Photoresist composition and method for forming photoresist pattern

Abstract

The present application discloses a photoresist composition and a method for forming a photoresist pattern. A photoresist composition includes: a conjugated resist additive; a photoactive compound; and a polymer resin. The conjugated resist additive is one or more selected from the group consisting of the following items: polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene and polyaniline. The polyacetylene, polythiophene, polystyrene, polyfluorene, polypyrrole, polyphenylene and polyaniline include substituents, and the substituents are selected from the group consisting of the following items: alkyl, ether, ester, alkenyl, aromatic, anthracene, alcohol, amine, carboxylic acid and amide. Another photoresist composition includes a polymer resin having a conjugated portion and a photoactive compound. The conjugated portion is one or more selected from the group consisting of the following items: polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene and polyaniline.

Description

Technical Field

[0001] The present disclosure generally relates to photoresist compositions and methods of forming photoresist patterns. Background Art

[0002] As consumer devices become smaller and smaller due to consumer demand, the individual components of these devices must also decrease in size. Semiconductor devices that constitute the main components of devices such as mobile phones, computer tablets, etc. are also forced to become smaller and smaller, and the individual devices within the semiconductor devices (e.g., transistors, resistors, capacitors, etc.) are also forced to decrease in size.

[0003] One implementation technique used in the manufacturing process of semiconductor devices is to use photolithographic materials. Such materials are applied to the surface of the layer to be patterned and then exposed to energy that is itself patterned. Such exposure modifies the chemical and physical properties of the exposed areas of the photosensitive material. This modification and the lack of modification in the areas of the unexposed photosensitive material can be used to remove one area without removing another area.

[0004] However, as the size of individual devices decreases, the process window for lithography processes becomes increasingly tighter. Therefore, advances in the field of lithography processes are necessary to maintain the ability to shrink devices, and further improvements are needed to meet the desired design standards so that the march toward smaller and smaller devices can be maintained.

[0005] As the semiconductor industry moves toward nanotechnology process nodes in pursuit of higher device density, higher performance, and lower cost, there are challenges in reducing semiconductor feature sizes. Extreme ultraviolet lithography (EUVL) has been developed to form smaller semiconductor device feature sizes and increase device density on semiconductor wafers. In order to improve EUVL, it is necessary to increase the wafer exposure dose. The wafer exposure dose can be increased by increasing the exposure power or increasing the resist photospeed. Low exposure dose may result in reduced line width resolution and reduced critical dimension uniformity. Summary of the invention

[0006] According to one embodiment of the present disclosure, a photoresist composition is provided, comprising: a conjugated resist additive; a photoactive compound; and a polymer resin. The conjugated resist additive is one or more selected from the group consisting of: polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene and polyaniline, wherein the polythiophene, polystyrene, polyfluorene, polypyrrole, polyphenylene and polyaniline are substituted by one or more substituents, and the one or more substituents are selected from the group consisting of: alkyl, ether, ester, alkenyl, aromatic, anthracene, alcohol, amine, carboxylic acid and amide.

[0007] According to another embodiment of the present disclosure, a photoresist composition is provided, comprising: a polymer resin having a conjugated portion; and a photoactive compound; wherein the conjugated portion is selected from one or more of the following: polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene and polyaniline.

[0008] According to another embodiment of the present disclosure, a method for forming a pattern in a photoresist is provided, comprising: forming a photoresist composition layer on a substrate; selectively exposing the photoresist layer to actinic radiation to form a latent pattern; and developing the latent pattern to form a pattern by applying a developer to the selectively exposed photoresist layer, wherein the photoresist composition comprises: a conjugated resist additive; a photoactive compound; and a polymer resin, wherein the conjugated resist additive is one or more selected from the group consisting of: polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene and polyaniline, wherein the polythiophene, polystyrene, polyfluorene, polypyrrole, polyphenylene and polyaniline are substituted with one or more substituents, and the one or more substituents are selected from the group consisting of: alkyl, ether, ester, alkenyl, aromatic, anthracene, alcohol, amine, carboxylic acid and amide. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The present disclosure can be best understood from the following detailed description when read in conjunction with the accompanying drawings. It should be emphasized that, in accordance with standard practice in the industry, various features are not drawn to scale and are only used for illustration purposes. In fact, the size of various features may be arbitrarily increased or reduced for clarity of discussion.

[0010] Figure 1 The process flow of manufacturing a semiconductor device according to an embodiment of the present disclosure is shown.

[0011] Figure 2 The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0012] Figure 3A and Figure 3B The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0013] Figure 4 The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0014] Figure 5 The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0015] Figure 6 The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0016] Fig. 7A and Figure 7B Photoresist composition components according to some embodiments of the present disclosure are shown.

[0017] Figure 8 The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0018] Fig.9A and Fig. 9B The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0019] Fig.10 The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0020] Fig.11 The process stages are shown in sequential operation according to an embodiment of the present disclosure.

[0021] Fig.12 The process stages are shown in sequential operation according to an embodiment of the present disclosure. DETAILED DESCRIPTION

[0022] It should be understood that the following disclosure provides many different embodiments or examples for realizing the different features of the present disclosure. Specific embodiments or examples of components and arrangements are described below to simplify the present disclosure. Of course, these are merely examples and are not intended to be restrictive. For example, the size of the element is not limited to the disclosed range or value, but may depend on the process conditions and / or desired properties of the device. In addition, in the following description, forming a first feature above or on a second feature may include an embodiment in which the first feature and the second feature are formed in direct contact, and may also include an additional feature that may be formed between the first feature and the second feature so that the first feature and the second feature may not be in direct contact. For simplicity and clarity, various features may be arbitrarily drawn in different proportions.

[0023] Additionally, spatially relative terms (e.g., "below," "beneath," "below," "above," "upper," etc.) may be used herein to facilitate description of the relationship of one element or feature shown in the figures relative to another element(s) or feature(s). These spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation shown in the figures. The device may be otherwise oriented (rotated 90 degrees or at other orientations), and the spatially relative descriptors used herein may likewise be interpreted accordingly. Additionally, the term "made of" may mean "comprising" or "consisting of."

[0024] Figure 1FIG. 1 shows a process flow 100 for manufacturing a semiconductor device according to an embodiment of the present disclosure. In some embodiments, in operation S110, a photoresist is coated on the surface of the layer or substrate 10 to be patterned to form a photoresist layer 15, such as Figure 2 Then, in some embodiments, the photoresist layer 15 undergoes a first baking operation S120 to evaporate the solvent in the photoresist composition. The photoresist layer 15 is baked at a temperature and time sufficient to cure and dry the photoresist layer 15. In some embodiments, the photoresist layer is heated to a temperature of about 40° C. and 120° C. for about 10 seconds to about 10 minutes.

[0025] After the first baking operation S120, in operation S130, the photoresist layer 15 is selectively exposed to actinic radiation 45 / 97 (see Figure 3A and Figure 3B ). In some embodiments, the photoresist layer 15 is selectively exposed to ultraviolet radiation. In some embodiments, the ultraviolet radiation is deep ultraviolet radiation (DUV). In some embodiments, the ultraviolet radiation is extreme ultraviolet (EUV) radiation. In some embodiments, the radiation is an electron beam.

[0026] like Figure 3A As shown, in some embodiments, exposure radiation 45 passes through photomask 30 before irradiating photoresist layer 15. In some embodiments, the photomask has a pattern to be replicated in photoresist layer 15. In some embodiments, the pattern is formed by an opaque pattern 35 on photomask substrate 40. Opaque pattern 35 can be formed of a material that is opaque to ultraviolet radiation, such as chrome, while photomask substrate 40 is formed of a material that is transparent to ultraviolet radiation, such as fused silica.

[0027] In some embodiments, the photoresist layer 15 is selectively exposed using extreme ultraviolet lithography to form exposed areas 50 and unexposed areas 52. In the extreme ultraviolet lithography operation, a reflective photomask 65 is used to form a patterned exposure light, such as Figure 3B As shown. The reflective photomask 65 includes a low thermal expansion glass substrate 70, on which a reflective multilayer 75 of Si and Mo is formed. A cap layer 80 and an absorption layer 85 are formed on the reflective multilayer 75. A rear conductive layer 90 is formed on the back side of the low thermal expansion substrate 70. In EUV lithography, EUV radiation 95 is directed to the reflective photomask 65 at an incident angle of about 6°. A portion 97 of the EUV radiation is reflected by the Si / Mo multilayer 75 toward the photoresist-coated substrate 10, while a portion of the EUV radiation incident on the absorption layer 85 is absorbed by the photomask. In some embodiments, additional optical devices (including mirrors) are located between the reflective photomask 65 and the photoresist-coated substrate.

[0028] Regions of the photoresist layer exposed to radiation 50 undergo a chemical reaction that changes its solubility in a subsequently applied developer relative to regions of the photoresist layer not exposed to radiation 52. In some embodiments, a portion of the photoresist layer exposed to radiation 50 undergoes a crosslinking reaction.

[0029] Next, in operation S140, the photoresist layer 15 is subjected to post-exposure baking. In some embodiments, the photoresist layer 15 is heated to a temperature of about 50° C. and 160° C. for about 20 seconds to about 120 seconds. The post-exposure baking can be used to promote the generation, dispersion and reaction of acids / bases / free radicals generated by the radiation 45 / 97 hitting the photoresist layer 15 during the exposure process. This promotion helps to generate or enhance a chemical reaction that produces a chemical difference between the exposed area 50 and the unexposed area 52 in the photoresist layer. These chemical differences also result in a solubility difference between the exposed area 50 and the unexposed area 52.

[0030] Subsequently, in operation S150, the selectively exposed photoresist layer is developed by applying a developer to the selectively exposed photoresist layer. Figure 4 As shown, developer 57 is supplied from dispenser 62 to photoresist layer 15. In some embodiments, the exposed portion of photoresist layer 50 is removed by developer 57, thereby forming a pattern of openings 55 in photoresist layer 15 to expose the substrate, such as Figure 5 shown.

[0031] In some embodiments, the pattern of openings 55 in the photoresist layer 15 is extended into the layer to be patterned or the substrate 10 to produce a pattern of openings 55' in the substrate 10, thereby transferring the pattern in the photoresist layer 15 to the substrate 10. Figure 6 As shown. The pattern is extended into the substrate by etching using one or more suitable etchants. In some embodiments, the unexposed photoresist layer 15 is at least partially removed during the etching operation. In other embodiments, after etching the substrate 10, the unexposed photoresist layer 15 is removed by using a suitable photoresist stripper solvent or by a photoresist ashing operation.

[0032] In some embodiments, substrate 10 includes a single crystal semiconductor layer at least on a surface portion thereof. Substrate 10 may include a single crystal semiconductor material, such as but not limited to Si, Ge, SiGe, GaAs, InSb, GaP, GaSb, InAlAs, InGaAs, GaSbP, GaAsSb, and InP. In some embodiments, substrate 10 is a silicon layer of a SOI (silicon on insulator) substrate. In some embodiments, substrate 10 is made of crystalline Si.

[0033] The substrate 10 may include one or more buffer layers (not shown) in its surface region. The buffer layer may be used to gradually change the lattice constant from the lattice constant of the substrate to the lattice constant of the subsequently formed source / drain region. The buffer layer may be formed of an epitaxially grown single crystal semiconductor material, such as but not limited to Si, Ge, GeSn, SiGe, GaAs, InSb, GaP, GaSb, InAlAs, InGaAs, GaSbP, GaAsSb, GaN, GaP, and InP. In an embodiment, a silicon germanium (SiGe) buffer layer is epitaxially grown on the silicon substrate 10. The germanium concentration of the SiGe buffer layer may increase from 30 atomic percent in the bottommost buffer layer to 70 atomic percent in the topmost buffer layer.

[0034] In some embodiments, the substrate 10 includes one or more layers of at least one metal, metal alloy, and a metal having a molecular formula MX a wherein M is a metal and X is N, S, Se, O, Si, and α is about 0.4 to about 2.5. In some embodiments, substrate 10 includes titanium, aluminum, cobalt, ruthenium, titanium nitride, tungsten nitride, tantalum nitride, and combinations thereof.

[0035] In some embodiments, the substrate 10 includes at least silicon or a molecular formula of MX b The substrate 10 is a dielectric of a metal oxide or nitride, wherein M is a metal or Si, X is N or O, and b is in the range of about 0.4 to about 2.5. In some embodiments, the substrate 10 includes silicon dioxide, silicon nitride, aluminum oxide, hafnium oxide, lanthanum oxide, and combinations thereof.

[0036] The photoresist layer 15 is a photosensitive layer that is patterned by exposure to actinic radiation. Typically, the chemical properties of the photoresist area hit by the incident radiation change in a manner that depends on the type of photoresist used. The photoresist layer 15 is a positive resist or a negative resist. A positive resist refers to a photoresist material that becomes soluble in a developer when exposed to radiation such as ultraviolet light, while the unexposed (or less exposed) photoresist area is insoluble in the developer. On the other hand, a negative resist refers to a photoresist material that becomes insoluble in a developer when exposed to radiation, while the unexposed (or less exposed) photoresist area is soluble in the developer. Areas of the negative resist that become insoluble when exposed to radiation may become insoluble due to cross-linking reactions caused by exposure to radiation.

[0037] Whether the resist is positive or negative may depend on the type of developer used to develop the resist. For example, some positive photoresists provide positive patterns (i.e., the exposed areas are removed by the developer) when the developer is a water-based developer (e.g., tetramethylammonium hydroxide (TMAH) solution). On the other hand, when the developer is an organic solvent, the same photoresist provides a negative pattern (i.e., the unexposed areas are removed by the developer). In addition, in some negative photoresists developed with TMAH solutions, the unexposed areas of the photoresist are removed by TMAH, and the exposed areas of the photoresist that undergo crosslinking when exposed to actinic radiation remain on the substrate after development.

[0038] In certain embodiments, the photoresist layer comprises a highly sensitive photoresist composition. In certain embodiments, the highly sensitive photoresist composition is highly sensitive to extreme ultraviolet (EUV) radiation. According to an embodiment of the present disclosure, the highly sensitive photoresist comprises a conjugated material in the photoresist composition. In certain embodiments, the conjugated material is an oligomer or polymer as a resist unit, an additive, or a resist unit and an additive mixture. In certain embodiments, the conjugated material is a conjugated portion in the main chain of a polymer, or a side group or side chain of a polymer. In certain embodiments, the material is a conjugated functionalized photoacid generator (PAG), a photodecomposable base (PDB), or a photobase generator (PBG).

[0039] In some embodiments, the weight average molecular weight of the conjugated material is in the range of about 50 to about 1000000. In some embodiments, the weight average molecular weight of the conjugated material is in the range of about 2500 to about 750000. In some embodiments, the weight average molecular weight of the conjugated material is in the range of about 5000 to about 500000. In some embodiments, the R group substituent on the conjugated material improves the photoresist contrast by improving the solubility of the photoresist composition components (including the optical switch component). In some embodiments, the R substituent on the conjugated material is a polar group, a non-polar group, an acid leaving group (ALG), or another conjugated group or a mixture of different R substituents. In some embodiments, the R substituent helps to adjust the electronic properties by electron donation or recovery behavior.

[0040] Conjugated materials provide a longer path for photons to be absorbed in the photoresist and a longer lifetime for delocalized electrons, resulting in more efficient generation of acid or base by photoacid or photobase generators. Conjugated materials provide more electron and hole generation and higher energy transfer efficiency at wavelengths from 10nm to 200nm.

[0041] Fig. 7A and Figure 7B Conjugated materials according to embodiments of the present disclosure are shown. Conjugated materials according to some embodiments have a low band gap. Fig. 7A Band gaps of some conjugated materials according to embodiments of the present disclosure are shown. In some embodiments, the band gap is in the range of about 0.3 eV to about 4 eV. In other embodiments, the band gap is in the range of about 1 eV to about 3 eV. In some embodiments, the conjugated material delocalizes the electron / hole and then increases the lifetime of the electron / hole for energy transfer (i.e. -e- →PAG). In addition, the conjugated system can also irradiate light (150-1000 nm) that can be absorbed by the photoacid generator (PAG), thereby increasing the acid yield.

[0042] In some embodiments, the conjugated material is a conjugated resist additive, and in other embodiments, the conjugated material is a moiety attached to a polymer resin. Fig. 7A As shown, the conjugated resist additive or conjugated resist polymer portion according to the embodiments of the present disclosure includes polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene, and polyaniline. The number of repeating units of the monomer n is in the range of 1 to about 500. In some embodiments, the conjugated resist additive or polymer portion includes one or more substituents R. As Fig. 7A As shown, the substituent R can be an alkyl, ether, ester, alkenyl, aryl, anthracene, alcohol, amine, carboxylic acid, or amide, wherein n is in the range of 1 to about 200. The substituent can improve solubility during the development of the photoresist. In an embodiment, one or more substituents include an acid leaving group. In an embodiment, the acid leaving group is attached to an alcohol substituent or a carboxylic acid substituent. In an embodiment, the conjugated resist additive includes a conjugated portion attached to a photoacid generator, a photodecomposable base, or a photobase generator. In an embodiment, the conjugated resist additive has a weight average molecular weight of 50 to 1000000.

[0043] In some embodiments, the conjugate resist additive includes:

[0044]

[0045] Wherein, PAG is a photoacid generator, PBG is a photobase generator, PDB is a photodecomposable base, and R is a substituent selected from the group consisting of alkyl, ether, ester, alkenyl, aryl, anthracene, alcohol, amine, carboxylic acid, or amide. In some embodiments, the substituent is a repeating unit, wherein the number of repeating units n is in the range of 1 to about 200.

[0046] In some embodiments, the polymer resin having a conjugated portion includes

[0047]

[0048] Wherein, R is an alkyl, ether, ester, alkenyl, aryl, anthracene, alcohol, amine, carboxylic acid, or amide. In some embodiments, the substituent is a repeating group, wherein the number n of the repeating groups is in the range of 1 to about 200.

[0049] In some embodiments, the conjugated moiety is a repeating unit in the backbone of the polymer, a repeating unit of a side group attached to the backbone of the polymer resin, or a repeating unit of a terminal group attached to the end of the backbone of the polymer resin.

[0050] In some embodiments, the photoresist composition includes a polymer resin having a first conjugated portion, and a photosensitive compound having a second conjugated portion. The first and second conjugated portions are the same or different, and the first and second conjugated portions are selected from the references herein. Fig. 7A One or more of the polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene and polyaniline.

[0051] In some embodiments, the photoresist composition according to the present disclosure includes metal oxide nanoparticles and one or more organic ligands. In some embodiments, the metal oxide nanoparticles are organic metals, including one or more metal oxide nanoparticles selected from the group including the following items: titanium dioxide, zinc oxide, zirconium dioxide, nickel oxide, cobalt oxide, manganese oxide, copper oxide, iron oxide, strontium titanate, tungsten oxide, vanadium oxide, chromium oxide, tin oxide, hafnium oxide, indium oxide, cadmium oxide, molybdenum oxide, tantalum oxide, niobium oxide, aluminum oxide and combinations thereof. As used herein, nanoparticles are particles with an average particle size between about 1nm and about 20nm. In some embodiments, the average particle size of the metal oxide nanoparticles is between about 2nm and about 5nm. In some embodiments, based on the weight of the first solvent, the amount of the metal oxide nanoparticles in the photoresist composition is about 1wt.% to about 15wt.%. In some embodiments, based on the weight of the first solvent, the amount of the nanoparticles in the photoresist composition is about 5wt.% to about 10wt.%. Metal oxide nanoparticles lower than about 1wt.%, the photoresist coating is too thin. Above about 15 wt. % metal oxide nanoparticles, the photoresist coating is too thick.

[0052] In some embodiments, the metal oxide nanoparticles are complexed with ligands. In some embodiments, the ligands are carboxylic acid or sulfonic acid ligands. For example, in some embodiments, zirconium oxide or hafnium oxide nanoparticles are complexed with methacrylic acid to form hafnium methacrylic acid (HfMAA) or zirconium (ZrMAA) methacrylic acid. In some embodiments, the metal oxide nanoparticles are complexed with ligands including aliphatic or aromatic groups. The aliphatic or aromatic groups can be unbranched, or have branches with cyclic or non-cyclic saturated side groups containing 1-9 carbons, including alkyl, alkenyl and phenyl. The branched groups can be further substituted with oxygen or halogen.

[0053] In some embodiments, the photoresist composition includes about 0.1wt.% to about 20wt.% of the ligand. In some embodiments, the photoresist includes about 1wt.% to about 10wt.% of the ligand. In some embodiments, the ligand concentration is about 10wt.% to about 40wt.% based on the weight of the metal oxide nanoparticles. Below about 10wt.% of the ligand, the organometallic photoresist does not work well. Above about 40wt.% of the ligand, it is difficult to form a photoresist layer. In some embodiments, the ligand is HfMAA or ZrMAA, which is dissolved in a coating solvent (e.g., propylene glycol methyl ether acetate (PGMEA)) in a weight range of about 5wt.% to about 10wt.%.

[0054] In some embodiments, the polymer resin and PAC are added to a solvent along with any desired additives or other agents for application. Once added, the mixture is mixed to achieve a uniform composition throughout the photoresist to ensure that there are no defects due to uneven mixing or uneven composition of the photoresist. Once mixed together, the photoresist can be stored prior to its use or used immediately.

[0055] The solvent can be any suitable solvent. In some embodiments, the solvent is one or more selected from the following items: propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, acetone, dimethylformamide (DMF), isopropyl alcohol (IPA), tetrahydrofuran (THF), methyl isobutyl carbinol (MIBC), n-butyl acetate (nBA), and 2-heptanone (MAK).

[0056] In some embodiments, the photoresist composition further comprises water at a concentration of 10 ppm to 250 ppm based on the total composition of water, the enhancing additive, and the first solvent.

[0057] In some embodiments, the photoresist composition includes a polymer resin and one or more photosensitive compounds (PAC). In some embodiments, the polymer resin includes a hydrocarbon structure (e.g., an alicyclic hydrocarbon structure) containing one or more groups (as described below) that will decompose (e.g., an acid-labile group) or otherwise react when mixed with an acid, base, or free radical generated by the PAC. In some embodiments, the hydrocarbon structure includes repeating units that form the backbone of the polymer resin. The repeating units may include acrylates, methacrylates, crotonates, vinyl esters, maleic diesters, fumaric diesters, itaconic diesters, (meth) acrylonitrile, (meth) acrylamide, styrene, vinyl ethers, combinations thereof, and the like.

[0058] In some embodiments, the specific structure of the repeating unit for the hydrocarbon structure includes one or more of the following: methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-alkyl-2-adamantyl (meth)acrylate or dialkyl (1-adamantyl)methyl (meth)acrylate, methyl methacrylate, methacrylic acid ... ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, acetoxyethyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-acetoxy-2-hydroxypropyl methacrylate, 3-chloroacetoxy-2-hydroxypropyl methacrylate, butyl crotonate, hexyl crotonate, and the like. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, acrylamide, methacrylamide, ethyl acrylamide, propyl acrylamide, n-butyl acrylamide, tert-butyl acrylamide, cyclohexyl acrylamide, 2-methoxyethyl acrylamide, dimethyl acrylamide , diethylacrylamide, phenylacrylamide, benzylacrylamide, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 2-methoxyethyl methacrylate, dimethyl methacrylate, diethyl methacrylate, phenyl methacrylamide, benzyl methacrylate, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc. Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, methoxy styrene, butoxy styrene, acetoxy styrene, hydroxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, vinyl methyl benzoate, α-methylstyrene, maleimide, vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, combinations of these, and the like.

[0059] In some embodiments, the polymer resin is polyhydroxystyrene, polymethyl methacrylate, or polyhydroxystyrene-tert-butyl acrylate, for example:

[0060]

[0061] In some embodiments, the repeating unit of the hydrocarbon structure also has a monocyclic or polycyclic hydrocarbon structure substituted therein, or a monocyclic or polycyclic hydrocarbon structure is a repeating unit to form an alicyclic hydrocarbon structure. In some embodiments, specific examples of monocyclic structures include bicycloalkanes, tricycloalkanes, tetracycloalkanes, cyclopentane, cyclohexane, etc. In some embodiments, specific examples of polycyclic structures include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0062] In some embodiments, the polymer resin includes Fig. 7A and Figure 7B Any conjugated moiety described. The conjugated moiety is a repeating unit in the backbone of the polymer, a repeating unit of a side group attached to the backbone of the polymer resin, or a repeating unit of a terminal group of the backbone of the polymer resin.

[0063] The group that decomposes (also referred to as a leaving group, or in some embodiments where the PAC is a photoacid generator, an acid labile group) is attached to a hydrocarbon structure so that it will react with the acid / base / radicals generated by the PAC during exposure. In some embodiments, the group that decomposes is a carboxylic acid group, a fluorinated alcohol group, a phenolic alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkyl-carbonyl)imino group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imino group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imino group, a tri(alkylcarbonyl)methylene group, a tri(alkylsulfonyl)methylene group, combinations thereof, and the like. In some embodiments, specific groups for fluorinated alcohol groups include fluorinated hydroxyalkyl groups, for example, a hexafluoroisopropanol group. Specific groups for carboxylic acid groups include acrylic acid groups, methacrylic acid groups, and the like.

[0064] In some embodiments, the polymer resin further comprises other groups attached to the hydrocarbon structure that help improve various properties of the polymerizable resin. For example, including a lactone group with the hydrocarbon structure helps reduce the amount of line edge roughness after developing the photoresist, thereby helping to reduce the number of defects that occur during development. In some embodiments, the lactone group comprises a ring having five to seven members, but any suitable lactone structure may alternatively be used for the lactone group.

[0065] In some embodiments, the polymer resin includes groups that can help increase the adhesion of the photoresist layer 15 to the underlying structure (e.g., substrate 10). Polar groups can be used to help increase adhesion. Suitable polar groups include hydroxyl, cyano, etc., but any suitable polar group may be used instead.

[0066] Optionally, the polymer resin includes one or more alicyclic hydrocarbon structures that do not contain groups that will decompose in some embodiments. In some embodiments, the hydrocarbon structure that does not contain groups that will decompose includes structures such as 1-adamantyl (meth)acrylate, tricyclodecyl (meth)acrylate, cyclohexyl (methacrylate), combinations of these, and the like.

[0067] Some embodiments of the photoresist include one or more photosensitive compounds (PAC).PAC is a photoactive component, for example, a photoacid generator (PAG), a photobase (PBG) generator, a photodecomposable base (PDB), a free radical generator, etc.PAC can be positive or negative. In some embodiments in which PAC is a photoacid generator, PAC includes halogenated triazines, onium salts, diazonium salts, aromatic diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imidosulfonates, oximesulfonates, diazonium disulfones, disulfones, o-nitrobenzenesulfonates, sulfonic acid esters, halogenated sulfonyloxy dicarboxylic acid imides, diazonium disulfones, α-cyanoamine-sulfonic acid esters, imidosulfonic acid esters, ketodiazole sulfones, sulfonyl diazo esters, 1,2-di(arylsulfonyl)hydrazine, nitrobenzyl esters, and S-triazine derivatives, or combinations thereof, etc.

[0068] Specific examples of the photoacid generator include α-(trifluoromethylsulfonyloxy)-bicyclo[2.2.1]hept-5-ene-2,3-dicarbon-o-diimide (MDT), N-hydroxynaphthalene dicarboximide (DDSN), benzoin toluenesulfonate, tert-butyl-α-(p-toluenesulfonyloxy) acetate and tert-butyl-α-(p-toluenesulfonyloxy) acetate, triarylsulfide and diaryliodonium hexafluoroantimonate, hexafluoroarsenate, trifluoromethanesulfonate, iodonium perfluorooctanesulfonate, N-camphorsulfonyloxynaphthalene dicarboximide, N-pentafluorophenylsulfonyloxynaphthalene dicarboximide, ionic iodonium sulfonate. (e.g., diaryliodonium (alkyl or aryl) sulfonates and bis-(di-tert-butylphenyl)iodonium camphorsulfonate), perfluoroalkanesulfonates (e.g., perfluoropentanesulfonate, perfluorooctanesulfonate, perfluoromethanesulfonate), aryl (e.g., phenyl or benzyl) trifluoromethanesulfonates (e.g., triphenyl trifluoromethanesulfonate or bis(tert-butylphenyl)iodonium trifluoromethanesulfonate); pyrogallol derivatives (e.g., trimellitic acid ester of pyrogallol), trifluoromethanesulfonates of hydroxyimides, α,α'-bissulfonyl-diazomethane, sulfonates of nitro-substituted benzyl alcohols, naphthoquinone-4-diazide, alkyl disulfones, and the like.

[0069] In some embodiments, the PAG is attached to the referenced Fig. 7A and Figure 7B One of the conjugated materials disclosed.

[0070] In some embodiments where PAC is a free radical generator, the PAC includes: n-phenylglycine; aromatic ketones including benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, p,p'-bis(dimethylamino)benzophenone, p,p'-bis(diethylamino)-benzophenone; anthraquinone, 2-ethyl anthraquinone; naphthoquinone; and phenanthranaquinone; benzoins, including benzoic acid, dimethyl benzyl ether, diisopropyl benzyl ether, n-butyl benzoate, dimethyl benzyl ether, methyl benzoic acid, and ethyl benzoic acid; benzyl derivatives, including dibenzyl, benzyl diphenyl disulfide, and benzyl dimethyl ketone; acridine derivatives, including 9-phenylacridine and 1,7-bis(9-acridinyl)heptane; thioflavones, including 2-chlorothioflavones, 2-methylthioflavones, 2,4-diethylthioflavones, and 1,7-bis(9-acridinyl)heptane; 1,1-dichloroacetophenone, 2,4-dimethylthioflavone and 2-isopropylthioflavone; acetophenones, including 1,1-dichloroacetophenone, p-tert-butyldichloroacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone and 2,2-dichloro-4-phenoxyacetophenone; 2,4,5-triarylimidazole dimers, including 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-dimethoxyphenylimidazole dimer and 2,2-dichloro-4-phenoxyacetophenone. dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylrimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer and 2-(p-methylmercaptophenyl)-4,5-diphenylimidazole dimer; combinations thereof, and the like.

[0071] In some embodiments, the PAC includes a quencher. In some embodiments, the quencher includes a photobase generator and a photodecomposable base. In embodiments where the PAC is a photobase generator (PBG), the PBG includes quaternary ammonium dithiocarbamates, α-aminoketones, molecules containing oxime carbamates (e.g., diphenylphenol neooxime hexamethylene dichloroethane), tetraorganoboric acid ammonium salts, and N-(2-nitrobenzyloxycarbonyl) cyclic amines, combinations of these, and the like.

[0072] In some embodiments where the PAC is a photodecomposable base (PBD), the PBD includes triphenylammonium hydroxide, triphenylsulfonium antimony hexafluoride, and triphenylsulfonium trifluoride.

[0073] In some embodiments, PBG and PBD are attached to the Fig. 7A and 7B One of the conjugated materials disclosed.

[0074] As will be appreciated by one of ordinary skill in the art, the compounds listed herein are intended only as illustrative examples of PACs, and are not intended to limit the embodiments to only those specifically described PACs. Rather, any suitable PAC may be used, and all such PACs are fully intended to be included within the scope of the present embodiments.

[0075] In some embodiments, a crosslinking agent is added to the photoresist. The crosslinking agent reacts with one group of one hydrocarbon structure in the polymer resin and also reacts with another group of another hydrocarbon structure to crosslink and bond the two hydrocarbon structures together. This bonding and crosslinking increases the molecular weight of the polymer product of the crosslinking reaction and increases the overall crosslinking density of the photoresist. The increase in density and crosslinking density helps to improve the pattern of the resist.

[0076] In some embodiments, the cross-linking agent has the following structure:

[0077]

[0078] Wherein C is carbon, n ranges from 1 to 15; A and B independently include hydrogen atoms, hydroxyl groups, halides, aromatic carbon rings or linear or cycloalkyl groups, alkoxy / fluorine, alkyl / fluoroalkoxy chains with carbon numbers between 1 and 12, and each carbon C contains A and B; the first terminal carbon C at the first end of the carbon C chain includes X, and the second terminal carbon C at the second end of the carbon chain includes Y, wherein X and Y independently include amine groups, thiol groups, hydroxyl groups, isopropanol groups or isopropylamine groups, unless n=1, then X and Y are bonded to the same carbon C. Specific examples of materials that can be used as crosslinking agents include the following structures:

[0079]

[0080] Alternatively, in some embodiments, a coupling agent is added in addition to or in place of a crosslinking agent added to the photoresist composition. In these embodiments, a coupling agent is added in addition to the crosslinking agent. The coupling agent assists the crosslinking reaction by reacting with groups on the hydrocarbon structure in the polymer resin before the crosslinking reactants, so that the reaction energy of the crosslinking reaction is reduced and the reaction rate is increased. The bonded coupling agent then reacts with the crosslinking agent, thereby coupling the crosslinking agent to the polymer resin.

[0081] Alternatively, in some embodiments where a coupling agent is added to the photoresist 12 without a cross-linking agent, the coupling agent is used to couple a group in one hydrocarbon structure in the polymer resin with a second group in another hydrocarbon structure in order to cross-link and bond the two polymers together. However, in such embodiments, the coupling agent is different from the cross-linking agent in that it does not remain as part of the polymer and only assists in bonding one hydrocarbon structure directly to another hydrocarbon structure.

[0082] In some embodiments, the coupling agent has the following structure:

[0083]

[0084] Wherein, R is a carbon atom, a nitrogen atom, a sulfur atom or an oxygen atom, M includes a chlorine atom, a bromine atom, an iodine atom, --NO2; --SO3-; --H--; --CN; --NCO, --OCN; --OCN; --CO2-; --OH; --OR*, --OC(O)CR*; --SR, --SO2N(R*) 2 ;--SO 2 R*;SOR;--OC(O)R*;--C(O)OR*;--C(O)R*;--Si(OR*) 3 ; --Si(R*) 3 ; ; epoxy group, etc.; R* is a substituted or unsubstituted C1-C12 alkyl group, C1-C12 aryl group, C1-C12 aralkyl group, etc. Specific examples of materials used as coupling agents in some embodiments include the following structures:

[0085]

[0086] The various components of the photoresist are placed in a solvent to aid in mixing and dispensing the photoresist. To aid in mixing and dispensing the photoresist, the choice of solvent is based at least in part on the materials selected for the polymer resin and the PAC. In some embodiments, the solvent is selected so that the polymer resin and the PAC can be uniformly dissolved into the solvent and dispensed onto the layer to be patterned.

[0087] In some embodiments of the photoresist composition, another quencher is added to inhibit the diffusion of the generated acid / base / radicals within the photoresist. The quencher improves the pattern configuration of the resist and the stability of the photoresist over time. In an embodiment, the quencher is an amine, such as a second low-fat amine, a third low-fat amine, etc. Specific examples of amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tripentylamine, diethanolamine and triethanolamine, alkanolamines, combinations thereof, and the like.

[0088] In some embodiments, an organic acid is used as a quencher. Specific examples of organic acids include malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid; phosphoric acid and its derivatives, such as phosphoric acid and its derivatives such as esters, di-n-butyl phosphate and diphenyl phosphate; phosphoric acid and its derivatives such as esters, such as dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate and dibenzyl phosphonate; and phosphoric acid and its derivatives such as esters, including phenylphosphonic acid.

[0089] Another additive added to some embodiments of the photoresist is a stabilizer, which helps prevent the undesired diffusion of acids generated during exposure of the photoresist. In some embodiments, stabilizers include nitrogen-containing compounds, including aliphatic primary, secondary, and tertiary amines; cyclic amines, including piperidine, pyrrolidine, morpholine; aromatic heterocycles, including pyridine, pyrimidine, purine; imines, including diazadicyclopentene, guanidine, imide, amide, etc. Alternatively, in some embodiments, ammonium salts are also used for stabilizers, including primary, secondary, tertiary, and quaternary alkyl and aryl ammonium salts of ammonium and alkoxides, including hydroxides, phenolates, carboxylates, aryl and alkyl sulfonates, sulfonamides, etc. Other cationic nitrogen-containing compounds are used in some embodiments, including pyridinium salts and salts of other heterocyclic nitrogen-containing compounds with anions, such as alkoxides, including hydroxides, phenolates, carboxylates, aryl and alkyl sulfonates, sulfonamides, etc.

[0090] Another additive in some embodiments of the photoresist is a dissolution inhibitor, which helps control the dissolution of the photoresist during development. In embodiments, bile esters can be used as dissolution inhibitors. Specific examples of dissolution inhibitors in some embodiments include cholic acid, deoxycholic acid, lithocholic acid, tert-butyl deoxycholate, tert-butyl lithocholic acid, and tert-butyl-3-acetyl lithocholic acid.

[0091] Another additive in some embodiments of photoresist is plasticizer.Plasticizer can be used to reduce the delamination and cracking between photoresist and bottom layer (for example, to be patterned layer).Plasticizer includes monomer, oligomer and polymer plasticizer, for example oligomeric and polyglycol ether, cyclic fatty acid ester and non-acidic reactive steroidal derivative material.The specific example of the material for plasticizer in certain embodiments includes dioctyl phthalate, didecyl phthalate, triethylene glycol dipropyl ester, dimethyl phthalate, trimethyl phosphate, dioctyl adipate, dibutyl sebacate, triacetin etc.

[0092] Colorants are another additive included in some embodiments of the photoresist. A colorant observer inspects the photoresist and detects any defects that may need to be remedied before further processing. In some embodiments, the colorant is a triarylmethane dye or a fine particle organic pigment. Specific examples of materials in some embodiments include crystal violet, methyl violet, ethyl violet, oil blue #603, Victoria pure blue BOH, malachite green, diamond green, phthalocyanine pigments, azo pigments, carbon black, titanium oxide, brilliant green dye (CI42020), Victoria pure blue FGA (Linebrow), Victoria BO (Linebrow) (CI42595), Victoria blue BO (CI44045), rhodamine 6G (CI45160), benzophenone compounds such as 2,4-dihydroxybenzophenone and 2,2',4,4'-tetrahydroxybenzophenone; salicylic acid compounds such as phenyl salicylate and 4-tert-butylphenyl salicylic acid; phenylacrylate compounds such as ethyl-2-cyano-3,3-diphenylacrylate and 2'-ethylhexyl-2- Cyano-3,3-diphenylacrylate; benzotriazole compounds, such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole and 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole; coumarin compounds, such as 4-methyl-7-diethylamino-1-benzopyran-2-one; thioketone compounds, such as diethylthioketone; stilbene compounds, naphthoic acid compounds, azo dyes, phthalocyanine blue, phthalocyanine green, iodine green, Victoria blue, crystal violet, titanium oxide, naphthalene black, photosensitive methyl violet, bromophenol blue and bromocresol green; laser dyes, such as rhodamine G6, coumarin 500, DCM (4-(biscyanomethyl)-2-methyl-6-(4-dimethylaminostyrene)-4H pyran), Keaton Red 620, pyrrolidine 580, etc. In addition, one or more colorants can be used in combination to provide the desired colorant.

[0093] In some embodiments of the photoresist, an adhesion additive is added to promote adhesion between the photoresist and the bottom layer (e.g., the pattern layer) to which the photoresist has been applied. In some embodiments, the adhesion additive includes a silane compound having at least one reactive substituent (e.g., a carboxyl group, a methacryl group, an isocyanate group, and / or an epoxy group). Specific examples of adhesion components include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidylpropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, benzimidazole and polybenzimidazole, low hydroxyalkyl substituted pyridine derivatives, nitrogen heterocyclic compounds, urea, thiourea, organophosphorus compounds, 8-oxoquinoline, 4-hydroxypteridine and its derivatives, 1,10-phenanthroline Phyline and its derivatives, 2,2'-bipyridine and its derivatives, benzotriazole, organophosphorus compounds, phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethyl ether aromatic amine, N-ethyldiethanolamine, N-ethylethanolamine and its derivatives, benzothiazole, and benzothiazole amine salts having a cyclohexyl ring and a morpholine ring, 3-glycidylpropyltrimethoxysilane, 3-glycidylpropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and combinations thereof.

[0094] In some embodiments of the photoresist, a surface leveler is added to help level the top surface of the photoresist so that the impinging light is not adversely modified by the uneven surface. In some embodiments, the surface leveler includes fluorinated fatty acid esters, hydroxyl-terminated fluorinated polyethers, fluorinated glycol polymers, silicones, acrylic polymer levelers, combinations thereof, and the like.

[0095] In some embodiments, the polymer resin and PAC and any desired additives or other agents are added to a solvent for application. Once added, the mixture is then mixed to obtain a uniform composition throughout the photoresist to ensure that there are no defects caused by uneven mixing or non-uniform composition of the photoresist. Once mixed together, the photoresist can be stored before use or used immediately.

[0096] like Figure 2 As shown, once prepared, the photoresist is applied to the layer to be patterned, such as substrate 10, to form a photoresist layer 15. In some embodiments, the photoresist is applied using a process such as spin coating, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, lamination, extrusion coating, a combination of these methods, etc. In some embodiments, the thickness of the photoresist layer 15 ranges from about 10 nm to about 300 nm.

[0097] After applying the photoresist layer 15 to the substrate 10, a pre-bake of the photoresist layer is performed in some embodiments to cure and dry the photoresist prior to radiation exposure (see Figure 1 ). Curing and drying of the photoresist layer 15 removes the solvent components while leaving behind the polymer resin, PAC, crosslinking agent, and other selected additives. In some embodiments, the prebake is performed at a temperature suitable for evaporating the solvent, such as between about 50° C. and 120° C., although the exact temperature depends on the material selected for the photoresist. The prebake is performed for a time sufficient to cure and dry the photoresist layer, such as between about 10 seconds and about 10 minutes.

[0098] Figure 3A and 3B The selective exposure of the photoresist layer is shown to form exposed areas 50 and unexposed areas 52. In some embodiments, radiation exposure is performed by placing the substrate coated with the photoresist in a photolithography tool. The photolithography tool includes a photolithography mask 30 / 65, an optical device, an exposure radiation source that provides 45 / 97 radiation for exposure, and a movable stage that supports and moves the substrate under the exposure radiation.

[0099] In some embodiments, a radiation source (not shown) provides radiation 45 / 97, such as ultraviolet light, to the photoresist layer 15 to induce a reaction of the PAC, which in turn reacts with the polymer resin to chemically change those areas of the photoresist layer impinged by the radiation 45 / 97. In some embodiments, the radiation is electromagnetic radiation, such as g-line (wavelength of about 436 nm), i-line (wavelength of about 365 nm), ultraviolet radiation, far ultraviolet radiation, extreme ultraviolet radiation, electron beam, etc. In some embodiments, the radiation source is selected from the group consisting of: mercury vapor lamp, xenon lamp, carbon arc lamp, KrF excimer laser lamp (wavelength 248 nm), ArF excimer laser lamp (wavelength 193 nm), F 2 Excimer laser light (wavelength 157nm) or CO 2 Laser excited Sn plasma (Extreme Ultraviolet, wavelength 13.5nm).

[0100] In some embodiments, optics (not shown) are used in the lithography tool to expand, reflect, or otherwise control the radiation 45 / 97 before or after it is patterned by the photomask 30 / 65. In some embodiments, the optics include one or more lenses, mirrors, filters, and combinations thereof to control the radiation 45 / 97 along its path.

[0101] In an embodiment, the patterned radiation 45 / 97 is extreme ultraviolet light having a wavelength of 13.5 nm, the PAC is a photoacid generator, the groups to be decomposed are carboxylic acid groups on a hydrocarbon structure, and a crosslinking agent is used. The patterned radiation 45 / 97 impinges on the photoacid generator, and the photoacid generator absorbs the impinging patterned radiation 45 / 97. This absorption causes the photoacid generator to generate protons (e.g., H + Atoms). When the proton strikes the carboxylic acid group on the hydrocarbon structure, the proton reacts with the carboxylic acid group, chemically changing the carboxylic acid group and changing the properties of the polymer resin. Then, in some embodiments, the carboxylic acid group reacts with a crosslinking agent to crosslink with other polymer resins in the exposed areas of the photoresist layer 15.

[0102] In some embodiments, exposure of photoresist layer 15 uses immersion lithography techniques. In this technique, an immersion medium (not shown) is placed between the final optics and the photoresist layer, and exposure radiation 45 is passed through the immersion medium.

[0103] After the photoresist layer 15 is exposed to the exposure radiation 45, a post-exposure bake is performed in some embodiments to assist in the generation, dispersion and reaction of the acid / base / radicals generated by the radiation 45 striking the PAC during exposure. This thermal assistance helps to generate or enhance chemical reactions that create chemical differences between the exposed areas 50 and the unexposed areas 52 within the photoresist layer 15. These chemical differences also result in differences in solubility between the exposed areas 50 and the unexposed areas 52. In some embodiments, the post-exposure bake occurs at a temperature in the range of about 50° C. to about 160° C. for about 20 seconds to about 120 seconds.

[0104] In some embodiments, the inclusion of a crosslinking agent in the chemical reaction helps the components of the polymer resin (e.g., individual polymers) to react and bond with each other, thereby increasing the molecular weight of the bonded polymers. Specifically, the initial polymer has a side chain of a carboxylic acid protected by one of the groups to be removed / acid-resistant groups. The group to be removed is removed in a deprotection reaction, which is reacted by a proton H + Initiation, the proton H + Generated by a photoacid generator, for example, during exposure or post-exposure baking. + First, the group to be removed / acid-resistant group is removed, and another hydrogen atom can replace the removed structure to form an unprotected polymer. Once deprotected, a cross-linking reaction occurs between the two separate deprotected polymers undergoing the deprotection reaction and the cross-linking agent in the cross-linking reaction. Specifically, the hydrogen atoms in the carboxyl group formed by the deprotection reaction are removed, and the oxygen atoms react and bond with the cross-linking agent. This bonding of the cross-linking agent to the two polymers not only bonds the two polymers to the cross-linking agent, but also bonds the two polymers to each other through the cross-linking agent, thereby forming a cross-linked polymer.

[0105] By increasing the molecular weight of the polymer through a cross-linking reaction, the new cross-linked polymer becomes less soluble in conventional organic solvent negative resist developers.

[0106] In some embodiments, the photoresist developer 57 includes a solvent, an acid, or a base. In some embodiments, the concentration of the solvent is from about 60 wt.% to about 99 wt.% based on the total weight of the photoresist developer. The concentration of the acid or base is from about 0.001 wt.% to about 20 wt.% based on the total weight of the photoresist developer. In certain embodiments, the concentration of the acid or base in the developer is from about 0.01 wt.% to about 15 wt.% based on the total weight of the photoresist developer.

[0107] In some embodiments, the developer 57 is applied to the photoresist layer 15 using a spin coating process. In the spin coating process, when the substrate coated with the photoresist is rotated, the developer 57 is applied to the photoresist layer 15 from above the photoresist layer 15, such as Figure 4 As shown. In some embodiments, the developer 57 is supplied at a rate of about 5 ml / min to about 800 ml / min, and the photoresist-coated substrate 10 is rotated at a speed of about 100 rpm to about 2000 rpm. In some embodiments, the developer is at a temperature between about 10° C. and about 80° C. In some embodiments, the developer operation lasts for about 30 seconds to about 10 minutes.

[0108] Although a spin coating operation is a suitable method for developing the photoresist layer 15 after exposure, it is intended to be illustrative and not intended to limit the embodiments. Instead, any suitable development operation may be used alternatively, including a dip process, a puddle process, and a spray method. All of these development operations are included within the scope of the embodiments.

[0109] During the development process, developer 57 dissolves the radiation exposed areas 50 of the cross-linked negative resist, exposing the surface of substrate 10, such as Figure 5 As shown, and leaves well-defined unexposed photoresist areas 52, which have higher definition than that provided by conventional negative photoresist lithography.

[0110] After the development operation S150, the remaining developer is removed from the substrate covered by the patterned photoresist. In some embodiments, a spin drying process is used to remove the remaining developer, although any suitable removal technique may be used. After the photoresist layer 15 is developed and the remaining developer is removed, additional processing is performed while the patterned photoresist layer 52 is in place. For example, in some embodiments, an etching operation using dry etching or wet etching is performed to transfer the pattern of the photoresist layer 52 to the underlying substrate 10, forming a Figure 6As shown in recess 55 ”, substrate 10 has a different etch resistance than photoresist layer 15 . In some embodiments, the etchant is more selective to substrate 10 than photoresist layer 15 .

[0111] In some embodiments, the substrate 10 and the photoresist layer 15 include at least one anti-etching molecule. In some embodiments, the anti-etching molecule includes molecules having a low Onishi number structure, a double bond, a triple bond, silicon, silicon nitride, titanium, titanium nitride, aluminum, aluminum oxide, silicon oxynitride, and combinations thereof.

[0112] In some embodiments, Figure 8 As shown, before forming the photoresist layer, the layer 60 to be patterned is disposed on the substrate. In some embodiments, the layer 60 to be patterned is a metallization layer or a dielectric layer, such as a passivation layer, disposed on the metallization layer. In embodiments where the layer 60 to be patterned is a metallization layer, the layer 60 to be patterned is formed of a conductive material using a metallization process and metal deposition techniques, including chemical vapor deposition, atomic layer deposition, and physical vapor deposition (sputtering). Similarly, if the layer 60 to be patterned is a dielectric layer, the layer 60 to be patterned is formed by a dielectric layer formation technique, including thermal oxidation, chemical vapor deposition, atomic layer deposition, and physical vapor deposition.

[0113] The photoresist layer 50 is then selectively exposed to actinic radiation 45 to form exposed regions 50 and unexposed regions 52 in the photoresist layer, such as Fig.9A and 9B As shown, this article is relative to Figure 3A and 3B As described herein, the photoresist is a negative photoresist where, in some embodiments, polymer crosslinking occurs in the exposed areas 50 .

[0114] like Fig.10 As shown, the exposed photoresist area 50 is developed by a dispensed developer 57 from a dispenser 62 to form a pattern of photoresist openings 55, as shown in FIG. Fig.11 The development operation is similar to the reference Figure 4 and Figure 5 The operation shown.

[0115] Then, if Fig.12 As shown, the pattern 55 in the photoresist layer 15 is transferred to the layer to be patterned 60 using an etching operation, and the photoresist layer is removed, as described with reference to FIG. 7 , to form a pattern 55″ in the layer to be patterned 60 .

[0116] The novel photoresist compositions and photolithography patterning methods according to the present disclosure provide higher semiconductor device feature resolution and density at higher wafer exposure throughput and reduce defects in a more efficient process than conventional exposure techniques. The novel photoresist compositions provide improved solubility of photoresist components in the photoresist composition.

[0117] An embodiment of the present disclosure is a photoresist composition comprising: a conjugated resist additive; a photoactive compound; and a polymer resin. The conjugated resist additive is one or more selected from the group consisting of: polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene and polyaniline. The polythiophene, polystyrene, polyfluorene, polypyrrole, polyphenylene and polyaniline are substituted by one or more substituents, and the one or more substituents are selected from the group consisting of: alkyl, ether, ester, alkenyl, aromatic, anthracene, alcohol, amine, carboxylic acid and amide. In an embodiment, the one or more substituents include an acid leaving group. In an embodiment, the conjugated resist additive has a band gap of 0.3 eV to 4 eV. In an embodiment, the conjugated resist additive includes a conjugated portion attached to a photoacid generator, a photodecomposable base or a photobase generator. In an embodiment, the conjugated resist additive has a weight average molecular weight of 50 to 1,000,000. In an embodiment, the composition further comprises metal oxide nanoparticles and one or more organic ligands. In an embodiment, the composition further comprises one or more solvents. In an embodiment, the polymer resin comprises

[0118]

[0119] And the conjugated anti-corrosion additive is selected from the group consisting of:

[0120]

[0121] wherein PAG is a photoacid generator, PBG is a photobase generator, and PDB is a photodecomposable base, and R is a substituent.

[0122] Another embodiment of the present disclosure is a photoresist composition, including a polymer resin having a conjugated portion; and a photoactive compound. The conjugated portion is selected from one or more of the following: polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene and polyaniline. In an embodiment, the polythiophene, polystyrene, polyfluorene, polypyrrole, polyphenylene and polyaniline are substituted by one or more substituents, and the one or more substituents are selected from the group consisting of the following items: alkyl, ether, ester, alkenyl, aromatic, anthracene, alcohol, amine, carboxylic acid and amide. In an embodiment, the one or more substituents include an acid leaving group. In an embodiment, the polymer resin having a conjugated portion has a weight average molecular weight of 50 to 1,000,000. In an embodiment, the photoresist composition includes metal oxide nanoparticles and one or more organic ligands. In an embodiment, the polymer resin having a conjugated portion is

[0123]

[0124] and R is a substituent. In an embodiment, the photoresist composition includes one or more solvents. In an embodiment, the conjugated moiety is a repeating unit of a side group on the main chain of the polymer resin.

[0125] Another embodiment of the present disclosure is a method of forming a pattern in a photoresist comprising: forming a layer of a photoresist composition on a substrate; and selectively exposing the photoresist layer to actinic radiation to form a latent pattern. The latent pattern is developed by applying a developer to the selectively exposed photoresist layer to form a pattern. The photoresist composition comprises: a conjugated resist additive; a photoactive compound; and a polymer resin. The conjugated resist additive is one or more selected from the group consisting of: polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene and polyaniline. In an embodiment, the polythiophene, polystyrene, polyfluorene, polypyrrole, polyphenylene and polyaniline are substituted with one or more substituents, and the one or more substituents are selected from the group consisting of: alkyl, ether, ester, alkenyl, aromatic, anthracene, alcohol, amine, carboxylic acid and amide. In an embodiment, the actinic radiation is extreme ultraviolet radiation. In an embodiment, the method includes heating the photoresist layer after selectively exposing the photoresist layer to actinic radiation to form a latent pattern and before developing the latent pattern. In an embodiment, the conjugated resist additive has a band gap of 0.3 eV to 4 eV. In an embodiment, the conjugated resist additive includes a conjugated portion attached to a photoacid generator, a photodecomposable base, or a photobase generator. In an embodiment, the conjugated resist additive has a weight average molecular weight of 50 to 1,000,000. In an embodiment, the photoresist composition further includes metal oxide nanoparticles and one or more organic ligands. In an embodiment, the photoresist composition further includes one or more solvents. In an embodiment, the polymer resin includes

[0126]

[0127] And the conjugated anti-corrosion additive is selected from the group consisting of:

[0128]

[0129] wherein PAG is a photoacid generator, PBG is a photobase generator, and PDB is a photodecomposable base, and R is a substituent.

[0130] Another embodiment of the present disclosure is a method of forming a pattern in a photoresist comprising: forming a photoresist composition layer on a substrate; and selectively exposing the photoresist layer to actinic radiation to form a latent pattern. The latent pattern is developed by applying a developer to the selectively exposed photoresist layer to form a pattern. The photoresist composition comprises: a polymer resin having a conjugated portion; and a photoactive compound. The conjugated portion is selected from one or more of the following: polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene and polyaniline. In an embodiment, the actinic radiation is extreme ultraviolet radiation. In an embodiment, the method comprises: heating the photoresist layer after selectively exposing the photoresist layer to actinic radiation to form a latent pattern and before developing the latent pattern. In an embodiment, the polythiophene, polystyrene, polyfluorene, polypyrrole, polyphenylene and polyaniline are substituted with one or more substituents selected from the group consisting of alkyl, ether, ester, alkenyl, aromatic, anthracene, alcohol, amine, carboxylic acid and amide. In an embodiment, the polymer resin having a conjugated portion has a weight average molecular weight of 1,000 to 1,000,000. In an embodiment, the photoresist composition includes metal oxide nanoparticles and one or more organic ligands. In an embodiment, wherein the polymer resin having a conjugated portion is

[0131]

[0132] wherein R is a substituent. In an embodiment, the photoresist composition comprises one or more solvents. In an embodiment, the conjugated portion is a repeating unit of a side group on the main chain of the polymer resin.

[0133] Another embodiment of the present disclosure is a photoresist composition, including a polymer resin having a first conjugated portion and a photoactive compound having a second conjugated portion. The first and second conjugated portions are the same or different, and the first and second conjugated portions are selected from one or more of the group consisting of the following items: polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene and polyaniline. In an embodiment, the polythiophene, polystyrene, polyfluorene, polypyrrole, polyphenylene and polyaniline are substituted by one or more substituents, and the one or more substituents are selected from the group consisting of the following items: alkyl, ether, ester, alkenyl, aromatic, anthracene, alcohol, amine, carboxylic acid and amide. In an embodiment, the one or more substituents include an acid leaving group, and the photoactive compound is a photoacid generator. In an embodiment, the composition includes metal oxide nanoparticles and one or more organic ligands.

[0134] Another embodiment of the present disclosure is a method of forming a pattern in a photoresist comprising: forming a photoresist composition layer on a substrate; and selectively exposing the photoresist layer to actinic radiation to form a latent pattern. The latent pattern is developed by applying a developer to the selectively exposed photoresist layer to form a pattern. The photoresist composition comprises: a polymer resin having a first conjugated portion; and a photoactive compound having a second conjugated portion. The first conjugated portion and the second conjugated portion are the same or different, and the first and second conjugated portions are selected from one or more of the following: polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene and polyaniline. In an embodiment, the actinic radiation is extreme ultraviolet radiation. In an embodiment, the method comprises heating the photoresist layer after selectively exposing the photoresist layer to actinic radiation to form a latent pattern and before developing the latent pattern. In an embodiment, the polythiophene, polystyrene, polyfluorene, polypyrrole, polyphenylene and polyaniline are substituted with one or more substituents selected from the group consisting of alkyl, ether, ester, alkenyl, aromatic, anthracene, alcohol, amine, carboxylic acid and amide. In an embodiment, the one or more substituents include an acid leaving group and the photoactive compound is a photoacid generator. In an embodiment, the photoresist composition includes metal oxide nanoparticles and one or more organic ligands.

[0135] Another embodiment of the present disclosure is a photoresist composition, comprising: a conjugated resist additive; a photoactive compound; and a polymer resin. The conjugated resist additive is a photobase generator or a photodecomposable base attached to one or more of the group consisting of the following items: polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene and polyaniline. In an embodiment, the polythiophene, polystyrene, polyfluorene, polypyrrole, polyphenylene and polyaniline are substituted by one or more substituents, and the one or more substituents are selected from the group consisting of the following items: alkyl, ether, ester, alkenyl, aromatic, anthracene, alcohol, amine, carboxylic acid and amide. In an embodiment, the one or more substituents include an acid leaving group. In an embodiment, the conjugated resist additive has a weight average molecular weight of 50 to 1,000,000. In an embodiment, the photoresist composition includes metal oxide nanoparticles and one or more organic ligands. In an embodiment, the photoresist composition also includes one or more solvents.

[0136] Another embodiment of the present invention is a photoresist composition, comprising: a conjugated resist additive, a photoactive compound and a polymer resin. The conjugated resist additive is a photo-generator or a photodecomposable base, which is attached to one or more of the group selected from polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polyferrous, polyphenylene and polyaniline. In one embodiment, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene sulfoxide and polyaniline are substituted with one or more substituents selected from the group selected from alkyl, ether, ester, olefin, aromatic, anthracene, alcohol, amino and carboxyl. Wood acid group and amide group. In one embodiment, one or more substituents include leaving acid groups. In one embodiment, the weight average molecular weight of the conjugated resist additive is 50 to 1000000. In one embodiment, the photoresist composition includes metal oxide nanoparticles and one or more organic ligands. In one embodiment, the photoresist composition includes one or more solvents.

[0137] The features of several embodiments or examples are summarized above so that those skilled in the art can better understand the various aspects of the present disclosure. Those skilled in the art should understand that they can easily use the present disclosure as a basis for designing or modifying other processes and structures to achieve the same purpose and / or achieve the same advantages of the embodiments or examples introduced herein. Those skilled in the art should also recognize that such equivalent structures do not deviate from the spirit and scope of the present disclosure, and they can make various changes, substitutions and changes in the present invention without departing from the spirit and scope of the present invention.

[0138] Example 1. A photoresist composition comprising: a conjugated resist additive; a photoactive compound; and a polymer resin, wherein the conjugated resist additive is one or more selected from the group consisting of: polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene and polyaniline, wherein the polythiophene, polystyrene, polyfluorene, polypyrrole, polyphenylene and polyaniline are substituted with one or more substituents, and the one or more substituents are selected from the group consisting of: alkyl, ether, ester, alkenyl, aromatic, anthracene, alcohol, amine, carboxylic acid and amide.

[0139] Example 2. The photoresist composition of Example 1, wherein the one or more substituents include an acid leaving group.

[0140] Example 3. The photoresist composition of Example 1, wherein the conjugated resist additive has a band gap of 0.3 eV to 4 eV.

[0141] Example 4. A photoresist composition according to Example 1, wherein the conjugated resist additive includes a conjugated portion attached to a photoacid generator, a photodecomposable base, or a photobase generator.

[0142] Example 5. The photoresist composition of Example 1, wherein the conjugated resist additive has a weight average molecular weight of 50 to 1,000,000.

[0143] Example 6. The photoresist composition of Example 1 further comprises metal oxide nanoparticles and one or more organic ligands.

[0144] Example 7. The photoresist composition of Example 1 further comprises one or more solvents.

[0145] Example 8. The photoresist composition of Example 1, wherein:

[0146] The polymer resin includes

[0147]

[0148] And the conjugated anti-corrosion additive is selected from the group consisting of:

[0149]

[0150] wherein PAG is a photoacid generator, PBG is a photobase generator, and PDB is a photodecomposable base, and R is a substituent.

[0151] Example 9. A photoresist composition comprising: a polymer resin having a conjugated portion; and a photoactive compound; wherein the conjugated portion is selected from one or more of the following: polyacetylene, polythiophene, polyphenylene vinylene, polyfluorene, polypyrrole, polyphenylene and polyaniline.

[0152] Example 10. A photoresist composition according to Example 9, wherein the polythiophene, polystyrene, polyfluorene, polypyrrole, polyphenylene and polyaniline are substituted by one or more substituents, and the one or more substituents are selected from the group consisting of: alkyl, ether, ester, alkenyl, aromatic, anthracene, alcohol, amine, carboxylic acid and amide.

[0153] Example 11. The photoresist composition of Example 10, wherein the one or more substituents include an acid leaving group.

[0154] Example 12. The photoresist composition according to Example 10, wherein the polymer resin having a conjugated portion is

[0155]

[0156] and R is a substituent.

[0157] Example 13. The photoresist composition of Example 9, wherein the polymer resin having a conjugated portion has a weight average molecular weight of 50 to 1,000,000.

[0158] Example 14. The photoresist composition of Example 9 further comprising metal oxide nanoparticles and one or more organic ligands.

[0159] Example 15. The photoresist composition of Example 9 further comprising one or more solvents.

[0160] Example 16. The photoresist composition of Example 9, wherein the conjugated portion is a repeating unit of a pendant group on the main chain of the polymer resin.

[0161] Example 17. A method for forming a pattern in a photoresist, comprising: forming a photoresist composition layer on a substrate; selectively exposing the photoresist layer to actinic radiation to form a latent pattern; and developing the latent pattern to form a pattern by applying a developer to the selectively exposed photoresist layer, wherein the photoresist composition comprises: a conjugated resist additive; a photoactive compound; and a polymer resin, wherein the conjugated resist additive is one or more selected from the group consisting of: polyacetylene, polythiophene, polyphenylene vinyl, polyfluorene, polypyrrole, polyphenylene and polyaniline, wherein the polythiophene, polystyrene, polyfluorene, polypyrrole, polyphenylene and polyaniline are substituted with one or more substituents, and the one or more substituents are selected from the group consisting of: alkyl, ether, ester, alkenyl, aromatic, anthracene, alcohol, amine, carboxylic acid and amide.

[0162] Example 18. The method of Example 17, wherein the actinic radiation is extreme ultraviolet radiation.

[0163] Example 19. The method of Example 17, further comprising heating the photoresist layer after selectively exposing the photoresist layer to actinic radiation to form a latent pattern and before developing the latent pattern.

[0164] Example 20. The method of Example 17, wherein the one or more substituents include an acid leaving group.

Claims

1. A photoresist composition, include: a polymer resin having a conjugated portion; as well as Photoactive compounds; wherein the conjugated portion is polythiophene, Wherein, the polymer resin having a conjugated portion is And R is a substituent, wherein the substituent R is an alkyl group, an ether group, an ester group, an alkenyl group, an aryl group, an anthracene group, an alcohol group, an amine group, a carboxylic acid group or an amide group, wherein n is in the range of 1 to 200.

2. The photoresist composition according to claim 1, in, The polymer resin having a conjugated portion has a weight average molecular weight of 50 to 1,000,000.

3. The photoresist composition according to claim 1, further comprising metal oxide nanoparticles and one or more organic ligands.

4. The photoresist composition according to claim 1, further comprising one or more solvents.

5. The photoresist composition according to claim 1, in, The conjugated portion is a repeating unit of a pendant group on the main chain of the polymer resin.

6. The photoresist composition according to claim 1, in, The conjugated portion has a band gap of 0.3 eV to 4 eV.

7. A method of forming a pattern in a photoresist, include: forming a photoresist composition layer over the substrate; selectively exposing the photoresist composition layer to actinic radiation to form a latent pattern; as well as developing the latent pattern by applying a developer to the selectively exposed photoresist composition layer to form a pattern, Wherein, the photoresist composition is the photoresist composition according to any one of claims 1-6.

8. The method according to claim 7, in, The actinic radiation is extreme ultraviolet radiation.

9. The method according to claim 7, further comprising: include: After selectively exposing the photoresist composition layer to actinic radiation to form a latent pattern and before developing the latent pattern, the photoresist composition layer is heated.

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