Photoresist composition and method for manufacturing semiconductor device

Abstract

The method for manufacturing a semiconductor device includes forming a photoresist layer including a photoresist composition on a substrate. The photoresist composition includes a photoactive compound, a polymer and a cross-linking agent. The polymer has the structure: #imgabs0# the cross-linking agent includes a structure selected from the following: ‑B1‑OH, ‑B2‑ORa, ‑B3‑NH2, ‑B4‑NR2 and #imgabs1# A1, A2, A3, B1, B2, B3, B4 and D are each C1 to C30 aryl, alkyl, cycloalkyl, hydroxyalkyl, alkoxy, alkoxyalkyl, acetyl, acetylalkyl, carboxyl, alkylcarboxyl, cycloalkylcarboxyl, hydrocarbon ring, heterocyclic group, chain, ring, stereo structure; R1, R2 and Ra are C4 to C15 chain, ring, stereo structure of alkyl, cycloalkyl, hydroxyalkyl, alkoxy or alkoxyalkyl, the ratio of x, y and z in the polymer is 0≤x / (x+y+z)≤1, 0≤y / (x+y+z)≤1 and 0≤z / (x+y+z)≤1, and in the same polymer, x, y and z are not 0.

Description

Technical Field

[0001] Some embodiments of the present disclosure relate to photoresist compositions and methods of manufacturing semiconductor devices. Background Art

[0002] As consumer electronic devices become smaller in response to consumer demand, the size of the individual components of these devices must be reduced. With the pressure to reduce the size of the individual devices (such as transistors, resistors, capacitors, etc.) in semiconductor devices, the semiconductor devices that constitute the main components of mobile phones, computer tablets, etc. are forced to shrink.

[0003] One technology that can be used in the semiconductor device manufacturing process is the use of photolithographic materials. Such materials are applied to the surface of the layer to be patterned, and then an energy source that has itself been patterned is used to expose the layer to be patterned. This exposure method modifies the chemical and physical properties of the exposed areas of the photosensitive material. This modification method can be used to remove one area without removing another area along with the unexposed areas of the photosensitive material that lack the modification.

[0004] However, as the size of individual devices decreases, the process window of the photolithography process becomes more and more narrow. As a result, the field of photolithography process development is necessary to maintain the ability to reduce device size, and further improvements are required to achieve the desired design specifications so that smaller components can be produced.

[0005] As the semiconductor industry evolves to nanotechnology processes, in pursuit of higher device density, higher performance and lower cost, the semiconductor feature size is facing the challenge of reduction. Extreme ultraviolet lithography (EUVL) is developed to form smaller semiconductor device feature sizes and increase device density on semiconductor wafers. In order to improve EUVL technology, it is expected to increase wafer exposure flux. Wafer exposure flux can be increased by increasing exposure power or increasing the sensitivity of photoresist. Summary of the invention

[0006] Embodiments of the present disclosure are methods of manufacturing semiconductor devices, including forming a photoresist layer including a photoresist composition on a substrate. Selectively exposing the photoresist layer to actinic radiation to form a latent pattern. Developing the latent pattern to form a pattern by applying a developer to the selectively exposed photoresist layer. The photoresist composition includes: a photoactive compound, a polymer, and a crosslinking agent. The polymer has a structure:

[0007]

[0008] wherein A1, A2, and A3 are independently substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C3 to C30 cycloalkyl, C1 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C30 cycloalkylcarboxyl, saturated or unsaturated C3 to C30 hydrocarbon ring, saturated or unsaturated C1 to C30 Heterocyclic group or C1 to C30 chain, ring or stereo structure; wherein R1 is a substituted or unsubstituted C4 to C15 chain, ring or stereo structure alkyl, C4 to C15 cycloalkyl, C4 to C15 hydroxyalkyl, C4 to C15 alkoxy or C4 to C15 alkoxyalkyl; wherein the ratio of x, y and z in the polymer is 0≤x / (x+y+z)≤1, 0≤y / (x+y+z)≤1 and 0≤z / (x+y+z)≤1, and in the same polymer, x, y and z are not 0. The crosslinking agent is a monomer, oligomer or polymer, and the monomer, oligomer or polymer comprises one or more structures selected from the following:

[0009] -B1-OH,

[0010] -B2-ORa,

[0011] -B3-NH2,

[0012] -B4-NR2 and

[0013]

[0014] wherein B1, B2, B3, B4 and D are independently substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C3 to C30 cycloalkyl, C2 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C3 The invention relates to a cycloalkylcarboxyl group having a saturated or unsaturated C3 to C30 hydrocarbon ring, a saturated or unsaturated C1 to C30 heterocyclic group, or a C1 to C30 chain, ring or stereostructure, and wherein R and Ra are each a substituted or unsubstituted C4 to C15 chain, ring or stereostructure alkyl group, a C4 to C15 cycloalkyl group, a C4 to C15 hydroxyalkyl group, a C4 to C15 alkoxy group or a C4 to C15 alkoxyalkyl group.

[0015] Other embodiments of the present disclosure are methods of manufacturing a semiconductor device, comprising forming a photoresist layer comprising a photoresist composition on a semiconductor wafer. The photoresist composition comprises a polymer and a crosslinker. Pattern-exposing the photoresist layer to actinic radiation. Heating the pattern-exposed photoresist layer at a first temperature. Removing portions of the photoresist layer exposed to the actinic radiation to form a patterned photoresist layer. After removing portions of the photoresist layer exposed to the actinic radiation, crosslinking the polymer in the patterned photoresist layer.

[0016] Some embodiments of the present disclosure are photoresist compositions, comprising: a photoactive compound, a polymer, and a crosslinking agent. The polymer has a structure:

[0017]

[0018] wherein A1, A2, and A3 are independently substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C3 to C30 cycloalkyl, C1 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C30 cycloalkylcarboxyl, saturated or unsaturated C3 to C30 hydrocarbon ring, saturated or unsaturated C1 to C30 Heterocyclic group or C1 to C30 chain, ring or stereo structure; wherein R1 is a substituted or unsubstituted C4 to C15 chain, ring or stereo structure alkyl, C4 to C15 cycloalkyl, C4 to C15 hydroxyalkyl, C4 to C15 alkoxy or C4 to C15 alkoxyalkyl; wherein the ratio of x, y and z in the polymer is 0≤x / (x+y+z)≤1, 0≤y / (x+y+z)≤1 and 0≤z / (x+y+z)≤1, and in the same polymer, x, y and z are not 0. The crosslinking agent is a monomer, oligomer or polymer, and the monomer, oligomer or polymer comprises one or more structures selected from the following:

[0019] -B1-OH,

[0020] -B2-ORa,

[0021] -B3-NH2,

[0022] -B4-NR2 and

[0023]

[0024] wherein B1, B2, B3, B4 and D are independently substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C3 to C30 cycloalkyl, C2 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C3 The invention relates to a cycloalkylcarboxyl group having a saturated or unsaturated C3 to C30 hydrocarbon ring, a saturated or unsaturated C1 to C30 heterocyclic group, or a C1 to C30 chain, ring or stereostructure, and wherein R and Ra are each a substituted or unsubstituted C4 to C15 chain, ring or stereostructure alkyl group, a C4 to C15 cycloalkyl group, a C4 to C15 hydroxyalkyl group, a C4 to C15 alkoxy group or a C4 to C15 alkoxyalkyl group. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] When read together with the accompanying drawings, the aspects of the present disclosure can be best understood from the following embodiments. Note that according to standard practice in this industry, various features are not drawn to scale. In fact, the dimensions of various features may be arbitrarily increased or reduced for clarity of discussion.

[0026] Figure 1 A process flow for manufacturing a semiconductor device according to some embodiments of the present disclosure is illustrated;

[0027] Figure 2 depicting process stages of continuous operation according to an embodiment of the present disclosure;

[0028] FIG. 3A to FIG. 3B illustrates the process stages of continuous operation according to some embodiments of the present disclosure;

[0029] Figure 4 illustrates the process stages of continuous operation according to some embodiments of the present disclosure;

[0030] Figure 5 illustrates the process stages of continuous operation according to some embodiments of the present disclosure;

[0031] Figure 6 illustrates the process stages of continuous operation according to some embodiments of the present disclosure;

[0032] Fig. 7A The process flow according to some embodiments of the present disclosure is illustrated; Figure 7B Examples of photoresist composition polymers according to some embodiments of the present disclosure are shown;

[0033] Figure 8 illustrates the process stages of continuous operation according to some embodiments of the present disclosure;

[0034] FIG. 9A to FIG. 9B illustrates the process stages of continuous operation according to some embodiments of the present disclosure;

[0035] Fig.10 illustrates the process stages of continuous operation according to some embodiments of the present disclosure;

[0036] Fig.11 illustrates the process stages of continuous operation according to some embodiments of the present disclosure;

[0037] Fig.12 illustrates the process stages of continuous operation according to some embodiments of the present disclosure;

[0038] Among them, the symbols are as follows:

[0039] 10: Substrate 15: Photoresist layer

[0040] 30: Mask 35: Opaque pattern

[0041] 40: Mask substrate 45: Radiation

[0042] 50: District 52: District

[0043] 52a: photoresist layer 55: opening

[0044] 55': Opening 55": Pattern

[0045] 57: Developer 60: Layer

[0046] 62: Dispenser 65: Mask

[0047] 70: substrate 75: multilayer

[0048] 80: Protective cover 85: Absorbent material layer

[0049] 90: Back semiconductor layer 95: Ultraviolet radiation

[0050] 97: Fallout 100: Process Flow

[0051] A: polymer B: polymer

[0052] C: Polymer S110: Operation

[0053] S120: Operation S130: Operation

[0054] S140: Operation S150: Operation

[0055] S160: Operation S170: Operation. DETAILED DESCRIPTION

[0056] The following disclosure provides many different embodiments or examples for implementing the different features of the subject matter provided. The following describes specific examples of components and arrangements to simplify the present disclosure. Of course, these are only examples and are not intended to be limiting. For example, in the following description, forming a first feature above or on a second feature may include an embodiment in which the first and second features are directly contacted, and may also include an embodiment in which additional features are formed between the first and second features so that the first and second features may not be in direct contact. In addition, the present disclosure may repeat component symbols and / or letters in various examples. This repetition is for the purpose of simplicity and clarity and does not itself specify the relationship between the various embodiments or configurations discussed.

[0057] Additionally, for ease of description, spatially relative terms, such as "below," "beneath," "below," "above," and "above," may be used herein to describe the relationship of one element or feature to another element or feature as illustrated in the figures. The spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.

[0058] Figure 1 A process flow 100 for manufacturing a semiconductor device according to some embodiments of the present disclosure is shown. In operation S110, in some embodiments, a photoresist composition is coated on a surface of a layer to be patterned or on a substrate 10 to produce a photoresist layer 15, such as Figure 2As shown. Then, in some embodiments, the photoresist layer 15 undergoes a first baking operation S120 (pre-exposure baking) to evaporate the solvent in the photoresist composition. The photoresist layer 15 is baked at a sufficient temperature and time to repair and dry the photoresist layer 15. In some embodiments, the photoresist layer is heated to about 40 degrees Celsius to about 120 degrees Celsius and lasts for about 10 seconds to about 10 minutes. A heating temperature lower than the disclosed range or a time less than the disclosed continuous range may result in incomplete removal of the solvent from the photoresist layer. A heating temperature higher than the disclosed range or a time longer than the disclosed continuous range may result in harmful chemical reactions in the photoresist layer. In some embodiments, the thickness of the photoresist layer 15 is between about 10 nanometers and about 300 nanometers. In some embodiments, the photoresist layer 15 has a thickness of less than 75 nanometers. In some embodiments, the thickness of the photoresist layer 15 is between about 25 nanometers and about 75 nanometers, and in other embodiments, the thickness of the photoresist layer 15 is between about 40 nanometers and about 65 nanometers. A photoresist layer thickness less than the disclosed range may result in insufficient photoresist coverage of a subsequently formed photoresist pattern. A photoresist layer thickness greater than the disclosed range may result in an unnecessarily thick photoresist layer, higher photoresist material costs, and reduced pattern resolution.

[0059] After the first baking operation S120, in operation S130, selectively under actinic radiation 45 / 97 (see FIG. 3A to FIG. 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 radiation (EUV). In some embodiments, the radiation is an electron beam.

[0060] like Figure 3A As shown, in some embodiments, exposure radiation 45 passes through mask 30 before irradiating photoresist layer 15. In some embodiments, mask 30 has a pattern to be replicated in photoresist layer 15. In some embodiments, the pattern is formed by an opaque pattern 35 on mask substrate 40. Optical opaque pattern 35 can be formed of a material opaque to ultraviolet radiation, such as chromium, while mask substrate 40 is formed of a material transparent to ultraviolet radiation, such as fused silica.

[0061] In some embodiments, EUV lithography is used to perform selective exposure of the photoresist layer 15 to form exposed areas 50 and unexposed areas 52. In the EUV lithography operation, the reflective mask 65 is used to form a patterned exposure light source, such as Figure 3BAs shown. The reflective mask 65 comprises a low thermal expansion glass substrate 70 and a reflective multilayer 75 of silicon and molybdenum, the reflective multilayer 75 being formed on the substrate 70. A protective cover 80 and an absorbing material layer 85 are formed on the reflective multilayer 75. A back conductor layer 90 is formed on the back side of the low thermal expansion substrate 70. In EUV lithography, EUV radiation 95 is directed toward the reflective mask 65 at an incident angle of about 6 degrees. A portion 97 of the EUV radiation is reflected by the silicon / molybdenum multilayer 75 to the photoresist-coated substrate 10, while a portion of the EUV radiation above the absorbing material layer 85 is absorbed by the mask. In some embodiments, more optical objects, including mirrors, are located between the reflective mask 65 and the photoresist-coated substrate.

[0062] The regions 50 of the photoresist layer that were exposed to the radiation react chemically relative to the regions 52 of the photoresist layer that were not exposed to the radiation, thereby changing their solubility in a subsequently applied developer.

[0063] Next, in operation S140, the photoresist layer 15 undergoes a post-exposure bake (PEB) (or second bake). In some embodiments, the photoresist layer is heated to about 50 degrees Celsius to about 160 degrees Celsius for about 20 seconds to about 120 seconds. The post-exposure bake can be used to assist in the generation, dispersion and reaction of acid ions / alkali ions / free radicals generated from the impact of radiation 45 / 97 on the photoresist layer 15 during exposure. This assistance helps to create or enhance chemical reactions and generate chemical differences between the exposed area 50 and the unexposed area 52 in the photoresist layer. These chemical differences also result in solubility differences between the exposed area 50 and the unexposed area 52. Heating at a temperature below the disclosed range or for a time less than the disclosed duration may result in incomplete generation, dispersion and reaction of acid ions / alkali ions / free radicals. Heating to a temperature above the disclosed range or for a duration greater than the disclosed range may cause deleterious chemical reactions in the photoresist layer or may unnecessarily increase the cost and manufacturing time of the semiconductor device.

[0064] In operation S150, a developer is applied to the selectively exposed photoresist layer to develop the selectively exposed photoresist layer. Figure 4 As shown, the developer 57 is provided from the dispenser 62 to the photoresist layer 15. In some embodiments, the developer 57 is used to remove the exposed area 50 of the photoresist layer, and a pattern of openings 55 is formed in the photoresist layer 15 to expose the substrate 10. Next, the developed photoresist layer 15 undergoes a hard bake (or third bake) operation S160 to crosslink the polymer in the remaining photoresist area to form a crosslinked photoresist layer 52a, as shown in FIG. Figure 5In some embodiments, after the hard bake of operation S160 , a wet cleaning or wet chemical treatment operation is performed on the substrate having the patterned photoresist layer in operation S170 .

[0065] In some embodiments, the pattern of openings 55 in the photoresist layer 15 extends into the layer to be patterned or into the substrate 10 to create a pattern of openings 55' in the substrate 10, thereby transferring the pattern of the photoresist layer 15 to the substrate 10, such as Figure 6 As shown. The pattern is extended into the substrate by etching, using one or more suitable etchants. In some embodiments, the cross-linked photoresist layer 52a is at least partially removed during the etching operation. In other embodiments, after etching the substrate 10, the cross-linked photoresist layer 52a is removed by using a suitable removal solvent or by a photoresist ashing operation.

[0066] In some embodiments, the substrate 10 comprises a semiconductor wafer. In some embodiments, the substrate 10 comprises a single crystal semiconductor layer at least on a surface portion. The substrate 10 may comprise a single crystal semiconductor material such as, but not limited to, silicon (Si), germanium (Ge), silicon germanium (SiGe), gallium arsenide (GaAs), indium antimonide (InSb), gallium phosphide (GaP), gallium antimonide (GaSb), indium aluminum arsenide (InAlAs), indium gallium arsenide (InGaAs), gallium antimony phosphide (GaSbP), gallium arsenide antimony (GaAsSb) and indium phosphide (InP). In some embodiments, the substrate 10 is a silicon layer of silicon-on insulator (SOI). In a specific embodiment, the substrate 10 is made of silicon crystal.

[0067] The substrate 10 may include one or more buffer layers (not shown) in the substrate 10. 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 regions. The buffer layer may be formed of epitaxially grown single crystal semiconductor materials, such as, but not limited to, silicon, germanium, germanium tin (GeSn), silicon germanium, gallium arsenide, indium antimonide, gallium phosphide, gallium antimonide, aluminum indium arsenide, indium gallium arsenide, gallium antimony phosphide, gallium arsenide antimony, gallium nitride (GaN), gallium phosphide (GaP), and indium phosphide. In an embodiment, a silicon germanium buffer layer is epitaxially grown on the substrate 10. The germanium concentration of the silicon germanium buffer layer may increase from 30 atomic percent in the bottom buffer layer to 70 atomic percent in the top buffer layer.

[0068] In some embodiments, the substrate 10 comprises at least one metal, metal alloy and a metal having a chemical formula MX awherein M is a metal, X is nitrogen (N), sulfur (S), selenium (Se), oxygen (O), silicon (Si), and a is between about 0.4 and about 2.5. In some embodiments, the substrate 10 comprises titanium (Ti), aluminum (Al), cobalt (Co), ruthenium (Ru), titanium nitride (TiN), tungsten nitride (WN), tantalum nitride (TaN), and combinations thereof.

[0069] In some embodiments, substrate 10 comprises a dielectric having at least one oxide or nitride of silicon or metal, wherein the oxide or nitride of silicon or metal has a chemical formula MX b , M is metal or silicon, X is nitrogen or oxygen, and b is between about 0.4 and about 2.5. In some embodiments, the substrate 10 comprises silicon dioxide, silicon nitride, aluminum oxide, hafnium oxide, lanthanum oxide, or combinations thereof.

[0070] The photoresist layer 15 is a photosensitive layer that is patterned by exposure to actinic radiation. Generally, depending on the type of photoresist used, the chemical properties of the photoresist areas hit by the incident radiation will change in different forms. Positive photoresist 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 areas are insoluble in the developer. In some embodiments, the photoresist is a positive photoresist and the developer is an aqueous developer, such as a tetramethylammonium hydroxide (TMAH) solution.

[0071] In some embodiments, the photoresist layer comprises a high-sensitivity photoresist composition. In some embodiments, the high-sensitivity photoresist composition has high sensitivity to extreme ultraviolet (EUV) radiation.

[0072] In some embodiments, the photoresist composition comprises a polymer having one or more photoactive compounds (PACs). In some embodiments, the polymer comprises a hydrocarbon structure (e.g., an alicyclic hydrocarbon structure) comprising one or more groups that decompose (e.g., acid labile groups) or reacts when mixed with acid ions, base ions, or free radicals generated from a photoactive compound (as described below). In some embodiments, the hydrocarbon structure comprises repeating units that form the backbone structure of the polymer. Such repeating units may comprise acrylates, methacrylates, crotonates, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth)acrylonitrile, (meth)acrylamide, styrene, vinyl ethers, or the like, or combinations thereof.

[0073] In some embodiments, the specific structure of the repeating unit used for the hydrocarbon structure includes one or more methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, isooctyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, cyclohexyl acrylate, benzyl acrylate, (meth) acrylate-2-alkyl-2-adamantyl ester (2-alkyl-2-adamantyl (meth) acrylate or (meth) acrylate dialkyl (1-adamantyl) methyl ester (dial kyl(1-adamantyl)methyl(meth)acrylate), methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, isooctyl 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, etc.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, methylacrylamide, ethylacrylamide, propylacrylamide, n-butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, 2-methoxyethylacrylamide, dimethylacrylamide, diethylacrylamide, phenylacrylamide, benzylacrylamide, methacrylamide, methylmethacrylamide, ethyl methacrylamide, propyl methacrylamide, n-butyl methacrylamide, tert-butyl methacrylamide, The styrene may be styrene, styrene toluene, styrene to dimethyl styrene, styrene to ethyl styrene, styrene to methyl styrene, styrene to ethyl styrene, styrene to ethyl styrene, styrene to butyl styrene, styrene to ethyl styrene, isopropyl styrene, styrene to butyl styrene, methoxy styrene, styrene to butyrate, styrene to methoxy, styrene to butyrate, styrene to butyl styrene, styrene to butyl styrene, styrene to methyl ...methyl styrene, styrene to methyl styrene, styrene to methyl styrene, styrene to methyl styrene, styrene to methyl styrene, styrene to methyl styrene, styrene to

[0074] In some embodiments, the repeating unit of the hydrocarbon structure also has a substituent of a monocyclic or polycyclic hydrocarbon structure, or a monocyclic or polycyclic hydrocarbon structure is a repeating unit to form an alicyclic hydrocarbon structure. In some embodiments, specific examples of the monocyclic structure include bicycloalkane, tricycloalkane, tetracycloalkane, cyclopentane, cyclohexane, or the like. In some embodiments, specific examples of the monocyclic structure include adamantane, norbornane, isobornane acetate, tricyclodecane, tetracyclododecane, or the like.

[0075] Fig. 7A The process flow of the reaction in the photoresist layer 15 is shown. The reaction is caused by the exposure operation S130, the development operation S150 and the baking operations S140 and S160. In some embodiments, the polymer composition includes a photoactive compound, a polymer and a crosslinking agent, wherein the polymer has a structure

[0076]

[0077] wherein A1, A2, and A3 are independently substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C3 to C30 cycloalkyl, C1 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C30 cycloalkylcarboxyl, saturated or unsaturated C3 to C30 hydrocarbon ring, saturated or unsaturated C1 to C30 heterocyclic group, or C 1 to C30 chain, ring or three-dimensional (3-D) structure; wherein R1 is a substituted or unsubstituted C4 to C15 chain, ring or three-dimensional (3-D) structure alkyl, C4 to C15 cycloalkyl, C4 to C15 hydroxyalkyl, C4 to C15 alkoxy or C4 to C15 alkoxyalkyl; wherein the ratio of x, y and z in the polymer is 0≤x / (x+y+z)≤1, 0≤y / (x+y+z)≤1 and 0≤z / (x+y+z)≤1, and in the same polymer, x, y and z are not 0. The crosslinking agent is a monomer, oligomer or polymer, and the monomer, oligomer or polymer comprises one or more structures selected from the following:

[0078] -B1-OH,

[0079] -B2-ORa,

[0080] -B3-NH2,

[0081] -B4-NR2 and

[0082]

[0083] wherein B1, B2, B3, B4 and D are independently substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C3 to C30 cycloalkyl, C2 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C30 cycloalkyl Carboxyl, saturated or unsaturated C3 to C30 hydrocarbon ring, saturated or unsaturated C1 to C30 heterocyclic group or C1 to C30 chain, ring or three-dimensional (3-D) structure; and wherein R and Ra are each substituted or unsubstituted C4 to C15 chain, ring or three-dimensional (3-D) structure alkyl, C4 to C15 cycloalkyl, C4 to C15 hydroxyalkyl, C4 to C15 alkoxy or C4 to C15 alkoxyalkyl. Each of the above groups may be substituted by one or more substituents, including halogen, such as fluoro, chloro, bromo or iodo or amine. In some embodiments, the C6 to C30 aryl in the polymer or crosslinker comprises benzyl, phenyl or fused aryl, including naphthyl and anthracene. In some embodiments, the three-dimensional (3-D) structure comprises adamantyl or norbornenyl. In some embodiments, the crosslinker comprises epoxy or amine.

[0084] In some embodiments, R1 of the polymer is an acid-labile group. The acid-labile group is selected from the group consisting of:

[0085]

[0086] Exposure to actinic radiation causes the R1 groups on the polymer in the exposed areas to decompose and form developer-soluble groups, such as Fig. 7A The exposed areas of the photoresist layer become soluble in the developer and are removed during the development operation. The remaining unexposed areas are cross-linked by a cross-linking agent during a subsequent hard bake, such as Fig. 7A The patterned, cross-linked photoresist layer 52a imparts enhanced etch resistance to the photoresist.

[0087] Figure 7B Some examples of photoresist polymers are shown. In some embodiments, Figure 7B The polymer A in the photoresist is used for photosensitive krypton fluoride (KrF) laser radiation. In some embodiments, Figure 7B The polymer B in is used for a photoresist having photosensitivity to argon fluoride (ArF) laser radiation, and in some embodiments, Figure 7BThe polymer C in is used in photoresists that are photosensitized to extreme ultraviolet radiation.

[0088] The acid-labile group is attached to a hydrocarbon structure, so that during exposure, the acid-labile group reacts with acid ions, base ions or free radicals generated from the photoactive compound. In some embodiments, the group that decomposes is a carboxylic acid group, a fluorinated alcohol group, a phenol group, a sulfonic group, a sulfonyl group, a sulfonamide group, a sulfonylimido group, a (alkylsulfonyl)(alkylcarbonyl)methylene group, a (alkylsulfonyl)(alkylcarbonyl)methylene group, a (alkylsulfonyl)(alkyl-carbonyl)imido group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imido group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imido group, a tris(alkylcarbonyl)methylene group, a tris(alkylsulfonyl)methylene group, a combination thereof, or the like. Particular groups for fluorinated alcohols include fluorinated hydroxyalkyl groups, such as hexafluoroisopropanol in some embodiments. Particular groups for carboxylic acid groups include acrylic acid, methacrylic acid, or the like.

[0089] In some embodiments, for example, when using extreme ultraviolet radiation, the photoresist composition according to the present disclosure is a metal-containing photoresist. The metal-containing photoresist comprises a metal center with one or more ligands in a solvent. In some embodiments, the photoresist comprises metal particles. In some embodiments, the metal particles are nanoparticles. As used herein, nanoparticles are particles with an average size between about 1 nanometer and about 20 nanometers. In some embodiments, in solution, the metal center is coordinated with one or more organic ligands, and the metal center comprises 1 to 18 metal particles. In some embodiments, in solution, the metal center comprises 3, 6, 9 or more metal nanoparticles, and the metal nanoparticles are coordinated with one or more organic ligands.

[0090] In some embodiments, the metal particles are one or more of the following metals: titanium (Ti), zinc (Zn), zirconium (Zr), nickel (Ni), cobalt (Co), manganese (Mn), copper (Cu), iron (Fe), strontium (Sr), tungsten (W), vanadium (V), chromium (Cr), tin (Sn), hafnium (Hf), indium (In), cadmium (Cd), molybdenum (Mo), tantalum (Ta), niobium (Nb), aluminum (Al), cesium (Cs), barium (Ba), lanthanum (La), cerium (Ce), silver (Ag), antimony (Sb), combinations thereof, or oxides thereof. In some embodiments, the metal particles include one or more of the group consisting of cerium, barium, lanthanum, indium, tin, aluminum, antimony, and oxides thereof.

[0091] In some embodiments, the metal nanoparticles have an average size between about 2 nanometers and about 5 nanometers. In some embodiments, the weight percentage concentration of the amount of metal nanoparticles in the photoresist composition is between about 0.5% and about 15%, based on the weight of the nanoparticles and the solution. In some embodiments, the weight percentage concentration of the amount of nanoparticles in the photoresist composition is between about 5% and about 10%, based on the weight of the nanoparticles and the solution. In some embodiments, the weight percentage concentration of the metal particles is between about 1% and about 7%, based on the weight of the solution and the metal particles. If the weight percentage concentration of the metal nanoparticles is less than 0.5%, the photoresist coating layer will be too thin. If the weight percentage concentration of the metal nanoparticles is greater than 15%, the photoresist coating layer will be too thick and too viscous.

[0092] In some embodiments, the metal center is coordinated with a thermally stable ligand, wherein the thermally stable ligand comprises a branched or unbranched, cyclic or acyclic saturated organic group, the saturated organic group comprising a C1 to C7 alkyl group or a C1-C7 fluoroalkyl group. The C1 to C7 alkyl group or the C1-C7 fluoroalkyl group comprises one or more substituents selected from the group consisting of: -CF3, -SH, -OH, =O, -S-, -P-, -PO2, -C(=O)SH, C(=O)OH, -C(=O)O-, -O-, -N-, -C(=O)NH, -SO2OH, -SO2SH, -SOH, and -SO2-. In some embodiments, the ligand comprises one or more substituents selected from the group consisting of: -CF3, -OH, -SH, and -C(=O)OH substituents.

[0093] In some embodiments, the ligand is a carboxylic acid or sulfate ligand. For example, in some embodiments, the ligand is methacrylic acid. In some embodiments, the metal particles are nanoparticles, and the metal nanoparticles are coordinated with ligands comprising aliphatic and aromatic groups. Aliphatic and aromatic groups may be free of branches, or have the following branches: cyclic or non-cyclic saturated side groups, the side groups contain 1 to 9 carbons, including alkyl, alkenyl and phenyl. The branched groups may be further substituted with oxygen or halogen. In some embodiments, each metal particle is coordinated with 1 to 25 ligand units. In some embodiments, each metal particle is coordinated with 3 to 18 ligand units.

[0094] In some embodiments, the photoresist composition comprises a ligand at a weight percentage concentration between about 0.1% and about 20% based on the weight of the photoresist composition. In some embodiments, the photoresist comprises a ligand at a weight percentage concentration between about 1% and about 10%. In some embodiments, the ligand concentration is between about 10% and about 40% based on the weight of the metal particles and the weight of the ligand. If the weight percentage concentration of the ligand is less than 10%, the organometallic photoresist does not function well. If the weight percentage concentration of the ligand is greater than 40%, it is difficult to form a consistent photoresist layer. In some embodiments, in a coating solution, such as propylene glycol methyl etheracetate (PGMEA), the weight percentage concentration range of the ligand dissolved is between about 5% and about 10% based on the weight of the ligand and the solvent.

[0095] In some embodiments, the copolymer and photoactive compound and any desired additives or chemicals are added to a solvent in an application. Once added, the mixture is mixed to achieve homogeneity throughout the photoresist composition to ensure that there are no defects caused by uneven mixing or non-homogeneous composition of the photoresist. Once mixed, the photoresist can be stored before use or used immediately.

[0096] The solvent may be any suitable solvent. In some embodiments, the solvent is one or more selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol ethyl ether (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, acetone, dimethylformamide (DMF), isopropanol (IPA), tetrahydrofuran (THF), 4-methyl-2-pentanol (MIBC), n-butyl acetate (nBA), and 2-heptanone (MAK).

[0097] In some embodiments, the photoresist composition further comprises water at a concentration of 10 to 250 parts per million, based on the total composition of water, the enhancement additive, and the first solvent.

[0098] In some embodiments, the polymer further comprises other groups attached to the hydrocarbon structure, which help to improve various properties of the polymer. For example, the hydrocarbon structure containing a lactone group helps to reduce the degree of edge roughness after developing the photoresist, thereby reducing the amount of defects in the development process. In some embodiments, the lactone group comprises a ring having five to seven members, although any suitable lactone structure can be used in the lactone group.

[0099] In some embodiments, the polymer includes groups that help improve adhesion between the photoresist layer 15 and the underlying structure (e.g., substrate 10). Polar groups can be used to improve adhesion. Suitable polar groups include hydroxyl, cyano, etc., although any suitable polar group can be used.

[0100] As appropriate, in some embodiments, the polymer comprises one or more alicyclic hydrocarbon structures, which do not contain a decomposable group. In some embodiments, the hydrocarbon structure that does not contain a decomposable group comprises, for example, a structure such as 1-adamantyl (meth) acrylate, tricyclodecyl (meth) acrylate, cyclohexyl (meth) acrylate, a combination thereof, or the like.

[0101] Some embodiments of the photoresist include one or more photoactive compounds. The photoactive compound is a component that has photoactivity, such as photoacid generators (PAG), photobase generators (PBG), photodecomposable bases (PDB), free radical generators, or the like. The photoactive compound can be positive or negative. In some embodiments where the photoactive compound is a photoacid generator, the photoactive compound comprises a halogenated triazine, an onium salt, a diazonium salt, an aromatic diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imide sulfonate, an oxime sulfonate, a diazo disulfone, a disulfone, an o-nitrobenzyl sulfone, a sulfonated ester, a halogenated sulfonyloxy dicarboximides, an α-cyanooxyamine sulfonate, a ketodiazo sulfone, a sulfonyldiazoester, a 1,2-di(arylsulfonyl)hydrazines, a nitrobenzyl ester, and an s-triazine derivative, a combination thereof, or the like.

[0102] Specific examples of photoacid generators include α-(trifluoromethylsulfonyloxy)-bicyclo[2.2.1]hept-5-ene-2,3-dicarb-o-ximide (MDT), N-hydroxy-naphthalimide (DDSN), benzoin p-toluenesulfonate (benzoin tosylate, t-butylphenyl-α-(p-toluenesulfonyloxy)-acetate and t-butyl-α-(p-toluenesulfonyloxy)-acetate, hexafluoroantimonates, hexafluoroarsenates, trifluoromethanesulfonates, iodonium perfluorooctanesulfonate, N-camphorsulfonyloxynaphthalimide, N-pentafluorophenylsulfonyloxynaphthalimide, ionic iodonium sulfonates such as diaryl iodonium iodonium) (alkyl or aryl) sulfonates and bis-(di-t-butylphenyl)iodonium camphanylsulfonate, perfluoroalkanesulfonates such as perfluoropentanesulfonate, perfluorooctanesulfonate, perfluoromethanesulfonate, aryl (e.g. phenyl or benzyl) trifluoromethanesulfonates such as triphenylsulfonium triflate or bis-(t-butylphenyl)iodonium triflate; pyrogallol derivatives (e.g. pyrogallol trimesylate), trifluoromethanesulfonate of hydroxyimine (e.g. trifluoromethanesulfonate of hydroxyimine) esters), α,α'-bis-sulfonyl-diazomethanes, sulfonates of nitrogen-substituted benzyl alcohols, naphthoquinone-4-diazides, alkyl disulfones or the like.

[0103] In some embodiments where the photoactive compound is a free radical generator, the photoactive compound comprises N-phenylglycine, aromatic ketones, including benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylethylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, p,p'-bis(dimethylamino)benzophenone, p,p'-bis(diethylamino)benzophenone; anthraquinone, 2-ethylanthraquinone; naphthoquinone; and phenanthrenequinone; benzoins, including benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin; benzyl derivatives, including bibenzyl, benzyl diphenyl diphenyl ether, and benzoin methyl ether. Sulfides (benzyldiphenyldisulfide) and benzyl dimethyl ketone; acridine derivatives, including 9-phenylacridine and 1,7-bis(9-acridinyl)heptane; thioxanthones, including 2-chlorothioxanthones, 2-methylthioxanthones, 2,4-diethylthioxanthones, 2,4-dimethylthioxanthones and 2-isopropylthioxanthones; 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 (2,4,5-triarylimidazole dimers), including 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-diphenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer and 2-(p-methylmercaptophenyl)-4,5-diphenylimidazole dimer, combinations thereof or the like.

[0104] In some embodiments, the photoactive compound comprises a photobase generator and a photolytic base. In embodiments where the photoactive compound is a photobase generator, the photobase generator comprises quaternary ammonium dithiocarbamates, α-amino ketones, oxime-urethane-containing molecules such as benzophenone oxime hexamethylene diamine ester, ammonium tetraorganylboratesalts and N-(2-nitrobenzoyloxycarbonyl) cyclic amines, combinations thereof, or the like.

[0105] In the embodiment where the photoactive compound is a photodecomposable base, the photodecomposable base includes triphenylsulfonium hydroxide, triphenylsulfonium antimonyhexafluoride, and trityltriphenylsulfonium.

[0106] Those skilled in the art will appreciate that the chemicals listed here are only examples of photoactive compounds and are not intended to limit the embodiments to the photoactive compounds described specifically. Furthermore, any suitable photoactive compound may be used, and all of these photoactive compounds are included in the scope of this disclosure.

[0107] In some embodiments where a coupling agent and a crosslinking agent are added, a coupling agent may be added in place of or in addition to a crosslinking agent added to the photoresist composition. The coupling agent assists the crosslinking reaction by reacting with groups in the hydrocarbon structure of the polymer prior to the addition of the crosslinking agent, thereby reducing the reaction energy of the crosslinking reaction and increasing the reaction rate. The bound coupling agent then reacts with the crosslinking agent, thereby coupling the crosslinking agent to the polymer.

[0108] The individual 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 solvent is selected based at least in part on the materials of the selected polymer and photoactive compound. In some embodiments, the solvent is selected so that the polymer and photoactive compound can be uniformly dissolved in the solvent and dispensed onto the layer to be patterned.

[0109] In some embodiments, the photoresist composition includes a quencher. In some embodiments of the photoresist composition, a quencher is added to inhibit the diffusion of acid ions / alkali ions / free radicals generated in the photoresist composition. The quencher improves the structure of the photoresist pattern and the long-term stability of the photoresist. In an embodiment, the quencher is an amine, such as a secondary lower fatty amine, a tertiary lower fatty amine, etc. Specific examples of amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tripentylamine, diethanolamine and triethanolamine, alkanolamine, and the like and combinations thereof.

[0110] In some embodiments, an organic acid is used as a quencher. Specific embodiments of organic acids include malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid; oxoacids of phosphorus and their derivatives, such as phosphoric acid and its derivatives such as its esters, di-n-butyl phosphate and diphenyl phosphate; such as phosphorous acid and its derivatives such as its esters, such as dimethyl phosphite, di-n-butyl phosphite, diphenyl phosphite and dibenzyl phosphite; and hypophosphorous acid and its derivatives such as its esters, including phenylphosphonic acid.

[0111] Another additive added to some embodiments of the photoresist is a stabilizer, which helps to avoid undesirable diffusion of acids generated during exposure of the photoresist. In some embodiments, the stabilizer includes nitrogen-containing compounds, including primary, secondary and tertiary aliphatic amines; cyclic amines, including piperidine, pyrrolidine, morpholine; aromatic heterocyclics, including pyridine, pyrimidine, purine; imines, including diazabicycloundecene, guanidine, imide, amide or the like. Alternatively, in some embodiments, ammonium salts can also be used as stabilizers, and the ammonium salts include ammonium ions, primary, secondary, tertiary and quaternary alkyl and aryl ammonium salts of alkoxides, and the ammonium salts of the above alkoxides include hydroxides, phenolates, carboxylates, aryl and alkyl sulfonates, sulfonamides or the like. In some embodiments, other cationic nitrogen-containing compounds are used, including pyridinium and other heterocyclic nitrogen-containing compounds with anions, such as alkoxides including hydroxides, phenolates, carboxylates, aryl and alkyl sulfonates, sulfonamides, etc.

[0112] Another additive added to the photoresist in some embodiments is a dissolution inhibitor, which helps control the dissolution of the photoresist during development. In embodiments, esters of bile salts can be used as dissolution inhibitors. In some embodiments, specific examples of dissolution inhibitors include cholic acid, deoxycholic acid, lithocholic acid, n-butyldeoxycholic acid, n-butyllithocholic acid, and n-butyl-3-acetyllithocholic acid.

[0113] Another additive added to some embodiments of the photoresist is a plasticizer. Plasticizers can be used to reduce delamination and cracking between the photoresist and the underlying layer (e.g., the layer to be patterned). Plasticizers include monomeric, oligomeric or polymeric plasticizers, such as oligomeric and polyethylene glycol ethers, alicyclic esters and non-acidic active steroid derivative materials. In some embodiments, specific examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dioctanoate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl ester, triacetyl glycerine or the like.

[0114] A coloring agent is another additive included in some embodiments of the photoresist. A coloring agent observer inspects the photoresist and identifies any defects that need to be remedied prior to processing. In some embodiments, the coloring agent is a triarylmethane dye or a particulate organic pigment. In some embodiments, specific examples of materials include crystal violet, methyl violet, ethyl violet, oil blue #603, Victoria Pure Blue BOH, malachite green, diamond green, phthalocyanine dyes, azo dyes, carbon black, titanium oxide, brilliant green dye (CI42020), Victoria Pure Blue FGA (Linebrow), Victoria BO (Linebrow) (CI42595), Victoria Blue BO (Victoria Blue BO) (CI44045), rhodamine 6G (CI45160), benzophenone compounds (e.g. 2,4-dihydroxybenzophenone and 2,2',4,4'-tetrahydroxybenzophenone; salicylic acid compounds, such as phenyl salicylate and 4-tert-butylphenyl salicylate), phenyl acrylate compounds (e.g. ethyl-2-cyano-3,3-diphenylacrylate and 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate), benzotriazole compounds (e.g. 2-(2- tert-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole and 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole), coumarin compounds (e.g., 4-methyl-7-diethylamino-1-benzopyran-2-one), thioxanthone compounds (e.g., diethylthioxanthone), stilbene compounds, naphthalic acid compounds, azo dyes, phthalocyanine blue, phthalocyanine chloride, iodine green, Victoria blue, naphthalene black, photosensitive methyl violet, bromophenol blue and bromocresol green, laser dyes (e.g., rhodamine G6, coumarin 500, 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran) (DCM), Kiton Red 620, methylenepyrrole 580, or the like. Additionally, combinations of one or more colorants may be used to provide the desired color.

[0115] In some embodiments, adhesion additives are added to the photoresist to promote adhesion between the photoresist and an underlying layer (e.g., a layer to be patterned) and the photoresist is applied to the layer. In some embodiments, the adhesion additive comprises a silane compound having at least one reactive substituent, such as a carboxyl group, a methacryloyl group, an isocyanate group, and / or an epoxy group. Specific examples of adhesive components include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetylsilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, benzimidazole and polybenzimidazole, pyridine derivatives substituted with lower hydroxyalkyl, nitrogen heterocyclic compounds, urea, thiourea, organophosphorus compounds, 8-oxoquinoline, 4-hydroxypteridine and its derivatives, 1,10-phenanthroline and Its derivatives, 2,2'-bipyridine and its derivatives, benzotriazole, phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethanolamine, N-ethyldiethanolamine, N-ethylethanolamine and its derivatives, benzothiazole, benzothiazole amine salts with cyclohexyl ring and morpholine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, combinations thereof or the like.

[0116] In some embodiments of the photoresist, surface leveling agents are added to help level the height of the top surface of the photoresist so that uneven surfaces do not adversely adjust incident light. In some embodiments, the surface leveling agent comprises a fluoroaliphatic ester, a fluorinated polyester having terminal hydroxyl groups, a fluorinated glycol polymer, a silicone, an acrylic polymer surface leveling agent, combinations thereof, or the like.

[0117] In some embodiments, in an application, the polymer and the photoactive compound and any desired additives or other agents are added to a solvent. Once added, the mixture is mixed to achieve homogeneity throughout the photoresist composition to ensure that there are no defects caused by uneven mixing or non-homogeneous composition of the photoresist. Once mixed, the photoresist can be stored before use or used immediately.

[0118] Once prepared, a photoresist is applied over the layer to be patterned, such as Figure 2As shown, for example, a substrate 10 is coated with 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, combinations thereof, or the like. In some embodiments, the thickness of the photoresist layer 15 is between about 10 nanometers and about 75 nanometers.

[0119] After applying the photoresist layer 15 to the substrate 10 in operation S110, a pre-exposure bake of the photoresist layer is performed in operation S120, in some embodiments, to repair and dry the photoresist before radiation exposure (see Figure 1 ). Repairing and drying the photoresist layer 15 removes the solvent components remaining in the polymer, photoactive compound and other selected additives. In some embodiments, the pre-exposure bake is performed at a temperature suitable for evaporating the solvent, such as between about 40 degrees Celsius and about 120 degrees Celsius, although the exact temperature depends on the material selected for the photoresist. The pre-exposure bake is performed for a period of time sufficient to repair and dry the photoresist layer, such as between about 10 seconds and about 10 minutes.

[0120] Figure 3A and Figure 3B The selective exposure of the photoresist layer is shown to form exposed areas 50 and unexposed areas 52. In some embodiments, the exposure process under radiation is performed by placing the photoresist-coated substrate in a photolithography tool. The photolithography tool includes a mask 30 / 65, an optic, an exposure radiation source that provides radiation 45 / 97 for the exposure process, and a movable stage for supporting and moving the substrate under the exposure radiation.

[0121] In some embodiments, a radiation source (not shown) provides radiation 45 / 97, such as ultraviolet light, to the photoresist layer 15 to promote the reaction of the photoactive compound, which in turn reacts with the polymer to chemically change the area of ​​the photoresist layer exposed to the radiation 45 / 97. In some embodiments, the radiation is electromagnetic radiation, such as g-line (wavelength of about 436 nanometers), i-line (wavelength of about 365 nanometers), ultraviolet radiation, far ultraviolet radiation, extreme ultraviolet radiation, electron beam, or the like. In some embodiments, the radiation source is selected from the group consisting of a mercury lamp, a xenon lamp, a carbon arc lamp, a krypton fluoride excimer laser lamp (wavelength of 248 nanometers), an argon fluoride excimer laser lamp (wavelength of 193 nanometers), a fluorine gas excimer laser lamp (wavelength of 157 nanometers), or a tin plasma excited by a carbon dioxide laser (extreme ultraviolet, wavelength of 13.5 nanometers).

[0122] In some embodiments, optics (not shown) are used in the lithography tool to expand, reflect, or control the radiation 45 / 97 before or after the radiation 45 / 97 is patterned by the mask 30 / 65. In some embodiments, the optics include one or more lenses, mirrors, filters, combinations thereof to control the radiation 45 / 97 along its path.

[0123] In an embodiment, the patterned radiation 45 / 97 is extreme ultraviolet light having a wavelength of 13.5 nanometers, the photoactive compound 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 strikes the photoacid generator, and the photoacid generator absorbs the striking, patterned radiation 45 / 97. This absorption causes the photoacid generator to begin generating protons (e.g., H + ions). When the proton strikes the carboxylic acid group on the carbon-hydrogen structure, the proton reacts with the carboxylic acid group, chemically changing the carboxylic acid group and changing the overall polymer properties.

[0124] In some embodiments, immersion lithography is used to expose the photoresist layer 15. In this technique, an immersion medium (not shown) is placed between the final optical object and the photoresist layer, and the exposure radiation 45 passes through the immersion medium.

[0125] After the photoresist layer 15 is exposed to the exposure radiation 45 / 97, in some embodiments, a post-exposure bake is performed to assist in the generation, dispersion and reaction of acid ions / base ions / free radicals that are generated by the radiation 45 / 97 striking the photoactive compound during the exposure. This thermal assistance helps to create or enhance the chemical reaction and produce chemical differences between the exposed areas 50 and the unexposed areas 52 in the photoresist layer 15. These chemical differences also result in solubility differences between the exposed areas 50 and the unexposed areas 52. In some embodiments, the post-exposure bake operation S140 occurs at a temperature between about 50 degrees Celsius and about 160 degrees Celsius, and the operation time is between about 20 seconds and about 120 seconds. In some embodiments, the post-exposure bake operation is performed at a temperature between 80 degrees Celsius and about 100 degrees Celsius.

[0126] In some embodiments, the photoresist developer 57 comprises a solvent and an acid or a base. In some embodiments, the weight percent concentration of the solvent is between about 60% and about 99% based on the total weight of the photoresist developer. The weight percent concentration of the acid or the base is between about 0.001% and about 20% based on the total weight of the photoresist developer. In a specific embodiment, the weight percent concentration of the acid or the base in the developer is between about 0.01% and about 15% based on the total weight of the photoresist developer.

[0127] 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 rotating, the developer 57 is applied to the photoresist layer 15 from above, such as Figure 4 As shown. In some embodiments, the developer 57 is provided at a rate between about 5 ml / min and about 800 ml / min, and the substrate 10 coated with the photoresist is rotated at a speed of about 100 to about 2000 revolutions per minute. In some embodiments, the temperature of the developer is between about 10 degrees Celsius and about 80 degrees Celsius. In some embodiments, the duration of the development operation is between about 30 seconds and about 10 minutes.

[0128] The spin coating process is a process suitable for developing the photoresist layer 15 after exposure, but is not intended to illustrate or limit the implementation. In addition, any suitable development operation can be used, including dip coating processes, puddle processes, and spray-on methods. These development operations are all included in the scope of the implementation.

[0129] In some embodiments, the photoresist is a positive photoresist, and during the development process, the developer 57 dissolves the radiation-exposed areas 50 in the positive photoresist, exposing the surface of the substrate 10, such as Figure 5 As shown, well-defined unexposed photoresist regions 52 are left.

[0130] After the development operation S150, the remaining developer is removed from the substrate covered with 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. Next, the patterned photoresist layer undergoes a hard bake operation S160. During the hard bake operation, the remaining portion of the crosslinker material in the photoresist region 52 is crosslinked, thereby increasing the molecular weight of the polymer in the remaining photoresist region 52 to form a patterned, crosslinked photoresist layer 52a. An example of crosslinking is shown in FIG. Fig. 7AIn. The cross-linked polymer provides better resistance to subsequent wet process operations (such as wet cleaning and wet etching) and dry etching operations. The hard baking operation S160 is performed at a higher temperature than the post-exposure baking S140. In some embodiments, the execution temperature of the hard baking operation S160 is at least 10 degrees Celsius higher than the post-exposure baking S140. In some embodiments, the hard baking operation S160 is performed at a temperature between about 60 degrees Celsius and about 200 degrees Celsius, and the duration is about 20 seconds to about 120 seconds. In some embodiments, the hard baking operation S160 is performed at a temperature between about 90 degrees Celsius and about 170 degrees Celsius. In some embodiments, the hard baking operation S160 is performed at a temperature between about 100 degrees Celsius and about 125 degrees Celsius. The specific temperature and duration of the hard baking depend on the specific cross-linking agent. The cross-linking agent is selected so that cross-linking is not caused during the pre-exposure baking and the post-exposure baking. Therefore, the cross-linking agent is selected so that cross-linking occurs at a temperature higher than the pre-exposure baking and the post-exposure baking temperature. Heating at a temperature lower than the disclosed range or for a duration shorter than the disclosed range may result in incomplete crosslinking of the photoresist layer. Heating at a temperature higher than the disclosed range or for a duration longer than the disclosed range may result in harmful chemical reactions in the photoresist layer.

[0131] After the hard bake operation S160, when the cross-linked photoresist layer 52a has not been removed, additional processes are performed. For example, in some embodiments, a wet cleaning or wet chemical treatment operation S170 is performed. The cross-linked photoresist layer 52a is resistant to dissolution and decomposition by wet chemicals used in the cleaning process or wet treatment (e.g., wet etching operation). In some embodiments, wet or dry etching is performed on the substrate 10 or on the layer to be patterned to transfer the pattern of the cross-linked photoresist layer 52a to the underlying substrate 10 and form a cross-linked photoresist layer 52a. Figure 6 The pattern 55" is shown. The cross-linked photoresist layer 52a provides improved etching resistance to the etching operation. The substrate 10 has a different etching resistance than the cross-linked photoresist layer 52a. In some embodiments, the etchant has a higher selectivity to the substrate 10 relative to the cross-linked photoresist layer 52a.

[0132] In some embodiments, the substrate 10 and the photoresist layer 15 include at least one etching resistance molecule. In some embodiments, the etching resistance molecule includes a molecule with a low Onishi number structure, a double bond, a triple bond, silicon, silicon nitride, titanium, titanium nitride, aluminum, aluminum oxide, silicon oxynitride, a combination thereof, or the like.

[0133] In some embodiments, before forming the photoresist layer, a layer 60 to be patterned is placed on the substrate 10, such as Figure 8 As shown. In some embodiments, the layer 60 to be patterned is a metallization layer or a dielectric layer disposed on the metallization layer, such as a passivation layer. In embodiments where the layer 60 to be patterned is a metallization layer, the layer 60 to be patterned is a conductive material formed using a metallization process and a metal deposition technique, 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, such as thermal oxidation, chemical vapor deposition, atomic layer deposition, and physical vapor deposition.

[0134] Next, the photoresist layer 15 is selectively exposed to actinic radiation 45 / 97 to form exposed areas 50 and unexposed areas 52 in the photoresist, as shown in FIG. Fig.9A and Fig. 9B As shown, and the description content is the same as Figure 3A and Figure 3B Related.

[0135] like Fig.10 As shown, the exposed photoresist region 50 is developed by dispensing a developer 57 from a dispenser 62 to form a pattern of photoresist openings 55, as shown in FIG. Fig.11 The development operation here is similar to Figure 4 , Figure 5 The description is similar.

[0136] After the development operation, the remaining developer is removed from the substrate, which is covered with the patterned photoresist. In some embodiments, a spin-drying process is used to remove the remaining developer, although any suitable removal technique can be used. The patterned photoresist is then subjected to a hard bake operation, as described above.

[0137] Then, if Fig.12 As shown, using an etching operation, the pattern of openings 55 in the cross-linked photoresist layer 52a is transferred to the layer 60 to be patterned and the photoresist layer is removed, as in Figure 6 As described, to form a pattern 55" in the layer 60 to be patterned.

[0138] Other embodiments include operations before, between, or after the above operations. In some embodiments, the disclosed method includes forming a semiconductor device, including a fin field effect transistor (FinFET) structure. In some embodiments, a plurality of active fins are formed on a semiconductor substrate. These embodiments further include etching the substrate from an opening of a patterned mask to form a trench in the substrate; filling the trench with a dielectric material; performing a chemical mechanical polishing (CMP) process to form a shallow trench isolation (STI) feature; and epitaxially growing or recessing the shallow trench isolation feature to form an active region similar to a fin. In some embodiments, one or more gate electrodes are formed on the substrate. Some embodiments include forming gate spacers, doped source / drain regions, contacts for gate / source / drain, etc. In other embodiments, a target pattern is formed as a metal line in a multi-layer interconnect structure. For example, the metal line can be formed in an inter-layer dielectric (ILD) layer of the substrate, and the substrate is etched to produce a trench. The trenches may be filled with a conductive material, such as a metal, and the conductive material may be polished using a process such as chemical mechanical polishing to expose the patterned interlayer dielectric layer, thereby forming metal lines in the interlayer dielectric layer. The above are non-limiting examples of devices / structures that may be formed and / or enhanced using the methods described herein.

[0139] In some embodiments, according to the embodiments of the present disclosure, active devices such as diodes, field-effect transistors (FETs), metal-oxide semiconductor field effect transistors (MOSFETs), complementary metal-oxide semiconductor (CMOS) transistors, bipolar transistors, high-voltage transistors, high-frequency transistors, fin field-effect transistors, other three-dimensional field-effect transistors, other memories, and combinations thereof are formed.

[0140] The innovative photoresist composition and photolithography patterning method according to the present disclosure provide higher semiconductor feature resolution, density and reduced defects at higher wafer exposure throughput in a more efficient process than conventional exposure techniques. The innovative photoresist composition provides enhanced solubility of photoresist components in the photoresist composition.

[0141] Positive photoresists may have less than desired etch resistance for wet semiconductor device manufacturing operations. Wet processes using acids or bases (e.g., wet cleaning or etching) may decompose the photoresist pattern. The photoresist composition and semiconductor manufacturing operations disclosed herein provide improved photoresist etch resistance for wet manufacturing processes. The photoresist composition and method disclosed herein use a cross-linking agent, and after the development operation, the remaining photoresist is cross-linked with the cross-linking agent. The remaining portion of the cross-linked photoresist provides improved etch resistance for wet manufacturing processes. In addition, the cross-linked photoresist layer also provides improved dry etching resistance.

[0142] Embodiments of the present disclosure are methods of manufacturing semiconductor devices, including forming a photoresist layer including a photoresist composition on a substrate. Selectively exposing the photoresist layer to actinic radiation to form a latent pattern. Developing the latent pattern to form a pattern by applying a developer to the selectively exposed photoresist layer. The photoresist composition includes: a photoactive compound, a polymer, and a crosslinking agent. The polymer has a structure:

[0143]

[0144] wherein A1, A2, and A3 are independently substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C3 to C30 cycloalkyl, C1 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C30 cycloalkylcarboxyl, saturated or unsaturated C3 to C30 hydrocarbon ring, saturated or unsaturated C1 to C30 Heterocyclic group or C1 to C30 chain, ring or stereo structure; wherein R1 is a substituted or unsubstituted C4 to C15 chain, ring or stereo structure alkyl, C4 to C15 cycloalkyl, C4 to C15 hydroxyalkyl, C4 to C15 alkoxy or C4 to C15 alkoxyalkyl; wherein the ratio of x, y and z in the polymer is 0≤x / (x+y+z)≤1, 0≤y / (x+y+z)≤1 and 0≤z / (x+y+z)≤1, and in the same polymer, x, y and z are not 0. The crosslinking agent is a monomer, oligomer or polymer, and the monomer, oligomer or polymer comprises one or more structures selected from the following:

[0145] -B1-OH,

[0146] -B2-Ora,

[0147] -B3-NH2,

[0148] -B4-NR2 and

[0149]

[0150] wherein B1, B2, B3, B4 and D are independently substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C3 to C30 cycloalkyl, C2 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C3 0 cycloalkylcarboxyl, saturated or unsaturated C3 to C30 hydrocarbon ring, saturated or unsaturated C1 to C30 heterocyclic group or C1 to C30 chain, ring or stereo structure, and R and Ra are each substituted or unsubstituted C4 to C15 chain, ring or stereo structure alkyl, C4 to C15 cycloalkyl, C4 to C15 hydroxyalkyl, C4 to C15 alkoxy or C4 to C15 alkoxyalkyl. In an embodiment, the method includes heating the photoresist layer at a first temperature in a first heating operation after selectively exposing the photoresist layer to actinic radiation to form a latent pattern and before developing the latent pattern. In an embodiment, the method includes heating the photoresist layer at a second temperature in a second heating operation after developing the latent pattern to crosslink the polymer, wherein the second temperature is higher than the first temperature. In an embodiment, the second temperature is at least 10 degrees Celsius higher than the first temperature. In an embodiment, the method includes performing a cleaning operation on the patterned photoresist layer and the substrate. In one embodiment, the cleaning operation comprises applying a liquid chemical to the patterned photoresist layer and the substrate. In one embodiment, R1 is an acid-labile group selected from one or more of the following:

[0151]

[0152] In an embodiment, the actinic radiation is ultraviolet radiation.

[0153] Other embodiments of the present disclosure are methods of manufacturing semiconductor devices, comprising forming a photoresist layer comprising a photoresist composition on a semiconductor wafer. The photoresist composition comprises a polymer and a crosslinker. Pattern-exposing the photoresist layer to actinic radiation. Heating the pattern-exposed photoresist layer at a first temperature. Removing the portion of the photoresist layer exposed to the actinic radiation to form a patterned photoresist layer. After removing the portion of the photoresist layer exposed to the actinic radiation, crosslinking the polymer in the patterned photoresist layer. In an embodiment, crosslinking the polymer in the patterned photoresist layer comprises heating the patterned photoresist layer at a second temperature, the second temperature being higher than the first temperature. The second temperature is at least 10 degrees Celsius higher than the first temperature. The photoresist composition further comprises a photoactive compound, and the polymer has the structure:

[0154]

[0155] wherein A1, A2, and A3 are independently substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C3 to C30 cycloalkyl, C1 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C30 cycloalkylcarboxyl, saturated or unsaturated C3 to C30 hydrocarbon ring, saturated or unsaturated C1 to C30 Heterocyclic group or C1 to C30 chain, ring or stereo structure; wherein R1 is a substituted or unsubstituted C4 to C15 chain, ring or stereo structure alkyl, C4 to C15 cycloalkyl, C4 to C15 hydroxyalkyl, C4 to C15 alkoxy or C4 to C15 alkoxyalkyl; wherein the ratio of x, y and z in the polymer is 0≤x / (x+y+z)≤1, 0≤y / (x+y+z)≤1 and 0≤z / (x+y+z)≤1, and in the same polymer, x, y and z are not 0. In an embodiment, the crosslinking agent is a monomer, an oligomer or a polymer, and the monomer, oligomer or polymer comprises one or more structures selected from the following:

[0156] -B1-OH

[0157] -B2-ORa,

[0158] -B3-NH2,

[0159] -B4-NR2 and

[0160]

[0161] wherein B1, B2, B3, B4 and D are independently substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C3 to C30 cycloalkyl, C2 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C3 wherein R and Ra are each a substituted or unsubstituted C4 to C15 chain, ring or stereo structure alkyl, C4 to C15 cycloalkyl, C4 to C15 hydroxyalkyl, C4 to C15 alkoxy or C4 to C15 alkoxyalkyl. In an embodiment, the method includes performing a cleaning operation on the patterned photoresist layer and the semiconductor wafer.

[0162] Another embodiment of the present disclosure is a photoresist composition, comprising: a photoactive compound, a polymer and a crosslinking agent. The polymer has a structure:

[0163]

[0164] wherein A1, A2, and A3 are independently substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C3 to C30 cycloalkyl, C1 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C30 cycloalkylcarboxyl, saturated or unsaturated C3 to C30 hydrocarbon ring, saturated or unsaturated C1 to C30 Heterocyclic group or C1 to C30 chain, ring or stereo structure; wherein R1 is a substituted or unsubstituted C4 to C15 chain, ring or stereo structure alkyl, C4 to C15 cycloalkyl, C4 to C15 hydroxyalkyl, C4 to C15 alkoxy or C4 to C15 alkoxyalkyl; wherein the ratio of x, y and z in the polymer is 0≤x / (x+y+z)≤1, 0≤y / (x+y+z)≤1 and 0≤z / (x+y+z)≤1, and in the same polymer, x, y and z are not 0. The crosslinking agent is a monomer, oligomer or polymer, and the monomer, oligomer or polymer comprises one or more structures selected from the following:

[0165] -B1-OH,

[0166] -B2-ORa,

[0167] -B3-NH2,

[0168] -B4-NR2 and

[0169]

[0170] wherein B1, B2, B3, B4 and D are independently substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C3 to C30 cycloalkyl, C2 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C3 0 cycloalkylcarboxyl, saturated or unsaturated C3 to C30 hydrocarbon ring, saturated or unsaturated C1 to C30 heterocyclic group or C1 to C30 chain, ring or stereo structure, and R and Ra are each substituted or unsubstituted C4 to C15 chain, ring or stereo structure alkyl, C4 to C15 cycloalkyl, C4 to C15 hydroxyalkyl, C4 to C15 alkoxy or C4 to C15 alkoxyalkyl. In an embodiment,

[0171] R1 is an acid-labile group, which is selected from one or more of the following:

[0172] In an embodiment, the photoactive compound is a photoacid generator. In an embodiment, the photoresist composition comprises a solvent. In an embodiment, the photoresist composition comprises metal oxide nanoparticles and one or more organic ligands. In an embodiment, the crosslinking agent comprises one or more epoxy groups.

[0173] Another embodiment of the present disclosure is a method of manufacturing a semiconductor device, comprising forming a photoresist layer comprising a photoresist composition on a substrate. Patterning the photoresist layer to form a patterned photoresist layer, and heating the patterned photoresist layer at a first temperature, the first temperature being sufficient to crosslink the patterned photoresist layer. The photoresist composition comprises: a photoactive compound, a polymer, and a crosslinking agent. The polymer has a structure:

[0174]

[0175] wherein A1, A2, and A3 are independently substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C3 to C30 cycloalkyl, C1 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C30 cycloalkylcarboxyl, saturated or unsaturated C3 to C30 hydrocarbon ring, saturated or unsaturated C1 to C30 Heterocyclic group or C1 to C30 chain, ring or stereo structure; wherein R1 is a substituted or unsubstituted C4 to C15 chain, ring or stereo structure alkyl, C4 to C15 cycloalkyl, C4 to C15 hydroxyalkyl, C4 to C15 alkoxy or C4 to C15 alkoxyalkyl; wherein the ratio of x, y and z in the polymer is 0≤x / (x+y+z)≤1, 0≤y / (x+y+z)≤1 and 0≤z / (x+y+z)≤1, and in the same polymer, x, y and z are not 0. The crosslinking agent is a monomer, oligomer or polymer, and the monomer, oligomer or polymer comprises one or more structures selected from the following:

[0176] -B1-OH,

[0177] -B2-ORa,

[0178] -B3-NH2,

[0179] -B4-NR2 and

[0180]

[0181] wherein B1, B2, B3, B4 and D are independently substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C3 to C30 cycloalkyl, C2 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C3 0 cycloalkylcarboxyl, saturated or unsaturated C3 to C30 hydrocarbon ring, saturated or unsaturated C1 to C30 heterocyclic group or C1 to C30 chain, ring or stereo structure, and wherein R and Ra are each substituted or unsubstituted C4 to C15 chain, ring or stereo structure alkyl, C4 to C15 cycloalkyl, C4 to C15 hydroxyalkyl, C4 to C15 alkoxy or C4 to C15 alkoxyalkyl. In an embodiment, the method comprises extending a pattern into the substrate, the pattern being defined by a patterned photoresist layer. In an embodiment, extending the pattern comprises etching the substrate. In an embodiment, patterning the photoresist layer comprises: pattern-exposing the photoresist layer under actinic radiation, heating the pattern-exposed photoresist layer at a second temperature, wherein the second temperature is lower than the first temperature, and developing the pattern-exposed photoresist layer after heating the pattern-exposed photoresist layer. In an embodiment, the actinic radiation is extreme ultraviolet radiation or an electron beam. In an embodiment, the method includes heating the photoresist layer at a third temperature before patterning the photoresist layer, wherein the third temperature is lower than the first temperature.

[0182] The foregoing summarizes the features of several embodiments so that those skilled in the art can better understand the 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 for implementing the same purpose and / or achieving the benefits of the embodiments described herein. Those skilled in the art should also recognize that such equivalent structures do not depart from the spirit and scope of the present disclosure, and that they can make various changes, substitutions and modifications herein without departing from the spirit and scope of the present disclosure.

Claims

1. A method for manufacturing a semiconductor device, characterized in that: Include: forming a photoresist layer including a photoresist composition on a substrate; selectively exposing the photoresist layer to actinic radiation to form a latent pattern; and developing the latent pattern to form a patterned photoresist layer by applying a developer to the selectively exposed photoresist layer, The photoresist composition comprises: Photoactive compounds; polymers; and Crosslinking agent, The polymer has a structure: wherein A1 and A2 are each a substituted or unsubstituted C6 to C30 aryl group, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C1 to C30 hydroxyalkyl group, a C2 to C30 alkoxy group, a C3 to C30 alkoxyalkyl group, a C2 to C30 acetyl group, a C3 to C30 acetylalkyl group, a C1 to C30 carboxyl group, a C2 to C30 alkylcarboxyl group, a C4 to C30 cycloalkylcarboxyl group, a saturated or unsaturated C3 to C30 hydrocarbon ring, a saturated or unsaturated C1 to C30 heterocyclic group, or a C1 to C30 chain, ring or stereostructure, wherein A3 is a substituted or unsubstituted C1 to C30 alkyl group, a C1 to C30 hydroxyalkyl group, a C2 to C30 alkoxy group, a C3 to C30 alkoxyalkyl group, a C2 to C30 acetyl group, a C3 to C30 acetylalkyl group, a C4 to C30 cycloalkylcarboxyl group, a saturated or unsaturated C1 to C30 heterocyclic group, or a C1 to C30 chain or stereostructure, wherein R1 is a substituted or unsubstituted C4 to C15 chain, ring or three-dimensional alkyl group, C4 to C15 cycloalkyl group, C4 to C15 hydroxyalkyl group, C4 to C15 alkoxy group or C4 to C15 alkoxyalkyl group, wherein a ratio of x, y and z in the polymer is 0≤x / (x+y+z)≤1, 0≤y / (x+y+z)≤1 and 0≤z / (x+y+z)≤1, and in the same polymer, x, y and z are not 0, The cross-linking agent is a monomer, oligomer or polymer, and the monomer, oligomer or polymer comprises one or more structures selected from the following: -B1-OH -B2-ORa -B3-NH2 -B4-NR2 wherein B1, B2, B3, B4 and D are independently substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C3 to C30 cycloalkyl, C2 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C3 The invention relates to a cycloalkylcarboxyl group having a saturated or unsaturated C3 to C30 hydrocarbon ring, a saturated or unsaturated C1 to C30 heterocyclic group, or a C1 to C30 chain, ring or stereostructure, and wherein R and Ra are each a substituted or unsubstituted C4 to C15 chain, ring or stereostructure alkyl group, a C4 to C15 cycloalkyl group, a C4 to C15 hydroxyalkyl group, a C4 to C15 alkoxy group or a C4 to C15 alkoxyalkyl group.

2. The method of claim 1, further comprising heating the photoresist layer at a first temperature in a first heating operation after selectively exposing the photoresist layer to the actinic radiation to form the latent pattern and before developing the latent pattern.

3. The method of claim 2, further comprising, after developing the latent pattern, in a second heating operation, heating the photoresist layer at a second temperature to crosslink the polymer, wherein the second temperature is higher than the first temperature. The method of claim 3 , wherein the second temperature is at least 10 degrees Celsius higher than the first temperature. 5 . The method of claim 3 , further comprising performing a cleaning operation on the patterned photoresist layer and the substrate.

6. The method of claim 5, wherein the cleaning operation comprises applying a liquid chemical onto the patterned photoresist layer and the substrate.

7. The method of claim 1, wherein R1 is an acid-labile group selected from one or more of the following: 。 8. The method of claim 1, wherein the actinic radiation is extreme ultraviolet radiation.

9. A method for manufacturing a semiconductor device, characterized in that: Include: forming a photoresist layer comprising a photoresist composition on a semiconductor wafer, wherein the photoresist composition comprises a polymer and a cross-linking agent; pattern-wise exposing the photoresist layer to actinic radiation; heating the pattern-exposed photoresist layer at a first temperature; removing portions of the photoresist layer exposed to the actinic radiation to form a patterned photoresist layer; and The polymer is cross-linked in the patterned photoresist layer after removing the portions of the photoresist layer exposed to the actinic radiation, wherein the photoresist composition further comprises a photoactive compound and the polymer has a structure: wherein A1 is a substituted or unsubstituted C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C1 to C30 hydroxyalkyl group, a C2 to C30 alkoxy group, a C3 to C30 alkoxyalkyl group, a C2 to C30 acetyl group, a C3 to C30 acetylalkyl group, a C1 to C30 carboxyl group, a C2 to C30 alkylcarboxyl group, a C4 to C30 cycloalkylcarboxyl group, a saturated or unsaturated C1 to C30 heterocyclic group, or a C1 to C30 chain or three-dimensional structure; wherein A2 and A3 are each substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C1 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C30 cycloalkylcarboxyl, saturated or unsaturated C3 to C30 hydrocarbon ring, saturated or unsaturated C1 to C30 heterocyclic group, or C1 to C30 chain, ring or stereostructure; Wherein R1 is a substituted or unsubstituted C4 to C15 chain, ring or three-dimensional structure alkyl, C4 to C15 cycloalkyl, C4 to C15 hydroxyalkyl, C4 to C15 alkoxy or C4 to C15 alkoxyalkyl; The ratio of x, y and z in the polymer is 0≤x / (x+y+z)≤1, 0≤y / (x+y+z)≤1 and 0≤z / (x+y+z)≤1, and in the same polymer, x, y and z are not 0.

10. The method of claim 9, wherein cross-linking the polymer in the patterned photoresist layer comprises heating the patterned photoresist layer at a second temperature, the second temperature being higher than the first temperature. The method of claim 10 , wherein the second temperature is at least 10 degrees Celsius higher than the first temperature.

12. The method of claim 9, wherein R1 is an acid-labile group selected from one or more of the following:

13. The method of claim 9, wherein the cross-linking agent is a monomer, oligomer or polymer comprising one or more structures selected from the group consisting of: -B1-OH -B2-ORa -B3-NH2 -B4-NR2 wherein B1, B2, B3, B4 and D are each a substituted or unsubstituted C6 to C30 aryl, C1 to C30 alkyl, C3 to C30 cycloalkyl, C2 to C30 hydroxyalkyl, C2 to C30 alkoxy, C3 to C30 alkoxyalkyl, C2 to C30 acetyl, C3 to C30 acetylalkyl, C1 to C30 carboxyl, C2 to C30 alkylcarboxyl, C4 to C30 cycloalkylcarboxyl, a saturated or unsaturated C3 to C30 hydrocarbon ring, a saturated or unsaturated C1 to C30 heterocyclic group, or a C1 to C30 chain, ring or stereostructure; And R and Ra are each a substituted or unsubstituted C4 to C15 chain, ring or three-dimensional structure alkyl group, C4 to C15 cycloalkyl group, C4 to C15 hydroxyalkyl group, C4 to C15 alkoxy group or C4 to C15 alkoxyalkyl group.

14. The method of claim 9, further comprising performing a cleaning operation on the patterned photoresist layer and the semiconductor wafer.

15. A photoresist composition, characterized in that: Include: Photoactive compounds; polymers; and Crosslinking agent, The polymer has a structure: wherein A1 and A2 are each a substituted or unsubstituted C6 to C30 aryl group, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C1 to C30 hydroxyalkyl group, a C2 to C30 alkoxy group, a C3 to C30 alkoxyalkyl group, a C2 to C30 acetyl group, a C3 to C30 acetylalkyl group, a C1 to C30 carboxyl group, a C2 to C30 alkylcarboxyl group, a C4 to C30 cycloalkylcarboxyl group, a saturated or unsaturated C3 to C30 hydrocarbon ring, a saturated or unsaturated C1 to C30 heterocyclic group, or a C1 to C30 chain or three-dimensional structure, wherein A3 is a substituted or unsubstituted C1 to C30 alkyl group, a C1 to C30 hydroxyalkyl group, a C2 to C30 alkoxy group, a C3 to C30 alkoxyalkyl group, a C2 to C30 acetyl group, a C3 to C30 acetylalkyl group, a C4 to C30 cycloalkylcarboxyl group, a saturated or unsaturated C1 to C30 heterocyclic group, or a C1 to C30 chain or stereostructure, wherein R1 is a substituted or unsubstituted C4 to C15 chain, ring or three-dimensional alkyl group, C4 to C15 cycloalkyl group, C4 to C15 hydroxyalkyl group, C4 to C15 alkoxy group or C4 to C15 alkoxyalkyl group, wherein a ratio of x, y and z in the polymer is 0≤x / (x+y+z)≤1, 0≤y / (x+y+z)≤1 and 0≤z / (x+y+z)≤1, and in the same polymer, x, y and z are not 0, The cross-linking agent is a monomer, oligomer or polymer, and the monomer, oligomer or polymer comprises one or more structures selected from the following: -B1-OH -B2-ORa -B3-NH2 -B4-NR2 wherein B1, B2, B3, B4 and D are each a substituted or unsubstituted C6 to C30 aryl group, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 hydroxyalkyl group, a C2 to C30 alkoxy group, a C3 to C30 alkoxyalkyl group, a C2 to C30 acetyl group, a C3 to C30 acetylalkyl group, a C1 to C30 carboxyl group, a C2 to C30 alkylcarboxyl group, a C4 to C30 cycloalkylcarboxyl group, a saturated or unsaturated C3 to C30 hydrocarbon ring, a saturated or unsaturated C1 to C30 heterocyclic group, or a C1 to C30 chain, ring or stereostructure, and wherein R and Ra are independently substituted or unsubstituted C4 to C15 chain, ring or three-dimensional structure alkyl, C4 to C15 cycloalkyl, C4 to C15 hydroxyalkyl, C4 to C15 alkoxy or C4 to C15 alkoxyalkyl.

16. The photoresist composition according to claim 15, wherein R1 is an acid-labile group selected from one or more of the following: 。 17. The photoresist composition as claimed in claim 15, wherein the photoactive compound is a photoacid generator.

18. The photoresist composition according to claim 15, further comprising a solvent.

19. The photoresist composition as claimed in claim 15, further comprising metal oxide nanoparticles and one or more organic ligands.

20. The photoresist composition as claimed in claim 15, wherein the crosslinking agent comprises one or more epoxy groups.

Images