Bottom antireflective coating compositions, preparation and use thereof

Abstract

The present invention provides a bottom antireflective coating composition and its preparation and use. The bottom antireflective coating composition comprises a polyoligoester resin containing phenolic hydroxyl groups, the structure of which is shown in Formula I. The bottom antireflective coating composition of the present invention has high photosensitivity, low development residue, excellent antireflective performance and good process compatibility. Formula I.

Description

Technical Field

[0001] This invention pertains to photolithography technology in the field of microelectronics manufacturing, specifically relating to a bottom anti-reflective coating (BAC) composition used in photolithography processes, particularly a photodegradable bottom anti-reflective coating composition that can be developed by an alkaline aqueous solution after exposure, and its preparation and application. Background Technology

[0002] As the feature size of integrated circuits continues to shrink, the wavelength of the exposure light source also shortens (e.g., KrF, ArF). The reflected light from high-refractive-index substrates (such as silicon, polysilicon, and metals) interferes with the incident light, causing standing wave and wobbling effects in the photoresist, which severely affects the pattern resolution and the control accuracy of critical dimensions (CD). To suppress this reflection, a bottom anti-reflective coating (BARC) is typically applied between the photoresist and the substrate.

[0003] Traditional BARC materials are mostly cross-linked organic polymers, which require additional dry etching (such as plasma etching) steps after development to remove them. This increases process complexity, cost, and time. In addition, dry etching can damage the underlying substrate and may cause pattern deformation due to etching selectivity issues.

[0004] To simplify the process, developable BARCs have emerged. These BARCs can be removed along with the photoresist in the exposed area during the photoresist development step, eliminating the need for separate dry etching. Existing developable BARCs are mostly based on acid-catalyzed chemical amplification reactions, for example, systems composed of hydroxyl-containing resins and acid-unstable crosslinking agents (such as melamine resins). After exposure and acid generation, during post-exposure baking (PEB), the acid catalyzes the breakage of crosslinking bonds, making the exposed area soluble instead of insoluble. However, these systems have some inherent drawbacks:

[0005] 1. Insufficient photosensitivity: A higher exposure dose is required to generate enough acid to completely destroy the cross-linked network.

[0006] 2. Developing residue: Since the polymer backbone itself is not broken, the dissociation of crosslinking points alone may not be enough to completely dissolve the macromolecular chain, which can easily form a difficult-to-remove "scum" on the substrate surface, resulting in defects.

[0007] 3. Narrow process window: PEB temperature and time have a significant impact on the decrosslinking reaction, and improper control can easily lead to pattern defects.

[0008] Therefore, there is an urgent need in this field to develop a new type of developable BARC that has high photosensitive properties and can be completely removed after development without leaving any residue. Summary of the Invention

[0009] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a novel alkaline water-developable bottom anti-reflective coating composition. This composition utilizes the unique acid-catalyzed degradation properties of polyorthoester polymers to achieve highly sensitive "chemical bond breaking" imaging, rather than traditional "de-crosslinking" imaging, thus ensuring residue-free development. This provides a new generation of photolithography pattern correction materials for advanced semiconductor manufacturing.

[0010] To achieve the above objectives, the present invention adopts the following technical solution:

[0011] A first aspect of the present invention provides a bottom antireflective coating composition comprising a polyorthoester resin containing phenolic hydroxyl groups, the structure of which is shown in Formula I:

[0012] Formula I

[0013] Wherein, at least one of R1 and R2 includes a group containing a phenolic hydroxyl structure, and the group containing a phenolic hydroxyl structure includes a C group containing a phenolic hydroxyl structure. 6~24 Aryl, C 7~40 Aryl alkyl, C 7~40 At least one of alkylaryl, fluorenyl, and polyphenylene structures linked by bridging bonds;

[0014] n is an integer between 10 and 500;

[0015] Wherein, m is the total number of moles of R1 and R2, and p is the sum of the number of moles of R1 containing phenolic hydroxyl groups p1 and the number of moles of R2 containing phenolic hydroxyl groups p2, satisfying: 10%m≤p≤70%m.

[0016] According to the bottom antireflective coating composition of the first aspect, at least one of R1 and R2 includes a group that does not contain a phenolic hydroxyl structure;

[0017] Wherein, the groups that do not contain phenolic hydroxyl structures include C 1-10 alkyl, C 3-10 cycloalkyl and C 1-10 At least one of the ether groups.

[0018] According to the bottom antireflective coating composition of the first aspect, the group containing the phenolic hydroxyl structure is selected from one or more of the following:

[0019] , , , , , , , , , , , , , , , , , , .

[0020] According to the bottom antireflective coating composition of the first aspect, the group without the phenolic hydroxyl structure is selected from one or more of the following:

[0021] , , , , .

[0022] According to the bottom antireflective coating composition of the first aspect, the Mw of the polyorthoester resin containing phenolic hydroxyl groups is 500~30000 g / mol; and / or

[0023] The polyorthoester resin containing phenolic hydroxyl groups has a PDI of 1.5 to 5.

[0024] According to the bottom antireflective coating composition of the first aspect, the Mw of the polyorthoester resin containing phenolic hydroxyl groups is preferably 1000~10000 g / mol; and / or

[0025] The polyorthoester resin containing phenolic hydroxyl groups has a PDI of 1.9 to 3.5.

[0026] According to the bottom antireflective coating composition of the first aspect, the composition further includes at least one of a crosslinking agent, a photoacid generator, other additives, and a solvent.

[0027] According to the bottom anti-reflective coating composition of the first aspect, the bottom anti-reflective coating composition comprises, by weight:

[0028] 1-10 parts of polyorthoester resin containing phenolic hydroxyl groups;

[0029] Crosslinking agent 0.05-5 parts;

[0030] Photo-acid-generating agent: 0.01-2 parts;

[0031] Other additives 0.0001-0.1 parts; and

[0032] Solvent: 85-98 parts.

[0033] According to the bottom antireflective coating composition of the first aspect, the crosslinking agent is a vinyl ether compound containing multiple functional groups; and / or

[0034] The photoacid generator is an ionic photoacid generator and / or a non-ionic photoacid generator; and / or

[0035] The other additives are selected from at least one of leveling agents and quenching agents; and / or

[0036] The solvent is selected from at least one of ketone solvents, ester solvents, ether solvents, and aromatic hydrocarbon solvents.

[0037] According to the bottom antireflective coating composition of the first aspect, the crosslinking agent is selected from at least one of ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, triethylene glycol divinyl ether, and cyclohexanediethanol divinyl ether; and / or

[0038] The photoacid-generating agent is selected from diphenyliodonium trifluoromethanesulfonate, diphenyliodonium camphor sulfonate, diphenyliodonium perfluoro-1-butanesulfonate, diphenyliodonium perfluorooctane sulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium tetrafluoroborate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, and bis(4-tert-butylphenyl)iodonium. Trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium perfluorooctanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium perfluoro-1-butylsulfonate, triphenylsulfonium perfluoro Octane sulfonate, p-Tolyldiphenylsulfonium trifluoromethanesulfonate, p-Tolyldiphenylsulfonium perfluorooctane sulfonate, p-Tolyldiphenylsulfonium perfluoro-1-butane sulfonate, p-Tolyldiphenylsulfonium camphor sulfonate, 2,4,6-Trimethylphenyldiphenylsulfonium trifluoromethane sulfonate, 4-tert-Butylphenyldiphenylsulfonium trifluoromethane sulfonate, 4-Phenylenylthiodiphenylsulfonium hexafluorophosphate, 1-(2-Naphthylmethyl)thiosulfonium trifluoromethane sulfonate, 4-Hydroxy-1-naphthyldimethylsulfonium trifluoromethane sulfonate, 2-Methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-Phenylen-4,6-bis(trichloromethyl)- 1,3,5-Triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxy-1-naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(benzo[d][1,3]dioxolane-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-dimethoxystyryl)- 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(2,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(2-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-butoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-pentoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, diphenyl disulfone, di-p-tolyl disulfone, bis(phenylsulfonyl)diazomethane, bis(4-chlorophenylsulfonyl)diazomethane, bis(p-tolylsulfonyl)diazomethane, bis(4-tert-butylphenylsulfonyl)diazomethane, bis(2,4-Dimethylbenzenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, (benzoyl)(phenylsulfonyl)diazomethane, 1-benzoyl-1-phenylmethyl p-toluenesulfonic acid, 2-benzoyl-2-hydroxy-2-phenylethyl p-toluenesulfonic acid, 1,2,3-phenyltriyl trimethanesulfonic acid, 2,6-dinitrobenzene p-toluenesulfonic acid, 2-nitrobenzene p-toluenesulfonic acid, 4-nitrobenzene p-toluenesulfonic acid, N-(phenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyl) N-(perfluoro-1-butanesulfonic acid) succinimide, N-(perfluorooctanesulfonic acid) succinimide, N-(perfluoro-1-butanesulfonic acid) phthalimide, N-(trifluoromethylsulfonyloxy) phthalimide, N-(perfluorooctanesulfonic acid) phthalimide, N-(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxylic acid imide, N-(perfluoro-1-butanesulfonic acid)-5-norbornene-2,3-dicarboxylic acid imide, N-(perfluorooctanesulfonic acid) At least one of -5-norbornene-2,3-dicarboxylic acid imide, N-(trifluoromethylsulfonyloxy)naphthyleneimide, N-(perfluoro-1-butanesulfonic acid)naphthyleneimide, N-(perfluorooctanesulfonic acid)naphthyleneimide, and N-(10-camphorsulfonyloxy)naphthyleneimide; and / or,

[0039] The leveling agent is selected from at least one of acrylic leveling agents, silicone leveling agents, and fluorocarbon leveling agents; and / or

[0040] The quencher is an amine compound and / or a photoalkalizing agent; and / or

[0041] The solvent is selected from at least one of propylene glycol methyl ether acetate, propylene glycol monoacetate, ethylene glycol methyl ether acetate, diethylene glycol, propylene glycol methyl ether, propylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, γ-butyrolactone, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0042] A second aspect of the present invention provides a semiconductor manufacturing method, comprising:

[0043] A photolithographic image formed by developing the bottom anti-reflective coating composition of the first aspect in an alkaline developing solution.

[0044] According to the method of the second aspect, the alkaline developing solution is selected from aqueous solutions of tetramethylammonium hydroxide (TMAH), potassium hydroxide, and sodium hydroxide.

[0045] A third aspect of the present invention provides a semiconductor device manufactured using the method of the second aspect.

[0046] The alkaline water-developable bottom anti-reflective coating composition provided by this invention represents a significant technological advancement, and its beneficial effects are specifically reflected in the following four aspects:

[0047] 1. Extremely high photosensitivity: Because the polymer backbone and cross-linked network break simultaneously, rather than a reversible reaction at a single cross-linking point, even a very small amount of acid in the system can trigger an "avalanche" chain degradation, significantly reducing the required exposure dose.

[0048] 2. No residue after development: The degradation products are clearly defined small molecules, rather than tangled polymer chains. They have excellent solubility in alkaline developer and can be completely rinsed out, effectively preventing the formation of defects.

[0049] 3. Excellent anti-reflection properties: By adjusting the polymer structure, the n-value (refractive index) and k-value (extinction coefficient) of the coating can be easily controlled to match photolithography processes of different wavelengths.

[0050] 4. Good process compatibility: It can use standard photolithography equipment and alkaline developers such as TMAH, without the need for additional investment. Attached Figure Description

[0051] Figure 1 It is a polyorthoester resin POE-S4 containing phenolic hydroxyl groups. 1 HNMR spectrum;

[0052] Figure 2 SEM images of the bottom antireflective coating composition 200 nm mL / S Eop morphology and bottom residue of the alkaline water developable bottom antireflective coating composition of Example 4.

[0053] Figure 3 SEM images of the bottom antireflective coating composition 200 nm / S developed with alkaline water in Comparative Example 3, showing the morphology of Eop and the bottom residue. Detailed Implementation

[0054] The present application will now be described in further detail with reference to the accompanying drawings and embodiments. Through these descriptions, the features and advantages of the present application will become clearer and more apparent.

[0055] The term “exemplary” as used herein means “serving as an example, embodiment, or illustration.” Any embodiment illustrated herein as “exemplary” is not necessarily to be construed as superior to or better than other embodiments. Although various aspects of embodiments are shown in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated otherwise.

[0056] Furthermore, the technical features involved in the different embodiments of this application described below can be combined with each other as long as they do not conflict with each other.

[0057] This invention provides a bottom anti-reflective coating composition comprising a polyorthoester resin containing phenolic hydroxyl groups, the structure of which is shown in Formula I:

[0058] Formula I

[0059] Wherein, at least one of R1 and R2 includes a group containing a phenolic hydroxyl structure, and the group containing a phenolic hydroxyl structure includes a C group containing a phenolic hydroxyl structure. 6~24 Aryl, C 7~40 Aryl alkyl, C 7~40 At least one of alkylaryl, fluorenyl, and polyphenylene structures linked by bridging bonds;

[0060] n is an integer between 10 and 500;

[0061] Wherein, m is the total number of moles of R1 and R2, and p is the sum of the number of moles of R1 containing phenolic hydroxyl groups p1 and the number of moles of R2 containing phenolic hydroxyl groups p2, satisfying: 10%m≤p≤70%m.

[0062] The bottom anti-reflective coating composition of this application includes a polyorthoester resin containing phenolic hydroxyl groups as a film-forming polymer. The phenolic hydroxyl groups on the polymer side chains undergo a cross-linking reaction with the vinyl ether bonds of the cross-linking agent under thermal action, forming a dense network structure insoluble in the developer. During exposure, a photoacid generator produces a strong acid, catalyzing the acidolysis reaction of the polyorthoester backbone and the orthoester bonds and vinyl ether bonds at the cross-linking points. This leads to the complete breakage of the polymer backbone and cross-linking network, generating small molecule products, thereby enabling the exposed area to dissolve rapidly and completely in an alkaline aqueous solution (such as 2.38% TMAH). This invention has advantages such as high photosensitivity, no residue after development, and good compatibility with advanced photolithography processes.

[0063] Specifically, for example, if the polyorthoester resin contains m1 moles of R1 and m2 moles of R2, then the total number of moles of R1 and R2 is m = m1 + m2. R1 and R2 can each independently include groups containing phenolic hydroxyl groups, where p1 is the number of moles of R1 containing phenolic hydroxyl groups and p2 is the number of moles of R2 containing phenolic hydroxyl groups. Therefore, the total number of moles of R1 and R2 containing phenolic hydroxyl groups is p = p1 + p2. In some specific embodiments, the number of moles p of R1 and R2 containing phenolic hydroxyl groups can be 10%m, 15%m, 20%m, 25%m, 30%m, 35%m, 40%m, 45%m, 50%m, 55%m, 60%m, 65%m, or 70%m.

[0064] In some specific embodiments, R1 and R2 may each independently include C6, C7, C8, C9, and C6 containing phenolic hydroxyl structures.10 、C 11 、C 12 、C 13 、C 14 、C 15 、C 16 、C 17 、C 18 、C 19 、C 20 、C 21 、C 22 、C 23 、C 24 of aryl, C7, C8, C9, C 10 、C 11 、C 12 、C 13 、C 14 、C 15 、C 16 、C 17 、C 18 、C 19 、C 20 、C 21 、C 22 、C 23 、C 24 、C 25 、C 26 、C 27 、C 28 、C 29 、C 30 、C 31 、C 32 、C 33 、C 34 、C 35 、C 36 、C 37 、C​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​29 C 30 C 31 C 32 C 33 C 34 C 35 C 36 C 37 C 38 C 39 C 40 At least one of the alkylaryl groups.

[0065] In some specific implementations, n can be 10, 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, or any combination thereof.

[0066] In one embodiment, at least one of R1 and R2 includes a group that does not contain a phenolic hydroxyl structure;

[0067] Wherein, the groups that do not contain phenolic hydroxyl structures include C 1-10 alkyl, C 3-10 cycloalkyl and C 1-10 At least one of the ether groups.

[0068] In some specific embodiments, the group without a phenolic hydroxyl structure may include C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 Alkyl groups, C3, C4, C5, C6, C7, C8, C9, C 10 cycloalkyl groups, and C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 At least one of the ether groups.

[0069] In some specific embodiments, in the bottom antireflective coating composition of the present invention, in the polyorthoester resin having the structure of Formula I, R1 and R2 can each be independently selected from groups containing phenolic hydroxyl structures and groups without phenolic hydroxyl structures, wherein the groups containing phenolic hydroxyl structures are selected from C groups containing phenolic hydroxyl structures. 6~24 Aryl, C 7~40 Aryl alkyl, C 7~40 At least one of alkylaryl, fluorenyl, and polyphenylene structures linked by bridging bonds, wherein the group without a phenolic hydroxyl structure is selected from C 1-10 alkyl, C 3-10 cycloalkyl, C 1-10 At least one of the ether groups.

[0070] In one embodiment, the group containing the phenolic hydroxyl structure is selected from one or more of the following:

[0071] , , , , , , , , , , , , , , , , , , ;

[0072] The group that does not contain a phenolic hydroxyl structure is selected from one or more of the following:

[0073] , , , , .

[0074] In one embodiment, the Mw of the polyorthoester resin containing phenolic hydroxyl groups is 500~30000 g / mol; and / or

[0075] The polyorthoester resin containing phenolic hydroxyl groups has a PDI of 1.5 to 5.

[0076] In one embodiment, the Mw of the polyorthoester resin containing phenolic hydroxyl groups is preferably 1000~10000 g / mol; and / or

[0077] The polyorthoester resin containing phenolic hydroxyl groups has a PDI of 1.9 to 3.5.

[0078] In some specific embodiments, the Mw of the polyorthoester resin containing phenolic hydroxyl groups can be 500 g / mol, 1000 g / mol, 2500 g / mol, 5000 g / mol, 7500 g / mol, 10000 g / mol, 20000 g / mol, 25000 g / mol, 3000 g / mol, or any combination thereof.

[0079] In some specific embodiments, the PDI of the polyorthoester resin containing phenolic hydroxyl groups can be 1.5, 1.7, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.7, 4.0, 4.2, 4.5, 4.8, 5.0, or any combination thereof.

[0080] In one embodiment, the composition further includes at least one of a crosslinking agent, a photoacid generator, other additives, and a solvent.

[0081] In one embodiment, the bottom antireflective coating composition comprises, by weight:

[0082] 1-10 parts of polyorthoester resin containing phenolic hydroxyl groups;

[0083] Crosslinking agent 0.05-5 parts;

[0084] Photo-acid-generating agent: 0.01-2 parts;

[0085] Other additives 0.0001-0.1 parts; and

[0086] Solvent: 85-98 parts.

[0087] In some specific embodiments, the bottom antireflective coating composition may comprise, by weight, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, or any combination thereof.

[0088] The bottom anti-reflective coating composition may include crosslinking agents in the following quantities: 0.05 parts, 0.1 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, or any combination thereof.

[0089] The bottom anti-reflective coating composition may include photoacid generators in amounts of 0.01 parts, 0.05 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, or any combination thereof.

[0090] The bottom anti-reflective coating composition may include other additives in amounts of 0.0001 parts, 0.0005 parts, 0.0008 parts, 0.001 parts, 0.003 parts, 0.005 parts, 0.008 parts, 0.01 parts, 0.03 parts, 0.05 parts, 0.08 parts, 0.1 parts, or any combination thereof.

[0091] The bottom antireflective coating composition may contain solvents in the range of 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98 parts or any combination thereof.

[0092] In one embodiment, the alkaline water-developable bottom antireflective coating composition wherein the crosslinking agent is a vinyl ether compound containing multiple functional groups;

[0093] Preferably, the crosslinking agent is selected from one or more of the following structures: ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, triethylene glycol divinyl ether, and cyclohexanediethanol divinyl ether.

[0094] In one embodiment, the alkaline water-developable bottom antireflective coating composition contains a photoacid generator that is an ionic or nonionic compound.

[0095] Preferably, the photoacid-generating agent is selected from one or more of the following: diphenyliodonium trifluoromethanesulfonate, diphenyliodonium camphor sulfonate, diphenyliodonium perfluoro-1-butanesulfonate, diphenyliodonium perfluorooctane sulfonate, 4-methoxyphenylphenyliodonium trifluoromethane sulfonate, bis(4-tert-butylphenyl)iodonium tetrafluoroborate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium perfluoro-1-butane sulfonate, bis(4-tert-butylphenyl)iodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium perfluorooctane sulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium Triphenylsulfonium camphor sulfonate, triphenylsulfonium perfluoro-1-butyl sulfonate, triphenylsulfonium perfluorooctane sulfonate, p-tolyl diphenylsulfonium trifluoromethane sulfonate, p-tolyl diphenylsulfonium perfluorooctane sulfonate, p-tolyl diphenylsulfonium perfluoro-1-butane sulfonate, p-tolyl diphenylsulfonium camphor sulfonate, 2,4,6-trimethylphenyl diphenylsulfonium trifluoromethane sulfonate, 4-tert-butylphenyl diphenylsulfonium trifluoromethane sulfonate, 4-phenylphenylthiodiphenylsulfonium hexafluorophosphate, 1-(2-naphthylmethyl)thiol-onium trifluoromethane sulfonate, 4-hydroxy-1-naphthyl dimethylsulfonium trifluoromethane sulfonate, 2-methyl-4,6-bis(trichloromethyl)- 1,3,5-Triazine, 2,4,6-Tris(trichloromethyl)-1,3,5-Triazine, 2-Pheny-4,6-Bis(trichloromethyl)-1,3,5-Triazine, 2-(4-chlorophenyl)-4,6-Bis(trichloromethyl)-1,3,5-Triazine, 2-(4-methoxyphenyl)-4,6-Bis(trichloromethyl)-1,3,5-Triazine, 2-(4-methoxy-1-naphthyl)-4,6-Bis(trichloromethyl)-1,3,5-Triazine, 2-(benzo[d][1,3]dioxolane-5-yl)-4,6-Bis(trichloromethyl)-1,3,5-Triazine, 2-(4-methoxystyryl)-4,6-Bis(trichloromethyl)-1,3,5-Triazine 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(2,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(2-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-butoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-pentoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine5-Triazine, diphenyl disulfone, di-p-tolyl disulfone, bis(phenylsulfonyl)diazomethane, bis(4-chlorophenylsulfonyl)diazomethane, bis(p-tolylsulfonyl)diazomethane, bis(4-tert-butylphenylsulfonyl)diazomethane, bis(2,4-dimethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, (benzoyl)(phenylsulfonyl)diazomethane, 1-Benzoyl-1-phenylmethyl p-toluenesulfonic acid, 2-benzoyl-2-hydroxy-2-phenylethyl p-toluenesulfonic acid, 1,2,3-phenyltriyl trimethanesulfonic acid, 2,6-dinitrobenzoyl p-toluenesulfonic acid, 2-nitrobenzene p-toluenesulfonic acid, 4-nitrobenzene p-toluenesulfonic acid, N-(phenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)succinimide Imide, N-(perfluoro-1-butanesulfonic acid) succinimide, N-(perfluorooctanesulfonic acid) succinimide, N-(perfluoro-1-butanesulfonic acid) phthalimide, N-(trifluoromethylsulfonyloxy) phthalimide, N-(perfluorooctanesulfonic acid) phthalimide, N-(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxylic acid imide, N-( N-(perfluoro-1-butanesulfonic acid)-5-norbornen-2,3-dicarboxylic acid imide, N-(perfluorooctanesulfonic acid)-5-norbornen-2,3-dicarboxylic acid imide, N-(trifluoromethylsulfonyloxy)naphthylimide, N-(perfluoro-1-butanesulfonic acid)naphthylimide, N-(perfluorooctanesulfonic acid)naphthylimide, N-(10-camphorsulfonyloxy)naphthylimide.

[0096] In one embodiment, the alkaline water-developable bottom antireflective coating composition includes other additives, which are one or both of leveling agents and quenchers.

[0097] Preferably, the leveling agent is selected from one or more of the following: acrylic leveling agents, silicone leveling agents, and fluorocarbon leveling agents, such as commercial products manufactured by BYK AG, DIC AG, and Shin-Etsu AG, for example: BYK 310, BYK 315, BYK 320, BYK 325, BYK 331, BYK 333, BYK 358N, BYK 3550, BYK 3560, F554, F563, R40, R41, KP341, etc.

[0098] Preferably, the quencher is an amine compound or a photoalkali-producing agent, preferably an organic base, such as: ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, triethanolamine, tripropylamine, triethoxyethanolamine, trioctylamine, tributylamine, trimethoxyethoxymethoxyethylamine, tetramethylammonium hydroxide, polyquaternium base, diaminodiphenyl sulfone, diaminodiphenylmethane, m-phenylenediamine, dicyandiamide, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, etc.; oxime esters, such as BASF's Irgacure OXE01. And OXE02; quaternary ammonium salts, such as o-nitrobenzyl quaternary ammonium salts, benzoin quaternary ammonium salts; imides, such as N-(2-nitrobenzyloxycarbonyl)pyrrolidine; formamides, such as o-nitrobenzyloxycarbonyl protected formamides; carbamates (urethanes), such as one or more of o-nitrobenzyl carbamates.

[0099] In one embodiment, the alkaline water-developable bottom antireflective coating composition uses a solvent selected from one or more of ketone solvents, ester solvents, ether solvents, and aromatic hydrocarbon solvents.

[0100] Preferably, the solvent is selected from one or more of the following: propylene glycol methyl ether acetate, propylene glycol monoacetate, ethylene glycol methyl ether acetate, diethylene glycol, propylene glycol methyl ether, propylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, γ-butyrolactone, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0101] The present invention also provides a photolithographic image formed by developing the aforementioned bottom anti-reflective coating composition in an alkaline developing solution.

[0102] In one embodiment, the alkaline developing solution is selected from aqueous solutions of tetramethylammonium hydroxide (TMAH), potassium hydroxide, and sodium hydroxide.

[0103] The present invention further provides a semiconductor device manufactured using the aforementioned method.

[0104] In some specific embodiments, the present invention provides a bottom antireflective coating composition that is alkaline water developable, comprising:

[0105] (A) Polyorthoester resin containing phenolic hydroxyl groups: as a film-forming substance and antireflective component, while its phenolic hydroxyl groups provide active sites for thermal crosslinking reaction.

[0106] (B) Vinyl ether crosslinking agent: Under heating conditions, it can undergo a highly efficient electrophilic addition reaction with the phenolic hydroxyl groups of polymer (A) to form a stable crosslinking network, making the coating insoluble in the developer in the unexposed area.

[0107] (C) Photoacid generator: generates strong acid under light irradiation, which acts as an initiator for catalytic degradation reaction.

[0108] (D) Additives: used to adjust the coating, sensitivity, morphology, etc. of the sample.

[0109] (E) Organic solvents: used to adjust the viscosity of the composition to make it suitable for spin coating processes.

[0110] The core mechanism of this invention lies in "thermally induced crosslinking and acid-induced total depolymerization":

[0111] Crosslinking process: During the pre-baking (soft baking) process after coating, heating (e.g., 150°C) causes the phenolic hydroxyl groups (-OH) on the side chains of polymer (A) to react with the vinyl ether groups (-O-CH=CH2) of the crosslinking agent (B) to form a crosslinked structure. This reaction requires no catalyst, is highly efficient, and can form a dense film that is insoluble in alkaline developing solutions.

[0112] Depolymerization process: During exposure, the photoacid generator (C) produces a strong acid (H). + Subsequently, during post-exposure baking (PEB) or development, this strong acid simultaneously catalyzes degradation at two key sites:

[0113] Degradation of polyorthoester backbone: Polyorthoesters are extremely sensitive to acids. Under acid catalysis, the orthoester bonds in their backbone will undergo hydrolytic breakage, rapidly decomposing the long-chain polymer into low-molecular-weight polyols and small-molecule orthoesters.

[0114] Degradation of crosslinking points: The crosslinking bond (ether bond structure) formed by divinyl ether and phenolic hydroxyl group is also unstable in a strong acid environment and will undergo acid decomposition, thereby releasing small molecular fragments.

[0115] Through the acid-catalyzed reaction described above, the material in the exposed area is completely degraded from the original highly cross-linked network polymer into a series of small molecule products. These small molecules have an extremely high dissolution rate in alkaline developing solutions (such as TMAH), and therefore can be quickly and thoroughly removed, fundamentally avoiding polymer residue.

[0116] This invention does not impose any special restrictions on the source of any raw materials; unless otherwise specified, they are all conventional products that can be obtained commercially.

[0117] In the following preparation examples:

[0118] Mw value testing: A GILLENT 1100 gel permeation chromatography instrument, USA; mobile phase: chromatographic grade THF; test temperature: 35℃; solvent flow rate: 1.0 mL / min; standard: polystyrene (PSt).

[0119] 1H-NMR assay: 400MHz AVANCE III type nuclear magnetic resonance (1H-NMR) from BRUKER, Switzerland, using deuterated dimethyl sulfoxide (DMSO-d6) as solvent and tetramethylsilane as internal standard.

[0120] Synthesis example

[0121] Synthesis of compound A:

[0122] 250 g (1.3 mol) of 2,2,2-trifluoro-N-(2,3-dihydroxypropanol)acetamide, 567 g (5.2 mol) of trimethyl orthoformate, 400 mL of dichloromethane, and 0.45 g of p-toluenesulfonic acid monohydrate (PTSA·H2O) were added to a pre-dried 5 L three-necked flask. The mixture was stirred overnight at room temperature. After the reaction was complete, a few drops of triethylamine were added to the flask, and the dichloromethane solvent was removed by rotary evaporation. The crude product was dissolved in 3 L of ethyl acetate (containing a small amount of triethylamine), and then extracted once each with 100 mL of saturated NaHCO3 solution and 1 L of saturated NaCl solution. The organic phase was collected, dried over anhydrous MgSO4, and finally concentrated by filtration to obtain 290 g of colorless oily compound A.

[0123]

[0124] Synthesis of compound B:

[0125] 61.2 g (0.264 mol) of compound A, 18.65 g (0.089 mol) of 5-(tert-butyl)-2,6-dihydroxymethylphenol, and a small amount of pyridinium p-toluenesulfonate (Py-PTSA) were added sequentially to a dried 250 mL single-necked reaction flask. The mixture was heated in an oil bath to 130 °C and stirred for 6 h. The reaction product, cooled to room temperature, was dissolved in 600 mL of ethyl acetate (containing a small amount of triethylamine), and then extracted twice with 200 mL of 6% NaHCO3 solution. The ethyl acetate was removed by rotary evaporation to obtain an intermediate product. This intermediate product was then dissolved in 200 mL of tetrahydrofuran, and 200 mL of 3M NaOH solution was added. The mixture was stirred overnight at room temperature, and the product was extracted twice with dichloromethane (DCM). The organic phase was dried overnight with anhydrous magnesium sulfate. The DCM was removed by rotary evaporation to obtain the crude product. The crude product was purified by silica gel column chromatography (dichloromethane:methanol = 1:1) to obtain the target product compound B (21.33 g).

[0126] The structure of compound B is:

[0127] .

[0128] Synthesis of compound C:

[0129] 51 g (0.22 mol) of compound A, 5.62 g (0.074 mol) of 1,3-propanediol, and a small amount of pyridinium p-toluenesulfonate (Py-PTSA) were added sequentially to a dried 250 mL single-necked reaction flask. The mixture was heated in an oil bath to 130 °C and stirred for 6 h. The reaction product, cooled to room temperature, was dissolved in 600 mL of ethyl acetate (containing a small amount of triethylamine), and then extracted twice with 200 mL of 6% NaHCO3 solution. The ethyl acetate was removed by rotary evaporation to obtain an intermediate product. This intermediate product was then dissolved in 200 mL of tetrahydrofuran, and 200 mL of 3M NaOH solution was added. The mixture was stirred overnight at room temperature, and the product was extracted twice with dichloromethane (DCM). The organic phase was dried overnight with anhydrous magnesium sulfate. The DCM was removed by rotary evaporation to obtain the crude product. The crude product was separated and purified by silica gel column chromatography (dichloromethane:methanol = 1:1) to obtain the target product compound C (12.70 g).

[0130] The structure of compound C is:

[0131] .

[0132] Synthesis of compound D:

[0133] 51 g (0.22 mol) of compound A, 7.84 g (0.074 mol) of diethylene glycol, and a small amount of pyridinium p-toluenesulfonate (Py-PTSA) were added sequentially to a dried 250 mL single-necked reaction flask. The mixture was heated in an oil bath to 130 °C and stirred for 6 h. The reaction product, cooled to room temperature, was dissolved in 600 mL of ethyl acetate (containing a small amount of triethylamine), and then extracted twice with 200 mL of 6% NaHCO3 solution. The ethyl acetate was removed by rotary evaporation to obtain an intermediate product. This intermediate product was then dissolved in 200 mL of tetrahydrofuran, and 200 mL of 3M NaOH solution was added. The mixture was stirred overnight at room temperature, and the product was extracted twice with dichloromethane (DCM). The organic phase was dried overnight with anhydrous magnesium sulfate. The DCM was removed by rotary evaporation to obtain the crude product. The crude product was purified by silica gel column chromatography (dichloromethane:methanol = 1:1) to obtain the target product compound D (14.65 g).

[0134] The structure of compound D is as follows:

[0135] .

[0136] Synthesis of compound E:

[0137] 51 g (0.22 mol) of compound A, 10.66 g (0.074 mol) of 1,4-cyclohexyldiethanol and a small amount of pyridinium p-toluenesulfonate (Py-PTSA) were added sequentially to a dried 250 mL single-necked reaction flask. The mixture was heated in an oil bath to 130 °C and stirred for 6 h. The reaction product, cooled to room temperature, was dissolved in 600 mL of ethyl acetate (containing a small amount of triethylamine), and then extracted twice with 200 mL of 6% NaHCO3 solution. The ethyl acetate was removed by rotary evaporation to obtain an intermediate product. This intermediate product was then dissolved in 200 mL of tetrahydrofuran, and 200 mL of 3M NaOH solution was added. The mixture was stirred overnight at room temperature, and the product was extracted twice with dichloromethane (DCM). The organic phase was dried overnight with anhydrous magnesium sulfate. The DCM was removed by rotary evaporation to obtain the crude product. The crude product was purified by silica gel column chromatography (dichloromethane:methanol = 1:1) to obtain the target product compound E (15.89 g).

[0138] The structure of compound E is:

[0139] .

[0140] Synthesis of compound F:

[0141] In a dried 2L round-bottom reaction flask, 29.51g (0.278 mol) of diethylene glycol, 179.18g (1.104 mol) of N,N,-carbonyldiimidazole (CDI), and 1L of DCM were added sequentially. The mixture was stirred overnight at room temperature under nitrogen atmosphere. The reactants were extracted three times with deionized water, and the organic phase was collected and dried overnight with anhydrous magnesium sulfate. After filtration and concentration, compound F (88.46g) was obtained in powder form.

[0142] The structure of compound F is:

[0143] .

[0144] Synthesis of compound G:

[0145] In a dried 500 mL round-bottom reaction flask, 16.70 g (0.058 mol) of 4,4'-methylenebis(2-hydroxymethyl-6-methylphenol), 37.33 g (0.23 mol) of N,N'-carbonyldiimidazole (CDI), and 250 mL of DCM were added sequentially. The mixture was stirred overnight at room temperature under nitrogen atmosphere. The reactants were extracted three times with deionized water, and the organic phase was collected and dried overnight with anhydrous magnesium sulfate. After filtration and concentration, compound G (27.24 g) was obtained in powder form.

[0146] The structure of compound G is as follows:

[0147] .

[0148] Synthesis of compound H:

[0149] In a dried 500 mL round-bottom reaction flask, 11.83 g (0.058 mol) of 5,8-dihydroxymethyl-2-naphthol, 37.33 g (0.23 mol) of N,N,-carbonyldiimidazole (CDI), and 250 mL of DCM were added sequentially. The mixture was stirred overnight at room temperature under nitrogen atmosphere. The reactants were extracted three times with deionized water. The organic phase was collected, dried overnight with anhydrous magnesium sulfate, filtered, and concentrated to obtain compound H (24.33 g) in powder form.

[0150] The structure of compound H is:

[0151] .

[0152] Preparation Example 1

[0153] Polyorthoester resin POE-S1 containing phenolic hydroxyl groups:

[0154] POE can be synthesized by polycondensation reaction. The specific steps of the synthesis are as follows: 16.48 g (0.04 mol) of compound B, 11.76 g (0.04 mmol) of compound F, 12.12 g (0.12 mol) of anhydrous triethylamine, and 400 mL of anhydrous DCM are precisely added to a dry 1 L globular flask. The reaction is stirred at room temperature for 5 days under nitrogen protection. The product is settled with ice-cold anhydrous diethyl ether, collected at the bottom, and dried under vacuum to obtain 17.64 g of polyorthoester resin POE-S1 containing phenolic hydroxyl groups. Its Mw = 8546 (g / mol) and PDI = 2.32.

[0155] The structural formula of POE-S1 is:

[0156] .

[0157] Preparation Example 2

[0158] Polyorthoester resin POE-S2 containing phenolic hydroxyl groups:

[0159] POE can be polymerized via a condensation reaction. The specific synthesis steps are as follows: 4.12 g (0.01 mol) of compound B, 8.34 g (0.03 mol) of compound C, 11.76 g (0.04 mmol) of compound F, 12.12 g (0.12 mol) of anhydrous triethylamine, and 400 mL of anhydrous DCM are precisely added to a dry 1 L g-shaped reaction flask. The reaction is stirred at room temperature for 5 days under nitrogen protection. The product is settled with ice-cold anhydrous diethyl ether, collected at the bottom, and dried under vacuum to obtain 14.22 g of polyorthoester resin POE-S2 containing phenolic hydroxyl groups. Its Mw = 10274 (g / mol) and PDI = 2.49.

[0160] The structural formula of POE-S2 is:

[0161] .

[0162] Preparation Example 3

[0163] Polyorthoester resin POE-S3 containing phenolic hydroxyl groups:

[0164] POE can be polymerized via a condensation reaction. The specific synthesis steps are as follows: 13.84 g (0.04 mol) of compound E, 4.76 g (0.01 mol) of compound G, 8.82 g (0.03 mmol) of compound F, 12.12 g (0.12 mol) of anhydrous triethylamine, and 400 mL of anhydrous DCM are precisely added to a dry 1 L g-shaped reaction flask. The reaction is stirred at room temperature for 5 days under nitrogen protection. The product is settled with ice-cold anhydrous diethyl ether, collected at the bottom, and dried under vacuum to obtain 13.22 g of polyorthoester resin POE-S3 containing phenolic hydroxyl groups. Its Mw = 13113 (g / mol) and PDI = 2.11.

[0165] The structural formula of POE-S3 is:

[0166] .

[0167] Preparation Example 4

[0168] Polyorthoester resin POE-S4 containing phenolic hydroxyl groups:

[0169] POE can be polymerized via a condensation reaction. The specific synthesis steps are as follows: 13.84 g (0.04 mol) of compound E, 3.92 g (0.01 mol) of compound H, 14.28 g (0.03 mol) of compound F, 12.12 g (0.12 mol) of anhydrous triethylamine, and 400 mL of anhydrous DCM are precisely added to a dry 1 L g-shaped reaction flask. The reaction is stirred at room temperature for 5 days under nitrogen protection. The product is settled with ice-cold anhydrous diethyl ether, collected at the bottom, and dried under vacuum to obtain 16.22 g of polyorthoester resin POE-S4 containing phenolic hydroxyl groups. Its Mw = 12119 (g / mol) and PDI = 2.04.

[0170] The structural formula of POE-S4 is:

[0171] .

[0172] POE-S4 1 HNMR spectrum as follows Figure 1 As shown.

[0173] Comparative Preparation Example 1

[0174] POE-R1 polyorthoester resin without phenolic hydroxyl groups:

[0175] POE can be synthesized by polycondensation reaction. The specific steps of the synthesis are as follows: 12.32 g (0.04 mmol) of compound D, 11.76 g (0.04 mmol) of compound F, 12.12 g (0.12 mol) of anhydrous triethylamine, and 400 mL of anhydrous DCM are precisely added to a dry 1 L globular flask. The reaction is stirred at room temperature for 5 days under nitrogen protection. The product is settled with ice-cold anhydrous diethyl ether, collected at the bottom, and dried under vacuum to obtain 18.22 g of phenol-free polyorthoester resin POE-R1. Its Mw = 8421 (g / mol) and PDI = 2.27.

[0176] The structural formula of POE-R1 is:

[0177] .

[0178] Comparative Preparation Example 2

[0179] Acrylic resin P (HS-MMA) containing poly(p-hydroxystyrene):

[0180] In a 250L four-necked flask equipped with a stirrer, condenser, constant-pressure dropping funnel, and thermometer, 0.05 mol of p-acetoxystyrene, 0.15 mol of acrylic acid, 0.01 mol of AIBN, and 100 ml of methanol were added. Stirring was started, and the temperature was set at 60℃. The reaction was allowed to proceed for 6 hours. Then, 0.5 g of 20 wt% sodium methoxide was added, and the reaction proceeded for another 2 hours. The solution was then added dropwise to pure water to precipitate the product. The filter cake was filtered and dried in a 45℃ oven for 24 hours to obtain acrylic resin P(HS-MMA) containing poly(p-hydroxystyrene). Its Mw = 10546 (g / mol) and PDI = 1.95.

[0181] The structural formula of P(HS-MMA) is:

[0182] .

[0183] Comparative preparation example 3

[0184] Naphthol-containing acrylic resin P (NP-MMA):

[0185] In a 250L four-necked flask equipped with a stirrer, condenser, constant-pressure dropping funnel, and thermometer, 0.05 mol of 4-acetoxynaphthalene, 0.15 mol of acrylic acid, 0.01 mol of AIBN, and 100 mL of methanol were added. Stirring was started, and the temperature was set at 60℃. The reaction was allowed to proceed for 6 hours. Then, 0.5 g of 20 wt% sodium methoxide was added, and the reaction proceeded for another 2 hours. The solution was then added dropwise to pure water to precipitate the resin. The filter cake was filtered and dried in a 45℃ oven for 24 hours to obtain naphthol-containing acrylic resin P(NP-MMA). Its Mw = 13590 (g / mol) and PDI = 2.13.

[0186] The structural formula of P(NP-MMA) is:

[0187] .

[0188] Application examples

[0189] The alkaline water-developable bottom anti-reflective coating composition consists of POE resin, crosslinking agent, photoacid generator, additives, and solvent prepared in the preparation example; it is prepared according to the mass parts in Table 2, shaken on a shaker for 24 h to allow them to fully dissolve, and filtered twice through a 0.2 μm pore size filter to obtain the alkaline water-developable bottom anti-reflective coating composition. The types of raw materials in the composition are shown in Table 1, and the mass parts of each raw material in the composition are shown in Table 2.

[0190] Table 1

[0191]

[0192] Table 2

[0193]

[0194] Because the above application examples involve differences in the matching of KrF and ArF exposure light sources, the following tests will be categorized and compared according to exposure differences.

[0195] The performance of the alkaline water-developable bottom antireflective coating composition suitable for ArF light sources prepared above was tested using the following methods:

[0196] Tests of the film thickness, n (refractive index), and k (extinction coefficient) values ​​of the alkaline water-developable bottom anti-reflective coating: The alkaline water-developable bottom anti-reflective coating composition was spin-coated onto a 12-inch silicon wafer at a certain rotation speed, and baked on a hot plate at 185°C for 1 minute to obtain the target film thickness (80±1nm). The thickness FT, n, and k values ​​of the carbon coating were then measured using an ellipsometer (Woollam RC2). A higher k value is better for achieving the desired bottom anti-reflective effect.

[0197] Eth (sensitivity) test of alkaline water-developable bottom anti-reflective coating: The alkaline water-developable bottom anti-reflective coating composition was spin-coated onto a 12-inch silicon wafer at a certain rotation speed, baked on a hot plate at 185°C for 1 min to obtain the target film thickness (80±1nm), and then exposed using ASML TWINSCAN XT:1460K (NA=0.76) at PEB temperature of 135°C for 30s, followed by development with 2.38% TMAH alkaline developer for 60s. The Eth value was then calculated. The smaller the Eth value, the lower the energy required and the higher the sensitivity.

[0198] The optimal exposure energy (Eop) and residue testing of the alkaline water-developable bottom antireflective coating were performed as follows: The alkaline water-developable bottom antireflective coating composition was spin-coated onto a 12-inch silicon wafer at a certain rotation speed and baked on a hot plate at 185°C for 1 min to obtain the target film thickness (80±1nm). The wafer was then exposed using an ASML TWINSCAN XT:1460K (NA=0.76) at a PEB temperature of 135°C for 30s, followed by development with 2.38% TMAH alkaline developer for 60s. The resulting lithographic image with its morphology was analyzed using SEM to observe the Eop energy at 90nm L / s and the residue at the bottom. A smaller Eop value indicates lower energy requirements and stronger photosensitivity; more asterisks (*) indicate a cleaner bottom, with ***** indicating no residue, **** indicating negligible residue, *** indicating linear residue, ** indicating sheet-like residue, and * indicating completely closed residue.

[0199] Measurement of dry etching rate: The alkaline water-developable bottom anti-reflective coating composition was spin-coated onto a 12-inch silicon wafer at a certain rotation speed and baked on a hot plate at 185°C for 1 min to obtain the target film thickness (80±1nm). Then, using an etching machine (ICP HAASRODE-E200A) with O2 gas as the etching gas, the dry etching rate of the alkaline water-developable bottom anti-reflective coating was measured. The dry etching rate of the alkaline water-developable bottom anti-reflective coating formed in Comparative Example 2 was assumed to be 1.00, and the dry etching rates of the alkaline water-developable bottom anti-reflective coatings in other application examples were calculated as dry etching rate ratios.

[0200] Dry etching rate ratio = (Dry etching rate of the bottom anti-reflective coating that can be developed with alkaline water) / (Dry etching rate using Comparative Example 2)

[0201] The lower the dry etching rate, the weaker the etching capability. In this process, the faster the dry etching, the better.

[0202] The test results are shown in Table 3 below:

[0203] Table 3

[0204]

[0205] The performance of the alkaline water-developable bottom antireflective coating composition suitable for KrF light sources prepared above was tested using the following methods:

[0206] Tests of the film thickness, n (refractive index), and k (extinction coefficient) values ​​of the alkaline water-developable bottom anti-reflective coating: The alkaline water-developable bottom anti-reflective coating composition was spin-coated onto a 12-inch silicon wafer at a certain rotation speed and baked on a hot plate at 185°C for 1 minute to obtain the target film thickness (120±1nm, 160±1nm). The thickness FT, n, and k values ​​of the carbon coating were then measured using an ellipsometer (Woollam RC2). A higher k value is better for achieving the desired bottom anti-reflective effect.

[0207] Eth (sensitivity) test of alkaline water-developable bottom anti-reflective coating: The alkaline water-developable bottom anti-reflective coating composition was spin-coated onto a 12-inch silicon wafer at a certain rotation speed, baked on a hot plate at 185°C for 1 min to obtain the target film thickness (120±1nm, 160±1nm), and then exposed using a Nikon S203B (NA=0.76) at a PEB temperature of 135°C for 30s, followed by development using 2.38% TMAH alkaline developer for 60s. The Eth value was then calculated. The smaller the Eth value, the lower the energy required and the higher the sensitivity.

[0208] The Eop (Optimal Exposure Energy) and Residue Test of the Alkali-Developable Anti-Reflective Coating for the Bottom: The alkali-developable anti-reflective coating composition was spin-coated onto a 12-inch silicon wafer at a certain rotation speed and baked on a hot plate at 185℃ for 1 min to obtain the target film thickness (120±1nm, 160±1nm). It was then exposed using a Nikon S203B (NA=0.76) at 135℃ for 30s, followed by development with 2.38% TMAH alkaline developer for 60s. The resulting lithographic image with morphology was observed using SEM to determine its Eop energy at 200nm L / s and the extent of residue at the bottom. A smaller Eop value indicates lower required energy and stronger photosensitivity; more asterisks (*) indicate a cleaner bottom, with ***** indicating no residue, **** indicating negligible residue, *** indicating linear residue, ** indicating sheet-like residue, and * indicating completely closed residue.

[0209] Dry etching rate measurement: The alkaline water-developable bottom anti-reflective coating composition was spin-coated onto a 12-inch silicon wafer at a certain rotation speed and baked on a hot plate at 185°C for 1 min to obtain the target film thickness (120±1nm, 160±1nm). Then, using an etching machine (ICP HAASRODE-E200A) with O2 gas as the etching gas, the dry etching rate of the alkaline water-developable bottom anti-reflective coating was measured. The dry etching rate of the alkaline water-developable bottom anti-reflective coating formed in Comparative Example 3 was assumed to be 1.00. The dry etching rates of the alkaline water-developable bottom anti-reflective coatings in other application examples were calculated as dry etching rate ratios.

[0210] Dry etching rate ratio = (Dry etching rate of the bottom anti-reflective coating that can be developed with alkaline water) / (Dry etching rate using Comparative Example 3)

[0211] The lower the dry etching rate, the weaker the etching capability. In this process, the faster the dry etching, the better.

[0212] The test results are shown in Table 4 below:

[0213] Table 4

[0214]

[0215] Figure 2 The morphology of the bottom antireflective coating composition 200 nm mL / s Eop and the bottom residue are shown in Example 4 of this application, which is alkaline water developable. Figure 3The morphology of the bottom antireflective coating composition 200 nml / s Eop and the bottom residue of Comparative Example 3 (which is alkaline water developable) are shown. It can be seen that the morphology of the bottom antireflective coating composition of Application Example 4 (which is alkaline water developable) is clear and there is no residue at the bottom.

[0216] As shown in Tables 3 and 4, the alkaline water-developable bottom antireflective coatings prepared by comparing the performance of polyorthoester resins containing phenolic hydroxyl groups (comparative examples 1, 2, and 3), polyorthoester resins without phenolic hydroxyl groups (comparative example 1), and styrene-acrylic resins containing phenolic hydroxyl groups with non-decomposing main chains (comparative example 2) under ArF exposure light source were significantly improved in terms of n, k, Eth, Eop, bottom morphology residue, and etching rate.

[0217] Similarly, by comparing the alkaline water-developable bottom antireflective coatings prepared with polyorthoester resin containing phenolic hydroxyl groups (using Comparative Examples 4 and 5) and acrylic resin containing naphthol that does not decompose in the main chain (using Comparative Examples 3 and 4) under KrF exposure light source, the overall performance was greatly improved in terms of n, k, Eth, Eop, morphology bottom residue, and etching rate.

[0218] This is attributed to the phenolic hydroxyl-containing polyorthoester resin used in this application, which has a decomposable main chain and decomposable crosslinked side chains, and is sensitive to acid. In summary, the alkaline-water-developable bottom anti-reflective coating composition based on phenolic hydroxyl-containing polyorthoester resin in this application maintains excellent anti-reflective capabilities while achieving developability of the BARC film layer, and produces superior developing images. This will save semiconductor manufacturing process steps and provide a new generation of photolithography patterning materials for advanced semiconductor manufacturing.

[0219] The present application has been described above with reference to preferred embodiments; however, these embodiments are merely exemplary and illustrative. Various substitutions and modifications can be made to the present application based on these embodiments, all of which fall within the protection scope of the present application.

Claims

1. A bottom anti-reflective coating composition, characterized in that, This includes polyorthoester resins containing phenolic hydroxyl groups, the structure of which is shown in Formula I: Formula I; Wherein, at least one of R1 and R2 includes a group containing a phenolic hydroxyl structure, and the group containing a phenolic hydroxyl structure includes a C group containing a phenolic hydroxyl structure. 6~24 Aryl, C 7~40 Aryl alkyl, C 7~40 At least one of alkylaryl, fluorenyl, and polyphenylene structures linked by bridging bonds; n is an integer between 10 and 500; Wherein, m is the total number of moles of R1 and R2, and p is the sum of the number of moles of R1 containing phenolic hydroxyl groups p1 and the number of moles of R2 containing phenolic hydroxyl groups p2, satisfying: 10%m≤p≤70%m.

2. The bottom anti-reflective coating composition according to claim 1, characterized in that, At least one of R1 and R2 includes a group that does not contain a phenolic hydroxyl structure; Wherein, the groups that do not contain phenolic hydroxyl structures include C 1-10 alkyl, C 3-10 cycloalkyl and C 1-10 At least one of the ether groups.

3. The bottom anti-reflective coating composition according to claim 1, characterized in that, The group containing the phenolic hydroxyl structure is selected from one or more of the following: ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， 。 4. The bottom anti-reflective coating composition according to claim 2, characterized in that, The group that does not contain a phenolic hydroxyl structure is selected from one or more of the following: ， ， ， ， 。 5. The bottom anti-reflective coating composition according to claim 1, characterized in that, The Mw of the polyorthoester resin containing phenolic hydroxyl groups is 500~30000 g / mol; and / or The polyorthoester resin containing phenolic hydroxyl groups has a PDI of 1.5 to 5.

6. The bottom anti-reflective coating composition according to claim 5, characterized in that, The Mw of the polyorthoester resin containing phenolic hydroxyl groups is 1000~10000 g / mol; and / or The polyorthoester resin containing phenolic hydroxyl groups has a PDI of 1.9 to 3.

5.

7. The bottom anti-reflective coating composition according to claim 1, characterized in that, The composition further includes at least one of a crosslinking agent, a photoacid generator, other additives, and a solvent; The other additives are selected from at least one of leveling agents and quenching agents.

8. The bottom anti-reflective coating composition according to claim 7, characterized in that, The bottom antireflective coating composition comprises, by weight: 1-10 parts of polyorthoester resin containing phenolic hydroxyl groups; Crosslinking agent 0.05-5 parts; Photo-acid-generating agent: 0.01-2 parts; Other additives 0.0001-0.1 parts; and Solvent: 85-98 parts.

9. The bottom anti-reflective coating composition according to claim 7, characterized in that, The crosslinking agent is a vinyl ether compound containing multiple functional groups; and / or The photoacid generator is an ionic photoacid generator and / or a non-ionic photoacid generator; and / or The solvent is selected from at least one of ketone solvents, ester solvents, ether solvents, and aromatic hydrocarbon solvents.

10. The bottom anti-reflective coating composition according to claim 9, characterized in that, The crosslinking agent is selected from at least one of ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, triethylene glycol divinyl ether, and cyclohexanediethanol divinyl ether; and / or The photoacid-generating agent is selected from diphenyliodonium trifluoromethanesulfonate, diphenyliodonium camphor sulfonate, diphenyliodonium perfluoro-1-butanesulfonate, diphenyliodonium perfluorooctane sulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium tetrafluoroborate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, and bis(4-tert-butylphenyl)iodonium. Trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium perfluorooctanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium perfluoro-1-butylsulfonate, triphenylsulfonium perfluoro Octane sulfonate, p-Tolyldiphenylsulfonium trifluoromethanesulfonate, p-Tolyldiphenylsulfonium perfluorooctane sulfonate, p-Tolyldiphenylsulfonium perfluoro-1-butane sulfonate, p-Tolyldiphenylsulfonium camphor sulfonate, 2,4,6-Trimethylphenyldiphenylsulfonium trifluoromethane sulfonate, 4-tert-Butylphenyldiphenylsulfonium trifluoromethane sulfonate, 4-Phenylenylthiodiphenylsulfonium hexafluorophosphate, 1-(2-Naphthylmethyl)thiosulfonium trifluoromethane sulfonate, 4-Hydroxy-1-naphthyldimethylsulfonium trifluoromethane sulfonate, 2-Methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-Phenylen-4,6-bis(trichloromethyl)- 1,3,5-Triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxy-1-naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(benzo[d][1,3]dioxolane-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-dimethoxystyryl)- 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(2,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(2-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-butoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-pentoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, diphenyl disulfone, di-p-tolyl disulfone, bis(phenylsulfonyl)diazomethane, bis(4-chlorophenylsulfonyl)diazomethane, bis(p-tolylsulfonyl)diazomethane, bis(4-tert-butylphenylsulfonyl)diazomethane, bis(2,4-Dimethylbenzylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, (benzoyl)(phenylsulfonyl)diazomethane, 1-benzoyl-1-phenylmethyl p-toluenesulfonic acid, 2-benzoyl-2-hydroxy-2-phenylethyl p-toluenesulfonic acid, 1,2,3-phenyltriyl trimethanesulfonic acid, 2,6-dinitrobenzene p-toluenesulfonic acid, 2-nitrobenzene p-toluenesulfonic acid, 4-nitrobenzene p-toluenesulfonic acid, N-(phenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)succinimide, N-(perfluoro-1-butanesulfonic acid)succinimide, N-(perfluorooctanesulfonic acid)succinimide, N-(perfluoro-1-butane) At least one of the following: N-(trifluoromethylsulfonyloxy)phthalimide, N-(perfluorooctanesulfonic acid)phthalimide, N-(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxylic acid imide, N-(perfluoro-1-butanesulfonic acid)-5-norbornene-2,3-dicarboxylic acid imide, N-(perfluorooctanesulfonic acid)-5-norbornene-2,3-dicarboxylic acid imide, N-(trifluoromethylsulfonyloxy)naphthyleneimide, N-(perfluoro-1-butanesulfonic acid)naphthyleneimide, N-(perfluorooctanesulfonic acid)naphthyleneimide, and N-(10-camphorsulfonyloxy)naphthyleneimide; and / or, The leveling agent is selected from at least one of acrylic leveling agents, silicone leveling agents, and fluorocarbon leveling agents; and / or The quencher is an amine compound and / or a photoalkalizing agent; and / or The solvent is selected from at least one of propylene glycol methyl ether acetate, propylene glycol monoacetate, ethylene glycol methyl ether acetate, diethylene glycol, propylene glycol methyl ether, propylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, γ-butyrolactone, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

11. A semiconductor manufacturing method, characterized in that, include: A photolithographic image formed by developing the bottom anti-reflective coating composition according to any one of claims 1 to 10 in an alkaline developing solution.

12. The semiconductor manufacturing method according to claim 11, wherein, The alkaline developing solution is selected from aqueous solutions of tetramethylammonium hydroxide (TMAH), potassium hydroxide, and sodium hydroxide.

13. A semiconductor device, characterized in that, It is manufactured using the semiconductor manufacturing method of claim 11 or 12.

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