to claim 8, wherein the film-forming resin and the organic solvent are mixed according to the formulation ratio and are vibrated away from light for 12 to 96 hours to be fully dissolved; the photoresist solution was then filtered through a 0.5 micron filter or less to obtain a photoresist composition.
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