Photoresist compositions and methods of forming photoresist patterns

Abstract

The present invention relates to a photoresist composition and a method of forming a photoresist pattern. The method for forming a photoresist pattern includes forming a photoresist layer comprising a photoresist composition on a substrate. The photoresist composition includes metal particles and a thermally stable ligand attached to the metal particles. The thermally stable ligand comprises a branched or unbranched, cyclic or acyclic, C1-C7 alkyl or C1-C7 fluoroalkyl. The C1-C7 alkyl or C1-C7 fluoroalkyl comprises one or more of the following: -CF3, -SH, -OH, =O, -S-, -P-, -PO2, -C(=O)SH, -C(=O)OH, -C(=O)O-, -O-, -N-, -C(=O)NH, -SO2OH, -SO2SH, -SOH, or -SO2-.

Description

[0001] This application is a divisional application of the invention patent application filed on November 26, 2020, with application number 202011350050.4 and invention title "Photoresist Composition and Method for Forming Photoresist Pattern".

[0002] Cross-reference to related applications This application claims priority to U.S. Provisional Patent Application No. 62 / 941,486, filed November 27, 2019, the entire disclosure of which is incorporated herein by reference. Background Technology

[0003] As consumer devices become smaller in response to consumer demand, the size of their components must also decrease. The semiconductor devices that make up the main components of devices such as mobile phones and tablet computers have been forced to become smaller, which in turn forces the size of the individual components within the semiconductor devices (e.g., transistors, resistors, capacitors, etc.) to also decrease.

[0004] One enabling technology used in the manufacturing process of semiconductor devices is the use of photolithography materials. These materials are applied to the surface of the layer to be patterned and then exposed to energy that has already patterned itself. This exposure alters the chemical and physical properties of the exposed areas of the photosensitive material. This alteration, along with the lack of alteration in the unexposed areas of the photosensitive material, can be used to remove one area without removing another.

[0005] However, as the size of individual devices decreases, the process window for photolithography becomes increasingly tight. Thus, advancements in photolithography are necessary to maintain the ability to scale down devices, and further improvements are needed to meet desired design standards so that progress can continue toward ever smaller parts.

[0006] As the semiconductor industry has progressed to nanometer technology nodes in pursuit of higher device density, higher performance, and lower costs, challenges remain in reducing semiconductor feature sizes. Extreme ultraviolet lithography (EUVL) has been developed to form smaller semiconductor device feature sizes and increase device density on semiconductor wafers. To improve EUVL, wafer exposure throughput needs to be increased. Wafer exposure throughput can be increased by increasing exposure power or increasing the photoresist light velocity. Low exposure doses can lead to reduced linewidth resolution and decreased critical dimensional uniformity. Summary of the Invention

[0007] According to one embodiment of the present invention, a photoresist composition is provided, the photoresist composition comprising: Metal particles, wherein the metal particles comprise at least one of zinc, zirconium, cobalt, manganese, iron, strontium, tungsten, vanadium, tin, hafnium, indium, cadmium, niobium, cesium, barium, lanthanum, cerium, antimony, and their oxides; and Ligands attached to the metal particles, The ligands described herein include C1-C7 alkyl or C1-C7 fluoroalkyl groups. The C1-C7 alkyl or C1-C7 fluoroalkyl group is branched or unbranched, cyclic or acyclic, and The C1-C7 alkyl or C1-C7 fluoroalkyl group comprises one or more of -C(=O)SH, -SO2SH and -SOH.

[0008] According to another embodiment of the present invention, a photoresist composition is provided, the photoresist composition comprising: A metal core, wherein the metal core comprises at least one selected from zinc, zirconium, cobalt, manganese, iron, strontium, tungsten, vanadium, tin, hafnium, indium, cadmium, niobium, cesium, barium, lanthanum, cerium, antimony, and their oxides; and The first ligand attached to the metal core, The first ligand comprises branched or unbranched, cyclic or acyclic C1-C7 alkyl or C1-C7 fluoroalkyl groups, and The C1-C7 alkyl or C1-C7 fluoroalkyl group comprises one or more of -C(=O)SH, -SO2SH, and -SOH; and The second ligand attached to the metal core, The second ligand is a material different from the first ligand.

[0009] According to another embodiment of the present invention, a photoresist composition is provided, the photoresist composition comprising: Metal nanoparticles, wherein the metal nanoparticles comprise at least one of zinc, zirconium, cobalt, manganese, iron, strontium, tungsten, vanadium, tin, hafnium, indium, cadmium, niobium, cesium, barium, lanthanum, cerium, antimony, and their oxides; and Ligands attached to the metal nanoparticles, The ligands described herein comprise branched or unbranched, cyclic or acyclic C1-C7 alkyl or C1-C7 fluoroalkyl groups, and The C1-C7 alkyl or C1-C7 fluoroalkyl group comprises one or more of -C(=O)SH, -SO2SH, and -SOH; and Solvent. Attached Figure Description

[0010] This disclosure will be best understood from the following detailed description when read in conjunction with the accompanying drawings. It should be emphasized that, in accordance with standard industry practice, the various features are not drawn to scale and are for illustrative purposes only. In fact, the dimensions of the various features may be arbitrarily increased or decreased for clarity of discussion.

[0011] Figure 1 The baking of the metal core and ligands in the corrosion inhibitor composition is shown.

[0012] Figure 2 A process flow for manufacturing a semiconductor device according to an embodiment of the present disclosure is shown.

[0013] Figure 3 The sequential operation of process stages according to one embodiment of the present disclosure is shown.

[0014] Figure 4A and Figure 4B The sequential operation of process stages according to one embodiment of the present disclosure is shown.

[0015] Figure 5 The sequential operation of process stages according to one embodiment of the present disclosure is shown.

[0016] Figure 6A and Figure 6B The sequential operation of process stages according to one embodiment of the present disclosure is shown.

[0017] Figure 7A and Figure 7B The sequential operation of process stages according to one embodiment of the present disclosure is shown.

[0018] Figure 8A and Figure 8B The ligand components of the resist composition according to some embodiments of the present disclosure are shown.

[0019] Figure 9A and Figure 9B The preparation of metal core / ligand complexes according to some embodiments of the present disclosure is shown.

[0020] Figure 10 The sequential operation of process stages according to one embodiment of the present disclosure is shown.

[0021] Figure 11A and Figure 11B The sequential operation of process stages according to one embodiment of the present disclosure is shown.

[0022] Figure 12 The sequential operation of process stages according to one embodiment of the present disclosure is shown.

[0023] Figure 13A and Figure 13B The sequential operation of process stages according to one embodiment of the present disclosure is shown.

[0024] Figure 14A and Figure 14B The sequential operation of process stages according to one embodiment of the present disclosure is shown. Detailed Implementation

[0025] It should be understood that the following disclosure provides many different embodiments or examples for implementing various features of this disclosure. Specific embodiments or examples of components and arrangements are described below to simplify this disclosure. Of course, these are merely examples and are not intended to be limiting. For example, the dimensions of elements are not limited to the disclosed range or values, but may depend on process conditions and / or desired characteristics of the device. Furthermore, the following description of forming a first feature above or on a second feature may include embodiments in which the first and second features are formed in direct contact, and may also include embodiments in which an additional feature may be formed between the first and second features such that the first and second features are not in direct contact. For simplicity and clarity, various features may be drawn at any scale.

[0026] Furthermore, for ease of description, spatial relative terms such as "below," "below," "under," "lower part," "above," and "upper part" are used herein to describe the relationship between one element or feature and one or more other elements or features as shown in the figures. In addition to the orientations depicted in the figures, spatial relative terms are also intended to cover different orientations of the device in use or operation. The device may be oriented in other ways (rotated 90 degrees or in other orientations), and the spatial relative descriptive terms used herein may be interpreted accordingly. Additionally, the term "made of" may mean "comprising" or "consisting of."

[0027] Metal-containing photoresists are ideal as photoresists with high sensitivity and high etch selectivity. The metal particles in metal-containing photoresists absorb high-energy photons, such as extreme ultraviolet (EUV) photons. Metal-containing photoresists comprise metal particles and ligands complexed to the metal particles. In some embodiments, the metal particles are nanoparticles, and in other embodiments, the metal particles are metal oxide particles. Figure 1A metal core 205 is shown, comprising one or more metal nanoparticles complexed with a plurality of ligand units 210, thereby forming a ligand-complexed metal core 200. During the baking of the photoresist layer (e.g., pre-exposure baking or post-exposure baking), the ligand units 210 can condense, which can lead to the formation of dross residue in the photoresist pattern after development. Thermally stable ligands are required to prevent ligand condensation during the baking operation and to inhibit dross formation in the photoresist pattern. Figure 1 As shown, since the thermally stable ligands do not condense during the baking operation, the ligand-complexed metal core 200 remains separated after baking.

[0028] Figure 2 A process flow 100 for manufacturing a semiconductor device according to embodiments of the present disclosure is shown. In operation S110, a photoresist composition is prepared. In some embodiments, the photoresist is a thermally stable photoresist. In some embodiments, the thermally stable photoresist composition is prepared by introducing a thermally stable ligand into a metal-containing photoresist composition. In other embodiments, the thermally stable ligand is mixed with another different ligand, and the two different ligands together form a complex of a metal core and a ligand.

[0029] In some embodiments, in operation S120, a resist composition is applied to the surface of the layer or substrate 10 to be patterned to form a resist layer 15, such as... Figure 3 As shown. In some embodiments, the resist layer 15 is a photoresist layer. Then, in some embodiments, the resist layer 15 undergoes a first baking operation S130 to evaporate the solvent in the resist composition. The resist layer 15 is baked (pre-baked) at a temperature and time sufficient to cure and dry the resist layer 15. In some embodiments, the resist layer is heated to a temperature of about 40°C and 120°C for about 10 seconds to about 10 minutes.

[0030] After the first (or pre)baking operation S130, the photoresist layer 15 is selectively exposed to photochemical radiation 45 / 97 in operation S130 (see...). Figure 4A and Figure 4B In some embodiments, the photoresist layer 15 is selectively exposed to ultraviolet radiation. In some embodiments, the ultraviolet radiation is deep ultraviolet radiation (DUV). In some embodiments, the ultraviolet radiation is extreme ultraviolet radiation (EUV). In some embodiments, the photochemical radiation is an electron beam.

[0031] In some implementations, such as Figure 4AAs shown, exposure radiation 45 passes through the photomask 30 before irradiating the photoresist layer 15. In some embodiments, the photomask has a pattern to be replicated in the photoresist layer 15. In some embodiments, this pattern is formed by an opaque pattern 35 on the photomask substrate 40. The opaque pattern 35 may be formed of a material that is opaque to ultraviolet radiation (e.g., chromium), while the photomask substrate 40 may be formed of a material that is transparent to ultraviolet radiation (e.g., fused silica).

[0032] In some embodiments, extreme ultraviolet (EUV) lithography is used to perform selective exposure of the photoresist layer 15 to form exposed regions 50 and unexposed regions 52. In some embodiments, such as Figure 4B As shown, in extreme ultraviolet (EUV) lithography, a reflective photomask 65 is used to form patterned exposure light. The reflective photomask 65 includes a low thermal expansion glass substrate 70 on which a Si and Mo reflective multilayer 75 is formed. A capping layer 80 and an absorption layer 85 are formed on the reflective multilayer 75. A post-conductive layer 90 is formed on the back side of the low thermal expansion substrate 70. In EUV lithography, EUV radiation 95 is incident on the reflective photomask 65 at an angle of approximately 6°. A portion 97 of the EUV radiation is reflected by the Si / Mo multilayer 75 toward the photoresist-coated substrate 10, while a portion of the EUV radiation incident on the absorption layer 85 is absorbed by the photomask. In some embodiments, additional optical devices, including mirrors, are located between the reflective photomask 65 and the photoresist-coated substrate.

[0033] The areas of the photoresist layer exposed to radiation 50 undergo a chemical reaction, thereby altering its solubility in a subsequently applied developer relative to the areas of the photoresist layer not exposed to radiation 52. In some embodiments, the portions of the photoresist layer exposed to radiation 50 undergo a crosslinking reaction.

[0034] Next, in operation S150, the photoresist layer 15 undergoes a second baking operation (or post-exposure baking). In some embodiments, the photoresist layer 15 is heated to temperatures of approximately 70°C and 160°C for approximately 20 seconds to approximately 120 seconds. Post-exposure baking can be used to assist in the generation, dispersion, and reaction of acids / bases / free radicals generated during exposure when radiation 45 / 97 strikes the photoresist layer 15. This assistance helps to generate or enhance chemical reactions that create chemical differences between the exposed regions 50 and unexposed regions 52 within the photoresist layer. These chemical differences also result in differences in solubility between the exposed regions 50 and unexposed regions 52.

[0035] Subsequently, in operation S160, the selectively exposed photoresist layer is developed by applying a developer to it. For example... Figure 5As shown, developer 57 is supplied from dispenser 62 to photoresist layer 15. In some embodiments, when the photoresist is a negative photoresist, the unexposed portions of photoresist layer 52 are removed by developer 57, thereby forming an opening pattern 55a in photoresist layer 15 to expose substrate 10, such as... Figure 6A As shown. In other embodiments, when the photoresist is a positive photoresist, the exposed portion of the photoresist layer 50 is removed by the developer 57, thereby forming an opening pattern 55b in the photoresist layer 15 to expose the substrate 10, as shown. Figure 6B As shown.

[0036] In some embodiments, the opening patterns 55a, 55b in the photoresist layer 15 extend into the layer or substrate 10 to be patterned, thereby generating opening patterns 55a', 55b' in the substrate 10, thus transferring the pattern in the photoresist layer 15 to the substrate 10, such as... Figure 7A and Figure 7B As shown. Using one or more suitable etchants, the pattern is extended into the substrate by etching. In some embodiments, at least a portion of the photoresist layer 15 remaining after the development operation is removed during the etching operation. In other embodiments, after etching the substrate 10, the remaining photoresist layer 15 is removed by using a suitable photoresist stripping solvent or by a photoresist ashing operation.

[0037] In some embodiments, substrate 10 includes a single-crystal semiconductor layer on at least its surface portion. Substrate 10 may comprise a single-crystal semiconductor material, such as, but not limited to, Si, Ge, SiGe, GaAs, InSb, GaP, GaSb, InAlAs, InGaAs, GaSbP, GaAsSb, and InP. In some embodiments, substrate 10 is a silicon layer of an SOI (silicon-on-insulator) substrate. In some embodiments, substrate 10 is made of crystalline Si.

[0038] The substrate 10 may include one or more buffer layers (not shown) in its surface region. The buffer layers can be used to gradually change the lattice constant from that of the substrate to the lattice constant of the subsequently formed source / drain regions. The buffer layers may be formed from epitaxially grown single-crystal semiconductor materials, such as, but not limited to, Si, Ge, GeSn, SiGe, GaAs, InSb, GaP, GaSb, InAlAs, InGaAs, GaSbP, GaAsSb, GaN, GaP, and InP. In one embodiment, a silicon-germanium (SiGe) buffer layer is epitaxially grown on the silicon substrate 10. The germanium concentration of the SiGe buffer layer can increase from 30 atomic percent in the bottom buffer layer to 70 atomic percent in the top buffer layer.

[0039] In some embodiments, the substrate 10 includes one or more layers of at least one metal, metal alloy, and having the formula MX. a The substrate 10 comprises a metal / nitride / sulfide / oxide / silicide, wherein M is a metal and X is N, S, Se, O, Si, and a is about 0.4 to about 2.5. In some embodiments, the substrate 10 comprises titanium, aluminum, cobalt, ruthenium, titanium nitride, tungsten nitride, tantalum nitride, and combinations thereof.

[0040] In some embodiments, the substrate 10 includes a dielectric having at least the form MX b The substrate 10 comprises silicon or a metal oxide or metal nitride, wherein M is a metal or Si, X is N or O, and b ranges from about 0.4 to about 2.5. In some embodiments, the substrate 10 comprises silicon dioxide, silicon nitride, aluminum oxide, hafnium oxide, lanthanum oxide, and combinations thereof.

[0041] In some embodiments, substrate 10 refers to any underlying layer on which a resist layer is formed. Substrate 10 is then patterned using photolithography and etching operations.

[0042] The photoresist layer 15 is a photosensitive layer patterned by exposure to photochemical radiation. Typically, the chemical properties of the photoresist regions impacted by incident radiation change in a manner depending on the type of photoresist used. The photoresist layer 15 is either a positive or negative photoresist. A positive photoresist is a photoresist material that becomes soluble in a developer when exposed to radiation (such as ultraviolet light), while the unexposed (or less exposed) areas of the photoresist are insoluble in the developer. Conversely, a negative photoresist is a photoresist material that becomes insoluble in a developer when exposed to radiation, while the unexposed (or less exposed) areas of the photoresist are soluble in the developer. Areas of a negative photoresist that become insoluble upon exposure to radiation may be due to a cross-linking reaction caused by the radiation exposure.

[0043] Whether a photoresist is positive or negative depends on the type of developer used to develop it. For example, when the developer is water-based (e.g., tetramethylammonium hydroxide (TMAH) solution), some positive photoresists provide a positive pattern (i.e., exposed areas are removed by the developer). On the other hand, when the developer is an organic solvent, the same photoresist provides a negative pattern (i.e., unexposed areas are removed by the developer). Furthermore, in some negative photoresists developed with TMAH solution, the unexposed areas of the photoresist are removed by TMAH, and the exposed areas of the photoresist that have undergone cross-linking after exposure to photochemical radiation remain on the substrate after development.

[0044] The resist compositions according to this disclosure are metal-containing resists. The metal-containing resists of this disclosure include a metal core complexed with one or more ligands in a solvent. In some embodiments, the resist comprises metal particles. In some embodiments, the metal particles are nanoparticles. As used herein, nanoparticles are particles with an average particle size of about 1 nm to about 20 nm. In some embodiments, a metal core comprising 1 to about 18 metal particles is complexed with one or more organic ligands in a solvent. In some embodiments, the metal core comprises 3, 6, 9, or more metal nanoparticles complexed with one or more organic ligands in a solvent.

[0045] In some embodiments, the metal particles are one or more of the following: titanium (Ti), zinc (Zn), zirconium (Zr), nickel (Ni), cobalt (Co), manganese (Mn), copper (Cu), iron (Fe), strontium (Sr), tungsten (W), vanadium (V), chromium (Cr), tin (Sn), hafnium (Hf), indium (In), cadmium (Cd), molybdenum (Mo), tantalum (Ta), niobium (Nb), aluminum (Al), cesium (Cs), barium (Ba), lanthanum (La), cerium (Ce), silver (Ag), antimony (Sb), combinations thereof, or oxides thereof. In some embodiments, the metal particles comprise one or more selected from the group consisting of: Ce, Ba, La, Ce, In, Sn, Ag, Sb, and oxides thereof.

[0046] In some embodiments, the average particle size of the metal nanoparticles is between about 2 nm and about 5 nm. In some embodiments, the amount of metal nanoparticles in the resist composition ranges from about 0.5 wt% to about 15 wt% based on the weight of the nanoparticles and solvent. In some embodiments, the amount of nanoparticles in the resist composition ranges from about 5 wt% to about 10 wt% based on the weight of the nanoparticles and solvent. In some embodiments, the concentration of metal particles ranges from 1 wt% to 7 wt% based on the weight of the solvent and metal particles. When the amount of metal nanoparticles is less than about 0.5 wt%, the resist coating is too thin. When the amount of metal nanoparticles is greater than about 15 wt%, the resist coating is too thick and viscous.

[0047] In some embodiments, the metal core is complexed with a thermally stable ligand (or a first ligand), wherein the thermally stable ligand comprises a branched or unbranched, cyclic or acyclic saturated organic group, including C1-C7 alkyl or C1-C7 fluoroalkyl groups. The C1-C7 alkyl or C1-C7 fluoroalkyl groups comprise one or more substituents selected from the group consisting of: -CF3, -SH, -OH, =O, -S-, -P-, -PO2, -C(=O)SH, -C(=O)OH, -C(=O)O-, -O-, -N-, -C(=O)NH, -SO2OH, -SO2SH, -SOH, and -SO2-. In some embodiments, the thermally stable ligand comprises one or more substituents selected from the group consisting of: -CF3, -OH, -SH, and -C(=O)OH substituents. The thermally stable ligand is a ligand that does not substantially react or condense with each other during pre-exposure baking or post-exposure baking.

[0048] Examples of C1-C7 thermally stable ligands are in Figure 8A and Figure 8B As shown in the diagram, thermally stable ligands are attached to the metal core. If the number of carbon atoms in the thermally stable ligand is greater than 7, the ligand may impair extreme ultraviolet radiation absorption.

[0049] In some embodiments, the metal particles are complexed with a second ligand. The second ligand differs from the first ligand or the thermally stable ligand. In some embodiments, the second ligand is a carboxylic acid or sulfonic acid ligand. For example, in some embodiments, the second ligand is methacrylic acid. In some embodiments, the metal particles are nanoparticles, and the metal nanoparticles are complexed with a ligand comprising an aliphatic or aromatic group. The aliphatic or aromatic group may be unbranched or branched, having cyclic or acyclic saturated side groups containing 1-9 carbons, including alkyl, alkenyl, and phenyl groups. The branched group may be further substituted with oxygen or halogen. In some embodiments, the second ligand is a branched or unbranched, aliphatic or aromatic, substituted or unsubstituted carboxylic acid or sulfonic acid ligand, wherein when the second ligand is substituted, the substituent is selected from one or more of C1-C9 alkyl, C2-C9 alkenyl, or C6-C9 phenyl groups.

[0050] In some embodiments, the concentration of the thermally stable ligand in the resist composition ranges from 7 wt% to 99 wt% based on the total weight of the thermally stable ligand and the second ligand. In some embodiments, the concentration of the thermally stable ligand ranges from 15 wt% to 85 wt% based on the total weight of the thermally stable ligand and the second ligand.

[0051] In some embodiments, each metal particle is complexed with 1 to 25 ligand units. In some embodiments, each metal particle is complexed with 3 to 18 ligand units.

[0052] In some embodiments, the resist composition comprises about 0.1 wt% to about 20 wt% of a thermally stable ligand and a second ligand, based on the total weight of the resist composition. In some embodiments, the resist comprises about 1 wt% to about 10 wt% of a thermally stable ligand and a second ligand. In some embodiments, the ligand concentration is about 10 wt% to about 40 wt% based on the weight of the metal particles and the ligand. When the ligand concentration is below about 10 wt%, the organometallic photoresist does not function well. When the ligand concentration is above about 40 wt%, it is difficult to form a uniform photoresist layer. In some embodiments, the one or more ligands are dissolved in a coating solvent (e.g., propylene glycol methyl ether acetate (PGMEA)) at a weight range of about 5 wt% to about 10 wt%, based on the weight of the one or more ligands and the solvent.

[0053] The solvent for the resist composition can be any suitable solvent. In some embodiments, the solvent is one or more of the following: propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, acetone, dimethylformamide (DMF), isopropanol (IPA), tetrahydrofuran (THF), methyl isobutyl methanol (MIBC), n-butyl acetate (nBA), or 2-heptanone (MAK).

[0054] Figure 9A and Figure 9B The preparation of metal core / ligand complexes according to some embodiments of the present disclosure is illustrated. Example A shows a mixture of a plurality of metal cores having attached second ligands and a plurality of metal cores having attached thermally stable ligands. The metal cores and ligands are synthesized to form thermally stable organometallic complexes. Example B is similar to Example A. In Example B, two thermally stable organometallic complexes are combined with each other to produce a larger thermally stable complex.

[0055] The resist composition according to embodiments of this disclosure comprises metal particles complexed in a solvent by thermally stable ligands. Some embodiments also include a second ligand.

[0056] In some embodiments, a metal core / ligand complex is formed by mixing metal particles with ligands. In some embodiments, the metal core / ligand complex forms spontaneously when the metal particles and ligands are mixed. In other embodiments, the mixture of metal particles and ligands is heated to a temperature of about 80°C to about 150°C for about 30 seconds to about 240 seconds to form the metal core / ligand complex.

[0057] In some embodiments, the resist composition according to embodiments of this disclosure, such as a photoresist, comprises a polymer or polymerizable monomer or oligomer and one or more photoactive compounds (PACs). In some embodiments, the concentration of the polymer, monomer, or oligomer is in the range of about 1% by weight to about 75% by weight, based on the total weight of the resist composition. In other embodiments, the concentration of the polymer, monomer, or oligomer is in the range of about 5% by weight to about 50% by weight. When the concentration of the polymer, monomer, or oligomer is below the disclosed range, the polymer, monomer, or oligomer has a negligible effect on the resist performance. At concentrations above the disclosed range, there is no substantial improvement in resist performance, or there is deterioration in the formation of a consistent resist layer.

[0058] In some embodiments, the polymerizable monomer or oligomer includes acrylic acid, acrylates, hydroxystyrene, or alkylene. In some embodiments, the polymer includes a hydrocarbon structure (e.g., an alicyclic hydrocarbon structure) containing one or more groups that would decompose (e.g., acid-labile groups) or otherwise react with acids, bases, or free radicals generated by PAC (further described below). In some embodiments, the hydrocarbon structure includes repeating units that form the backbone of the polymer resin. These repeating units may include acrylates, methacrylates, crotonates, vinyl esters, maleate diesters, fumarate diesters, itaconic acid diesters, (meth)acrylonitrile, (meth)acrylamide, styrene, vinyl ethers, combinations thereof, etc.

[0059] In some embodiments, the specific structure of the repeating unit for the hydrocarbon structure includes one or more of the following: methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-alkyl-2-adamantyl (meth)acrylate or dialkyl (1-adamantyl) methyl acrylate, methyl methacrylate, methyl acrylate, etc. Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, acetoxyethyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-acetoxy-2-hydroxypropyl methacrylate, 3-chloroacetoxy-2-hydroxypropyl methacrylate, butyl crotonate, hexyl crotonate, etc. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, acrylamide, methacrylamide, ethyl acrylamide, propyl acrylamide, n-butyl acrylamide, tert-butyl acrylamide, cyclohexyl acrylamide, 2-methoxyethyl acrylamide, and dimethyl acrylamide. Diethylacrylamide, phenylacrylamide, benzylacrylamide, methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, n-butylmethacrylamide, tert-butylmethacrylamide, cyclohexylmethacrylamide, 2-methoxyethylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, phenylmethacrylamide, benzylmethacrylamide, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc. Examples of styrene include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, methoxystyrene, butoxystyrene, acetoxystyrene, hydroxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinyl methyl benzoate, α-methylstyrene, maleimide, vinylpyridine, vinylpyrrolidone, vinylcarbazole, and combinations thereof.

[0060] In some embodiments, the polymer is polyhydroxystyrene, polymethyl methacrylate, or polyhydroxystyrene tert-butyl acrylate, for example. . In some embodiments, the repeating unit of the hydrocarbon structure also has a monocyclic or polycyclic hydrocarbon structure that substitutes for it, or the monocyclic or polycyclic hydrocarbon structure is the repeating unit, so as to form an alicyclic hydrocarbon structure. In some embodiments, specific examples of monocyclic structures include bicyclic alkanes, tricyclic alkanes, tetracyclic alkanes, cyclopentane, cyclohexane, etc. In some embodiments, specific examples of polycyclic structures include adamantane, norcamphene, isocamphene, tricyclic decane, tetracyclic dodecane, etc.

[0061] The decomposed group (also called a leaving group, or, in some embodiments where the PAC is a photoacid generator, an acid-labile group) is attached to the hydrocarbon structure, so that the group will react with the acid / base / free radical generated by the PAC during exposure. In some embodiments, the decomposed group is a carboxylic acid group, a fluorinated alcohol group, a phenolic alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonyl imide group, a (alkylsulfonyl)(alkylcarbonyl)methylene group, a (alkylsulfonyl)(alkyl-carbonyl)imino group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imino group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imino group, a tri(alkylcarbonyl)methylene group, a tri(alkylsulfonyl)methylene group, a combination of these, etc. Specific groups used for fluorinated alcohol groups include fluorinated hydroxyalkyl groups, such as hexafluoroisopropanol groups in some embodiments. Specific groups used for carboxylic acid groups include acrylic acid groups, methacrylic acid groups, etc.

[0062] In some embodiments, the polymer also includes other groups attached to the hydrocarbon structure, which contribute to improving various properties of the polymerizable resin. For example, including a lactone group on the hydrocarbon structure helps reduce the amount of line edge roughness after the photoresist has been developed, thereby helping to reduce the number of defects occurring during development. In some embodiments, the lactone group comprises a ring having five to seven members, but any suitable lactone structure can be alternatively used for the lactone group.

[0063] In some embodiments, the polymer includes groups that help increase the adhesion of the photoresist layer 15 to the underlying structure (e.g., substrate 10). Polar groups can be used to help increase adhesion. Suitable polar groups include hydroxyl, cyano, etc., but any suitable polar group can be used alternatively.

[0064] In some embodiments, optionally, the polymer comprises one or more alicyclic hydrocarbon structures that do not contain any groups that will decompose. In some embodiments, the hydrocarbon structures that do not contain any groups that will decompose comprise, for example, structures such as 1-adamantyl (meth)acrylate, tricyclodecyl (meth)acrylate, cyclohexyl (meth)acrylate, and combinations thereof.

[0065] Some embodiments of photoresists include one or more photoactive compounds (PACs). PACs are photoactive components, such as photoacid generators (PAGs), photoalkali generators (PBGs), photodegradable bases (PDBs), free radical generators, etc. PACs can have positive or negative effects. In some embodiments where the PAC is a photoacid generator, the PAC includes triazine halides, onium salts, diazonium salts, aromatic diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, disulfones, o-nitrobenzyl sulfonates, sulfonated esters, halosulfonyloxydicarboximides, diazonium sulfones, α-cyanooxyamine sulfonates, imide sulfonates, ketone diazonium sulfones, sulfonyl diazonium esters, 1,2-di(arylsulfonyl)hydrazine, nitrobenzyl esters, and s-triazine derivatives, combinations thereof, etc.

[0066] Specific examples of photoacid-generating agents include α-(trifluoromethanesulfonyloxy)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (MDT), N-hydroxy-naphthaleneimide (DDSN), benzoin toluenesulfonate, tert-butylphenyl-α-(p-toluenesulfonyloxy)-acetate and tert-butyl-α-(p-toluenesulfonyloxy)-acetate, triarylsulfonium and diaryliodonium hexafluoroantimonate, hexafluoroarsenate, trifluoromethanesulfonate, iodonium perfluorooctane sulfonate, N-camphorsulfonyloxynaphthaleneimide, N-pentafluorobenzenesulfonyloxynaphthaleneimide, ionic iodonium sulfonate (e.g. diaryliodonium(alkyl) Aryl sulfonates or diaryl iodonium (aryl) sulfonates and bis-(di-tert-butylphenyl)iodonium camphene sulfonates), perfluoroalkane sulfonates (e.g., perfluoropentane sulfonate, perfluorooctane sulfonate, perfluoromethane sulfonate), aryl (e.g., phenyl or benzyl) trifluoromethane sulfonates (e.g., triphenylsulfonium trifluoromethane sulfonate or bis-(tert-butylphenyl)iodonium trifluoromethane sulfonate); pyrogallol derivatives (e.g., trimethyl sulfonate of pyrogallol), trifluoromethane sulfonates of hydroxyimide, α,α'-bis-sulfonyl-diazomethane, sulfonates of nitro-substituted benzyl alcohol, naphthoquinone-4-diazide, alkyl disulfone, etc.

[0067] In some embodiments where PAC is a free radical generator, PAC includes n-phenylglycine; aromatic ketones, including benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, p,p'-bis(dimethylamino)benzophenone, p,p'-bis(diethylamino)- Benzophenone; anthraquinones, 2-ethylanthraquinone; naphthoquinones; and phenanthrenequinones; benzoin derivatives, including benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin-phenyl ether, methylbenzoin, and ethylbenzoin; benzyl derivatives, including dibenzyl, benzyl diphenyl disulfide, and benzyl dimethyl ketal; acridine derivatives, including 9-phenyl acridine and 1,7-bis(9-acridyl)heptane; thioxanthones, including 2-chlorothioxanthone, 2-methylthioxanthone, 2,4- Diethylthioxanthone, 2,4-dimethylthioxanthone, and 2-isopropylthioxanthone; acetophenone, including 1,1-dichloroacetophenone, p-tert-butyldichloroacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2,2-dichloro-4-phenoxyacetophenone; 2,4,5-triarylimidazolium dimers, including 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl) Imidazole dimers, including 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimers, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium dimers, 2-(p-methoxyphenyl)-4,5-diphenylimidazolium dimers, 2,4-di(p-methoxyphenyl)-5-phenylimidazolium dimers, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazolium dimers, and 2-(p-methylmercaptophenyl)-4,5-diphenylimidazolium dimers; combinations thereof, etc.

[0068] In some embodiments, the PAC includes a quencher. In some embodiments, the quencher includes a photoalkali-generating agent and a photodegradable base. In embodiments where the PAC is a photoalkali-generating agent (PBG), the PBG includes quaternary ammonium dithiocarbamate, α-amino ketone, oxime-carbamate-containing molecules (e.g., dibenzoylbenzyl oxime hexamethylene dicarbamate), tetra-organoborate ammonium salts, and N-(2-nitrobenzyloxycarbonyl)cyclic amines, combinations thereof, etc.

[0069] In some embodiments where PAC is a photodegradable base (PBD), PBD includes triphenylsulfonium hydroxide, triphenylsulfonium antimony hexafluoride, and triphenylsulfonium trifyl.

[0070] In some embodiments, the concentration of the photoactive compound ranges from about 0.1 wt% to about 20 wt% based on the total weight of the resist composition. In other embodiments, the concentration of the photoactive compound ranges from about 1 wt% to about 15 wt%. When the concentration of the photoactive compound is below the disclosed range, the photoactive compound has a negligible effect on the resist performance. At concentrations above the disclosed range, there is no substantial improvement in the resist performance.

[0071] As those skilled in the art will recognize, the compounds listed herein are intended only as illustrative examples of PACs and are not intended to limit the implementation to only those specifically described. Rather, any suitable PAC can be used, and all such PACs are fully intended to be included within the scope of the embodiments of the invention.

[0072] In some embodiments, a crosslinking agent is added to the photoresist. The crosslinking agent reacts with a group from one hydrocarbon structure in the polymer and also with a second group from a separate hydrocarbon structure in the polymer, to crosslink and bond the two hydrocarbon structures together. This bonding and crosslinking increases the molecular weight of the polymer product of the crosslinking reaction and increases the overall bonding density of the photoresist. This increase in density and bonding density helps to improve the resist pattern.

[0073] In some embodiments, other additives in the photoresist composition include quenchers for neutralizing excess acid formed by photoacid-generating agents. In some embodiments, another additive is a stabilizer, which helps prevent undesirable diffusion of acid generated during photoresist exposure. Another additive in some embodiments of the photoresist is a dissolution inhibitor to help control dissolution of the photoresist during development. Another additive in some embodiments of the photoresist is a plasticizer. Plasticizers can be used to reduce delamination and cracking between the photoresist and the underlying layer (e.g., the layer to be patterned). Colorants are another additive included in some embodiments of the photoresist. Colorants help observers inspect the photoresist and identify any defects that may need to be corrected before further processing. Adhesion additives are added to some embodiments of the photoresist to promote adhesion between the photoresist and the underlying layer (e.g., the layer to be patterned) on which the photoresist has already been applied. In some embodiments of photoresist, surface leveling agents are added to help level the top surface of the photoresist so that incident light is not adversely modified by an unleveled surface.

[0074] In some embodiments, the polymer, monomer, or oligomer and PAC, along with any desired additives or other reagents, are added to a solvent for application. Once added, the mixture is blended to achieve a homogeneous composition throughout the photoresist, ensuring no defects arise due to uneven mixing or a heterogeneous composition of the photoresist. Once blended, the photoresist can be stored and used later or used immediately.

[0075] Once ready, apply the photoresist to the layer to be patterned, such as... Figure 3 As shown, for example, a photoresist layer 15 is formed on substrate 10. In some embodiments, the photoresist is applied using methods such as spin coating, dip coating, air knife coating, curtain coating, wire rod coating, concave coating, lamination, extrusion coating, and combinations thereof. In some embodiments, the thickness of the photoresist layer 15 is in the range of about 10 nm to about 300 nm.

[0076] In some embodiments, after the photoresist layer 15 has been applied to the substrate 10, a pre-baking of the photoresist layer is performed to cure and dry the photoresist before radiation exposure (see [link]). Figure 2 The curing and drying of the photoresist layer 15 removes the solvent, leaving behind organometallic compounds and optionally polymers, monomers, oligomers, photoactive compounds, and other selected additives. In some embodiments, pre-baking is performed at a temperature suitable for solvent evaporation (e.g., between about 40°C and 120°C), but the precise temperature depends on the material selected for the photoresist. Pre-baking is performed for a time sufficient to cure and dry the photoresist layer, for example, between about 10 seconds and about 10 minutes.

[0077] Figure 4A and Figure 4B Selective exposure of a photoresist layer is illustrated to form exposed regions 50 and unexposed regions 52. In some embodiments, exposure to radiation is performed by placing a photoresist-coated substrate in a photolithography tool. The photolithography tool includes a photomask 30 / 65, optics, an exposure radiation source providing radiation 45 / 97 for exposure, and a movable platform for supporting and moving the substrate under exposure radiation.

[0078] In some embodiments, a radiation source (not shown) supplies radiation 45 / 97 (e.g., ultraviolet light) to the photoresist layer 15, and this radiation is absorbed by metal particles or a photoactive compound to induce a reaction in the photoresist layer to chemically alter those regions of the photoresist layer struck by the radiation 45 / 97. In some embodiments, the radiation is electromagnetic radiation, such as gamma rays (wavelength about 436 nm), i-rays (wavelength about 365 nm), ultraviolet radiation, far ultraviolet radiation, extreme ultraviolet radiation, electron beams, etc. In some embodiments, the radiation source is selected from the group consisting of: mercury vapor lamps, xenon lamps, carbon arc lamps, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), or Sn plasma excited by a CO2 laser (extreme ultraviolet light, wavelength 13.5 nm).

[0079] In some embodiments, optics (not shown) are used in the photolithography tool to extend, reflect, or otherwise control the radiation 45 / 97 before or after it is patterned by the photomask 30 / 65. In some embodiments, the optics include one or more lenses, mirrors, filters, and combinations thereof to control the radiation 45 / 97 along the path of the optics.

[0080] In some embodiments, the photoresist layer 15 is exposed using immersion lithography. In such techniques, an immersion medium (not shown) is placed between the final optics and the photoresist layer, and exposure radiation 45 passes through the immersion medium.

[0081] In some embodiments, post-exposure baking is performed after the photoresist layer 15 has been exposed to exposure radiation 45 to promote reactions initiated during selective exposure to photochemical radiation. In some embodiments that include photoactive compounds, post-exposure baking facilitates the generation, dispersion, and reaction of acids / bases / free radicals generated during exposure when radiation 45 strikes the PAC. This thermal assistance helps to generate or enhance chemical reactions that create chemical differences between exposed regions 50 and unexposed regions 52 within the photoresist layer 15. These chemical differences also result in differences in solubility between exposed regions 50 and unexposed regions 52. In some embodiments, post-exposure baking occurs at a temperature ranging from about 70°C to about 160°C for a period between about 20 seconds and about 120 seconds.

[0082] In some embodiments, the photoresist developer 57 comprises a solvent and an acid or base. In some embodiments, the concentration of the solvent is from about 60% to about 99% by weight, based on the total weight of the photoresist developer. The concentration of the acid or base is from about 0.001% to about 20% by weight, based on the total weight of the photoresist developer. In some embodiments, the concentration of the acid or base in the developer is from about 0.01% to about 15% by weight, based on the total weight of the photoresist developer.

[0083] In some embodiments, the developer comprises a solvent selected from the group consisting of: propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, acetone, dimethylformamide (DMF), isopropanol (IPA), tetrahydrofuran (THF), methyl isobutyl methanol (MIBC), n-butyl acetate (nBA), 2-heptanone (MAK), and isobutyl propionate. In other embodiments, the developer is an aqueous solvent, including a tetramethylammonium hydroxide (TMAH) solution.

[0084] In some embodiments, a spin coating process is used to apply developer 57 onto photoresist layer 15. In the spin coating process, such as... Figure 5 As shown, while a substrate coated with photoresist is spin-coated, developer 57 is applied to the photoresist layer 15 from above the photoresist layer 15. In some embodiments, the developer is supplied at a rate between about 5 ml / min and about 800 ml / min, while the substrate coated with photoresist is spin-coated at a speed between about 100 rpm and about 2000 rpm. In some embodiments, the developer is at a temperature between about 10°C and about 80°C. In some embodiments, the developing operation lasts between about 30 seconds and about 10 minutes.

[0085] While spin coating is a suitable method for developing the photoresist layer 15 after exposure, it is intended to be illustrative and not to limit the implementation. Instead, any suitable development operation can be used, including immersion processes, puddle processes, and spray coating methods. All such development operations are included within the scope of this implementation.

[0086] During the development process, such as Figure 6AAs shown, developer 57 dissolves the unexposed radiation area 52 of the negative photoresist to form a pattern 55a, thereby exposing the surface of substrate 10 and leaving a well-defined exposed photoresist area 50 with improved clarity compared to that provided by conventional negative photoresist lithography. In other embodiments, such as Figure 6B As shown, developer 57 dissolves the radiation exposure area 50 of positive resist to form pattern 55b, thereby exposing the surface of substrate 10 and leaving a well-defined unexposed photoresist area 52, which has improved clarity compared to the clarity provided by conventional negative photoresist lithography.

[0087] After development operation S150, residual developer is removed from the substrate covered with patterned photoresist. In some embodiments, a spin-drying process is used to remove the residual developer, but any suitable removal technique can be used. After the photoresist layer 15 has been developed and the residual developer has been removed, additional processing is performed while the patterned photoresist layers 50, 52 are in place. For example, in some embodiments, an etching operation using dry etching or wet etching is performed to transfer the patterns 55a, 55b of the photoresist layers onto the underlying substrate 10, thereby forming recesses 55a', 55b', such as... Figure 7A and Figure 7B As shown. The substrate 10 has different etch resistance than the photoresist layer 15. In some embodiments, the etchant is more selective for the substrate 10 than for the photoresist layer 15.

[0088] In some embodiments, the substrate 10 and the photoresist layer 15 contain at least one anti-etching molecule. In some embodiments, the anti-etching molecule includes molecules with low Onish number structures, double bonds, triple bonds, silicon, silicon nitride, titanium, titanium nitride, aluminum, aluminum oxide, silicon oxynitride, combinations thereof, etc.

[0089] In some embodiments, the layer 60 to be patterned is disposed on the substrate before the photoresist layer is formed, such as... Figure 10 As shown. In some embodiments, the layer 60 to be patterned is a metallization layer, or a dielectric layer, such as a passivation layer, disposed above the metallization layer. In embodiments where the layer 60 to be patterned is a metallization layer, the layer 60 to be patterned is formed from a conductive material using metallization processes and metal deposition techniques (including chemical vapor deposition, atomic layer deposition, and physical vapor deposition (sputtering)). Similarly, if the layer 60 to be patterned is a dielectric layer, the layer 60 to be patterned can be formed using dielectric layer formation techniques including thermal oxidation, chemical vapor deposition, atomic layer deposition, and physical vapor deposition.

[0090] The photoresist layer 50 is then selectively exposed to photochemical radiation 45 to form exposed areas 50 and unexposed areas 52 within the photoresist layer, such as... Figure 11A and Figure 11B As shown and in conjunction with this article Figure 4A and Figure 4B As described.

[0091] like Figure 12 As shown, the photoresist layer 15 is developed by dispensing developer 57 from dispenser 62 to form a layer as shown in the diagram. Figure 13A and Figure 13B The photoresist opening patterns 55a and 55b are shown. In this document, the development operation is similar to the reference... Figures 5 to 6B The described development operation. In some embodiments, when the photoresist is a negative photoresist, the unexposed portions of the photoresist layer 52 are removed by the developer 57, thereby forming an opening pattern 55a in the photoresist layer 15 to expose the substrate 10, such as... Figure 13A As shown. In other embodiments, when the photoresist is a positive photoresist, the exposed portion of the photoresist layer 50 is removed by the developer 57, thereby forming an opening pattern 55b in the photoresist layer 15 to expose the substrate 10, as shown. Figure 13B As shown.

[0092] Then as Figure 14A and Figure 14B As shown, as referenced Figure 7A and Figure 7B As explained, the patterns 55a and 55b in the photoresist layer 15 are transferred to the patterned layer 60 using an etching operation, and the photoresist layer is removed to form patterns 55a'' and 55b'' in the patterned layer 60.

[0093] The novel photoresist composition and photolithographic patterning method of this disclosure provide higher semiconductor device feature resolution and density with a more efficient process, higher wafer exposure throughput, and reduced defects compared to conventional exposure techniques. The novel photoresist composition and method suppress dross formation after development, thereby providing improved photoresist pattern resolution. Photolithography operations using embodiments of this disclosure provide a dross formation reduction of more than 20% compared to photolithography operations without the embodiments of this disclosure.

[0094] This disclosure discloses a method for forming a photoresist pattern, the method comprising forming a photoresist layer comprising a photoresist composition on a substrate. The photoresist composition comprises metal particles and a thermally stable ligand attached to the metal particles. The thermally stable ligand comprises a branched or unbranched, cyclic or acyclic C1-C7 alkyl or C1-C7 fluoroalkyl group. The C1-C7 alkyl or C1-C7 fluoroalkyl group comprises one or more of the following: -CF3, -SH, -OH, =O, -S-, -P-, -PO2, -C(=O)SH, -C(=O)OH, -C(=O)O-, -O-, -N-, -C(=O)NH, -SO2OH, -SO2SH, -SOH, or -SO2-. The photoresist layer is selectively exposed to photochemical radiation, and the photoresist layer is developed to form a pattern in the photoresist layer. In one embodiment, the method includes heating the photoresist layer before selectively exposing it to photochemical radiation. In one embodiment, the photochemical radiation is an electron beam or extreme ultraviolet radiation. In one embodiment, the method includes heating the selectively exposed photoresist layer before developing it. In one embodiment, the metal particles are nanoparticles. In one embodiment, the metal particles comprise metal oxides. In one embodiment, the metal particles comprise one or more of the following: titanium, zinc, zirconium, nickel, cobalt, manganese, copper, iron, strontium, tungsten, vanadium, chromium, tin, hafnium, indium, cadmium, molybdenum, tantalum, niobium, aluminum, cesium, barium, lanthanum, cerium, silver, antimony, combinations thereof, or oxides thereof. In one embodiment, the photoresist composition comprises one or more solvents selected from the group consisting of propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, acetone, dimethylformamide (DMF), isopropanol (IPA), tetrahydrofuran (THF), methyl isobutyl methanol (MIBC), n-butyl acetate (nBA), or 2-heptanone (MAK). In one embodiment, the photoresist composition comprises a second ligand attached to the metal particles, wherein the second ligand is a material different from the thermally stable ligand. In one embodiment, the second ligand is a branched or unbranched, aliphatic or aromatic, substituted or unsubstituted carboxylic or sulfonic acid ligand, wherein when the second ligand is substituted, the substituent is selected from one or more of C1-C9 alkyl, C2-C9 alkenyl, C6-C9 phenyl, or combinations thereof.

[0095] Another embodiment of this disclosure is a method of manufacturing a semiconductor device, the method comprising forming a resist layer over a substrate; and forming a potential pattern in the resist layer. The pattern is formed in the resist layer by removing a portion of the resist layer, and the pattern in the resist layer is extended into the substrate. The resist layer includes a metal core and a first ligand attached to the metal core. The first ligand comprises a branched or unbranched, cyclic or acyclic saturated C1-C7 organic group, wherein the C1-C7 organic group comprises H or F, and one or more of -CF3, -SH, -OH, =O, -S-, -P-, -PO2, -C(=O)SH, -C(=O)OH, -C(=O)O-, -O-, -N-, -C(=O)NH, -SO2OH, -SO2SH, -SOH, and -SO2-. In one embodiment, extending the pattern into the substrate comprises etching the substrate. In one embodiment, the method includes heating the resist layer at a temperature of 70°C to 160°C after forming a latent pattern and before forming the pattern. In one embodiment, the method includes heating the resist layer at a temperature of 40°C to 120°C before forming the latent pattern. In one embodiment, the resist layer includes a second ligand attached to the metal core, wherein the second ligand is formed of a material different from the first ligand. In one embodiment, forming the resist layer includes depositing a resist composition on a substrate, wherein the resist composition includes: a metal core, a first ligand attached to the metal core, and a solvent. The concentration of metal particles is in the range of 0.5 wt% to 15 wt% based on the weight of the solvent and the metal core. In one embodiment, the concentration of the metal core is in the range of 1 wt% to 7 wt% based on the weight of the solvent and the metal core. In one embodiment, forming a latent pattern in the resist layer includes exposing the resist layer patternwise to extreme ultraviolet radiation or an electron beam. In one embodiment, the second ligand is a substituted or unsubstituted, branched or unbranched, aliphatic or aromatic carboxylic acid or sulfonic acid ligand, wherein the substituent is one or more of C1-C9 alkyl, C2-C9 alkenyl and C6-C9 phenyl.

[0096] Another embodiment of this disclosure includes a photoresist composition comprising metal particles and a first ligand attached to the metal particles. The first ligand comprises a branched or unbranched, cyclic or acyclic saturated C1-C7 organic group, wherein the C1-C7 organic group comprises H or F, and one or more of -CF3, -SH, -OH, =O, -S-, -P-, -PO2, -C(=O)SH, -C(=O)OH, -C(=O)O-, -O-, -N-, -C(=O)NH, -SO2OH, -SO2SH, -SOH, and -SO2-. In one embodiment, the metal particles are nanoparticles. In one embodiment, the metal particles comprise one or more of the following: titanium, zinc, zirconium, nickel, cobalt, manganese, copper, iron, strontium, tungsten, vanadium, chromium, tin, hafnium, indium, cadmium, molybdenum, tantalum, niobium, aluminum, cesium, barium, lanthanum, cerium, silver, antimony, combinations thereof, or oxides thereof. In one embodiment, the photoresist composition comprises a second ligand attached to the metal particles, wherein the second ligand is a material different from the first ligand. In one embodiment, the second ligand is a branched or unbranched, aliphatic or aromatic, substituted or unsubstituted carboxylic or sulfonic acid ligand, wherein when the second ligand is substituted, the substituent is selected from C1-C9 alkyl, C2-C9 alkenyl, C6-C9 phenyl, or combinations thereof. In one embodiment, the photoresist composition comprises a solvent. In one embodiment, the solvent is one or more of the following: propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, acetone, dimethylformamide (DMF), isopropanol (IPA), tetrahydrofuran (THF), methyl isobutyl methanol (MIBC), n-butyl acetate (nBA), or 2-heptanone (MAK). In one embodiment, the concentration of the metal particles is in the range of 0.5% by weight to 15% by weight, based on the solvent and the weight of the metal particles. In one embodiment, the metal particles comprise one or more of Cs, Ba, La, Ce, In, Sn, Ag, Sb, or their oxides. In one embodiment, the average particle size of the metal particles is between 2 nm and 5 nm.

[0097] Another embodiment of this disclosure is a method of manufacturing a semiconductor device, the method comprising forming a resist layer comprising a resist composition on a substrate. A pattern is formed in the resist layer, and the pattern is extended into the substrate. The resist composition comprises: a solvent, metal nanoparticles, a first ligand attached to the metal nanoparticles, and a second ligand attached to the metal nanoparticles. The first ligand comprises a branched or unbranched, cyclic or acyclic C1-C7 alkyl or C1-C7 fluoroalkyl group, wherein the C1-C7 alkyl or C1-C7 fluoroalkyl group comprises one or more of the following: -CF3, -SH, -OH, =O, -S-, -P-, -PO2, -C(=O)SH, -C(=O)OH, -C(=O)O-, -O-, -N-, -C(=O)NH, -SO2OH, -SO2SH, -SOH, or -SO2-. The second ligand is a branched or unbranched, aliphatic or aromatic, substituted or unsubstituted carboxylic or sulfonic acid ligand, wherein when the second ligand is substituted, the substituent is selected from one or more of C1-C9 alkyl, C2-C9 alkenyl, or C6-C9 phenyl, and the second ligand is a material different from the first ligand. In one embodiment, extending the pattern into the substrate includes etching the substrate. In one embodiment, forming the pattern includes selectively exposing the resist layer to extreme ultraviolet radiation or an electron beam; and applying a developer to the selectively exposed resist layer to remove a portion of the resist layer. In one embodiment, the method includes heating the resist layer at a temperature of 70°C to 160°C after selectively exposing the resist layer. In one embodiment, the method includes heating the resist layer at a temperature of 40°C to 120°C before selectively exposing the resist layer. In one embodiment, the metal nanoparticles comprise one or more of the following: titanium, zinc, zirconium, nickel, cobalt, manganese, copper, iron, strontium, tungsten, vanadium, chromium, tin, hafnium, cadmium, molybdenum, tantalum, niobium, aluminum, cesium, barium, lanthanum, cerium, indium, silver, antimony, their oxides, or alloys thereof. In one embodiment, the concentration of the metal nanoparticles is in the range of 0.5% by weight to 15% by weight, based on the solvent and the weight of the metal nanoparticles. In one embodiment, the resist composition comprises a second ligand, wherein the second ligand is a material different from the first ligand. In one embodiment, the second ligand is a branched or unbranched, aliphatic or aromatic, substituted or unsubstituted carboxylic or sulfonic acid ligand, wherein when the second ligand is substituted, the substituent is selected from one or more of C1-C9 alkyl, C2-C9 alkenyl, or C6-C9 phenyl, and combinations thereof. In one embodiment, the resist composition comprises a polymer or polymerizable monomer or oligomer.

[0098] Another embodiment of this disclosure is a photoresist composition comprising: a metal core, a first ligand attached to the metal core, and a second ligand attached to the metal core. The first ligand comprises a branched or unbranched, cyclic or acyclic C1-C7 alkyl or C1-C7 fluoroalkyl group, wherein the C1-C7 alkyl or C1-C7 fluoroalkyl group comprises one or more of the following: -CF3, -SH, -OH, =O, -S-, -P-, -PO2, -C(=O)SH, -C(=O)OH, -C(=O)O-, -O-, -N-, -C(=O)NH, -SO2OH, -SO2SH, -SOH, or -SO2-. The second ligand is a different material from the first ligand. In one embodiment, the metal core is formed of multiple nanoparticles. In one embodiment, the metal core comprises one or more of the following: titanium, zinc, zirconium, nickel, cobalt, manganese, copper, iron, strontium, tungsten, vanadium, chromium, tin, hafnium, cadmium, molybdenum, tantalum, niobium, aluminum, cesium, barium, lanthanum, cerium, indium, silver, antimony, oxides of these or alloys thereof. In one embodiment, the resist composition comprises a solvent, and the concentration of the metal core is in the range of 0.5% by weight to 15% by weight, based on the weight of the solvent and the metal core. In one embodiment, the concentration of the metal core is in the range of 1% by weight to 7% by weight, based on the weight of the solvent and the metal core. In one embodiment, the second ligand is a branched or unbranched, aliphatic or aromatic, substituted or unsubstituted carboxylic or sulfonic acid ligand, wherein when the second ligand is substituted, the substituent is selected from one or more of C1-C9 alkyl, C2-C9 alkenyl, or C6-C9 phenyl. In one embodiment, the concentration of the first ligand is in the range of 7 wt% to 99 wt% based on the total weight of the first and second ligands. In one embodiment, the concentration of the first ligand is in the range of 15 wt% to 85 wt% based on the total weight of the first and second ligands. In one embodiment, the resist composition comprises a polymer, a polymerizable monomer, or an oligomer. In one embodiment, the resist composition comprises a photoactive compound.

[0099] Another embodiment of this disclosure is a photoresist composition comprising: metal nanoparticles, a thermally stable ligand attached to the metal nanoparticles, a second ligand attached to the metal nanoparticles, and a solvent. The thermally stable ligand comprises branched or unbranched, cyclic or acyclic saturated C1-C7 organic groups, wherein the C1-C7 organic groups comprise H or F, and one or more of -CF3, -SH, -OH, =O, -S-, -P-, -PO2, -C(=O)SH, -C(=O)OH, -C(=O)O-, -O-, -N-, -C(=O)NH, -SO2OH, -SO2SH, -SOH, and -SO2-. The second ligand is a branched or unbranched, aliphatic or aromatic, substituted or unsubstituted carboxylic or sulfonic acid ligand, wherein when the second ligand is substituted, the substituent is selected from one or more of C1-C9 alkyl, C2-C9 alkenyl, or C6-C9 phenyl. In one embodiment, the metal nanoparticles comprise one or more of the following: titanium, zinc, zirconium, nickel, cobalt, manganese, copper, iron, strontium, tungsten, vanadium, chromium, tin, hafnium, cadmium, molybdenum, tantalum, niobium, aluminum, cesium, barium, lanthanum, cerium, indium, silver, antimony, their oxides or alloys thereof. In one embodiment, the concentration of the metal nanoparticles is in the range of 0.5 wt% to 15 wt% based on the weight of the solvent and the metal nanoparticles. In one embodiment, the concentration of the metal nanoparticles is in the range of 1 wt% to 7 wt% based on the weight of the solvent and the metal nanoparticles. In one embodiment, the concentration of the thermally stable ligand is in the range of 7 wt% to 99 wt% based on the total weight of the thermally stable ligand and the second ligand. In one embodiment, the concentration of the thermally stable ligand is in the range of 15% to 85% by weight, based on the total weight of the thermally stable ligand and the second ligand. In one embodiment, the second ligand is substituted or unsubstituted methacrylic acid. In one embodiment, a single metal nanoparticle is complexed with 1 to 25 ligand units. In one embodiment, the metal nanoparticles are complexed into a metal core comprising up to 18 metal nanoparticles. In one embodiment, the photoresist composition comprises a polymer or a polymerizable monomer or oligomer. In one embodiment, the photoresist composition comprises a photoactive compound.

[0100] This disclosure also includes the following exemplary embodiments: Embodiment 1. A photoresist composition, the photoresist composition comprising: Metal particles, wherein the metal particles comprise at least one of zinc, zirconium, cobalt, manganese, iron, strontium, tungsten, vanadium, tin, hafnium, indium, cadmium, niobium, cesium, barium, lanthanum, cerium, antimony, and their oxides; and Ligands attached to the metal particles, The ligands described herein include C1-C7 alkyl or C1-C7 fluoroalkyl groups. The C1-C7 alkyl or C1-C7 fluoroalkyl group is branched or unbranched, cyclic or acyclic, and The C1-C7 alkyl or C1-C7 fluoroalkyl group comprises one or more of -C(=O)SH, -SO2SH and -SOH.

[0101] Embodiment 2. The photoresist composition according to Embodiment 1 further comprises a solvent.

[0102] Example 3. The photoresist composition according to Example 2, wherein the solvent is one or more selected from propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, acetone, dimethylformamide (DMF), isopropanol (IPA), tetrahydrofuran (THF), methyl isobutyl methanol (MIBC), n-butyl acetate (nBA), or 2-heptanone (MAK).

[0103] Embodiment 4. The photoresist composition according to Embodiment 3, wherein the concentration of the metal particles is in the range of about 0.5% by weight to about 15% by weight, based on the weight of the solvent and the metal particles.

[0104] Embodiment 5. The photoresist composition according to Embodiment 4, wherein the concentration of the metal ions is in the range of 1% to 7% by weight, based on the weight of the solvent and the metal particles.

[0105] Embodiment 6. The photoresist composition according to Embodiment 1, wherein the metal particles include one or more of Cs, Ba, La, Ce, In, Sn, Sb or their oxides.

[0106] Embodiment 7. The photoresist composition according to Embodiment 1 further comprises a polymer or a polymerizable monomer or oligomer.

[0107] Embodiment 8. The photoresist composition according to Embodiment 1 further comprises a photoactive compound.

[0108] Embodiment 9. A photoresist composition, said photoresist composition comprising: A metal core, wherein the metal core comprises at least one selected from zinc, zirconium, cobalt, manganese, iron, strontium, tungsten, vanadium, tin, hafnium, indium, cadmium, niobium, cesium, barium, lanthanum, cerium, antimony, and their oxides; and The first ligand attached to the metal core, The first ligand comprises branched or unbranched, cyclic or acyclic C1-C7 alkyl or C1-C7 fluoroalkyl groups, and The C1-C7 alkyl or C1-C7 fluoroalkyl group comprises one or more of -C(=O)SH, -SO2SH, and -SOH; and The second ligand attached to the metal core, The second ligand is a material different from the first ligand.

[0109] Embodiment 10. The photoresist composition according to Embodiment 9 further comprises a solvent; and Based on the weight of the solvent and the metal core, the concentration of the metal core is in the range of 0.5% to 15% by weight.

[0110] Embodiment 11. The photoresist composition according to Embodiment 10, wherein the second ligand is a branched or unbranched, aliphatic or aromatic, substituted or unsubstituted carboxylic or sulfonic acid ligand.

[0111] Embodiment 12. The photoresist composition according to Embodiment 9, wherein the concentration of the first ligand is in the range of 7% to 99% by weight, based on the total weight of the first ligand and the second ligand.

[0112] Embodiment 13. The photoresist composition according to Embodiment 9, wherein the metal core comprises one or more of Cs, Ba, La, Ce, In, Sn, Sb or oxides thereof.

[0113] Embodiment 14. The photoresist composition according to Embodiment 11, wherein the second ligand is substituted with a substituent selected from one or more of C1-C9 alkyl, C2-C9 alkenyl or C1-C9 phenyl.

[0114] Embodiment 15. The photoresist composition according to Embodiment 12, wherein the concentration of the first ligand is in the range of 15% to 85% by weight based on the total weight of the first ligand and the second ligand.

[0115] Embodiment 16. A photoresist composition, said photoresist composition comprising: Metal nanoparticles, wherein the metal nanoparticles comprise at least one of zinc, zirconium, cobalt, manganese, iron, strontium, tungsten, vanadium, tin, hafnium, indium, cadmium, niobium, cesium, barium, lanthanum, cerium, antimony, and their oxides; and Ligands attached to the metal nanoparticles, The ligands described herein comprise branched or unbranched, cyclic or acyclic C1-C7 alkyl or C1-C7 fluoroalkyl groups, and The C1-C7 alkyl or C1-C7 fluoroalkyl group comprises one or more of -C(=O)SH, -SO2SH, and -SOH; and Solvent.

[0116] Embodiment 17. The photoresist composition according to Embodiment 16, wherein the metal nanoparticles have an average ion size between 2 nm and 5 nm.

[0117] Embodiment 18. The photoresist composition according to Embodiment 16, wherein the metal nanoparticles include one or more of Cs, Ba, La, Ce, In, Sn, Sb or oxides thereof.

[0118] Embodiment 19. The photoresist composition according to Embodiment 16 further comprises a polymer or a polymerizable monomer or oligomer.

[0119] Embodiment 20. The photoresist composition according to Embodiment 16 further comprises a photoactive compound.

[0120] Several features of embodiments or examples have been outlined above to enable those skilled in the art to better understand various aspects of this disclosure. Those skilled in the art should understand that they can readily use this disclosure as the basis for designing or modifying other processes and structures to achieve the same purposes and / or benefits as the embodiments or examples described herein. Those skilled in the art should also recognize that such equivalent constructions do not depart from the spirit and scope of this disclosure, and that various changes, substitutions, and modifications can be made therein without departing from the spirit and scope of this disclosure.

Claims

1. A photoresist composition, said photoresist composition comprising: Metal particles, wherein the metal particles comprise at least one of zinc, zirconium, cobalt, manganese, iron, strontium, tungsten, vanadium, tin, hafnium, indium, cadmium, niobium, cesium, barium, lanthanum, cerium, antimony, and their oxides; and Ligands attached to the metal particles, The ligands described herein include C1-C7 alkyl or C1-C7 fluoroalkyl groups. The C1-C7 alkyl or C1-C7 fluoroalkyl group is branched or unbranched, cyclic or acyclic, and The C1-C7 alkyl or C1-C7 fluoroalkyl group comprises one or more of -C(=O)SH, -SO2SH and -SOH.

2. The photoresist composition according to claim 1, further comprising a solvent.

3. The photoresist composition according to claim 2, wherein the solvent is one or more selected from propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, acetone, dimethylformamide (DMF), isopropanol (IPA), tetrahydrofuran (THF), methyl isobutyl methanol (MIBC), n-butyl acetate (nBA), or 2-heptanone (MAK).

4. The photoresist composition according to claim 3, wherein the concentration of the metal particles is in the range of about 0.5% by weight to about 15% by weight, based on the weight of the solvent and the metal particles.

5. The photoresist composition according to claim 4, wherein, Based on the weight of the solvent and the metal particles, the concentration of the metal ions is in the range of 1% to 7% by weight.

6. The photoresist composition according to claim 1, wherein, The metal particles include one or more of Cs, Ba, La, Ce, In, Sn, Sb or their oxides.

7. The photoresist composition according to claim 1, further comprising a polymer or polymerizable monomer or oligomer.

8. The photoresist composition according to claim 1, further comprising a photoactive compound.

9. A photoresist composition, said photoresist composition comprising: A metal core, wherein the metal core comprises at least one selected from zinc, zirconium, cobalt, manganese, iron, strontium, tungsten, vanadium, tin, hafnium, indium, cadmium, niobium, cesium, barium, lanthanum, cerium, antimony, and their oxides; and The first ligand attached to the metal core, The first ligand comprises branched or unbranched, cyclic or acyclic C1-C7 alkyl or C1-C7 fluoroalkyl groups, and The C1-C7 alkyl or C1-C7 fluoroalkyl group comprises one or more of -C(=O)SH, -SO2SH, and -SOH; and The second ligand attached to the metal core, The second ligand is a material different from the first ligand.

10. A photoresist composition, said photoresist composition comprising: Metal nanoparticles, wherein the metal nanoparticles comprise at least one of zinc, zirconium, cobalt, manganese, iron, strontium, tungsten, vanadium, tin, hafnium, indium, cadmium, niobium, cesium, barium, lanthanum, cerium, antimony, and their oxides; and Ligands attached to the metal nanoparticles, The ligands described herein comprise branched or unbranched, cyclic or acyclic C1-C7 alkyl or C1-C7 fluoroalkyl groups, and The C1-C7 alkyl or C1-C7 fluoroalkyl group comprises one or more of -C(=O)SH, -SO2SH, and -SOH; and Solvent.

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