Base composition and method for manufacturing semiconductor device

Abstract

The method for manufacturing a semiconductor device includes forming a bottom layer on a substrate. The bottom layer includes a polymer having a main polymer chain with a side chain target group and a side chain organic group or a side chain photoacid generator group. The main polymer chain is polystyrene, polyhydroxystyrene, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polyacrylic acid, polyvinyl ester, polymethacrylonitrile or polymethacrylamide. The side chain target group is a substituted or unsubstituted C2 to C30 diol group, C1 to C30 aldehyde group or C3 to C30 ketone group. The side chain organic group is a C3 to C30 aliphatic or aromatic group having a photosensitive functional group, and the side chain photoacid generator group is a substituted C3 to C50 aliphatic or aromatic group. A photoresist layer is formed on the bottom layer. The photoresist layer is selectively exposed. The exposed photoresist layer is developed to form a pattern.

Description

Technical Field

[0001] Some embodiments of the present disclosure relate to methods of manufacturing an underlying composition and a semiconductor device. Background Art

[0002] As consumer electronic devices become smaller and smaller in response to consumer demand, the size of the individual components of these devices must also 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 semiconductor device manufacturing 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 modifies the chemical and physical properties of the exposed areas of the photosensitive material. This modification can be used to remove one area without removing another area along with unexposed areas of the photosensitive material that lack the modification.

[0004] However, as the size of individual devices decreases, the process window of photolithography becomes increasingly tighter. As a result, the field of photolithography must maintain the ability to shrink device size and further improvements are required to achieve the desired design specifications so that the process can continue to produce smaller components. Summary of the invention

[0005] According to an embodiment of the present disclosure, a method for manufacturing a semiconductor device includes forming a photoresist bottom layer on a semiconductor substrate. The photoresist bottom layer includes a polymer, the polymer includes a main polymer chain having a plurality of side chain target groups and a plurality of side chain organic groups or a plurality of side chain photoacid generator groups. The main polymer chain is selected from the group including: polystyrene, polyhydroxystyrene, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polyacrylic acid, polyvinyl ester, polymaleate, polymethacrylonitrile and polymethacrylamide. The side chain target group is one or more selected from the group including: C2 to C30 diol groups, C1 to C30 aldehyde groups and C3 to C30 ketone groups. The side chain organic group is a C3 to C30 aliphatic or aromatic group having at least one photosensitive functional group, and the side chain photoacid generator group is a C3 to C50 substituted aliphatic or aromatic group. A photoresist layer is formed on the photoresist bottom layer. The photoresist layer is selectively exposed to actinic radiation. The selectively exposed photoresist layer is developed to form a photoresist pattern.

[0006] Another embodiment of the present disclosure is a method for manufacturing a semiconductor device, comprising forming a photoresist base layer on a semiconductor substrate. The photoresist base layer comprises a polymer having a plurality of side chain target groups. A photoresist layer is formed on the photoresist base layer. The photoresist layer and the photoresist base layer are selectively exposed to actinic radiation. Chemical reporter molecules are generated in a plurality of portions of the photoresist base layer exposed to actinic radiation. The chemical reporter molecules are one or more selected from the group comprising: electrons, oxygen molecules, water, hydrogen ions, hydroxides, cations, anions, and C1 to C10 groups substituted with functional groups, wherein the functional groups are one or more selected from the group comprising: fluorine, chlorine, bromine, iodine, hydroxyl, carboxylic acid, thiol, azido, sulfinyl, alkenyl, alkynyl, imine, ether, ester, aldehyde, ketone, amide, sulfone, alkylcarboxyl, cyanide, heavy alkenyl, alkanol, amine, phosphine, phosphite, anilino, pyridyl, and pyrrolyl. In the portion of the photoresist layer exposed to actinic radiation, small molecules are generated by the interaction between the chemical reporter molecule and the side chain target group. The small molecule is one or more selected from the group consisting of electrons, oxygen molecules, water, hydrogen ions, hydroxides, cations, anions, and C1 to C10 groups substituted with functional groups, wherein the functional group is one or more selected from the group consisting of fluorine, chlorine, bromine, iodine, hydroxyl, carboxylic acid, thiol, azido, sulfinyl, alkenyl, alkynyl, imine, ether, ester, aldehyde, ketone, amide, sulfone, alkyl carboxyl, cyanide, heavy alkenyl, alkanol, amine, phosphine, phosphite, aniline, pyridyl, and pyrrol. The small molecule diffuses from the photoresist layer into the portion of the photoresist layer exposed to actinic radiation. The selectively exposed photoresist layer is developed to form a patterned photoresist layer.

[0007] Another embodiment of the present disclosure is a bottom layer composition, comprising a polymer, the polymer comprising a main polymer chain having a plurality of side chain target groups and a plurality of side chain organic groups or a plurality of side chain photoacid generator groups. The main polymer chain is selected from the group comprising: polystyrene, polyhydroxystyrene, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polyacrylic acid, polyvinyl ester, polymaleate, polymethacrylonitrile and polymethacrylamide. The side chain target group is one or more substituted or unsubstituted selected from the group comprising: C2 to C30 diol groups, C1 to C30 aldehyde groups and C3 to C30 ketone groups, wherein the side chain organic group is a C3 to C30 aliphatic or aromatic group having at least one photosensitive functional group, and wherein the side chain photoacid generator group is a C3 to C50 substituted aliphatic or aromatic group. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] When accompanied by Figure 1When read together, 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 size of various features may be arbitrarily increased or reduced for clarity of discussion.

[0009] Figure 1 A process flow for manufacturing a semiconductor device according to some embodiments of the present disclosure is shown.

[0010] Figure 2 Serially operated process stages are shown according to an embodiment of the present disclosure.

[0011] Figure 3A and Figure 3B Depicted are process stages of sequential operation according to some embodiments of the present disclosure.

[0012] Figure 4 Depicted are process stages of sequential operation according to some embodiments of the present disclosure.

[0013] Figure 5 Depicted are process stages of sequential operation according to some embodiments of the present disclosure.

[0014] Figure 6 Depicted are process stages of sequential operation according to some embodiments of the present disclosure.

[0015] Figure 7 Depicted are chemical reactions that underlying materials undergo when exposed to actinic radiation according to some embodiments of the present disclosure.

[0016] Fig. 8A and Figure 8B Depicted are chemical reactions that underlying materials undergo when exposed to actinic radiation according to some embodiments of the present disclosure.

[0017] Fig. 9 The bottom layer composition according to some embodiments of the present disclosure is shown.

[0018] Fig.10 The bottom layer composition according to some embodiments of the present disclosure is shown.

[0019] Fig.11 A photoacid generator according to some embodiments of the present disclosure is depicted.

[0020] Fig. 12A , Fig. 12B , Fig. 12C , Fig.12D , Fig.12E and Fig.12F Reactions for producing small molecules according to some embodiments of the present disclosure are depicted.

[0021] Fig.13 The bottom layer composition according to some embodiments of the present disclosure is shown.

[0022] Figure 14 and Fig. 14B A process of generating a base from a photobase generator according to some embodiments of the present disclosure is shown. Fig. 14C Reactions for producing small molecules according to some embodiments of the present disclosure are depicted.

[0023] Fig.15A An organometallic precursor according to some embodiments of the present disclosure is shown. Fig. 15B Depicted are the reactions that an organometallic precursor undergoes when exposed to actinic radiation. Fig. 15C Examples of organometallic precursors according to some embodiments of the present disclosure are shown. Fig.15D An organometallic photoresist material according to some embodiments of the present disclosure is shown. Fig.15E The reactions that an organometallic photoresist material according to some embodiments of the present disclosure undergoes are shown.

[0024] Fig.16 Reactions that components of a photoresist composition undergo due to exposure to actinic radiation and heating are illustrated according to some embodiments of the present disclosure.

[0025] Fig.17 Serially operated process stages are shown according to an embodiment of the present disclosure.

[0026] Fig.18A and Fig.18B Depicted are process stages of sequential operation according to some embodiments of the present disclosure.

[0027] Fig.19 Depicted are process stages of sequential operation according to some embodiments of the present disclosure.

[0028] Fig. 20 Depicted are process stages of sequential operation according to some embodiments of the present disclosure.

[0029] Fig.21 Depicted are process stages of sequential operation according to some embodiments of the present disclosure.

[0030] The reference numerals are:

[0031] 10: Substrate

[0032] 15: Photoresist layer

[0033] 20: Bottom

[0034] 20a: Partial

[0035] 20b: Partial

[0036] 30: Photomask

[0037] 35: Opaque pattern

[0038] 40: Photomask substrate

[0039] 45: Radiation

[0040] 50: District

[0041] 52: District

[0042] 55: Opening

[0043] 55': Opening

[0044] 55”: Pattern

[0045] 57: Developer

[0046] 60: Layer

[0047] 62: Dispenser

[0048] 65: Photomask

[0049] 70: Substrate

[0050] 75: Multilayer

[0051] 80: Protective cover

[0052] 85: Absorbent material layer

[0053] 90: Back conductor layer

[0054] 95: Ultraviolet radiation

[0055] 97: Radiation

[0056] 100: Process flow

[0057] S110: Operation

[0058] S120: Operation

[0059] S130: Operation

[0060] S140: Operation

[0061] S150: Operation

[0062] S160: Operation

[0063] S170: Operation

[0064] B: Group

[0065] CL: Crosslinker

[0066] D: Group

[0067] E: Group

[0068] L: Ligand

[0069] M + : Metal Center

[0070] PAG: Photoacid generator

[0071] PBG: Photobase Generator

[0072] TAG: Thermal acid generator DETAILED DESCRIPTION

[0073] The following disclosure provides many different embodiments or examples of different features for achieving the provided objectives. Specific examples of components and arrangements are described below to simplify the present disclosure. Of course, these are only examples and are not intended to be limiting. For example, forming a first feature above or on a second feature in the following description may include embodiments in which the first and second features are formed in direct contact, and may also include embodiments 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.

[0074] 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 component or feature to another component 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. Additionally, the term "made of" may mean "comprising" or "consisting of."

[0075] Extreme ultraviolet (EUV) for achieving sub-20nm half pitch resolution is being developed towards mass production at the next generation (sub-5nm) node. In order to reduce the cost of high energy exposure sources and provide good image resolution, EUV lithography requires high performance photoresists with high sensitivity. Metal resists have been developed to provide high sensitivity and good resolution. However, pattern collapse, increased line width roughness, and line edge roughness may occur. Embodiments of the present disclosure improve the integrity of the photoresist pattern, reduce line width roughness, line edge roughness, and fines. Embodiments of the present disclosure allow the use of less exposure dose.

[0076] 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 base layer composition is coated on a surface of a layer to be patterned (target layer) or on a substrate 10 to form a photoresist base layer 20, such as Figure 2 As shown. In some embodiments, the photoresist bottom layer 20 has a thickness between about 2 nanometers and about 300 nanometers. In some embodiments, the photoresist bottom layer 20 has a thickness between about 20 nanometers and about 100 nanometers. Then, in some embodiments, the photoresist bottom layer 20 undergoes a first baking operation S120 to evaporate the solvent in the bottom layer composition. The bottom layer 20 is baked at a sufficient temperature and time to repair and dry the bottom layer 20. In some embodiments, the bottom layer is heated to about 80 degrees Celsius to about 300 degrees Celsius and lasts for about 10 seconds to about 10 minutes. In some embodiments, the heating temperature of the bottom layer is between about 160 degrees Celsius and about 250 degrees Celsius.

[0077] Next, in operation S130, in some embodiments, a photoresist layer composition is coated on the photoresist bottom layer 20 to form an anti-corrosion layer 15, such as Figure 2 As shown. In some embodiments, the resist layer 15 is a photoresist layer. The photoresist layer 15 then undergoes a second baking operation S140 (or a pre-exposure baking operation) to evaporate the solvent in the photoresist composition. The photoresist layer 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 150 degrees Celsius and lasts for about 10 seconds to about 10 minutes. In some embodiments, before baking the photoresist bottom layer 20, a photoresist layer composition is coated on the photoresist bottom layer 20, and the photoresist layer 15 and the photoresist bottom layer 20 are baked together in a single baking operation to remove the solvents of the two layers.

[0078] After the second (or pre-exposure) baking operation S140 of the photoresist layer 15, in operation S150, the photoresist layer 15 is selectively exposed to 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 radiation is electromagnetic radiation, such as g-line (wavelength of about 436 nanometers), i-line (wavelength of about 365 nanometers), ultraviolet radiation, deep 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).

[0079] like Figure 3A As shown, in some embodiments, exposure radiation 45 passes through a photomask 30 before irradiating the photoresist layer 15. In some embodiments, the photomask 30 has a pattern to be replicated in the photoresist layer 15. In some embodiments, the pattern is formed by an opaque pattern 35 on a photomask blank 40. The opaque pattern 35 can be formed of a material opaque to ultraviolet radiation, such as chrome, while the photomask blank 40 is formed of a material transparent to ultraviolet radiation, such as fused silica.

[0080] 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, a reflective mask 65 is used to form a patterned exposure light source, such as Figure 3B As shown. The reflective mask 65 includes a low thermal expansion glass substrate 70 and a reflective multilayer 75 of silicon and molybdenum, and the reflective multilayer 75 is 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. Part of the EUV radiation 97 is reflected by the silicon / molybdenum multilayer 75 to the photoresist-coated substrate 10, while part 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.

[0081] The photoresist layer, the regions 50 exposed to the radiation, react chemically relative to the regions 52 of the photoresist layer that were not exposed to the radiation, thereby changing the solubility in a subsequently applied developer. In some embodiments, the regions 50 of the photoresist layer that were exposed to the radiation undergo a crosslinking reaction. In addition to causing chemical reactions in the photoresist layer 15, a portion of the radiation 45 / 97 also passes through the photoresist layer 15 and causes reactions in the photoresist bottom layer 20. The reactions in the photoresist bottom layer 20 result in the generation of small molecules, which then diffuse into the photoresist layer 15. Figure 3A and Figure 3B An exposed portion 20 b and an unexposed portion 20 a in the photoresist bottom layer 20 are shown.

[0082] Next, in operation S160, the photoresist layer 15 and the photoresist bottom layer 20 undergo a third bake (or post-exposure bake (PEB)). In some embodiments, the photoresist layer 15 is heated to about 50 degrees Celsius to about 200 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. The post-exposure bake also helps small molecules diffuse from the exposed portion 20b of the photoresist bottom layer 20 into the photoresist layer 15. This assistance helps to create or enhance the chemical reaction that causes the chemical difference between the exposed area 50 and the unexposed area 52 in the photoresist layer.

[0083] In operation S170, a developer is applied to the selectively exposed photoresist layer to develop the selectively exposed photoresist layer. Figure 4 As shown, developer 57 is provided from dispenser 62 to photoresist layer 15. In some embodiments, unexposed regions 52 of the photoresist layer are removed by developer 57 to form a pattern of openings 55 in photoresist layer 15 to expose unexposed portions 20a of the underlying layer, such as Figure 5 shown.

[0084] In some embodiments, the pattern of openings 55 in the photoresist layer 15 extends through the bottom layer 20 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 6As shown. The pattern is extended into the substrate by etching, using one or more suitable etchants. In some embodiments, the etching process removes the unexposed portions 20a of the bottom layer between the photoresist pattern features (i.e., the exposed areas 50). In some embodiments, during the etching operation, the photoresist layer pattern (i.e., the exposed areas 50) is at least partially removed. In other embodiments, after etching the substrate 10, the photoresist layer pattern (i.e., the exposed areas 50) and the exposed portions 20b of the bottom layer under the photoresist layer pattern are removed by using a suitable removal solvent or by a photoresist ashing operation.

[0085] In some embodiments, the substrate 10 includes a single crystal semiconductor layer at least at a surface portion. The substrate 10 may include 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.

[0086] 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 silicon 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.

[0087] In some embodiments, the substrate 10 comprises one or more layers of at least one metal, metal alloy and a metal having the chemical formula MX a A metal nitride / sulfide / oxide / silicide of , wherein 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 includes titanium (Ti), aluminum (Al), cobalt (Co), ruthenium (Ru), titanium nitride (TiN), tungsten nitride (WN), tantalum nitride (TaN) and combinations thereof.

[0088] 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.

[0089] In some embodiments, the photoresist bottom layer 20 improves the adhesion between the photoresist layer 15 and the substrate. In some embodiments, the photoresist bottom layer 20 acts as a bottom anti-reflective coating (BARC). The bottom anti-reflective coating absorbs the actinic radiation passing through the photoresist layer, thereby preventing the actinic radiation from reflecting on the substrate or the target layer and exposing the unintentionally exposed portions of the photoresist layer. Therefore, the bottom anti-reflective coating improves the line width roughness and line edge roughness of the photoresist pattern.

[0090] The photoresist bottom layer 20 is made of a polymer composition, wherein the polymer has a pendant target group. In some embodiments, the polymer has one or more pendant target groups and a pendant organic group. In some embodiments, the pendant organic group includes a photosensitive functional group, including a chemical reporter molecule, such as Figure 7 In some embodiments, the polymer is a stimuli-responsive polymer. Stimuli-responsive polymers are substances that are sensitive to specific external stimuli and can change their chemical or physical properties upon exposure to the external stimulus.

[0091] In some embodiments, the side chain organic groups are aromatic groups, photoacid generators (PAGs) and other sensitizers. In some embodiments, a photosensitive compound is included in the polymer composition, such as a photoacid generator or a photobase generator (PBG). Upon exposure to actinic radiation, the photosensitive functional group or the photosensitive compound releases a chemical reporter molecule, and the chemical reporter molecule is transferred from the photosensitive functional group or the photosensitive compound to the target group. Upon receiving the chemical reporter molecule, the target group releases a desired small molecule, such as Figure 7 The small molecules are then diffused into the photoresist layer 15 by heating the photoresist bottom layer 20 and the photoresist layer 15 , wherein the small molecules can promote chemical reactions such as hydrolysis, condensation, nucleophilic addition and acid-base reaction.

[0092] In some embodiments, the chemical reporter molecule comprises an electron, an anion, a cation, a + , O 2 , H 2 O、NH 3 , HF, HCl, ROH or RNH 2 , wherein R is a C1 to C10 group. R contains a functional group selected from the following groups: -I, -Br, -Cl, -NH 2 、-COOH、-OH、-SH、-N 3 , -S(=O)-, alkenyl, alkynyl, imine, ether, ester, aldehyde, ketone, amide, sulfone, carboxyl, acetate, cyanide, heavy olefin, alcohol, amine, phosphine, phosphite, aniline, pyridine and pyrrol.

[0093] In some embodiments, the small molecule comprises an electron, an anion, a cation, H + , O 2 , H 2 O、NH 3 , HF, HCl, ROH or RNH 2 , wherein R is a C1 to C10 group. R contains a functional group selected from the following groups: -I, -Br, -Cl, -F, -NH 2 、-COOH、-OH、-SH、-N 3 , -S(=O)-, alkenyl, alkynyl, imine, ether, ester, aldehyde, ketone, amide, sulfone, carboxyl, acetate, cyanide, heavy alkenyl, alcohol, amine, phosphine, phosphite, anilino, pyridyl and pyrrolyl. In some embodiments, the chemical reporter molecule and the small molecule are different molecules.

[0094] The first reaction mechanism is shown in Fig. 8A In this embodiment, water is a small molecule released from a target group having a diol group. The chemical reporter molecule is H released by the interaction of actinic radiation with the PAG. + PAG can be a photosensitive functional group on a side chain organic group, or a separate compound in a photoresist composition. Under exposure to actinic radiation, PAG releases H + And H + Transfer from PAG to diol group. + When the diol groups are exposed to light, the diol groups release water molecules. The water molecules then diffuse into the photoresist layer 15 during the post-exposure bake and further promote chemical reactions such as hydrolysis, condensation, nucleophilic addition, or acid-base reactions. In some embodiments, the behavior of small molecules (such as water) in the photoresist layer allows a reduced exposure dose to be used during the selective exposure operation.

[0095] According to the second reaction mechanism in some embodiments, water is generated as a small molecule from a target group having a carbonyl group (e.g., an aldehyde or a ketone). The polymer composition includes a photobase generator PBG. Figure 8B As shown, the interaction between actinic radiation and PBG generates amines as chemical reporter molecules. The amines then react with the carbonyl (R-CR(=O)) of the target group on the polymer and generate water molecules while forming a C=N double bond. The water molecules then diffuse into the photoresist layer 15 during the post-exposure bake and promote chemical reactions in the photoresist layer, such as hydrolysis, condensation, nucleophilic addition, or acid-base reaction. In some embodiments, the behavior of small molecules (such as water) in the photoresist layer allows the use of reduced exposure doses in selective exposure operations.

[0096] In some embodiments, the polymer composition of the photoresist bottom layer 20 includes a polymer having one or more side chain diol target groups D and one or more side chain organic groups B, and the photoacid generator PAG is an independent compound in the polymer composition, such as Fig. 9 As shown. Because of the actinic radiation, PAG generates photoacid, which then triggers the diol group D to release water molecules in the exposed area during the post-exposure bake. The water molecules then diffuse into the photoresist layer. In some embodiments, the photoresist is a metal-containing photoresist. Water promotes the cross-linking of the metal-containing photoresist, or generates metal oxides in the exposed area during the post-exposure bake. Because of the water replenishment from the bottom layer, the metal-containing photoresist is strengthened and the exposure dose can be reduced. In some embodiments, the polymer composition may optionally include a thermal acid generator TAG, a cross-linking agent CL and an additive, such as a surfactant.

[0097] The diol group D may be a 1,n-diol, wherein n>0. The structure of the diol group D may be acyclic or cyclic, and the cyclic structure may be aromatic or non-aromatic. In some embodiments, the diol group D is a substituted or unsubstituted C2 to C30 group. In some embodiments, the C2 to C30 group is replaced by one or more -I, -Br, -Cl, -F, -NH 2 、-COOH、-OH、-SH、-N 3 , -S(=O)-, alkenyl, alkynyl, imine, ether, ester, aldehyde, ketone, amide, sulfone, acetate, carboxylic acid, cyanide, heavy alkenyl, alcohol, amine, phosphine, phosphite, aniline, pyridyl or pyrrol.

[0098] The organic group B may be a non-cyclic or cyclic structure, and the cyclic structure may be an aromatic or non-aromatic ring. In some embodiments, the organic group B is a substituted or unsubstituted C1 to C30 group. In some embodiments, the C1 to C30 group is replaced by one or more -I, -Br, -Cl, -F, -NH 2 、-COOH、-OH、-SH、-N 3 , -S(=O)-, alkenyl, alkynyl, imine, ether, ester, aldehyde, ketone, amide, sulfone, acetyl, carboxylic acid, or cyanide.

[0099] The crosslinking agent CL of the photoresist bottom layer 20 can be any suitable crosslinking agent. The crosslinking agent CL reacts with the functional groups of one polymer and the functional groups of another polymer to crosslink and bond the two polymer chains together. This bonding and crosslinking increases the molecular weight of the polymer product of the crosslinking reaction and increases the overall density of the bottom layer. In some embodiments, the crosslinking agent is an independent component of the photoresist bottom layer polymer composition. In other embodiments, the crosslinking agent is connected to the polymer in the photoresist bottom layer polymer composition.

[0100] In some embodiments, the cross-linker CL has the following structure:

[0101]

[0102] In other embodiments, the cross-linking agent CL has the following structure:

[0103]

[0104] Wherein C is carbon, n is between 1 and 15, A and B each comprise a hydrogen atom, a hydroxyl group, a halide, an aromatic carbocyclic ring, or a linear or cyclic alkyl, alkoxy / fluoro, alkyl / fluoroalkoxy chain having 1 to 12 carbons, and each carbon comprises A and B. The first terminal carbon at the first tail of the carbon chain comprises X, and the second terminal carbon at the second tail of the carbon chain comprises Y, wherein X and Y each comprise an amine group, a thiol group, a hydroxyl group, an isopropanol group, or an isopropylamine group, except when n is equal to 1, X and Y are bonded to the same carbon. Specific examples of materials that can be used as crosslinking agents include the following:

[0105]

[0106] In some embodiments, a coupling agent may be added in place of or in addition to a crosslinking agent added to the photoresist bottom layer composition. The coupling agent assists the crosslinking reaction by reacting with functional groups on the polymer prior to 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.

[0107] In some embodiments, the coupling reagent has the following structure:

[0108]

[0109] Wherein, R is a carbon atom, a nitrogen atom, a sulfur atom or an oxygen atom, and M includes a chlorine atom, a bromine atom, an iodine atom, --NO 2 、--SO 3 -, --H--, --CN, --NCO, --OCN, --CO 2 -, --OH, --OR*, --OC(O)CR*, --SR, --SO 2 N(R*) 2 --SO 2 R*, SOR, --OC(O)R*, --C(O)OR*, --C(O)R*, --Si(OR*) 3 、--Si(R*) 3 , epoxy or the like, and R* is a substituted or unsubstituted C1 to C12 alkyl, C1 to C12 aryl, C1 to C12 aralkyl or the like. In some embodiments, specific examples of materials that can be used for the coupling agent include the following:

[0110]

[0111] In some embodiments, the thermal acid generator is one or more molecules selected from the group consisting of:

[0112]

[0113]

[0114] and

[0115]

[0116] wherein 0≤n≤10, and R is hydrogen or a substituted or unsubstituted C1 to C10 alkyl group. In some embodiments, the thermal acid generator is NH 4 + C 4 F 9 SO 3 - With NH 4 + CF 3 SO 3 - Selected from.

[0117] In some embodiments, the first baking operation S120 activates TAG and generates acid. Some of the acid generated by TAG can diffuse from the bottom layer 20 into the photoresist layer 15, and small molecules can be generated due to the acid generated by TAG. However, the effect of TAG on the photoresist layer 15 is limited because most of the acid generated by TAG is used to crosslink the bottom polymer. In addition, in some embodiments, the TAG left after the crosslinking of the bottom polymer evaporates during the first baking. Compared with the small molecules generated by the photoacid generator PAG, the small molecules generated by TAG are negligible. Compared with the amount of acid generated by the photoacid generator PAG, any acid generated by TAG and remaining before the post-exposure baking operation S160 is negligible. Therefore, in some embodiments, the effect of TAG in the photoresist baking operation S140, the radiation exposure operation S150, the post-exposure baking operation S160, and the development operation S170 is negligible compared to the effect of PAG.

[0118] The bottom layer comprises a PAG or a combination of PAG and TAG in a weight percent concentration between about 0.1% and about 20% of the total weight of the polymer composition. At a weight percent concentration below about 0.1%, there may not be enough PAG or TAG to provide the desired effect. At a weight percent concentration above about 20%, no significant improvement in the photoresist pattern profile may be obtained.

[0119] In some embodiments, an additive such as a surfactant is added to the photoresist bottom polymer composition. In some embodiments, the surfactant comprises a nonionic surfactant, a polymer having a fluorinated aliphatic group, a surfactant comprising at least one fluorine atom and / or at least one silicon atom, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl aryl ether, a polyoxyethylene-polyoxypropylene block copolymer, a sorbitan fatty acid ester, and a polyoxyethylene sorbitan fatty acid ester.

[0120] In some embodiments, specific examples of materials for surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, Polyoxyethylene monostearate sorbitan, polyoxyethylene trioleate sorbitan, polyoxyethylene tristearate sorbitan, polyoxyethylene monostearate sorbitan, polyethylene glycol distearate, polyethylene glycol dilaurate, polyethylene glycol, polypropylene glycol, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, fluorinated cationic surfactants, fluorinated nonionic surfactants, fluorinated anionic surfactants, cationic and anionic surfactants, combinations thereof, or the like.

[0121] In some embodiments, the main chain of the polymer is selected from the group consisting of polystyrene, polyhydroxystyrene, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polyacrylic acid, polyvinyl ester, polymaleate, polymethacrylonitrile and polymethacrylamide. In some embodiments, the side chain organic groups are photosensitive functional groups that release chemical reporter molecules in the portion of the photoresist bottom layer exposed by actinic radiation. In some embodiments, the organic group is a substituted or unsubstituted C3 to C30 aliphatic or aromatic group and has at least one photosensitive functional group. In some embodiments, the photosensitive functional group is one or more epoxy groups, azo groups, alkyl halide groups, imino groups, alkenyl groups, alkynyl groups, peroxide groups, ketone groups, aldehyde groups, heavy alkenyl groups, aromatic groups or heterocyclic groups. The aromatic group can be phenyl, naphthyl, phenanthrenyl, anthracenyl, propylene naphthyl and other aromatic groups containing three to ten membered rings. In some embodiments, the side chain target group contains a substituted cyclic or non-cyclic structure. The cyclic structure may be an aromatic or non-aromatic ring. In some embodiments, the target group is a C1 to C30 group containing a functional group, and the functional group is one or more groups selected from the following groups: -I, -Br, -Cl, -NH 2 、-COOH、-OH、-SH、-N 3 , -S(=O)-, alkenyl, alkynyl, imine, ether, ester, aldehyde, ketone, amide, sulfone, carboxyl, cyanide, heavy alkenyl, alcohol, diol, triol, amine, phosphine, phosphite, aniline, pyridine and pyrrol.

[0122] In some embodiments, various components of the photoresist bottom polymer composition are mixed in a solvent to facilitate application of the polymer composition on a substrate. In some embodiments, the solvent is one or more solvents selected from the group consisting of propylene glycol methyl ether acetate (PGMEA), 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), methyl isobutyl carbinol (MIBC), n-butyl acetate (nBA), and 2-heptanone (MAK).

[0123] In some embodiments, the PAG is attached to a polymer in the photoresist bottom polymer composition, such as Fig.10 As shown. The polymer comprises a diol group D and an organic group B. The connected PAG generates a photoacid chemical reporter molecule after exposure, and then the photoacid triggers the diol group to release small molecules, such as water, in the exposure area during the post-exposure baking operation. The water molecules then diffuse into the photoresist layer. In some embodiments, the photoresist is a metal-containing photoresist. Water promotes the cross-linking of the metal-containing photoresist, or generates metal oxides in the exposure area during the post-exposure baking. Because of the water replenishment from the bottom layer, the metal-containing photoresist is strengthened and the exposure dose can be reduced. In some embodiments, the polymer composition may optionally include a thermal acid generator TAG, a cross-linking agent CL and an additive, such as a surfactant.

[0124] In some embodiments, the free PAG compound (shown in Fig. 9 ) and the PAG group connected (shown in Fig.10) is one or more compounds or groups selected from the following groups, which group includes C3 to C50 alkyl groups containing fluorine atoms and having at least one photosensitive functional group. The photosensitive functional group includes sulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorobutanesulfonate, dimethylsulfonium trifluoromethanesulfonate, iodonium salts, diphenyliodonium perfluorobutanesulfonate, norbornene dicarboximido perfluorobutanesulfonate, epoxy groups, azo groups, alkyl halide groups, imine groups, alkenyl groups, alkynyl groups, peroxide groups, ketone groups, aldehyde groups, heavy alkenyl groups, aromatic groups or heterocyclic groups. The aromatic group can be phenyl, naphthyl, phenanthrenyl, anthracenyl, propylene naphthyl or other aromatic groups containing one or more three-membered to ten-membered rings. According to some embodiments of the present disclosure, some examples of photoacid generators are shown in Fig.11 middle.

[0125] The diol group D, the organic group B, the crosslinking agent CL, TAG and the additives can be any reference Fig. 9 The composition comprises diol groups, organic groups, crosslinking agents, TAGs and additives disclosed herein.

[0126] FIG. 12A to FIG. 12F Various water-generating reaction mechanisms of the side chain target groups on the photoresist primer polymer according to some embodiments of the present disclosure are shown. Fig. 12A The process of removing water by the pinacol rearrangement reaction is shown. + ) chemical reporter molecules react with diol groups to release water. Fig. 12B In the case of 1,2-diol, the hydroxyl group of the diol functional group is a substituent on the cyclic alkyl structure. When the 1,2-diol structure reacts with an acid, water is released. Fig. 12C The process of coupling 1,2-diols by ring expansion to release water is shown. After reacting with an acid, the five-membered alkyl ring expands to a six-membered ring as soon as a water molecule is released. Fig.12D The process of releasing water from the target group in the cyclization of 1,n-diols (where n = 4) is shown. The reaction of the target group with an acid releases water and forms a five-membered heterocyclic ring. Fig.12E Shown is the release of water from the cyclic alcohol targeting group and the subsequent formation of a carbon-carbon double bond upon reaction with an acid. Fig.12F The process of releasing two water molecules by a two-step reaction of a target group of a triol target group with an acid molecule is shown.

[0127] In some embodiments, a second mechanism is used to generate small molecules. In the second mechanism, a photobase generator is used to generate a chemical reporter molecule, and the target group is a carbonyl group, such as an aldehyde group or a ketone group. In some embodiments, the polymer composition comprises a polymer having one or more side chain carbonyl target groups E and one or more side chain organic groups B. PBG is an independent compound in the polymer composition, such as Fig.13 As shown. Due to the relationship of actinic radiation, PBG generates a photobase, such as an amine, which then triggers the carbonyl group E to release water molecules in the exposed area during the post-exposure bake. The water molecules then diffuse into the photoresist layer. In some embodiments, the photoresist is a metal-containing photoresist. Water promotes the cross-linking of the metal-containing photoresist, or generates metal oxides in the exposed area during the post-exposure bake. Because of the replenishment of water from the bottom layer, the metal-containing photoresist is strengthened and the exposure dose can be reduced. In some embodiments, the polymer composition may optionally include a thermal acid generator TAG, a cross-linking agent CL and an additive, such as a surfactant.

[0128] In some embodiments, the target group E has a carbonyl group. In some embodiments, the target group may be an aldehyde group, a ketone group, an ester group, an amide group, or any suitable group containing a carbonyl group. In some embodiments, the side chain target group comprises a substituted acyclic or cyclic structure. The cyclic structure may be an aromatic or non-aromatic ring. In some embodiments, the target group is a C1 to C30 group comprising a functional group, and the functional group is one or more groups selected from the following groups: -I, -Br, -Cl, -NH 2 、-COOH、-OH、-SH、-N 3 , -S(=O)-, alkenyl, alkynyl, imine, ether, ester, aldehyde, ketone, amide, sulfone, carboxyl, cyanide, heavy alkenyl, alcohol, amine, phosphine, phosphite, aniline, pyridine and pyrrol.

[0129] The organic group B, crosslinking agent CL, TAG and additives can be any reference Fig. 9 The composition comprises an organic group, a crosslinking agent, a TAG and an additive disclosed in the disclosure.

[0130] Fig.14A and Fig. 14B Examples of photobase generators are shown, and a reaction is shown in which the photobase generator is exposed to actinic radiation to generate an amine chemical reporter molecule. In some embodiments, R1 and R2 are substituted or unsubstituted C1 to C15 alkyl groups. Fig. 14C An amine chemistry reporter molecule is shown reacting with a carbonyl group on a target group to produce water as a small molecule. In this reaction, the amine reacts with the carbonyl group to form a C=N double bond on the target group while releasing a water molecule.

[0131] In some embodiments, the photobase generator is one or more molecules selected from the group consisting of quaternary ammonium dithiocarbamates, α-amino ketones, oxime-urethane-containing molecules such as benzophenone oxime hexamethylene diurethane, ammonium tetraorganylborate salts and N-(2-nitrobenzoyloxycarbonyl) cyclic amine, combinations thereof, or the like. In some embodiments, the thermal base generator is one or more molecules selected from the group consisting of:

[0132]

[0133] In some embodiments, the photoresist bottom layer 20 is formed by preparing a bottom layer coating composition of any of the components of the polymer composition disclosed herein in a solvent. The solvent can be any solvent suitable for dissolving the polymer and the selected components of the composition. The bottom layer coating composition is coated on the substrate 10 or the target layer by, for example, spin coating. The bottom layer composition is then baked to dry the bottom layer, as described in reference. Figure 1 Explained.

[0134] In some embodiments, the thickness of the photoresist bottom layer 20 is between about 2 nanometers and about 300 nanometers, and in other embodiments, the thickness of the photoresist bottom layer 20 is between about 20 nanometers and about 100 nanometers. In some embodiments, the thickness of the photoresist bottom layer 20 is between about 40 nanometers and about 80 nanometers. The thickness of the photoresist bottom layer below the disclosed range may not be sufficient to provide sufficient photoresist adhesion, line width roughness improvement and anti-reflective properties. The thickness of the photoresist bottom layer above the disclosed range may be unnecessarily thick and may not further improve the degree of photoresist layer adhesion, line width roughness and fines reduction.

[0135] In some embodiments, the photoresist layer 15 is a photosensitive layer 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. The photoresist layer 15 is either a positive photoresist or a negative photoresist. 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. On the other hand, negative photoresist refers to a photoresist material that becomes insoluble in a developer when exposed to radiation, while the unexposed (or less exposed) photoresist areas are soluble in the developer. When exposed to radiation, the negative photoresist areas that become insoluble may become insoluble due to a cross-linking reaction caused by exposure to radiation.

[0136] Whether a photoresist is positive or negative depends on the type of developer used to develop the photoresist. For example, some positive photoresists provide positive patterns (i.e., exposed areas are removed by the developer) when the developer is an aqueous developer, such as a tetramethylammonium hydroxide (TMAH) solution. On the other hand, the same photoresist provides negative patterns (i.e., unexposed areas are removed by the developer) when the developer is an organic solution. Furthermore, in some negative photoresists developed with a tetramethylammonium hydroxide solution, the unexposed areas of the photoresist are removed by the tetramethylammonium hydroxide, and the exposed areas of the photoresist are cross-linked upon exposure to actinic radiation and remain on the substrate after development is completed.

[0137] In some embodiments, the photoresist layer 15 is made of a photoresist composition comprising a first compound or a first precursor and a second compound or a second precursor combined in a gaseous state. The first precursor or the first compound has a chemical formula M a R b X c of organometallic compounds, such as Fig.15A As shown, wherein M is at least one of tin (Sn), bismuth (Bi), antimony (Sb), indium (In), tellurium (Te), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), cobalt (Co), molybdenum (Mo), tungsten (W), aluminum (Al), gallium (Ga), silicon (Si), germanium (Ge), phosphorus (P), arsenic (As), yttrium (Y), lanthanum (La), cerium (Ce) or lutetium (Lu), and R is a substituted or unsubstituted alkyl, alkenyl or carboxylate. In some embodiments, M is selected from the group consisting of tin, bismuth, antimony, indium, tellurium and combinations thereof. In some embodiments, R is a C3 to C6 alkyl, alkenyl or carboxylate. In some embodiments, R is selected from the group consisting of propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, isohexyl, sec-hexyl, tert-hexyl and combinations thereof. X is a ligand, ion or other moiety that can react with the second compound or the second precursor, and in some embodiments, 1≤a≤2, b≥1, c≥1 and b+c≤5. In some embodiments, the alkyl, alkenyl or carboxylate is substituted with one or more fluorine groups. In some embodiments, the organometallic precursor is a dimer, such as Fig.15A As shown, each monomer unit is bonded together by an amine group. Each monomer unit has the chemical formula M as defined above a R b X c .

[0138] In some embodiments, R is an alkyl group, such as C n H 2n+1, wherein n≥3. In some embodiments, R is fluorinated, for example, having the chemical formula C n F x H ((2n+1)-x) In some embodiments, R has at least one beta-hydrogen or beta-fluorine. In some embodiments, R is selected from the group consisting of isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl, sec-pentyl, and combinations thereof.

[0139] In some embodiments, X is any moiety that is easily replaced by a second compound or a second precursor to form a moiety of M-OH. This moiety can be selected from the group consisting of amines (including dialkylamines and monoalkylamines), alkoxy groups, carboxylates, halogens, and sulfonates. In some embodiments, the sulfonate group is substituted with one or more amine groups. In some embodiments, the halogen is one or more atoms selected from the group consisting of fluorine, chlorine, bromine, and iodine. In some embodiments, the sulfonate group comprises substituted or unsubstituted C1 to C3 groups.

[0140] In some embodiments, the first organometallic compound or the first organometallic precursor comprises a metal center M + Connected to the metal center M + The ligand L, such as Fig. 15B In some embodiments, the metal center M + For metal oxides. In some embodiments, the ligand L comprises aliphatic or aromatic groups of C3 to C12. The aliphatic or aromatic group may be unbranched or branched with cyclic or non-cyclic saturated side chain groups, the side chain groups containing 1 to 9 carbons, including alkyl, alkenyl and phenyl. The branched groups may be further substituted by oxygen or halogen. In some embodiments, the aliphatic or aromatic groups of C3 to C12 comprise heterocyclic groups. In some embodiments, the aliphatic or aromatic groups of C3 to C12 are connected to the metal by ether or ester bonding. In some embodiments, the aliphatic or aromatic groups of C3 to C12 comprise nitrite or sulfonate substituents.

[0141] In some embodiments, the organometallic precursor or organometallic compound comprises secondary hexyltri(dimethylamino)tin, tert-hexyltri(dimethylamino)tin, isohexyltri(dimethylamino)tin, n-hexyltri(dimethylamino)tin, secondary amyltri(dimethylamino)tin, tert-amyltri(dimethylamino)tin, isopentyltri(dimethylamino)tin, n-amyltri(dimethylamino)tin, secondary butyltri(dimethylamino)tin, tert-butyltri(dimethylamino)tin, isobutyltri(dimethylamino)tin, n-butyltri(dimethylamino)tin, isopropyltri(dimethylamino)tin, n-propyl tri(diethylamino)tin and similar alkyl tri(tert-butoxy)tin compounds, including sec-hexyl tri(tert-butoxy)tin, tert-hexyl tri(tert-butoxy)tin, isohexyl tri(tert-butoxy)tin, n-hexyl tri(tert-butoxy)tin, sec-pentyl tri(tert-butoxy)tin, tert-pentyl tri(tert-butoxy)tin, isopentyl tri(tert-butoxy)tin, n-pentyl tri(tert-butoxy)tin, tert-butyl tri(tert-butoxy)tin, isobutyl tri(butoxy)tin, n-butyl tri(butoxy)tin, sec-butyl tri(butoxy)tin, isopropyl tri(tert-butoxy)tin or n-propyl tri(butoxy)tin. In some embodiments, the organometallic precursor or organometallic compound is fluorinated. In some embodiments, the organometallic precursor or compound has a boiling point below about 200 degrees Celsius.

[0142] In some embodiments, the first compound or the first precursor comprises one or more unsaturated bonds that can pair with functional groups (eg, hydroxyl groups) on the surface of the substrate or the intermediate bottom layer to improve the adhesion of the photoresist layer to the substrate or the bottom layer.

[0143] In some embodiments, the second precursor or second compound is at least one of an amine, a borane, a phosphine, or water. In some embodiments, the amine has a chemical formula N p H n X m , wherein 0≤n≤3, 0≤m≤3, when p is 1, n+m=3, when p is 2, n+m=4, and each X is a halogen selected from fluorine, chlorine, bromine and iodine. In some embodiments, borane has a chemical formula B p H n X m , wherein 0≤n≤3, 0≤m≤3, when p is 1, n+m=3, when p is 2, n+m=4, and each X is a halogen selected from fluorine, chlorine, bromine and iodine. In some embodiments, the phosphine has the chemical formula P p H n X m , wherein 0≤n≤3, 0≤m≤3, when p is 1, n+m=3, when p is 2, n+m=4, and each X is independently a halogen selected from fluorine, chlorine, bromine and iodine.

[0144] Fig. 15B The diagram shows the reactions that a metal precursor undergoes when exposed to actinic radiation. Due to the exposure to actinic radiation, the ligand L is removed from the metal center M of the metal precursor. + separate, and two or more metal precursor centers are bonded to each other.

[0145] Fig. 15C Examples of organometallic precursors according to some embodiments of the present disclosure are shown. Fig. 15C In the above, Bz is a benzene group. Fig.15D Tin oxide organometallic photoresist materials according to some embodiments of the present disclosure are shown. Fig.15E Depicted are reactions that a tin oxide organometallic photoresist may undergo when exposed to actinic radiation hv according to some embodiments of the present disclosure. Different final products may be obtained depending on whether the exposed organometallic photoresist is exposed to air, nitrogen, water, or a combination thereof.

[0146] In some embodiments, the operation S130 of depositing the photoresist composition is performed by a vapor deposition operation. In some embodiments, the vapor deposition operation includes atomic layer deposition (ALD) or chemical vapor deposition (CVD). In some embodiments, the atomic layer deposition includes plasma-enhanced atomic layer deposition (PE-ALD), and the chemical vapor deposition includes plasma-enhanced chemical vapor deposition (PE-CVD), metal-organic chemical vapor deposition (MO-CVD), atmospheric pressure chemical vapor deposition (AP-CVD), and low pressure chemical vapor deposition (LP-CVD). In other embodiments, the organic metal photoresist is applied to the substrate 10 or the target layer by a spin coating operation.

[0147] In some embodiments, the photoresist layer 15 is formed to a thickness between about 5 nanometers and about 50 nanometers, and in other embodiments, to a thickness between about 10 nanometers and about 30 nanometers. One of ordinary skill in the art will appreciate that the present disclosure also contemplates additional thickness ranges within the explicit ranges described above. The thickness can be estimated using non-contact methods (X-ray reflectivity and / or ellipsometry) based on the optical properties of the photoresist layer. In some embodiments, the thickness of each photoresist layer is relatively uniform to facilitate processing. In some embodiments, the thickness of the deposited photoresist layer does not vary by more than ±25% of the average thickness, and in other embodiments, the thickness of the deposited photoresist layer does not vary by more than ±10% of the average photoresist layer thickness. In some embodiments, the evaluation of the uniformity of the photoresist layer (e.g., high uniformity deposition on a large substrate) can exclude a 1 cm edge, meaning that when evaluating the uniformity of the layer, the 1 cm portion within the edge of the coating is not evaluated. One of ordinary skill in the art will appreciate that the present disclosure also contemplates additional ranges within the explicit ranges described above.

[0148] In some embodiments, the organometallic compound comprises tin (Sn), antimony (Sb), bismuth (Bi), indium (In), tellurium (Te) as the metal component, however, the present disclosure is not limited to these metals. In other embodiments, additional suitable metals include titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), cobalt (Co), molybdenum (Mo), tungsten (W), aluminum (Al), gallium (Ga), silicon (Si), germanium (Ge), phosphorus (P), arsenic (As), yttrium (Y), lanthanum (La), cerium (Ce), lutetium (Lu) or a combination thereof. Additional metals may be used as substitutes for tin, antimony, bismuth, indium, tellurium or exist simultaneously with tin, antimony, bismuth, indium, tellurium.

[0149] The specific metal used can significantly affect the absorbance of radiation. Therefore, the metal composition can be selected based on the expected radiation and the absorption cross-section. Tin, antimony, bismuth, tellurium and indium provide strong absorption of extreme ultraviolet light at 13.5 nanometers. Hafnium provides good absorption of electron beam and extreme ultraviolet radiation. Metal compositions containing titanium, vanadium, molybdenum or tungsten have strong absorption at long wavelengths to provide sensitivity to ultraviolet light, such as at a wavelength of 248 nanometers.

[0150] Fig.16 Reactions that components of a photoresist composition undergo due to exposure to actinic radiation and heating are illustrated according to some embodiments of the present disclosure. Fig.16 FIG. 4 shows an exemplary chemical structure of a photoresist layer at each stage of a photoresist patterning method according to some embodiments of the present disclosure. Fig.16 As shown, the photoresist composition includes an organic metal compound (such as SnX 2 R2 ) and a second compound (e.g., ammonia (NH 3 )). When the organometallic compound is combined with ammonia, the organometallic compound reacts with some of the ammonia in the gas phase to form a reaction product having an amine group attached to the metal (tin) of the organometallic compound. The amine groups in the deposited photoresist layer have hydrogen bonds, which can substantially increase the boiling point of the deposited photoresist layer and help prevent outgassing of the metal-containing photoresist material. In addition, the hydrogen bonds of the amine groups can help control the effect of moisture on the quality of the photoresist layer.

[0151] When subsequently exposed to EUV radiation, the organometallic compound absorbs the EUV radiation and one or more organic R groups are cleaved from the organometallic compound to form an amine metal compound in the radiation exposed areas. Then, when a post-exposure bake is performed, in some embodiments, the amine metal compound crosslinks through the amine groups, such as Fig.16 In some embodiments, the EUV exposure causes partial crosslinking of the amine metal compound.

[0152] After post-exposure baking, the latent pattern in the photoresist layer is developed to form a patterned photoresist layer. In some embodiments, the photoresist developer 57 comprises a solvent and an acid or a base. In some embodiments, the weight percentage concentration of the solvent is between about 60% and about 99% based on the total weight of the photoresist developer. The weight percentage concentration of the acid or base in the developer is between about 0.001% and about 20% based on the total weight of the photoresist developer. In some embodiments, the weight percentage concentration of the acid or base in the developer is between about 0.01% and about 15% based on the total weight of the photoresist developer.

[0153] 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 photoresist-coated substrate 10 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.

[0154] The spin coating process is a process suitable for developing the photoresist layer 15 after exposure, but is only for illustration and not limitation. In addition, any suitable developing operation may be used, including dip coating processes, puddle processes, and spray-on methods. These developing operations are all included in the scope of the embodiment.

[0155] During the development process, the developer 57 dissolves the unexposed radiation areas 52 of the cross-linked negative photoresist, exposing the surface of the bottom layer 20, such as Figure 5 , leaving well-defined exposed photoresist areas 50, and providing better definition capabilities than conventional negative photoresist photolithography.

[0156] After the development operation S170, the remaining developer is removed from the substrate covered by the patterned photoresist. In some embodiments, a spin-drying process is used to remove the remaining developer, although any suitable removal technique may be used. After the photoresist layer 15 is developed and the remaining developer is removed, additional processes are performed while the patterned photoresist layer (i.e., the exposed area 50) has not been removed. For example, in some embodiments, an etching operation is performed using dry or wet etching to transfer the pattern of the photoresist layer (i.e., the exposed area 50) through the bottom layer 20 to the substrate 10 below and form a Figure 6 The substrate 10 and the bottom layer 20 have different etching resistances than the photoresist layer 15. In some embodiments, the etchant has a higher selectivity for the substrate 10 and the bottom layer 20 relative to the photoresist layer 15. In some embodiments, different etchants or etching parameters are used to etch the non-photocleaved portion 20a of the bottom layer and then etch the substrate 10.

[0157] In some embodiments, a target layer 60 to be patterned is placed on the substrate 10, such as Fig.17 As shown. In some embodiments, the target layer 60 is a metallization layer or a dielectric layer disposed on the metallization layer, such as a passivation layer. In embodiments where the target layer 60 is a metallization layer, the target layer 60 is a conductor 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 target layer 60 is a dielectric layer, the target layer 60 is formed by a dielectric layer formation technique, such as thermal oxidation, chemical vapor deposition, atomic layer deposition, and physical vapor deposition.

[0158] Next, the photoresist layer 15 and the photoresist bottom layer 20 are selectively exposed to actinic radiation 45 / 97 to form exposed regions 50, exposed portions 20b and unexposed regions 52, unexposed portions 20a in the photoresist layer and the bottom layer, respectively. Fig.18A and Fig.18B As shown, and the description content is the same as Figure 3A and Figure 3B In some embodiments, the photoresist described herein is a negative photoresist, wherein cross-linking of the polymer occurs in the exposed areas 50 .

[0159] like Fig.19 As shown, the non-exposed photoresist region 52 is developed by dispensing the developer 57 from the dispenser 62 to form a pattern of the photoresist opening 55, as shown in FIG. Fig. 20 The development operation here is similar to Figure 4 , Figure 5 The description is similar.

[0160] Then, if Fig.21 As shown, an etching operation is used to transfer the pattern of the opening 55 in the photoresist layer 15 to the target layer 60 through the unexposed portion 20a of the photoresist bottom layer, and remove the photoresist layer 15 and the exposed portion 20b of the photoresist bottom layer, as shown in FIG. Figure 6 As described, a pattern 55″ is formed in the target layer 60.

[0161] In some embodiments, an intermediate layer is provided between the substrate 10 or the target layer 60 and the photoresist bottom layer 20 (or the bottom anti-reflective coating). The intermediate layer may have a composition that provides anti-reflective properties and / or hard mask properties for photolithography operations. In some embodiments, the intermediate layer comprises a silicon-containing layer (e.g., a silicon hard mask material). The intermediate layer may comprise an inorganic polymer containing silicon. In other embodiments, the intermediate layer comprises a siloxane polymer. In other embodiments, the intermediate layer comprises silicon oxide (e.g., spin-on glass (SOG)), silicon nitride, silicon oxynitride, polysilicon, a metal-containing organic polymer material, the metal-containing organic polymer material containing a metal, such as titanium, titanium nitride, aluminum and / or tantalum and / or other suitable materials. The intermediate layer may be connected to an adjacent layer, for example, by covalent bonds, hydrogen bonds, or hydrophilic-hydrophilic forces.

[0162] In some embodiments, the photoresist layer 15 comprises a chromophore, a counter ion, and a quencher.

[0163] In some embodiments, the photoresist patterning operation includes a second exposure to actinic radiation after the development operation to harden the photoresist or enhance the contrast of the photoresist pattern after the development operation. In some embodiments, the second exposure is performed at a wavelength different from the first exposure. In some embodiments, the second exposure is performed at a wavelength less than 250 nanometers and is performed by at least one of a krypton fluoride laser, an argon fluoride laser, extreme ultraviolet light, or an electron beam.

[0164] Other embodiments include operations before, between, or after the above operations. In some embodiments, the method of the disclosure 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 a substrate from a patterned masked opening 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, a metal line can be formed in an inter-layer dielectric (ILD) layer of a 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.

[0165] In some embodiments, according to the embodiments of the present disclosure, active components 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.

[0166] The photoresist bottom layer of the present disclosure undergoes a dehydration reaction under exposure to actinic radiation and after post-exposure baking. As a result, the molecular weight of the polymer in the bottom layer composition decreases. The solubility of the polymer in alcohols decreases after exposure and post-exposure baking. In some embodiments, cobaltous chloride test paper and dried copper sulfate test paper analysis indicate that the water content of the bottom layer composition increases. In addition, in embodiments where the target group includes a diol, nuclear magnetic resonance (NMR), infrared, and Raman analysis show that after exposure and post-exposure baking, the intensity of the polymer OH group decreases, and the intensity of the polymer C=O group increases.

[0167] When comparing the photoresist underlayer composition of the present disclosure having the target group containing diol groups with a polyhydroxystyrene (PHS) photoresist underlayer composition not according to the present disclosure, the molecular weight, pH, OH and C=O groups by NMR, IR, Raman, time-of-flight secondary ion massspectrometry (TOF-SIMS), water contact angle, thickness and thermogravimetric analysis (TGA) (only exposure to actinic radiation) of the polyhydroxystyrene-based underlayer are unchanged after exposure to actinic radiation and post-exposure baking. On the other hand, the photoresist underlayer composition according to the present disclosure shows a decrease in polymer weight (e.g., decrease in water), a more acidic or more basic pH, a decrease in polymer OH intensity and an increase in polymer C=O intensity by NMR, IR, Raman, a decrease in oxygen % by TOF-SIMS, an increase in water contact angle, a decrease in thickness and a weight loss by thermogravimetric analysis (only exposure to actinic radiation).

[0168] If the metal photoresist covered on the photoresist base layer is compared before and after the steps of exposure to actinic radiation and post-exposure baking, the photoresist formed on the base layer made of the polymer composition (having a target group including a diol group) according to an embodiment of the present disclosure has several improved properties compared to the base layer made of polyhydroxystyrene not according to an embodiment of the present disclosure. For example, the photoresist formed on the base layer according to an embodiment of the present disclosure has an increased photoresist film, increased density, increased moisture content, increased metal-oxygen bonding ratio, reduced carbon ratio by time-of-flight secondary ion mass spectrometry, and increased metal-OH group and metal-O bonding strength by nuclear magnetic resonance, infrared, and Raman, compared to the patterned photoresist formed on the polyhydroxystyrene base layer not according to an embodiment of the present disclosure. Furthermore, after patterning the photoresist by development, the photoresist formed on the bottom layer according to the embodiments of the present disclosure has an increased photoresist contrast curve, requires a lower photoresist exposure dose, has a stronger photoresist mechanical line strength, a larger peeling window, and increased throughput.

[0169] Embodiments of the present disclosure reduce the exposure dose for the photoresist layer, while improving line width roughness, increasing the stripping window and reducing fines. For example, a 30-nanometer-thick photoresist layer comprising a polymer having a diol target group reduces the exposure dose by about 11% compared to a bottom layer made of polyhydroxystyrene and not comprising the disclosed target group and chemical reporter molecule. At the same time, when the photoresist layer is exposed using an exposure dose reduced by 11%, the use of a bottom layer according to the present disclosure can also provide about 3% improvement in line width roughness, about 9% improvement in stripping window and about 4% reduction in fines. Thicker photoresist bottom layers provide a larger amount of small molecules to the photoresist layer. However, a thinner photoresist bottom layer, such as a 5-nanometer-thick photoresist bottom layer made of a polymer composition having a diol target group according to the present disclosure, provides about 9% improvement in stripping window compared to a 30-nanometer-thick photoresist bottom layer made of polyhydroxystyrene that is not an embodiment of the present disclosure. In addition, a 5-nanometer-thick bottom layer also provides about 1% improvement in line width roughness and reduction in fines.

[0170] Compared to conventional exposure techniques, novel underlying compositions and semiconductor device manufacturing methods according to embodiments of the present disclosure provide higher semiconductor device feature resolution and density at higher wafer exposure throughput, reduced defect counts, and more efficient processes. Embodiments of the present disclosure improve the adhesion between the photoresist pattern and the substrate, thereby preventing pattern collapse and avoiding pattern fines. Embodiments of the present disclosure improve the integrity of the photoresist pattern, reduce line width roughness, reduce line edge roughness and fines. Embodiments of the present disclosure allow for reduced photoresist dosage and improved semiconductor device yields.

[0171] According to an embodiment of the present disclosure, a method for manufacturing a semiconductor device includes forming a photoresist bottom layer on a semiconductor substrate. The photoresist bottom layer includes a polymer, the polymer includes a main polymer chain having a plurality of side chain target groups and a plurality of side chain organic groups or a plurality of side chain photoacid generator groups. The main polymer chain is selected from the group including: polystyrene, polyhydroxystyrene, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polyacrylic acid, polyvinyl ester, polymaleate, polymethacrylonitrile and polymethacrylamide. The side chain target group is one or more selected from the group including: C2 to C30 diol groups, C1 to C30 aldehyde groups and C3 to C30 ketone groups. The side chain organic group is a C3 to C30 aliphatic or aromatic group having at least one photosensitive functional group, and the side chain photoacid generator group is a C3 to C50 substituted aliphatic or aromatic group. A photoresist layer is formed on the photoresist bottom layer. The photoresist layer is selectively exposed to actinic radiation. The selectively exposed photoresist layer is developed to form a photoresist pattern. In an embodiment, the main polymer chain comprises a side chain organic group having at least one photosensitive group, and the photosensitive group is selected from the group comprising: epoxy group, azo group, alkyl halide group, imine group, alkenyl group, alkynyl group, peroxide group and a combination thereof. In one embodiment, the main polymer chain comprises a side chain photoacid generator group, and the side chain photoacid generator group is selected from the group consisting of onium salts, sulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorobutanesulfonate, dimethylsulfonium trifluoromethanesulfonate, iodonium salts, diphenyliodonium perfluorobutanesulfonate, norbornene dicarboximido perfluorobutanesulfonate, fluorinated triazines, diazonium salts, aromatic diazonium salts, phosphonium salts, imide sulfonates, oxime sulfonates, diazo disulfones, disulfones, o-nitrobenzylmethyl sulfonates, sulfonated esters, halogenated sulfonyloxy dicarboximides, α-cyanooxyamine sulfonates, ketodiazo sulfones, sulfonyldiazo esters, 1,2-di(arylsulfonyl)hydrazides, nitrobenzyl esters, and s-triazines. In one embodiment, the photoresist underlayer further comprises a photobase generator compound. In an embodiment, the photoresist base layer further comprises a photoacid generator compound. In an embodiment, the photoresist base layer further comprises a thermal acid generator. In an embodiment, the side chain target group is substituted with one or more substituents selected from the group consisting of fluorine, chlorine, bromine, iodine, hydroxyl, thiol, azido, sulfonyl, alkenyl, alkynyl, imine, ether, ester, peroxide, amide, sulfone, carboxyl, carbonyl, heavy alkenyl, amine, phosphine, triol, anilino, pyridine, pyrrolyl, cyanide, phosphite, and combinations thereof. In an embodiment, the method further comprises heating the photoresist base layer at a temperature between 150 degrees Celsius and 250 degrees Celsius before forming the photoresist layer. In an embodiment, the method further comprises heating the selectively exposed photoresist layer and the photoresist base layer at a temperature between 50 degrees Celsius and 200 degrees Celsius before developing the selectively exposed photoresist layer.

[0172] Another embodiment of the present disclosure is a method for manufacturing a semiconductor device, comprising forming a photoresist base layer on a semiconductor substrate. The photoresist base layer comprises a polymer having a plurality of side chain target groups. A photoresist layer is formed on the photoresist base layer. The photoresist layer and the photoresist base layer are selectively exposed to actinic radiation. Chemical reporter molecules are generated in a plurality of portions of the photoresist base layer exposed to actinic radiation. The chemical reporter molecules are one or more selected from the group comprising: electrons, oxygen molecules, water, hydrogen ions, hydroxides, cations, anions, and C1 to C10 groups substituted with functional groups, wherein the functional groups are one or more selected from the group comprising: fluorine, chlorine, bromine, iodine, hydroxyl, carboxylic acid, thiol, azido, sulfinyl, alkenyl, alkynyl, imine, ether, ester, aldehyde, ketone, amide, sulfone, alkylcarboxyl, cyanide, heavy alkenyl, alkanol, amine, phosphine, phosphite, anilino, pyridyl, and pyrrolyl. In the portion of the photoresist layer exposed to actinic radiation, small molecules are generated by the interaction between the chemical reporter molecule and the side chain target group. The small molecule is one or more selected from the group consisting of electrons, oxygen molecules, water, hydrogen ions, hydroxides, cations, anions, and C1 to C10 groups substituted with functional groups, wherein the functional group is one or more selected from the group consisting of fluorine, chlorine, bromine, iodine, hydroxyl, carboxylic acid, thiol, azido, sulfinyl, alkenyl, alkynyl, imine, ether, ester, aldehyde, ketone, amide, sulfone, alkyl carboxyl, cyanide, heavy alkenyl, alkanol, amine, phosphine, phosphite, aniline, pyridyl, and pyrrol. The small molecule diffuses from the photoresist layer into the portion of the photoresist layer exposed to actinic radiation. The selectively exposed photoresist layer is developed to form a patterned photoresist layer. In an embodiment, the method further comprises heating the photoresist bottom layer at a temperature between 150 degrees Celsius and 250 degrees Celsius before forming the photoresist layer. In an embodiment, diffusing the small molecule comprises heating the selectively exposed photoresist layer and the photoresist bottom layer at a temperature between 50 degrees Celsius and 200 degrees Celsius before developing the selectively exposed photoresist layer. In an embodiment, the photoresist layer comprises an organometallic material. In an embodiment, the actinic radiation is extreme ultraviolet radiation. In an embodiment, the small molecule is different from the chemical reporter molecule.

[0173] Another embodiment of the present disclosure is a bottom layer composition, comprising a polymer, the polymer comprising a main polymer chain having a plurality of side chain target groups and a plurality of side chain organic groups or a plurality of side chain photoacid generator groups. The main polymer chain is selected from the group comprising: polystyrene, polyhydroxystyrene, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polyacrylic acid, polyvinyl ester, polymaleate, polymethacrylonitrile and polymethacrylamide. The side chain target group is one or more substituted or unsubstituted selected from the group comprising: C2 to C30 diol groups, C1 to C30 aldehyde groups and C3 to C30 ketone groups, wherein the side chain organic group is a C3 to C30 aliphatic or aromatic group having at least one photosensitive functional group, and wherein the side chain photoacid generator group is a C3 to C50 substituted aliphatic or aromatic group. In an embodiment, the polymer comprises a side chain organic group having at least one photosensitive group, and the photosensitive group is selected from the group comprising epoxy group, azo group, alkyl halide group, imine group, alkenyl group, alkynyl group, peroxide group and combinations thereof. In an embodiment, the polymer comprises a side chain photoacid generator group, and the side chain photoacid generator group is selected from the group consisting of onium salts, sulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorobutanesulfonate, dimethylsulfonium trifluoromethanesulfonate, iodonium salts, diphenyliodonium perfluorobutanesulfonate, norbornene dicarboximido perfluorobutanesulfonate, fluorinated triazines, diazonium salts, aromatic diazonium salts, phosphonium salts, imide sulfonates, oxime sulfonates, diazo disulfones, disulfones, o-nitrobenzylmethyl sulfonates, sulfonated esters, halogenated sulfonyloxy dicarboximides, α-cyanooxyamine sulfonates, ketodiazo sulfones, sulfonyldiazo esters, 1,2-di(arylsulfonyl)hydrazides, nitrobenzyl esters, and s-triazines. In an embodiment, the bottom layer composition further comprises a photobase generator. In an embodiment, the bottom layer composition further comprises a photoacid generator compound. In an embodiment, the bottom layer composition further comprises a solvent. In an embodiment, the bottom layer composition further comprises a surfactant. In an embodiment, the side chain target group is substituted by one or more substituents selected from the following groups: fluorine, chlorine, bromine, iodine, hydroxyl, thiol, azido, sulfonyl, alkenyl, alkynyl, imine, ether, ester, peroxide, amide, sulfone, carboxyl, carbonyl, heavy alkenyl, amine, phosphine, triol, anilino, pyridine, pyrrolyl, cyanide, phosphite and combinations thereof. In an embodiment, the polymer comprises a side chain organic group, and the side chain organic group comprises a substituted or unsubstituted phenyl, naphthyl, phenanthrenyl, anthracenyl, propylene naphthyl and aromatic groups in combination thereof. In an embodiment, a crosslinker is attached to the polymer.

[0174] Another embodiment according to the present disclosure is a method of manufacturing a semiconductor device, comprising forming a first layer on a semiconductor substrate. The first layer comprises a polymer, the polymer comprising a main polymer chain having a plurality of side chain target groups and a plurality of side chain organic groups or a plurality of side chain photoacid generator groups. The side chain target groups are substituted or unsubstituted one or more selected from the group comprising: C2 to C30 diol groups, C1 to C30 aldehyde groups, and C3 to C30 ketone groups. A photoresist layer is formed on the first layer. Water is generated in a first portion of the first layer. The water in the first portion of the first layer diffuses to a first portion in a corresponding photoresist layer. A second portion of the photoresist layer is removed, wherein the second portion of the photoresist layer is different from the first portion of the photoresist layer. After removing the second portion of the photoresist layer, the first portion of the photoresist layer remains. In an embodiment, the method comprises heating the first layer at a temperature between 150 degrees Celsius and 250 degrees Celsius before forming the photoresist layer. In an embodiment, generating water in the first portion of the first layer comprises exposing the first portion of the first layer to extreme ultraviolet radiation. In an embodiment, diffusing the water includes heating the first layer and the photoresist layer at a temperature between 50 degrees Celsius and 200 degrees Celsius before removing the second portion of the photoresist layer. In an embodiment, the method includes heating the photoresist layer and the first layer at a temperature between 40 degrees Celsius and 150 degrees Celsius before generating water in the first portion of the first layer. In an embodiment, the photoresist layer includes an organic metal material. In an embodiment, the method includes removing the second portion of the first layer, wherein the second portion of the first layer corresponds to the second portion of the photoresist layer. In an embodiment, the method includes removing a portion of the semiconductor substrate corresponding to the second portion of the first layer and the second portion of the photoresist layer. In an embodiment, the target layer is located between the semiconductor substrate and the first layer, and further includes removing a portion of the target layer corresponding to the second portion of the first layer and the second portion of the photoresist layer.

[0175] The foregoing summarizes the features of several embodiments so that those skilled in the art can better understand 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: A photoresist bottom layer is formed on a semiconductor substrate, wherein the photoresist bottom layer comprises a polymer, including: A main polymer chain having a plurality of side chain target groups, a plurality of side chain organic groups or a plurality of side chain photoacid generator groups, wherein the main polymer chain is selected from the group consisting of polystyrene, polyhydroxystyrene, polyacrylate, polymethyl methacrylate, polyacrylic acid, polyvinyl ester, polymaleate, polymethacrylonitrile and polymethacrylamide, wherein the plurality of side chain target groups are one or more substituted or unsubstituted groups selected from the group consisting of: C2 to C30 diol groups, C1 to C30 aldehyde groups, and C3 to C30 ketone groups, wherein the plurality of side chain organic groups are C3 to C30 aliphatic or aromatic groups having at least one photosensitive functional group, wherein the photosensitive functional group is selected from the group consisting of an epoxy group, an azo group, an alkyl halide group, an imine group, an alkenyl group, an alkynyl group, a peroxide group, and a combination thereof, and wherein the plurality of side chain photoacid generator groups are selected from the group consisting of onium salts, sulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorobutanesulfonate, dimethylsulfonium trifluoromethanesulfonate, iodonium salts, diphenyliodonium perfluorobutanesulfonate, norbornene dicarboximido perfluorobutanesulfonate, fluorinated triazines, diazonium salts, aromatic diazonium salts, phosphonium salts, imide sulfonates, oxime sulfonates, diazo disulfones, disulfones, o-nitrobenzylmethyl sulfonates, sulfonated esters, halogenated sulfonyloxy dicarboximides, α-cyanooxyamine sulfonates, ketodiazo sulfones, sulfonyldiazo esters, 1,2-bis(arylsulfonyl)hydrazides, nitrobenzyl esters, and s-triazines; forming a photoresist layer on the photoresist bottom layer; selectively exposing the photoresist layer and the photoresist bottom layer to actinic radiation; generating a chemical reporter molecule in portions of the photoresist bottom layer exposed to the actinic radiation; generating a small molecule in the portions of the photoresist bottom layer exposed to the actinic radiation by an interaction between the chemical reporter molecule and the plurality of pendant target groups; diffusing the small molecules in the portions of the photoresist bottom layer into corresponding portions of the photoresist layer, the portions of the corresponding photoresist layer being exposed to the actinic radiation, wherein the small molecules are water; and The selectively exposed photoresist layer is developed to form a photoresist pattern.

2. The method of claim 1, wherein the photoresist bottom layer further comprises a photobase generator compound.

3. The method of claim 1, wherein the photoresist bottom layer further comprises a photoacid generator compound.

4. The method of claim 1, wherein the photoresist bottom layer further comprises a thermal acid generator compound.

5. The method of claim 1, wherein the plurality of side chain target groups are substituted with one or more substituents selected from the group consisting of fluorine, chlorine, bromine, iodine, hydroxyl, thiol, azido, sulfonyl, alkenyl, alkynyl, imine, ether, ester, peroxide, amide, sulfone, carboxyl, carbonyl, heavy alkenyl, amine, phosphine, triol, anilino, pyridyl, pyrrolyl, cyanide, phosphite, and combinations thereof.

6. The method of claim 1, further comprising heating the photoresist bottom layer at a temperature between 150 degrees Celsius and 250 degrees Celsius before forming the photoresist layer.

7. The method of claim 1, further comprising heating the selectively exposed photoresist layer and the photoresist bottom layer at a temperature between 50 degrees Celsius and 200 degrees Celsius before developing the selectively exposed photoresist layer.

8. A method for manufacturing a semiconductor device, characterized in that: Include: Forming a photoresist bottom layer on a semiconductor substrate, wherein the photoresist bottom layer comprises a polymer having a plurality of side chain target groups; forming a photoresist layer on the photoresist bottom layer; selectively exposing the photoresist layer and the photoresist bottom layer to actinic radiation; generating a chemical reporter molecule in portions of the photoresist layer exposed to the actinic radiation, wherein the chemical reporter molecule is one or more selected from the group consisting of: oxygen molecules, water, or a group having one or more selected from the group consisting of: electrons, hydrogen ions, hydroxides, and C1 to C10 substituted by a functional group, wherein the functional group is one or more groups selected from the group consisting of fluorine, chlorine, bromine, iodine, carboxylic acid, hydroxyl, thiol, azido, sulfinyl, alkenyl, alkynyl, imine, ether, ester, aldehyde, ketone, amide, sulfone, alkylcarboxyl, cyanide, heavy alkenyl, alkanol, amino, phosphine, phosphite, anilino, pyridyl and pyrrolyl; generating a small molecule in the portions of the photoresist bottom layer exposed to the actinic radiation by an interaction between the chemical reporter molecule and the plurality of pendant target groups, The small molecule is one or more selected from the group consisting of: oxygen molecules, water, or one or more selected from the group consisting of: electrons, hydrogen ions, hydroxides, and a C1 to C10 group substituted by a functional group, wherein the functional group is one or more groups selected from the group consisting of fluorine, chlorine, bromine, iodine, carboxylic acid, hydroxyl, thiol, azido, sulfinyl, alkenyl, alkynyl, imine, ether, ester, aldehyde, ketone, amide, sulfone, alkylcarboxyl, cyanide, heavy alkenyl, alkanol, amino, phosphine, phosphite, anilino, pyridyl and pyrrolyl; diffusing the small molecules from the photoresist bottom layer into the portions of the photoresist layer exposed to the actinic radiation; and The selectively exposed photoresist layer is developed to form a patterned photoresist layer.

9. The method of claim 8, further comprising heating the photoresist bottom layer at a temperature between 150 degrees Celsius and 250 degrees Celsius before forming the photoresist layer.

10. The method of claim 8, wherein diffusing the small molecules comprises heating the selectively exposed photoresist layer and the photoresist bottom layer at a temperature between 50 degrees Celsius and 200 degrees Celsius before developing the selectively exposed photoresist layer. The method of claim 8 , wherein the photoresist layer comprises an organic metal material.

12. The method of claim 8, wherein the actinic radiation is extreme ultraviolet radiation.

13. The method of claim 8, wherein the small molecule is different from the chemical reporter molecule.

14. A bottom layer composition, characterized in that: Include: A polymer comprising: A main polymer chain having a plurality of side chain target groups, a plurality of side chain organic groups or a plurality of side chain photoacid generator groups, wherein the main polymer chain is selected from the group consisting of polystyrene, polyhydroxystyrene, polyacrylate, polymethyl methacrylate, polyacrylic acid, polyvinyl ester, polymaleate, polymethacrylonitrile and polymethacrylamide, wherein the plurality of side chain target groups are one or more substituted or unsubstituted groups selected from the group consisting of: C2 to C30 diol groups, C1 to C30 aldehyde groups, and C3 to C30 ketone groups, wherein the plurality of side chain organic groups are C3 to C30 aliphatic or aromatic groups having at least one photosensitive functional group, wherein the photosensitive functional group is selected from the group consisting of an epoxy group, an azo group, an alkyl halide group, an imine group, an alkenyl group, an alkynyl group, a peroxide group, and a combination thereof, and wherein the plurality of side chain photoacid generator groups are selected from the group consisting of onium salts, sulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorobutanesulfonate, dimethylsulfonium trifluoromethanesulfonate, iodonium salts, diphenyliodonium perfluorobutanesulfonate, norbornene dicarboximido perfluorobutanesulfonate, fluorinated triazines, diazonium salts, aromatic diazonium salts, phosphonium salts, imide sulfonates, oxime sulfonates, diazo disulfones, disulfones, o-nitrobenzylmethyl sulfonates, sulfonated esters, halogenated sulfonyloxy dicarboximides, α-cyanooxyamine sulfonates, ketodiazo sulfones, sulfonyldiazo esters, 1,2-bis(arylsulfonyl)hydrazides, nitrobenzyl esters, and s-triazines; The photosensitive functional group is configured to release a chemical reporter molecule upon exposure to actinic radiation, and the chemical reporter molecule is transferred from the photosensitive functional group to the plurality of pendant target groups to generate water.

15. The bottom layer composition as claimed in claim 14, further comprising a photobase generator.

16. The bottom layer composition as claimed in claim 14, further comprising a photoacid generator compound.

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