A pentiphenyl derivative, its preparation and use in photolithography

Abstract

The present application belongs to the field of photoetching technology, and relates to a pentaphenyl derivative, a preparation method thereof and application of the pentaphenyl derivative in photoetching. A photoetching glue composition containing the pentaphenyl derivative can be prepared to obtain a uniform film, the film has good resolution, photosensitivity, adhesion, is easy to store, and the molecular glass as a base component does not precipitate in the film preparation process. The photoetching glue composition prepared by the present application has good film forming property, high thermal stability, is not easy to change in storage, and has low viscosity, and does not need to use an additional solvent for dilution in the use process. After electron beam exposure and development, the exposure pattern has high contrast, excellent resolution and good sensitivity, and can reach a photoetching line width of 40 nm.

Description

Technical Field

[0001] This invention belongs to the field of photolithography technology, specifically relating to a pentylene derivative, its preparation method, and its application in photolithography. Background Technology

[0002] Microelectronics technology developed alongside integrated circuits, especially very large-scale integrated circuits (VLSI), and is one of the core technologies of the information industry, having a profound impact on the national economy. In the late 1950s, scientists invented germanium and silicon integrated circuits, and the emergence of integrated circuits propelled the rapid development of semiconductor technology. Modern electronic devices demand increasingly smaller integrated circuit (chip) sizes and higher integration densities. Since the 1980s, photolithography technology has evolved from G-line (436nm) and I-line (365nm) lithography to deep ultraviolet (248nm, 193nm) lithography, and then to next-generation lithography technologies such as extreme ultraviolet lithography (EUVL), nanoimprint lithography, and electron beam lithography. Correspondingly, photoresists have also changed. Advanced lithography technologies have enabled increasingly higher integration densities and continuously smaller sizes. The smallest feature size of integrated circuits has moved from the micrometer and sub-micrometer levels to the nanometer level.

[0003] Photolithography and related processes are the backbone of the nanotechnology revolution. Current optical lithography processes limit the feature size of microelectronic circuit components manufactured by the wavelength of the exposure radiation. Researchers are developing new lithography techniques and photoresist materials to meet the growing demand for higher resolution and better sensitivity. Extreme ultraviolet (EUV) lithography and electron beam lithography, in particular, can achieve nanoscale patterns with feature sizes below 10 nm. In the development of faster and smaller semiconductor devices, novel photoresist materials and lithography processes are currently being jointly explored and researched by industry and academia.

[0004] As the exposure wavelength changes from ultraviolet (UV) to deep ultraviolet (DUV) and then to extreme ultraviolet (EUV), the feature size formed on the photoresist becomes smaller and smaller. In order to avoid the photoresist from collapsing easily under small feature size, the thickness of the photoresist film is also reduced. Therefore, the etching resistance of the photoresist itself needs to be improved to meet the requirements of subsequent chip processing. Summary of the Invention

[0005] The purpose of this invention is to provide pentadienyl derivatives and their preparation methods.

[0006] Another object of the present invention is to provide a positive photoresist composition containing the above-mentioned pentadienyl derivative.

[0007] This invention provides compounds represented by formula (I):

[0008]

[0009] Wherein, R is one of the following groups: -OC 1-12 Alkyl-COO-C 1-12 Alkyl, -OCOO-C 1-12 Alkyl, -OCOO-C 3-20 cycloalkyl;

[0010] n is 1, 2, 3, 4 or 5;

[0011] m can be 1, 2, 3, or 4;

[0012] R' and R1 may be the same or different, and are independently selected from H and C. 1-12 Alkyl, C 1-12 Alkoxy, halogenated C 1-12 Alkyl, Halogenated C 1-12 Alkoxy, -OC 1-12 Alkyl-COO-C 1-12 Alkyl, -OCOO-C 1-12 Alkyl or -OCOO-C 3-20 Cycloalkyl.

[0013] According to an embodiment of the present invention, R is one of the following groups: -OC 1-6 Alkyl-COO-C 1-6 Alkyl, -OCOO-C 1-6 Alkyl or -OCOO-C 3-12 cycloalkyl;

[0014] n is 1, 2, 3, 4 or 5;

[0015] R' and R1 are selected from H.

[0016] According to a preferred embodiment of the present invention, R is selected from the following groups:

[0017]

[0018] The * in the above groups is the linking site; n is 1, 2 or 3.

[0019] In one embodiment, n is 3, and the R substitution is at any consecutive adjacent or non-adjacent position on the benzene ring.

[0020] In one embodiment, n is 2, and the R are all substituted at the meta position of the benzene ring, or all substituted at two ortho positions, or at any two positions of ortho, meta, or para.

[0021] In one embodiment, n is 1, and the R is substituted at the ortho, meta, or para position on the benzene ring.

[0022] As an example, the compounds shown in Formula I are selected from the following:

[0023]

[0024] The present invention also provides a method for synthesizing the compound represented by formula (I) as described above, comprising the following steps:

[0025]

[0026] Compound I' reacts with compound RL to give the compound shown in formula I; where L is a halogen or OR; R, m, and n have the definitions described above;

[0027] Where R1 and R' in equation I are -OC 1-12 Alkyl-COO-C 1-12 Alkyl, -OCOO-C 1-12 Alkyl or -OCOO-C 3-12 In the case of cycloalkanes, R'1 and R” in formula I' are OH;

[0028] Where R1 and R' in equation I are H and C 1-12 Alkyl, C 1-12 Alkoxy, halogenated C 1-12 Alkyl, Halogenated C 1-12 In the case of alkoxy groups, R'1 and R” in formula I' do not participate in the reaction and are equivalent to R1 and R' in formula I.

[0029] According to an embodiment of the present invention, the reaction is carried out under the action of a base, preferably at least one of 4-dimethylaminopyridine (DMAP) or potassium carbonate, and the reaction temperature is preferably 20-80°C; the reaction solvent is preferably at least one of tetrahydrofuran and 1-methyl-2-pyrrolidone.

[0030] According to an embodiment of the present invention, the compound shown in formula I' is obtained by reacting two compounds as follows:

[0031]

[0032] Wherein, R'1, R”, m and n have the definitions described above; L1 is -B(OH)2 or -B(OC)2. 1-12 Alkyl)2.

[0033] According to an embodiment of the present invention, in the reaction for preparing formula I', the reaction is carried out under the action of a palladium-containing catalyst, preferably at least one of tetra(triphenylphosphine)palladium(O), [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride, tetra(triphenylphosphine)palladium(O), tetra(tri-tert-butylphosphine)palladium(O), tetra(trimethoxyphosphine)palladium(O), bis(1,2-bis(diphenylphosphine)ethane)palladium(O), and bis(1,3-bis(diphenylphosphine)propane)palladium(O); the reaction is preferably carried out under the action of a base, preferably at least one of sodium carbonate, cesium carbonate, potassium acetate, potassium phosphate, tetrabutylammonium fluoride, cesium fluoride, or potassium fluoride; the solvent for the reaction is preferably at least one of acetone, toluene, 1,4-dioxane, tetrahydrofuran, and anisole; the reaction temperature can be 60°C to 150°C, preferably 80°C to 120°C.

[0034] The present invention also provides the application of the compound shown in formula (I) in the preparation of photoresists.

[0035] The present invention also provides a photoresist composition comprising a compound of formula (I).

[0036] According to an embodiment of the present invention, the photoresist composition is a positive photoresist composition.

[0037] According to an embodiment of the present invention, the photoresist composition comprises a compound of formula (I), a photoresist solvent, and a photoacid-generating agent.

[0038] Preferably, the photoresist composition contains, by mass fraction, 0.1% wt to 10% wt of the compound of formula (I) and 0.01% wt to 1% wt of the photoacid-generating agent.

[0039] According to an embodiment of the present invention, the photoresist composition may also contain other photoresists and acid diffusion inhibitors, etc.

[0040] Preferably, the photoresist composition contains 0% wt to 0.1% wt of an acid diffusion inhibitor by mass fraction.

[0041] According to an embodiment of the present invention, in the photoresist composition, the compound represented by formula (I) is a compound of formula (Ia), that is, R in the compound represented by formula (I) is... n is 3.

[0042] According to an embodiment of the present invention, in the photoresist composition, the compound represented by formula (I) is a compound of formula (Ib), that is, R in the compound represented by formula (I) is... n is 2,

[0043] According to an embodiment of the present invention, in the photoresist composition, the compound represented by formula (I) is a compound of formula (Ic), that is, R in the compound represented by formula (I) is... n is 1.

[0044] According to an embodiment of the present invention, the photo-induced acid-producing agent can be ionic or nonionic, such as at least one selected from triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorobutyl sulfonate (triphenylsulfonium perfluorobutyl sulfonate), bis(4-tert-butylphenyl)iodonium p-toluenesulfonate, N-hydroxynaphthalimide trifluoromethanesulfonate, 2-phenyl-(4-phenylthio)phenylthiohexafluoroantimonate, benzyl(4-hydroxyphenyl)methylthiodonium hexafluoroantimonate, etc.

[0045] According to an embodiment of the present invention, the photoresist solvent may be selected from at least one of propylene glycol methyl ether acetate (PGMEA), ethyl lactate, ethylene glycol monomethyl ether, cyclohexanone, etc.

[0046] According to an embodiment of the present invention, the acid diffusion inhibitor may be selected from n-octylamine, tri-n-octylamine, N-methyldi-n-octylamine, tert-octylamine, etc.

[0047] According to embodiments of the present invention, the photoresist composition may further include other additives, such as sensitizers, surfactants, dyes, stabilizers, cosolvents, etc.

[0048] The present invention also provides the application of the photoresist composition described above in photolithography processes such as 365nm photolithography, 248nm photolithography, 193nm photolithography, extreme ultraviolet lithography (EUVL) and electron beam lithography (EBL).

[0049] The present invention also provides a photoresist coating comprising the compound shown in formula (I).

[0050] The present invention also provides a method for preparing the photoresist coating, comprising spin-coating the photoresist composition onto a substrate.

[0051] Preferably, the coating method is to spin-coat the substrate using a spin coater.

[0052] Preferably, the substrate can be a silicon wafer, a silicon dioxide wafer, or a compound semiconductor wafer. The silicon wafer is preferably a silicon wafer that has undergone hydrophobic treatment.

[0053] Beneficial effects

[0054] 1. The compound represented by formula (I) of this invention is a stereosymmetrical amorphous small molecule compound with a simple molecular structure, controllable molecular weight, simple synthesis steps, and high thermal stability. It does not precipitate during baking and is not easily denatured during photolithography, thus meeting the requirements of photolithography technology. The film structure does not change during high-temperature baking.

[0055] 2. Compared with traditional polymer photoresists, the compound represented by formula (I) of this invention has a high carbon-hydrogen ratio due to its large phenyl content, thus providing a photoresist material with high etching resistance.

[0056] 3. The photoresist composition of the present invention can be used to prepare uniform thin films with good resolution and photosensitivity (photoresist sensitivity can reach 70 μC / cm). 2 The photoresist composition prepared by this invention exhibits good film-forming properties, high thermal stability, minimal degradation during storage, and low viscosity, eliminating the need for additional solvent dilution during use. After electron beam exposure and development, the exposed pattern demonstrates high contrast, excellent resolution, and good sensitivity, achieving a lithographic linewidth of 40 nm. It also possesses high etching resistance and a higher etching ratio compared to silicon.

[0057] Terminology Definitions and Explanations

[0058] Unless otherwise defined, all technical terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the subject matter of the claims pertains.

[0059] In this application, some substituents marked with an asterisk (*) indicate connection sites.

[0060] "More than three" means three or more.

[0061] The term "halogen" includes F, Cl, Br, or I.

[0062] Term "C" 1-12 "alkyl" should be understood to refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably C12. 1-6 Alkyl group. "C" 1-6 "alkyl" should be understood to preferably represent a straight-chain or branched saturated monovalent hydrocarbon group having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, or their isomers. In particular, the group has 1, 2, or 3 carbon atoms ("C..."). 1-3 Alkyl), such as methyl, ethyl, n-propyl or isopropyl.

[0063] Term "C" 3-20 "Cycloalkyl" should be understood to refer to a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3 to 20 carbon atoms, preferably "C". 3-12 cycloalkyl. The term "C" 3-12 "Cycloalkyl" should be understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms. The C... 3-12 Cycloalkyl groups can be monocyclic hydrocarbon groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl, or bicyclic hydrocarbon groups such as decahydronaphthalene ring; they can also be C14. 7-12 Bridged cycloalkyl groups, such as norbornene, adamantane, and bicyclo[2,2,2]octane.

[0064] The above refers to the term "C" 1-12 The definition of "alkyl" also applies to compounds containing "C". 1-12 Other terms for "alkyl", such as the term "C 1-12 Alkoxy, halogenated C 1-12 Alkyl groups, etc. Attached Figure Description

[0065] Figure 1 The positive photoresist composition B-1 prepared in Example 2 is spin-coated onto a silicon wafer as a photoresist film;

[0066] Figure 2 This is a SEM image of the 365nm ultraviolet exposure in Example 4;

[0067] Figure 3 This is a SEM image of electron beam exposure in Example 5;

[0068] Figure 4 This is a SEM image of the cross-section of the silicon wafer after etching in Example 6. Detailed Implementation

[0069] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0070] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0071] Example 1: Synthesis and preparation of compound (Ib)

[0072]

[0073] 3.88 g (10 mmol) of compound (II), 0.19 g (1 mmol) of cuprous iodide, 1.2 g (10 mmol) of benzaldehyde oxime, and 6.52 g (20 mmol) of cesium carbonate were weighed and added sequentially to a 150 mL three-necked flask. Then, 80 mL of dimethyl sulfoxide was added, and the mixture was refluxed and stirred at 80 °C for 18–24 h. After the reaction was complete, the reaction mixture was extracted with ethyl acetate and water. The resulting organic phase was dried over anhydrous sodium sulfate and then separated by column chromatography using ethyl acetate:tetrahydrofuran (v:v) 1:1. The solvent was removed from the resulting organic phase, and the solid was dried under vacuum at 60 °C to give 2.12 g of compound (III), with a yield of 81%. MALDI-TOF (C 18 H 14 O2), m / z: 262.10.

[0074] 2.62 g (10 mmol) of compound (III) obtained in the previous step was placed in a 150 mL three-necked flask, and 100 mL of acetonitrile solution containing 8 g (50 mmol) of elemental bromine was added. The mixture was stirred at 25 °C for 5 h. After the reaction was complete, the remaining bromine was neutralized with an aqueous sodium thiosulfate solution, and the acetonitrile in the system was evaporated. The reaction solution was then extracted with ethyl acetate, and the resulting organic phase was dried with anhydrous sodium sulfate. The solvent was then evaporated from the organic phase, and the resulting solid was dried under vacuum at 60 °C to give 4.85 g of compound (IV), with a yield of 84%. MALDI-TOF(C 18 H 10 (Br4O2), m / z: 573.74.

[0075] 5.72 g (10 mmol) of compound (Ⅳ) obtained in the previous step was placed in a 250 mL three-necked flask, and 9.24 g (60 mmol) of 3,5-dihydroxyphenylboronic acid, 0.116 g of tetrakis(triphenylphosphine)palladium (0.1 mmol) and 100 mL of 1,4-dioxane solvent were added. Then, 5.52 g (40 mmol) of potassium carbonate was dissolved in 50 mL of water and added to the reaction flask. The reaction was carried out at 90–100 °C for 16 h. After the reaction, the system separated into layers. The organic phase was dried with anhydrous magnesium sulfate and rotary evaporated to obtain the crude product. The crude product was washed three times with n-hexane, filtered to obtain compound (Ⅴ-b), which was dried and weighed to 5.75 g, with a yield of 83%. MALDI-TOF(C 42 H 30 O 10 ),m / z:694.18.

[0076] Finally, 6.94 g (10 mmol) of compound (V-b) obtained in the previous step was placed in a 250 mL three-necked flask, and 26.2 g (120 mmol) of di-tert-butyl dicarbonate was added, followed by 150 mL of tetrahydrofuran and 0.122 g (1 mmol) of 4-dimethylaminopyridine. The mixture was reacted at 25 °C for 10 h. After the reaction was complete, 300 mL of ethyl acetate and 300 mL of water were added to the reaction solution, and the mixture was extracted to obtain a yellow organic phase. The obtained organic phase was dried over anhydrous magnesium sulfate and then rotary evaporated to an oily viscous substance. 500 mL of n-hexane was added to the oily viscous substance, and the mixture was heated to 75 °C and refluxed for 8 h. After cooling and filtration, 15.23 g of the white product I-b was obtained, with a yield of 90%. MALDI-TOF(C 92 H 110 O 30 ),m / z:1694.71.

[0077] Example 2: Preparation of positive photoresist composition B-1

[0078] Weigh 300 mg of compound (Ib) prepared in Example 1, 22.5 mg of the photoacid-generating agent N-hydroxynaphthalimide trifluoromethanesulfonic acid, and measure 10 ml of the photoresist solvent propylene glycol monomethyl ether acetate (PGMEA) to prepare a photoresist solution. After ultrasonic treatment for half an hour, filter the solution three times through a 0.20 μm polytetrafluoroethylene film to prepare a positive photoresist composition B-1. Spin-coat photoresist composition B-1 onto a silicon wafer to obtain a uniform and complete photoresist film, as shown below. Figure 1 As shown.

[0079] Example 3: Preparation of positive photoresist composition B-2

[0080] Weigh 300 mg of compound (Ib) prepared in Example 1, 15 mg of photoacid-generating agent perfluorobutylsulfonate triphenylsulfonate, and measure 10 ml of photoresist solvent propylene glycol monomethyl ether acetate (PGMEA) to prepare a photoresist solution. After ultrasonic treatment for half an hour, filter it three times through a 0.20 μm polytetrafluoroethylene membrane to prepare a positive photoresist composition.

[0081] Example 4: 365nm UV lithography performance of positive photoresist composition B-1

[0082] A photoresist composition with a concentration of 30 mg / ml of compound (Ib) was prepared according to Example 2. A silicon wafer treated with HMDS was selected. Spin coating parameters were set to 3000 rpm / 90 s, and pre-baking parameters were set to 100°C / 120 s. The film thickness was measured to be approximately 50 nm using an ellipsometry. I-line (365 nm) photolithography was performed at 30 mJ / cm. 2The post-baking parameters were 70℃ / 20s, the developing parameters were 0.26N TMAH aqueous solution / 60s, and the rinsing parameters were deionized water / 60s. SEM images were acquired using a Hitachi 8230 scanning electron microscope after exposure. Specific lithography results are shown below. Figure 2 As shown, the stripe width is 2μm.

[0083] Example 5: Electron beam lithography performance of positive photoresist composition B-2

[0084] A photoresist composition with a compound (Ib) concentration of 30 mg / ml was prepared according to Example 3. A silicon wafer treated with HMDS was selected. Spin coating parameters were set to 3000 rpm / 90 s, and pre-baking parameters were set to 100°C / 120 s. The film thickness was measured to be approximately 50 nm using an ellipsometry. Exposure was performed using an electron beam with an accelerating voltage of 100 kV at 70 μC / cm. 2 The post-baking parameters were 70℃ / 20s, the developing parameters were 0.26N TMAH aqueous solution / 60s, and the rinsing parameters were deionized water / 60s. SEM images were acquired using a Hitachi 8230 scanning electron microscope after exposure. Specific lithography results are shown below. Figure 3 As shown, the stripe width is 40 nm.

[0085] Example 6: Etching resistance of positive photoresist composition B-1

[0086] The silicon wafer after photolithography and development in Example 5 was etched in an SF6 / O2 atmosphere to obtain a silicon wafer cross-section with an etching ratio of 7:1. The specific etching results are as follows. Figure 4 As shown, the obtained photoresist composition demonstrates high etching resistance, a higher etching ratio compared to silicon, and good photosensitivity.

[0087] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. The compound represented by formula (I): （I） in, R is -OCOO-C 1-6 alkyl; n is 2; m is 1; R1 is selected from H.

2. The compound according to claim 1, wherein, R is -OCOO-C 1-4 alkyl.

3. The compound according to claim 1 or 2, wherein, The compound shown in formula (I) is selected from the following compounds: 。 4. The use of the compound according to any one of claims 1-3 in the preparation of photoresists.

5. A photoresist composition comprising the compound according to any one of claims 1-3.

6. The application of the photoresist composition of claim 5 in 365nm lithography, 248nm lithography, 193nm lithography, extreme ultraviolet lithography and electron beam lithography processes.

7. A photoresist coating comprising the compound according to any one of claims 1-3.

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