193nm photoresist film-forming resin, preparation method thereof and positive photoresist composition

Abstract

The invention discloses 193nm photoresist film-forming resin, a preparation method thereof and a positive photoresist composition, and belongs to the technical field of semiconductor microelectronic chemistry. The 193nm positive photoresist contains film-forming resin and a photoacid generator, and the film-forming resin contains the following components in percentage by mole: 5-40% of a composition unit containing a cholic acid derivative; 10%-50% of a constituent unit containing a polar group; 10%-40% of a unit containing an acid-sensitive group; the cholic acid derivative unit is at least one compound conforming to a chemical general formula (I); the constituent unit of the polar group refers to at least one compound conforming to a chemical general formula (II); the acid-sensitive group unit is at least one compound conforming to a chemical general formula (III). The cholic acid-containing derivative is introduced as a film-forming resin unit, so that the adhesiveness, the dissolution inhibition effect and the graphic contrast of the film-forming resin can be improved, and the line edge roughness is reduced.

Description

technical field

[0001] The invention relates to a photoresist used in ultra-large-scale integrated circuit chips, in particular to a photoresist using 193nm deep ultraviolet single beam light as an exposure light source, and belongs to the technical field of semiconductor microelectronic chemistry. Background technique

[0002] Photoresist, also known as photoresist, refers to an etching-resistant film material whose solubility changes under irradiation or radiation of ultraviolet light, electron beam, ion beam, X-ray, etc. In recent years, with the trend of miniaturization, light weight and portability of electronic and electrical products, the integration of VLSI chips has become higher and higher, and the wavelength of the lithography exposure light source of semiconductor chips has been continuously shortened, from 365nm (i-line) Developed to 248nm (KrF), 193nm (ArF), 13nm (EUV). In order to improve the sensitivity of the photoresist, the current mainstream KrF, ArF, an...

Examples

Embodiment 1

[0033] In a nitrogen-filled state, 10 g of lithocholic acid methacrylate (monomer I, formula I) protected by T-boc, 60 g of valerolactone methacrylate (monomer II, formula II), 30 g of methyl methacrylate were mixed with Add adamantyl acrylate (monomer III, formula III) and 500 mL of tetrahydrofuran into a 1000 mL four-neck reaction flask, then add 2 g of azobisisobutyronitrile (AIBN) dropwise, stir well, heat to 60-70 °C, keep After 3 hours, the reaction was quickly quenched with an ice bath and cooled to room temperature, precipitated in ether, filtered through a Buchner funnel, and the filter cake was dried. The filter cake was dissolved in tetrahydrofuran, precipitated in methanol again, filtered and placed in a vacuum drying oven at 50°C for 48 hours to obtain the photoresist film-forming resin 1#, and the weight-average molecular weight Mw of the film-forming resin was measured by GPC =27300, molecular weight distribution PDI=1.87.

[0034]

Embodiment 2

[0036] In a nitrogen-filled state, 20 g of lithocholic acid methacrylate (monomer I, formula I) protected by T-boc, 50 g of valerolactone methacrylate (monomer II, formula II), 30 g of 3- Hydroxyadamantanol methacrylate (monomer III, formula III) and 500 mL of tetrahydrofuran were added to a 1000 mL four-neck reaction flask, and then 2 g of azobisisobutyronitrile (AIBN) was added dropwise, fully stirred, and heated to 60~ 70° C. for 4 hours, then the reaction was quickly stopped with an ice bath and cooled to room temperature, precipitated in ether, filtered with a Buchner funnel, and the filter cake was dried. The filter cake was dissolved in tetrahydrofuran, precipitated in methanol again, filtered and then placed in a vacuum drying oven at 50°C for 48 hours to obtain the photoresist film-forming resin 2#. The weight-average molecular weight Mw of the film-forming resin was measured by GPC =28700, molecular weight distribution PDI=1.75.

[0037]

Embodiment 3

[0039] In the state of being filled with nitrogen, 30 g of chenodeoxycholate methacrylate (monomer I, formula I) protected by T-boc, 40 g of mevalonolide methacrylate (monomer II, formula II) were mixed together. ), 30g of 3-hydroxyadamantanol methacrylate (monomer III, formula III) and 500mL of methyl ethyl ketone were added to a 1000mL four-neck reaction flask, and then 2g of azobisisobutyronitrile (AIBN) was added dropwise. ), fully stirred, heated to 60 ~ 70 ℃, kept for 5 hours, and then quickly stopped the reaction with an ice bath and fell to room temperature, precipitated in ether, filtered with a Buchner funnel, and dried the filter cake. The filter cake was dissolved in methyl ethyl ketone, precipitated in methanol again, filtered and dried in a vacuum drying oven at 50°C for 48 hours to obtain the photoresist film-forming resin 3#. The weight average molecular weight Mw=31300, and the molecular weight distribution PDI=1.87.

[0040]

technical field

[0001] The invention relates to a photoresist used in ultra-large-scale integrated circuit chips, in particular to a photoresist using 193nm deep ultraviolet single beam light as an exposure light source, and belongs to the technical field of semiconductor microelectronic chemistry. Background technique

[0002] Photoresist, also known as photoresist, refers to an etching-resistant film material whose solubility changes under irradiation or radiation of ultraviolet light, electron beam, ion beam, X-ray, etc. In recent years, with the trend of miniaturization, light weight and portability of electronic and electrical products, the integration of VLSI chips has become higher and higher, and the wavelength of the lithography exposure light source of semiconductor chips has been continuously shortened, from 365nm (i-line) Developed to 248nm (KrF), 193nm (ArF), 13nm (EUV). In order to improve the sensitivity of the photoresist, the current mainstream KrF, ArF, an...

Examples

Embodiment 1

[0033] In a nitrogen-filled state, 10 g of lithocholic acid methacrylate (monomer I, formula I) protected by T-boc, 60 g of valerolactone methacrylate (monomer II, formula II), 30 g of methyl methacrylate were mixed with Add adamantyl acrylate (monomer III, formula III) and 500 mL of tetrahydrofuran into a 1000 mL four-neck reaction flask, then add 2 g of azobisisobutyronitrile (AIBN) dropwise, stir well, heat to 60-70 °C, keep After 3 hours, the reaction was quickly quenched with an ice bath and cooled to room temperature, precipitated in ether, filtered through a Buchner funnel, and the filter cake was dried. The filter cake was dissolved in tetrahydrofuran, precipitated in methanol again, filtered and placed in a vacuum drying oven at 50°C for 48 hours to obtain the photoresist film-forming resin 1#, and the weight-average molecular weight Mw of the film-forming resin was measured by GPC =27300, molecular weight distribution PDI=1.87.

[0034]

Embodiment 2

[0036] In a nitrogen-filled state, 20 g of lithocholic acid methacrylate (monomer I, formula I) protected by T-boc, 50 g of valerolactone methacrylate (monomer II, formula II), 30 g of 3- Hydroxyadamantanol methacrylate (monomer III, formula III) and 500 mL of tetrahydrofuran were added to a 1000 mL four-neck reaction flask, and then 2 g of azobisisobutyronitrile (AIBN) was added dropwise, fully stirred, and heated to 60~ 70° C. for 4 hours, then the reaction was quickly stopped with an ice bath and cooled to room temperature, precipitated in ether, filtered with a Buchner funnel, and the filter cake was dried. The filter cake was dissolved in tetrahydrofuran, precipitated in methanol again, filtered and then placed in a vacuum drying oven at 50°C for 48 hours to obtain the photoresist film-forming resin 2#. The weight-average molecular weight Mw of the film-forming resin was measured by GPC =28700, molecular weight distribution PDI=1.75.

[0037]

Embodiment 3

[0039] In the state of being filled with nitrogen, 30 g of chenodeoxycholate methacrylate (monomer I, formula I) protected by T-boc, 40 g of mevalonolide methacrylate (monomer II, formula II) were mixed together. ), 30g of 3-hydroxyadamantanol methacrylate (monomer III, formula III) and 500mL of methyl ethyl ketone were added to a 1000mL four-neck reaction flask, and then 2g of azobisisobutyronitrile (AIBN) was added dropwise. ), fully stirred, heated to 60 ~ 70 ℃, kept for 5 hours, and then quickly stopped the reaction with an ice bath and fell to room temperature, precipitated in ether, filtered with a Buchner funnel, and dried the filter cake. The filter cake was dissolved in methyl ethyl ketone, precipitated in methanol again, filtered and dried in a vacuum drying oven at 50°C for 48 hours to obtain the photoresist film-forming resin 3#. The weight average molecular weight Mw=31300, and the molecular weight distribution PDI=1.87.

[0040]

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