CN117148671A - Photoresist composed of pterene compound, and preparation method and application thereof - Google Patents

Photoresist composed of pterene compound, and preparation method and application thereof Download PDF

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Publication number
CN117148671A
CN117148671A CN202210576179.XA CN202210576179A CN117148671A CN 117148671 A CN117148671 A CN 117148671A CN 202210576179 A CN202210576179 A CN 202210576179A CN 117148671 A CN117148671 A CN 117148671A
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China
Prior art keywords
parts
pterene
photoresist composition
organic solvent
photoresist
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CN202210576179.XA
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Chinese (zh)
Inventor
方书农
王溯
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Shanghai Xinyang Semiconductor Material Co Ltd
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Shanghai Xinyang Semiconductor Material Co Ltd
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Priority to CN202210576179.XA priority Critical patent/CN117148671A/en
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor

Abstract

The invention discloses a photoresist composed of a pterene compound, a preparation method and application thereof. The photoresist composition provided by the invention comprises the following components: a pterene A shown in the following formula, a pterene B shown in the following formula, a photoacid generator, an organic solvent and an organic base. The photoresist can be used for EUV lithography, has the characteristics of high resolution, high sensitivity and high photosensitivity, and has wide application prospect.

Description

Photoresist composed of pterene compound, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photoresist, and particularly relates to a photoresist composed of a pterene compound, and a preparation method and application thereof.
Background
With the continuous development of modern semiconductor technology and the wide application of the technology in the fields of electronic equipment, communication equipment information security, entertainment equipment and the like, the technology becomes the most active technical field in the world today, and the technology is widely penetrated into various aspects of our work and life. The fabrication of integrated circuits is a core field of the semiconductor industry, and each time the integrated circuits are updated, the development history of the photolithography technique is the development history of the integrated circuits, and the level of the photolithography technique determines the fabrication level of the integrated circuits.
The principle of photoetching is that a layer of photoresist with high photosensitivity is covered on the surface of a silicon wafer, and then light rays (ultraviolet light, deep ultraviolet light and extreme ultraviolet light are generally used for irradiating the surface of the silicon wafer through a mask, and the photoresist irradiated by the light rays can react. Thereafter the irradiated/non-irradiated photoresist is washed away with a specific solvent, and the transfer of the circuit pattern from the mask to the silicon wafer is achieved. Photolithography has undergone a revolution in the contact/proximity, equi-magnification projection, reduction step projection, scanning step projection exposure modes, full spectrum exposure at exposure wavelengths from 300 to 450nm, to 436nm G-line, 365nm I-line, 248nm KrF laser, to the most widely used 193nm ArF laser, to the 13.5nm extreme ultraviolet, electron beam and x-ray currently being widely studied, with fabrication nodes from 0.5mm, 0.1mm, 90nm to 30nm, and even lower. Extreme ultraviolet lithography differs from conventional optical lithography by having an extremely short wavelength. However, most of the elements have strong absorption to the euv, so that the conventional long wavelength photoresist is not suitable for the euv lithography, and thus a new euv photoresist system needs to be developed. Photolithography is one of the most critical technologies in integrated circuit fabrication, and the successful application of each generation of photolithography greatly promotes the development of integrated circuits, so that the integrated circuits have higher integration level and lower cost. Photolithography is a process that exposes a photoresist material coated on a surface of a semiconductor substrate to transfer fine geometric patterns on a mask to the semiconductor substrate. The resolution of the lithographic patterns is higher and higher, i.e., the integrated circuit integration is higher and the critical dimensions are smaller and smaller.
Currently, the semiconductor industry is in agreement that extreme ultraviolet lithography (Extreme Ultraviolet, EUV,13.5 nm) is the next generation of lithography with great potential. The final resolution will be limited only by the material properties of the photoresist at very short wavelengths. The EUV lithography can be used to generate a circuit diagram with higher resolution, thereby greatly improving the integration density of an integrated circuit and the performance of electronic devices. Research into photoresist and photolithography processes suitable for EUV lithography is a hotspot and difficulty in lithography research.
EUV photoresists must have low absorbance, high transparency, high etch resistance, high resolution, high sensitivity, low exposure dose, high environmental stability, low outgassing, and low line edge roughness. The development of EUV photoresists has been limited by three factors: resolution, line edge roughness, and photosensitivity, which are generally in a relationship to one another. In early lithography, polymeric photoresists were most widely used, and thus polymeric photoresist systems were first applied to EUV lithography. The industry is in need of developing EUV photoresists that improve resolution.
Disclosure of Invention
The invention aims to solve the technical problems that the existing EUV photoresist has few types and poor selectivity. Thus, a photoresist composition composed of a pterene compound, a preparation method and application thereof are provided. The photoresist provided by the invention has the characteristics of high resolution, high sensitivity and high photosensitivity, and has wide application scenes.
The invention provides a photoresist composition, which comprises the following components: a pterene A shown in the following formula, a pterene B shown in the following formula, a photoacid generator, an organic solvent and an organic base;
50-70 parts of the pterene A by weight and 30-50 parts of the pterene B by weight.
In the photoresist composition, the photoacid generator may be a photoacid generator conventional in the photoresist field, for example
In the photoresist composition, the organic solvent may be an organic solvent conventional in the photoresist field, such as an ester solvent; ethyl lactate is preferred.
In the photoresist composition, the organic base may be an organic base conventional in the photoresist field, preferably an organic weak base such as trioctylamine.
In the photoresist composition, the parts by weight of the pterene a is preferably 60 parts.
In the photoresist composition, the parts by weight of the pterene B is preferably 40 parts.
In the photoresist composition, the parts by weight of the photoacid generator may be conventional in the art, for example, 1 to 10 parts, preferably 7 parts.
In the photoresist composition, the parts by weight of the organic solvent may be parts conventional in the art, for example, 1000 to 2000 parts, preferably 1500 parts.
In the photoresist composition, the organic base may be present in parts by weight as is conventional in the art, preferably 0.2 to 1 part, more preferably 0.5 part.
In a specific embodiment, the photoacid generator is 1-10 parts by weight
The organic solvent is 1000-2000 parts by weight of ethyl lactate;
the organic base is trioctylamine with the weight of 0.2-1 part.
In a specific embodiment, the photoresist composition consists of the following components: the pterene A, the pterene B, the photoacid generator, the organic solvent and the organic base;
wherein the compound A refers to the type and content of the compound A; the pterene B refers to the type and content of the pterene B; the photoacid generator refers to the type and content of the photoacid generator; the organic base refers to the kind and content of the organic base.
The photoresist composition is preferably composed of any one of the following components of pterene A, pterene B, photoacid generator, organic solvent and organic base in parts by weight;
photoresist composition 1:60 parts of the pterene A, 40 parts of the pterene B, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 2:50 parts of the pterene A, 30 parts of the pterene B, 1 part of the photoacid generator, 1000 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 3:55 parts of the pterene A, 35 parts of the pterene B, 3 parts of the photoacid generator, 1200 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 4:65 parts of the pterene A, 45 parts of the pterene B, 5 parts of the photoacid generator, 1600 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 5:70 parts of the pterene A, 50 parts of the pterene B, 10 parts of the photoacid generator, 2000 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 6:66 parts of the pterene A, 38 parts of the pterene B, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 7:62 parts of the pterene A, 46 parts of the pterene B, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 8:50 parts of the pterene A, 50 parts of the pterene B, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
in the photoresist compositions 1 to 8, the photoacid generator isThe organic solvent is ethyl lactate, and the organic base is trioctylamine.
The invention also provides a preparation method of the photoresist composition, which comprises the following steps: and uniformly mixing the components of the photoresist composition.
After the mixing, a filtering step can be further included. The filtration may be carried out in a manner conventional in the art, preferably by filtration using an ultra-high molecular weight polyethylene membrane. The pore diameter of the ultra-high molecular weight polyethylene film is preferably 0.1 μm.
The invention also provides a method for forming patterns by using the photoetching technology, which comprises the following steps:
step 1: coating the photoresist composition on the surface of a substrate, and baking to obtain a photoresist layer;
step 2: and (3) exposing, baking and developing the photoresist layer obtained in the step (1) to obtain a photoresist pattern.
In step 1, the substrate may be a substrate conventional in the art, preferably a wafer, such as an 8 inch wafer.
In step 1, the coating method may be a conventional method in the art, preferably spin coating with a spin coater.
In step 1, when spin coating using a spin coater is selected, the number of coater revolutions is preferably 2000 to 3000 revolutions per minute, for example 2500 revolutions per minute.
The thickness of the photoresist layer in step 1 may be conventional in the art, preferably 40-60nm, for example 50nm.
In step 1, the baking temperature may be a baking temperature conventional in the art, preferably 70-90 ℃, for example 80 ℃.
In step 1, the baking time may be a baking time conventional in the art, preferably 50 to 70 seconds, for example 60 seconds.
In step 2, the baking temperature may be a baking temperature conventional in the art, preferably 120-140 ℃, for example 130 ℃.
In step 2, the baking time may be a baking time conventional in the art, preferably 50 to 70 seconds, for example 60 seconds.
In step 2, the development may be performed as is conventional in the art, and the developer typically used is an aqueous solution of tetramethylammonium hydroxide, for example, an aqueous solution of tetramethylammonium hydroxide having a mass fraction of 2.38%.
The above preferred conditions can be arbitrarily combined on the basis of not deviating from the common knowledge in the art, and thus, each preferred embodiment of the present invention can be obtained.
The resin is self-made, and other used reagents and raw materials are commercially available.
The invention has the positive progress effects that: the photoresist provided by the invention has better resolution, photosensitivity and lower line edge roughness. Therefore, the EUV photoresist composition has good application prospect.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Preparation of Photoresist compositions examples 1-8 and comparative examples 1-8
According to the combination and content shown in Table 1, the components are uniformly mixed, and an ultra-high molecular weight polyethylene film with the thickness of 0.1 mu m is adopted for filtration, so as to obtain the photoresist composed of the pterene compound;
wherein pterene A is
Wherein pterene B is
Wherein the photoacid generator isThe organic solvent is ethyl lactate; the organic base is trioctylamine.
TABLE 1
Effect examples
EUV exposure and inspection
Preparing and exposing a photoresist film: the prepared photoresist was coated on an 8-inch wafer at 2500RPM using a spin coater, and heated at 80 ℃ for 60 seconds on a hot plate to obtain a photoresist film. The average film thickness was measured at 25 points by an optical film thickness measuring system F50 (Filmetrics) and 50nm. Extreme ultraviolet exposure was performed on an upper sea light source interference reticle stage (BL 08U 1B) and then baked at 130℃for 60 seconds. Finally, the resultant film was developed in a 2.38wt% aqueous solution of tetramethylammonium hydroxide (TMAH), thereby obtaining a pattern.
LER assay: LER of the 50-nm LS pattern was measured under FE-SEM (Hitachi SU 9000).
LWR assay: LWR of the 50-nm LS pattern was measured under CD-SEM (HITACHI, CD-SEM, CG 5000).
Sensitivity detection: an Eth value was used as a sensitivity index. Stepped 25-point exposures (e.g., 0.5 mJ/cm) of different energies were performed on 8 inch wafers 2 ,1mJ/cm 2 ,1.5mJ/cm 2 ...), post-baking (PEB), developing, and measuring the film thickness thereof, the film thickness thereof being recorded as Eth just reaching 0nm.
And (3) detecting the resolution: under the conditions given the above sensitivity, the limit resolution (minimum limit width when separating and resolving lines and spaces) at the exposure dose (dose of electron beam irradiation) is taken as the LS resolution.
TABLE 2
EB exposure and detection
Preparing and exposing a photoresist film: the photoresist was coated on an 8-inch wafer using a spin coater at 2500RPM, and heated at 80 ℃ for 60 seconds on a hot plate to obtain a photoresist film. The average film thickness was measured at 25 points by an optical film thickness measuring system F50 (Filmetrics) and 50nm. The photoresist was exposed to an electron beam using an EB writing system Elionix ELS-G100 (Elionix, acceleration voltage 100 KeV) and baked at 130 ℃ for 60 seconds. Finally, the resultant film was developed in a 2.38wt% aqueous solution of tetramethylammonium hydroxide (TMAH), thereby obtaining a pattern.
Eop: the optimal exposure (Eop) is defined as the exposure dose that provides 1:1 resolution at the top and bottom of a 50-nm 1:1 line-and-space (LS) pattern.
LER assay: LER of the 50-nm LS pattern was measured under FE-SEM (Hitachi SU 9000).
LWR assay: LWR of the 50-nm LS pattern was measured under CD-SEM (HITACHI, CD-SEM, CG 5000).
And (3) detecting the resolution: under the conditions given above Eop, the limit resolution (minimum limit width when separating and resolving lines and spaces) at the exposure dose (dose of electron beam irradiation) was taken as LS resolution.
TABLE 3 Table 3

Claims (10)

1. A photoresist composition comprising the following components: a pterene A shown in the following formula, a pterene B shown in the following formula, a photoacid generator, an organic solvent and an organic base;
50-70 parts of the pterene A by weight and 30-50 parts of the pterene B by weight.
2. The photoresist composition of claim 1, wherein the photoresist composition meets one or more of the following conditions;
(1) The photoacid generator is
(2) The organic solvent is an ester solvent;
(3) The organic base is an organic weak base.
3. The photoresist composition of claim 1, wherein the organic solvent is ethyl lactate;
and/or, the organic base is trioctylamine.
4. The photoresist composition of claim 1, wherein the photoresist composition meets one or more of the following conditions;
(1) The weight portion of the pterene A is 60 portions;
(2) The weight portion of the pterene B is 40 portions;
(3) The photo-acid generator comprises 1-10 parts by weight of the photo-acid generator;
(4) The organic solvent is 1000-2000 parts by weight;
(5) The organic base is 0.2-1 part by weight.
5. The photoresist composition of claim 4, wherein the photoresist composition meets one or more of the following conditions;
(1) The photo-acid generator comprises 7 parts by weight of the photo-acid generator;
(2) The organic solvent is 1500 parts by weight;
(3) The organic base is 0.5 part by weight.
6. The photoresist composition of claim 1, wherein the photoacid generator is 1 to 10 parts by weight
The organic solvent is 1000-2000 parts by weight of ethyl lactate;
the organic base is trioctylamine with the weight of 0.2-1 part.
7. The photoresist composition according to any one of claims 1 to 6, consisting of: the pterene A, the pterene B, the photoacid generator, the organic solvent and the organic base.
8. The photoresist composition of claim 1, which is composed of any one of the following components of pterene a, pterene B, photoacid generator, organic solvent and organic base in parts by weight;
photoresist composition 1:60 parts of the pterene A, 40 parts of the pterene B, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 2:50 parts of the pterene A, 30 parts of the pterene B, 1 part of the photoacid generator, 1000 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 3:55 parts of the pterene A, 35 parts of the pterene B, 3 parts of the photoacid generator, 1200 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 4:65 parts of the pterene A, 45 parts of the pterene B, 5 parts of the photoacid generator, 1600 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 5:70 parts of the pterene A, 50 parts of the pterene B, 10 parts of the photoacid generator, 2000 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 6:66 parts of the pterene A, 38 parts of the pterene B, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 7:62 parts of the pterene A, 46 parts of the pterene B, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
photoresist composition 8:50 parts of the pterene A, 50 parts of the pterene B, 7 parts of the photoacid generator, 1500 parts of the organic solvent and 0.5 part of the organic base;
in the photoresist compositions 1 to 8, the photoacid generator isThe organic solvent is lactic acidEthyl ester, wherein the organic base is trioctylamine.
9. A method of preparing a photoresist composition according to any one of claims 1 to 8, wherein the components of the photoresist composition are mixed uniformly.
10. A method of patterning by photolithography, the method comprising the steps of:
step 1: coating the photoresist composition according to claims 1-8 on the surface of a substrate, and baking to obtain a photoresist layer;
step 2: and (3) exposing, baking and developing the photoresist layer obtained in the step (1) to obtain a photoresist pattern.
CN202210576179.XA 2022-05-24 2022-05-24 Photoresist composed of pterene compound, and preparation method and application thereof Pending CN117148671A (en)

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Application Number Priority Date Filing Date Title
CN202210576179.XA CN117148671A (en) 2022-05-24 2022-05-24 Photoresist composed of pterene compound, and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN117148671A true CN117148671A (en) 2023-12-01

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