Branched compositions for lithographic patterning cross-reference to related applications

Abstract

Disclosed are compositions and methods for photolithography that employ branched compositions, such as graft or bottlebrush polymers. In one embodiment, a photoresist composition includes a graft polymer that, due to lower surface energy and reduced chain entanglement, migrates to the upper region of the resist layer during application to form an in-situ barrier that minimizes the leaching of photoresist components into an immersion lithography fluid, thereby reducing contamination of the exposure tool without requiring a separate topcoat. The graft polymers can also be formulated into top coats, top anti-reflective coatings, or used as surfactants in rinse solutions to prevent pattern collapse. These compositions can be formulated to be free of per- and polyfluoroalkyl substances (PFAS), offering an environmentally safer alternative for advanced lithographic processes.

Description

[0001] PDH-005

[0002] BRANCHED COMPOSITIONS FOR LITHOGRAPHIC PATTERNING CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] [1] This application claims the priority and benefit of U.S. Provisional Application No. 63 / 694,165, filed on September 12, 2024, U.S. Provisional Application No. 63 / 721,449, filed on November 16, 2024, and U.S. Provisional Application No. 63 / 721,450, filed on November 16, 2024, which applications are hereby incorporated herein by reference in their entirety.

[0004] FIELD OF THE DISCLOSURE

[0005] [2] The present disclosure relates to new lithographic compositions, including photoresists, top coats, top anti-reflective coatings, and process solutions, that comprise graft polymers and are useful in photolithography processes. The disclosure also relates to coated substrates formed from these compositions and methods for their use in patterning. These compositions can be used to improve lithographic performance by addressing key challenges such as component leaching, pattern collapse, and optical reflection.

[0006] BACKGROUND

[0007] [3] Photoresists are photosensitive films used for transfer of an image to a substrate. A coating layer of a photoresist is formed on a substrate and the photoresist layer is then exposed through a photomask to a source of activating radiation. The photomask has areas that are non-transmissive to activating radiation and other areas that are transparent to activating radiation. Exposure to activating radiation provides a photoinduced chemical transformation of the photoresist coating to thereby transfer the pattern of the photomask to the photoresist coated substrate. Following exposure, the photoresist is developed to provide a relief image that permits selective processing of a substrate.

[0008] [4] The growth of the semiconductor industry is driven by Moore's law which states that the complexity of an integrated circuit device doubles on average every two years. This necessitates the need to lithographically transfer patterns and structures with ever decreasing feature size. One approach to achieving smaller feature sizes is to use shorter wavelengths of light, however, the difficulty in finding materials that are transparent below 193 nm has led to the option of using immersion lithography to increase the numerical aperture of the lens by simply using a liquid to focus more light into the film. Immersion lithography employs a relatively high refractive index fluid between the last surface of an imaging device (e.g., KrF or ArF stepper) and the first surface on a wafer or other substrate.

[0009] [5] Certain efforts have been made to address problems associated with immersion lithography. See U.S. Patent Application Publication 2005 / 0084794. For immersion lithography, which uses a high- refractive-index fluid between the exposure tool and the wafer to achieve smaller feature sizes, a key issue is the migration or "leaching" of photoresist components into the immersion fluid. The migration PDH-005 of photoacid generators (PAGs) or other materials into the immersion fluid can damage the exposure tool and reduce image resolution. The typical solutions to this problem are either a separate top coat or an embedded barrier layer material, and these materials usually rely on per- and polyfluoroalkyl substances (PFAS).

[0010] [6] Another challenge in photolithography is optical reflection at the bottom of the substrate, which causes light intensity to vary sinusoidally along the depth of the photoresist, resulting in dimensional fluctuations and poor controllability. Top anti-reflective coatings (TARC) are a solution to this problem. TARC materials are applied as a thin film on the surface of the photoresist to cause destructive interference of reflected light. TARC is simpler to remove than bottom anti-reflective coating (BARC), as it only requires a developing solution. However, conventional TARC compositions often contain PFAS.

[0011] [7] Another challenge in patterning is pattern collapse, which is becoming a more significant problem due to the higher aspect ratios of new-generation devices. For a photoresist layer with a large aspect ratio, capillary forces during processing with developer or rinse solutions can cause the pattern to collapse. A primary cause of pattern collapse is the capillary force of water during the postdevelopment drying stage. Traditional approaches to reduce this, such as freeze-drying or using supercritical fluids, require extra manufacturing steps and specialized equipment not commonly found in semiconductor fabrication. Another common approach is adding a surfactant to the rinse liquid to lower its surface tension. These surfactants commonly employ PFAS.

[0012] [8] PFAS "forever chemicals" do not break down easily, accumulate in the environment, and pose potential health risks, making their replacement critical for public health and the environment. We now provide new compositions and processes for immersion photolithography that are free from PFAS components, including barrier materials, surfactants, and TARCs.

[0013] SUMMARY

[0014] [9] The present disclosure provides compositions and methods for advanced photolithography, utilizing graft polymers to address challenges such as component leaching, pattern collapse, and optical reflection, often without the use of per- and polyfluoroalkyl substances (PFAS).

[0015]

[0010] In a first aspect, the disclosure provides a photoresist composition comprising an acid-labile polymer, a photoacid generator, and a graft polymer. Making reference to FIG. 1, the graft polymer 100 (in this example, one having a "bottle brush morphology"), comprises a backbone 102 (hereinafter the "backbone" or "backbone polymer") of length "I" that is reacted to the grafted polymeric sidechain 104 (hereinafter the "sidechain" or "sidechain polymer"). The sidechain can be covalently attached to the backbone 102 along a portion of the length of the backbone or along the entire length of the backbone 102. The sidechain 104 can also be covalently bonded to the backbone 102 along the entire PDH-005 length of the backbone and could extend radially outward in any direction or combination of directions from the backbone or along a portion of a circumference of the backbone. The graft polymer 100 acts as an embedded barrier material that migrates to the surface of a photoresist layer, thereby reducing the leaching of photoresist components into an immersion lithography fluid.

[0016]

[0011] In a second aspect, the disclosure provides a coated substrate comprising a layer of the aforementioned photoresist composition. This substrate benefits from the in-situ barrier formed by the graft polymer, exhibiting reduced surface contamination and improved compatibility with immersion lithography processes. Making reference to the coated substrate 200 shown in FIG. 2, in one example, a layer of a photoresist 206 having a photoresist top surface 206A and a photoresist bottom surface 206B opposite the photoresist top surface 206A, is located on top of the one or more layers to be patterned 204 having a top surface 204A and a bottom surface 204B opposite the top surface 204A and the substrate 202 having a substrate top surface 202A and a substrate bottom surface 202B opposite substrate top surface 202A. The photoresist layer 206 comprises a graft polymer, which forms a graft polymer sub-layer 208' after it is applied and processed. The graft polymer layer 208' has a top surface 208'A that is co-planar with the photoresist top surface 206A and extends downward to a sub-layer bottom surface 208'B located within the photoresist 206. In the example in FIG. 2, the photoresist bottom surface 206B is in direct contact with top surface 204A to be patterned; and the bottom surface 204B is in direct contact with substrate top surface 202A. Those of skill in the art will recognize that there can be additional layers in the coated substrate 200 beyond the ones shown.

[0017]

[0012] In a third aspect, the disclosure provides a method for forming a patterned mask using the photoresist composition. The method shown in FIG. 3 and described in the process flow diagram in FIG. 4 involves a layer of a photoresist 206 on top of one or more layers to be patterned 204 and the substrate 202. The photoresist comprises a graft polymer 208, which in some embodiments is uniformly distributed throughout the photoresist 206 after coating. Next, a layer of graft polymer 208' forms on top of the modified photoresist layer 206'. This layer 208' forms an in-situ barrier, resulting in reduced resist component leaching during immersion lithography processes. Then, the photoresist 206' may be patterned with actinic radiation 310 through a photomask 312. The photomask has optically transparent regions 314 and optically opaque regions 316 corresponding to regions of the resist layer to be unexposed and exposed, respectively, by the activating radiation. Next, a postexposure bake (PEB) is performed, which forms a latent image defined by the boundary between exposed regions 206' and unexposed regions 206". The graft polymer also changes solubility during the PEB to form a modified layer of graft polymer 208" that is soluble in the developer. Finally, the photoresist layer is developed to remove exposed regions 206' and the modified layer of graft polymer PDH-005

[0018] 208", leaving unexposed regions 206", thus forming a resist pattern having a plurality of features separated by gaps 318.

[0019]

[0013] In a fourth aspect, the disclosure provides a method for forming a patterned mask that includes applying a top coat composition containing a graft polymer located on top of a photoresist layer. This method leverages the protective properties of the graft polymer top coat to prevent resist component leaching during immersion exposure. The method shown in FIG. 5 and described in the process flow diagram in FIG. 6 involves a layer of a photoresist 506 on top of one or more layers to be patterned 204 and the substrate 202. A layer of graft polymer 508 is applied on top of the photoresist 506. This layer forms a barrier, resulting in reduced resist component leaching during immersion lithography processes. Then, the photoresist 506 may be patterned with actinic radiation 310 through a photomask 312. The photomask has optically transparent regions 314 and optically opaque regions 316 corresponding to regions of the resist layer to be unexposed and exposed, respectively, by the activating radiation. Next, a post-exposure bake (PEB) is performed, which forms a latent image defined by the boundary between exposed regions 506' and unexposed regions 506". The graft polymer also changes solubility during the PEB to form a modified top coat 508' that is soluble in the developer. Finally, the photoresist layer is developed to remove exposed regions 506' and the modified top coat 508', leaving unexposed regions 506", thus forming a resist pattern having a plurality of features separated by gaps 510.

[0020]

[0014] In a fifth aspect, the disclosure provides a coated substrate featuring a photoresist layer located underneath a separate top coat layer containing a graft polymer. This top coat serves as a dedicated barrier layer, preventing resist component leaching and providing a protective interface between the coated substrate and the immersion fluid. Making reference to the coated substrate 500 shown in FIG. 5B, in one example, a layer of a photoresist 506 is located on top of the one or more layers to be patterned 204 and the substrate 202. A layer of top coat comprising a graft polymer 508 is on top of the photoresist 506.

[0021]

[0015] In a sixth aspect, the disclosure provides a method for forming a patterned mask using a top anti-reflective coating (TARC) that contains a graft polymer. This method involves applying the graft polymer TARC over the photoresist before exposure to actinic radiation to suppress standing wave effects and reflective notching. The method shown in FIG. 7 and described in the process flow diagram in FIG. 8 involves a layer of a photoresist 506 on top of one or more layers to be patterned 204 and the substrate 202. A layer of TARC comprising a graft polymer 708 is applied on top of the photoresist 506. Then, the photoresist 506 may be patterned with actinic radiation 310 through a photomask 312. The photomask has optically transparent regions 314 and optically opaque regions 316 corresponding to regions of the resist layer to be unexposed and exposed, respectively, by the activating radiation. PDH-005

[0022] Next, a post-exposure bake (PEB) is performed, which forms a latent image defined by the boundary between exposed regions 506' and unexposed regions 506". The graft polymer also changes solubility during the PEB to form a modified TARC layer 708' that is soluble in the developer. Finally, the photoresist layer is developed to remove exposed regions 506' and the modified TARC 708', leaving unexposed regions 506", thus forming a resist pattern having a plurality of features separated by gaps 510.

[0023]

[0016] In a seventh aspect, the disclosure provides a coated substrate featuring a photoresist layer located underneath a separate TARC containing a graft polymer. Making reference to the coated substrate 700 shown in FIG. 7B, in one example, a layer of a photoresist 506 is located on top of the one or more layers to be patterned 204 and the substrate 202. A layer of TARC comprising a graft polymer 708 is on top of the photoresist 506. The unique architecture of the graft polymer allows for precise tuning of the TARCs refractive index and thickness to minimize reflections, leading to as much as 90% decrease in reflection.

[0024]

[0017] In an eighth aspect, the disclosure provides a method for forming a patterned mask wherein the developed photoresist is treated with a process solution containing a graft polymer. This process solution, such as a rinse, utilizes an amphiphilic graft polymer as a surfactant to lower the surface tension of the rinse liquid, thereby preventing pattern collapse of features during drying. The method shown is described in the process flow diagram in FIG. 9. It involves first providing a semiconductor substrate to be patterned; forming a layer of a photoresist composition on the substrate, where the photoresist composition includes an acid-labile polymer and a photoacid generator; exposing the photoresist film to actinic radiation; developing the photoresist film with a developer; and finally treating the developed photoresist film with a process solution comprising a graft polymer.

[0025]

[0018] Accordingly, the present disclosure comprises compositions, processes, and articles that address the foregoing needs.

[0026] BRIEF DESCRIPTION OF THE DRAWINGS

[0027]

[0019] The present disclosure will be described with reference to the following drawing, in which like reference numerals denote like features, and in which:

[0028]

[0020] FIG. 1 is a cartoon of a graft polymer in accordance with the disclosure.

[0029]

[0021] FIG. 2 is a side view of a portion of a coated substrate in accordance with one embodiment of the disclosure.

[0030]

[0022] FIGS. 3A-3E are side views of a portion of a coated substrate during steps in a process flow for forming a photolithographic pattern in accordance with one embodiment of the disclosure.

[0031]

[0023] FIG. 4 is a process flow diagram in accordance with one embodiment of the disclosure. PDH-005

[0032]

[0024] FIGS. 5A-5E are side views of a portion of a coated substrate during steps in a process flow for forming a photolithographic pattern in accordance with one embodiment of the disclosure. FIG. 5B is a side view of a portion of a coated substrate in accordance with one embodiment of the disclosure.

[0033]

[0025] FIG. 6 is a process flow diagram in accordance with one embodiment of the disclosure.

[0034]

[0026] FIGS. 7A-7E are side views of a portion of a coated substrate during steps in a process flow for forming a photolithographic pattern in accordance with one embodiment of the disclosure. FIG. 7B is a side view of a portion of a coated substrate in accordance with one embodiment of the disclosure.

[0035]

[0027] FIG. 8 is a process flow diagram in accordance with one embodiment of the disclosure.

[0036]

[0028] FIG. 9 is a process flow diagram in accordance with one embodiment of the disclosure.

[0037] DESCRIPTION

[0038]

[0029] The following description sets forth exemplary embodiments of the present technology. It should be recognized, however, that such description is not intended as a limitation on the scope of the present disclosure but is instead provided as a description of exemplary embodiments.

[0039]

[0030] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art. As used herein, the below terms have the following meanings unless specified otherwise. Any methods, devices and materials similar or equivalent to those described herein may also be used in the practice of the compositions and methods described herein. The following definitions are provided to facilitate understanding of certain terms used frequently herein and are not meant to limit the scope of the present disclosure. All references referred to herein are incorporated by reference in their entirety.

[0040]

[0031] The term "comprise" and variations thereof, such as, "comprises" and "comprising" are to be construed in an open, inclusive sense, that is, as "including, but not limited to." The term "consisting essentially of" is construed to mean that the composition / process (a) necessarily includes the listed ingredients / steps and (b) is open to unlisted ingredients / steps that do not materially affect the basic and novel properties of the composition / process. The term "consisting of" is closed-ended and excludes any element, step, or ingredient not specifically mentioned after that phrase. Further, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Thus, references to "the embodiment" includes a plurality of such embodiments.

[0041]

[0032] In some embodiments, there are a number of possible alternatives that can be chosen. In such cases, the terminology "at least one of [A], [B] and [C]" or "one or more of [A], [B] and [C]" is used to mean "either [A], [B], [C] or any possible combination of [A], [B] and [C]," such as [A] and [B] or [A], [B], and [C], In cases where "[A] or [B]" is used, it should be interpreted as "either or both" and not as alternatives - e.g., "[A] or [B]" is equivalent to "[A] or [B] or the combination [A] and [B]." For PDH-005 sake of clarity, the disclosure may include "and combinations thereof" to further clarify that in cases where alternatives are listed, the list further comprises combinations thereof.

[0042]

[0033] It is noted that the terms "substantially" and "about" may be utilized herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. These terms are also utilized herein to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue. For example, reference to "about" a value or parameter herein includes (and describes) embodiments that are directed to that value or parameter per se. In certain embodiments, the term "about" includes the indicated amount ± 10%. In other embodiments, the term "about" includes the indicated amount ± 5%. In certain other embodiments, the term "about" includes the indicated amount ± 1%. Also, to the term "about X" includes description of "X."

[0043]

[0034] "Ring," "cycle," "cyclic," "alicyclic", or like terms generally refer to at least one continuous closed loop, ring, or chain of atoms and can include, for example, saturated alicyclics, unsaturated alicyclics, aromatics, hetero-aromatics (heteroaryl), and like cyclic classifications, or combinations thereof, including monocyclic, bicyclic, tricyclic, and like conventional designations.

[0044]

[0035] "Alkyl" includes linear alkyls and branched alkyls. "Substituted alkyl" or "optionally substituted alkyl" refers to an alkyl substituent, which can include, for example, a linear alkyl or a branched alkyl having from 1 to 4 optional substituents selected from, for example, hydroxyl (—OH), halogen, amino (—NHz or — NR2), nitro (— NO2), acyl (— C(=O)R), alkylsulfonyl (— S(=O)2R), alkoxy (—OR), (C3- io)cycloalkyl, and like substituents, where R is a hydrocarbyl, aryl, Het, or like moieties, such as a monovalent alkyl or a divalent alkylene having from 1 to about 10 carbon atoms. For example, a hydroxy substituted alkyl, can be a 2-hydroxy substituted propylene of the formula — CH?— CH(OH)— CH2— , an alkoxy substituted alkyl, can be a 2-methoxy substituted ethyl of the formula — CH?— CH2— O— CH3, an amino substituted alkyl, or can be a 1-dialkylamino substituted ethyl of the formula — CH(NR2)— CH3.

[0045]

[0036] "Cycloalkyl" includes cyclic alkyls. "Substituted cycloalkyl" or "optionally substituted cycloalkyls" refers to a cycloalkyl substituent having from 1 to 4 optional substituents selected from, for example, alkyl, alkenyl, alkynyl, hydroxyl (—OH), halogen, amino (— NH2or — NR2), nitro (— NO2), acyl (— C(=O)R), alkylsulfonyl (— S(=O)2R), alkoxy (—OR), and like substituents .

[0046]

[0037] "Alkoxyl" includes an alkyl group bound to the base structure via an oxygen atom, -O-R1, wherein R1can include optionally substituted linear alkyls or branched alkyls as described above. PDH-005

[0047]

[0038] "Alkoxylcarbonyl" includes an alkyl group bound the base structure via an oxygen, with a carbonyl group adjacent the oxygen, -O-C^OJ-R1, wherein R1can include optionally substituted linear alkyls or branched alkyls as described above.

[0048]

[0039] "Carboxyl" means a moiety composed of carbon bonded to both an oxygen and a hydroxyl group, -C(=O)-O-H.

[0049]

[0040] "Hydroxyl" mean an -O-H chemical moiety.

[0050]

[0041] "Cyano" means a -CEN chemical moiety.

[0051]

[0042] "Halogen" or "halo" includes fluoro (-F), chloro (-CI), bromo (-Br), or iodo (-1) moieties.

[0052]

[0043] "Aryl" includes a mono- or divalent-phenyl radical or an ortho-fused bicyclic carbocyclic radical having about nine to twenty ring atoms in which at least one ring is aromatic. Aryl (Ar) can include substituted aryls, such as a phenyl radical having from 1 to 5 substituents, for example, alkyl, alkoxy, halo, and like substituents.

[0053]

[0044] "Het" or "Heteroalkyl" includes a four-(4), five-(5), six-(6), or seven-(7) membered saturated or unsaturated heterocyclic ring having 1, 2, 3, or 4 heteroatoms selected from the group consisting of oxy, thio, sulfinyl, sulfonyl, selenium, tellurium, and nitrogen, which ring is optionally fused to a benzene ring. Het also includes "heteroaryl," which encompasses a radical attached via a ring carbon of a monocyclic aromatic ring containing five or six ring atoms consisting of carbon and 1, 2, 3, or 4 heteroatoms each selected from the group consisting of non-peroxide oxy, thio, and N(X) wherein X is absent or is H, O, (Ci-galkyl, phenyl, or benzyl, and a radical of an ortho-fused bicyclic heterocycle of about eight to ten ring atoms derived therefrom, particularly a benzo-derivative or one derived by fusing a propylene, trimethylene, or tetramethylene diradical thereto.

[0054]

[0045] Alkyl, alkoxy, etc., include both straight and branched groups; but reference to an individual radical such as "propyl" embraces only the straight chain radical, a branched chain isomer such as "isopropyl" being specifically referred to.

[0055]

[0046] The carbon atom content of various hydrocarbon-containing (i.e., hydrocarbyl) moieties can alternatively be indicated by a prefix designating a lower and upper number of carbon atoms in the moiety, i.e., the prefix Cj.j indicates a moiety of the integer "i" to the integer"]" carbon atoms, inclusive. Thus, for example, (Ci-Cg)alkyl or Ci-galkyl refers to an alkyl of one to eight carbon atoms, inclusive, and hydrocarbyloxy such as (Ci-Cg)alkoxy or Ci.galkoxy refers to an alkoxy radical (—OR) having an alkyl group of one to eight carbon atoms, inclusive. Specifically, a Ci-galkyl can be, for example, methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, 3-pentyl, hexyl, heptyl, or octyl; (Cg-ujcycloalkyl can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, including bicyclic, tricyclic, or multi-cyclic substituents, and like substituents. PDH-005

[0056]

[0047] A specific "hydrocarbyl" can be, for example, (Cio-2o)hydrocarbyl, including all intermediate chain lengths and values, and (Cs-izjcyclohydrocarbyl including all intermediate values and ring sizes.

[0057]

[0048] Ci-galkoxy can be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, iso-butoxy, secbutoxy, pentoxy, 3-pentoxy, hexyloxy, 1-methylhexyloxy, heptyloxy, octyloxy, and like substituents.

[0058]

[0049] A — C(=O)(C3-7)alkyl- or — (C2.7)alkanoyl can be, for example, acetyl, propanoyl, butanoyl, pentanoyl, 4-methylpentanoyl, hexanoyl, or heptanoyl. Aryl (Ar) can be, for example, phenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, tetrahydronaphthyl, or indanyl. Het can be, for example, pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl, or heteroaryl. Heteroaryl can be, for example, furyl, imidazolyl, triazolyl, triazinyl, oxazoyl, isoxazoyl, thiazolyl, isothiazoyl, pyrazolyl, pyrrolyl, pyrazinyl, tetrazolyl, pyridyl, (or its N-oxide), thienyl, pyrimidinyl (or its N-oxide), indolyl, isoquinolyl (or its N-oxide) or quinolyl (or its N-oxide).

[0059]

[0050] Other conditions suitable for formation and modification of the compounds or like products of the disclosure, from a variety of starting materials or intermediates, as disclosed and illustrated herein are available. For example, see Feiser and Feiser, "Reagents for Organic Synthesis", Vol. 1, et seq., 1967; March, J. "Advanced Organic Chemistry," John Wiley & Sons, 4Supth / Suped. 1992; House, H. O., "Modem Synthetic Reactions," 2nded., W. A. Benjamin, New York, 1972; and Larock, R. C., "Comprehensive Organic Transformations," 2nded., 1999, Wiley-VCH Publishers, New York.

[0060]

[0051] The term "Mn" used herein and in the appended claims in reference to a polymer of the present disclosure is the number average molecular weight of the polymer (in g / mol) determined according to the method used herein in the Examples. The term "Mw" used herein and in the appended claims in reference to a polymer of the present disclosure is the weight average molecular weight of the polymer (in g / mol) determined according to the method used herein in the Examples.

[0061]

[0052] The term "PDI" or "D" used herein and in the appended claims in reference to a polymer of the present disclosure is the polydispersity (also called polydispersity index or simply "dispersity") of the polymer determined according to the following equation:

[0062] PDI = D = Mw / Mn

[0063]

[0053] The term "polymer" refers to a molecule comprised of two or more (e.g., 10 or more) repeating units which are covalently bonded together. In certain embodiments, a polymer comprises 10 or more, 50 or more, 100 or more, 1000 or more, 2000 or more, or 4000 or more repeating units. In certain embodiments, a polymer comprises more than 4000 repeating units. The repeating units of a polymer are referred to as "monomers." A "homopolymer" is a polymer that consists of a single repeating monomer. A "copolymer" is a polymer that comprises two or more different monomer subunits. Copolymers include, but are not limited to, random, block, alternating, segmented, linear, branched, grafted, and tapered copolymers. A polymer may have an overall molecular weight of 50 PDH-005

[0064] Daltons (Da) or greater, 100 Da or greater, 500 Da or greater, 1000 Da or greater, 2000 Da or greater, 5000 Da or greater, 10000 Da or greater, 20000 Da or greater, or 50000 Da or greater.

[0065]

[0054] The term "resin" refers to a polymeric material, or a precursor thereof, that serves as a principal component of a composition, often acting as a binder, matrix, film-former, or structural component. The resin may comprise one or more monomers, oligomers, prepolymers, or polymers, and can exist as a blend or copolymer of different resin types.

[0066]

[0055] The term "oligomer" refers to a polymeric compound composed of a small number of monomer units, from 2 to about 20. Oligomers may be linear, branched, or cyclic, and can be homooligomers or copolymers.

[0067]

[0056] The term "graft polymer" refers to a polymer comprising a polymeric backbone of repeating units, wherein one or more of the repeating units are covalently bonded to polymeric sidechains. The polymeric backbone may consist of a single type of monomer or include two or more different monomeric subunits. The polymeric sidechains may be homopolymers or copolymers and may have linear or branched architectures. Graft polymers can vary in the length, density, and spatial distribution of their sidechains, allowing for precise tuning of physical, chemical, and interfacial properties. In some embodiments, the sidechains are uniformly distributed along the backbone; in others, the distribution may be irregular or blockwise.

[0068]

[0057] The term "bottlebrush polymer" refers to a specific type of graft polymer characterized by a high grafting density, in which a majority, such as all or nearly all, of the repeating units in the polymeric backbone are substituted with polymeric sidechains. This dense and regular grafting pattern results in an extended, cylindrical morphology resembling the bristles of a bottlebrush. Bottlebrush polymers exhibit unique physical properties, including reduced chain entanglement, large hydrodynamic volume, and anisotropic molecular conformations. The backbone of a bottlebrush polymer may be composed of a single repeating unit or multiple monomeric subunits. In bottlebrush copolymers, compositional blocks may be defined by changes in the chemical identity of the polymeric sidechains rather than the backbone.

[0069]

[0058] The term "polymeric backbone" refers to a linear polymer chain composed of repeating units, which serves as the central scaffold onto which sidechains are covalently attached in a graft polymer. In bottlebrush polymers, the polymeric backbone may be formed from a single monomer or multiple different monomeric subunits, and may be synthesized via controlled polymerization methods such as ROMP, ATRP, or RAFT.

[0070]

[0059] The term "polymeric sidechain" refers to a polymer segment covalently grafted to the polymeric backbone of a graft polymer. These sidechains may be identical or compositionally distinct, and may include homopolymers or copolymers with linear or branched architectures. In bottlebrush PDH-005 copolymers, blocks are often defined by the sequence and identity of these sidechains rather than by the backbone.

[0071]

[0060] A "hyperbranched polymer" is a highly branched, irregular macromolecule formed through the random or statistical polymerization of multifunctional monomers. Hyperbranched polymers lack a defined linear backbone and do not exhibit the uniform side-chain distribution seen in graft and bottlebrush polymers. Instead, they have a globular, tree-like structure with a high density of terminal functional groups.

[0072]

[0061] As used herein, the term "(meth)acrylate" or "(meth)acrylate monomer" refers to both acrylate and methacrylate species. For example, the term "methyl (meth)acrylate" refers to both methyl acrylate and methyl methacrylate. Similarly, the term "poly(meth)acrylate" refers to both acrylate and methacrylate polymer species. For example, the term "polymethyl (meth)acrylate" refers to both polymethyl acrylate and polymethyl methacrylate.

[0073] Graft polymers

[0074]

[0062] Materials of the present disclosure include graft polymers. The structural regularity and dense grafting of graft polymers impart unique physical properties not found in hyperbranched architectures, including reduced chain entanglement, high hydrodynamic volume, tunable anisotropy, and the ability to adopt extended or cylindrical conformations in solution. These features make graft and bottlebrush polymers especially well-suited for applications requiring controlled interfacial and mechanical behavior, such as in advanced photolithography materials.

[0075]

[0063] The polymeric backbone, or "backbone”, serves as the central scaffold for sidechain attachment and plays a role in determining the overall architecture and rigidity of the polymer. Polymeric backbones are synthetically accessible via controlled polymerization techniques and can offer functional handles or structural features, such as ring strain or pendant groups, that facilitate high-density grafting and uniform sidechain distribution.

[0076]

[0064] The polymeric sidechains of a graft polymer, or "sidechains", can be composed of various polymeric or oligomeric segments, and their composition can be tailored to achieve specific physical or chemical properties. This tunability makes graft polymers highly versatile for applications ranging from drug delivery systems and self-assembly materials to advanced coatings and nanocomposites. Additionally, their unusual shape and reduced tendency to entangle compared to linear polymers give them interesting rheological properties, making them a subject of considerable interest in the field of polymer science.

[0077]

[0065] FIG. 1 is a cartoon of a graft polymer 100 (having a bottle brush morphology) that comprises a polymeric backbone 102 (hereinafter the "backbone" or "backbone polymer") of length "I" that is reacted to the grafted polymeric sidechain 104 (hereinafter the "sidechain" or "sidechain polymer"). PDH-005

[0078] The sidechain can be covalently reacted to the backbone along a portion of the length of the backbone or along the entire length of the backbone. The sidechain can also be covalently bonded to the backbone along the entire length of the backbone and could extend radially outward in any direction or combination of directions from the backbone or along a portion of the circumference of the backbone.

[0079]

[0066] The polymeric backbone is used, in one example, to form the backbone 102 of the graft polymer. It is advantageous for the polymeric backbone that forms the backbone to allow for sequential polymerization of macromonomers to manufacture the graft polymers. The backbone can be one that comprises a ring along the chain backbone. The backbone and the sidechain can be selected from the following polymer species: a polyacetal, a polyacetylene, a polyacrylamide, a polyacrylate, a polyacrylic, a polyamide, a polyamideimide, a polyamine, a polyamino acid, a polyanhydride, a polyarylate, a polyarylsulfone, a polybenzimidazole, a polybenzothiazole, a polybenzothiazinophenothiazine, a polybenzoxazole, a polybutylene succinate, a polycaprolactone, a polycarborane, a polycarbonate, a polydibenzofuran, a polydioxoisoindoline, a polyester, a polyether, a polyether ether ketone, a polyetherimide, a polyetherketone, a polyether ketone ketone, a polyethersulfone, a polyethylene, a polyethylene adipate, a poly(ethyl ethylene) phosphate, a polyglycolic acid, a polyhydroxyalkanoate, a polyhydroxybutyrate, a polyimide, a polylactide, a polynorbornene, a polyolefin, a polyoxabicyclononane, a polyoxadiazole, a poly(oxazoline), a polyoxindole, a polyoxoisoindoline, a polyoxymethylene, a polypeptide, a polyphenylene sulfide, a polyphosphazene, a polyphthalide, a polypiperazine, a polypiperidine, a polypyrazinoquinoxaline, a polypyrazole, a polypyridazine, a polypyridine, a polypyrrolidine, a polypyromellitimide, a polyalkylene glycol, a polyquinoxaline, a polysaccharide, a polysilane, a polysilazane, a polysiloxane, a polystyrene, a polysulfide, a polysulfonamide, a polysulfonate, a polysulfone, a polytetrafluoroethylene, a polytetramethylene glycol, a polythioester, a polytriazine, a polytriazole, a polyurethane, a polyurea, a polyvinyl alcohol, a polyvinyl chloride, a polyvinyl ester, a polyvinyl ether, a polyvinyl halide, a polyvinyl ketone, a polyvinyl nitrile, or a polyvinyl thioether, or the like, or a combination including at least one of the foregoing polymers.

[0080]

[0067] In some embodiments, the graft polymer comprises acid-labile groups such as an acid-labile ester, carbonate, or acetal groups. For example, the -OH group of p-hydroxystyrene may be protected with a tert-butyloxycarbonyl protecting group. As will be appreciated by one having ordinary skill in the art, various protecting groups may be used for this reason. Acid-labile groups include, for example: tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups, or ketal groups. Acid-labile groups are also commonly referred to in the art as "acid-sensitive groups", "acid- PDH-005 decomposable groups", "acid-cleavable groups," "acid-cleavable protecting groups," "acid-labile protecting groups," "acid-leaving groups," and "acid-sensitive groups." In other embodiments, the graft polymer comprises free acid or alcohol groups.

[0081]

[0068] The acid-labile group which, on decomposition, forms a carboxylic acid on the polymer is preferably a tertiary ester group of the formula — C(O)OC(R1)3 or a group of the formula — C(O)OC(R2)2OR3, wherein: R1is each independently linear C1-20 alkyl, branched C3-20 alkyl, monocyclic or polycyclic C3-20 cycloalkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, monocyclic or polycyclic C3- 20 cycloalkenyl, monocyclic or polycyclic Cg-2oaryl, or monocyclic or polycyclic C2-20 heteroaryl, preferably linear Ci.g alkyl, branched C3-6 alkyl, or monocyclic or polycyclic C3-10 cycloalkyl, each of which is substituted or unsubstituted, each R1optionally including as part of its structure one or more groups chosen from — O— , — C(O)— , — C(O)— O— , or — S— , and any two R1groups together optionally forming a ring; R2is independently hydrogen, fluorine, linear C1-20 alkyl, branched C3-20 alkyl, monocyclic or polycyclic C3-20 cycloalkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, monocyclic or polycyclic C3-20 cycloalkenyl, monocyclic or polycyclic Cg-2oaryl, or monocyclic or polycyclic C2- 20 heteroaryl, preferably hydrogen, linear Ci.g alkyl, branched C3-6 alkyl, or monocyclic or polycyclic C3- 10 cycloalkyl, each of which is substituted or unsubstituted, each R2optionally including as part of its structure one or more groups chosen from — O— , — C(O)— , — C(O)— O— , or — S— , and the R2groups together optionally forming a ring; and R3is linear C1-20 alkyl, branched C3-20 alkyl, monocyclic or polycyclic C3-20 cycloalkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, monocyclic or polycyclic C3- 20 cycloalkenyl, monocyclic or polycyclic Cg-2oaryl, or monocyclic or polycyclic C2-20 heteroaryl, preferably linear Ci.g alkyl, branched C3-6 alkyl, or monocyclic or polycyclic C3-10 cycloalkyl, each of which is substituted or unsubstituted, R3optionally including as part of its structure one or more groups chosen from — O— , — C(O)— , — C(O)— O— , or — S— , and one R2together with R3optionally forming a ring. In some embodiments, the monomer is a vinyl aromatic, (meth)acrylate, or norbornyl monomer. The total content of polymerized units comprising an acid-decomposable group which forms a carboxylic acid group on the polymer is from 10 to 100 mol %, from 10 to 90 mol %, or from 25 to 75 mol %, based on total polymerized units of the polymer.

[0082]

[0069] The polymer can further include as polymerized a monomer comprising an acid-labile group, the decomposition of which group forms an alcohol group or a fluoroalcohol group on the polymer. Suitable such groups include, for example, an acetal group of the formula — COC(R2)2OR3— , or a carbonate ester group of the formula — OC(O)O— , wherein R is as defined above. In some embodiments, the monomer is a vinyl aromatic (including styrene and p-hydroxystyrene), an acrylate, a methacrylate, or a norbornene. If present in the polymer, the total content of polymerized units comprising an acid-decomposable group, the decomposition of which group forms an alcohol group PDH-005 or a fluoroalcohol group on the polymer, is from 10 to 90 mol %, or from 25 to 75 mol %, based on total polymerized units of the polymer.

[0083]

[0070] The backbone or sidechain polymer units may be derived from polymerization of a monomer including, but not limited to, substituted or unsubstituted norbomene, olefin, cyclic olefin, norbomene anhydride, cyclooctene, cyclopentadiene, styrene, or acrylate. In other embodiments, the repeating backbone units are derived from monomers not listed here. Some backbone units useful in the present disclosure may be obtained from a ring opening metathesis polymerization (ROMP) reaction, an addition polymerization reaction, a free-radical polymerization, or a condensation polymerization reaction. In an exemplary embodiment, the backbone polymer is polynorbornene. The ring of the polynorbornene repeat units may, if desired, be substituted with an alkyl group, an araalkyl group, or an aryl group. In another exemplary embodiment, the backbone polymer is a polyacrylate or polymethacrylate. In other embodiments, the backbone polymer may be selected from a polypeptide, a polysiloxane, a polycaprolactone, or a poly(oxazoline).

[0084]

[0071] The number of repeat units in the backbone polymer (that forms the backbone of the copolymer) is about 3 to about 75, specifically about 10 to about 60, specifically about 25 to about 45. The number average molecular weight of the backbone is 200 to 10,000 grams per mole as measured by gel permeation chromatography (GPC). In a preferred embodiment, the number average molecular weight of the backbone is 3,050 to 5,500 grams per mole as measured by GPC.

[0085]

[0072] The backbone polymer has grafted onto it the sidechain polymer thereby forming a graft polymer. In one embodiment, the backbone polymer has grafted onto it one or more different types of grafted polymers. In another embodiment, the backbone polymer has grafted onto it two or more different types of sidechain polymers. The backbone polymer or the grafted polymer can thus be a block copolymer, an alternating copolymer, an alternating block copolymer, a random copolymer, a random block copolymer, or a combination thereof.

[0086]

[0073] Similarly, the sidechain polymer can be a homopolymer, a random copolymer, an alternating copolymer, or a block copolymer, and can have linear or branched architectures. In some embodiments, the sidechain polymer is a homopolymer. The backbone or sidechain polymer can comprise any of the polymer species defined above.

[0087]

[0074] In some embodiments, the sidechain polymer comprises a surface energy reducing moiety. The surface energy reducing moiety facilitates a high degree of self-assembly when the graft polymer is disposed upon a substrate. In some embodiments, the surface energy reducing moiety comprises a fluorine-containing group such as a perfluoroalkyl group, a silicon-containing group such as a polydimethylsiloxane, an alkyl group such as a linear C10-C30 linear or branched alkyl group, or a combination thereof. The sidechain polymer may be covalently or ionically bonded onto the backbone PDH-005 polymer. In an exemplary embodiment, the sidechain polymer is covalently bonded onto the backbone polymer. In some embodiments, the sidechain polymer comprises acid-labile groups such as acid-labile ester or acetal groups. In other embodiments, the sidechain polymer comprises free acid or alcohol groups.

[0088]

[0075] In some embodiments, the sidechain polymer is a polyolefin, a polyethylene, a polypropylene, a poly(alpha-olefin), or a copolymer thereof. In an exemplary embodiment, the sidechain polymer is polyethylene. In other embodiments, the sidechain polymer is a polymer derived from a conjugated diene. Examples of conjugated dienes include butadiene, isoprene, 2,3-dimethylbutadiene, 2- phenylbutadiene, 1,3-pentadiene, 2-methyl-l,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3- cyclohexadiene, 2-methyl-l,3-octadiene, 1,3,7-octatriene, myrcene, chloroprene, and farnesene. These conjugated dienes may be used alone or in combination of any two or more. In other embodiments, the sidechain polymer is a polymer derived from hydrogenation of the above conjugated diene polymers, for example hydrogenated polybutadiene, hydrogenated polyisoprene, and the like.

[0089]

[0076] In other embodiments, the sidechain polymer comprises an acrylate or methacrylate monomer of the formula CH2=CR4(COOR5), wherein R4at each occurrence is independently selected from hydrogen and a C1-C4 alkyl group; and R5at each occurrence is independently selected from the group consisting of a linear C1-20 alkyl, branched C3-20 alkyl, monocyclic or polycyclic C3-20 cycloalkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, monocyclic or polycyclic C3-20 cycloalkenyl, monocyclic or polycyclic Cg-2oaryl, or monocyclic or polycyclic C2-20 heteroaryl, preferably linear Ci.g alkyl, branched C3-6 alkyl, or monocyclic or polycyclic C3-10 cycloalkyl, each of which is substituted or unsubstituted, R3optionally including as part of its structure one or more groups chosen from — O— , — C(O)— , — C(O)— O— , or — S— . In some embodiments, preferred acrylate or methacrylate monomers may be selected from alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and benzyl (meth)acrylate; alkylcyclopentyl (meth)acrylates or alkyl-adamantyl (meth)acrylates including 1-ethyl-l-cyclopentyl (meth)acrylate, 1-ethyl-l-cyclohexyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 2-methyl-2- adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate; monomers comprising of a lactone structure, a cyclic carbonate structure, or a sultone structure, including a-gamma-butyrolactone (meth)acrylate, (3,5-dihydroxy-l- adamantyloxycarbonyl)methyl (meth)acrylate, 2-methyl-2-adamantyloxycarbonylmethyl (meth)acrylate, adamantyloxycarbonylmethyl (meth)acrylate, and 2-ethyl-2- adamantyloxycarbonylmethyl (meth)acrylate; hydroxy-functional (meth)acrylates such as 2- PDH-005 hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3- hydroxy-l-adamantyl (meth)acrylate, 3-hydroxy-l-adamantyl (meth)acrylate, 3,5-dihydroxy-l- adamantyl (meth)acrylate, and caprolactone modified hydroxyethyl (meth)acrylates; acidic and anionic (meth)acrylates such as methacrylic acid, acrylic acid, 2-(methacryloyloxy)ethyl acetoacetate, and phosphoethyl (meth)acrylate; amine and amide-functional (meth)acrylates such as 2- (dimethylamino)ethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate, and acrylamide and N- substituted acrylamides; and ether-functional (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylates, 2- methoxyethyl (meth)acrylate, hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yl (meth)acrylate, tetrahydro-2-oxo-3-furyl (meth)acrylate, and 2-(5-oxo-4-oxatricyclo[4.2.1.03,7]nonan- 2-yloxy)-2-oxoethyl (meth)acrylate. In some embodiments, the sidechain polymer is a copolymer comprising two or more alkyl (meth)acrylates. In other embodiments, the sidechain polymer comprises acid-labile groups such as acid-labile ester or acetal groups or anhydrides, examples of which are defined above.

[0090]

[0077] In some embodiments, the sidechain polymer comprises a hydrophilic segment. The hydrophilic segment is a portion of the macromonomer that is composed of a hydrophilic polymer. The hydrophilic polymer may be water soluble and / or capable of forming a hydrogel upon exposure to water. In preferred embodiments, the sidechain polymer comprises a water soluble polymer. Suitable examples of the sidechain polymer may include, but are not limited to, poly(acrylic acid-co- alkyl acrylate), poly(acrylic acid-co-alkyl methacrylate), poly(ethyl ethylene) phosphate, polyethylene glycol-co-propylene glycol), poly(methacrylic acid-co-alkyl acrylate), poly(methacrylic acid-co-alkyl methacrylate), poly(N-isopropylacrylamide), poly(N-vinylpyrrolidone-co-acrylic acid), poly(N- vinylpyrrolidone-co-dimethyl maleate), poly(N-vinylpyrrolidone-co-itaconic acid), poly(N- vinylpyrrolidone-co-itaconic anhydride), poly(N-vinylpyrrolidone-co-maleic acid), poly(N- vinylpyrrolidone-co-maleic anhydride), poly(N-vinylpyrrolidone-co-methacrylic acid), poly(N- vinylpyrrolidone-co-methyl acrylate), poly(N-vinylpyrrolidone-co-methyl itaconate), poly(N- vinylpyrrolidone-co-methyl methacrylate), poly(N-vinylpyrrolidone-co-vinyl acetate), poly(N- vinylpyrrolidone-co-vinyl alcohol), poly(oxazoline), poly(vinyl methyl ether-co-maleic anhydride), polyacrylamide, polyacrylic acid, polyether, polyethylene glycol, polyglycolic acid, polylactic acid, polymethacrylic acid, polyoxymethylene, polypropylene glycol, polytetramethylene glycol, polyvinyl alcohol, and polyvinylpyrrolidone, or combinations thereof.

[0091]

[0078] In some embodiments, the graft polymer comprises an alkali-soluble group. Examples of the alkali-soluble groups include groups having a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an PDH-005

[0092] (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)-imide group, a tris(alkylcarbonyl)methylene group or a tris(alkylsulfonyl)methylene group. Among these alkali-soluble groups, a phenolic hydroxyl group, a carboxylic acid group, and a sulfonic acid group are preferred.

[0093]

[0079] In preferred embodiments, the graft polymer is free of per- and polyfluoroalkyl substances. In preferred embodiments, the graft polymer is free of fluorine (i.e., does not contain a fluorine and is not substituted by a fluorine-containing group). In other preferred embodiments, the graft polymer is free of silicon (i.e., does not contain a silicon atom and is not substituted by a silicon-containing group).

[0080] The sidechain polymer generally has a number of repeat units of 5 to 1000, such as 7 to 100 and 8 to 50. In one embodiment, the sidechain polymer has a number average molecular weight of 300 to 10000 Daltons when measured using gel permeation chromatography (GPC).

[0094]

[0081] In some embodiments, the graft polymer can comprise structures shown in the Formulas (I - V). PDH-005

[0095] (IV)

[0096] (V)

[0097]

[0082] In the Formula (I), the graft polymer comprises repeat units of D to form the backbone, while repeat units of A are grafted onto the backbone. The grafts comprising A termed sidechain polymer are grafted onto the backbone of the polymer as seen in the structure of Formula (I), where repeat units of D form the chain backbone and where repeat units of A are grafted onto the backbone. A and D represent monomers and can be selected from any of the species listed above. The number of repeat units e and x can be the same or different from each other. The number of repeat units e and repeat units x can be the same or different from each other. In an exemplary embodiment, each of e can be an amount of 10 to 1000, while x can also be an amount of 2 to 100.

[0098]

[0083] In the Formula (II), the graft polymer comprises repeat units of D to form the backbone, while repeat units of A and B are copolymerized into a polymer chain that is grafted onto the backbone. A, B, and D represent monomers and can be selected from any of the species listed above. The number of repeat units e, x, and y can be the same or different from each other. The number of repeat units e and repeat units x can be the same or different from each other. In an exemplary embodiment, each of e can be an amount of 10 to 1000, while x and y can also be an amount of 2 to 100. The sidechain polymer in this case is a copolymer and can be a random copolymer, an alternating copolymer, or a block copolymer, and can have linear or branched architectures.

[0099]

[0084] In the Formula (III), the graft polymer comprises repeat units of D and E to form the backbone, while repeat units of A are grafted onto the backbone. A, D, and E represent monomers and can be selected from any of the species listed above. The number of repeat units e, f, and x can be the same or different from each other. The number of repeat units e, f, and repeat units x can be the same or different from each other. In an exemplary embodiment, each of e and f can be an amount of 10 to PDH-005

[0100] 1000, while x can also be an amount of 2 to 100. The backbone polymer in this case is a copolymer and can be a random copolymer, an alternating copolymer, or a block copolymer.

[0101]

[0085] In the Formula (IV), the graft polymer comprises repeat units of D and F to form the backbone, while repeat units of A and B are grafted onto the backbone. A, B, D, and F represent monomers and can be selected from any of the species listed above. The number of repeat units e, g, x, and y can be the same or different from each other. The number of repeat units e, g, x, and y can be the same or different from each other. In an exemplary embodiment, each of e and g can be an amount of 10 to 1000, while x and y can also be an amount of 2 to 100. The backbone polymer in this case is a copolymer and can be a random copolymer, an alternating copolymer, or a block copolymer.

[0102]

[0086] In the Formula (V), the graft polymer comprises repeat units of D to form the backbone, while repeat units of A and B are grafted onto the backbone. A, B, and D represent monomers and can be selected from any of the species listed above. Each of L1, LA, and LBis independently a linker selected from the group consisting of a bond, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted carbocyclylene, optionally substituted heterocyclylene, optionally substituted arylene, optionally substituted heteroarylene, and combinations thereof. The number of repeat units e, x, and y can be the same or different from each other. The number of repeat units e, x, and y can be the same or different from each other. In an exemplary embodiment, each of e can be an amount of 10 to 1000, while x and y can also be an amount of 2 to 100. In some embodiments, A and B are the same.

[0103]

[0087] The disclosure also relates to a method of manufacturing the graft polymer. The method comprises producing a series of macromonomers (that form the backbone polymer) and then performing sequential grafting-through polymerizations to create the graft polymer. Alternatively, grafting-onto or grafting-from techniques can be used for the graft polymer syntheses.

[0104]

[0088] The polymer can be manufactured in a batch process or in a continuous process. The batch process or the continuous process can involve a single or multiple reactors, single or multiple solvent and single or multiple catalysts (also termed initiators).

[0105]

[0089] In one embodiment, in one method of producing the graft polymer, the sidechain polymer is synthesized separately from the second polymer. The sidechain polymer is reactively bonded to the second polymer to form the graft polymer.

[0106]

[0090] In some embodiments, the graft polymer is manufactured by reacting a precursor to the backbone polymer with a chain transfer agent to form backbone polymer precursor-chain transfer agent moiety in a first reactor. The backbone polymer precursor-chain transfer agent moiety is then reacted with a precursor to the sidechain polymer to form the sidechain polymer using a free radical initiator such as azobisisobutyronitrile, or a controlled polymerization such as reversible addition- PDH-005 fragmentation chain transfer (RAFT) polymerization. The sidechain polymer is covalently bonded to the precursor of the backbone polymer during the RAFT polymerization, which is conducted in the first reactor in the presence of a first solvent and a first initiator. The precursor to the backbone polymer is then polymerized via ring opening metathesis polymerization (ROMP) to form the sidechain polymer. The ROMP reaction may be conducted in the first reactor or in another reactor. The graft polymer comprises the backbone polymer with the sidechain polymer grafted onto it.

[0107]

[0091] The second polymer may be polymerized in a second reactor if desired. A precursor to the backbone polymer is reacted with a chain transfer agent to form a backbone polymer precursor-chain transfer agent moiety. The backbone polymer precursor-chain transfer agent moiety is then reacted with the precursor to the second polymer to form the second polymer using RAFT polymerization. The second polymer is covalently bonded to the sidechain polymer precursor-chain transfer agent moiety during the RAFT polymerization, which is conducted in the presence of a second solvent and a second initiator. Since the second polymer is a copolymer, there are two or more precursors that are reacted together with the precursor to the backbone polymer to form the second graft polymer. The precursor to the second polymer is then polymerized via a second ring opening metathesis polymerization (ROMP) to form the second polymer. The second polymer comprises the backbone polymer with the second polymer grafted onto it. In the production of the first and the second polymers, the first reactor may be the same as the second reactor, the first solvent may be the same as the second solvent and the first initiator may be the same as the second initiator. In one embodiment, the first reactor may be different from the second reactor, the first solvent may be different from the second solvent and the first initiator may be different from the second initiator.

[0108]

[0092] In one embodiment, the sidechain polymer is reacted with the second polymer in a second ring opening metathesis polymerization to form the graft polymer. The second ring opening metathesis polymerization may be conducted in either the first reactor, the second reactor or in a third reactor. The graft polymer is then purified by a variety of different methods that are listed below. In another embodiment, the backbone polymer is synthesized first using a monomer as an inimer, a species capable of initiating a chain growth. The backbone is grown first, and then the sidechain polymer is prepared using a "grafting-from" polymerization to prepare the graft polymer.

[0109]

[0093] As noted above, the sidechain polymer, the second polymer and the graft polymer may be purified by a variety of methods. Purification of the respective polymers is optional. The reactants, the respective polymers, and the graft polymer may be purified prior to and / or after the reaction. Purification may include washing, filtration, precipitation, decantation, centrifugation, distillation, or the like, or a combination comprising at least one of the foregoing methods of purification. PDH-005

[0110]

[0094] In one exemplary embodiment, all reactants including the solvents, initiators, endcapping agents and quenchers are purified prior to the reaction. It is generally desirable to use reactants, solvents and initiators that are purified to an amount of greater than or equal to about 90.0 wt % purity, specifically greater than or equal to about 95.0 wt % purity and more specifically greater than about or equal to about 99.0 wt % purity. In another exemplary embodiment, after polymerization to form the graft polymer, it may be subjected to purification by methods that include washing, filtration, precipitation, decantation, centrifugation or distillation. Purification to remove substantially all metallic impurities and metallic catalyst impurities may also be conducted. The reduction of impurities reduces defects in integrated circuits used in electronic devices.

[0111] Barrier Materials for Immersion Lithography

[0112]

[0095] Embodiments of the disclosure relate to photoresist compositions and photolithography processes. One challenge in immersion lithography relates to undesired migration of acid and / or other resist materials from a photoresist layer into the immersion fluid layer. This is shown in FIG. 2A-B.

[0113]

[0096] Among other things, the acid or other photoresist materials that migrate into the immersion fluid can damage the exposure tool as well as reduce resolution of an image patterned into a photoresist layer. Accordingly, the present disclosure provides photoresists and photoresist processes that can achieve reduced migration of materials by application of graft polymers. The inventive graft polymers can be deployed in two manners as barrier materials. The first is as an embedded barrier layer material, where the graft polymer is blended directly into the photoresist composition. This material migrates to the top of the photoresist layer during processing to form an in-situ barrier. The second approach is a barrier layer formed by applying a top coat, where this top coat layer is located on the photoresist layer.

[0114] Photoresist Comprising Graft Polymer

[0115]

[0097] In one embodiment, the present disclosure relates to photoresist compositions that comprise

[0116] (A) a resin or polymer comprising an acid-labile group (referred to here as an "acid-labile polymer");

[0117] (B) a compound capable of generating an acid upon irradiation with actinic rays or actinic radiation (sometimes referred to as a "photoacid generator" or "PAG"); (C) a graft polymer; (D) a solvent, and optionally, one or more of the following: (E) a basic compound or base generator, (F) surfactant, (G) photo-decomposable quencher, and (H) other additives.

[0118] (A) Acid-labile Polymer

[0119]

[0098] The acid-labile polymer, sometimes referred to as a polymer of which solubility in an alkali developer increases and solubility in an organic solvent decreases under the action of an acid, is a polymer or resin having an acid-labile group capable of decomposing under the action of an acid to PDH-005 produce an alkali-soluble or otherwise solubilizing group on the main chain of the polymer. Examples of acid-labile groups and polymers comprising such are listed above.

[0120]

[0099] In some embodiments, this polymer is preferably comprised of monomer units having a monocyclic or polycyclic alicyclic hydrocarbon structure and being capable of increasing the solubility in an alkali developer and decreasing the solubility in an organic solvent under the action of an acid, because the polarity of the polymer is greatly changed between before and after irradiation of actinic radiation and when the resist film is developed using a positive developer (preferably an alkali developer) and a negative developer (preferably an organic solvent), the dissolution contrast is enhanced. Furthermore, the polymer having a monocyclic or polycyclic alicyclic hydrocarbon structure generally has high hydrophobicity and favors a high development rate at the time of developing the resist film in a region of weak light irradiation intensity with a negative developer (preferably an organic developer), and the developability on use of a negative developer is enhanced.

[0121]

[0100] The acid-labile polymer for use in the present disclosure may contain, in addition to the abovedescribed repeating units and polymer species, various repeating structural units for the purpose of controlling dry etching resistance, suitability for standard developer, adhesion to substrate, resist profile and properties generally required of the resist, such as resolving power, heat resistance and sensitivity. Examples of such a repeating structural unit include, but are not limited to, repeating structural units corresponding to the monomers and polymer species described below. By virtue of such a repeating structural unit, the performance required of the alicyclic hydrocarbon-based acid- decomposable polymer, particularly, (1) solubility in coating solvent, (2) film-forming property (glass transition point), (3) solubility in positive or negative developer, (4) film loss (selection of hydrophilic, hydrophobic or alkali-soluble group), (5) adhesion of unexposed area to substrate, (6) dry etching resistance, and the like, can be subtly controlled.

[0122]

[0101] The polymer may contain a repeating unit having a lactone structure or a sultone structure. The repeating unit having a lactone structure or a sultone structure may be used in combination of two or more kinds thereof. In the case where the polymer contains a repeating unit having a lactone structure or a sultone structure, the content of the repeating unit having a lactone structure or a sultone structure ranges preferably from 5 mol % to 60 mol %, more preferably from 5 mol % to 55 mol %, and still more preferably from 10 mol % to 50 mol % based on all repeating units of the polymer. Further, the polymer may have a repeating unit having a cyclic carbonate ester structure, a repeating unit having a hydroxyl group or a cyano group.

[0123]

[0102] The polymer may or may not contain a repeating unit having an acid group, but in the case of containing a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 25 mol % or less, and more preferably 20 mol % or less, based on all repeating PDH-005 units in the polymer. When the polymer contains a repeating unit having an acid group, the content of the repeating unit having an acid group in the polymer is usually 1 mol % or more.

[0124]

[0103] The polymer may further have a repeating unit having an alicyclic hydrocarbon structure and / or an aromatic ring structure which have no polar group (for example, the acid group, the hydroxyl group, and the cyano group) and not exhibiting acid acid sensitivity.

[0125]

[0104] When the composition of the present disclosure is for ArF exposure, from the viewpoint of transparency to ArF light, the polymer used in the composition of the present disclosure preferably has substantially no aromatic ring (specifically, the ratio of a repeating unit having an aromatic group in the resin is preferably 5 mol % or less, more preferably 3 mol % or less, and ideally 0 mol %, that is, the resin does not have an aromatic group), and the polymer preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

[0126]

[0105] The polymer may be synthesized, for example, by polymerization of radicals, cations, or anions of an unsaturated monomer, corresponding to each structure. Further, it is also possible to obtain a target resin by using an unsaturated monomer corresponding to a precursor of each structure to perform polymerization, and then performing a polymer reaction.

[0127]

[0106] In the case where the compositions of the disclosure are irradiated with KrF excimer laser light, electron beam, X-ray or high-energy beam having a wavelength of 50 nm or less (EUV and the like), the polymer may have a repeating unit having an aromatic ring. The repeating unit having an aromatic ring is not particularly limited, and is exemplified in the above described descriptions of the repeating units. Examples thereof may include a styrene unit, a hydroxystyrene unit, a phenyl(meth)acrylate unit, and a hydroxyphenyl(meth)acrylate. More specifically, examples of the polymer may include a resin having a hydroxystyrene-based repeating unit, and a hydroxystyrene- based repeating unit protected by an acid-decomposable group, and a resin having a repeating unit having the aromatic ring, and a repeating unit in which a carboxylic acid moiety of (meth)acrylic acid is protected by an acid-decomposable group.

[0128]

[0107] The polymer in the present disclosure may be synthesized and purified by a conventional method (e.g., radical polymerization). In regard to the synthesis and purification methods, see, e.g., the description in paragraphs 0201 to 0202 of Japanese Patent Application Laid-Open No. 2008- 292975. The weight average molecular weight of the polymer in the present disclosure is 7,000 or more as described above, preferably in a range of 7,000 to 200,000, more preferably 7,000 to 50,000, still more preferably 7,000 to 40,000, and particularly preferably 7,000 to 30,000, in terms of polystyrene by the GPC method. If the weight average molecular weight is less than 7,000, the solubility in an organic developer becomes higher, and thus, there is a concern that a fine pattern may not be formed. PDH-005

[0129]

[0108] The polydispersity (molecular weight distribution) is usually in a range of 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.4 to 2.0. The smaller the molecular weight distribution is, the better the resolution and resist shape are, and the smoother the side wall of the resist pattern is, and thus roughness is excellent.

[0130]

[0109] Examples of the monomer include a compound having one addition-polymerizable unsaturated bond selected from styrenics, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, norbornenes, and vinyl esters. Other than these, an addition-polymerizable unsaturated compound copolymerizable with the monomers corresponding to the above-described various repeating structural units may be copolymerized. In the acid-labile polymer, the molar ratio of respective repeating structural units contained is appropriately determined to control the dry etching resistance of resist, suitability for standard developer, adhesion to substrate, resist profile and performances generally required of the resist, such as resolving power, heat resistance and sensitivity.

[0131] (B) Photoacid Generator

[0132]

[0110] The photoresist composition of the present disclosure contains a photoacid generator (PAG). The PAG which can be used may be appropriately selected from a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photo-decoloring agent for coloring matters, a photo-discoloring agent, a known compound used for microresist or the like and capable of generating an acid upon irradiation with actinic radiation, and mixtures thereof. Any suitable PAG may be used in the photosensitive compositions of the present disclosure. Choice of PAG may be based upon such factors as acidity, catalytic activity, volatility, diffusivity, and solubility. Examples of PAGs include a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imidosulfonate, an oxime sulfonate, a diazodisulfone, a disulfone and an o-nitrobenzyl sulfonate. Suitable classes of PAGs generating sulfonic acids include, but are not limited to, sulfonium or iodonium salts, oximidosulfonates, bissulfonyldiazomethanes, and nitrobenzylsulfonate esters. The PAG may be in non-polymerized or polymeric form, for example, present in a polymerized repeating unit of the polymer matrix. In some embodiments, the PAG is a polymeric PAG, wherein the PAG is introduced into the main or side chain of the polymer.

[0133]

[0111] The photoresist composition may optionally comprise a plurality of PAGs. The plural PAGs may be polymeric, non-polymeric, or may include both polymeric and non-polymeric PAGs. In some embodiments, each of the plurality of PAGs is non-polymeric. In some embodiments, when a plurality of PAGs are used, a first PAG comprises a sulfonate group on the anion and a second PAG comprises an anion that is free of sulfonate groups, such anion containing for example, a sulfonamidate group, a sulfonimidate group, a methide group, or a borate group such as described above. PDH-005

[0134]

[0112] The photoresist composition may include a non-polymerized PAG in an amount from about 1 to 65 wt %, from about 5 to 55 wt %, or from about 8 to 30 wt %, based on total solids of the photoresist composition. In some embodiments, the photoresist composition may include two or more different non-polymerized PAGs in a combined amount from about 1 to 65 wt %, from about 5 to 55 wt %, or from about 8 to 30 wt %, based on total solids of the photoresist composition. In some embodiments, the PAG mixtures comprise 2 or 3 PAGs. Such mixtures may be of the same class or different classes. Examples of preferred mixtures include sulfonium salts with bissulfonyldiazomethane compounds, sulfonium salts and imidosulfonates, and two sulfonium salts.

[0135] (C) Graft Polymer

[0136]

[0113] The photoresist composition includes a graft polymer as described above. Preferred graft polymers for use in photoresists of the disclosure include those formed from any one or more of the monomers described above for forming graft polymers. More preferably, graft polymers for use in photoresists of the disclosure comprise acid-labile groups, such as acid-labile ester or acetal groups, including such groups as described above. Preferred graft polymers for use in photoresists of the disclosure also will be soluble in the same organic solvent(s) used to formulate the photoresist composition. In some embodiments, the photoresist compositions include a single graft polymer, but can optionally include one or more additional graft polymers. The graft polymer may be present in a photoresist composition in relatively small amounts and still provide effective results. For instance, the graft polymer material may be suitable present in about 0.1 to 20 wt% based on total weight of the composition.

[0137]

[0114] In some embodiments, graft polymers for use in photoresists of the disclosure also will have lower surface energy and / or reduced chain entanglement than the acid-labile resin or polymer component. The lower surface energy can facilitate segregation or migration of the graft polymers to top or upper portions of an applied photoresist coating layer. Additionally, reduced chain entanglement also can be preferred because it can facilitate efficient migration (higher diffusion coefficient) of the one or more graft polymers materials to upper regions of the applied photoresist coating layer. In general, a graft polymer exhibits significantly reduced chain entanglement compared to its linear analog due to its densely grafted side chains, which sterically hinder inter-chain interactions and limit entanglement density.

[0138]

[0115] In other embodiments, graft polymers for use in photoresists of the disclosure also will be soluble or become soluble upon post exposure bake (PEB, e.g. 120° C for 60 seconds) in photoresist developer compositions (e.g. 0.26N aqueous alkaline solution). Thus, in addition to acid-labile groups such as acetals and esters as discussed above, other aqueous base-solubilizing groups may be included in the graft polymer such as hydroxyl, carboxy and the like. In preferred embodiments, the graft PDH-005 polymer does not comprise a perfluorinated alkyl substance. In other preferred embodiments, the graft polymer does not comprise fluorine.

[0139] (D) Solvent

[0140]

[0116] The photoresist composition further includes a solvent for, among other things, dissolving the components of the composition or facilitating its coating on a substrate. In some embodiments, the solvent may include an organic-based solvent system comprising one or more organic solvents. The term "organic-based" means that the solvent system includes greater than 50 wt% organic solvent based on weight of solvent in the total composition, greater than 90 wt%, greater than 95 wt%, greater than 99 wt% or 100 wt% organic solvents, based on total solvents of the composition. Generally, the solvent may comprise one or more of a ketone-based solvent, an ester-based solvent, an alcohol- based solvent, an amide-based solvent, an ether-based solvent, a hydrocarbon-based solvent, or a combination thereof. The total solvent content (i.e., cumulative solvent content for all solvents) in the photoresist compositions is from 40 to 99 wt %, from 70 to 99 wt %, or from 85 to 99 wt %, based on total weight of the photoresist composition. The desired solvent content will depend, for example, on the desired thickness of the coated photoresist layer and coating conditions.

[0141] (E) Basic Compound or Base Generator

[0142]

[0117] The photoresist composition of the present disclosure may comprise a basic compound or base additive or base generator for reducing the change of performance in aging from exposure until heating or to act as a diffusion control agent. One purpose of the base additive is to scavenge protons present in the photosensitive composition prior to being irradiated by the actinic radiation. The base prevents attack and cleavage of the acid labile groups by the undesirable acids, thereby increasing the performance and stability of the photosensitive composition. In addition, the base can act as a diffusion control agent to prevent the photogenerated acid from migrating too far after exposure and lowering resolution. The percentage of base in the photosensitive composition should be significantly lower than the PAG or otherwise the photosensitivity becomes too low. The preferred range of the base compounds, when present, is from about 3 wt % to about 50 wt % of the PAG.

[0143]

[0118] Suitable examples of base additives include, but are not limited to, amine, guanidines, aminopyrrolidines, pyrazoles, pyrazolines, piperazines, aminomorpholines, aminoalkylmorpholines and piperidines, imidazoles, diazabicyclo compounds, anilines, hydroxyalkylamines, and hydroxyanilines. The base additive may be in non-polymeric or polymer-bound form. When in polymeric form, the quencher may be present in polymerized units on the graft polymer. The polymerized units containing the quencher are present in an amount of from 0.1 to 30 mole %, preferably from 1 to 10 mole %, and more preferably from 1 to 2 mole %, based on total repeating units of the polymer. PDH-005

[0144] (F) Surfactant

[0145]

[0119] The photoresist composition of the present disclosure may further comprise a surfactant. When the photoresist composition of the present disclosure contains the surfactant, a resist pattern with good sensitivity, resolution and adhesion as well as less development defects can be obtained when an exposure light source of 250 nm or less, particularly 220 nm or less, is used. Exemplary surfactants include those which exhibit an amphiphilic nature, meaning they possess a hydrophilic head group or groups, which have a strong affinity for water, and a long hydrophobic tail, which is organophilic and repels water. Suitable surfactants may be ionic (i.e., anionic, cationic, or amphoteric) or non-ionic.

[0146] (G) Photo-decomposable quencher

[0147]

[0120] Photo-decomposable quenchers generate a weak acid upon irradiation. The acid generated from a photo-decomposable quencher is not strong enough to react rapidly with acid-labile groups that are present in the polymer binder. Examples of photo-decomposable quenchers include, for example, photo-decomposable cations, and preferably those also useful for preparing strong acid generator compounds, paired with an anion of a weak acid (pKa>-l) such as, for example, an anion of a Ci-20 carboxylic acid or C1-20 sulfonic acid. Exemplary photo-decomposable quenchers are onium carboxylates, preferably an iodonium salt or a sulfonium salt. The photo-decomposable quencher may be in non-polymeric or polymer-bound form. The content of the onium carboxylate in the composition is generally from 0.1 to 20 mass %, preferably from 0.5 to 10 mass %, more preferably from 1 to 7 mass %, based on the entire solid content of the composition.

[0148] (H) Other Additives

[0149]

[0121] The positive resist composition of the present disclosure may further contain, for example, an actinic or contrast dye, an anti-striation agent, a plasticizer, a speed enhancer, a photosensitizer, a light absorbent, an alkali-soluble resin, a dissolution inhibitor, or a compound for accelerating dissolution in a developer (for example, a phenol compound having a molecular weight of 1,000 or less, or a carboxyl group-containing alicyclic or aliphatic compound), a resin having at least either a fluorine atom or a silicon atom, and the like, or combinations thereof. If present, the optional additives are present in the photoresist compositions in an amount from 0.01 to 10 wt %, based on total solids of the photoresist composition.

[0150]

[0122] The photoresists used in accordance with the disclosure are generally prepared following known procedures. For example, a photoresist of the disclosure can be prepared as a coating composition by dissolving the components of the photoresist in the solvent(s) of choice. The total solvent content (i.e., cumulative solvent content for all solvents) in the composition is preferably from 60 to 99.9 wt %, more preferably from 85 to 99 wt %, and still more preferably from 90 to 99 wt %, PDH-005 based on total weight of the composition. The desired solvent content will depend, for example, on the desired thickness of the coated layer and coating conditions. The resulting composition may optionally be filtered to remove any undissolved particles and / or treated to remove metal ions.

[0151]

[0123] Particularly preferred photoresists employing graft polymers of the disclosure can exhibit reduced migration (leaching) of photoresist components into the immersion fluid during contact of the immersion fluid during an exposure step. Significantly, such reduced migration of photoresist materials into immersion fluid can be achieved without applying any type of cover or top coat barrier layer over the photoresist and interposed between the resist layer and immersion fluid.

[0152]

[0124] In certain embodiments, the photoresist employing graft polymer of the disclosure exhibit a solubility switch to facilitate both compatibility with the immersion lithographic process and efficient post-exposure removal. Specifically, a film of the photoresist should possess a hydrophobic surface character prior to exposure to prevent absorption or mixing with the aqueous immersion fluid and to maintain pattern integrity during exposure. In one embodiment, a film of the photoresist before exposure should possess a water contact angle of 70 to 90 degrees. In an exemplary embodiment, it is desirable for a film of the photoresist to have a preferred water contact angle of 85 to 90 degrees before exposure. Upon exposure, the material should undergo a chemical or physical transformation that increases its hydrophilicity, resulting in a water contact angle of 70 degrees or less, thereby enabling its dissolution or removal in standard aqueous developer or rinse solutions. The hydrophobic- to-hydrophilic transition may be achieved via mechanisms such as photoacid generation, cleavage of hydrophobic protecting groups, or modification of polar functional groups on the graft polymer. This solubility switch ensures that the graft polymer does not interfere with the photochemical performance of the underlying resist and can be cleanly removed following exposure without leaving residue or causing pattern collapse.

[0153] Top Coat Composition Comprising Graft Polymer

[0154]

[0125] In some embodiments, the present disclosure relates to top coat compositions that contain (A) a graft polymer; (B) a solvent, and optionally, one or more of the following: (C) optional additives, selected from acids or acid generators; basic compounds or base generators; surfactants; photo- decomposable quenchers; and other additives.

[0155] (A) Graft polymer

[0156]

[0126] The top coat composition comprising a graft polymer comprises a graft polymer selected from those described above. In some embodiments, the top coat compositions include a single graft polymer, but can optionally include one or more additional graft polymers or other polymers. The graft polymer is present in an amount of from 0.1 to 20 wt % based on total weight of the composition. In preferred embodiments, the graft polymer is free of per- and polyfluoroalkyl substances. In other PDH-005 preferred embodiments, the graft polymer is free of fluorine. In other preferred embodiments, the graft polymer is free of silicon (i.e., does not contain a silicon atom and is not substituted by a sil iconcontaining group).

[0157] (B) Solvent

[0158]

[0127] The top coat composition comprising a graft polymer comprises a solvent. Accordingly, the solvent may be any suitable solvent that may facilitate coating of the top coat on the photoresist layer, provided that it does not dissolve the photoresist. The solvent is chosen from water, organic solvents and mixtures thereof. The solvent component is present in an amount of from 90 to 99 wt % based on total solids of the composition. Suitable solvents may be selected from those listed above. The desired solvent content will depend, for example, on the desired thickness of the coated layer and coating conditions.

[0159] (C) Optional additives

[0160]

[0128] In some embodiments, the top coat composition comprising a graft polymer of the present disclosure comprises an acid or acid generator; basic compound or base generator; surfactant; photo- decomposable quencher; and other additives. Suitable examples of these optional additives are listed above. If present, the optional additives are present in the composition in an amount from 0.01 to 10 wt %, based on total solids of the composition.

[0161]

[0129] In some embodiments, the top coat compositions further include an acid or acid generator. The acid to be used in the anti-reflective coating composition of the present disclosure may be an organic acid or an inorganic acid. Preferred examples of the organic acid include alkylsulfonic acids, alkylbenzenesulfonic acids, alkylcarboxylic acids, alkylbenzenecarboxylic acids, and those obtained by replacing all or part of the hydrogen atoms of the alkyl group described above with fluorine atoms. As the aforementioned alkyl group, those which contain 1 to 20 carbon atoms are preferred. These organic acids are used in an additional amount of usually 0.1% by weight to 2.0% by weight, preferably 0.5% by weight to 1.0% by weight, in the composition. The acid or generated acid in the case of an acid generator should be sufficient with heat to cause cleavage of the bonds of acid-labile groups of the polymer. The acid or acid generator is present in the composition in an amount of from about 0.01 to 20 wt % based on the total solids of the composition. Preferred organic acids or acid generators are those that are free of per- and polyfluoroalkyl substances or free of fluorine.

[0162]

[0130] In some embodiments, the top coat compositions further include a basic compound or base generator. The basic compound is present for purposes of neutralizing acid generated in the surface region of the underlying photoresist layer by stray light which reaches what are intended to be unexposed (dark) regions of the photoresist layer. This allows for improvement in depth of focus in the defocus area and exposure latitude by controlling unwanted deprotection reactions in the PDH-005 unexposed areas. As a result, irregularities in the profile, for example, necking and T-topping, in formed resist patterns can be minimized or avoided.

[0163]

[0131] To allow for effective interaction between the basic compound and the acid generated in the dark areas of the underlying photoresist layer, the basic compound should be of a non-surfactant- type. That is, the basic compound should not be of a type that migrates to the top surface of the top coat layer due, for example, to a low surface free energy relative to other components of the top coat composition. In such a case, the basic quencher would not be appreciably present at the photoresist layer interface for interaction with the generated acid to prevent acid deprotection. The basic compound should therefore be of a type that is present at the top coat layer / photoresist layer interface, whether being uniformly dispersed through the top coat layer or forming a graded or segregated layer at the interface. Such a segregated layer can be achieved by selection of a basic compound having a high surface free energy relative to other components of the top coat composition. Suitable basic compounds and base generators can be selected from those defined above.

[0164]

[0132] The top coat compositions used in accordance with the disclosure are generally prepared following known procedures. For example, a top coat composition of the disclosure can be prepared as a coating composition by dissolving the components of the top coat composition in the solvent(s) of choice. The resulting composition may optionally be filtered to remove any undissolved particles and / or treated to remove metal ions.

[0165]

[0133] Top coats of the disclosure comprising graft polymers can exhibit reduced migration (leaching) of underlying photoresist components into the immersion fluid during exposure. In certain embodiments, the top coat materials comprising graft polymers of the disclosure exhibit a solubility switch to facilitate both compatibility with the immersion lithographic process and efficient postexposure removal. Specifically, a film of the top coat should possess a hydrophobic surface character prior to exposure to prevent absorption of, or mixing with, the aqueous immersion fluid and to maintain pattern fidelity during the exposure step. In one embodiment, a top coat film before exposure exhibits a water contact angle in the range of 70 to 90 degrees. In an exemplary embodiment, the top coat exhibits a preferred water contact angle of 85 to 90 degrees prior to exposure. Upon exposure, the material undergoes a chemical or physical transformation that increases its hydrophilicity, resulting in a water contact angle of 70 degrees or less, thereby enabling dissolution or removal in standard aqueous developer or rinse solutions. The hydrophobic-to- hydrophilic transition may be achieved through mechanisms such as photoacid generation, cleavage of hydrophobic protecting groups, or modification of polar functional groups on the graft polymer. This solubility switch ensures that the top coat does not interfere with the photochemical PDH-005 performance of the underlying photoresist and can be cleanly removed after exposure without leaving residue or inducing pattern collapse.

[0166] Top Anti-Reflective Coating Comprising Graft Polymer

[0167]

[0134] Another embodiment of the present disclosure relates to anti-reflective coatings (TARCs) useful for photolithography. TARCs play a critical role in photolithography by minimizing light reflection and standing wave effects at the resist interface, thereby improving critical dimension control and pattern fidelity. The unique architecture of graft or graft polymers, featuring a densely grafted side-chain structure, provides enhanced film uniformity, low surface roughness, and tunable optical properties, making them particularly well-suited for TARC applications. These polymers can be designed to achieve the desired refractive index and solubility profile, enabling efficient coating, exposure, and post-exposure removal. In some embodiments, the present disclosure relates to anti- reflective coating compositions that contain (A) a graft polymer; (B) a solvent, and optionally, (C) an acid or acid generator; (D) a basic compound or base generator; and (E) other additives.

[0168] (A) Graft polymer

[0169]

[0135] Examples of graft polymers useful for the inventive anti-reflective coating compositions may be selected from those graft polymers described above. In some embodiments, the graft polymer comprises a hydrophilic polymer. The hydrophilic polymer may be water soluble and / or capable of forming a hydrogel upon exposure to water. In preferred embodiments, the graft polymer comprises a water soluble polymer. In some embodiments, the top coat compositions include a single graft polymer, but can optionally include one or more additional graft polymers or other polymers. In preferred embodiments, the graft polymer is free of per- and polyfluoroalkyl substances. In other preferred embodiments, the graft polymer is free of fluorine. In other preferred embodiments, the graft polymer is free of silicon. The graft polymer is present in an amount of from 0.1 to 20 wt % based on total weight of the composition.

[0170]

[0136] In order to obtain anti-reflective properties, it is generally believed to be necessary to satisfy the conditions of the following Formula 6 and Formula 7: wherein ntarc represents a refractive index of an anti-reflective coating, and nresist represents a refractive index of a resist; wherein dtarc represents a thickness of the anti-reflective coating, X represents a wavelength of energy rays, and x represents an odd integer. PDH-005

[0171]

[0137] In certain embodiments, the refractive index of the top anti-reflective coating composition can be tuned through selection of monomers for the backbone and sidechain polymers. For example, incorporation of aromatic or highly polarizable monomers can increase refractive index, while aliphatic or fluorinated monomers can reduce it. This allows for formulation of materials with a refractive index closely matched to the square root of the refractive index of the underlying photoresist, thereby optimizing destructive interference and minimizing reflective notching. In some embodiments, the TARC can reduce the reflectivity at the air-resist interface from an initial reflectivity of 25% down to less than 5%, in preferred embodiments less than 2%, and in more preferred embodiments less that 1% (representing a reduction of over 90%).

[0172] (B) Solvent

[0173]

[0138] The anti-reflective coating composition comprises a solvent. In preferred embodiments, the solvent is an aqueous solvent, with water being most preferred as the majority by weight of the total solvent. As the water, water from which organic impurities and metal ions are removed by distillation, ion-exchange treatment, filter treatment or various adsorption treatments is preferred.

[0174]

[0139] Additionally, it is possible to use a water-soluble organic solvent together with water for the purpose of improving coating properties of the anti-reflective coating composition. As the water- soluble organic solvent, any solvent may be used that dissolves in water in a concentration of 0.1% by weight or more, and there are illustrated, for example, alcohols, amides, aromatic compounds, carboxylic acids, carboxylic anhydrides, diols, esters, ethers, halocarbons, hydrocarbons, ketones, lactates, nitriles, phenols, pyruvates, sulfoxides and sulfones. These specific examples are illustrated merely as examples of the organic solvents, and do not limit the organic solvents to be used in the present disclosure in any way.

[0175] (C) Acid or acid generator

[0176]

[0140] In some embodiments, the anti-reflective coating composition of the present disclosure comprises an acid. The acid to be used in the anti-reflective coating composition of the present disclosure may be an organic acid, organic acid generator, or an inorganic acid. Examples of the organic acid include alkylsulfonic acids, alkylbenzenesulfonic acids, alkylcarboxylic acids, alkylbenzenecarboxylic acids, and those obtained by replacing all or part of the hydrogen atoms of the alkyl group described above with fluorine atoms. Additional examples are listed above. Preferred organic acids or acid generators are those that are free per- and polyfluoroalkyl substances or free of fluorine.

[0177]

[0141] These organic acids are used in an additional amount of usually 0.1% by weight to 2.0% by weight, preferably 0.5% by weight to 1.0% by weight, in the anti-reflective coating composition. PDH-005

[0178]

[0142] Examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, hydrofluoric acid and hydrobromic acid. These inorganic acids are added in order to reduce pH of the anti-reflective coating composition to 7 or less, and the amount thereof to be used is determined in connection with the amount of the basic compound to be described hereinafter, but is usually 0.01% by weight to 0.2% by weight based on the anti-reflective coating composition. These organic acids and the inorganic acids may be used alone or in combination of two or more thereof. In other embodiments, the anti-reflective coating composition comprises an acid or acid generator selected from those listed above.

[0179]

[0143] In some embodiments, the acidic state of the anti-reflective coating composition is required to be 7 or less in pH. Particularly, in the case where the photoresist is a positive-working chemically amplified photoresist, the pH of the anti-reflective coating composition is in the range of preferably 1.0 to 6.0, more preferably 1.0 to 4.0, still more preferably 1.6 to 2.6.

[0180] (D) Basic Compound or Base Generator

[0181]

[0144] In some embodiments, the anti-reflective coating composition of the present disclosure comprises a basic compound. Examples of the basic compound include amines and other bases listed above. These bases are introduced into the composition preferably as base salts previously formed with, for example, carboxylic acids in the polymer. Alternatively, the base may be introduced into the anti-reflective coating composition by mixing the base with the polymer in, for example, an aqueous solution to prepare previously an aqueous solution of an base salt of the polymer, and using this aqueous solution as a material for producing the anti-reflective coating composition. Of course, it is possible to add the base together with the polymer and an acid upon preparation of the composition to incorporate thereby the base in the composition. In this occasion, the ratio of the acid group such as carboxylic acid of the polymer to the base is preferably in the range of 1:0.6 to 1:1.2, more preferably 1:0.7 to 1:1.1, in terms of chemical equivalent weight ratio.

[0182] (E) Other additives

[0183]

[0145] The anti-reflective coating composition of the present disclosure may be compounded, as needed, with other additives. Examples of such additives include surfactants such as nonionic surfactants, anionic surfactants and amphoteric surfactants to be added for the purpose of improving coating properties. Suitable examples of these surfactants are listed above. The anti-reflective coating composition of the present disclosure may further contain optional additives from those listed above. If present, the optional additives are present in the compositions in an amount from 0.01 to 10 wt%, based on total solids of the composition.

[0184]

[0146] The anti-reflective coating compositions of the present disclosure are generally prepared following known procedures. For example, an anti-reflective coating composition can be prepared by PDH-005 dissolving the components in the solvent(s) of choice. The resulting composition may optionally be filtered to remove any undissolved particles and / or treated to remove metal ions.

[0185] Process Solution Comprising Graft Polymer

[0186]

[0147] Another embodiment of the present disclosure is directed to process solutions that are used to reduce the number of defects incurred during the manufacturing of the semiconductor device and methods of using the same. The surfactant within the process solution— present in minor amounts— aids in removing particulates that may lead to defects through dispersion. In certain embodiments, the process solution of the present disclosure may reduce post-development defects by improving the wetting of the solution on the surface of the patterned photoresist layer. The improved wetting of the process solution may remove any residues left inside the contact holes or within dense features. The process solution of the present disclosure, when employed as a post-development rinse, may also reduce the capillary forces exerted on the patterned lines thereby contributing to pattern collapse defects. Further, the process solution works more effectively in dynamic rinse situations with relatively minor foam generation compared to other surfactants presently used in the art.

[0187]

[0148] The process solution of the present disclosure can be used in a variety of processes related to the manufacture of a semiconductor device such as for example, lithography process solutions, i.e., rinse, resist, edge bead remover, and anti-reflective coating solutions; post-etching process solutions, i.e., sidewall film, stripper, post-strip / ash rinse solutions; wafer cleaning process solutions, i.e., additives to RCA or other standard cleaning solutions, super-critical CO2 cleaning solutions; and process solutions for critical cleaning or precision cleaning for aerospace applications. In certain embodiments, the process solution of the present disclosure may be employed as a lithography rinse solution. The surfactant within the process solution may allow for the reduction of equilibrium and dynamic surface tension while minimizing foaming.

[0188]

[0149] In some embodiments, the process solution composition comprises (A) a surfactant comprising a graft polymer; (B) a solvent, and optionally, (C) a dispersant; and (D) other additives.

[0189] (A) Surfactant comprising a graft polymer

[0190]

[0150] The inventive process solutions comprise at least one surfactant comprising a graft polymer. Surfactants comprising graft polymers suitable for process solutions exhibit an amphiphilic nature, meaning that they can be both hydrophilic and hydrophobic at the same time. Examples of graft polymers useful for the inventive process solution comprising graft polymer compositions may be selected from those graft polymers described above. In some embodiments, the process solution compositions include a single graft polymer, but can optionally include one or more additional graft polymers or other polymers. In some embodiments, the graft polymer comprises a hydrophilic polymer. The hydrophilic polymer may be water soluble and / or capable of forming a hydrogel upon PDH-005 exposure to water. In some embodiments, the graft polymer comprises a water soluble polymer. In other embodiments, the graft polymer is free of per- and polyfluoroalkyl substances. In other preferred embodiments, the graft polymer is free of fluorine. In other preferred embodiments, the graft polymer is free of silicon. The graft polymer is present in an amount of from 0.001 to 1 wt% based on total weight of the composition.

[0191] (B) Solvent

[0192]

[0151] The process solution of the present disclosure comprises a solvent selected from an aqueousbased solvent and / or non-aqueous-based solvent. The term "aqueous" as used herein, describes a solvent or liquid dispersing medium, which comprises at least 80 weight percent, preferably 90 weight percent, and more preferably at least 95 weight percent water. The preferred aqueous-based solvent is deionized water. In embodiments wherein the process solution is aqueous-based, it is desirable that the composition demonstrates a dynamic surface tension of less than 45 dynes / cm at a concentration of less than or equal to 5 weight percent in water at 23° C and 1 bubble / second according to the maximum-bubble-pressure method of measuring surface tension described in Langmuir 1986, 2, 428- 432, which is incorporated herein by reference in its entirety.

[0193]

[0152] In embodiments where a non-aqueous solvent is used in addition to or in place of an aqueous solvent such as water, the non-aqueous solvent selected will not react with the at least one surfactant contained therein, other additives within the process solution, or the substrate itself. Suitable solvents include, but are not limited to: alcohols, amides, aromatic compounds, carboxylic acids, carboxylic anhydrides, diols, esters, ethers, halocarbons, hydrocarbons, ketones, lactates, nitriles, phenols, pyruvates, sulfoxides and sulfones. The non-aqueous solvents enumerated above may be used alone or in combination with two or more solvents. In certain embodiments, the process solution may contain at least one non-aqueous solvent that is miscible in an aqueous solvent or is water-miscible. In these embodiments, the amount of non-aqueous solvent within the process solution may range from about 1 to about 50% by weight, with the balance of the solvent within the process solution comprising an aqueous solvent.

[0194] (C) Dispersant

[0195]

[0153] The process solution may optionally contain a dispersant. The amount of dispersant that is added to the process solution ranges from about 10 to about 10,000 ppm, preferably about 10 to about 5,000 ppm, and more preferably from about 10 to about 1,000 ppm. The term dispersant, as used herein, describes compounds that enhance the dispersion of particles such as dust, processing residue, hydrocarbons, metal oxides, pigment or other contaminants within the process solution. Dispersants suitable for the present disclosure preferably have a number average molecular weight that ranges from about 10 to about 10,000. PDH-005

[0196]

[0154] The dispersant may be an ionic or a nonionic compound. The ionic or nonionic compound may further comprise a copolymer, an oligomer, or a surfactant, alone or in combination. The term copolymer, as used herein, relates to a polymer compound consisting of more than one polymeric compound such as block, star, or grafted copolymers. Examples of a nonionic copolymer dispersant include polymeric compounds such as the tri-block EO-PO-EO co-polymers PLURONIC® L121, L123, L31, L81, L101 and P123 (BASF, Inc.). Examples of ionic oligomer dispersants include SMA® 1440 and 2625 oligomers (Elf Alfochem). Alternatively, the dispersant may comprise an additional surfactant listed from those above. In some embodiments, the dispersant comprises a graft polymer.

[0197] (D) Other additives

[0198]

[0155] Various other additives may be optionally added to the process solution depending upon the application. These additives may include, but are not limited to, stabilizers, dissolving aids, colorants, wetting agents, antifoamers, buffering agents, and other additional surfactants. Generally, unless otherwise stated, the amount of each of these additives would be about 0.0001 to 1 percent by weight, more preferably 0.0001 to 0.1 percent by weight, based upon the total weight of the process solution. In embodiments where one or more additional surfactants are added to the process solution, the surfactant may be any of the surfactants disclosed herein or provided in the reference McCutcheon's Emulsifiers and Detergents.

[0199]

[0156] The process solution of the present disclosure may be prepared by mixing the graft polymer with aqueous and / or non-aqueous solvents and any additional additives. In certain embodiments, the mixing may be done at a temperature range of about 40 to 60° C to affect dissolution of the ingredients contained therein. The resulting process solution may optionally be filtered to remove any undissolved particles that could potentially harm the substrate.

[0200] Pattern Forming Methods

[0201]

[0157] The present disclosure provides methods for lithographic processing. Some embodiments relate to an immersion exposure protocol, while others relate to a dry exposure protocol. Patterning methods have been described in detail (see Mack, C.A. (2012) Fundamental Principles of Optical Lithography: The Science of Microfabrication. Wiley. DOI:10.1002 / 9780470723876). Methods using the compositions of the disclosure will now be described. Suitable substrates on which the photoresist compositions can be coated include electronic device substrates. A wide variety of electronic device substrates may be used in the present disclosure, such as: semiconductor wafers; polycrystalline silicon substrates; packaging substrates such as multichip modules; flat panel display substrates; substrates for light emitting diodes (LEDs) including organic light emitting diodes (OLEDs); and the like, with semiconductor wafers being typical. Such substrates are composed of one or more of silicon, poly silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, PDH-005 sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates may be in the form of wafers such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs. Such substrates may be any suitable size. Typical wafer substrate diameters are 200 to 300 millimeters (mm), although wafers having smaller and larger diameters may be suitably employed according to the present disclosure. The substrates may include one or more layers or structures which may optionally include active or operable portions of devices being formed.

[0202]

[0158] In one example, one or more layers to be patterned are selected from a hardmask layer, for example, a spin-on-carbon (SOC), amorphous carbon, or metal hardmask layer, a CVD layer such as a silicon nitride (SiN), a silicon oxide (SiO), or silicon oxynitride (SiON) layer, an organic or inorganic underlayer or anti-reflective coating, or combinations thereof, are provided on an upper surface of the substrate prior to coating a photoresist composition of the present disclosure. Such layers, together with an overcoated photoresist layer, form a lithographic material stack.

[0203]

[0159] Optionally, a layer of an adhesion promoter may be applied to the substrate surface prior to coating the photoresist compositions. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films may be used, such as silanes, including organosilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or an aminosilane coupler such as gamma-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those sold under the AP 3000, AP 8000, and AP 9000S designations, available from DuPont Electronics & Imaging (Marlborough, Mass.).

[0204]

[0160] The photoresist composition is then coated on the substrate by any suitable method, including spin coating, spray coating, dip coating, doctor blading, or the like. For example, applying the layer of photoresist may be accomplished by spin coating the photoresist in solvent using a coating track, in which the photoresist is dispensed on a spinning wafer. During dispensing, the wafer is spun at a speed of up to 4,000 rotations per minute (rpm), for example, from 200 to 3,000 rpm, for example, 1,000 to 2,500 rpm, for a period from 15 to 120 seconds to obtain a layer of the photoresist composition on the substrate. It will be appreciated by those skilled in the art that the thickness of the coated layer may be adjusted by changing the spin speed and / or the solids content of the composition. A photoresist layer formed from the compositions of the disclosure has a dried layer thickness from 10 to 1000 nanometers (nm), preferably from 15 to 500 nm, and more preferably from 20 to 200 nm.

[0205]

[0161] The photoresist composition is next soft-baked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving adhesion of the layer to the substrate. The soft bake is performed, for example, on a hotplate or in an oven, with a hotplate being typical. The soft bake temperature and time will depend, for example, on the particular photoresist composition and PDH-005 thickness. The soft bake temperature is from 90 to 170° C, and more preferably from 110 to 150° C. The soft bake time is from 10 seconds to 20 minutes, more preferably from 1 minute to 10 minutes, and still more preferably from 1 minute to 5 minutes. The heating time can be readily determined by one of ordinary skill in the art based on the ingredients of the composition.

[0206]

[0162] In some embodiments, a layer of a top coat composition or top anti-reflection coating may next be applied on top of the layer of photoresist composition before patterning. When immersion photolithography is employed, a layer of a top coat composition described above comprising a graft polymer may be applied on top of the layer of photoresist composition. The top coat composition is coated and processed in similar fashion as described above for applying the photoresist composition, including coating and soft-baking.

[0207]

[0163] In other embodiments, a top anti-reflective coating composition of the disclosure may be coated on top of the layer of photoresist composition before patterning. The top coat composition is coated and processed in similar fashion as described above for applying the photoresist composition, including coating and soft-baking. The film thickness of the anti-reflective coating composition of the present disclosure is preferably, in view of anti-reflecting function, satisfies the afore-mentioned Formulae 6 and 7 as much as possible. The film thickness is preferably 80 to 10,000 A, more preferably 330 A to 990 A. Also, application of the anti-reflective coating composition can be conducted by any of conventionally known coating methods such as a spin coating method. It will be appreciated by those skilled in the art that the thickness of the coated layer may be adjusted by changing the spin speed and / or the solids content of the composition.

[0208]

[0164] The combined film stack is next pattern-wise exposed to activating radiation to create a difference in solubility between exposed and unexposed regions to form a latent image in the photoresist composition. The exposure is conducted through a patterned photomask that has optically transparent and optically opaque regions corresponding to regions of the resist layer to be exposed and unexposed, respectively. Such exposure may, alternatively, be conducted without a photomask in a direct writing method, as used for e-beam lithography. The activating actinic radiation has a wavelength of sub-400 nm, sub-300 nm or sub-200 nm, with 248 nm (KrF), or 13.5 nm (EUV) wavelengths. The methods find use in immersion or dry (non-immersion) lithography techniques. The exposure energy is from 1 to 200 millijoules per square centimeter (mJ / cm2), preferably from 10 to 100 mJ / cm2, and more preferably from 20 to 50 mJ / cm2, dependent upon the exposure tool and components of the photoresist composition.

[0209]

[0165] Following exposure of the photoresist layer, a post-exposure bake (PEB) of the exposed photoresist layer is performed. The PEB can be conducted, for example, on a hotplate or in an oven, with a hotplate being typical. Conditions for the PEB will depend, for example, on the particular PDH-005 photoresist composition and layer thickness. The PEB is conducted at a temperature from 80 to 150° C, and a time from 30 to 120 seconds. A latent image defined by the polarity-switched (exposed regions) and unswitched regions (unexposed regions) is formed in the photoresist.

[0210]

[0166] The exposed photoresist layer is then developed with a suitable developer to selectively remove those regions of the layer that are soluble in the developer while the remaining insoluble regions form the resulting photoresist pattern relief image. In embodiments employing the inventive top anti-reflection coating, this composition serves to prevent multiple reflections within the photoresist film, increase the amount of reduction in thickness of the photoresist film upon development with a developer after exposure, and form a pattern having a rectangular cross-sectional pattern and not having T-top or round top. The resulting photoresist pattern relief image has a substantially vertical profile devoid of standing waves and / or a T-shaped cross section.

[0211]

[0167] In the case of a positive-tone development (PTD) process, the exposed regions of the photoresist layer are removed during development and unexposed regions remain. Conversely, in a negative-tone development (NTD) process, the exposed regions of the photoresist layer remain, and unexposed regions are removed during development. Application of the developer may be accomplished by any suitable method such as described above with respect to application of the photoresist composition, with spin coating being typical. The development time is for a period effective to remove the soluble regions of the photoresist, with a time of from 5 to 60 seconds being typical. Development is conducted at room temperature.

[0212]

[0168] Suitable developers for a PTD process include aqueous base developers, for example, quaternary ammonium hydroxide solutions such as tetramethylammonium hydroxide (TMAH), preferably 0.26 normal (N) TMAH, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like. Suitable developers for an NTD process are organic solvent-based, meaning the cumulative content of organic solvents in the developer is 50 wt % or more, 95 wt % or more, 98 wt % or more, or 100 wt %, based on total weight of the developer. Suitable organic solvents for the NTD developer include, for example, those chosen from ketones, esters, ethers, hydrocarbons, and mixtures thereof. In some examples, the developer is 2-heptanone or n-butyl acetate.

[0213]

[0169] In some embodiments, a process solution comprising a graft polymer (i.e., the process solution) is preferably used to treat the surface of a substrate during or after the development step. The process solution is preferably applied to the surface of the substrate as a prepared solution. In alternative embodiments, however, the process solution can be prepared within the rinse stream just prior to or during contact with the substrate surface. For example, a certain quantity of one or more graft polymers can be injected into a continuous stream of water and / or non-aqueous solvent medium PDH-005 that optionally includes other additives thereby forming the process solution. In some embodiments of the present disclosure, a portion of the graft polymer may be added to the substrate after application of the process solution. In this case, the process solution may be formed in multiple steps during the processing of the substrate. In still other embodiments of the present disclosure, the graft polymer can be also deposited upon or through the material of a high surface area device such as a cartridge or filter (which may or may not include other additives). A stream of water and / or nonaqueous solvent then passes through the cartridge or filter thereby forming the process solution. In still another embodiment of the present disclosure, the process solution is prepared during the contacting step. In this connection, at least one graft polymer is introduced via a dropper or other means to the surface of the substrate. Water and / or non-aqueous solvent medium is then introduced to the surface of the substrate and mixes with the graft polymer on the surface of the substrate thereby forming the process solution.

[0214]

[0170] In an alternative embodiment of the disclosure, a concentrated composition comprising a graft polymer is provided that may be diluted in water and / or non-aqueous solvents to provide the process solution. A concentrated composition of the disclosure, or "concentrate" allows one to dilute the concentrate to the desired strength and pH. A concentrate also permits longer shelf life and easier shipping and storage of the product.

[0215]

[0171] A variety of means can be employed in contacting the process solution with the substrate surface. The actual conditions of the contacting step (i.e., temperature, time, and the like) may vary over wide ranges and are generally dependent on a variety of factors such as, but not limited to, the nature and amount of residue on the surface of the substrate and the hydrophobicity or hydrophilicity of the substrate surface, etc. The contact step can be conducted in either a dynamic method such as, for example, a streamline process for applying the process solution over the surface of the substrate or in a static method such as, for example, a puddle rinse or immersing the substrate within a bath containing the process solution. The process solution may also be sprayed onto the surface of the substrate in a dynamic method such as in a continuous process or sprayed onto the surface and allowed to remain there in a static method. In certain embodiments, the contacting step is conducted in a static method. The duration of the contacting step, or time of contact of the process solution to the substrate surface, can vary from a fraction of a second to hundreds of seconds. Preferably, the duration can range from 1 to 200 seconds, preferably from 1 to 150 seconds, and more preferably from 1 to 40 seconds. The temperature range for the contacting step can vary from 10 to 100° C and more preferably from 10 to 40° C.

[0216]

[0172] Regardless of whether the contacting step is static or dynamic, it is preferred that the process solution comprising a graft polymer or concentrate be applied to a still-wet substrate surface. In one PDH-005 embodiment, for example, the process solution is employed as a rinse solution after the development of the photoresist layer. In this connection, the photoresist-coated substrate is developed via a developer solution. After developing, the process solution is applied to the substrate surface as a rinse in addition to, or in place of, a deionized water rinse. While the substrate is still wet with developer solution and / or deionized water, the process solution may be applied in a dynamic manner or in a static manner such as by puddling it onto the surface of the substrate. During dispensing, the substrate is spun slowly at a speed, for example, of 100 revolutions per minute ("rpm") to distribute the process solution over the substrate surface. For a dynamic process, the substrate is spun slowly while the process solution is dispensed continuously on the substrate. For a static process such as the puddle process, the substrate is allowed to rest for a brief period, for example, 15 seconds. After the rinse step with the process solution is complete, the rinsed wafer is then dried, for example, by spin drying at a higher rpm.

[0217]

[0173] In yet a further embodiment of the present disclosure, there is provided a method for selecting the process solution comprising a graft polymer that will minimize the number of pattern collapse defects for patterned, photoresist-coated substrates. In this regard, the method comprises determining the surface tension and measuring the contact angle of a process solution containing the graft polymer. The process solution is first applied to the surface of a sample photoresist-coated substrate. The surface tension, preferably dynamic surface tension, of the process solution may be determined according to the maximum-bubble-pressure method as described herein. The contact angle of the process solution, which is the angle between the baseline of a droplet of process solution on the surface of the substrate and the tangent at the droplet base, is then measured. In certain embodiments, a high-speed camera may be used to capture the spreading of the droplet at a speed of 2 frames per second for a 2 minute interval and the contact angle can be measured on the photographic image.

[0218]

[0174] Once the surface tension and contact angle for the process solution is obtained, the surface tension is then multiplied by the cosine of the contact angle measurement to provide a certain value referred to herein as an "adhesion tension value". Lower adhesion tension values for the process solution correlate to a greater reduction in pattern collapse defects. Adhesion tension values of 30 or less indicate, preferably 25 or less, or more preferably 20 or less indicate that the process solution may be more effective in reducing the number of pattern collapse defects compared to deionized rinse solutions or process solutions containing other surfactants described in the prior art. If the adhesion tension value is acceptable (i.e., 30 or less), the process solution may then be used for a production lot. The concentration of the graft polymer is determined by the smallest adhesion tension value calculated at different concentrations for each comprising a graft polymer or surfactant. In PDH-005 certain embodiments, the process solution reduced the number of pattern collapse defects by 25% or greater, preferably 50% or greater, and more preferably 75% or greater relative to a deionized water rinse for patterned and developed photoresist coated substrates having an aspect ratio of 3.0 or greater, and a pitch of 1:1.4 or greater, or a normalized aspect ratio of at least 0.015 1 / nm.

[0219]

[0175] Other embodiments of the disclosure include coated substrates formed from the compositions of the disclosure. In one embodiment, the coated substrate includes: (a) a substrate having one or more layers to be patterned on a surface thereof; and (b) a layer of a photoresist composition over the one or more layers to be patterned, where the layer of the photoresist composition comprises a graft polymer. In some embodiments, the coated substrate comprises a layer of photoresist composition comprising a graft polymer that is free of per- and polyfluoroalkyl substances. In other embodiments, the coated substrate comprises a layer of photoresist composition comprising a graft polymer that is free of fluorine. In other embodiments, the coated substrate comprises a layer of photoresist composition comprising a graft polymer that is free of silicon. In one embodiment, the coated substrate comprising a layer of photoresist comprising a graft polymer provides a receding water contact angle in excess of 70 degrees before exposure to actinic radiation. In an exemplary embodiment, the coated substrate comprising a layer of photoresist comprising a graft polymer provides a water contact angle of 85 to 90 degrees before exposure to actinic radiation. In another exemplary embodiment, the coated substrate comprising a layer of photoresist comprising a graft polymer provides a receding water contact angle of less than 70 degrees after exposure to actinic radiation.

[0220]

[0176] In another embodiment, the coated substrate includes: (a) a substrate having one or more layers to be patterned on a surface thereof; (b) a layer of a photoresist composition over the one or more layers to be patterned; and (c) a layer of a top coat composition over the layer of the photoresist composition over the one or more layers to be patterned, where the layer of the top coat composition comprises a graft polymer. In some embodiments, the coated substrate comprises a layer of top coat composition comprising a graft polymer that is free of per- and polyfluoroalkyl substances. In other embodiments, the coated substrate comprises a layer of top coat composition comprising a graft polymer that is free of fluorine. In other embodiments, the coated substrate comprises a layer of top coat composition comprising a graft polymer that is free of silicon. In one embodiment, the coated substrate comprising a layer of top coat composition comprising a graft polymer provides a receding water contact angle in excess of 70 degrees before exposure to actinic radiation. In an exemplary embodiment, the coated substrate comprising a layer of top coat composition provides a water contact angle of 85 to 90 degrees before exposure to actinic radiation. In another exemplary PDH-005 embodiment, the coated substrate comprising a layer of top coat composition provides a receding water contact angle of less than 70 degrees after exposure to actinic radiation.

[0221]

[0177] In another embodiment, the coated substrate includes: (a) a substrate having one or more layers to be patterned on a surface thereof; (b) a layer of a photoresist composition over the one or more layers to be patterned; and (c) a layer of an anti-reflective coating composition over the layer of the photoresist composition over the one or more layers to be patterned, where the layer of the anti- reflective coating composition comprises a graft polymer. In some embodiments, the coated substrate comprises a layer of anti-reflective coating composition comprising a graft polymer that is free of per- and polyfluoroalkyl substances. In other embodiments, the coated substrate comprises a layer of anti- reflective coating composition comprising a graft polymer that is free of fluorine. In other embodiments, the coated substrate comprises a layer of anti-reflective coating composition comprising a graft polymer that is free of silicon.

[0222]

[0178] Making reference to the coated substrate 200 shown in FIG. 2, in one example, a layer of a photoresist 206 having a photoresist top surface 206A and a photoresist bottom surface 206B opposite the photoresist top surface 206A, is located on top of the one or more layers to be patterned 204 having a top surface 204A and a bottom surface 204B opposite the top surface 204A and the substrate 202 having a substrate top surface 202A and a substrate bottom surface 202B opposite substrate top surface 202A. The photoresist layer 206 comprises a graft polymer, which forms a graft polymer sub-layer 208' after it is applied and processed. The graft polymer layer 208' has a top surface 208'A that is co-planar with the photoresist top surface 206A and extends downward to a sub-layer bottom surface 208'B located within the photoresist 206. In the example in FIG. 2, the photoresist bottom surface 206B is in direct contact with top surface 204A to be patterned; and the bottom surface 204B is in direct contact with substrate top surface 202A. Those of skill in the art will recognize that there can be additional layers in the coated substrate 200 beyond the ones shown.

[0223]

[0179] In one embodiment, a process flow for forming a photolithographic pattern is provided. Referring to FIG. 3A, a layer of a photoresist 206 is depicted over the one or more layers to be patterned 204 and the substrate 202. The photoresist comprises a graft polymer 208, which in some embodiments is uniformly distributed throughout the photoresist 206 after coating.

[0224]

[0180] Next, as shown in FIG. 3B, a layer of graft polymer 208' forms on top of the modified photoresist layer 206'. This layer formation can occur during spin coating and pre-exposure baking due to the graft polymer possessing a lower surface energy and / or reduced chain entanglement than the acid-labile resin or polymer component of the photoresist composition, which can facilitate segregation or migration of the graft polymers to top or upper portions of an applied photoresist layer. PDH-005

[0225]

[0181] Then, as shown in FIG. 3C, the photoresist 206' may be patterned with actinic radiation 310 through a photomask 312. The photomask has optically transparent regions 314 and optically opaque regions 316 corresponding to regions of the resist layer to be unexposed and exposed, respectively, by the activating radiation.

[0226]

[0182] Next, as shown in FIG. 3D, a post-exposure bake (PEB) is performed, which forms a latent image defined by the boundary between exposed regions 206' and unexposed regions 206". The graft polymer also changes solubility during the PEB to form a modified layer of graft polymer 208" that is soluble in the developer.

[0227]

[0183] Finally, as shown in FIG. 3E, the photoresist layer is developed to remove exposed regions 206' and the modified layer of graft polymer 208", leaving unexposed regions 206", thus forming a resist pattern having a plurality of features separated by gaps 318.

[0228]

[0184] A flow diagram for the patterning process from this embodiment is shown in FIG. 4. At Step 401, a semiconductor substrate to be patterned is provided. Next, at Step 402, a layer of a photoresist composition is located on the substrate, where the photoresist composition includes an acid-labile polymer, a photoacid generator, and a graft polymer, where the graft polymer comprises a backbone polymer and a sidechain polymer where the sidechain polymer is grafted onto the backbone polymer. Then, at Step 403, the photoresist film is exposed to actinic radiation. Finally, at Step 404, the photoresist film is developed with a developer.

[0229]

[0185] Another embodiment of the disclosure is depicted in FIG. 5. Referring now to FIG. 5A, a layer of a photoresist 506 is depicted over the one or more layers to be patterned 204 and the substrate 202. Next, as shown in FIG. 5B, a layer of a top coat 508 comprising a graft polymer is applied on top of photoresist layer 506. This layer is applied by any suitable coating method as described above.

[0230]

[0186] FIG. 5B depicts the coated substrate 500 of one embodiment of the disclosure, comprising a substrate 202 coated with one or more layers to be patterned 204, further coated with a layer of photoresist 506 comprising an acid-labile polymer and a photoacid generator, further coated with a layer of a top coat composition 508, wherein the top coat composition comprises a graft polymer.

[0231]

[0187] Then, as shown in FIG. 5C, the photoresist 506 may be patterned with actinic radiation through a photomask 312, which has optically transparent regions 314 and optically opaque regions 316 corresponding to regions of the resist layer to be exposed and unexposed, respectively, by the activating radiation.

[0232]

[0188] Next, as shown in FIG. 5D, a post-exposure bake is performed, which forms a latent image defined by the boundary between exposed regions 506" and unexposed regions 506'. The graft polymer also changes solubility during the PEB to form a modified layer of graft polymer 508' that is soluble in the developer. PDH-005

[0233]

[0189] Finally, as shown in FIG. 5E, the photoresist layer is developed to remove exposed regions 506" and the modified layer of graft polymer 508', leaving unexposed regions 506' and forming a resist pattern plurality of features separated by gaps 510.

[0234]

[0190] A flow diagram for the patterning process from this embodiment is shown in FIG. 6. At Step 601, a semiconductor substrate to be patterned is provided. Next, at Step 602, a layer of a photoresist composition is located on the substrate, where the photoresist composition includes an acid-labile polymer and a photoacid generator. Then, at Step 603, a layer of a top coat composition is located on the substrate, wherein the top coat composition comprises a graft polymer, where the graft polymer comprises a backbone polymer and a sidechain polymer where the sidechain polymer is grafted onto the backbone polymer. Then, at Step 604, the photoresist film is exposed to actinic radiation. Finally, at Step 605, the photoresist film is developed with a developer.

[0235]

[0191] Another embodiment of the disclosure is depicted in FIG. 7. Referring now to FIG. 7A, a layer of a photoresist 506 is depicted over the one or more layers to be patterned 204 and the substrate 202. Next, as shown in FIG. 7B, a layer of a TARC 708 comprising a graft polymer is applied on top of photoresist layer 506. This layer is applied by any suitable coating method as described above.

[0236]

[0192] Fig. 7B depicts the coated substrate 700 of one embodiment of the disclosure, comprising a substrate 202 coated with one or more layers to be patterned 204, further coated with a layer of photoresist 506, further coated with a layer of a TARC 708, wherein the TARC composition comprises a graft polymer.

[0237]

[0193] Then, as shown in FIG. 7C, the photoresist 506 may be patterned with actinic radiation through a photomask 312, which has optically transparent regions 314 and optically opaque regions 316 corresponding to regions of the resist layer to be exposed and unexposed, respectively, by the activating radiation.

[0238]

[0194] Next, as shown in FIG. 7D, a post-exposure bake is performed, which forms a latent image defined by the boundary between exposed regions 506" and unexposed regions 506'. The graft polymer also changes solubility during the PEB to form a modified layer of TARC 708' that is soluble in the developer.

[0239]

[0195] Finally, as shown in FIG. 7E, the photoresist layer is developed to remove exposed regions 506" and the modified TARC 708', leaving unexposed regions 506' and forming a resist pattern plurality of features separated by gaps 510.

[0240]

[0196] A flow diagram for the patterning process from this embodiment is shown in FIG. 8. At Step 801, a semiconductor substrate to be patterned is provided. Next, at Step 802, a layer of a photoresist composition is located on the substrate, where the photoresist composition includes an acid-labile polymer and a photoacid generator. Then, at Step 803, a layer of a top anti-reflective coating PDH-005 composition is located on the substrate, wherein the top anti-reflective coating composition comprises a graft polymer, where the graft polymer comprises a backbone polymer and a sidechain polymer where the sidechain polymer is grafted onto the backbone polymer. Then, at Step 804, the photoresist film is exposed to actinic radiation. Finally, at Step 805, the photoresist film is developed with a developer.

[0241]

[0197] A flow diagram for a final embodiment of the disclosure is shown in FIG.9, wherein the process includes treating the developed photoresist film with a process solution comprising a graft polymer. At Step 901, a semiconductor substrate to be patterned is provided. Next, at Step 902, a layer of a photoresist composition is located on the substrate, where the photoresist composition includes an acid-labile polymer and a photoacid generator. Then, at Step 903, the photoresist film is exposed to actinic radiation. Next, at Step 904, the photoresist film is developed with a developer. Finally, at Step 905, the developed photoresist film is treated with a process solution comprising a graft polymer, where the graft polymer comprises a backbone polymer and a sidechain polymer, where the sidechain polymer is grafted onto the backbone polymer.

[0242]

[0198] The photoresist pattern of the foregoing embodiments may be used, for example, as an etch mask, thereby allowing the pattern to be transferred to one or more sequentially underlying layers by known etching techniques, such as by dry-etching such as reactive ion etching. The photoresist pattern may, for example, be used for pattern transfer to an underlying hardmask layer which, in turn, is used as an etch mask for pattern transfer to one or more layers below the hardmask layer. If the photoresist pattern is not consumed during pattern transfer, it may be removed from the substrate by known techniques, for example, oxygen plasma ashing. The photoresist compositions may, when used in one or more such patterning processes, be used to fabricate semiconductor devices such as memory devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs, as well as other electronic devices.

Claims

PDH-005We claim:

1. A photoresist composition comprising: a. an acid-labile polymer; b. a photoacid generator; and c. a graft polymer, the graft polymer comprising: i. a backbone polymer; and ii. a sidechain polymer; wherein the sidechain polymer is grafted onto the backbone polymer.

2. The composition of Claim 1, wherein the graft polymer comprises: a. a polyacetal, a polyacetylene, a polyacrylamide, a polyacrylate, a polyacrylic, a polyamide, a polyamideimide, a polyamine, a polyamino acid, a polyanhydride, a polyarylate, a polyarylsulfone, a polybenzimidazole, a polybenzothiazole, a polybenzothiazinophenothiazine, a polybenzoxazole, a polybutylene succinate, a polycaprolactone, a polycarborane, a polycarbonate, a polydibenzofuran, a polydioxoisoindoline, a polyester, a polyether, a polyether ether ketone, a polyetherimide, a polyetherketone, a polyether ketone ketone, a polyethersulfone, a polyethylene, a polyethylene adipate, a poly(ethyl ethylene) phosphate, a polyglycolic acid, a polyhydroxyalkanoate, a polyhydroxybutyrate, a polyimide, a polylactide, a polynorbornene, a polyolefin, a polyoxabicyclononane, a polyoxadiazole, a poly(oxazoline), a polyoxindole, a polyoxoisoindoline, a polyoxymethylene, a polypeptide, a polyphenylene sulfide, a polyphosphazene, a polyphthalide, a polypiperazine, a polypiperidine, a polypyrazinoquinoxaline, a polypyrazole, a polypyridazine, a polypyridine, a polypyrrolidine, a polypyromellitimide, a polyalkylene glycol, a polyquinoxaline, a polysaccharide, a polysilane, a polysilazane, a polysiloxane, a polystyrene, a polysulfide, a polysulfonamide, a polysulfonate, a polysulfone, a polytetrafluoroethylene, a polytetramethylene glycol, a polythioester, a polytriazine, a polytriazole, a polyurethane, a polyurea, a polyvinyl alcohol, a polyvinyl chloride, a polyvinyl ester, a polyvinyl ether, a polyvinyl halide, a polyvinyl ketone, a polyvinyl nitrile, or a polyvinyl thioether, ora combination including at least one of the foregoing polymers.

3. The composition of Claim 1, wherein the graft polymer comprises acid-labile ester and / or acetal groups.PDH-0054. The composition of Claim 1, wherein the composition is free of fluorine, silicon, or a combination of both fluorine and silicon.

5. The composition of Claim 1, wherein the graft polymer is free of fluorine, silicon, or a combination of both fluorine and silicon.

6. The composition of Claim 1, wherein the graft polymer comprises a polynorbornene, a poly(meth)acrylate, or a polyolefin.

7. The composition of Claim 1, wherein the backbone polymer of the graft polymer comprises a polynorbornene or a polyacrylate.

8. The composition of Claim 1 or 7, wherein the sidechain polymer of the graft polymer comprises a polyacrylate, polymethacrylate, or a polyolefin.

9. A coated substrate, comprising: a. one or more layers to be patterned on a surface thereof; and b. a layer of a photoresist composition on the one or more layers to be patterned; wherein the composition comprises: i. an acid-labile polymer; ii. a photoacid generator; and ill. a graft polymer, the graft polymer comprising:

1. a backbone polymer; and2. a sidechain polymer; wherein the sidechain polymer is grafted onto the backbone polymer.

10. The coated substrate of Claim 9, wherein the graft polymer comprises: a. a polyacetal, a polyacetylene, a polyacrylamide, a polyacrylate, a polyacrylic, a polyamide, a polyamideimide, a polyamine, a polyamino acid, a polyanhydride, a polyarylate, a polyarylsulfone, a polybenzimidazole, a polybenzothiazole, a polybenzothiazinophenothiazine, a polybenzoxazole, a polybutylene succinate, a polycaprolactone, a polycarborane, a polycarbonate, a polydibenzofuran, a polydioxoisoindoline, a polyester, a polyether, a polyether ether ketone, a polyetherimide, a polyetherketone, a polyether ketone ketone, a polyethersulfone, aPDH-005 polyethylene, a polyethylene adipate, a poly(ethyl ethylene) phosphate, a polyglycolic acid, a polyhydroxyalkanoate, a polyhydroxybutyrate, a polyimide, a polylactide, a polynorbornene, a polyolefin, a polyoxabicyclononane, a polyoxadiazole, a poly(oxazoline), a polyoxindole, a polyoxoisoindoline, a polyoxymethylene, a polypeptide, a polyphenylene sulfide, a polyphosphazene, a polyphthalide, a polypiperazine, a polypiperidine, a polypyrazinoquinoxaline, a polypyrazole, a polypyridazine, a polypyridine, a polypyrrolidine, a polypyromellitimide, a polyalkylene glycol, a polyquinoxaline, a polysaccharide, a polysilane, a polysilazane, a polysiloxane, a polystyrene, a polysulfide, a polysulfonamide, a polysulfonate, a polysulfone, a polytetrafluoroethylene, a polytetramethylene glycol, a polythioester, a polytriazine, a polytriazole, a polyurethane, a polyurea, a polyvinyl alcohol, a polyvinyl chloride, a polyvinyl ester, a polyvinyl ether, a polyvinyl halide, a polyvinyl ketone, a polyvinyl nitrile, or a polyvinyl thioether, ora combination including at least one of the foregoing polymers.

11. The coated substrate of Claim 9, wherein the composition is free of fluorine, silicon, or a combination of both fluorine and silicon.

12. The coated substrate of Claim 9, wherein the graft polymer is free of fluorine, silicon, or a combination of both fluorine and silicon.

13. The coated substrate of Claim 9, wherein the graft polymer comprises a polynorbornene, a polyacrylate, or a polyolefin.

14. The coated substrate of Claim 9, wherein the backbone polymer of the graft polymer comprises a polynorbornene or a polyacrylate.

15. The coated substrate of Claim 9, wherein the sidechain polymer of the graft polymer comprises a polyacrylate, polymethacrylate, or a polyolefin.

16. The coated substrate of Claim 9, wherein the coated substrate provides a receding water contact angle of in excess of 70 degrees before exposure to actinic radiation.

17. The coated substrate of Claim 9, wherein the coated substrate provides a receding water contact angle of less than 70 degrees after exposure to actinic radiation.PDH-00518. A method for forming a patterned mask, the method comprising: a. providing a semiconductor substrate; b. forming a layer of a photoresist composition on the substrate; wherein the photoresist composition comprises; i. an acid-labile polymer; ii. a photoacid generator; and ill. a graft polymer, the graft polymer comprising:

1. a backbone polymer; and2. a sidechain polymer; wherein the sidechain polymer is grafted onto the backbone polymer; and c. exposing the photoresist film with actinic radiation; and d. developing the photoresist film with a developer.

19. The method of Claim 18, wherein the graft polymer comprises: a. a polyacetal, a polyacetylene, a polyacrylamide, a polyacrylate, a polyacrylic, a polyamide, a polyamideimide, a polyamine, a polyamino acid, a polyanhydride, a polyarylate, a polyarylsulfone, a polybenzimidazole, a polybenzothiazole, a polybenzothiazinophenothiazine, a polybenzoxazole, a polybutylene succinate, a polycaprolactone, a polycarborane, a polycarbonate, a polydibenzofuran, a polydioxoisoindoline, a polyester, a polyether, a polyether ether ketone, a polyetherimide, a polyetherketone, a polyether ketone ketone, a polyethersulfone, a polyethylene, a polyethylene adipate, a poly(ethyl ethylene) phosphate, a polyglycolic acid, a polyhydroxyalkanoate, a polyhydroxybutyrate, a polyimide, a polylactide, a polynorbornene, a polyolefin, a polyoxabicyclononane, a polyoxadiazole, a poly(oxazoline), a polyoxindole, a polyoxoisoindoline, a polyoxymethylene, a polypeptide, a polyphenylene sulfide, a polyphosphazene, a polyphthalide, a polypiperazine, a polypiperidine, a polypyrazinoquinoxaline, a polypyrazole, a polypyridazine, a polypyridine, a polypyrrolidine, a polypyromellitimide, a polyalkylene glycol, a polyquinoxaline, a polysaccharide, a polysilane, a polysilazane, a polysiloxane, a polystyrene, a polysulfide, a polysulfonamide, a polysulfonate, a polysulfone, a polytetrafluoroethylene, a polytetramethylene glycol, a polythioester, a polytriazine, a polytriazole, a polyurethane, a polyurea, a polyvinyl alcohol, a polyvinyl chloride, aPDH-005 polyvinyl ester, a polyvinyl ether, a polyvinyl halide, a polyvinyl ketone, a polyvinyl nitrile, or a polyvinyl thioether, ora combination including at least one of the foregoing polymers.

20. The method of Claim 18, wherein the graft polymer comprises acid-labile ester and / or acetal groups.

21. The method of Claim 18, wherein the composition is free of fluorine, silicon, or a combination of both fluorine and silicon.

22. The method of Claim 18, wherein the graft polymer is free of fluorine, silicon, or a combination of both fluorine and silicon.

23. The method of Claim 18, wherein the graft polymer comprises a polynorbornene, a polyacrylate, or a polyolefin.

24. The method of Claim 18, wherein the backbone polymer of the graft polymer comprises a polynorbornene or a polyacrylate.

25. The method of Claim 18 or 24, wherein the sidechain polymer of the graft polymer comprises a polyacrylate, polymethacrylate, or a polyolefin.

26. A method for forming a patterned mask, the method comprising: a. providing a semiconductor substrate; b. forming a layer of a photoresist composition located on the substrate comprising coating the semiconductor substrate with a photoresist composition; wherein the photoresist composition comprises; i. an acid-labile polymer; ii. a photoacid generator; and c. forming a layer of a top coat composition located on the layer of photoresist composition; wherein the top coat composition comprises a graft polymer, the graft polymer comprising: i. a backbone polymer; and ii. a sidechain polymer; the sidechain polymer being grafted onto the backbone polymer; andPDH-005 d. exposing the photoresist film with actinic radiation; and e. developing the photoresist film with a developer.

27. The method of Claim 26, wherein the graft polymer comprises: a. a polyacetal, a polyacetylene, a polyacrylamide, a polyacrylate, a polyacrylic, a polyamide, a polyamideimide, a polyamine, a polyamino acid, a polyanhydride, a polyarylate, a polyarylsulfone, a polybenzimidazole, a polybenzothiazole, a polybenzothiazinophenothiazine, a polybenzoxazole, a polybutylene succinate, a polycaprolactone, a polycarborane, a polycarbonate, a polydibenzofuran, a polydioxoisoindoline, a polyester, a polyether, a polyether ether ketone, a polyetherimide, a polyetherketone, a polyether ketone ketone, a polyethersulfone, a polyethylene, a polyethylene adipate, a poly(ethyl ethylene) phosphate, a polyglycolic acid, a polyhydroxyalkanoate, a polyhydroxybutyrate, a polyimide, a polylactide, a polynorbornene, a polyolefin, a polyoxabicyclononane, a polyoxadiazole, a poly(oxazoline), a polyoxindole, a polyoxoisoindoline, a polyoxymethylene, a polypeptide, a polyphenylene sulfide, a polyphosphazene, a polyphthalide, a polypiperazine, a polypiperidine, a polypyrazinoquinoxaline, a polypyrazole, a polypyridazine, a polypyridine, a polypyrrolidine, a polypyromellitimide, a polyalkylene glycol, a polyquinoxaline, a polysaccharide, a polysilane, a polysilazane, a polysiloxane, a polystyrene, a polysulfide, a polysulfonamide, a polysulfonate, a polysulfone, a polytetrafluoroethylene, a polytetramethylene glycol, a polythioester, a polytriazine, a polytriazole, a polyurethane, a polyurea, a polyvinyl alcohol, a polyvinyl chloride, a polyvinyl ester, a polyvinyl ether, a polyvinyl halide, a polyvinyl ketone, a polyvinyl nitrile, or a polyvinyl thioether, ora combination including at least one of the foregoing polymers.

28. The method of Claim 26, wherein the graft polymer comprises acid-labile ester and / or acetal groups.

29. The method of Claim 26, wherein the graft polymer is free of fluorine, silicon, or a combination of both fluorine and silicon.

30. The method of Claim 26, wherein the graft polymer comprises a polynorbornene, a polyacrylate, or a polyolefin.PDH-00531. The method of Claim 26, wherein the backbone polymer of the graft polymer comprises a polynorbornene or a polyacrylate.

32. The method of Claim 26 or 31, wherein the sidechain polymer of the graft polymer comprises a polyacrylate, polymethacrylate, or a polyolefin.

33. The method of Claim 26, wherein the layer of a top coat composition further comprises an acid or acid generator.

34. A coated substrate, comprising: a. one or more layers to be patterned on a surface thereof; and b. a layer of a photoresist composition located on the one or more layers to be patterned; wherein the composition comprises: i. an acid-labile polymer; ii. a photoacid generator; and c. layer of a top coat composition located on the layer of photoresist composition; wherein the top coat composition comprises a graft polymer, the graft polymer comprising: i. a backbone polymer; and ii. a sidechain polymer; the sidechain polymer being grafted onto the backbone polymer.

35. The coated substrate of Claim 34, wherein the graft polymer comprises: a. a polyacetal, a polyacetylene, a polyacrylamide, a polyacrylate, a polyacrylic, a polyamide, a polyamideimide, a polyamine, a polyamino acid, a polyanhydride, a polyarylate, a polyarylsulfone, a polybenzimidazole, a polybenzothiazole, a polybenzothiazinophenothiazine, a polybenzoxazole, a polybutylene succinate, a polycaprolactone, a polycarborane, a polycarbonate, a polydibenzofuran, a polydioxoisoindoline, a polyester, a polyether, a polyether ether ketone, a polyetherimide, a polyetherketone, a polyether ketone ketone, a polyethersulfone, a polyethylene, a polyethylene adipate, a poly(ethyl ethylene) phosphate, a polyglycolic acid, a polyhydroxyalkanoate, a polyhydroxybutyrate, a polyimide, a polylactide, a polynorbornene, a polyolefin, a polyoxabicyclononane, a polyoxadiazole, a poly(oxazoline), a polyoxindole, a polyoxoisoindoline, a polyoxymethylene, a polypeptide, a polyphenylene sulfide, a polyphosphazene, a polyphthalide, a polypiperazine, aPDH-005 polypiperidine, a polypyrazinoquinoxaline, a polypyrazole, a polypyridazine, a polypyridine, a polypyrrolidine, a polypyromellitimide, a polyalkylene glycol, a polyquinoxaline, a polysaccharide, a polysilane, a polysilazane, a polysiloxane, a polystyrene, a polysulfide, a polysulfonamide, a polysulfonate, a polysulfone, a polytetrafluoroethylene, a polytetramethylene glycol, a polythioester, a polytriazine, a polytriazole, a polyurethane, a polyurea, a polyvinyl alcohol, a polyvinyl chloride, a polyvinyl ester, a polyvinyl ether, a polyvinyl halide, a polyvinyl ketone, a polyvinyl nitrile, or a polyvinyl thioether, ora combination including at least one of the foregoing polymers.

36. The coated substrate of Claim 34, wherein the graft polymer comprises acid-labile ester and / or acetal groups.

37. The coated substrate of Claim 34, wherein the graft polymer is free of fluorine, silicon, or a combination of both fluorine and silicon.

38. The coated substrate of Claim 34, wherein the graft polymer comprises a polynorbornene, a polyacrylate, or a polyolefin.

39. The coated substrate of Claim 34, wherein the backbone polymer of the graft polymer comprises a polynorbornene or a polyacrylate.

40. The coated substrate of Claim 34, wherein the sidechain polymer of the graft polymer comprises a polyacrylate, polymethacrylate, or a polyolefin.

41. The coated substrate of Claim 34, wherein the coated substrate provides a receding water contact angle of in excess of 70 degrees before exposure to actinic radiation.

42. The coated substrate of Claim 34, wherein the coated substrate provides a receding water contact angle of less than 70 degrees after exposure to actinic radiation.

43. A method for forming a patterned mask, the method comprising: a. providing a semiconductor substrate; b. forming a layer of a photoresist composition on the substrate; wherein the photoresist composition comprises;PDH-005 i. an acid-labile polymer; and ii. a photoacid generator; and c. forming a layer of an anti-reflective coating composition on the layer of photoresist composition; wherein the anti-reflective coating composition comprises a graft polymer, the graft polymer comprising: i. a backbone polymer; and ii. a sidechain polymer; the sidechain polymer being grafted onto the backbone polymer; and d. exposing the resist film with actinic radiation; and e. developing the resist film with a developer.

44. The method of Claim 43, wherein the graft polymer comprises: a. a polyacetal, a polyacetylene, a polyacrylamide, a polyacrylate, a polyacrylic, a polyamide, a polyamideimide, a polyamine, a polyamino acid, a polyanhydride, a polyarylate, a polyarylsulfone, a polybenzimidazole, a polybenzothiazole, a polybenzothiazinophenothiazine, a polybenzoxazole, a polybutylene succinate, a polycaprolactone, a polycarborane, a polycarbonate, a polydibenzofuran, a polydioxoisoindoline, a polyester, a polyether, a polyether ether ketone, a polyetherimide, a polyetherketone, a polyether ketone ketone, a polyethersulfone, a polyethylene, a polyethylene adipate, a poly(ethyl ethylene) phosphate, a polyglycolic acid, a polyhydroxyalkanoate, a polyhydroxybutyrate, a polyimide, a polylactide, a polynorbornene, a polyolefin, a polyoxabicyclononane, a polyoxadiazole, a poly(oxazoline), a polyoxindole, a polyoxoisoindoline, a polyoxymethylene, a polypeptide, a polyphenylene sulfide, a polyphosphazene, a polyphthalide, a polypiperazine, a polypiperidine, a polypyrazinoquinoxaline, a polypyrazole, a polypyridazine, a polypyridine, a polypyrrolidine, a polypyromellitimide, a polyalkylene glycol, a polyquinoxaline, a polysaccharide, a polysilane, a polysilazane, a polysiloxane, a polystyrene, a polysulfide, a polysulfonamide, a polysulfonate, a polysulfone, a polytetrafluoroethylene, a polytetramethylene glycol, a polythioester, a polytriazine, a polytriazole, a polyurethane, a polyurea, a polyvinyl alcohol, a polyvinyl chloride, a polyvinyl ester, a polyvinyl ether, a polyvinyl halide, a polyvinyl ketone, a polyvinyl nitrile, or a polyvinyl thioether, ora combination including at least one of the foregoing polymers.

45. The method of Claim 43, wherein the graft polymer comprises a hydrophilic polymer.PDH-00546. The method of Claim 43, wherein the graft polymer is water-soluble.

47. The method of Claim 43, wherein the graft polymer is free of fluorine, silicon, or a combination of both fluorine and silicon.

48. The method of Claim 43, wherein the backbone polymer of the graft polymer comprises a polynorbornene, a polyacrylate, a polypeptide, a polysiloxane, a polycaprolactone, or a poly(oxazoline).

49. The method of Claim 43, wherein the sidechain polymer of the graft polymer comprises a poly(acrylic acid-co-alkyl acrylate), poly(acrylic acid-co-alkyl methacrylate), poly(ethyl ethylene) phosphate, poly(ethylene glycol-co-propylene glycol), poly(methacrylic acid-co-alkyl acrylate), poly(methacrylic acid-co-alkyl methacrylate), poly(N-isopropylacrylamide), poly(N-vinylpyrrolidone- co-acrylic acid), poly(N-vinylpyrrolidone-co-dimethyl maleate), poly(N-vinylpyrrolidone-co-itaconic acid), poly(N-vinylpyrrolidone-co-itaconic anhydride), poly(N-vinylpyrrolidone-co-maleic acid), poly(N-vinylpyrrolidone-co-maleic anhydride), poly(N-vinylpyrrolidone-co-methacrylic acid), poly(N- vinylpyrrolidone-co-methyl acrylate), poly(N-vinylpyrrolidone-co-methyl itaconate), poly(N- vinylpyrrolidone-co-methyl methacrylate), poly(N-vinylpyrrolidone-co-vinyl acetate), poly(N- vinylpyrrolidone-co-vinyl alcohol), poly(oxazoline), poly(vinyl methyl ether-co-maleic anhydride), polyacrylamide, polyacrylic acid, polyether, polyethylene glycol, polyglycolic acid, polylactic acid, polymethacrylic acid, polyoxymethylene, polypropylene glycol, polytetramethylene glycol, polyvinyl alcohol, and polyvinylpyrrolidone, or combinations thereof.

50. The method of Claim 43, wherein the layer of an anti-reflective coating composition further comprises an acid or acid generator.

51. The method of Claim 43, wherein the layer of an anti-reflective coating composition further comprises an acid or acid generator that is free of fluorine.

52. A coated substrate, comprising: a. one or more layers to be patterned on a surface thereof; and b. a layer of a photoresist composition located on the one or more layers to be patterned; wherein the composition comprises:PDH-005 i. an acid-labile polymer; ii. a photoacid generator; and c. a layer of an anti-reflective coating composition located on the layer of photoresist composition; wherein the anti-reflective coating composition comprises a graft polymer, the graft polymer comprising: i. a backbone polymer; and ii. a sidechain polymer; the sidechain polymer being grafted onto the backbone polymer.

53. The coated substrate of Claim 52, wherein the graft polymer comprises: a. a polyacetal, a polyacetylene, a polyacrylamide, a polyacrylate, a polyacrylic, a polyamide, a polyamideimide, a polyamine, a polyamino acid, a polyanhydride, a polyarylate, a polyarylsulfone, a polybenzimidazole, a polybenzothiazole, a polybenzothiazinophenothiazine, a polybenzoxazole, a polybutylene succinate, a polycaprolactone, a polycarborane, a polycarbonate, a polydibenzofuran, a polydioxoisoindoline, a polyester, a polyether, a polyether ether ketone, a polyetherimide, a polyetherketone, a polyether ketone ketone, a polyethersulfone, a polyethylene, a polyethylene adipate, a poly(ethyl ethylene) phosphate, a polyglycolic acid, a polyhydroxyalkanoate, a polyhydroxybutyrate, a polyimide, a polylactide, a polynorbornene, a polyolefin, a polyoxabicyclononane, a polyoxadiazole, a poly(oxazoline), a polyoxindole, a polyoxoisoindoline, a polyoxymethylene, a polypeptide, a polyphenylene sulfide, a polyphosphazene, a polyphthalide, a polypiperazine, a polypiperidine, a polypyrazinoquinoxaline, a polypyrazole, a polypyridazine, a polypyridine, a polypyrrolidine, a polypyromellitimide, a polyalkylene glycol, a polyquinoxaline, a polysaccharide, a polysilane, a polysilazane, a polysiloxane, a polystyrene, a polysulfide, a polysulfonamide, a polysulfonate, a polysulfone, a polytetrafluoroethylene, a polytetramethylene glycol, a polythioester, a polytriazine, a polytriazole, a polyurethane, a polyurea, a polyvinyl alcohol, a polyvinyl chloride, a polyvinyl ester, a polyvinyl ether, a polyvinyl halide, a polyvinyl ketone, a polyvinyl nitrile, or a polyvinyl thioether, ora combination including at least one of the foregoing polymers.

54. The coated substrate of Claim 52, wherein the graft polymer comprises a hydrophilic polymer.

55. The coated substrate of Claim 52, wherein the graft polymer is water-soluble.PDH-00556. The coated substrate of Claim 52, wherein the graft polymer is free of fluorine, silicon, or a combination of both fluorine and silicon.

57. The coated substrate of Claim 52, wherein the backbone polymer of the graft polymer comprises a polynorbornene, a polyacrylate, a polypeptide, a polysiloxane, a polycaprolactone, or a poly(oxazoline).

58. The coated substrate of Claim 52, wherein the sidechain polymer of the graft polymer comprises a poly(acrylic acid-co-alkyl acrylate), poly(acrylic acid-co-alkyl methacrylate), poly(ethyl ethylene) phosphate, poly(ethylene glycol-co-propylene glycol), poly(methacrylic acid-co-alkyl acrylate), poly(methacrylic acid-co-alkyl methacrylate), poly(N-isopropylacrylamide), poly(N- vinylpyrrolidone-co-acrylic acid), poly(N-vinylpyrrolidone-co-dimethyl maleate), poly(N- vinylpyrrolidone-co-itaconic acid), poly(N-vinylpyrrolidone-co-itaconic anhydride), poly(N- vinylpyrrolidone-co-maleic acid), poly(N-vinylpyrrolidone-co-maleic anhydride), poly(N- vinylpyrrolidone-co-methacrylic acid), poly(N-vinylpyrrolidone-co-methyl acrylate), poly(N- vinylpyrrolidone-co-methyl itaconate), poly(N-vinylpyrrolidone-co-methyl methacrylate), poly(N- vinylpyrrolidone-co-vinyl acetate), poly(N-vinylpyrrolidone-co-vinyl alcohol), poly(oxazoline), poly(vinyl methyl ether-co-maleic anhydride), polyacrylamide, polyacrylic acid, polyether, polyethylene glycol, polyglycolic acid, polylactic acid, polymethacrylic acid, polyoxymethylene, polypropylene glycol, polytetramethylene glycol, polyvinyl alcohol, and polyvinylpyrrolidone, or combinations thereof.

59. The coated substrate of Claim 52, wherein the layer of an anti-reflective coating composition further comprises an acid or acid generator.

60. The coated substrate of Claim 52 wherein the layer of an anti-reflective coating composition further comprises an acid or acid generator that is free of fluorine.

61. A method for forming a patterned mask, the method comprising: a. providing a semiconductor substrate; b. forming a layer of a photoresist composition on the substrate; wherein the photoresist composition comprises an acid-labile polymer and a photoacid generator; and c. exposing the resist film with actinic radiation; andPDH-005 d. developing the resist film with a developer; and e. treating the developed resist film with a process solution comprising a graft polymer, the graft polymer comprising:

1. a backbone polymer; and2. a sidechain polymer; wherein the sidechain polymer is grafted onto the backbone polymer.

62. The method of Claim 61, wherein the graft polymer comprises: a. a polyacetal, a polyacetylene, a polyacrylamide, a polyacrylate, a polyacrylic, a polyamide, a polyamideimide, a polyamine, a polyamino acid, a polyanhydride, a polyarylate, a polyarylsulfone, a polybenzimidazole, a polybenzothiazole, a polybenzothiazinophenothiazine, a polybenzoxazole, a polybutylene succinate, a polycaprolactone, a polycarborane, a polycarbonate, a polydibenzofuran, a polydioxoisoindoline, a polyester, a polyether, a polyether ether ketone, a polyetherimide, a polyetherketone, a polyether ketone ketone, a polyethersulfone, a polyethylene, a polyethylene adipate, a poly(ethyl ethylene) phosphate, a polyglycolic acid, a polyhydroxyalkanoate, a polyhydroxybutyrate, a polyimide, a polylactide, a polynorbornene, a polyolefin, a polyoxabicyclononane, a polyoxadiazole, a poly(oxazoline), a polyoxindole, a polyoxoisoindoline, a polyoxymethylene, a polypeptide, a polyphenylene sulfide, a polyphosphazene, a polyphthalide, a polypiperazine, a polypiperidine, a polypyrazinoquinoxaline, a polypyrazole, a polypyridazine, a polypyridine, a polypyrrolidine, a polypyromellitimide, a polyalkylene glycol, a polyquinoxaline, a polysaccharide, a polysilane, a polysilazane, a polysiloxane, a polystyrene, a polysulfide, a polysulfonamide, a polysulfonate, a polysulfone, a polytetrafluoroethylene, a polytetramethylene glycol, a polythioester, a polytriazine, a polytriazole, a polyurethane, a polyurea, a polyvinyl alcohol, a polyvinyl chloride, a polyvinyl ester, a polyvinyl ether, a polyvinyl halide, a polyvinyl ketone, a polyvinyl nitrile, or a polyvinyl thioether, ora combination including at least one of the foregoing polymers.

63. The method of Claim 61, wherein the graft polymer comprises acid-labile ester and / or acetal groups.

64. The method of Claim 61, wherein the graft polymer comprises a water soluble polymer.PDH-00565. The method of Claim 61, wherein the composition is free of fluorine, silicon, or a combination of both fluorine and silicon.

66. The method of Claim 61, wherein the graft polymer comprises a polynorbornene, a polyacrylate, or a polyolefin.

67. The method of Claim 61, wherein the sidechain polymer of the graft polymer comprises a poly(acrylic acid-co-alkyl acrylate), poly(acrylic acid-co-alkyl methacrylate), poly(ethyl ethylene) phosphate, poly(ethylene glycol-co-propylene glycol), poly(methacrylic acid-co-alkyl acrylate), poly(methacrylic acid-co-alkyl methacrylate), poly(N-isopropylacrylamide), poly(N-vinylpyrrolidone- co-acrylic acid), poly(N-vinylpyrrolidone-co-dimethyl maleate), poly(N-vinylpyrrolidone-co-itaconic acid), poly(N-vinylpyrrolidone-co-itaconic anhydride), poly(N-vinylpyrrolidone-co-maleic acid), poly(N-vinylpyrrolidone-co-maleic anhydride), poly(N-vinylpyrrolidone-co-methacrylic acid), poly(N- vinylpyrrolidone-co-methyl acrylate), poly(N-vinylpyrrolidone-co-methyl itaconate), poly(N- vinylpyrrolidone-co-methyl methacrylate), poly(N-vinylpyrrolidone-co-vinyl acetate), poly(N- vinylpyrrolidone-co-vinyl alcohol), poly(oxazoline), poly(vinyl methyl ether-co-maleic anhydride), polyacrylamide, polyacrylic acid, polyether, polyethylene glycol, polyglycolic acid, polylactic acid, polymethacrylic acid, polyoxymethylene, polypropylene glycol, polytetramethylene glycol, polyvinyl alcohol, and polyvinylpyrrolidone, or combinations thereof.

68. The method of Claim 61, wherein the concentration of the graft polymer in the process solution is from 0.001 to 1 wt% based on total weight of the process solution composition.

69. The method of Claim 61, wherein the process solution further comprises a water-soluble organic solvent.

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