Catalyst-free crosslinking of propiolate functionalized molecules and polymers

Abstract

Disclosed is a novel method for preparing a crosslinked film without the use of a catalyst. The propiolic acid ester is obtained by grafting propiolic acid with glycidyl or epoxy under mild conditions by using a phosphonium catalyst. The propiolic acid ester can be thermally crosslinked at temperatures as low as 120 DEG C (such that the polymer film is insoluble), while some embodiments can be photoinduced crosslinked upon exposure to DUV light. The resulting cross-linked membrane is equivalent to or better than an acid-catalyzed epoxide cross-linked membrane in stability, and can be used in a variety of different applications.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Patent Application Serial No. 63 / 534,246, filed August 23, 2023, entitled “CATALYST-FREE CROSSLINKING OF PROPIOLATE-ESTER-FUNCTIONALIZED MOLECULES AND POLYMERS”, which is incorporated herein by reference in its entirety. Background Technology Technical Field

[0004] This disclosure relates to materials and methods for fabricating microelectronic structures. Background Technology

[0005] Crosslinked films are ubiquitous in industrial applications, and various methods have been researched and developed to promote the rapid formation of covalent bonds between polymer chains or small molecules. These can be broadly categorized into two types: small molecules with multiple functional groups react with side groups on polymer chains, and side groups can react with each other to form a crosslinked network.

[0006] In the first case of thermally crosslinked membranes, key examples involve 1,3,4,6-tetra(methoxymethyl)glycourea (TMMGU) and other derivatives, which can react with side-chain hydroxyl groups in the presence of an acid to form a crosslinked network, with the resulting methanol being volatile enough to leave the membrane. Multiple epoxy groups on the small molecule can also act as effective crosslinking agents with side-chain hydroxyl or phenolic groups. Vinyl ethers can react with side-chain carboxylic acids and phenols without additional catalysts. Since these methods all rely on the random distribution of small-molecule crosslinking agents throughout the polymer membrane, they can be limited by non-uniformity and varying degrees of crosslinking / rigidity of the resulting network. Furthermore, an acid catalyst is required, demanding a hindered acid to prevent premature crosslinking, or accepting defects from the crosslinking reaction while simultaneously preventing the inclusion of acid-sensitive groups in the crosslinked membrane.

[0007] The second broad type of crosslinking chemistry involves self-reactive groups, such as epoxides, which rapidly form crosslinked films under acid or base catalysis. Glycidyl groups are particularly common in photolithography-related films due to their storage stability and ease of reaction (i.e., rapid crosslinking) at mild temperatures. Polymers containing poly(benzyl azide) have also shown the ability to crosslink in films by losing nitrogen, but the required temperature of 250°C limits the incorporation of other functionalities into the polymer, and the toxicity of azides makes it a less preferred pathway.

[0008] Other methods, such as thiol-ene reactions or copper-catalyzed alkyne-azide coupling, have been used for crosslinking, but generally, this crosslinking is photoinduced or not used for thin films. The need for copper as a catalyst, coupled with metal contamination, has also hindered the use of alkyne-azide click coupling in photolithography-related fields.

[0009] To date, all described methods require a catalyst (typically an acid) and a potentially small-molecule crosslinking agent, both of which can increase the non-uniformity of the resulting film and introduce potential defects. Therefore, there is a need to improve the formation of crosslinked films. Summary of the Invention

[0010] In one embodiment, a method of forming a structure is provided. The method includes forming an underlayer on a stack. The underlayer is formed from a composition comprising a compound including an alkynyl carboxylic acid that reacts with an epoxy group. Optionally, one or more intermediate layers are formed on the underlayer, and if one or more intermediate layers are present, an uppermost intermediate layer is present on the surface of the substrate. If one or more intermediate layers are present, a photoresist layer is applied to the one or more intermediate layers; or if no intermediate layers are present, a photoresist layer is applied to the underlayer.

[0011] In a further embodiment, this disclosure provides a structure comprising a substrate having a surface. Optionally, one or more intermediate layers are present on the surface of the substrate, and if one or more intermediate layers are present, a topmost intermediate layer is present on the surface of the substrate. A bottom layer is present on the surface of the substrate, or if a topmost intermediate layer is present, a bottom layer is present on the topmost intermediate layer, and photoresist is present on the bottom layer. The bottom layer comprises a compound including an alkyne carboxylic acid that reacts with an epoxy group.

[0012] In another embodiment, this disclosure provides a method comprising reacting an alkynyl carboxylic acid with an epoxy group at a temperature of about 100°C or lower to form a reaction product.

[0013] This disclosure further provides compounds having the following formulas: .

[0014] In yet another further embodiment, a crosslinked layer comprising an alkynyl carboxylic acid that reacts with an epoxy group is provided. Attached Figure Description

[0015] Figure 1 It is a 75° tile angle scanning electron microscope (SEM) image of the 40 / 80nm line / space pattern generated in Example 31.

[0016] Figure 2 It is a 75° angled SEM image of the 14 / 28nm line / space pattern generated in Example 32.

[0017] Figure 3 This is a graph showing the thickness of the material from Example 20 before and after using the PGMEA strip membrane relative to the baking temperature, as tested in Example 33.

[0018] Figure 4 This is a graph showing the thickness of the material from Example 21 before and after using the PGMEA strip membrane relative to the baking temperature, as tested in Example 33.

[0019] Figure 5 The graph shows the thickness of the material from Example 25 before and after using the PGMEA extraction membrane relative to the baking temperature, as tested in Example 33.

[0020] Figure 6 The graph shows the thickness of the material from Example 26 before and after using the PGMEA extraction membrane relative to the baking temperature, as tested in Example 33.

[0021] Figure 7 This is a graph showing the thickness ratio relative to the dose before and after PGMEA extraction, as tested in Example 34. Detailed Implementation

[0022] To address the problems discussed in the background section, a catalyst-free, self-crosslinking technique has been invented for crosslinking films. Generally, alkynyl carboxylic acids react with epoxy groups. For example, in some embodiments, propynic acid is grafted onto a glycidyl group or epoxy group on a monomer or polymer to form a propynic ester. Preferably, the resulting compound comprises the following components: , in This indicates the connection point between this part and the remaining part of the compound, and R is selected from oxygen, carbon, or nitrogen. It will be understood that multiple parts exist on the same compound, wherein the R groups are the same or different (e.g., oxygen, carbon, and / or nitrogen on the same compound), and / or different compounds with the same or different R groups may exist.

[0023] The monomers and / or polymers can be used in a variety of thin film-forming compositions, including those for photolithography. For example, they can be used to fabricate self-crosslinking spin-coated carbon substrates for photolithographic pattern transfer. Furthermore, this concept can be applied to film-forming compositions for antireflection or adhesion layer functions, such as EUV substrates or reflection control in 193-nm photolithography. Formula (I) shows an example of a general reaction scheme for the reaction of alkynyl carboxylic acids with epoxy groups.

[0024] (I)

[0025] Composition

[0026] 1. Single-unit implementation

[0027] The preferred functionalized monomers described herein are the result of the reaction of an epoxy-containing monomer with an alkynyl carboxylic acid in the presence of a catalyst and a solvent. In some embodiments, the reaction temperature is about 100°C or lower, thereby inhibiting or preventing the self-reaction and gelation of the alkynyl ester during synthesis. Preferably, the reaction is carried out at a temperature of about 50°C to about 100°C, more preferably about 55°C to about 100°C, and most preferably about 60°C to about 75°C for about 4 hours to about 36 hours, preferably about 12 hours to about 30 hours, and more preferably about 22 hours to about 26 hours.

[0028] Suitable alkynyl carboxylic acids include those selected from C3 to C8 alkynyl carboxylic acids, including those selected from: propynic acid, butynic acid, 4-pentynic acid, 5-hexynic acid, or mixtures thereof.

[0029] Suitable epoxy-containing monomers include those containing a glycidyl group. In some embodiments, the monomer is selected from: tri-(2,3-epoxypropyl)isocyanurate (TEPIC-S), bisphenol A diglycidyl ether, 9,9-bis(4-glycidyloxyphenyl)fluorene, tri-(4-hydroxyphenyl)methane triglycidyl ether, or combinations thereof.

[0030] Preferably, the alkynyl carboxylic acid and monomer are included in sufficient quantities such that the molar ratio of the alkynyl carboxylic acid to the epoxy group is about 0.8:1 to about 1.2:1, more preferably about 0.9:1 to about 1.1:1, and even more preferably about 1:1. This typically yields about 3% to about 40% alkynyl carboxylic acid, preferably about 5% to about 35% alkynyl carboxylic acid, and more preferably about 10% to about 30% alkynyl carboxylic acid, and / or about 20% to about 95% epoxy-containing monomer, preferably about 25% to about 85% epoxy-containing monomer, and more preferably about 30% to about 75% epoxy-containing monomer, based on the total weight of solids in 100% of the reaction solution.

[0031] Suitable catalysts include, but are not limited to, quaternary ammonium or phosphonium catalysts, such as benzyltriethylammonium chloride (BTEAC), ethyltriphenylphosphonium bromide (ETTPB), tetrabutylphosphonium bromide, tetrabutylammonium iodide, or combinations thereof. Preferably, the catalyst is present in the reaction solution in an amount of about 0.5% to about 5% by weight, preferably about 1% to about 3% by weight, and more preferably about 2% to about 2.5% by weight, based on the total solid weight of 100% of the reaction solution.

[0032] Preferred reaction solvents include protic solvents or co-solvents because they limit side reactions. Examples of suitable reaction solvents include those selected from: propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether (PGEE), cyclopentanone, cyclohexanone, anisole, acetophenone, benzyl alcohol, γ-butyrolactone (GBL), γ-valerate lactone (GVL), tetrahydrofurfuryl alcohol, or mixtures thereof. The reaction is completed to a sufficiently high degree that separation of the resulting functionalized monomers is unnecessary, and the mother liquor can be used for formulation without further preparation or separation.

[0033] Preferably, the amount of the reaction solvent in the reaction solution is about 50% to about 80% by weight, more preferably about 50% to about 75% by weight, and more preferably about 50% to about 70% by weight, based on a total weight of 100% by weight of the reaction solution.

[0034] Formula II illustrates some implementations of the functionalized monomer.

[0035] (II)

[0036] 2. Polymer Implementation Method

[0037] Preferred polymers for surface modification as described herein are polymers comprising one or more epoxy-containing monomers, which are subsequently functionalized with alkyne carboxylic acids in the presence of a catalyst and solvent. As used herein, unless otherwise stated, the term "polymer" is intended to include oligomers. As used in the text, oligomers comprise 10 or fewer repeating units.

[0038] In some embodiments, the reaction temperature is about 100°C or lower, thereby inhibiting or preventing the self-reaction and gelation of the alkynyl ester during synthesis. Preferably, the reaction is carried out at a temperature of about 50°C to about 100°C, more preferably about 55°C to about 100°C, and most preferably about 60°C to about 75°C for about 4 hours to about 36 hours, preferably about 12 hours to about 30 hours, and more preferably about 22 hours to about 26 hours.

[0039] Suitable alkynyl carboxylic acids include those selected from C3 to C8 alkynyl carboxylic acids, including those selected from: propynic acid, butynic acid, 4-pentynic acid, 5-hexynic acid, or mixtures thereof.

[0040] Suitable polymers comprising one or more epoxy-containing monomers include polymers comprising one or more monomers comprising glycidyl groups. Suitable polymers include those selected from: epoxy-cresyl phenolic varnish (ECN), poly(glycidyl methacrylate) (poly(GMA)), epoxy-phenylphenolic varnish (EPON), poly(4-glycidyloxystyrene), bisphenol A phenolic varnish-epoxy, poly(glycidyl acrylate), or combinations thereof.

[0041] Preferably, the alkynyl carboxylic acid and polymer are included in sufficient quantities such that the molar ratio of the alkynyl carboxylic acid to the epoxy group is about 0.8:1 to about 1.2:1, more preferably about 0.9:1 to about 1.1:1, and even more preferably about 1:1. This typically yields about 3% to about 40% alkynyl carboxylic acid, preferably about 5% to about 35% alkynyl carboxylic acid, and more preferably about 10% to about 30% alkynyl carboxylic acid, and / or about 60% to about 95% wt% polymer, preferably about 65% to about 90% wt% polymer, and more preferably about 70% to about 80% wt% polymer, based on the total solid weight in 100% of the reaction solution.

[0042] In some embodiments, the epoxy-containing monomer is copolymerized with one or more comonomers. Suitable comonomers include those selected from styrene, methyl methacrylate, benzyl methacrylate, 4-methylstyrene, pentafluorostyrene, butyl methacrylate, 2-isopropyl-2-adamantyl methacrylate, cyclohexyl methacrylate, 1-adamantyl methacrylate, 4-tert-butoxycarbonyloxystyrene, or combinations thereof. When comonomers are included, the comonomers are typically included in a molar ratio of about 0.2:1 to about 9:1, preferably about 0.5:1 to about 8:1, more preferably about 0.5:1 to about 8:1, and even more preferably about 0.5:1 to about 6:1 to the epoxy-containing monomer.

[0043] Suitable catalysts include, but are not limited to, quaternary ammonium or phosphonium catalysts, such as benzyltriethylammonium chloride (BTEAC), ethyltriphenylphosphonium bromide (ETTPB), tetrabutylphosphonium bromide, tetrabutylammonium iodide, or combinations thereof. Preferably, the catalyst is present in the reaction solution in an amount of about 0.1 wt% to about 5 wt%, preferably about 0.5 wt% to about 3 wt%, and more preferably about 1.5 wt% to about 2.5 wt%, based on the total solid weight of 100 wt% of the reaction solution.

[0044] Preferred reaction solvents include protic solvents or co-solvents because they limit side reactions. Examples of suitable reaction solvents include those selected from: PGME, PGMEA, PGEE, cyclopentanone, cyclohexanone, anisole, acetophenone, benzyl alcohol, GBL, GVL, tetrahydrofurfuryl alcohol, or mixtures thereof. The reaction yield is high enough that the resulting functionalized polymer does not need to be separated, and the mother liquor can be used for formulation without further preparation or separation.

[0045] Preferably, the amount of the reaction solvent in the reaction solution is about 50% to about 90% by weight, more preferably about 50% to about 80% by weight, and more preferably about 50% to about 75% by weight, based on the total weight of the reaction solution taken as 100% by weight.

[0046] Formula III shows an exemplary polymer formed from functionalized monomers.

[0047] (III)

[0048] The weight-average molecular weight (Mw) of the polymers described herein (measured by gel permeation chromatography) is preferably from about 1,500 g / mol to about 80,000 g / mol, and more preferably from about 4,000 g / mol to about 10,000 g / mol.

[0049] In one embodiment, the polymer is substantially composed of one or more types of epoxy-containing monomers, or even one or more types of epoxy-containing monomers. In another embodiment, the polymer is substantially composed of one or more types of epoxy-containing monomers, and one or more of the aforementioned comonomers.

[0050] 3. Composition

[0051] The composition comprises the aforementioned functionalized polymer and / or the aforementioned functionalized monomer dispersed or dissolved in a solvent system. The combined weight of the polymer and / or monomer is preferably used in an amount of about 0.1% to about 35% by weight, more preferably about 0.2% to about 5% by weight, based on a total weight of 100% of the composition.

[0052] Preferred solvent systems include one or more solvents selected from the group consisting of PGME, PGMEA, PGEE, cyclopentanone, cyclohexanone, anisole, GBL, GVL, or mixtures thereof. Preferably, the solvent system is used in an amount of about 65% to about 99.9% by weight, more preferably about 95% to about 99.8% by weight, based on a total weight of 100% of the composition.

[0053] The composition may contain optional ingredients, such as those selected from surfactants, polymers, additives, and mixtures thereof. In some embodiments, the composition contains less than about 0.1% of a crosslinking agent, preferably less than about 0.05% of a crosslinking agent, and more preferably about 0% of a crosslinking agent, based on 100% by weight of the composition. Additionally or alternatively, the composition may contain less than about 0.1% of a catalyst (e.g., a copper catalyst), less than about 0.05% of a catalyst, and even more preferably about 0% of a catalyst, based on 100% by weight of the composition.

[0054] In some embodiments, the composition contains less than about 5% by weight, preferably less than about 1%, and more preferably about 0% silicon, based on total solids in 100% by weight of the composition.

[0055] In one or more embodiments, the composition comprises less than about 5% by weight, preferably less than about 1%, and more preferably about 0% nanoparticles, based on total solids in 100% by weight of the composition.

[0056] In some embodiments, the composition consists essentially of, or even consists of, functionalized polymers and / or functionalized monomers dispersed or dissolved in a solvent system.

[0057] The above-mentioned components are mixed together in the solvent system to form a specific composition. Additionally, optional components (e.g., surfactants) may be suitably dispersed in the solvent system simultaneously. Preferably, the composition is filtered before use, for example, using a 0.1-μm or 0.2-μm PTFE filter.

[0058] Using the composition method

[0059] A method for forming microelectronic structures, particularly suitable for photolithography, is provided. Any microelectronic substrate can be used, but the substrate is preferably a semiconductor substrate, such as substrates selected from: silicon, SiGe, SiO2, Si3N4, SiON, aluminum, tungsten, tungsten silicide, gallium arsenide, germanium, tantalum, tantalum nitride, Ti3N4, hafnium, HfO2, ruthenium, indium phosphide, tetramethylsilicate and tetramethylcyclotetrasiloxane combinations (such as products sold under the name CORAL), SiCOH (such as products sold under the name Black Diamond by SVM (Santa Clara, California, USA), glass, or combinations thereof. An optional intermediate layer can be formed on the substrate prior to processing, wherein a TiN or SiO2 layer is preferred. The substrate may be planar, or may include topographic features (vias, trenches, contact holes, protrusions, lines, etc.). As used herein, "topography" refers to the height or depth of a structure in or on the surface of the substrate.

[0060] The above-described self-crosslinking composition can be formed into an underlayer, wherein the underlayer can serve as a spin-coated carbon layer, an antireflective layer, and / or an adhesive layer (e.g., in EUV applications).

[0061] 1. The bottom layer of this invention is a spin-coated carbon layer.

[0062] When the above composition is used as a spin-coated carbon (SOC) layer (also known as a carbon-rich layer), a SOC composition layer is formed on the substrate or any intermediate layer (e.g., a primer layer). The SOC layer can be formed by any known application method, one preferred method being spin-coating at a speed of about 750 rpm to about 2300 rpm, and preferably about 1200 rpm to about 1800 rpm for a time period of about 10 seconds to about 60 seconds, and preferably about 15 seconds to about 40 seconds. Preferably, the SOC composition has good spin bowl compatibility and does not react with or form precipitates with common photoresist solvents such as PGME, PGMEA, ethyl lactate, cyclohexanone, or mixtures thereof.

[0063] After the SOC composition is applied, it is preferably heated to a temperature of about 110°C to about 250°C, and more preferably about 160°C to about 180°C, for about 10 seconds to about 120 seconds, and preferably about 30 seconds to about 60 seconds, in order to evaporate the solvent and crosslink the layer.

[0064] In another embodiment, the SOC composition can be crosslinked by exposure to radiation. Subsequently, the SOC layer is fully or partially (e.g., patterned) exposed to radiation at a dose of approximately 10 mJ / cm². 2 Approximately 2,000 mJ / cm 2 Preferably, it is about 80 mJ / cm 2 Approximately 1,000 mJ / cm 2 And more preferably about 140 mJ / cm 2 Approximately 300 mJ / cm 2 The wavelength is from about 170 nm to about 365 nm, preferably from about 172 nm to about 365 nm.

[0065] After baking, the average thickness of the SOC layer is preferably about 1 nm to about 2,000 nm, more preferably about 5 nm to about 300 nm, and even more preferably about 5 nm to about 60 nm. The average thickness is determined by averaging the thickness measurements at five different locations on the SOC layer, which are obtained using elliptic polarization.

[0066] After baking, the resulting SOC layer preferably contains more than about 65% by weight of carbon, more preferably more than about 80% by weight of carbon, and even more preferably about 85% by weight to about 90% by weight of carbon, based on 100% by weight of the final SOC layer of the composition (i.e., the SOC layer is "carbon-rich").

[0067] In one embodiment, the SOC layer has good SC-1 tolerance because it is unaffected by exposure to SC-1 cleaning solvent at about 60°C for at least about 30 minutes.

[0068] A hard mask layer can be applied to the SOC layer or any intermediate layer that may exist on the SOC layer. The hard mask layer can be formed by any known application method, such as chemical vapor deposition ("CVD") or plasma-enhanced chemical vapor deposition ("PECVD"). Another preferred method includes spin-coating at a speed of about 1,000 rpm to about 5,000 rpm, and preferably about 1,250 rpm to about 1,750 rpm for a time period of about 30 seconds to about 120 seconds, and preferably about 45 seconds to about 75 seconds. A suitable hard mask layer should have a high etch bias relative to the underlying layer. Preferred hard mask layers have a high silicon content material, preferably at least about 30% by weight of silicon, and more preferably about 35% by weight to about 40% by weight of silicon, based on the total weight of the hard mask layer.

[0069] Suitable hard mask layers are commercially available and can be formed from compositions comprising polymers or oligomers (e.g., silanes, siloxanes, silsesquioxanes, silicon nitrides, silicon nitrides, polycrystalline silicon, amorphous silicon, or combinations thereof) dissolved or dispersed in a solvent system. Some preferred monomers or polymers for use in hard mask layers are selected from: phenethyltrimethoxysilane (“PETMS”), 2-(methyl ester)ethyltrimethoxysilane (“CMETMS”), tetraethoxysilane (“TEOS”), methyltrimethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane (“MTMS”), ethyltrimethoxysilane (“ETMS”), (3-glycidoxypropyl)triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (“ECHTMS”), and mixtures thereof. Any optional components (such as surfactants, acid catalysts, base catalysts, and / or crosslinking agents) are dissolved together with the polymer, monomers, and / or oligomers in the solvent system. Preferably, the solid content of the preferred hard mask composition will be from about 0.1% by weight to about 70% by weight, more preferably from about 0.5% by weight to about 10% by weight, and even more preferably from about 0.5% by weight to about 1% by weight, based on 100% by weight of the total weight of the composition.

[0070] After applying the hard mask composition, it is preferably heated to a temperature of about 100°C to about 300°C, more preferably about 150°C to about 250°C, for about 30 seconds to about 120 seconds, more preferably about 45 seconds to about 60 seconds, to evaporate the solvent. After baking, the average thickness of the hard mask layer (measured and averaged at five locations by elliptic polarization) is preferably about 5 nm to about 50,000 nm, more preferably about 5 nm to about 1,000 nm, and even more preferably about 10 nm to about 30 nm.

[0071] Subsequently, photoresist (i.e., an imaging layer) may be applied to the SOC layer, or photoresist may be applied to any hard mask layer or other intermediate layer on the SOC layer to form a photoresist layer. The photoresist layer can be formed by any conventional method, one preferred method being: spin-coating the photoresist composition at a speed of about 350 rpm to about 4,000 rpm (preferably about 1,000 rpm to about 2,500 rpm) for a period of about 10 seconds to about 60 seconds (preferably about 10 seconds to about 30 seconds). Subsequently, optionally, the photoresist layer is subjected to post-application baking (“PAB”) at a temperature of at least about 70°C, preferably about 80°C to about 150°C, and more preferably about 100°C to about 150°C, for a period of about 30 seconds to about 120 seconds. After baking, the average thickness of the photoresist layer (as determined above) is typically about 5 nm to about 120 nm, preferably about 10 nm to about 50 nm, and more preferably about 20 nm to about 40 nm.

[0072] Subsequently, the photoresist layer is patterned by exposing it to radiation at a dose of approximately 10 mJ / cm². 2 Approximately 200 mJ / cm 2 Preferably, it is about 15 mJ / cm 2 Approximately 100 mJ / cm 2 And more preferably about 20 mJ / cm 2 Approximately 80 mJ / cm 2 The wavelength is from about 13.5 nm to about 365 nm, preferably from about 13.5 nm to about 248 nm. Suitable wavelengths include DUV, i-line, ArF, KrF, and EUV wavelengths. More specifically, the photoresist layer is exposed using a mask located above the surface of the photoresist layer. The mask has regions designed to allow radiation to be reflected from or pass through the mask and to contact the surface of the photoresist layer. The remaining portion of the mask is designed to absorb light to prevent radiation from contacting the surface of the photoresist layer in certain areas. Those skilled in the art will readily understand that the arrangement of the reflective and absorbing portions depends on the desired pattern formed in the photoresist layer, and thus in the final substrate or any intermediate layer.

[0073] After exposure, the photoresist layer is preferably baked after exposure (“PEB”) at a temperature of less than about 180°C, preferably about 60°C to about 140°C, and more preferably about 80°C to about 130°C for a period of about 30 seconds to about 120 seconds (preferably about 30 seconds to about 90 seconds).

[0074] The photoresist layer is then brought into contact with a developer to form a pattern. Depending on whether the photoresist used is positive-working or negative-working, the developer removes either the exposed or unexposed portions of the photoresist layer, thus forming the pattern. The pattern is then transferred through the layers and finally to the substrate. This pattern transfer can be performed via plasma etching (such as CF4 etchant or O2 etchant) or wet etching or development processes.

[0075] 2. The bottom layer of this invention serves as an anti-reflective layer, an adhesive layer, or an assist layer.

[0076] When the composition of the present invention is used as an antireflective layer, an adhesive layer, or an auxiliary layer, the layer of the composition of the present invention is formed on the substrate or any intermediate layer (e.g., a SOC layer or a hard mask layer).

[0077] When the SOC is present as an intermediate layer, regardless of the SOC composition used, the SOC layer can be formed by any known application method, one preferred method being spin coating for a period of about 10 seconds to about 90 seconds, and preferably about 30 seconds to 60 seconds, at a speed of about 500 rpm to about 3,000 rpm, and preferably about 1,200 rpm to about 2,000 rpm. Preferably, the SOC composition has good spin-coating compatibility, i.e., it does not react with or form precipitates with common photoresist solvents such as PGME, PGMEA, ethyl lactate, cyclohexanone, or mixtures thereof.

[0078] After applying the SOC composition, the SOC composition is preferably heated to a temperature of about 140°C to about 250°C, and more preferably about 160°C to about 220°C, for about 10 seconds to about 120 seconds, and more preferably about 30 seconds to about 60 seconds, thereby evaporating the solvent.

[0079] After baking, the average thickness of the SOC layer is preferably about 50 nm to about 3 µm, more preferably about 100 nm to about 300 nm, and even more preferably about 150 nm to about 200 nm. The average thickness is determined by averaging the thickness measurements at five different locations on the SOC layer, and these thickness measurements are obtained using elliptic polarization.

[0080] After baking, the resulting SOC layer preferably contains more than about 75% by weight of carbon, more preferably more than about 80% by weight of carbon, and even more preferably about 85% by weight to about 90% by weight of carbon, based on 100% by weight of the final layer of the composition (i.e., the SOC layer is "carbon-rich").

[0081] Preferably, the SOC layer exhibits little or no shrinkage. That is, after heating to about 200°C for about 10 minutes, the average thickness decreases by less than about 5%, and even more preferably, after heating to about 300°C for about 10 minutes, the thickness decreases by less than about 5%. In some cases, the shrinkage of the SOC layer may be negative, i.e., the layer thickness increases after the baking conditions, indicating that the SOC layer swells. (In these cases, it is presumed that the SOC layer may become less dense after high-temperature baking, resulting in minimal weight loss and slight film swelling.) In one embodiment, the SOC layer exhibits good SC-1 tolerance because it is unaffected by exposure to an SC-1 cleaning solution at about 60°C for more than about 30 minutes.

[0082] A hard mask layer can be applied to the SOC layer or any intermediate layer that may exist on the SOC layer. The hard mask layer can be formed by any known application method, such as chemical vapor deposition ("CVD") or plasma-enhanced chemical vapor deposition ("PECVD"). Another preferred method includes spin-coating at a speed of about 1,000 rpm to about 5,000 rpm, and preferably about 1,250 rpm to about 1,750 rpm for a time period of about 30 seconds to about 120 seconds, and preferably about 45 seconds to about 75 seconds. A suitable hard mask layer should have a high etch bias relative to the underlying layer. Preferred hard mask layers have a high silicon content material, preferably at least about 30% by weight of silicon, and more preferably about 35% by weight to about 40% by weight of silicon, based on the total weight of the hard mask layer. Suitable hard mask layers are commercially available and can be formed from compositions comprising polymers or oligomers (e.g., silanes, siloxanes, silsesquioxanes, silicon oxynitrides, silicon nitrides, polycrystalline silicon, amorphous silicon, and combinations thereof) dissolved or dispersed in a solvent system. Some preferred monomers or polymers for use in hard mask layers are selected from: phenethyltrimethoxysilane (“PETMS”), 2-(methyl ester)ethyltrimethoxysilane (“CMETMS”), tetraethoxysilane (“TEOS”), methyltrimethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane (“MTMS”), ethyltrimethoxysilane (“ETMS”), (3-glycidoxypropyl)triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (“ECHTMS”), and mixtures thereof. Any optional components (such as surfactants, acid catalysts, base catalysts, and / or crosslinking agents) are dissolved together with the polymer, monomers, and / or oligomers in the solvent system. Preferably, the solids content of the preferred hard mask composition will be from about 0.1% to about 70% by weight, more preferably from about 0.5% to about 10% by weight, and even more preferably from about 0.5% to about 1% by weight, based on 100% by weight of the total weight of the composition.

[0083] After applying the hard mask composition, it is preferably heated to a temperature of about 100°C to about 300°C, more preferably about 150°C to about 250°C, for about 30 seconds to about 120 seconds, more preferably about 45 seconds to about 60 seconds, to evaporate the solvent. After baking, the average thickness of the hard mask layer (measured and averaged at five locations by elliptic polarization) is preferably about 5 nm to about 50,000 nm, more preferably about 5 nm to about 1,000 nm, and even more preferably about 10 nm to about 30 nm.

[0084] After applying the hard mask composition, an antireflective layer or adhesive layer can be formed by any known application method. The antireflective layer or adhesive layer comprises the functionalized polymer or monomer described above. A preferred method is spin-coating at a speed of about 500 rpm to about 3,000 rpm, and preferably about 1,200 rpm to about 2,000 rpm, for a time period of about 10 seconds to about 90 seconds, and preferably about 30 seconds to 60 seconds. Preferably, the antireflective layer or adhesive layer has good spin-coating compatibility, preventing it from reacting with or forming deposits with common photoresist solvents such as PGME, PGMEA, ethyl lactate, cyclohexanone, or mixtures thereof.

[0085] After applying the antireflective layer, adhesive layer, or auxiliary layer composition, it is preferably heated to a temperature of about 110°C to about 250°C, and more preferably about 160°C to about 180°C, for about 10 seconds to about 120 seconds, and preferably about 30 seconds to about 60 seconds, thereby evaporating the solvent and crosslinking the layer.

[0086] In another embodiment, the antireflective layer, adhesive layer, or auxiliary layer composition can be cross-linked by exposure to radiation. Subsequently, the antireflective layer, adhesive layer, or auxiliary layer is fully or partially (e.g., patterned) exposed to radiation at a dose of about 10 mJ / cm². 2 Approximately 2,000 mJ / cm 2 Preferably, it is about 80 mJ / cm 2 Approximately 1,000 mJ / cm 2 And more preferably about 140 mJ / cm 2 Approximately 300 mJ / cm 2 The wavelength is from about 170 nm to about 365 nm, preferably from about 172 nm to about 365 nm.

[0087] After baking, the average thickness of the antireflective layer, adhesive layer, or auxiliary layer is preferably about 1 nm to about 2,000 nm, more preferably about 5 nm to about 80 nm, and even more preferably about 5 nm to about 40 nm. The average thickness is determined by averaging the thickness measurements at five different locations on the antireflective layer or adhesive layer, and these thickness measurements are obtained using elliptic polarization.

[0088] In some embodiments, the underlying layer preferably has light-absorbing properties. For example, the refractive index (n value) of the cured antireflective layer at 193 nm or 248 nm will be at least about 1.2, preferably about 1.3 to about 2, and more preferably about 1.4 to about 1.8. At the wavelength of use (e.g., 193 nm, 248 nm, or 365 nm), the extinction coefficient (k value) of the antireflective layer is at least about 0.001, preferably about 0.01 to about 0.8, and more preferably about 0.05 to about 0.6. By changing the refractive index, extinction coefficient, and thickness of the layers, suitable combinations can be obtained to reduce the reflectivity of the stack to <1%.

[0089] Subsequently, photoresist (i.e., an imaging layer) may be applied to the antireflection layer, adhesion layer, or auxiliary layer, or photoresist (i.e., an imaging layer) may be applied to any intermediate layer on the antireflection layer, adhesion layer, or auxiliary layer to form a photoresist layer. The photoresist layer can be formed by any conventional method, one preferred method being: spin-coating the photoresist composition at a speed of about 350 rpm to about 4,000 rpm (preferably about 1,000 rpm to about 2,500 rpm) for a period of about 10 seconds to about 60 seconds (preferably about 10 seconds to about 30 seconds). Subsequently, optionally, the photoresist layer is subjected to post-application baking (“PAB”) at a temperature of at least about 70°C, preferably about 80°C to about 150°C, and more preferably about 100°C to about 150°C, for a period of about 30 seconds to about 120 seconds. After baking, the average thickness of the photoresist layer (as determined above) is typically about 5 nm to about 120 nm, preferably about 10 nm to about 50 nm, and more preferably about 20 nm to about 40 nm.

[0090] Subsequently, the photoresist layer is patterned by exposing it to radiation at a dose of approximately 10 mJ / cm². 2 Approximately 200 mJ / cm 2 Preferably, it is about 15 mJ / cm 2 Approximately 100 mJ / cm 2 And more preferably about 20 mJ / cm 2 Approximately 80 mJ / cm 2The wavelength is from about 13.5 nm to about 365 nm, preferably from about 13.5 nm to about 248 nm. Suitable wavelengths include DUV, i-line, ArF, KrF, and EUV wavelengths. More specifically, the photoresist layer is exposed using a mask located above the surface of the photoresist layer. The mask has regions designed to allow radiation to be reflected from or pass through the mask and to contact the surface of the photoresist layer. The remaining portion of the mask is designed to absorb light to prevent radiation from contacting the surface of the photoresist layer in certain areas. Those skilled in the art will readily understand that the arrangement of the reflective and absorbing portions depends on the desired pattern formed in the photoresist layer, and thus in the final substrate or any intermediate layer.

[0091] After exposure, the photoresist layer is preferably baked after exposure (“PEB”) at a temperature of less than about 180°C, preferably about 60°C to about 140°C, and more preferably about 80°C to about 130°C for a period of about 30 seconds to about 120 seconds (preferably about 30 seconds to about 90 seconds).

[0092] The photoresist layer is then brought into contact with a developer to form a pattern. Depending on whether the photoresist used is positive-working or negative-working, the developer removes either the exposed or unexposed portions of the photoresist layer, thus forming the pattern. The pattern is then transferred through the layers and finally to the substrate. This pattern transfer can be performed via plasma etching (such as CF4 etchant or O2 etchant) or wet etching or development processes.

[0093] Other advantages of the various implementations will become apparent to those skilled in the art after reviewing the disclosure herein and the following working examples. It should be understood that, unless otherwise indicated herein, the various implementations described herein are not necessarily mutually exclusive. For example, a feature described or depicted in one implementation may be included in other implementations, but is not necessarily required to be included in other implementations. Therefore, this disclosure covers various combinations and / or integrations of the particular implementations described herein.

[0094] As used herein, when the phrase “and / or” is used to list two or more items, it indicates that any one of the listed items may be used alone, or any combination of two or more of the listed items may be used. For example, if a composition is described as containing or not containing components A, B and / or C, then the composition may contain or not contain: A only; B only; C only; a combination of A and B; a combination of A and C; a combination of B and C; or a combination of A, B and C.

[0095] This description also uses numerical ranges to quantify certain parameters relating to the various embodiments. It should be understood that when a numerical range is provided, the range should be interpreted as providing written support for claims that specify only the lower limit of the range and claims that specify only the upper limit of the range. For example, the disclosed numerical range of about 10 to about 100 provides written support for claims that specify "about greater than 10" (no upper limit) and claims that specify "about less than 100" (no lower limit).

[0096] Example

[0097] The following embodiments illustrate methods according to this disclosure. However, it should be understood that these embodiments are provided by way of illustration and nothing therein should be construed as limiting the overall scope.

[0098] Example 1

[0099] Grafting propargyl acid onto bisphenol A diglycidyl ether

[0100] In this embodiment, 5.11 g of diglycidyl ether bisphenol A (Sigma-Aldrich, St. Louis, MO), 2.10 g of propargyl acid (Alfa Aesar, Tewksbury, MA), 0.278 g of ethyltriphenylphosphonium bromide (EtPPB) (Sigma-Aldrich, St. Louis, MO), and 29.94 g of propylene glycol monomethyl ether (PGME) (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a round-bottom flask, and the mixture was heated at 60°C for 24 hours. The reaction was cooled to room temperature and collected as a mother liquor.

[0101] Example 2

[0102] Grafting propargyl acid onto tris(4-hydroxyphenyl)methane triglycidyl ether

[0103] In this embodiment, 6.91 g of tris(4-hydroxyphenyl)methane triglycidyl ether (Sigma-Aldrich, St. Louis, MO), 3.15 g of propynic acid (Alfa Aesar, Tewksbury, MA), 0.139 g of ethyltriphenylphosphonium bromide (EtPPB) (Sigma-Aldrich, St. Louis, MO), and 40.80 g of propylene glycol monomethyl ether (PGME) (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a round-bottom flask, and the mixture was heated at 60°C for 24 hours. The reaction was cooled to room temperature and collected as the mother liquor.

[0104] Example 3

[0105] Grafting propargyl acid onto tris(2,3-epoxypropyl)isocyanurate

[0106] In this embodiment, 5.95 g of tris(2,3-epoxypropyl)isocyanurate (TEPIC) (Sigma-Aldrich, St. Louis, MO), 4.20 g of propynic acid (Alfa Aesar, Tewksbury, MA), 0.140 g of ethyltriphenylphosphonium bromide (EtPPB) (Sigma-Aldrich, St. Louis, MO), 15.44 g of propylene glycol monomethyl ether (PGME) (Fujifilm Ultrapure Solutions, Carrolton, TX), and 15.44 g of propylene glycol monomethyl ether acetate (PGMEA) (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a round-bottom flask, and the mixture was heated at 60°C for 24 hours. The reaction was cooled to room temperature and collected as the mother liquor.

[0107] Example 4

[0108] Propyridine acid was grafted onto 9,9-bis(4-hydroxyphenyl)fluorene diglycidyl ether.

[0109] In this embodiment, 6.94 g of 9,9-bis(4-hydroxyphenyl)fluorene diglycidyl ether (PDGE) (TCI Chemicals, Portland, OR), 2.1 g of propynic acid (Alfa Aesar, Tewksbury, MA), 0.278 g of ethyltriphenylphosphonium bromide (EtPPB) (Sigma-Aldrich, St. Louis, MO), 13.98 g of propylene glycol monomethyl ether (PGME) (Fujifilm Ultrapure Solutions, Carrolton, TX), and 13.98 g of propylene glycol monomethyl ether acetate (PGMEA) (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a round-bottom flask, and the mixture was heated at 60°C for 24 hours. The reaction was cooled to room temperature and collected as a mother liquor.

[0110] Example 5

[0111] Grafting propargyl acid onto epoxy-cresyl phenolic varnish

[0112] In this embodiment, 2.85 g of epoxy-cresyl phenolic varnish (ECN) (Kukdo Chemical Co., Ltd., Seoul, Korea), 1.05 g of propynic acid (Alfa Aesar, Tewksbury, MA), 0.171 g of ethyltriphenylphosphonium bromide (EtPPB) (Sigma-Aldrich, St. Louis, MO), and 6.29 g of propylene glycol monomethyl ether (PGME) (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a round-bottom flask, and the mixture was heated at 60°C for 24 hours. The reaction was cooled to room temperature and collected as the mother liquor.

[0113] Example 6

[0114] Synthetic polymer 1

[0115] In this embodiment, the following were added to a round-bottom flask: 7.61 g of methyl methacrylate (TCI Chemicals, Portland, OR), 0.53 g of benzyl methacrylate (TCI Chemicals, Portland, OR), 0.11 g of 4-methylstyrene (TCI Chemicals, Portland, OR), 2.13 g of glycidyl methacrylate (Monomer Polymer and Dajac Labs, Ambler, PA), 0.673 g of 4-cyano-4-(((dodecylthio)thiocarbonyl)thio)valeric acid (BM1432) (Boron Molecular, Raleigh, NC), and 0.0274 g of azobisisobutyronitrile (AIBN) (Charkit, Norwalk, Connecticut). The flask contained 21.96 g of propylene glycol monomethyl ether acetate (PGMEA) (Fujifilm Ultrapure Solutions, Carrolton, TX) and was bubbled with nitrogen for 10 minutes. The flask was then placed in an oil bath and heated at 70°C for 24 hours. The reaction was cooled to room temperature and collected as the mother liquor.

[0116] Example 7

[0117] Propynoic acid was grafted onto polymer 1 from Example 6.

[0118] In this embodiment, 16.47 g of polymer 1 mother liquor (synthesized in Example 6), 0.056 g of ethyltriphenylphosphonium bromide (EtPPB) (Sigma-Aldrich, St. Louis, MO), 0.52 g of propargyl acid (Alfa Aesar, Tewksbury, MA), and 10.98 g of propylene glycol monomethyl ether (PGME) (Fujifilm Ultrasound Solutions, Carrolton, TX) were added to a round-bottom flask, stirred at 60°C for 24 hours, and then cooled to room temperature and stored as mother liquor.

[0119] Example 8

[0120] Synthetic polymer 2

[0121] In this embodiment, 3.5 g of methyl methacrylate, 3.52 g of benzyl methacrylate (TCI Chemicals, Portland, OR), 2.95 g of 4-methylstyrene (TCI Chemicals, Portland, OR), 2.84 g of glycidyl methacrylate (Monomer Polymer and Dajac Labs, Ambler, PA), 0.673 g of 4-cyano-4-(((dodecylthio)thiocarbonyl)thio)valeric acid (BM1432) (BoronMolecular, Raleigh, NC), 0.0274 g of azobisisobutyronitrile (AIBN) (Charkit, Norwalk, CT), and 25.65 g of propylene glycol monomethyl ether acetate (PGMEA) (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a round-bottom flask, and the mixture was bubbled with nitrogen for 10 minutes. The flask was then placed in an oil bath and heated at 85°C for 24 hours. The reaction was cooled to room temperature and collected as the mother liquor.

[0122] Example 9

[0123] Grafting propynic acid into polymer 2 from Example 8

[0124] In this embodiment, 15.39 g of polymer 2 mother liquor (synthesized in Example 8), 0.059 g of ethyltriphenylphosphonium bromide (EtPPB) (Sigma-Aldrich, St. Louis, MO), 0.56 g of propionic acid (Alfa Aesar, Tewksbury, MA), and 5.13 g of propylene glycol monomethyl ether (PGME) (Fujifilm UltrapureSolutions, Carrolton, TX) were added to a round-bottom flask, stirred at 60°C for 24 hours, and then cooled to room temperature and stored as mother liquor.

[0125] Example 10

[0126] Synthetic polymer 3

[0127] In this embodiment, 4.59 g of 2-isopropyl-2-adamantyl methacrylate (TCI Chemicals, Portland, OR), 4.62 g of glycidyl methacrylate (Monomer Polymer and Dajac Labs, Ambler, PA), 0.336 g of 4-cyano-4-(((dodecylthio)thiocarbonyl)thio)valeric acid (BM1432) (Boron Molecular, Raleigh, NC), 0.0137 g of azobisisobutyronitrile (AIBN) (Charkit, Norwalk, CT), and 18.42 g of propylene glycol monomethyl ether acetate (PGMEA) (Fujifilm UltrapureSolutions, Carrolton, TX) were added to a round-bottom flask, and the mixture was bubbled with nitrogen for 10 minutes. The flask was then placed in an oil bath and heated at 70°C for 24 hours. The reaction was cooled to room temperature and collected as the mother liquor.

[0128] Example 11

[0129] Propynoic acid was grafted onto polymer 3 from Example 10.

[0130] In this embodiment, 11.05 g of polymer 3 mother liquor (synthesized in Example 9), 0.097 g of ethyltriphenylphosphonium bromide (EtPPB) (Sigma-Aldrich, St. Louis, MO), 0.91 g of propionic acid (Alfa Aesar, Tewksbury, MA), and 3.68 g of propylene glycol monomethyl ether (PGME) (Fujifilm UltrapureSolutions, Carrolton, TX) were added to a round-bottom flask, stirred at 60°C for 24 hours, and then cooled to room temperature and stored as mother liquor.

[0131] Example 12

[0132] Synthetic polymer 4

[0133] In this embodiment, 28.43 g of glycidyl methacrylate (Monomer Polymer and Dajac Labs, Ambler, PA), 1.34 g of 4-cyano-4-(((dodecylthio)thiocarbonyl)thio)valeric acid (BM1432) (Boron Molecular, Raleigh, NC), 0.0547 g of azobisisobutyronitrile (AIBN) (Charkit, Norwalk, CT), and 56.86 g of propylene glycol monomethyl ether acetate (PGMEA) (Fujifilm Ultrasound Solutions, Carrolton, TX) were added to a round-bottom flask, and the mixture was bubbled with nitrogen for 10 minutes. The flask was then placed in an oil bath and heated at 70°C for 24 hours. The reaction was cooled to room temperature and collected as the mother liquor.

[0134] Example 13

[0135] Synthetic polymer 5

[0136] In this embodiment, 95.11 g of methyl methacrylate (TCI chemicals, Portland, OR), 7.11 g of glycidyl methacrylate (Monomer Polymer and Dajac Labs, Ambler, PA), 7.76 g of 4-cyano-4-(((dodecylthio)thiocarbonyl)thio)valeric acid (Boron Molecular, Raleigh, NC), 0.316 g of 2,2'-azobis(2-methylpropionitrile) (AIBN) (Charkit, Norwalk, CT), and 204.44 g of PGMEA (Fujifilm Ultra Pure Solutions, Inc., Carrollton, TX) were added to a round-bottom flask, and the mixture was bubbled with N2 for 10 minutes. The reaction was maintained at 70°C under a nitrogen atmosphere with magnetic stirring for 24 hours.

[0137] Example 14

[0138] Propynoic acid was grafted onto polymer 5 from Example 13.

[0139] In this embodiment, 30.67 g of Polymer 5 mother liquor (synthesized in Example 13), 0.093 g of ethyltriphenylphosphonium bromide (EtPPB) (Sigma-Aldrich, St. Louis, MO), 0.35 g of propionic acid (Alfa Aesar, Tewksbury, MA), and 20.44 g of propylene glycol monomethyl ether (PGME) (Fujifilm Ultrasound Solutions, Carrolton, TX) were added to a round-bottom flask, stirred at 60°C for 24 hours, and then cooled to room temperature and stored as mother liquor.

[0140] Example 15

[0141] Synthetic polymer 6

[0142] In this embodiment, 9.01 g of methyl methacrylate (TCI chemicals, Portland, OR), 1.42 g of glycidyl methacrylate (Monomer Polymer and Dajac Labs, Ambler, PA), 0.673 g of 4-cyano-4-(((dodecylthio)thiocarbonyl)thio)valeric acid (BoronMolecular, Raleigh, NC), 0.027 g of 2,2'-azobis(2-methylpropionitrile) (AIBN) (Charkit, Norwalk, CT), and 20.86 g of PGMEA (Fujifilm Ultra Pure Solutions, Inc., Carrollton, TX) were added to a round-bottom flask, and the mixture was bubbled with N2 for 10 minutes. The reaction was maintained at 70°C under a nitrogen atmosphere with magnetic stirring for 24 hours.

[0143] Example 16

[0144] Grafting propynic acid into polymer 6 from Example 15

[0145] In this embodiment, 15.64 g of polymer 5 mother liquor (synthesized in Example 15), 0.093 g of ethyltriphenylphosphonium bromide (EtPPB) (Sigma-Aldrich, St. Louis, MO), 0.35 g of propionic acid (Alfa Aesar, Tewksbury, MA), and 10.43 g of propylene glycol monomethyl ether (PGME) (Fujifilm Ultrasound Solutions, Carrolton, TX) were added to a round-bottom flask, stirred at 60°C for 24 hours, and then cooled to room temperature and stored as mother liquor.

[0146] Example 17

[0147] 9-ACA, pentafluorobenzoic acid, and propynic acid were grafted onto polymer 4 from Example 12.

[0148] In this embodiment, 10.66 g of polymer 4 mother liquor (synthesized in Example 11), 1.11 g of 9-anthracarboxylic acid (Midori Kagaku, Tokyo, Japan), 2.54 g of pentafluorobenzoic acid (TCI Chemicals, Portland, OR), 0.186 g of ethyltriphenylphosphonium bromide (EtPPB) (Sigma-Aldrich, St. Louis, MO), 0.52 g of propynic acid (Alfa Aesar, Tewksbury, MA), and 7.92 g of propylene glycol monomethyl ether (PGME) (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a round-bottom flask. The mixture was stirred at 60°C for 24 hours, then cooled to room temperature and stored as mother liquor.

[0149] Example 18

[0150] Pentafluorobenzoic acid, 3,5-diiodosalicylic acid, and propynic acid were grafted onto polymer 4 from Example 12.

[0151] In this embodiment, 10.66 g of polymer 4 mother liquor (synthesized in Example 11), 2.12 g of pentafluorobenzoic acid (TCI chemicals, Portland, OR), 2.92 g of 3,5-diiodosalicylic acid (TCICchemicals, Portland, OR), 0.186 g of ethyltriphenylphosphonium bromide (EtPPB) (Sigma-Aldrich, St. Louis, MO), 0.52 g of propynic acid (Alfa Aesar, Tewksbury, MA), and 9.31 g of propylene glycol monomethyl ether (PGME) (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a round-bottom flask. The mixture was stirred at 60°C for 24 hours, then cooled to room temperature and stored as mother liquor.

[0152] Example 19

[0153] 3,5-Diiodosalicylic acid and propargyl acid were grafted onto epoxy-cresylphenol varnish.

[0154] In this embodiment, 3.8 g of epoxy-cresyl phenolic varnish (ECN) (Kukdo Chemical Co., Ltd., Seoul, Korea), 4.68 g of 3,5-diiodosalicylic acid (TCI chemicals, Portland, OR), 0.278 g of ethyltriphenylphosphonium bromide (EtPPB) (Sigma-Aldrich, St. Louis, MO), 0.56 g of propynic acid (Alfa Aesar, Tewksbury, MA), and 13.98 g of propylene glycol monomethyl ether (PGME) (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a round-bottom flask, stirred at 60°C for 24 hours, and then cooled to room temperature and stored as a mother liquor.

[0155] Example 20

[0156] Synthetic polymer 7

[0157] In this embodiment, 5.51 g of 4-(tert-butoxycarbonyloxy)styrene (Heraeus Epurio, Dayton, OH), 3.55 g of glycidyl methacrylate (Monomer Polymer and Dajac Labs, Ambler, PA), 0.336 g of 4-cyano-4-(((dodecylthio)thiocarbonyl)thio)valeric acid (BM1432) (Boron Molecular, Raleigh, NC), 0.0137 g of azobisisobutyronitrile (AIBN) (Charkit, Norwalk, CT), and 18.12 g of propylene glycol monomethyl ether acetate (PGMEA) (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a round-bottom flask, and the mixture was bubbled with nitrogen for 10 minutes. The flask was then placed in an oil bath and heated at 80°C for 24 hours. The reaction was cooled to room temperature and collected as the mother liquor.

[0158] Example 21

[0159] Grafting propynic acid into polymer 7 from Example 20

[0160] In this embodiment, 24.46 g of polymer 7 mother liquor (synthesized in Example 20), 0.167 g of ethyltriphenylphosphonium bromide (EtPPB) (Sigma-Aldrich, St. Louis, MO), 1.58 g of propionic acid (Alfa Aesar, Tewksbury, MA), and 9.90 g of propylene glycol monomethyl ether (PGME) (Fujifilm UltrapureSolutions, Carrolton, TX) were added to a round-bottom flask, stirred at 60°C for 24 hours, and then cooled to room temperature and stored as mother liquor.

[0161] Example 22

[0162] Synthetic polymer 8

[0163] In this embodiment, 10.09 g of cyclohexyl methacrylate (TCI Chemicals, Portland, OR), 2.84 g of glycidyl methacrylate (Monomer Polymer and Dajac Labs, Ambler, PA), 0.538 g of 4-cyano-4-(((dodecylthio)thiocarbonyl)thio)valeric acid (BM1432) (BoronMolecular, Raleigh, NC), 0.0219 g of azobisisobutyronitrile (AIBN) (Charkit, Norwalk, CT), and 26.99 g of propylene glycol monomethyl ether acetate (PGMEA) (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a round-bottom flask, and the mixture was bubbled with nitrogen for 10 minutes. The flask was then placed in an oil bath and heated at 70°C for 24 hours. The reaction was cooled to room temperature and collected as the mother liquor.

[0164] Example 23

[0165] Propynoic acid was grafted onto polymer 8 from Example 22.

[0166] In this embodiment, 16.98 g of polymer 8 mother liquor (synthesized in Example 22), 0.065 g of ethyltriphenylphosphonium bromide (EtPPB) (Sigma-Aldrich, St. Louis, MO), 0.613 g of propionic acid (Alfa Aesar, Tewksbury, MA), and 6.34 g of propylene glycol monomethyl ether (PGME) (Fujifilm UltrapureSolutions, Carrolton, TX) were added to a round-bottom flask, stirred at 60°C for 24 hours, and then cooled to room temperature and stored as mother liquor.

[0167] Example 24

[0168] Formulate the product from Example 1

[0169] In this embodiment, 5.00 g of the functionalized stock solution from Example 1, 4 g of PGME (Fujifilm Ultrapure Solutions, Carrolton, TX), and 11 g of PGMEA (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a 100-mL Aicello bottle and mixed for 5 minutes. The resulting solution was filtered using a 0.1-µm PTFE endpoint filter.

[0170] Example 25

[0171] Formulating the product from Example 5

[0172] In this embodiment, 2.50 g of the functionalized stock solution from Example 5, 7.50 g of PGME (Fujifilm Ultrapure Solutions, Carrolton, TX), and 11 g of PGMEA (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a 100-mL Aicello bottle and mixed for 5 minutes. The resulting solution was filtered using a 0.1-µm PTFE endpoint filter.

[0173] Example 26

[0174] Formulating the functionalized polymer 1 from Example 7

[0175] In this embodiment, 6.00 g of the functionalized polymer 1 stock solution from Example 6, 60 g of propylene glycol monomethyl ether acetate (PGMEA) (Fujifilm Ultrapure Solutions, Carrolton, TX), and 34 g of propylene glycol monomethyl ether (PGME) (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a 100-mL Aicello flask and mixed for 24 hours. The resulting solution was filtered using a 0.1-µm PTFE endpoint filter.

[0176] Example 27

[0177] Formulating the functionalized polymer 2 from Example 9

[0178] In this embodiment, 6.00 g of the functionalized polymer 2 stock solution from Example 8, 60 g of propylene glycol monomethyl ether acetate (PGMEA) (Fujifilm Ultrapure Solutions, Carrolton, TX), and 34 g of propylene glycol monomethyl ether (PGME) (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a 100-mL Aicello bottle and mixed for 24 hours. The resulting solution was filtered using a 0.1-µm PTFE endpoint filter.

[0179] Example 28

[0180] Formulating the functionalized polymer 3 from Example 11

[0181] In this embodiment, 0.8 g of the functionalized polymer 3 stock solution from Example 11, 65.2 g of propylene glycol monomethyl ether acetate (PGMEA) (Fujifilm Ultrapure Solutions, Carrolton, TX), and 34 g of propylene glycol monomethyl ether (PGME) (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a 100-mL Aicello flask and mixed for 24 hours. The resulting solution was filtered using a 0.1-µm PTFE endpoint filter.

[0182] Example 29

[0183] Formulating the functionalized polymer 5 from Example 14

[0184] In this embodiment, 5.00 g of the functionalized stock solution from Example 14, 7.5 g of PGME (Fujifilm Ultrapure Solutions, Carrolton, TX), and 7.5 g of PGMEA (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a 100-mL Aicello bottle and mixed for 5 minutes. The resulting solution was filtered using a 0.1-µm PTFE endpoint filter.

[0185] Example 30

[0186] Formulating the functionalized polymer 6 from Example 16

[0187] In this embodiment, 5.00 g of the functionalized stock solution from Example 16, 7.50 g of PGME (Fujifilm Ultrapure Solutions, Carrolton, TX), and 7.50 g of PGMEA (Fujifilm Ultrapure Solutions, Carrolton, TX) were added to a 100-mL Aicello bottle and mixed for 5 minutes. The resulting solution was filtered using a 0.1-µm PTFE endpoint filter.

[0188] Example 31

[0189] 193-nm immersion exposure

[0190] The material formulated in Example 27 was coated onto a 300-mm silicon wafer by spin-coating at 1,500 rpm for 60 seconds, followed by baking at 205°C for 60 seconds. The material formulated in Example 26 was coated on top of the material layer from Example 27 and baked at 205°C for 60 seconds. AIM5484 photoresist from JSR was coated onto the material layer from Example 12 by spin-coating at 1,185 rpm and baked at 120°C for 60 seconds as post-applied bake (PAB). Subsequently, the wafer was exposed to different doses of 193-nm radiation, followed by baking at 100°C for 60 seconds, and then developed with an alkaline aqueous solution to reveal the pattern. Figure 1 The image shows an SEM image of the chip.

[0191] Example 32

[0192] EUV exposure

[0193] The material formulated in Example 28 was coated onto a 300-mm silicon wafer by spin-coating at 1,500 rpm for 60 seconds, followed by baking at 160°C for 60 seconds. Pentaline photoresist (TOK, Kangawa, Japan) was coated on top of the material layer from Example 28 by spin-coating at 1,800 rpm and baked at 110°C for 60 seconds as a post-applied bake (PAB). Subsequently, the wafer was exposed to different doses of EUV radiation in an ASML NXE3400 scanner, followed by baking at 90°C for 60 seconds, and then developed with an alkaline aqueous solution to reveal the pattern. Figure 2 SEM images of the chip are provided.

[0194] Example 33

[0195] Crosslinking test

[0196] The material formulated in Example 24 was coated onto multiple 100-mm silicon wafers by spin coating at 1,500 rpm for 60 seconds, followed by baking at different temperatures for 60 seconds. Figure 3 The thickness of the film formed after baking and the film after subsequent washing with PGMEA is shown as a function of baking temperature.

[0197] The material formulated in Example 25 was coated onto multiple 100-mm silicon wafers by spin coating at 1,500 rpm for 60 seconds, followed by baking at different temperatures for 60 seconds. Figure 4 The thickness of the film formed after baking and the film after subsequent washing with PGMEA is shown as a function of baking temperature.

[0198] The material formulated in Example 29 was coated onto multiple 100-mm silicon wafers by spin coating at 1,500 rpm for 60 seconds, followed by baking at different temperatures for 60 seconds. Figure 5 The thickness of the film formed after baking and the film after subsequent washing with PGMEA is shown as a function of baking temperature.

[0199] The material formulated in Example 30 was coated onto multiple 100-mm silicon wafers by spin coating at 1,500 rpm for 60 seconds, followed by baking at different temperatures for 60 seconds. Figure 6 The thickness of the film formed after baking and the film after subsequent washing with PGMEA is shown as a function of baking temperature.

[0200] Example 34

[0201] Photocrosslinking

[0202] The material formulated in Example 25 was coated onto a 100-mm silicon wafer by spin-coating at 1,500 rpm for 60 seconds, followed by baking at 80°C for 60 seconds. Subsequently, the film was exposed to broadband UV radiation at different doses (measured at 254 nm) using an Oriel Solar Simulator, and then washed with PGMEA. The thickness before and after PGMEA extraction was measured using elliptic polarization. Figure 7 The proportions are shown as a function of dosage.

Claims

1. A method for forming a structure, the method comprising: An underlayer is formed on the stack, the underlayer being formed of a composition comprising a compound including an alkynyl carboxylic acid that reacts with an epoxy group; Optionally, one or more intermediate layers are formed on the bottom layer, and if one or more intermediate layers exist, an uppermost intermediate layer exists on the surface of the substrate; as well as If one or more intermediate layers are present, a photoresist layer is applied to the one or more intermediate layers; or if no intermediate layer is present, a photoresist layer is applied to the bottom layer.

2. The method of claim 1, wherein the forming comprises: The composition is applied to the stack, and the composition is subjected to one or both of heating or UV radiation to induce cross-linking of the compound.

3. The method as described in claim 1 or 2, wherein: (a) The composition contains less than about 0.1% by weight of a crosslinking agent, based on a weight of 100% by weight of the composition; (b) The compound is self-crosslinked; or (c) Both (a) and (b) are true.

4. The method according to any one of claims 1 to 3, wherein the alkynyl carboxylic acid is selected from C3 to C8 alkynyl carboxylic acids.

5. The method according to any one of claims 1 to 4, wherein the alkynyl carboxylic acid is selected from: propynic acid, butynic acid, 4-pentynic acid, 5-hexynic acid, or mixtures thereof.

6. The method according to any one of claims 1 to 5, wherein the compound is selected from: monomeric compounds, oligomeric compounds, polymeric compounds, or mixtures thereof.

7. The method of any one of claims 1 to 6, wherein the epoxy group is present as a part of: (i) The compound is selected from the following: tri-(2,3-epoxypropyl)isocyanurate, bisphenol A diglycidyl ether, 9,9-bis(4-glycidyloxyphenyl)fluorene, tri-(4-hydroxyphenyl)methane triglycidyl ether, or mixtures thereof; (ii) A polymer selected from the following: epoxy-cresyl phenolic varnish, poly(glycidyl methacrylate), epoxy-phenylphenolic varnish, poly(4-glycidyloxystyrene), bisphenol A phenolic varnish epoxy resin, poly(glycidyl acrylate), or mixtures thereof; or (iii) Combinations of (i) and (ii).

8. The method of any one of claims 1 to 7, wherein the compound is selected from one or more of the following: 。 9. The method of any one of claims 1 to 8, wherein the stack comprises: A substrate having a surface; and Optionally, one or more additional intermediate layers on the surface, if one or more additional intermediate layers exist, then there is a topmost additional intermediate layer on the surface, if the topmost additional intermediate layer exists, then the bottom layer is located on the topmost additional intermediate layer, or if there are no additional intermediate layers, then the bottom layer is located on the surface.

10. The method of claim 9, wherein the substrate comprises: silicon, SiGe, SiO2, Si3N4, SiON, SiCO:H, a combination of tetramethylsilicate and tetramethylcyclotetrasiloxane, aluminum, tungsten, tungsten silicide, gallium arsenide, germanium, tantalum, tantalum nitride, Ti3N4, hafnium, HfO2, ruthenium, indium phosphide, or glass.

11. The method of any one of claims 1 to 8, wherein the method further comprises: Expose the photoresist layer to radiation; After the photoresist layer is subjected to irradiation, a pattern is formed in the photoresist layer; as well as Transfer the pattern to the bottom layer.

12. The method of any one of claims 1 to 11, wherein the underlying layer comprises an antireflective layer, a carbon-rich layer, or an adhesive layer.

13. A structure comprising: Substrate, which has a surface; Optionally, one or more intermediate layers are present on the surface of the substrate; if one or more intermediate layers are present, an uppermost intermediate layer is present on the surface of the substrate. A bottom layer, located on the surface of the substrate, or on the uppermost intermediate layer if one exists, comprising a compound comprising an alkynyl carboxylic acid that reacts with an epoxy group; and Photoresist on the underlying layer.

14. The structure of claim 13, wherein the alkynyl carboxylic acid is selected from C3 to C8 alkynyl carboxylic acids.

15. The structure of claim 13 or 14, wherein the alkynyl carboxylic acid is selected from: propynic acid, butynic acid, 4-pentynic acid, 5-hexynic acid, or mixtures thereof.

16. The structure according to any one of claims 13 to 15, wherein the compound is selected from: monomeric compounds, oligomeric compounds, polymeric compounds, or mixtures thereof.

17. The structure of any one of claims 13 to 16, wherein the epoxy group is present as a part of: (i) The compound is selected from the following: tri-(2,3-epoxypropyl)isocyanurate, bisphenol A diglycidyl ether, 9,9-bis(4-glycidyloxyphenyl)fluorene, tri-(4-hydroxyphenyl)methane triglycidyl ether, or mixtures thereof; (ii) A polymer selected from the following: epoxy-cresyl phenolic varnish, poly(glycidyl methacrylate), epoxy-phenylphenolic varnish, poly(4-glycidyloxystyrene), bisphenol A phenolic varnish-epoxy, poly(glycidyl acrylate), or mixtures thereof; or (iii) Combinations of (i) and (ii).

18. The structure of any one of claims 13 to 17, wherein the compound is selected from one or more of the following: 。 19. The structure of any one of claims 13 to 18, wherein the underlying layer comprises an antireflective layer, a carbon-rich layer, or an adhesive layer.

20. The structure according to any one of claims 13 to 19, wherein the substrate comprises: silicon, SiGe, SiO2, Si3N4, SiON, SiCO:H, a combination of tetramethylsilicate and tetramethylcyclotetrasiloxane, aluminum, tungsten, tungsten silicide, gallium arsenide, germanium, tantalum, tantalum nitride, Ti3N4, hafnium, HfO2, ruthenium, indium phosphide, or glass.

21. A method, the method comprising: The alkynyl carboxylic acid reacts with an epoxy group at a temperature of about 100°C or lower to form the reaction product.

22. The method of claim 21, wherein the reaction is carried out in a reaction solution in which the molar ratio of alkynyl carboxylic acid to epoxy group is about 0.8:1 to about 1.2:

1.

23. The method of claim 21 or 22, wherein the reaction is carried out at a temperature of about 50°C to about 100°C.

24. The method of any one of claims 21 to 23, wherein the reaction is carried out for about 4 hours to about 36 hours.

25. The method according to any one of claims 21 to 24, wherein the alkynyl carboxylic acid is selected from C3 to C8 alkynyl carboxylic acids.

26. The method according to any one of claims 21 to 25, wherein the alkynyl carboxylic acid is selected from: propynic acid, butynic acid, 4-pentynic acid, 5-hexynic acid, or mixtures thereof.

27. The method of any one of claims 21 to 26, wherein the epoxy group is present as a part of: monomeric compounds, oligomeric compounds, polymeric compounds, or two or more of the foregoing.

28. The method of any one of claims 21 to 27, wherein the epoxy group is present as a part of: (i) The compound is selected from the following: tri-(2,3-epoxypropyl)isocyanurate, bisphenol A diglycidyl ether, 9,9-bis(4-glycidyloxyphenyl)fluorene, tri-(4-hydroxyphenyl)methane triglycidyl ether, or mixtures thereof; (ii) A polymer selected from the following: epoxy-cresyl phenolic varnish, poly(glycidyl methacrylate), epoxy-phenylphenolic varnish, poly(4-glycidyloxystyrene), bisphenol A phenolic varnish-epoxy, poly(glycidyl acrylate), or mixtures thereof; or (iii) Combinations of (i) and (ii).

29. The method of any one of claims 21 to 28, wherein the reaction product is selected from one or more of the following: 。 30. A compound having a chemical formula selected from the following: 。 31. A crosslinking layer comprising an alkynyl carboxylic acid that reacts with an epoxy group.

32. The crosslinked layer of claim 31, wherein the alkynyl carboxylic acid is selected from C3 to C8 alkynyl carboxylic acids.

33. The crosslinked layer of claim 31 or 32, wherein the alkynyl carboxylic acid is selected from: propynic acid, butynic acid, 4-pentynic acid, 5-hexynic acid, or mixtures thereof.

34. The crosslinked layer according to any one of claims 31 to 33, wherein the epoxy group is present as a part of: monomeric compounds, oligomeric compounds, polymeric compounds, or two or more of the foregoing.

35. The crosslinked layer according to any one of claims 31 to 34, wherein the epoxy groups are present as a subset of: (i) The compound is selected from the following: tri-(2,3-epoxypropyl)isocyanurate, bisphenol A diglycidyl ether, 9,9-bis(4-glycidyloxyphenyl)fluorene, tri-(4-hydroxyphenyl)methane triglycidyl ether, or mixtures thereof; (ii) A polymer selected from the following: epoxy-cresyl phenolic varnish, poly(glycidyl methacrylate), epoxy-phenylphenolic varnish, poly(4-glycidyloxystyrene), bisphenol A phenolic varnish epoxy resin, poly(glycidyl acrylate), or mixtures thereof; or (iii) Combinations of (i) and (ii).

36. The crosslinked layer according to any one of claims 31 to 35, wherein the compound is selected from one or more of the following: 。 37. The crosslinked layer according to any one of claims 31 to 36, wherein the compound comprises a portion having the following structure: , in This indicates the connection point between the stated portion and the remaining portion of the compound, where R is selected from oxygen, carbon, or nitrogen.

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