Pattern treatment compositions and methods for lithographic patterning

Abstract

Novel pattern treatment compositions and methods for their use in the fabrication of electronic devices are disclosed, particularly for creating high-resolution patterns with improved uniformity. The compositions contain one or more polymers with a reactive surface attachment group or a precursor to such a group, a catalyst, and a solvent. The described methods involve coating a substrate with the composition, activating the catalyst to induce a grafting reaction between the polymer and the substrate surface, and then rinsing away any unbound material to form a uniform grafted layer. These processes are shown to improve uniformity metrics and provide higher feature density than possible with single exposure lithographic methods. Methods for controlling and adjusting the thickness and uniformity of the grafted layer are also disclosed.

Description

[0001] PDH-014

[0002] PATTERN TREATMENT COMPOSITIONS AND METHODS FOR LITHOGRAPHIC PATTERNING CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] [1] This application claims the priority and benefit of U. S. Provisional Application No.

[0004] 63 / 726,909, filed on December 2, 2024; U. S. Provisional Application No. 63 / 726,923, filed on December 2, 2024; U. S. Provisional Application No. 63 / 726,934, filed on December 2, 2024; U. S. Provisional Application No. 63 / 729,765, filed on December 9, 2024; U. S. Provisional Application No. 63 / 744,295, filed on January 12, 2025; U. S. Provisional Application No. 63 / 744,296, filed on January 12, 2025; U. S. Provisional Application No, 63 / 744,298, filed on January 12, 2025; and U. S. Provisional Application No. 63 / 744,300, filed on January 12, 2025; and U. S. Provisional Application No. 63 / 892,203, filed on October 2, 2025; which applications are hereby incorporated herein by reference in their entirety.

[0005] FIELD OF THE DISCLOSURE

[0006] [2] The disclosure relates generally to the manufacture of electronic devices. More specifically, this disclosure relates to methods of advanced patterning. The disclosure also relates to pattern treatment compositions useful in and electronic devices formed by the methods. The disclosure finds particular applicability in the manufacture of semiconductor devices for providing high resolution paterns.

[0007] BACKGROUND

[0008] [3] The semiconductor industry's drive for greater integration density has pushed existing photolithography to its resolution limits. While advancements like 193 nm immersion lithography have extended capabilities, they are now inadequate for next-generation devices. The pursuit of extreme ultraviolet (EUV) lithography is hampered by its high cost and technical complexities, creating a pressing need for alternative process schemes that improve the uniformity of patterned features.

[0009] [4] Existing high-density patterning techniques, such as double patterning and self-aligned processes, suffer from significant uniformity challenges. Double patterning is highly susceptible to alignment errors, leading to substantial variations in feature size and shape across the substrate. Self-aligned processes, while mitigating alignment issues, often produce non-ideal features that lack uniformity, negatively impacting device performance. PDH-014

[0010] [5] Furthermore, surface roughness is a critical factor directly impacting device performance and yield. A non-uniform surface leads to inconsistent photoresist coating and light reflection, compromising feature dimensions. This also results in non-uniform etching and deposition, creating irregularities and defects that can cause mechanical failures and degrade overall yield.

[0011] [6] Accordingly, there is a continuing need for methods that address these resolution and uniformity issues. It is desirable to develop compositions and processes that can efficiently form high-resolution patterns while simultaneously improving critical dimension uniformity (CDU), line edge roughness (LER), and feature shape uniformity. There is also a need for improved methods of forming high resolution patterns with feature density beyond the limits of single patterning with existing lithography tools.

[0012] [7] The present disclosure addresses these limitations by providing novel methods to improve patterning in electronic device fabrication.

[0013] SUMMARY

[0014] [8] The present disclosure relates to pattern treatment compositions and methods of their use.

[0015] [9] In a first aspect, the disclosure provides a pattern treatment composition comprising: one or more polymers having a reactive surface attachment group or reactive surface attachment group precursor; a catalyst; and a solvent. The disclosed compositions have utility in methods for grafting polymers to a surface. The catalyst improves the efficiency of the grafting reaction between the polymer's reactive surface attachment group and the surface. In embodiments where the polymer comprises a reactive surface attachment group precursor, the catalyst functions to convert the precursor to the active reactive surface attachment group, thereby enabling the grafting reaction. The use of catalysts that can be activated by an external stimulus, such as photoacid generators activated by light, provides for the spatial tailoring of grafting density. This enables the formation of patterned surfaces with selectively functionalized areas, offering improved control over surface modification.

[0016]

[0010] In a second aspect, the disclosure provides a method of forming a coated substrate comprising: providing a substrate; coating a pattern treatment composition over the substrate, wherein the pattern treatment composition comprises a polymer comprising a reactive surface attachment group or reactive surface group precursor, a catalyst, and a solvent; baking the substrate; treating the substrate with a rinsing agent comprising a solvent to remove residual, unbound said pattern treatment composition, thereby forming a grafted layer of pattern treatment PDH-014

[0017] composition over the substrate; and optionally, determining a dimensional property of the grafted layer of pattern treatment composition. Making reference to the coated substrate 200 shown in FIG. 2, in one example, a layer of a pattern treatment composition 204 is located on top of the one or more layers to be patterned 202 and the substrate 200. The substrate is then baked to drive the reaction of the reactive surface attachment group to bond it to the one or more layers to be patterned. After the coated substrate is rinsed to remove residual, unbound pattern treatment composition, a grafted layer of the pattern treatment composition 204a is formed over one or more layers 202 above the substrate 200.

[0018]

[0011] In a third aspect, the disclosure provides a method of forming a coated substrate comprising: providing a substrate; coating a pattern treatment composition over the substrate, wherein the pattern treatment composition comprises a polymer comprising a reactive surface attachment group or reactive surface group precursor, a catalyst, and a solvent; exposing at least a portion of the substrate to electromagnetic radiation; baking the substrate; treating the substrate with a rinsing agent comprising a solvent to remove residual, unbound said pattern treatment composition, thereby forming a grafted layer of pattern treatment composition over the substrate; and optionally, determining a dimensional property of the grafted layer of pattern treatment composition. Making reference to FIG. 4, in one example, a layer of a pattern treatment composition 204 is located on top of the one or more layers to be patterned 202 and the substrate 200. Then, at least a portion of the substrate is exposed to electromagnetic radiation 406, using either a flood exposure or location-specific dose delivery method. The substrate is baked to drive the reaction of the reactive surface attachment group to bond it to the one or more layers to be patterned. After the coated substrate is rinsed to remove residual, unbound pattern treatment composition, forming a grafted layer of the pattern treatment composition over one or more layers 202 above the substrate 200. The grafted layer has two regions of different thickness: a first region 204b with thickness, to, and a second region 204c with thickness,, where > to.

[0019]

[0012] In a fourth aspect, the disclosure provides a method of forming a coated substrate comprising: providing a substrate; coating a first pattern treatment composition over the substrate, wherein the pattern treatment composition comprises a polymer comprising a reactive surface attachment group or reactive surface group precursor, a catalyst, and a solvent; baking the substrate; treating the substrate with a rinsing agent comprising a solvent to remove residual, unbound said pattern treatment composition, thereby forming a grafted layer of pattern treatment PDH-014

[0020] composition over the substrate; determining a dimensional property of the grafted layer of first pattern treatment composition; coating a second pattern treatment composition over the substrate, wherein the pattern treatment composition comprises a polymer comprising a reactive surface attachment group or reactive surface group precursor, a catalyst, and a solvent; exposing at least a portion of the substrate to electromagnetic radiation; baking the substrate; treating the substrate with a rinsing agent comprising a solvent to remove residual, unbound said second pattern treatment composition, thereby forming a grafted layer of combined first and second pattern treatment composition over the substrate; and optionally, determining a dimensional property of the grafted layer of pattern treatment composition. This method can be used to improve uniformity in thickness of the grafted layer of patern treatment composition across a substrate such as a silicon wafer.

[0021]

[0013] In a fifth aspect, the disclosure provides a method of forming a coated substrate comprising: providing a first substrate; coating a pattern treatment composition over the first substrate, wherein the patern treatment composition comprises a polymer comprising a reactive surface attachment group or reactive surface group precursor, a catalyst, and a solvent; baking the first substrate; treating the first substrate with a rinsing agent comprising a solvent to remove residual, unbound said pattern treatment composition, thereby forming a grafted layer of pattern treatment composition over the first substrate; determining a dimensional property of the grafted layer of pattern treatment composition; providing a second substrate; coating a pattern treatment composition over the second substrate, wherein the pattern treatment composition comprises a polymer comprising a reactive surface attachment group or reactive surface group precursor, a catalyst, and a solvent; exposing at least a portion of the second substrate to electromagnetic radiation; baking the second substrate; treating the second substrate with a rinsing agent comprising a solvent to remove residual, unbound said pattern treatment composition, thereby forming a grafted layer of pattern treatment composition over the second substrate; and optionally, determining a dimensional property of the grafted layer of pattern treatment composition. This method can be used to improve uniformity in thickness of the grafted layer of pattern treatment composition across a substrate such as a silicon wafer, where the information from one wafer is used to inform process conditions for the next wafer to be processed. Making reference to FIG. 7, in one example, a patterned mask 708 is provided above the one or more layers to be patterned 202 above the substrate 200. The features of the patterned mask 708 are separated by gaps 710a PDH-014

[0022] and 710b, where gap 710a has a first dimension, di, and gap 710b has a second dimension d, where tfc > d\. A coating of pattern treatment composition 204 is formed over patterned mask 708, the one or more layers 202, and the substrate 200. A portion of the substrate is then exposed to electromagnetic radiation 406. A grafted layer of the pattern treatment composition is then formed over the patterned mask 708, with pattern treatment composition 204b and pattern treatment composition 204c corresponding to regions with and without exposure to electromagnetic radiation, respectively. New gaps 710c and 710d are formed with new dimensions, namely gap 710c with a third dimension, s, and gap 710d with a fourth dimension, d.

[0023]

[0014] In a sixth aspect, the disclosure provides a method of forming a coated substrate comprising: providing a substrate characterized by a first level of uniformity7; coating a pattern treatment composition over the substrate, wherein the pattern treatment composition comprises a polymer comprising a reactive surface attachment group or reactive surface group precursor, a catalyst, and a solvent; baking the substrate; treating the substrate with a rinsing agent comprising a solvent to remove residual, unbound said pattern treatment composition, thereby forming a grafted layer of patern treatment composition over the substrate; and determining a second level of uniformity; wherein the second level of uniformity is lower than the first level of uniformity. This method can be used to improve uniformity of a substrate, where the application of the pattern treatment composition provides an improvement in uniformity of the substrate.

[0024]

[0015] In a seventh aspect, a method of forming a pattern is provided, comprising: providing a semiconductor substrate comprising a first patterned mask comprising a plurality of features over a layer to be patterned; forming a layer of a pattern treatment composition over the first patterned mask to form a second patterned mask, wherein the pattern treatment composition comprises a polymer comprising a reactive surface attachment group or reactive surface attachment group precursor, such that the layer coats sidewalls of the features; and removing the first patterned mask to expose the underlying layer, thereby forming a third patterned mask having a greater pattern density than the first patterned mask. Making reference to FIG. 9A-9C, in one example, a first patterned mask 708 is provided on the one or more layers to be patterned 202 on the substrate 200. A grafted layer of a patern treatment composition 204 is then applied to on the sidewalls of the first paterned mask 708 to form a second patterned mask having gaps 910. Next, the first patterned mask 708 is removed to form a third paterned mask comprising gaps 910 and 912, thereby PDH-014

[0025] exposing layer 202 on substrate 200 m the regions previously covered by the first patterned mask. The resulting third patterned mask has a greater pattern density than the first patterned mask.

[0026]

[0016] In an eighth aspect, a method of forming a pattern is provided, comprising: providing a semiconductor substrate comprising a first patterned mask comprising a plurality of features over a layer to be patterned; forming a layer of a pattern treatment composition over the first patterned mask to form a second patterned mask, wherein the pattern treatment composition comprises a polymer comprising a reactive surface attachment group or reactive surface attachment group precursor, such that the layer coats sidewalls of the features; and removing the first patterned mask to expose the underlying layer, thereby forming a third patterned mask having a greater pattern density than the first patterned mask; forming a layer of a second composition over the substrate in regions adjacent to the pattern treatment composition; removing the pattern treatment composition, thereby forming a fourth patterned mask comprising a plurality7of features formed from the second composition and having a greater pattern density than the first patterned mask. Making reference to FIG. 11 A-11E, in one example, the process begins with the same first three steps as in the seventh aspect. A first patterned mask 708 is provided on the one or more layers to be patterned 202 on the substrate 200. A grafted layer of a pattern treatment composition 204 is then applied to on the sidewalls of the first patterned mask 708 to form a second paterned mask having gaps 910. Next, the first patterned mask 708 is removed to form a third patterned mask comprising gaps 910 and 912, thereby exposing layer 202 on substrate 200 in the regions previously covered by the first patterned mask. Then, the substrate is then coated with a second composition 1114 that fills gaps 910 and 912. Finally, the pattern treatment composition is removed to create a fourth patterned mask comprising a plurality of features 1114a comprising the second composition separated by gaps 1116. The resulting fourth patterned mask has a greater pattern density7than the first patterned mask.

[0027]

[0017] In a ninth aspect, a method of forming a pattern is provided, comprising: providing a semiconductor substrate comprising a first patterned mask comprising a plurality of features over a layer to be patterned; forming a layer of a pattern treatment composition over the first patterned mask to form a second patterned mask, wherein the pattern treatment composition comprises a polymer comprising a reactive surface attachment group or reactive surface attachment group precursor, such that the layer coats sidewalls of the features; forming a layer of a second composition over the substrate in regions adjacent to the coated sidewalls; and removing the PDH-014

[0028] pattern treatment composition from the sidewalls of the first patterned mask, thereby forming a third patterned mask comprising a plurality of features formed from the first patterned mask and the second composition, the third patterned mask having a greater pattern density than the first patterned mask.

[0029]

[0018] Making reference to FIG. 13 A- 13D, in one example, the process begins with the same first two steps as m the seventh aspect. A first patterned mask 708 is provided on the one or more layers to be patterned 202 on the substrate 200. A grafted layer of a pattern treatment composition 204 is then applied to on the sidewalls of the first patterned mask 708 to form a second patterned mask having gaps 910. Next, the substrate is then coated with a second composition 1114 that fills gaps 910. Finally, the pattern treatment composition is removed to create a third patterned mask comprising a plurality of features including the first paterned mask 708 and new features 1114a comprising the second composition separated by gaps 1318. The resulting third patterned mask has a greater pattern density than the first paterned mask.

[0030]

[0019] In a tenth aspect, a method of forming a patern is provided, comprising: providing a substrate comprising a first patterned mask comprising a plurality of features over a layer to be patterned; forming a hardmask layer over the first patterned mask and the layer to be patterned to form a second patterned mask; forming a layer of a pattern treatment composition over the hardmask layer, wherein the pattern treatment composition comprises a polymer comprising a reactive surface attachment group or reactive surface attachment group precursor, a catalyst, and a solvent; and treating the substrate with a rinsing agent comprising a solvent to remove residual, unbound said polymer, thereby forming a third patterned mask. Making reference to FIG. 15 A-15D, in one example, the process begins with a first patterned mask 708 provided on the one or more layers to be patterned 202 on the substrate 200. A layer of a hardmask 1522 is applied over the substrate, coating the first patterned mask 708 provided on the one or more layers to be patterned 202, forming a second patterned mask with gaps 1524. A grafted layer of a pattern treatment composition 204 is then applied on the hardmask 1522 to form a third patterned mask with gaps 1526. Next, the first patterned mask 708 is removed to create a fourth patterned mask comprising a plurality of features formed from hardmask 1522 and the pattern treatment composition 204 having gaps 1526a and 1528. The resulting fourth patterned mask has a greater pattern density than the first patterned mask. PDH-014

[0031]

[0020] In an eleventh aspect, a method of forming a pattern is provided, comprising: providing a semiconductor substrate comprising a layer to be patterned; forming a layer of a photoresist on the layer to be patterned; exposing the photoresist layer with a single exposure using EUV radiation with a numerical aperture of 0.5 or less or X-ray radiation to generate a latent image in the photoresist layer; and developing the photoresist layer to form a plurality of features, wherein the plurality of features comprise holes and / or pillars; wherein said plurality of features has a pitch of 35 nanometers or less; a critical dimension uniformity 3-sigma of less than 15% of a nominal critical dimension; and a defect rate of less than 1 defect per million holes.

[0032]

[0021] In a twelfth aspect, methods are provided of forming relief images, comprising: providing a substrate comprising a first patterned mask over a layer to be patterned; forming a second patterned mask over the first patterned mask; forming a layer of a pattern treatment composition over the second patterned mask, wherein the pattern treatment composition comprises a polymer comprising a reactive surface atachment group or reactive surface atachment group precursor and a catalyst; forming a layer of a second composition over the substrate in regions adjacent to the pattern treatment composition; removing the pattern treatment composition, thereby forming a third paterned mask comprising a plurality of features and having a greater pattern density than the first patterned mask; and optionally, transferring the patern using the combined patterned mask. Making reference to FIG. 17 / X-17G, in one example, a first patterned mask 708 is provided on the one or more layers to be patterned 202 on the substrate 200. A second paterned mask 1730 is then formed above the first patterned mask 708 on the one or more layers to be patterned 202 on the substrate 200. Next, a grafted layer of the pattern treatment composition 204 is formed on the sidewalls of the second patterned mask 1730. Then, a second composition 1114 is applied to fill gaps. Next, pattern treatment composition is then removed to form a new patterned mask comprising the second patterned mask 1730 and features 1114a comprising the second composition and exposing the first patterned mask 708 and portions of the layer 202 through gaps 1732. Finally, the exposed areas of the first patterned mask 708 can be removed to form the final modified first patterned mask 708a which has been cut in selected areas.

[0033]

[0022] In a thirteenth aspect, methods are provided of forming relief images, comprising: providing a substrate comprising a first patterned mask over a layer to be patterned; forming a layer of a pattern treatment composition over the first patterned mask to form a second patterned mask, wherein the patern treatment composition comprises a polymer comprising a reactive PDH-014

[0034] surface attachment group or reactive surface attachment group precursor and a catalyst; forming a layer of a second composition over the substrate in regions adjacent to the pattern treatment composition; removing the pattern treatment composition, thereby forming a third patterned mask comprising a plurality of features and having a greater pattern density than the first patterned mask; and forming a fourth patterned mask over the first, second, and third patterned masks; and optionally, transferring the pattern using the combined patterned mask. Making reference to FIG.

[0035] 19A-19G, in one example, a first patterned mask 708 is provided on the one or more layers to be patterned 202 on the substrate 200. A grafted layer of a pattern treatment composition 204 is then applied to on the sidewalls of the first patterned mask 708 to form a second patterned mask with gaps 910. Next, the substrate is then coated with a second composition 1114 that fills gaps 910. The patern treatment composition is then removed to create a third paterned mask comprising the first paterned mask 708 and features 1114a comprising the second composition separated by gaps 1318 and thereby exposing layer 202 on substrate 200 in the regions previously covered by the first paterned mask. A fourth patterned mask 1934 is then formed above the third patterned mask such that the first patterned mask 708 and the layer 202 are only exposed in selected areas. Finally, exposed sections of the layer 202 are removed to form modified layer 202a and expose the substrate 200 in the selected areas.

[0036]

[0023] These methods collectively enable the creation of highly resolved patterns with improved roughness and uniformity, increased precision, and higher feature density, surpassing the limitations of conventional lithographic techniques.

[0037] DESCRIPTION OF THE DRAWINGS

[0038]

[0024] The present disclosure will be described with reference to the following drawing, in which like reference numerals denote like features, and in which:

[0039]

[0025] FIG. 1 is a block-flow diagram of a method in accordance with one or more embodiments of the present disclosure.

[0040]

[0026] FIGS. 2A-2C are side views of a portion of a coated substrate during steps in a process flow for forming a photolithographic patern in accordance with one embodiment of the disclosure. For clarity' of description, the substrate and the various layers formed thereon are depicted with a "top surface" oriented towards the top of the drawing and a "bottom surface" oriented towards the bottom. PDH-014

[0041]

[0027] FIG. 3 is a block-flow diagram of a method in accordance with one or more embodiments of the present disclosure.

[0042]

[0028] FIGS. 4A-4D 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, with top and bottom surfaces as indicated above.

[0043]

[0029] FIG. 5 is a block-flow diagram of a method in accordance with one or more embodiments of the present disclosure.

[0044]

[0030] FIG. 6 is a block-flow diagram of a method in accordance with one or more embodiments of the present disclosure.

[0045]

[0001] FIGS. 7A-7D 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, with top and bottom surfaces as indicated above,

[0046]

[0032] FIG. 8 is a block-flow diagram of a method in accordance with one or more embodiments of the present discl osure.

[0047]

[0033] FIGS. 9A-9C 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, with top and bottom surfaces as indicated above.

[0048]

[0034] FIG. 10 is a block-flow diagram of a method in accordance with one or more embodiments of the present disclosure.

[0049]

[0035] FIGS. 11 A- 1 IE 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, with top and bottom surfaces as indicated above.

[0050]

[0036] FIG. 12 is a block-flow diagram of a method in accordance with one or more embodiments of the present disclosure.

[0051]

[0037] FIGS. 13A-13E 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, with top and bottom surfaces as indicated above.

[0052]

[0038] FIG. 14 is a block-flow diagram of a method in accordance with one or more embodiments of the present disclosure. PDH-014

[0053]

[0039] FIGS. 15A-15D 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, with top and bottom surfaces as indicated above.

[0054]

[0040] FIG. 16 is a block-flow diagram of a method in accordance with one or more embodiments of the present disclosure.

[0055]

[0041] FIGS. 17A-17G are side views of a portion of a coated substrate during steps m a process flow for forming a photolithographic pattern in accordance with one embodiment of the disclosure, with top and bottom surfaces as indicated above.

[0056]

[0042] FIG. 18 is a block-flow diagram of a method in accordance with one or more embodiments of the present discl osure.

[0057]

[0043] FIGS. 19A-19G 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, with top and bottom surfaces as indicated above.

[0058] DESCRIPTION

[0059]

[0044] 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.

[0060]

[0045] 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 m their entirety.

[0061]

[0046] 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 PDH-014

[0062] 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.

[0063]

[0047] 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 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.

[0064]

[0048] 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.”

[0065]

[0049] “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.

[0066]

[0050] The term “organic” refers to any material, compound, or composition comprising a carbon backbone, including, but not limited to, polymers, organic monomers, and organic small molecules, which may optionally include heteroatoms such as O, N, S, and P.

[0067]

[0051] The term “inorganic” refers to any compound or material whose primary structure is generally based on elements other than carbon, and whose molecular structure does not include a carbon backbone. PDH-014

[0068]

[0052] “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 — NRz), 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 — CHz — CH(OH) — CHz —, an alkoxy substituted alkyl, can be a 2-methoxy substituted ethyl of the formula — CH2 — CH2 — O — CH3, an amino substituted alkyl, or can be a 1 -dialkylamino substituted ethyl of the formula — CH(NRz) — CH3

[0069]

[0053] " 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 ( — NH2 or — NR2), nitro ( — NO2), acyl ( — C(==O)R), alkylsulfonyl ( — S(==O)zR), alkoxy ( — OR), and like substituents.

[0070]

[0054] “Alkoxy!” includes an alkyl group bound to the base structure via an oxygen atom, O R, wherein R can include optionally substituted linear alkyls or branched alkyls as described above.

[0071]

[0055] “Alkoxylcarbonyl” includes an alkyl group bound the base structure via an oxygen, with a carbonyl group adjacent the oxygen, O C(:::O) R, wherein R can include optionally substituted linear alkyls or branched alkyls as described above.

[0072]

[0056] “Carboxyl” means a moiety composed of carbon bonded to both an oxygen and a hydroxyl group, -C(=O)“O--H.

[0073]

[0057] “Hydroxyl” means an ~O~-H chemical moiety.

[0074]

[0058] “Cyano” means a ~C=N chemical moiety.

[0075]

[0059] “Halogen” or “halo” includes fluoro (-F), chloro (—Cl), bromo (~Br), or iodo (-1) moieties.

[0076]

[0060] “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.

[0077]

[0061] “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-4)alkyl, 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 tetraniethyiene diradical thereto.

[0078]

[0062] 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.

[0079]

[0063] 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 Ci-j indicates a moiety of the integer “i” to the integer “j” carbon atoms, inclusive. Thus, for example, (Ci-C8)alkyl or Ci-salkyl refers to an alkyl of one to eight carbon atoms, inclusive, and hydrocarbyloxy such as (Ci-C8)alkoxy or Ci-salkoxy refers to an alkoxy radical (OR) having an alkyl group of one to eight carbon atoms, inclusive. Specifically, a Ci-salkyl can be, for example, methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, tert¬ butyl, pentyl, 3-pentyl, hexyl, heptyl, or octyl; (C3-i2)cycloalkyl can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, including bicyclic, tricyclic, or multi-cyclic substituents, and like substituents.

[0080]

[0064] A specific “hydrocarbyl” can be, for example, (Cio-2o)hydrocarbyl, including all intermediate chain lengths and values, and (C3-i2)cyclohydrocarbyl including all intermediate values and ring sizes.

[0081]

[0065] Ci-salkoxy can be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec- butoxy, pentoxy, 3 -pentoxy, hexyloxy, 1 -methylhexyloxy, heptyloxy, octyloxy, and like substituents.

[0082]

[0066] 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, antliracenyl, 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).

[0083]

[0067] Other conditions suitable for formation and mod ification 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.

[0084] 1, et seq., 1967; March, J. “Advanced Organic Chemistry,” John Wiley & Sons, 4Supth / Suped.

[0085] 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,

[0086]

[0068] The term “MP" 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 “A / w” 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.

[0087]

[0069] The term “PDF 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:

[0088] PD / === D = MF / FP

[0089]

[0070] 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 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.

[0071] The term “reszh” refers to a polymeric material, or a precursor thereof, that selves 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.

[0090]

[0072] The term “oligomer” refers to a polymeric compound composed of a small number of monomer units, typically from 2 to about 20. Oligomers may be linear, branched, or cyclic, and can be homooligomers or copolymers.

[0091]

[0073] The term " (meth) acrylate" or " (meth) crylate 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 "pofy(meth)acrylale" refers to both acrylate and methacrylate polymer species. For example, the term "polymethyl (melh)acrylate" refers to both polymethyl acrylate and polymethyl methacrylate.

[0092]

[0074] The term “pattern density” refers to a quantitative measure of the fractional area of a substrate occupied by lithographically defined features within a specified region. It is typically expressed as a ratio or a percentage, calculated as the total surface area of the features divided by the total area of the specified region.

[0093]

[0075] The term "greater pattern density", when applied to, for example, a final paterned mask (e.g., the third patterned mask) relative to a first patterned mask (precursor pattern), refers to an increase in the number of features per unit area. This increase in density is achieved, in some embodiments, through the formation of new, intervening features relative to the precursor pattern, often resulting in the insertion of one new feature for every one pre-existing feature. Accordingly, “greater pattern density” generally refers to an increase in the number of features per unit area of least about 1%, at least about 5%, at least about 10%, at least about 25%, at least about 50%, at least about 75%, or at least about 100%; or an increase in the number of features per unit area from about 1% to about 100%, about 5% to about 50%, about 10% to about 60%, about 25% to about 75%, about 10% to about 90%, about 20% to about 80%, about 50% to about 100%, about 75% to about 125%, about 80% to about 150%, about 50% to about 200% or about 100% to about 200%.

[0094]

[0076] The term “feature” refers to an individual, intentionally formed geometric structure on or in a substrate, created as a result of a lithographic process. Common examples of features include, but are not limited to, lines, spaces, pillars, and holes. PDH-014

[0095]

[0077] The present disclosure provides pattern treatment compositions and methods of treating substrates with these compositions.

[0096] Pattern treatment compositions

[0097]

[0078] One embodiment of the present disclosure relates to pattern treatment compositions comprising one or more polymers having a reactive surface attachment group or reactive surface attachment group precursor, a catalyst, a solvent, and may include one or more additional, optional components.

[0098] Polymer having a reactive surface attachment group or reactive surface attachment group precursor

[0099]

[0079] Suitable polymers include, for example, those that can become bonded to (i.e., grafted) to the surface of the substrate through the reactive surface attachment group to form a layer over the substrate. The layer is typically formed by hydrogen or covalent bonding of the polymer to the surface of the substrate.

[0100]

[0080] Suitable polymers include homopolymers and copolymers including random copolymers and block copolymers (BCPs) The random copolymers can include two, three, four or more different units. The block copolymers can be multiblock copolymers. The multiblocks can include, for example, diblocks, triblocks, tetrablocks, or more blocks, wherein one or more block can include a random copolymer. The blocks can be part of a linear copolymer, a branched copolymer where the branches are grafted onto a backbone (these copolymers are also sometimes called “comb copolymers”), a star copolymer, and the like.

[0101]

[0081] Particularly preferred polymers include those that can bond (e.g. covalent linkage) or otherwise complex or coordinate (e.g. hydrogen or ionic bond) to one or more materials present on the substrate. For instance, a component that comprises an appropriate reactive moiety at one chain end or along the main chain, i.e. a hydroxyl end group for the case of oxide features, to allow for covalent attachment to the substrate. The component also can be a polymer or copolymer containing more than one reactive group to allow attachment.

[0102]

[0082] Suitable polymers include homopolymers and copolymers including random copolymers and block copolymers (BCPs). The random copolymers can include two, three, four or more different units. The block copolymers can be multiblock copolymers. The multiblocks can include, for example, diblocks, triblocks, tetrablocks, or more blocks, wherein one or more block can PDH-014

[0103] include a random copolymer. The blocks can be part of a linear copolymer, a branched copolymer where the branches are grafted onto a backbone (these copolymers are also sometimes called “comb copolymers”), a star copolymer, and the like.

[0104]

[0083] Suitable polymers include, for example: organic polymers such as optionally substituted polystyrene, poly(alkylacrylates), poly(alkylmethacrylates), poly(2-vinylpyridine), poly(4-vinylpyridine), poly(arylene oxides), polyethylene, polypropylene, hydrogenated polybutadiene, polycyclohexylethylene, polynorbornene, alternating copolymer of styrene and maleic anhydride or maleimide such as poly(styrene-alt-maleic anhydride) and poly(styrene-alt-maleimide), a polyacetal, a polycarbonate, a polyester, a polyamide, a polyamideimide, a polyaryl sulfone, a polyethersulfone, a polyphenylene sulfide, a polyvinyl chloride, a polysulfone, a polyimide, a polyetherimide, a polytetrafluoroethylene, a polyetherketone, a polyether etherketone, a polyether ketone ketone, a polybenzoxazole, a poly oxadiazole, a polybenzothiazin ophenothiazine, a polybenzothiazole, a polypyrazinoqumoxaline, a polypyromellitimide, a polyquinoxaline, a polybenzimidazole, a polyoxindole, a polyoxoisoindoline, a polydioxoisoindolme, a polytriazine, a polypyndazme, a polypiperazine, a polypyndine, a polypiperidine, a polytriazole, a polypyrazole, a polypyrrolidine, a polycarborane, a polyoxabicyclononane, a polydibenzofuran, a polyphthalide, a polyanhydride, a polyvinyl ether, a polyvinyl thioether, a polyvinyl alcohol, a polyvinyl ketone, a polyvinyl halide, a polyvinyl nitrile, a polyvinyl ester, a polysulfonate, a polynorbornene, a polysulfide, a polythioester, a polysulfonamide, a polyurea, a polyphosphazene, a polysilazane, a polyurethane, or a combination including at least one of the foregoing polymers; block copolymers of styrene and 2-vmylpyridine such as poly(styrene-block-2-vinlpyridine), block copolymers of styrene and 4-vinylpyridme such as poly(styrene-block-4-vinlpyridine); and combinations of any of the foregoing as a random or block copolymer. Such polymers can be optionally substituted, for example, with one or more substituent such as a halogen (i.e., F, Cl, Br, I), hydroxyl, amino, thiol, carboxyl, carboxylate, ether ( — O — ), ester, amide, nitrile, sulfide, disulfide, nitro, Ci-is alkyl, Ci-is alkenyl (including norbornenyl), Ci-i8 alkoxyl, C2-18 alkenoxyl, C5-18 aryl, C5-18 aryloxy 1, G>-i 8 alkylaryl, Ce-i8 alkylaryloxyl, or with a reactive surface attachment group as described herein. Selection of a suitable polymer will depend, for example, on desired etch selectivity with respect to other materials used in the process, target thickness and solubility in the formulation, and rinse solvent. PDH-014

[0105]

[0084] In some embodiments, the polymer comprises silicon. Suitable silicon-containing polymers include, for example: optionally substituted polysiloxanes such as polydimethylsiloxane; organosilanes such as poly(trimethyl(4-vinylphenyl)silane; polymers comprising polyhedral oligomeric silsesquioxane compounds such as a cage-type polyhedral oligomeric silsesquioxane material; and polymers comprising incomplete-cage type silsesquioxanes. In other embodiments, silicon-containing polymers are derived from monomers comprising 3-(trimetlioxysilyl)propyl acrylate, 3-(triethoxysilyl)propyl acrylate, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane acrylate, tetraethylorthosilicate acrylate, silicone acrylates, polydimethylsiloxane-acrylate, hexam ethyldi siloxane acrylate, octamethylcyclotetrasiloxane acrylate, trimethylsilylmethyl acrylate, dimethylsiloxypropyl acrylate, alkoxysilane acrylate derivatives, methoxyphenyl silyl acrylate, trimethyl-(2-methylene-but-3-enyl)silane, tert-butyldimethyl(4-vinylphenoxy)silane, tert-butyldimethyl(oxiran-2-ylmethoxy)silane, trimethyl(4-vinylphenyl)silane, and combinations thereof,

[0106]

[0085] In some embodiments, the polymer comprises a metal. Examples of metal-containing polymers include polyferrocenylethylene, polyferrocenylmethylsilane, poly(cobaltocene-silane), poly(nickelocene derivatives), poly(chromocene derivatives), transition metal carbene polymers, platinum acetylide polymers, poly(organostannanes), polyaluminoxanes, polyboranes, poly(arylgold), gold-thiolate polymers, silver-functionalized polymers, lanthanide complex polymers, metal-doped polypyrrole, metal-doped polyaniline, cobalt porphyrin polymers, and nickel phthalocyanine polymers.

[0107]

[0086] In some embodiments, the polymer comprises the following Formula (1):

[0108] (I)

[0109]

[0110] wherein X is 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 Co-30 aryl, or monocyclic or polycyclic Ce-30 heteroaryl, each of which is substituted or un substituted, each optionally including as part of its structure one or more groups chosen from — O—, — C(O)—, — C(O)— O—, — CH2O—, — NH—, — N(Ci-Cs alkyl)—, or — PDH-014

[0111] S —; or a silicon containing moiety, including a linear C1-20 alkylsiloxane, branched C3-20 alkylsiloxane, or a monocyclic or polycyclic C3-20 cycloalkylsiloxane, each of which is substituted or unsubstituted, each optionally including as part of its structure one or more functional groups chosen from — O —, — C(O) —, — C(O) — O —, — CH2O —, — NH —, — N(Ci-Cs alkyl) —, or — S —, and wherein the silicon can also be a part of a larger chain forming a siloxane backbone, such as a polysiloxane chain;

[0112] L is optionally present. Where L is present, it is a linking group selected from a linear or branched alkyl having 1 to about 8 carbon atoms that is optionally substituted. Where L is absent, the bond connects directly to M;

[0113] M is any one selected from the following substituents;

[0114]

[0115] where L1is optionally present. Where Llis present, it is a linking group selected from an alkyl having 1 to about 8 carbon atoms that is optionally substituted with one or more groups chosen from — O—, — C(O)—, — C(O)— O—, — CH2O—, — NH—, — N(Ci-Cs alkyl)—, or — S—. Where Llis absent, the bond connects directly to the silicon containing unit.

[0116]

[0087] Particularly preferred pattern treatment compositions include polymer brush compositions. The term “brush composition” or “brush layer” is utilized herein to refer to a layer formed by covalent or coordinate (e.g. hydrogen or ionic bond) bonding of a polymeric organic material to a surface. In some embodiments, the brush layer may comprise a siloxane; and may be formed from a siloxane-containing precursor such as, for example, a precursor comprising PDH-014

[0117] poly(dimethylsiloxane) (PDMS). In some embodiments, the brush layer may be formed from precursors comprising other organic polymers either in addition to, or alternatively to, siloxane-containing polymers. The brush layer precursors have one or more substituents suitable for reacting with surfaces to thereby covalently bond (i.e., graft) the brush layer to the surfaces.

[0118]

[0088] The polymer comprises a reactive surface attachment group for forming a bond, typically hydrogen bond or a covalent bond, with the hardmask layer. The reactive surface attachment group can be present, for example, as an end group or as a group pendant to the polymer backbone such as in one or more repeat unit of the polymer. The particular site on the hardmask layer with which the reactive surface attachment group will depend on the material of the hard mask layer. For example, in the case of a silicon oxide, silicon nitride or silicon oxynitride hardmask layer, the reactive surface attachment group can be suitable for reacting with silanol along exposed surfaces of the hardmask layer to form a bond. Suitable reactive surface attachment groups include, for example, one or more group chosen from: hydroxyl; sulfhydryl; carboxyl; epoxide; amine, for example, primary amines such as N-methyl amine, N-ethyl amine, 1 -aminopropane, 2- aminopropane and N-t-butylamine, secondary amines such as dimethylamine, methylethylamine and diethylamine, and tertiary amines such as trimethylamine; amide, for example, alkylamides such as N -methylamide, N-ethylamide, N-phenylamide and N,N-dimethylamide; imine, for example, primary and secondary aldimines and ketimines; diazine, for example optionally substituted pyrazine, piperazine, phenazine; diazole, for example, optionally substituted pyrazole, thiadiazole and imidazole; optionally substituted pyridine, for example, pyridine, 2-vinylpyridine and 4-vinylpyridine; pyridinium; optionally substituted pyrrolidone, for example, 2-pyrrolidone, N-vinylpyrrolidone and cyclohexyl pyrrolidine; and combinations thereof. Of these, hydroxy is preferred. The reactive surface attachment group can optionally take the form of a ring pendant to the polymer backbone, for example, pyridine, indole, imidazole, triazine, pyrrolidine, azacyclopropane, azacyclobutane, piperidine, pyrrole, purine, diazetidine, dithiazine, azocane, azonane, quinoline, carbazole, acridine, indazole and benzimidazole.

[0119]

[0089] In some embodiments, the polymer comprises a reactive surface attachment group that is masked by a protecting group, referred to herein as a reactive surface attachment group precursor. In its native state, the polymer does not directly comprise a reactive surface attachment group but instead comprises a reactive surface attachment group precursor. The reactive surface attachment group can be formed by treatment of the composition to expose the reactive surface attachment PDH-014

[0120] group precursor and enable surface attachment. In some embodiments, the reactive surface attachment group precursor comprises an acid-labile group capable of decomposing under the action of an acid to produce a carboxylic acid or alcohol. Acid-labile groups are also commonly referred to in the art as “acid-decomposable groups”, “acid-cleavable groups,” “acid-cleavable protecting groups,” “acid-labile protecting groups,” “acid-leaving groups,” and “acid-sensitive groups”.

[0121]

[0090] The acid-labile group which, on decomposition, forms a carboxylic acid is preferably a tertiary ester group of the formula — C(O)OC(R1)3 or an acetal group of the formula — C(O)OC(R2)2OR3, wherein: R s 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 C6-20 aryl, or monocyclic or polycyclic C2-20 heteroaryl, preferably linear C1-6 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 C6-20 aryl, or monocyclic or polycyclic C2-20 heteroaryl, preferably hydrogen, linear C1-6alkyl, 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 C6-20 aryl, or monocyclic or polycyclic C2-20 heteroaryl, preferably linear Ci-6 alkyl, branched C’3-6 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 other embodiments, the acid-labile group forms an alcohol group or a fluoroalcohol group decomposition. 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 each R is as defined above. PDH-014

[0122]

[0091] In some embodiments, preferred pattern treatment composition polymers will have an Ohnishi parameter (O. P.), defined as the ratio of the total number of atoms in a repeat unit of the polymer chain (N) to the difference between the total number of carbon atoms (Nc) and total number of oxygen atoms (No) in the same repeat unit, O. P.=N / (Nc-No), lower than 2 for sufficiently slow etch rate in common organic etch processes, i.e. O2 or N2 / H2 plasma etch processes. In other embodiments, preferred pattern treatment compositions comprise polymers comprising silicon which can have a differential etch rate to organic and metal containing films. In some embodiments, the pattern treatment composition preferably has an etch rate that is less than the etch rate of the patterned mask, for example, where the etch rate of the pattern treatment composition is at least 20, 30, 40, 50, 60, 70 or 80 percent lower than the etch rate of the patterned mask.

[0123]

[0092] In some embodiments, the pattern treatment composition is applied by spin coating as a solution of a polymer in a solvent. The polymer should have good solubility in the solvent used to apply the pattern treatment composition and in the solvent used to rinse and remove residual, ungrafted polymer (i.e., polymer not bonded to the hardmask layer) from the substrate. The content of the polymer in the pattern treatment composition will depend, for example, on the desired coating thickness of the composition. The polymer is typically present in the composition in an amount of from 50 to 100 wt %, more typically from 70 to 100 wt % or 90 to 100 wt %, based on total solids of the pattern treatment composition. The weight average molecular weight of the polymer is typically less than 400,000, preferably from 2000 to 200,000, more preferably from 2000 to 125,000 or from 10,000 to 30,000 g / mol. Suitable polymers for use in the pattern treatment compositions are commercially available and / or can readily be made by persons skilled in the art.

[0124]

[0093] The polymer can be subjected to purification prior to being combined with the other components of the pattern treatment composition for removal of metallic and / or non-metallic impurities. Purification can involve, for example, one or more of washing, slurrying, centrifugation, filtration, distillation, decantation, evaporation and treatment with ion exchange beads. Additionally or alternatively, the pattern treatment composition can be purified, for example, by filtration and / or treatment with ion exchange beads. Through purification of the polymer and / or pattern treatment composition, metal impurity levels of 10 ppb or less can be achieved.

[0125] Catalysts PDH-014

[0126]

[0094] In some embodiments, brush grafting is accomplished by hydrolytic condensation between the functional polymer and the surface to be grafted. The hydrolytic condensation can be promoted by use of a catalyst. In some embodiments, the catalyst is selected from one or more kinds of compounds preferably selected from an acid or an acid generator such as a thermal acid generator (TAG) or photoacid generator (PAG). In some embodiments, the acid is an inorganic acid or an organic acid. In preferred embodiments, the catalyst is free of fluorine. The catalyst is preferably used in an amount of 1 0-6to 10 moles, preferably 1 0-5to 5 moles, more preferably 1 0-4to 1 mole, relative to 1 mole of reactive group on the functional polymer.

[0127]

[0095] Preferable acids are organic acids including both non-aromatic acids and aromatic acids optionally having fluorine substitution. Suitable organic acids include, for example: carboxylic acids and polycarboxylic acids such as alkanoic acids, including formic acid, acetic acid, propionic acid, butyric acid, dichloroacetic acid, trichloroacetic acid, perfluoroacetic acid, perfluorooctanoic acid, oxalic acid malonic acid and succinic acid; hydroxy alkanoic acids, such as citric acid; aromatic carboxylic acids such as benzoic acid, fluorobenzoic acid, hydroxybenzoic acid and naphthoic acid; organic phosphorus acids such as dimethylphosphoric acid and dimethylphosphinic acid; and sulfonic acids such as optionally fluorinated alkylsulfonic acids including methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, 1-butanesulfonic acid, 1 -perfluorobutanesulfonic acid, 1,1, 2,2-tetrafluorobutane-l -sulfonic acid, 1,1, 2, 2-tetrafluoro-4-hydroxybutane- 1 -sulfonic acid, 1 -pentanesulfonic acid, 1 -hexanesulfonic acid, and 1 -heptanesulfonic acid.

[0128]

[0096] In some embodiments, the solubility shifting agent is an aromatic sulfonic acid. The aromatic sulfonic acid is of general Formula (2):

[0129] (SO3H)b

[0130] Ar1

[0131]

[0132] wherein Ar1represents an aromatic group, which may be carbocyclic, heterocyclic, or a combination thereof. The aromatic group may be monocyclic, for example, phenyl or pyridyl, or polycyclic, for example biphenyl, and can include plural fused aromatic rings such as naphthyl, PDH-014

[0133] anthracenyl, pyrenyl or quinolinyl; or fused ring systems having both aromatic and non-aromatic rings such as 1,2,3,4-tetrahydronaphthalene, 9, 1 O-dihydroanthracene or fluorene. A wide variety of aromatic groups may be used for Ar1. The aromatic group typically has from 5 to 40 carbons, preferably from 6 to 35 carbons, and more preferably from 6 to 30 carbons. Suitable aromatic groups include, but are not limited to: phenyl, biphenyl, naphthalenyl, anthracenyl, phenanthrenyl, pyrenyl, tetracenyl, triphenylenyl, tetraphenyl, benzo[f]tetraphenyl, benzo[m]tetraphenyl, benzo[k]tetraphenyl, pentacenyl perylenyl, benzo [a] pyrenyl, benzo[e]pyrenyl, benzo[ghi]perylenyl, coronenyl, quinolonyl, 7,8-benzoquinolinyl, fluorenyl, and 12H-dibenzo[b,h]fluorenyl. Of these, phenyl is particularly preferred. R4independently represents a halogen atom, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted carbocyclic aryl, substituted or unsubstituted heterocyclic aryl, substituted or unsubstituted alkoxy, or a combination thereof. R4may also include one or more groups such as ester, carboxy, ether, or a combination thereof, a represents an integer of 0 or more and b represents an integer of 1 or more, provided that a+b is not greater than the total number of available aromatic carbon atoms of Ar1. In preferred embodiments, the acid is free of fluorine. In preferred embodiments, R4independently represents a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C20 aryl group or a combination thereof, optionally containing one or more group chosen from carbonyl, carbonyloxy, sulfonamido, ether, thioether, a substituted or unsubstituted alkylene group, or a combination thereof; and a is independently an integer from 0 to 5.

[0134]

[0097] The aromatic acid is preferably a sulfonic acid comprising a phenyl, biphenyl, naphthyl, anthracenyl, thiophene or furan group. The aromatic acid is preferably chosen from one or more aromatic sulfonic acids of the following general formulas (3)-(8):

[0135] SO3H

[0136] (R5)a

[0137]

[0138] wherein: R5independently represents a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C20 aryl group or a combination thereof, optionally containing one or more group chosen from carbonyl, carbonyloxy, sulfonamido, ether, thioether, a substituted or PDH-014

[0139] unsubstituted alkylene group, or a combination thereof; Z1independently represents a group chosen from carboxyl, hydroxy, nitro, cyano, C1to C8alkoxy, formyl and sulfonic acid; c and d are independently an integer from 0 to 5; and c+d is 5 or less;

[0140]

[0141] wherein: R6and R7each independently represents a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C20 aryl group or a combination thereof, optionally containing one or more group chosen from carbonyl, carbonyloxy, sulfonamide, ether, thioether, a substituted or unsubstituted alkylene group, or a combination thereof; Z2and Z3each independently represents a group chosen from carboxyl, hydroxy, nitro, cyano, C1to C8alkoxy, formyl and sulfonic acid; e and f are independently an integer from 0 to 4; e+f is 4 or less; g and h are independently an integer from 0 to 3; and g+h is 3 or less;

[0142]

[0143] wherein: R8, R9and R10each independently represents a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C20 aryl group or a combination thereof, optionally containing one or more group chosen from carbonyl, carbonyloxy, sulfonamido, ether, thioether, a substituted or unsubstituted alkylene group, or a combination thereof; Z4, Z5and Zbeach independently represents a group chosen from carboxyl, hydroxy, nitro, cyano. C1to C8alkoxy, formyl and sulfonic acid; i and j are independently an integer from 0 to 4; i+j is 4 or less; k and 1 are independently an integer from 0 to 2; k+1 is 2 or less; m and n are independently an integer from 0 to 3; and m+n is 3 or less; PDH-014

[0144] (6)

[0145]

[0146] (Z

[0147] wherein: R]’, R12and R13each independently represents a substituted or unsubstituted Ci -C20 alkyl group, a substituted or unsubstituted C5-C20 aryl group or a combination thereof, optionally containing one or more group chosen from carbonyl, carbonyloxy, sulfonamido, ether, thioether, a substituted or unsubstituted alkylene group, or a combination thereof; Z7, Z8and Z9each independently represents a group chosen from carboxyl, hydroxy, nitro, cyano, C1to C8alkoxy, formyl and sulfonic acid; o and p are independently an integer from 0 to 4; o+p is 4 or less; q and r are independently an integer from 0 to 1; q+r is 1 or less; s and t are independently an integer from 0 to 4; and s+t is 4 or less;

[0148] (R14)uSO3H

[0149]

[0150] wherein: R14and R15each independently represents a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C20 aryl group or a combination thereof, optionally containing one or more group chosen from carboxyl, carbonyl, carbonyloxy, sulfonamido, ether, thioether, a substituted or unsubstituted alkylene group, or a combination thereof; Z10and Z11each independently represents a group chosen from hydroxy, nitro, cyano, C1to C8alkoxy, formyl and sulfonic acid; u and v are independently an integer from 0 to 5; u+v is 5 or less; w and x are independently an integer from 0 to 3; and w+x is 3 or less; and

[0151] (8)

[0152]

[0153] SO3H

[0154] wherein: X is O or S; R16independently represents a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C20 aryl group or a combination thereof, optionally PDH-014

[0155] containing one or more group chosen from carbonyl, carbonyloxy, sulfonamido, ether, thioether, a substituted or unsubstituted alkylene group, or a combination thereof; Z12independently represents a group chosen from carboxyl, hydroxy, nitro, cyano, C1to C8alkoxy, formyl and sulfonic acid; y and z are independently an integer from 0 to 3; and y+z is 3 or less. For each of the structures, it should be clear that the R1— R16groups can optionally form a fused structure together with their respective associated rings. PDH-014

[0156]

[0098] Exemplary aromatic sulfonic acids include, without limitation, the following:

[0157]

[0158] PDH-014

[0159]

[0160]

[0099] In some embodiments, the acid is a Lewis acid. A Lewis acid is a chemical species that contains an empty orbital which is capable of accepting an electron pair. This term is known in the art. Some examples of Lewis acids include boron trihalides, organoboranes (for example, PDH-014

[0161] tris(pentafluorophenyl)borane), boron trifluoride, tetrafluorosilane (S1F4), and aluminum trihalides (for example, AICL).

[0162]

[0100] Suitable thermal acid generators include those capable of generating the acids described above. The thermal acid generator can be non-ionic or ionic. Suitable nonionic thermal acid generators include, for example, cyclohexyl trifluoromethyl sulfonate, methyl trifluoromethyl sulfonate, cyclohexyl p-toluenesulfonate, methyl p-toluenesulfonate, cyclohexyl 2,4,6-triisopropylbenzene sulfonate, nitrobenzyl esters, benzoin tosylate, 2-nitrobenzyl tosylate, tris(2,3-dibromopropyl)-1,3,5-triazine-2,4,6-trione, alkyl esters of organic sulfonic acids, p- toluenesulfonic acid, dodecylbenzenesulfonic acid, oxalic acid, phthalic acid, phosphoric acid, camphorsulfonic acid, 2,4,6- trimethylbenzene sulfonic acid, triisopropylnaphthalene sulfonic acid, 5-nitro-o-toluene sulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzene sulfonic acid, 2-nitrobenzene sulfonic acid, 3 -chlorobenzene sulfonic acid, 3 -bromobenzene sulfonic acid, 2-fluorocaprylnaphthalene sulfonic acid, dodecylbenzene sulfonic acid, 1- naphthol-5- sulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl -benzene sulfonic acid, and their salts, and combinations thereof. Suitable ionic thermal acid generators include, for example, dodecylbenzenesulfonic acid triethylamine salts, dodecylbenzenedisulfonic acid triethylamine salts, p-toluene sulfonic acid-ammonium salts, p-toluene sulfonic acid-pyridinium salts, sulfonate salts, such as carbocyclic aryl and heteroaryl sulfonate salts, aliphatic sulfonate salts, and benzenesulfonate salts. Compounds that generate a sulfonic acid upon activation are generally suitable. Preferred thermal acid generators include p-toluenesulfonic acid ammonium salts, and heteroaryl sulfonate salts.

[0163]

[0101] Preferably, the TAG is ionic with a reaction scheme for generation of a sulfonic acid as shown below:

[0164] heat

[0165] RSO₃⁻ X⁺ → RSO₃H +

[0166] wherein RSO3 ~ is the TAG anion and

[0167]

[0168] is the TAG cation, preferably an organic cation. In preferred embodiments, the TA is an ionic thermal acid generator represented by the Formula (9): (A⁻)(BH)+(9) in which A is the anion of an organic or inorganic acid. In preferred embodiments, A is the anion of an organic or inorganic acid having a pKa of not more than 3; and (BH)+is the the monoprotonated form of a nitrogen-containing base B. Suitable nitrogen-containing bases B include, for example: optionally substituted amines such as ammonia, difluoromethylammonia, PDH-014

[0169] Ci -2.0 alkyl amines, and C3-30 aryl amines, for example, nitrogen-containing heteroaromatic bases such as pyridine or substituted pyridine (e.g., 3-fluoropyridine), pyrimidine and pyrazine; nitrogen-containing heterocyclic groups, for example, oxazole, oxazoline, or thiazoline. The foregoing nitrogen-containing bases B can be optionally substituted, for example, with one or more group chosen from alkyl, aryl, halogen atom (preferably fluorine), cyano, nitro and alkoxy. Of these, base B is preferably a heteroaromatic base.

[0170]

[0102] Base B typically has a pKa from 0 to 5.0, or between 0 and 4.0, or between 0 and 3.0, or between 1.0 and 3.0. As used herein, the term “pKa” is used in accordance with its art- recognized meaning, that is, pKais the negative log (to the base 10) of the dissociation constant of the conjugate acid (BH)+of the basic moiety (B) in aqueous solution at about room temperature. In certain embodiments, base B has a boiling point less than about 170 °C, or less than about 160 °C, 150 °C, 140 °C, 130 °C, 120 °C, 110 °C, 100 °C or 90 °C.

[0171]

[0103] Exemplary suitable nitrogen-containing cations (BH)+include NH₄⁺, CF₂HNH₃⁺, CF₃CH₂NH₃⁺, (CH3)3NH+, (C2H5)3NH+, (CH₃)₂(C₂H5)NH+and the following: PDH-014

[0172] Me ’'%> *** q** 's- > / /

[0173] Et -|\|+

[0174] H

[0175]

[0176] in which Y is alkyl, preferably, methyl or ethyl.

[0177]

[0104] In other embodiments, the catalyst is 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.

[0178]

[0105] Examples of PAGs include a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imidosulfonate, an oxime sulfonate, a diazodi sulfone, a disulfone an o-nitrobenzyl sulfonate, a cyclopentadienyl salt, and an indenyl salt. Suitable classes of PAGs generating sulfonic acids include, but are not limited to, sulfonium or iodonium salts, PDH-014

[0179] 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.

[0180]

[0106] The 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,

[0181]

[0107] Suitable cations for PAGs include onium cations, for example, sulfonium and Iodonium cations, for example, those of the following general Formula (10):

[0182] +X— (R17)aa (10) wherein X is S or I, wherein when X is I then aa is 2, and when X is S then aa is 3; R17is independently chosen from organic groups such as optionally substituted C1-30 alkyl, polycyclic or monocyclic C3-30 cycloalkyl, polycyclic or monocyclic C6-30 aryl, or a combination thereof; wherein when X is S, two of the R groups together optionally form a ring.

[0183]

[0108] Exemplary suitable iodonium cations include the following: PDH-014

[0184]

[0185] PDH-014

[0186]

[0109] Exemplary suitable sulfonium cations include the following:

[0187]

[0188] PDH-014

[0189]

[0110] Additional examples of suitable photoacid generators include, but are not limited to, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium perfluorobutanesulfonate, methylphenyldiphenylsulfonium perfluorooctanesulfonate, 4-n-butoxyphenyldiphenylsulfonium perfluorobutanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium perfluorobutanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium benzenesulfonate, 2,4,6- trimethylphenyldiphenylsulfonium 2,4,6-triisopropylbenzenesulfonate, phenylthiophenyldiphenylsulfonium 4-dodecylbenzensulfonic acid, tris(-t-butylphenyl)sulfonium perfluorooctanesulfonate, tris(-t-butylphenyl)sulfonium perfluorobutanesulfonate, tris(-t-butylphenyl)sulfonium 2,4,6-triisopropylbenzenesulfonate, tris(-t-butylphenyl)sulfonium benzenesulfonate, and phenylthiophenyl diphenylsulfonium perfluorooctanesulfonate.

[0190]

[0111] Examples of suitable iodonium salts include, but are not limited to, diphenyl iodonium perfluorobutanesulfonate, bis-(t-butylphenyl)iodonium perfluorobutanesulfonate, bis-(t-butylphenyl)iodonium, perfluorooctanesulfonate, diphenyl iodonium perfluorooctanesulfonate, bis-(t-butylphenyl)iodonium benzenesulfonate, bis-(t-butylphenyl)iodonium 2,4,6-triisopropylbenzenesulfonate, and diphenyliodonium 4-methoxybenzensulfonate.

[0191]

[0112] Examples of tris(perfluoroalkylsulfonyl)methide and tris(perfluoroalkylsulfonyl)imide PAGs can be found in U. S. Pat. Nos. 5,554,664 and 6,306,555, each of which is incorporated herein in its entirety. / Additional examples of PAGs of this type can be found in Proceedings of SPIE, Vol. 4690, pp. 817-828 (2002). Suitable methide and imide PAGs include, but are not limited to, triphenylsulfonium tris(trifluoromethylsulfonyl)methide, methylphenyldiphenylsulfonium tris(perfluoroethylsulfonyl)methide, triphenylsulfonium tris(perfluorobutylsulfonyl)methide, triphenylsulfonium bis(trifluoromethylsulfonyl)imide, triphenylsulfonium bis(perfluoroethylsulfonyl)imide, and triphenylsulfonium bis(perfluorobutylsulfonyl)imide.

[0192]

[0113] Further examples of suitable photoacid generators are bis(p-toluenesulfonyl)diazomethane, methylsulfonyl p-toluenesulfonyldiazomethane, 1 -cyclo-hexylsulfonyl- 1 -( 1, 1 - dimethylethylsulfonyl)diazomethane, bis( 1, 1 -dimethylethylsulfonyl)diazomethane, bis( 1 -methylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, 1-p-toluenesulfonyl-l-cyclohexylcarbonyldiazomethane, 2-methyl-2-(p-toluenesulfonyl)propiophenone, 2-methanesulfonyl-2-methyl-(4-methylthiopropiophenone, 2,4-methyl-2-(p-toluenesulfonyl)pent-3-one, 1 -diazo- l-methylsulfonyl-4-phenyl-2-butanone, 2-(cyclohexylcarbonyl-2-(p- PDH-014

[0193] toluenesulfonyl)propane, 1 -cyclohexylsulfonyl- 1 cyclohexylcarbonyldiazomethane, 1 -diazo- 1 - cyclohexylsulfonyl-3,3-dimethyl-2-butanone, 1 -diazo- 1 -(1, 1 -dimethylethylsulfonyl)-3,3-dimethyl-2-butanone, 1 -acetyl- 1 -(1 -methylethylsulfonyl)diazomethane, 1 -diazo- 1 -(p-toluenesulfonyl)-3,3-dimetliyl-2-butanone, l-diazo-l-benzenesulfonyl-3,3-dimetliyl-2-butanone, 1 -diazo- 1 -(p-toluenesulfonyl)-3-methyl-2-butanone, cyclohexyl 2-diazo-2-(p-toluenesulfonyl)acetate, tert-butyl 2-diazo-2-benzenesulfonylacetate, isopropyl-2-diazo-2- methanesulfonylacetate, cyclohexyl 2-diazo-2-benzenesulfonylacetate, tert-butyl 2 diazo-2-(p-toluenesulfonyl)acetate, 2-nitrobenzyl p-toluenesulfonate, 2, 6- dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-trifluoromethylbenzenesulfonate.

[0194]

[0114] Additional PAG compounds include, for example: onium salts, for example, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-t-butyphenyliodonium perfluorobutanesulfonate, and di-t-butylphenyliodonium camphorsulfonate. Non-ionic sulfonates and sulfonyl compounds are also known to function as photoacid generators, e.g., nitrobenzyl derivatives, for example, 2-nitrobenzyl-p-toluenesulfonate, 2,6-dimtrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p- toluenesulfonate; sulfonic acid esters, for example, l,2,3-tris(methanesulfonyloxy)benzene, 1,2,3- tris(trifluoromethanesulfonyloxy)benzene, and l,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, for example, bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane; glyoxime derivatives, for example, bis-O-(p-toluenesulfonyl)-a-dimethylglyoxime, and bis-O-(n-butanesulfonyl)-a-dimethylglyoxime; sulfonic acid ester derivatives of an N-hydroxyimide compound, for example, N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester; and halogen-containing triazme compounds, for example, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-l,3,5-triazine. Suitable non-polymerized photoacid generators are further described in U. S. Pat. No.

[0195] 8,431,325 to Hashimoto et al. in column 37, lines 11-47 and columns 41-91. Other suitable sulfonate PAGs include sulfonated esters and sulfonyloxy ketones, nitrobenzyl esters, s-triazine derivatives, benzoin tosylate, t-butylphenyl a-(p-toluenesulfonyloxy)-acetate, and t-butyl a-(p- toluenesulfonyloxy)-acetate; as described in U. S. Pat. Nos. 4,189,323 and 8,431,325. PAGs that are onium salts typically comprise an anion having a sulfonate group or a non-sulfonate type group, PDH-014

[0196] such as a sulfonamidate group, a sulfonimidate group, a methide group, or a borate group. Additional examples of acids and PAGs are given in PCT Pat. Publ. W02025 / 038907.

[0197]

[0115] The composition may optionally comprise a plurality of PAGs. 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.

[0198]

[0116] In other embodiments, the catalyst is selected from one or more kinds of compounds preferably selected from a base or basic compound comprising hydroxides, carboxylates, amines, imines, amides, and mixtures thereof. Preferred basic compounds can be selected from organic amines, organic ammonium hydroxides, alkali metal hydroxides and alkaline earth metal hydroxides. In some embodiments, the base or basic compound comprises a base generator such as a thermal base generator or photobase generator.

[0199]

[0117] Suitable examples of organic amines include, but are not limited to, amines, guanidines, aminopyrrolidines, pyrazoles, pyrazolines, piperazines, aminomorpholines, aminoalkylmorpholines and piperidines. More preferred examples of the compound include a compound having an imidazole structure, a diazabicyclo structure, a trialkylamine structure, an aniline structure or a pyridine structure; an alkylamine derivative having a hydroxyl group and / or an ether bond; and an aniline derivative having a hydroxyl group and / or an ether bond.

[0200]

[0118] Specific examples of bases include ammonium carbonate, ammonium hydroxide, ammonium hydrogen phosphate, ammonium phosphate, tetramethylammonium carbonate, tetramethylammonium hydroxide, tetramethylammonium hydrogen phosphate, tetramethylammonium phosphate, tetraethylammonium carbonate, tetraethylammonium hydroxide, tetraethylammonium hydrogen phosphate, tetraethylammonium phosphate, and combinations thereof.

[0201]

[0119] Amines include aliphatic amines, cycloaliphatic amines, aromatic amines and heterocyclic amines. The amine may be a primary, secondary or tertiary amine. The amine may be a monoamine, diamine or polyamine. Suitable amines may include C1-30 organic amines, imines, or amides, or may be a C1-30 quaternary ammonium salt of a strong base (e.g., a hydroxide or alkoxide) or a weak base (e.g., a carboxylate). PDH-014

[0202]

[0120] Suitable examples of base additives include, but are not limited to, cyclopropylamine, cyclobutylamine, cyclopentylamine, dicyclopentylamine, dicyclopentylmethylamine, dicyclopentylethylamine, cyclohexylamine, dimethylcyclohexylamine, dicyclohexylamine, dicyclohexylmethylamine, dicyclohexylethylamine, dicyclohexylbutylamine, cyclohexyl-t-butylamine, cycloheptylamine, cyclooctylamine, 1 -adamantanamine, 1-dimethylaminoadamantane, 1 -diethylaminoadamantane, 2-adamantanamine, 2- dimethylaminoadamantane, 2-aminonorbornene, 3-noradamantanamine, 2-methylimidazole, tetramethyl ammonium hydroxide, tetrabutylammonium hydroxide, triisopropylamine, trioctylamine, tridodecylamine, 4-dimethylaminopyridine, 4,4'-diaminodiphenyl ether, 2,4,5-triphenylimidazole, 1,4-diazabicyclo[4.3.0]non-5-ene, l,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, guanidine, 1, 1 -dimethylguanidine, 1, 1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridme, 4-aminopyridine, 2-dimethylaminopyridine, 2-diethylaminopyridine, 2-(aminomethyl)pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, n-(2-aminoethyl)piperazine, n-(2-aminoethyl)piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1-(2-aminoethyl)pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-ammo-3-methyl-l-p-tolylpyrazole, pyrazine, 2-(aminomethyl)-5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, n-aminomorpholine, n-(2-aminoethyl)morpholine, trimethylimidazole, triphenylimidazole, methyldiphenylimidazole, tripropylamine, dodecylamine, tris(2-hydroxypropyl)amine, tetrakis(2-hydroxypropyl)ethylenediamine, diphenylamine, triphenylamine, aminophenol, 2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane, troger’s base, diazabicycloundecene, and diazabicyclononene.

[0203]

[0121] Examples of amides include tert-butyl-l,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate and tert-butyl 4-hydroxypiperidine-l-carboxylate, n-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, n-ethyl-2-pyrrolidone, tetramethylurea, n,n'-dimethylpropyleneurea, diisopropylurea, n-hydroxy ethylacetamide, n-methylacetamide, benzamide, pivalamide, and n- phenylacetamide. Examples of quaternary alkyl ammonium salts include tetrabutylammonium hydroxide or tetrabutylammonium lactate. PDH-014

[0204]

[0122] In another embodiment, the amine is a hydroxyamine. Examples of hydroxyamines include hydroxyamines having one or more hydroxyalkyl groups each having 1 to about 8 carbon atoms, and preferably 1 to about 5 carbon atoms such as hydroxymethyl, hydroxy ethyl and hydroxybutyl groups. Specific examples of hydroxy amines include mono-, di- and tri- ethanolamine, 3-amrno-1 -propanol, 2-amino-2-methyl-l -propanol, 2-amino-2-ethyl- 1,3 -propanediol, tris(hydroxymethyl)aminomethane, N-methylethanolamine, 2-dietliylamino-2-methyl- 1 -propanol and triethanolamine.

[0205]

[0123] Suitable base generators may be thermal base generators. A thermal base generator forms a base upon heating above a first temperature, typically about 140 °C or higher. The thermal base generator may include a functional group such as an amide, sulfonamide, imide, imine, O-acyl oxime, benzoyloxycarbonyl derivatives, quarternary ammonium salt, nifedipine, carbamate, and combinations thereof.

[0206]

[0124] Exemplary thermal base generators include: o-{(.beta.- (dimethylamino)ethyl)aminocarbonyl}benzoic acid, o- {(.gamma.-(dimethylamino) propyl)aminocarbonyl} benzoic acid, 2,5-bis{(.beta.-(dimethylamino)ethyl)aminocarbonyl} terephthalic acid, 2,5-bis {(.gamma.-(dimethylamino)propyl)aminocarbonyl} terephthalic acid, 2,4-bis{(.beta.- (dimethylamino)ethyl)aminocarbonyl} isophthalic acid, 2,4-bis {(.gamma. - (dimethylamino)propyl) aminocarbonyl] isophthalic acid, and combinations thereof.

[0207] Solvent

[0208]

[0125] The pattern treatment composition further includes a solvent. Suitable solvent materials to formulate and cast the pattern treatment composition exhibits excellent solubility characteristics with respect to the non-solvent components of the composition, but do not appreciably dissolve the underlying layers to be treated. The solvent is typically chosen from organic solvents, aqueous solvents, and mixtures thereof. 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 m 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 PDH-014

[0209] 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.

[0210] Optional components

[0211]

[0126] In one or more embodiments, the pattern treatment composition includes a fluorescent chemical marker. The fluorescent chemical marker may be any suitable fluorescent chemical that may be included in a pattern treatment composition. In some embodiments, the fluorescent chemical marker may be chemically bonded to the polymers having a reactive surface attachment group or reactive surface group precursor m the pattern treatment composition. Suitable fluorescent chemicals may emit fluorescence at a wavelength ranging from about 200 nm to about 5000 nm. The fluorescent chemical marker may be included in the pattern treatment composition in an amount ranging from about 10'7mol / liter to about 10’2mol / liter. The fluorescent chemical marker of one or more embodiments may be a fluorescent dye. Suitable fluorescent dyes include pyrenes, BODIPY dyes, cyanine 3 dyes, cyanine 5 dyes, cyanine 5.5 dyes, cyanine 7 dyes, fluorescein dyes, rhodamine dye, Coumarin dyes, 800CW dye, BP Fluor 680, BP Fluor 647, BP Fluor 594, BP Fluor 568, BP Fluor 546, BP Fluor 555, BP Fluor 350, BP Fluor 488, BP Fluor 430, BP Fluor 532, 4-(9H-carbazol-9-yl)benzoate, and 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)4H-pyran. In other embodiments, the fluorescent chemical marker, such as those listed above, may be included as a functional group on the polymer of the patern treatment composition.

[0212]

[0127] The pattern treatment composition can include one or more optional components, including a surfactant, an antioxidant, an anti-striation agent, a plasticizer, an additive polymer, or other additives. If present, the optional additives are typically present m the photoresist compositions in an amount from 0.01 to 10 wt %, based on total solids of the photoresist composition.

[0213]

[0128] The pattern treatment composition can be prepared following known procedures. For example, the compositions can be prepared by dissolving the polymer and other optional solid components of the composition in the solvent component. The desired total solids content of the compositions will depend on factors such as the particular polymer(s) in the composition and desired final layer thickness. Preferably, the solid content of the pattern treatment composition is from 1 to 10 wt % based on the total weight of the composition. PDH-014

[0214]

[0129] The components of the pattern treatment composition can be subjected to purification prior to being combined with the other components of the pattern treatment composition for removal of metallic and / or non-metallic impurities. Purification can involve, for example, one or more of washing, slurrying, centrifugation, filtration, distillation, decantation, evaporation and treatment with ion exchange beads. Additionally or alternatively, the pattern treatment composition can be purified, for example, by filtration and / or treatment with ion exchange beads. Through purification of the components and / or pattern treatment composition, metal impurity levels of 10 ppb or less can be achieved.

[0215] Substrate treatment methods

[0216]

[0130] Methods in accordance with the disclosure will now be described. A substrate is first provided which may include various layers and features formed on a surface thereof. 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 typically composed of one or more of silicon, poly silicon, silicon oxide, silicon nitride, silicon oxynitride, a compound semiconductor (e.g., Ill- V or II-V1), silicon germanium, gallium arsenide, glass, quartz, ceramic, aluminum, sapphire, tungsten, titanium, titanium¬ tungsten, nickel, copper, gold, and the like. 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. Typically, the substrate is a semiconductor wafer, such as single crystal silicon or compound semiconductor wafer, and may have one or more layers and patterned features formed on a surface thereof. 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. The underlying base substrate material itself may optionally be patterned, for example, when it is desired to form trenches in the substrate material. In the case of patterning the base substrate material itself, the pattern shall be considered to be formed in a layer of the substrate. PDH-014

[0217]

[0131] One or more layers to be patterned may be provided over the substrate. The layers may comprise a wide variety of materials, encompassing conductive, dielectric, and semiconductor layers. Conductive layers include metals like aluminum, copper, molybdenum, tantalum, titanium, and tungsten, along with their alloys such as Al-Cu and Ti-W, and metal compounds such as titanium nitride, tungsten silicide, and titanium aluminum nitride; doped semiconductors such as doped amorphous silicon, doped polysilicon, doped carbon, and doped gallium arsenide; and transparent conductors like Indium tin oxide and fluorine-doped tin oxide. Dielectric materials consist of silicon-based compounds including silicon oxide, silicon nitride, silicon oxynitride, silicon oxy carbide, and porous silicon dioxide; high-k dielectrics such as hafnium oxide, zirconium oxide, aluminum oxide, aluminum oxynitride, titanium oxide, tungsten oxide, strontium titanate, barium strontium titanate, and spin-on metal hard masks; low-k dielectrics such as fluormated silicon glass and organic polymers such as benzocyclobutenes and polyimides. Semiconductor materials consist of silicon-based materials such as single-crystal silicon, amorphous silicon, polysilicon, and silicon carbide, compound semiconductors such as amorphous carbon, tin oxide, gallium nitride, indium phosphide, and cadmium telluride, as well as emerging 2D materials such as graphene and molybdenum disulfide. The layer may also comprise an organic or silicon-contaming anti-reflection coating or a spin-on carbon material. In various embodiments, the layer may be from 1 nm to 1000 nm thick. The layers to be etched can be formed by various techniques, for example: atomic layer deposition ( ALD), chemical vapor deposition (CVD) such as plasma- enhanced CVD, low-pressure CVD or epitaxial growth; physical vapor deposition (PVD) such as sputtering or evaporation; or electroplating; or spin-coating, or any other useful technique. In some embodiments, the substrate or one or more layers to be patterned comprises a fluorescent chemical marker as described above.

[0218]

[0132] In some embodiments, the substrate further comprises a patterned mask comprising features extending therein and defining a pattern, for example, a patterned mask characterized by a plurality of features, such as lines, holes, or posts, that are separated by gaps. In some embodiments, the patterned mask comprises carbon. In some embodiments, the patterned mask comprises a photoresist. In some embodiments, the photoresist is a chemically amplified photosensitive composition that comprises a polymer and a photoacid generator. The polymer may be any standard polymer typically used in photoresist material and may particularly be a polymer having acid-labile groups. In some embodiments, the photoresist is a negative resist comprising a PDH-014

[0219] composition that becomes insoluble upon exposure to actinic radiation. In other embodiments, the photoresist is a negative tone developed photoresist. In some embodiments, the photoresist comprises a metal or a metalloid or an atom with a high patterning radiation-absorption cross¬ section (e.g., an EUV absorption cross-section that is equal to or greater than 1×107cm2 / mol). In some embodiments, the metal is tin, bismuth), tellurium, cesium, antimony, indium, molybdenum, hafnium, iodine, zirconium, iron, cobalt, nickel, copper, zinc, silver, platinum, or lead, or a combination thereof.

[0220]

[0133] Coatings of the photoresist can be achieved through various means known by those of ordinary skill m the art, such as spin coating and dry deposition. In preferred embodiments, coatings of the photoresist can be patterned using radiation to form the first relief pattern. Suitable radiation sources include extreme ultraviolet (EUV, 13.5 nm), ultraviolet (UV, 400-100 nm), X-ray (0.1-10 nm), or electron beam (EB) radiation. Radiation can generally be directed to the substrate material through a mask or a radiation beam can be controllably scanned across the substrate to form a latent image within the resist coating.

[0221]

[0134] The amount of electromagnetic radiation can be characterized by a fluence or dose which is obtained by the integrated radiative flux over the exposure time. In some embodiments, suitable radiation fluences can be from about 1 mJ / cm2to about 200 mJ / cm2, in further embodiments from about 2 mJ / cm2to about 150 mJ / cm2and in further embodiments from about 3 mJ / cm2to about 100 mJ / cm2. In an embodiment, the EUV radiation can be done at a dose of less than or equal to about 150 mJ / cm2or with an electron beam at a dose equivalent to or not exceeding about 2 mC / cm2at 30 kV. A person of ordinary skill in the art will recognize that additional ranges of radiation fluences within the explicit ranges above are contemplated and are within the present disclosure.

[0222]

[0135] Following exposure to radiation and the formation of a latent image, a subsequent post¬ exposure bake (PEB) is typically performed. In some embodiments, the PEB can be performed at temperatures from about 45 °C to about 250 °C, in additional embodiments from about 50 °C to about 190 °C, and m further embodiments from about 60 °C to about 175 °C. The post exposure heating can generally be performed for at least about 0.1 minute, in further embodiments from about 0.5 minutes to about 30 minutes and in additional embodiments from about 0.75 minutes to about 10 minutes. A person of ordinary skill in the art will recognize that additional ranges of PEB PDH-014

[0223] temperatures and times within the explicit ranges above are contemplated and are within the present disclosure.

[0224]

[0136] The photoresists can be developed using either positive tone or negative tone patterning. For example, when an aqueous acid or base solution, for example comprising tetraalkyl ammonium hydroxide, is used as a developer, positive tone patterning can be realized wherein the exposed material is dissolved away and the unexposed material remains. In contrast, when an organic solvent is used as a developer, negative tone patterning is realized wherein the unexposed material is dissolved away and the exposed material remains.

[0225]

[0137] Suitable developers for a positive tone 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 negative tone developed (NTD) process are organic solvent-based, meaning the cumulative content of organic solvents in the developer is 50 wt % or more, typically 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.

[0226]

[0138] 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 typically conducted at room temperature.

[0227]

[0139] As previously described, the patterned mask may include features separated by gaps. In one or more embodiments, the features of the patterned mask may have a thickness of about 300 to 3000 A. The gaps separating the features may leave portions of the substrate or layers to be patterned exposed.

[0228]

[0140] In some embodiments, the patterned mask is stabilized prior to coating with the pattern treatment composition. Various resist stabilization techniques, also known as freeze processes, have been proposed such as ion implantation, UV curing, thermal hardening, thermal curing and chemical curing. Techniques are described, for example, in US2008 / 0063985A1, US 2008 / 0199814A1 and US 2010 / 0330503A1. In other embodiments, the substrate is optionally PDH-014

[0229] treated to further condense the material and to further dehydrate, densify, or remove residual developer from the patterned mask. This is typically done by baking the substrate at 100 °C to 600CC for at least one minute in air, vacuum, or an inert gas (like Ar or Na). Non-thermal methods, such as UV exposure or an Oa plasma treatment, can also be used for similar purposes.

[0230]

[0141] In other embodiments, the patterned mask comprises a material as defined above for the composition of the one or more layers to be patterned. In some embodiments, the patterned mask comprises silicon or a metal. The patterned mask may be formed by a photolithographic process as described above followed by an etch transfer to record the resist pattern in the one or more layers to be patterned. Pattern transfer can be conducted, for example, by known anisotropic dry¬ etching techniques. The etch process may be an isotropic or anisotropic etch process, using any suitable dry etchant, such as chlorine, boron trichloride, hydrogen bromide, sulfur hexafluoride, carbon tetrafluoride, trifluoromethane, oxygen, nitrogen, argon, xenon difluoride, silicon tetrachloride, or other suitable etch gas,

[0231]

[0142] In some embodiments, a hard mask material is applied over the patterned mask and layers to be patterned. Suitable hardmask materials are known in the art and include those materials and application techniques described above for the layers to be patterned. In some embodiments, the hardmask material is selected from silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, hafnium oxide, zirconium oxide, aluminum oxide, aluminum oxynitride, titanium oxide, or tungsten oxide. The thickness of the hardmask layer is typically from I to 50 nm, for example, from 5 to 20 nm.

[0232]

[0143] The pattern treatment composition may then be applied to the substrate by any of a variety of techniques including spin coating or dry deposition. After applying a layer of the pattern treatment composition, the coated substrate is then preferably treated to activate the catalyst and induce the surface attachment reaction. Thermal treatment, e.g., a bake on a hot plate, is preferred and can enhance bonding or complexing of the pattern treatment composition to the substrate. Suitable thermal treatment conditions may include heating in excess of 150 °C or 200 °C for 0.5 to 15 minutes depending on the specific materials utilized.

[0233]

[0144] In some embodiments, the catalyst may be activated prior to thermal treatment by exposure to actinic radiation. Suitable radiation sources include extreme ultraviolet (EUV), ultraviolet (UV), X-ray, or electron beam (EB) radiation. Radiation can generally be directed to the substrate material through a mask or a radiation beam can be controllably scanned across the substrate to PDH-014

[0234] form a latent image within the resist coating. In preferred embodiments, a thermal treatment is performed after exposure to radiation. Suitable thermal treatment conditions may include heating in excess of 150 °C or 200CC for 0.5 to 15 minutes depending on the specific materials utilized.

[0235]

[0145] After activation of the catalyst and surface attachment, the pattern treatment composition that is unattached to the substrate is suitably removed, for example by rinsing the coated substrate with a suitable solvent. Removal of the residual, unbound pattern treatment composition forms a grafted layer of the pattern treatment composition over the one or more layers to be patterned. Suitable solvents for the rinsing agent can include, for example, organic solvents, aqueous solvents and combinations thereof, including those solvents listed above. It may be desirable to use the same solvent used in the pattern treatment composition. The rinsing agent can be applied to the substrate by known techniques, for example, by spin-coating. The rinsing time is for a period effective to remove the un-bonded polymer, with a time of from 15 to 120 seconds being typical. The rinse is typically conducted at room temperature. Optionally, a post-rinse bake can be conducted for one or more of removing residual rinse solvent, inducing relaxation of the polymer chains and densification of the polymer layer, and minimizing surface area of the polymer layer. The post-rinse bake, if used, is typically conducted at a temperature of from about 70 to 150 °C and a time of from about 30 to 120 seconds.

[0236]

[0146] Following removal of the unattached pattern treatment composition material, the substrate may be annealed if desired, for example by heating in excess of 100 °C for 1, 2 or more minutes. The thickness of the formed pattern treatment composition can be controlled through selection or tailoring of one or more components of the composition and / or processing conditions. In particular, by selection of the molecular weight and / or blend ratios of one or more polymer components of the composition, the coating layer thickness can be controlled. In general, use of higher molecular weight polymers as components of the composition, including polymers that have a weight average molecular weight in excess of 1,000; 5,000; 10,000; 15,000; or 20,000, can enable forming greater pattern treatment composition coating layer thicknesses of greater widths. Inclusion of the catalyst generally produces larger coating layer thicknesses. In embodiments where actinic radiation is used to activate the catalyst, the coating layer thickness can be spatially tailored across the substrate surface.

[0237]

[0147] In some embodiments, the substrate is optionally treated to convert the layer of the pattern treatment composition to a modified layer. In preferred embodiment, the layer of pattern treatment PDH-014

[0238] composition comprises a poly(siloxane) that can be converted to a SiOx-iike material. In some embodiments, the treatment comprises exposing the annealed film to a reactive plasma or a reactive ion etching atmosphere. Most preferably, the treatment comprises exposing the annealed film to a reactive plasma or a reactive ion etching atmosphere, wherein the atmosphere comprises a plasma composed of a low pressure ionized oxidizing gas (preferably Ch).

[0239] Measuring uniformity

[0240]

[0148] A substrate with various layers is characterized by an initial surface roughness and / or uniformity. A patterned mask, utilized in photolithography, has a surface topography that includes patterned features and unpatterned regions. The surface of said patterned mask, including the top surfaces, sidewalls, and base areas of its features, also exhibits a surface roughness. The surface roughness and uniformity of the substrate and the patterned mask are critical characteristics, influencing light transmission, pattern fidelity, and ultimately the performance of the final lithographically-defined device.

[0241]

[0149] The surface roughness and uniformity of the substrate and patterned mask are quantifiable using a plurality of metrics derived from surface topography measurements. These metrics include general parameters for overall surface characterization as well as specific parameters for patterned features. The most common parameters include:

[0242] a. Arithmetic Mean Roughness: i\ metric defining the average absolute deviation of a surface profile from a mean line, providing a general measure of the overall surface texture.

[0243] b. Root Mean Square Roughness (Rq): A metric defining the square root of the mean of the squares of profile deviations, which is more sensitive to extreme peaks and valleys than Ra.

[0244] c. Maximum Height (Rz): A metric defining the average height difference between the highest peak and lowest valley within a designated sampling length, which is critical for identifying extreme topological features.

[0245] d. Total Roughness (Rt): A metric defining the vertical distance between the highest peak and lowest valley across the entire measured surface profile.

[0246] e. Power Spectral Density (PSD): A metric providing frequency- domain information about roughness, useful for analyzing the periodicity of features and understanding the PDH-014

[0247] origins of roughness. Said PSD can distinguish between long-wavelength roughness and short-wavelength roughness.

[0248]

[0150] Furthermore, the roughness of the patterned mask is characterized by specific metrics related to the integrity of the lithographically-defined features, such as roughness and uniformity across a distribution of the features, including uniformity in dimensions, shape, and peripheral surface characteristics. These metrics are typically quantified using the following parameters: a. Line Edge Roughness (LER): The statistical variation or deviation of a single feature edge from an ideal, straight line, typically quantified as the 3o standard deviation of the deviations.

[0249] b. Line Width Roughness (LWR): The statistical variation in the width of a patterned feature along its length, resulting from the combined effect of the roughness of both edges.

[0250] c. Critical Dimension Uniformity (CDU): The statistical variation of the Critical Dimension (CD) across a population of features, typically quantified as the or range of CD values.

[0251] d. Circularity: The deviation of a feature’ s shape from a perfect circle, typically quantified as the difference between the diameters of the inscribed and circumscribed circles.

[0252]

[0151] The surface and feature characteristics can be measured by advanced metrology techniques, including: Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM), White Light Interferometry (WLI), Stylus Profilometry, X-Ray Reflectometry (XRR), Optical Microscopy, Focused Ion Beam (FIB), Ellipsometry, and Scatterometry. The substrate and / or patterned mask possesses a first level of uniformity, characterized by the metrics defined above, such as a first CDU, a first LER, a first LWR, and a first circularity.

[0253]

[0152] In some embodiments, a method of measuring the uniformity is then employed again to characterize a second level of uniformity, which can be characterized by metrics defined above, such as a second roughness, a second CDLT, a second LER, a second LWR, or a second Circularity. Said second level of uniformity is greater than the first level. In preferred embodiments, the aforementioned process reduces heterogeneity and irregularities across the population of features, thereby achieving a greater level of uniformity. For instance, the second CDU, LER, LWR, and / or Circularity metrics are lower than their respective first metrics. By selectively modifying the features, such as by depositing a material that preferentially shapes the features to have a PDH-014

[0254] substantially uniform geometry, the differences between the shapes can be alleviated. The resulting pattern, having features that are approximately the same size and shape as one another, is then characterized as having a greater level of uniformity. Furthermore, a pattern where features possess irregular peripheral surfaces is considered to have a low level of uniformity. By applying a process to reduce these irregularities, such as a self-smoothing technique, the pattern can be elevated to a greater level of uniformity. This reduction of irregularity ensures that the features' shapes are more consistent and less susceptible to the negative effects of edge roughness and non-uniformity. In preferred embodiments, the second metric is lower than the first metric. In preferred embodiments, the second level of uniformity is lower than the first level of uniformity by 5% or more, more preferably by 10% or more, and more preferably by 15% or more.

[0255] Adjusting thickness

[0256]

[0153] Additional embodiments of the disclosure provide methods to adjust thickness of the grafted pattern treatment composition layer. In conventional processes of the prior art, this thickness can vary due to process fluctuations from wafer to wafer during manufacturing, or within a single wafer due to local variations in process parameters across the wafer. Such variation results in undesirable non-uniformity and poor performance. Processes defined below address such non-uniformity by providing schemes for adjusting the thickness of the grafted pattern treatment composition layer, either from wafer to wafer, or within wafer. Some embodiments of this process use location-specific critical alteration / correction flows and processes for improvement of thickness uniformity, and in some embodiments shifting of thickness targeting as well, making use, in some embodiments, of measurement information in a feed forward process control scheme by means of localized dose control.

[0257]

[0154] In these embodiments, after formation of the pattern treatment composition layer, a method of determining a dimensional property (i.e., a measurement) of the layer may be performed by a method selected from the group consisting of gravimetric analysis, spectroscopic analysis, and microscopic analysis, or other suitable method. A measurement can be sensitized specifically according to the disclosed labelling technique (e.g, fluorescent labelling). In methods according to one or more embodiments, a calibration curve on any controlled parameter such as thickness, width, or diameter may be generated in order to achieve precise measurements. Methods herein may also have a feedforward calibration (to account for thickness variation). PDH-014

[0258]

[0155] For example, a series of different inputs on a range of otherwise identical areas may be created. This can be on a single substrate, by taking advantage of site-to-site differences, or on a group of substrates. For optical applications, this can include changing a dose. For thermal applications, this can include changing time and temperature. Then the changes may be measured using a calibrated metrology system on the coated substrate as well as an after etch calibration. A look-up table may then be created, or a machine learning / artificial intelligence network may be created and used, or a calibration linearity may be created (for example, 1 nm of diameter per second of time). The generation of calibration curves for such purpose is conventional in the art, though applied herein on unconventional materials.

[0259]

[0156] In one embodiment, techniques include measuring a weight change. The weight change may be measured on the substrate level only. An incoming substrate may be measured to identify an initial weight. Then, processing may be executed, including coating with a pattern treatment composition, and processing to form the coating layer. After processing, the wafer may be measured again to identify a modified weight and / or a difference in weight,

[0260]

[0157] In one or more embodiments, processing of optical methods includes measuring a change in diameter / width by using calibrations from the measurement system in question and calculating a correction curve for each target area. Optionally, a smoothed calculation can be created, and any input from feedforward can be used. It will be understood that feedforward indicates incorporating measurements to modify the process if the measurement deviates from a predetermined value. Data measured and calculated according to methods described herein can be used to correct a hot plate, to change the mean temperature or to correct an optical tool, which corrects for variance using optical dose. Thus, measurements described herein may be used to optimize scanners and track tools.

[0261]

[0158] Based on measured values, parameters for a subsequent substrate can be adjusted based on current data. This may be an adjustment to the unique thermal or optical activation. In one or more embodiments, to increase the thickness or width of the grafted layer of the pattern treatment composition, the temperature / time may be adjusted to increase the amount of grafting. For example, after calibration, if the known tradeoff is 1 nm coating layer thickness per 10 seconds bake time, and if the measured amount of thickness was off by 0.23 nm, then the process time would change by 0.23 sec. In an optical tuning case, where, for example, there are optically activated portions of the pattern treatment composition, there will be a calibration of dose vs. size. PDH-014

[0262] If, for example, that is 1 mJ / cc per nanometer, then a 0.23 nm shift will need 1 mJ of dose to adjust and may be updated accordingly.

[0263]

[0159] In some embodiments, the substrate is exposed to electromagnetic radiation to adjust the thickness of the grafted pattern treatment composition layer by activation of a catalyst, e.g., a photoacid generator. This exposure process can be from any generic radiation source, for example, a lamp, a laser, a bulb, etc. The electromagnetic radiation source's exposure wavelength could be, but is not limited to, any wavelength, or range of wavelengths between 170 - 450 nm, which are wavelengths typically used by the industry in photolithography, with exemplary wavelengths being at / around 193 nm, at / around 266 nm, or at / around 365 nm,

[0264]

[0160] According to an embodiment, the dose of electromagnetic radiation applied to different regions of the wafer is varied. For example, the dose delivered to the wafer can be location specific to create localized concentrations of acid molecules in the pattern treatment composition. The location-specific dose can be controlled through various means, including: use of a digital pixelbased projection system with a light source that can focus an image or pattern onto a wafer; a galvo-controlled mirror system with location-specific dose control by modulation of laser pulse frequency; rotating and translating the wafer under a fixed light source; or other known patterning methods.

[0265]

[0161] In embodiments where the substrate comprises a patterned mask, e.g., an array of lines, pillars, or holes, the aforementioned processes can be used to alter the size of these features. For example, coating a layer of the pattern treatment composition will increase the size of line or pillar features (i.e., shrink the size of gaps between adjacent lines) and decrease the size of contact holes. In such embodiments, the CD uniformity can vary across a surface of a substrate (i.e., wafer). For example, a given wafer can have one CD value in a center portion of the wafer, while having another CD value closer to an edge of a wafer. A wafer can also have CDs that vary based on order of exposure progression, such as when using a stepper exposure system. Depending on the particular area of a given wafer, CDs may be too large or too small, and the CD variation may be spread randomly across the wafer, may be based on radial location, and / or may correlate with particular features such as location of scribe lanes.

[0266]

[0162] Compared to prior art, the location-specific dose exposure processes described herein can more easily manipulate WIW CD alteration amount process control due to being able to apply localized differences in exposure dose on the wafer (which leads to localized differences in PDH-014

[0267] thickness of pattern treatment composition, which ultimately facilitates localized differences in CD changes). Depending on the location-specific dose exposure hardware (or hardware combinations thereof), the CD signature / systematic within-exposure shot / die (WIS) can be corrected as well as WIW systematics (for instance, radial systematics, which is a WIW CD systematic that is highly correlated with radius position, or tilt systematics, which is a WIW CD systematic that is highly correlated with a single axis when tilt orientation is known). There are many pathways to feed forward WIS control. Two such correction schemes (but not limited to) include applying an averaged field signature of all dies on the wafer (or series of wafers, or any subset thereof) or by using a die-by-die specific correction strategy. Likewise, there are many pathways to feed forward WIW radial or tilt control. Two such methods for WIW radial control are 1) representing the CD wafer map by the radial terms within a multi-degree (radial / azimuthal) Zernike polynomial fit, or 2) fitting a high order polynomial to the averaged CD response through radius. Two such methods for WIW tilt control are 1) representing the CD wafer map by the 1stdegree radial terms within a Zernike polynomial fit, or 2) by finding the optimal angle at which averaging along the axes that is perpendicular to axes of interest, best represents experimental dataset.

[0268]

[0163] In sum, the aforementioned offers an alternative way to maximize the CD alteration amount achievable. Finally, it uses location-specific CD alteration / correction flows and processes for improvement of CD uniformity, and in some embodiments shifting of CD targeting as well, making use, in some embodiments, of metrology information in a feed forward process control scheme by means of localized dose control of an exposure process step. With this modified approach to CD alteration, WIW control schemes can also be more realizable; allowing for tighter CD alteration or patterning CD control.

[0269]

[0164] Individual embodiments of methods incorporating the foregoing details will now be described.

[0270]

[0165] FIG. 1 illustrates a flow diagram for the method of forming a coated substrate in accordance with one embodiment of the disclosure. At step 101, a substrate is provided. Next, in step 102, a layer of a pattern treatment composition is disposed over the substrate, where the pattern treatment composition comprises a polymer comprising a reactive surface attachment group or reactive surface group precursor and a catalyst. Then, in step 103, the substrate is baked. Next, in step 104, residual, unbound pattern treatment composition is removed to form a grafted layer of the pattern PDH-014

[0271] treatment composition over the substrate. Finally, at step 105, an optional measurement is performed to determine the thickness of the grafted layer of first pattern treatment composition.

[0272]

[0166] The coated substrate at various steps of the process from FIG. 1 is shown in FIG. 2. FIG.

[0273] 2A depicts one or more layers to be patterned 202 above the substrate 200. FIG. 2B depicts the original coating of pattern treatment composition 204 over one or more layers 202 above the substrate 200. FIG. 2C depicts the coated substrate after removing residual, unbound pattern treatment composition, with a grafted layer of the pattern treatment composition 204a over one or more layers 202 above the substrate 200.

[0274]

[0167] FIG. 3 is a flow diagram for one embodiment of a process for forming a coated substrate in accordance with one embodiment of the disclosure, where the thickness of the pattern treatment composition is adjusted by exposure to electromagnetic radiation. At step 301, a substrate is provided. Next, in step 302, a layer of a first pattern treatment composition is disposed over the substrate. Then, in step 303, at least a portion of the substrate is exposed to electromagnetic radiation, using either a flood exposure or location-specific dose delivery method. Next, at step 304, the substrate is baked. Then, in step 305, residual, unbound first patern treatment composition is removed to form a grafted layer of the first pattern treatment composition over the substrate. Then, at step 306, an optional measurement to determine a dimensional property is performed to determine the thickness of the grafted layer of first pattern treatment composition.

[0275]

[0168] This process in FIG. 3 can be used in combination with the process outlined in FIG. 1 in a feed forward control scheme. For example, a substrate can be processed according to the flow outlined in FIG. 1. If the measurement shows deviation in thickness from the desired state, the information can be fed forward to the next substrate to be processed, and the process outlined in FIG. 3 can be used to adjust the thickness of the grafted layer of first pattern treatment composition.

[0276]

[0169] The coated substrate at various steps of the process from FIG. 3 is shown in FIG. 4. FIG.

[0277] 4A depicts one or more layers to be patterned 202 above the substrate 200. FIG. 4B depicts the original coating of pattern treatment composition 204 over one or more layers 202 above the substrate 200. FIG. 4C depicts the process of exposing a part of the substrate to electromagnetic radiation 406. FIG. 4D finally depicts the coated substrate after removing residual, unbound pattern treatment composition, with a grafted layer of the patern treatment composition over one or more layers 202 above the substrate 200. The grafted layer has two regions of different PDH-014

[0278] thickness: a first region 204b with thickness, to, and a second region 204c with thickness, ti, where t > to.

[0279]

[0170] FIG. 5 is a flow diagram for one embodiment of a process for forming a coated substrate in accordance with one embodiment of the disclosure, where the thickness of the pattern treatment composition is adjusted. At step 501, a substrate is provided. Next, in step 502, a layer of a first pattern treatment composition is disposed over the substrate. Then, in step 503, the substrate is baked. Next, in step 504, residual, unbound first pattern treatment composition is removed to form a grafted layer of the first pattern treatment composition over the substrate. Then, at step 505, an optional measurement is performed to determine the thickness of the grafted layer of first pattern treatment composition. Next, at step 506, a layer of a second pattern treatment composition is formed over the substrate. The second pattern treatment composition can be the same as or different from the first pattern treatment composition. At step 507, the substrate is optionally exposed to electromagnetic radiation, using either a flood exposure or location-specific dose delivery method. Next, at step 508, the substrate is baked. Then, at step 509, residual, unbound second pattern treatment composition is removed to form a combined grafted layer of the first and second pattern treatment compositions over the substrate. Finally, at step 510, an optional measurement is performed to determine the thickness of the combined grafted layer of first and second pattern treatment compositions.

[0280]

[0171] FIG. 6 is another flow diagram for one embodiment of a process for forming a coated substrate in accordance with one embodiment of the disclosure, wherein a feed forward process is employed. At step 601, a first substrate is provided. Next, in step 602, a layer of a pattern treatment composition is disposed over the substrate. Then, in step 603, the substrate is baked. Next, in step 604, residual, unbound pattern treatment composition is removed to form a grafted layer of the pattern treatment composition over the substrate. Then, at step 605, a measurement is performed to determine the thickness of the grafted layer of pattern treatment composition. Next, at step 606, a second substrate is provided. Next, in step 607, a layer of a pattern treatment composition is disposed over the substrate. Then, at step 608, the substrate is exposed to electromagnetic radiation, using either a flood exposure or location-specific dose delivery method. Next, at step 609, the substrate is baked. Next, in step 610, residual, unbound pattern treatment composition is removed to form a grafted layer of the pattern treatment composition over the substrate. Finally, PDH-014

[0281] at step 611, a measurement is performed to determine the thickness of the grafted layer of pattern treatment composition.

[0282]

[0172] The coated substrate at various steps of the process from FIG. 6 is shown in FIG. 7. FIG.

[0283] 7 A depicts a patterned mask 708 above the one or more layers to be patterned 202 above the substrate 200. The features of the patterned mask 708 are separated by gaps 710a and 710b, where gap 710a has a first dimension, i, and gap 710b has a second dimension di, where di > di. FIG.

[0284] 7B depicts the coating of pattern treatment composition 204 over patterned mask 708, the one or more layers 202, and the substrate 200. FIG. 7C depicts the process of exposing a part of the substrate to electromagnetic radiation 406. FIG. 7D finally depicts the coated substrate after removing residual, unbound pattern treatment composition, with a grafted layer of the pattern treatment composition over the patterned mask 708. The mask is coated with pattern treatment composition 204b and patern treatment composition 204c, corresponding to regions with and without exposure to electromagnetic radiation, respectively. New gaps 710c and 710d are formed with new dimensions, namely gap 710c with a third dimension, di, and gap 71 Od with a fourth dimension, di. In one embodiment, an initial ratio of chJdi and a final ratio of di / d are defined, with ch being the greater of the initial two dimensions and di being the greater of the final two dimensions, and wherein the final ratio is less than the initial ratio. In a further embodiment, the final dimensional ratio du'ch is in a range from about 0.90 to 1.10. In a particularly preferred embodiment, the value of (d / ds - I) is no more than 25% of the value of (d d - 1).

[0285]

[0173] FIG. 8 is a flow diagram for the method of forming a coated substrate in accordance with another embodiment of the disclosure. At step 801, a substrate is provided comprising a first patterned mask on a layer to be patterned on the substrate. Next, in step 802, a layer of a pattern treatment composition is formed over the first patterned mask. Finally, m step 803, the first patterned mask is removed to form a third patterned mask.

[0286]

[0174] FIG. 9A-9C are top-down and cross-sectional views (top diagram and bottom diagram, respectively) of a substrate through various steps of the process. The cross-sectional views are taken along dashed line A-A in the respective top-down view. FIG. 9A shows the first patterned mask 708 on the one or more layers to be paterned 202 on the substrate 200. The substrate, layers to be patterned, and patterned mask compromise materials as described above and are prepared according to the foregoing methods. The first patterned mask 708 can be formed by various techniques as described above. In some embodiments, the first patterned mask 708 is PDH-014

[0287] formed by direct lithographic patterning. In other embodiments, the first patterned mask 708 is provided by etch transferring into a layer. The substrate can optionally be heat treated to further condense the patterned mask material and to further dehydrate, densify, or remove residual developer from the material to form the first patterned mask 708.

[0288]

[0175] In some embodiments, the features of the first patterned mask 708 are cylindrical in geometry forming, for example, a circular or elliptical cylinder. In other embodiments, the features of the first patterned mask 708 are square or rectangular prisms. The features typically have a height of from 200 to 2000 A, preferably from 300 to 1200 A, a diameter of from 100 to 700 A, preferably from 200 to 500 A and a pitch of from 150 to 1200 A, In some embodiments, the first paterned mask comprises a plurality of pillars (also referred to as posts). In other embodiments, the first patterned mask comprises a plurality of holes. In further embodiments, the first paterned mask comprises a plurality of lines separated by spaces. The features are typically disposed of an ordered array, for example, a rectangular array such as a square array. Other array types including rectangular oblong arrays can be used in the described methods.

[0289]

[0176] FIG. 9B is the coated substrate after removing residual, unbound pattern treatment composition, with a grafted layer of the pattern treatment composition 204 on the sidewalls of the first patterned mask 708 over one or more layers 202 above the substrate 200. This forms a second patterned mask with gaps 910 formed between adjacent features of the first patterned mask. The grafted layer of the patern treatment composition 204 has a layer thickness 204a, which can be controlled through selection or tailoring of one or more components of the pattern treatment composition. In particular, by selection of the molecular weight and / or blend ratios of one or more polymer components of the pattern treatment composition, the coating layer thickness can be controlled and thereby the width of the formed gaps 910 can be controlled. In general, use of higher molecular weight polymers as components of the pattern treatment composition, including polymers that have a weight average molecular weight in excess of 1,000; 5,000; 10,000; 15,000; or 20,000, can enable forming larger layer thickness 204a and thereby produce smaller gaps 910.

[0290]

[0177] As shown in the drawing in FIG. 9C, the first patterned mask 708 is next removed to form a third patterned mask comprising gaps 910 and gaps 912, thereby exposing layer 202 on substrate 200 in the regions previously covered by the first patterned mask. Suitable etching techniques and chemistries for etching the patterned mask composition are known in the art and PDH-014

[0291] will depend, for example, on the particular materials. Dry-etching processes such as reactive ion etching are typical. In some embodiments, the etching process is conducted to first remove the top layer of the pattern treatment composition above the first patterned mask to expose the first patterned mask. This leaves a third patterned mask comprising a pattern formed from the remaining portions of the pattern treatment composition 204 that was coated on the sidewalls of the first patterned mask 708. In the case of the illustrated square pillar array of FIG. 9, a single gap 910 is present at the center of and equidistant from each of the original four surrounding neighboring pillars. The pillar pattern dimensions, pitch and hardmask and polymer layer thicknesses should be chosen such that, at a minimum, adjacent coated pillar patterns after residual polymer removal are in contact with each other. This third patterned mask can then be used to transfer the pattern into the layers to be patterned using known etch techniques. Further processing, for example, one or more of coating, etching and photolithographic processes, are conducted on the substrate to form a finished device.

[0292]

[0178] The process described above and represented by FIG. 9A-9C results in features having a square array. The process can also be modified to produce a hexagonal array. The description set forth above with respect to FIG. 9A-9C is applicable to the modified process, with differences described below. A hexagonal array of pillar patterns is surrounded equidistantly by six neighboring pillars, the neighboring pillars forming a hexagonal pattern. In this process scheme, two holes are formed between and in line with every other pillar along the perimeter of each hexagon. In other words, a single depression corresponding to a hole is formed at the center of each equilateral triangle formed by the center pillar and any two adjacent pillars along the perimeter of the hexagon.

[0293]

[0179] FIG. 10 is a flow diagram for the method of forming a coated substrate in accordance with another embodiment of the disclosure. At step 1001, a substrate is provided comprising a first patterned mask on a layer to be patterned on the substrate. Next, in step 1002, a layer of a pattern treatment composition is formed over the first patterned mask to form a second patterned mask. Then, in step 1003, the first patterned mask is removed to form a third patterned mask. Next, in step 1004, a layer of a second composition is applied on the substrate to fill the gaps. Finally, in step 1005, the pattern treatment composition is removed to form a fourth patterned mask comprising pillars. PDH-014

[0294]

[0180] FIG. 11A-11E depicts top-down and cross-sectional views (top diagram and bottom diagram, respectively) of a substrate through various steps of the process. The cross-sectional views are taken along dashed line A-A m the respective top-down view. The description set forth above with respect to FIG. 9A-9C is applicable to FIG. 11A-11C. FIG. 11 A show’s the first patterned mask 708 on the one or more layers to be patterned 202 on the substrate 200. FIG. 1 IB shows the coated substrate after removing residual, unbound pattern treatment composition, with a grafted layer of the pattern treatment composition 204 on the sidewalls of the first patterned mask 708 over one or more layers 202 above the substrate 200. The resulting second patterned mask comprises formed gaps 910. FIG, 4C then shows the substrate after removal of the first paterned mask 708 to form a third paterned mask comprising gaps 910 and gaps 912, thereby exposing layer 202 on substrate 200 in the regions previously covered by the first patterned mask.

[0295]

[0181] As shown in FIG. 1 ID, the substrate is then coated with a second composition 1114 that fills gaps 910 and 912, The second composition can be cast into a planarizing film of uniform thickness over the topography created by the original features with the pattern treatment composition. In some embodiments, the second composition is a homogeneous single phase. Preferably, the second composition has an etch rate that is less than the etch rate of the pattern treatment composition, for example, where the etch rate of the second composition is at least 20, 30, 40, 50, 60, 70 or 80 percent less than the etch rate of the subsequently applied pattern treatment composition.

[0296]

[0182] Suitable second compositions include formulations comprising silicon-containing compositions, for instance polysiloxanes (such as poly dimethylsiloxane), silsesquioxanes, silicon- containing polyacrylates and polymethacrylates, silicon-containing polystyrenes, spin-on glasses, or other silicon-containing compositions; carbon-based compositions, for instance organic polymers, anti-reflective coating compositions, spin-on carbons, or other carbon- based materials; and metal-containing compositions, for instance oxides of titanium, hafnium, and zirconium, spin- on metal hard masks, metal-oxo / hydroxo compositions, metal-containing polymers, or other metal-containing materials; and combinations thereof. In some embodiments, the second composition comprises a similar or identical composition to that used to form the first paterned mask such that the etch rate of the second composition is similar to that of the first patterned mask. Following coating with a second composition, the substrate may be annealed if desired, for PDH-014

[0297] example by heating in excess of 100 °C for 1, 2 or more minutes. Importantly, the pattern treatment composition and the second composition are selected such that they are not miscible when heated but remain separated into discrete phases.

[0298]

[0183] As shown in FIG. 1 IE, the pattern treatment composition is removed to create a fourth patterned mask comprising a plurality of features 1114a comprising the second composition separated by gaps 1116. Suitable etching techniques are described above. The resulting fourth patterned mask comprises a plurality of pillars with a greater pattern density' than the first patterned mask.

[0299]

[0184] FIG. 12 is a flow diagram for the method of forming a coated substrate in accordance with another embodiment of the disclosure. At step 1201, a substrate is provided comprising a first patterned mask on a layer to be patterned on the substrate. Next, in step 1202, a layer of a pattern treatment composition is formed on the first patterned mask to form a second patterned mask. Then, in step 1203, a layer of a second composition is applied on the substrate in regions adjacent to the coated sidewalls and filling gaps. Next, in step 1204, the pattern treatment composition is removed to form a third patterned mask. Finally, and optionally, in step 1205, a layer of a third composition is applied over the substrate to fill gaps.

[0300]

[0185] FIG. 13A-13E depicts top-down and cross-sectional views (top diagram and bottom diagram, respectively) of a substrate through various steps of the process. The cross-sectional views are taken along dashed line A-A in the respective top-down view. The description set forth above with respect to FIG. 13A-13B is applicable to FIG. 9A-9B, with differences thereafter described below. FIG. 13A shows the first patterned mask 708 on the one or more layers to be patterned 202 on the substrate 200. FIG. 13B shows the coated substrate after removing residual, unbound pattern treatment composition, with a grafted layer of the pattern treatment composition 204 over one or more layers 202 above the substrate 200. The resulting second patterned mask comprises formed gaps 910.

[0301]

[0186] As shown in FIG. 13C, the substrate is coated with a second composition 1114 that fills areas bared by the first patterned mask 708 with coated sidewalls of the pattern treatment composition 204 to fill the gaps 910 with the second composition 1114. The second composition can be selected from and processed as described above.

[0302]

[0187] As shown in FIG. 13D, the pattern treatment composition is removed to create a third patterned mask comprising a plurality of pillars, including pillars 708 and pillars 1114a. PDH-014

[0303] Removal of the pattern treatment composition can bare the underlying layer to be patterned and form gaps 1318. The resulting third patterned mask comprises a plurality of pillars. Suitable etching techniques and chemistries for etching the pattern treatment composition are known in the art and will depend, for example, on the particular materials of these layers. Dry-etching processes such as reactive ion etching are typical.

[0304]

[0188] Optionally, as shown in FIG. 13E, gaps 1318 can then be filled with a third composition 1320 to form a pattern with three discrete materials, sometimes referred to as an ABC pattern. The third composition can be applied by any known film forming technique. In one embodiment, the third composition can be cast into a planarizing film of uniform thickness over the topography created by the third patterned mask. In some embodiments, the third composition is a homogeneous single phase. Preferably, the third composition has an etch rate that is less than the etch rate of the second composition, for example, where the etch rate of the third composition is at least 20, 30, 40, 50, 60, 70 or 80 percent less than the etch rate of the second composition.

[0305]

[0189] Suitable third compositions include formulations described above for the second composition, including silicon-containing compositions, carbon-based compositions, and metalcontaining compositions. In some embodiments, the third composition comprises a similar or identical composition to that used to form the first patterned mask such that the etch rate of the third composition is similar to that of the first patterned mask. Following coating with a third composition, the substrate may be annealed if desired, for example by heating in excess of 100 °C for 1, 2 or more minutes. Importantly, the third composition and the second composition are selected such that they are not miscible when heated but remain separated into discrete phases.

[0306]

[0190] FIG. 14 illustrates a flow diagram for the method of forming a coated substrate in accordance with another embodiment of the disclosure. At step 1401, a substrate is provided comprising a first patterned mask on a layer to be patterned on the substrate. Next, in step 1402, a layer of a hard mask is disposed on the substrate to form a second patterned mask. The hardmask can be selected from and processed as described above. Then, at step 1403, a layer of a pattern treatment composition is formed on the hardmask to form a third patterned mask. Finally, in step 1404, the first patterned mask is removed to form a fourth patterned mask.

[0307]

[0191] FIG. 15A-15D depicts top-down and cross-sectional views (top diagram and bottom diagram, respectively) of a substrate through various steps of the process. The cross-sectional views are taken along dashed line A- A in the respective top-down view. The description set forth PDH-014

[0308] above with respect to FIG. 9 A is applicable to FIG. 15A, with differences described below. The drawings show a first patterned mask comprising a plurality of pillars, but the method can also be applied to a first patterned mask comprising a plurality of holes.

[0309]

[0192] FIG. 15A shows the first patterned mask 708 on the one or more layers to be patterned 202 on the substrate 200. FIG. 15B shows the coated substrate following application of a hard mask layer 1522 over the first patterned mask 708 on the one or more layers to be patterned 202 on the substrate 200. The resulting second patterned mask comprises formed pillars separated by gaps 1524.

[0310]

[0193] FIG. 15C shows the coated substrate after removing residual, unbound pattern treatment composition, with a grafted layer of the pattern treatment composition 204 over the hard mask layer 1522 over the first patterned mask 708 on the one or more layers to be patterned 202 on the substrate 200. The resulting third patterned mask comprises newly formed gaps 1526.

[0311]

[0194] As shown in FIG. 15D, the first patterned mask 708 is removed to create a fourth patterned mask comprising a plurality of gaps, including gaps 1526a and gaps 1528, and bearing the layer to be patterned 202, Suitable etching techniques and chemistries for etching through the pattern treatment composition and hard mask layers on top of the first patterned mask as well as the first patterned mask composition are known m the art and will depend, for example, on the particular materials of these layers. Dry-etching processes such as reactive ion etching are typical.

[0312]

[0195] In certain embodiments, the methods described herein provide a quantitative increase in feature density relative to the original lithographically defined pattern. By way of example, consider an initial patterned mask comprising a square array of pillars having a center-to-center pitch Lo(sq) in both the X and Y directions. Upon forming a layer of pattern treatment composition on the sidewalls of the pillars and subsequently removing the original patterned mask (or, in complementary embodiments, removing the pattern treatment composition to yield pillars from the patterned mask and a second composition), the resulting array of features is rotated by approximately 45° relative to the original lattice. For a square array, the distance between nearest-neighbor features in the final pattern is reduced by a factor of 2 relative to the original pitch according to Equation 1: PDH-014

[0313] Ll(sq) - U)

[0314]

[0315]

[0196] In one embodiment, a final pattern having a pitch Zi(Sq) of approximately 32 nm may be obtained from an original square array having a pitch Zo(Sq) of approximately 32 * v'2 = 45.3 nm. In another embodiment, a final pattern having a pitch Zi(sq) of approximately 35 nm may be obtained from an original square array having a pitch Lo(sg) of approximately 35 x V2 = 49.535. In each case, the final pattern contains approximately twice the number of features per unit area as the original pattern.

[0316]

[0197] It should be understood that while the absolute value of Zi(sq) may be tuned by adjusting the original pitch Zo(sq) and the geometry’ of the applied sidewall film (e.g., thickness of the pattern treatment composition and etch bias), the \[2 pitch reduction and the corresponding two-fold increase in feature density are inherent geometric results of the square-array transformation, independent of the specific materials or process chemistries employed.

[0317]

[0198] In another embodiment, an initial patterned mask comprising a hexagonal (triangular) array forms the patterned mask. The self-aligned process places new features at the centers of the equilateral triangles formed by nearest-neighbor posts. The union of the original lattice and these interstitial sites forms a lattice with a reduced nearest-neighbor spacing by a factor of VT Accordingly, the final pitch is represented by Equation 2:

[0318] _L0(hex)Ll(hex) — (2)

[0319]

[0320]

[0199] In one embodiment, a final pattern having a pitch Zi(hex) of approximately 32 nm may be obtained from an original hexagonal array having a pitch o(hex) of approximately 32 x y3 = 55.4 nm. In another embodiment, a final pattern having a pitch Zi(hex) of approximately 35 nm may be obtained from an original hexagonal array having a pitch Lo(hex) of approximately 35

[0321]

[0322] x = 60.6. In each case, the final pattern contains approximately three times the number of features per unit area as the original pattern. The resulting array is rotated by approximately 30° relative to the original hexagonal lattice.

[0323]

[0200] The pitch ranges described herein, including final pitches of approximately 35 nm and below achieved by the disclosed pitch-division methods, are of particular importance in advanced semiconductor manufacturing. Forming such tight feature pitches is challenging to accomplish PDH-014

[0324] using conventional EUV lithography at numerical apertures (NA = 0.33). At these dimensions, single-exposure EUV processes generally suffer from reduced process windows, image contrast limitations, and increased defectivity. Conventional approaches to achieve such pitches would require either the adoption of high-numerical-aperture (high-NA) EUV lithography tools (NA > 0.5), or X-ray lithography tools, which are not yet widely deployed and entail significant capital investment, or the use of more complicated multi-patterning processes that increase mask count, process complexity, and cost. The methods disclosed herein enable the formation of these advanced pitch ranges without the need for high-NA EUV or complex multi-patterning schemes, providing a simplified, self-aligned approach that reduces overlay error risk and improves pattern fidelity.

[0325]

[0201] A significant advantage of the present disclosure is the achievement of exceptionally low defectivity when patterning hole arrays at a pitch of 35 nm or less. In the art, critical failures for such patterns include missing holes and bridging defects, where adjacent features merge. These are considered "killer" defects, as a single such failure can render a device inoperable, drastically reducing manufacturing yield. Conventional EUV lithography, due to the stochastic effects that dominate at these small scales, produces these defects at a rate often too high for commercially viable high-volume manufacturing. The processes disclosed herein, by contrast, mitigates these stochastic failures to produce highly regular arrays. Preferably, a pattern formed by the disclosed method exhibits a combined total killer defect rate of less than 1 defect per million holes (DPMH), more preferably, less than 0.1 DPMH, and in some embodiments, can be less than 100 defects per billion holes (DPBH). This represents a substantial improvement, achieving a defectivity rate that is at least an order of magnitude lower than that typically observed for conventional mask- based EUV processes under similar sub-35 nm pitch conditions.

[0326]

[0202] In addition to reducing killer defects, the disclosed processes provide exceptional control over feature size, achieving a superior critical dimension uniformity (CDU). The resulting features preferably exhibit a 3 -sigma uniformity of less than 20% of the nominal feature dimension, a critical threshold for ensuring consistent device performance. In some embodiments, the 3 -sigma uniformity is less than 15% of the nominal feature dimension.

[0327]

[0203] FIG. 16 is a flow diagram for the method of forming a coated substrate in accordance with another embodiment of the disclosure. At step 1601, a substrate is provided comprising a first patterned mask on a layer to be patterned on the substrate. Next, in step 1602, a second patterned PDH-014

[0328] mask is formed over the first patterned mask on a layer to be patterned on the substrate. Then, in step 1603, a layer of a pattern treatment composition is then formed over the second patterned mask. Next, in step 1604, a layer of a second composition is formed over the substrate to fill gaps. Then, in step 1605, the pattern treatment composition is removed to expose portions of the first patterned mask. Finally, in step 1606, the pattern is transferred using the combined patterned mask.

[0329]

[0204] FIG. 17A-17G are top-down and cross-sectional views (top diagram and bottom diagrams, respectively) of a substrate through various steps of the process. The cross-sectional views are taken along dashed lines A-A and B-B in the respective top-down view as indicated in the figures. FIG. 17A shows the first patterned mask 708 on the one or more layers to be patterned 202 on the substrate 200. FIG, 17B shows the second patterned mask 1730 above the first patterned mask 708 on the one or more layers to be patterned 202 on the substrate 200. The second patterned mask can be formed using techniques and composed of materials as described above. The second patterned mask may be made of a second photoresist and may be formed by photolithographic methods, both of which are described above. The second photoresist may be the same as or different from the first photoresist. The photolithographic methods may also be the same or different. For example, the first patterned mask may be formed using 193 nm radiation, while the second patterned mask may be formed using EUV. In the embodiment shown in FIG. 17B, the second patterned mask 1730 is in direct contact with the one or more layers to be patterned 202. In other embodiments, a separate layer (not shown) is applied to fill topography and planarize the substrate before forming the second patterned mask.

[0330]

[0205] FIG. 17C shows the coated substrate after removing residual, unbound pattern treatment composition, with a grafted layer of the pattern treatment composition 204 on the sidewalls of the second patterned mask 1730 over the first patterned mask 708 and one or more layers 202 above the substrate 200. FIG. 17D then shows the substrate after coating with a second composition 1114 that fills gaps. The layer of the second composition can be formed using techniques and composed of materials as described above. FIG. 17E then shows the substrate after removal of the pattern treatment composition 204 to form a new patterned mask comprising the second patterned mask 1730 and features 1114a comprising the second composition and exposing the first patterned mask 708 and portions of the layer 202 through gaps 1732. The cross-sectional views taken along dashed lines A-A and B-B m the respective top-down views PDH-014

[0331] show that the first patterned mask 708 and portions of the layer 202 are only exposed in selected areas.

[0332]

[0206] FIG. 17F shows the coated substrate after the pattern is transferred using the combined patterned mask, wherein exposed sections of the first patterned mask 708 have been removed to expose the layer 202. This removal can be accomplished using known anisotropical etch techniques. FIG. 17Gthen shows the coated substrate after the removal of the second patterned mask 1730 and second composition 1114a, showing the final modified first patterned mask 708a which has been cut in selected areas. The removal of the compositions can be accomplished using known removal techniques such as dry or wet etching,

[0333]

[0207] FIG, 18 is a flow diagram for the method of forming a coated substrate in accordance with another embodiment of the disclosure. At step 1801, a substrate is provided comprising a first patterned mask on a layer to be patterned on the substrate. Next, in step 1802, a layer of a pattern treatment composition is then formed over the first patterned mask to form a second patterned mask. Next, in step 1803, a layer of a second composition is formed over the substrate to fill gaps. Then, in step 1804, the pattern treatment composition is removed to form a third patterned mask. Next, in step 1805, a fourth patterned mask is formed over the first, second, and third patterned masks on a layer to be patterned on the substrate. Finally, in step 1806, the pattern is transferred using the combined patterned mask.

[0334]

[0208] FIG. 19A-19G are top-down and cross-sectional views (top diagram and bottom diagrams, respectively) of a substrate through various steps of the process. The cross-sectional views are taken along dashed lines A-A and B-B in the respective top-down view as indicated in the figures. The description set forth above with respect to FIG. 13A-13D is applicable to FIG.

[0335] 19A-19D. FIG. 19A shows the first patterned mask 708 on the one or more layers to be patterned 202 on the substrate 200. FIG. 19B shows the coated substrate after removing residual, unbound pattern treatment composition, with a grafted layer of the pattern treatment composition 204 on the sidewalls of the first patterned mask 708 over one or more layers 202 above the substrate 200. The resulting second patterned mask comprises formed gaps 910. FIG. 19C then shows the substrate after coating with a second composition 1114 that fills gaps 910. FIG. 19D then shows the substrate after removal of the pattern treatment composition 204 to form a third patterned mask comprising the first patterned mask 708 and features 1114a comprising the second PDH-014

[0336] composition separated by gaps 1318 and thereby exposing layer 202 on substrate 200 in the regions previously covered by the first patterned mask.

[0337]

[0209] FIG. 19E shows the fourth patterned mask 1934 above the third patterned mask. The fourth patterned mask can be formed using techniques and composed of materials as described above. In the embodiment shown in FIG. 19E, the fourth patterned mask 1934 is in direct contact with the one or more layers to be patterned 202. In other embodiments, a separate layer (not shown) is applied to fill topography and planarize the substrate before forming the second patterned mask. The cross-sectional views taken along dashed lines A- A and B-B in the respective top-down views show that the first fourth patterned mask 1934 is formed such that the first patterned mask 204 and the layer 202 are only exposed in selected areas.

[0338]

[0210] FIG. 19F shows the coated substrate after the pattern is transferred using the fourth patterned mask 1934, wherein exposed sections of the layer 202 have been removed to form modified layer 202a and expose the substrate 200. This removal can be accomplished using known anisotropical etch techniques. FIG. 19G then shows the coated substrate after the removal of the patterned masks, showing the final modified layer 202a which has been etched in selected areas. The removal of the compositions can be accomplished using known removal techniques such as dry or wet etching.

[0339]

[0211] In additional embodiments, the foregoing processes can be conducted multiple times on the same substrate to form stacked patterns. For example, a substrate may be provided comprising a first patterned mask on a layer to be patterned on the substrate. Next, a layer of a pattern treatment composition is formed over the first patterned mask to give a second patterned mask. Then, a layer of a second composition is formed over the substrate to fill gaps. Next, a third patterned mask is formed on top of the layer of the second composition and second patterned mask in a different direction from the first patterned mask. In one embodiment, the first patterned mask and third patterned mask comprise a plurality of lines and spaces, wherein the third patterned mask is rotated at an angle from the direction of the first patterned mask. In some embodiments, the angle between the primary direction of the first and third patterned mask is 60 degrees or 90 degrees. These methods produce an overlapping crossgrid pattern that can be used to form contact holes or vias.

[0340]

[0212] The patterns provided by the foregoing methods may be further processed, including transferring the patterns into the one or more layers to be patterned. In one embodiment, the patterns can be transferred by implanting dopant through the openings to form dopant implant PDH-014

[0341] regions within locations defined by the openings. In some embodiments, the implanted dopant may be either n-type or p-type dopant utilized to form conductively-doped regions of the layers. In other embodiments, the patterns may be anisotropically etched to transfer the patterns into the layers and / or substrate.

[0342]

[0213] These materials and processes are useful for creating relief patterns with higher feature density than possible from single exposure photolithographic processes. Importantly, the resulting relief patterns are self aligned to the original mask pattern, thereby mitigating problems with overlay error inherent to comparative processes using multiple photolithographic exposures. These self-aligned relief patterns are also useful to form self-aligned line cut patterns,

[0343]

[0214] While specific embodiments have been described in detail, those skilled in the art will appreciate that many modifications are possible without materially departing from the disclosure. Accordingly, all such modifications are intended to be included within the scope of the following claims. Furthermore, any techniques described as a series of discrete operations have been presented for clarity of understanding. This order of description should not be construed as a requirement, as these operations may be performed in a different order, combined, omitted, or supplemented in other embodiments.

[0344]

[0215] The compositions and methods described herein may 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-014CLAIMSWe claim:

1. A pattern treatment composition comprising:one or more polymers having a reactive surface attachment group or reactive surface attachment group precursor;a catalyst; anda solvent.

2. A pattern treatment composition of Claim 1, wherein the polymer is of the general Formula (1):(1)wherein X is 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 (Nso aryl, or monocyclic or polycyclic Ce-30 heteroaryl, each of which is substituted or unsubstituted, each optionally including as part of its structure one or more groups chosen from — O —, — C(O) —, — C(O) — O —, — CH2O —, — NH —, — N(Ci-Cs alkyl) —, or — S —; or a silicon containing moiety, including a linear C1-20 alkylsiloxane, branched C3-20 alkylsiloxane, or a monocyclic or polycyclic C3-20 cycloalkylsiloxane, each of which is substituted or unsubstituted, each optionally including as part of its structure one or more functional groups chosen from — O —, — C(O) —, — C(O) — O —, — CH2O —, — NH —, — N(Ci-Cs alkyl) —, or — S —, and wherein the silicon can also be a part of a larger chain forming a siloxane backbone, such as a polysiloxane chain;L is optionally present. Where L is present, it is a linking group selected from a linear or branched alkyl having 1 to about 8 carbon atoms that is optionally substituted. Where L is absent, the bond connects directly to M;M is any one selected from the following substituents;PDH-014where L1is optionally present. Where L1is present, it is a linking group selected from an alkyl having 1 to about 8 carbon atoms that is optionally substituted with one or more groups chosen fromO - -C(O) - C(O) O -, - -CH2O - NH - -N(Ci-Cs alkyl)--, or S Where L1is absent, the bond connects directly to the silicon containing unit.

3. A pattern treatment composition of Claim 1, wherein the one or more polymers comprises a polystyrene, poly(alkylacrylate), poly(alkylmethacrylate), poly(vinylpyridine), poly(arylene oxide), polyethylene, polypropylene, hydrogenated polybutadiene, polycyclohexylethylene, alternating copolymer of styrene and maleic anhydride or maleimide, polynorbornene, or polysiloxane.

4. A pattern treatment composition of Claim 1, wherein the one or more polymers comprises silicon or a metal.

5. A pattern treatment composition of Claim 1, w’herein the reactive surface attachment group comprises a hydroxyl, sulfhydryl, carboxyl, epoxide, amine, amide, imine, diazine, diazole, optionally substituted pyridine, pyridinium, optionally substituted pyrrolidone, or combinations thereof.

6. A pattern treatment composition of Claim 1, wherein the reactive surface attachment group precursor is selected from a tertiary alkyl ester group, a secondary or tertiary’ aryl ester group, a secondary7or tertiary ester group having a combination of alkyl and aryl groups, a tertiary alkoxy group, an acetal group, or a ketal group.PDH-0147. A pattern treatment composition of Claim 1, wherein the one or more polymers having a reactive surface attachment group or reactive surface group precursor has the reactive moiety at one chain end.

8. A pattern treatment composition of Claim 1, wherein the catalyst is free of fluorine.

9. A pattern treatment composition of Claim 1, w’herein the catalyst is selected from an acid, thermal acid generator, or a photoacid generator.

10. A pattern treatment composition of Claim 1, w’herein the catalyst comprises an aromatic acid of the general Formula (2):(SO3H)b(2)wherein Ar1represents a C5-C40 monocyclic or polycyclic aromatic aryl group; R1independently represents a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C20 aryl group or a combination thereof, optionally containing one or more group chosen from carbonyl, carbonyloxy, sulfonamide, ether, thioether, a substituted or unsubstituted alkylene group, or a combination thereof; and a is independently an integer from 0 to 5.

11. A pattern treatment composition of Claim 1, w’herein the catalyst comprises a thermal acid generator of the general Formula (9):(A⁻)(BH)+(9) in which A~ is the anion of an organic or inorganic acid having a pKa of not more than 3; and (BH)+is the monoprotonated form of a nitrogen-containing base B having a pKa between 0 and 5.0, and a boiling point less than 170 °C.

12. A pattern treatment composition of Claim 1, w’herein the catalyst comprises an aromatic acid of the general Formula (10):X (R17)aa (10) wherein X is S or I, wherein when X is I then aa is 2, and when X is S then aa is 3; R17is independently chosen from organic groups such as optionally substituted C1-30 alkyl, polycyclic orPDH-014monocyclic C3-30 cycloalkyl, polycyclic or monocyclic Ce-30 aryl, or a combination thereof, wherein when X is S, two of the R groups together optionally form a ring.

13. A method of forming a coated substrate comprising:providing a substrate;coating a pattern treatment composition over the substrate, wherein the pattern treatment composition comprises a polymer comprising a reactive surface attachment group or reactive surface group precursor, a catalyst, and a solvent;baking the substrate;treating the substrate with a rinsing agent comprising a solvent to remove residual, unbound said pattern treatment composition, thereby forming a grafted layer of pattern treatment composition over the substrate; andoptionally, determining a dimensional property of the grafted layer of pattern treatment composition,14, The method of Claim 13, wherein the polymer is of the general Formula (1):(1)wherein X is 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 Ce-30 aryl, or monocyclic or polycyclic CAso heteroaryl, each of which is substituted or unsubstituted, each optionally including as part of its structure one or more groups chosen from — O —, — C(O) —, — C(O) — O —, — CH2O —, — NH —, — N(Ci-Cs alkyl) —, or — S —; or a silicon containing moiety, including a linear C1-20 alkylsiloxane, branched C3-20 alkylsiloxane, or a monocyclic or polycyclic C3-20 cycloalkylsiloxane, each of which is substituted or unsubstituted, each optionally including as part of its structure one or more functional groups chosen from — O —, — C(O) —, — C(O) — O —, — CH2O —, — NH —, — N(Ci-Cs alkyl) —, or — S —, and wherein the silicon can also be a part of a larger chain forming a siloxane backbone, such as a poly siloxane chain;PDH-014L is optionally present. Where L is present, it is a linking group selected from a linear or branched alkyl having 1 to about 8 carbon atoms that is optionally substituted. Where L is absent, the bond connects directly to M;M is any one selected from the following substituents;where L1is optionally present. Where L1is present, it is a linking group selected from an alkyl having 1 to about 8 carbon atoms that is optionally substituted with one or more groups chosen from — O—, — C(O)—, — C(O)— O—, — CH2O—, — NH—, — N(Ci-Cs alkyl)—, or — S—. Where L1is absent, the bond connects directly to the silicon containing unit.

15. The method of Claim 13, wherein the one or more polymers comprises a polystyrene, poly(alkylacrylate), poly(alkylmethacrylate), poly(vinylpyridine), poly( arylene oxide), polyethylene, polypropylene, hydrogenated polybutadiene, polycyclohexylethylene, alternating copolymer of styrene and maleic anhydride or maleimide, polynorbornene, or polysiloxane.

16. The method of Claim 13, wherein the one or more polymers comprises silicon or a metal.

17. The method of Claim 13, wherein the reactive surface attachment group comprises a hydroxyl, sulfhydryl, carboxyl, epoxide, amine, amide, imine, diazine, diazole, optionally substituted pyridine, pyridinium, optionally substituted pyrrolidone, or combinations thereof.

18. The method of Claim 13, wherein the pattern treatment composition is ionic or hydrogen bonded to the substrate.PDH-01419. The method of Claim 13, wherein the reactive surface attachment group precursor is selected from a tertiary alkyl ester group, a secondary or tertiary aiyl ester group, a secondary or tertiary ester group having a combination of alkyl and aryl groups, a tertiary alkoxy group, an acetal group, or a ketal group.

20. The method of Claim 13, wherein the one or more polymers having a reactive surface attachment group or reactive surface group precursor has the reactive moiety at one chain end.

21. The method of Claim 13, wherein the catalyst is free of fluorine.

22. The method of Claim 13, wherein the catalyst is selected from an acid, thermal acid generator, or a photoacid generator.

23. The method of Claim 13, wherein the catalyst comprises an aromatic acid of the general Formula (2):(SO3H)b(2)i Ar1Jwherein Ar1represents a C5-C40 monocyclic or polycyclic aromatic aryl group; R4independently represents a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C20 aryl group or a combination thereof, optionally containing one or more group chosen from carbonyl, carbonyloxy, sulfonamido, ether, thioether, a substituted or unsubstituted alkylene group, or a combination thereof; and a is independently an integer from 0 to 5.

24. The method of Claim 13, wherein the catalyst comprises a thermal acid generator of the general Formula (9):(A’)(BH)+(9) in which A is the anion of an organic or inorganic acid having a pKa of not more than 3; and (BH)!is the monoprotonated form of a nitrogen-containing base B having a pKa between 0 and 5.0, and a boiling point less than 170 °C.

25. The method of Claim 13, wherein the catalyst comprises an aromatic acid of the general Formula (10):+X—(R17)aa (10)PDH-014wherein X is S or I, wherein when X is 1 then aa is 2, and when X is S then aa is 3; R17is independently chosen from organic groups such as optionally substituted Ci-so alkyl, polycyclic or monocyclic C3-30 cycloalkyl, polycyclic or monocyclic Ce-30 aryl, or a combination thereof, wherein when X is S, two of the R groups together optionally form a ring.

26. The method of Claim 13, further comprising exposing at least a portion of the substrate to electromagnetic radiation after coating a pattern treatment composition over the substrate.

27. The method of Claim 13 further comprising:characterizing a first level of uniformity of the substrate before forming the grafted layer of pattern treatment composition;characterizing a second level of uniformity of the substrate after forming the grafted layer of pattern treatment composition;wherein the second level of uniformity is lower than the first level of uniformity by 5% or more,28. A method of forming a pattern, comprising:providing a semiconductor substrate comprising a first patterned mask comprising a plurality of features over a layer to be patterned;forming a layer of a pattern treatment composition over the first patterned mask to form a second patterned mask, wherein the pattern treatment composition comprises a polymer comprising a reactive surface attachment group or reactive surface attachment group precursor, such that the layer coats sidewalls of the features; andremoving the first patterned mask to expose the underlying layer, thereby forming a third patterned mask having a greater pattern density than the first patterned mask.

29. The method of Claim 28, wherein the first patterned mask comprises a plurality of pillars or holes.

30. The method of Claim 28, wherein the first patterned mask comprises at least one of carbon, silicon, or a metal.

31. The method of Claim 28, wherein the first patterned mask comprises an organic polymer, a photoresist, an organic anti-reflection coating, carbon hard mask, or spin-on carbon.

32. The method of Claim 28, wherein the first patterned mask comprises silicon oxide, silicon nitride, silicon oxynitride, or a silicon bottom anti-reflective coating.PDH-01433. The method of Claim 28, wherein the first patterned mask comprises tin, bismuth, tellurium, cesium, antimony, indium, molybdenum, hafnium, iodine, zirconium, titanium, iron, cobalt, nickel, copper, zinc, silver, platinum, or lead, or a combination thereof.

34. The method of Claim 28, wherein the pattern treatment composition is covalently bonded to the first patterned mask.

35. The method of Claim 28, wherein the pattern treatment composition is ionic or hydrogen bonded to the first patterned mask.

36. The method of Claim 28, wherein the polymer is of the general Formula (1):(1)wherein X is 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 Ce-3o aryl, or monocyclic or polycyclic Co-30 heteroaryl, each of which is substituted or unsubstituted, each optionally including as part of its structure one or more groups chosen from — O —, — C(O) —, — C(O) — O —, — CH2O —, — NH —, — N(Ct-Cs alkyl) —, or — S —; or a silicon containing moiety, including a linear C1-20 alkylsiloxane, branched C3-20 alkylsiloxane, or a monocyclic or polycyclic C3-20 cycloalkylsiloxane, each of which is substituted or unsubstituted, each optionally including as part of its structure one or more functional groups chosen from — O —, — C(O) —, — C(O) — O —, — CH2O —, — NH —, — N(Ct-Cs alkyl) —, or — S —, and wherein the silicon can also be a part of a larger chain forming a siloxane backbone, such as a polysiloxane chain;L is optionally present. Where L is present, it is a linking group selected from a linear or branched alkyl having 1 to about 8 carbon atoms that is optionally substituted. Where L is absent, the bond connects directly to M;M is any one selected from the following substituents;PDH-014where L1is optionally present. Where L1is present, it is a linking group selected from an alkyl having 1 to about 8 carbon atoms that is optionally substituted with one or more groups chosen fromO - -C(O) - C(O) O - -CH2O - NH - -N(Ci-Cs alkyl)--, or S Where L1is absent, the bond connects directly to the silicon containing unit.

37. The method of Claim 28, wherein the polymer comprises a polystyrene, poly(alkylacrylate), poly(alkylmethacrylate), poly(vinylpyridine), poly( arylene oxide), polyethylene, polypropylene, hydrogenated polybutadiene, polycyclohexylethylene, alternating copolymer of styrene and maleic anhydride or maleimide, polynorbornene, or polysiloxane.

38. The method of Claim 28, wherein the polymer comprises silicon or a metal.

39. The method of Claim 28, wherein the reactive surface attachment group comprises a hydroxyl, sulfhydryl, carboxyl, epoxide, amine, amide, imine, diazine, diazole, optionally substituted pyridine, pyridinium, optionally substituted pyrrolidone, or combinations thereof.

40. The method of Claim 28, wherein the reactive surface attachment group precursor is selected from a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of alkyl and aryl groups, a tertiary alkoxy group, an acetal group, or a ketal group.

41. The method of Claim 28, wherein the polymer comprises a reactive surface attachment group at one chain end.

42. The method of Claim 28, wherein the pattern treatment composition comprises a catalyst.PDH-01443. The method of Claim 42, wherein the catalyst is free of fluorine.

44. The method of Claim 42, wherein the catalyst is selected from an acid, thermal acid generator, or a photoacid generator.

45. The method of Claim 42, wherein the catalyst comprises an aromatic acid of the general Formula (2):|SO3H)b(2)■: Ar*:' "X(R4)awherein Ar1represents a C5-C40 monocyclic or polycyclic aromatic aryl group; R4independently represents a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C20 aryl group or a combination thereof, optionally containing one or more group chosen from carbonyl, carbonyloxy, sulfonamido, ether, thioether, a substituted or unsubstituted alkylene group, or a combination thereof; and a is independently an integer from 0 to 5.

46. The method of Claim 42, wherein the catalyst comprises a thermal acid generator of the general Formula (9):(A’)(BH)+ (9) in which A is the anion of an organic or inorganic acid having a pKa of not more than 3; and (BH is the monoprotonated form of a nitrogen-containing base B having a pKa between 0 and 5.0, and a boiling point less than 170 °C.

47. The method of Claim 42, wherein the catalyst comprises an aromatic acid of the general Formula (10):X (R17)aa (10) wherein X is S or I, wherein when X is I then aa is 2, and when X is S then aa is 3; R17is independently chosen from organic groups such as optionally substituted C1-30 alkyl, polycyclic or monocyclic C3-30 cycloalkyl, polycyclic or monocyclic Ce-30 aryl, or a combination thereof, wherein when X is S, two of the R groups together optionally form a ring.PDH-01448. A method of any of claims 28-47, further comprising:forming a layer of a second composition over the substrate in regions adjacent to the pattern treatment composition; andremoving the pattern treatment composition, thereby forming a fourth patterned mask comprising a plurality of features formed from the second composition and having a greater pattern density than the first patterned mask.

49. The method of Claim 48, wherein the second composition comprises at least one of carbon, silicon, or a metal.

50. The method of Claim 48, wherein the second composition comprises a polysiloxane, silsesquioxanes, silicon-containing poly(meth)acrylate, silicon-containing polystyrene, or spin-on glass.

51. The method of Claim 48, wherein the second composition comprises an organic polymer, an anti -reflective coating composition, a spin-on carbon hard mask, or other carbon based materials.

52. The method of Claim 48, wherein the second composition comprises tin, bismuth, tellurium, cesium, antimony, indium, molybdenum, hafnium, iodine, zirconium, titanium, iron, cobalt, nickel, copper, zinc, silver, platinum, or lead, or a combination thereof.

53. A method of forming a pattern, comprising:providing a semiconductor substrate comprising a first patterned mask comprising a plurality of features over a layer to be patterned;forming a layer of a pattern treatment composition over the first patterned mask to form a second patterned mask, wherein the pattern treatment composition comprises a polymer comprising a reactive surface attachment group or reactive surface attachment group precursor and a catalyst, such that the layer coats sidewalls of the features;forming a layer of a second composition over the substrate in regions adjacent to the coated sidewalls; andremoving the pattern treatment composition from the sidewalls of the first patterned mask, thereby forming a third patterned mask comprising a plurality of features formed from the first patterned mask and the second composition, the third patterned mask having a greater pattern density than the first patterned mask.PDH-01454. The method of Claim 53, wherein the first patterned mask comprises a plurality of pillars or holes.

55. The method of Claim 53, wherein the first patterned mask comprises at least one of carbon, silicon, or a metal.

56. The method of Claim 53, wherein the first patterned mask comprises an organic polymer, photoresist, organic anti-reflection coating, carbon hard mask, or spin-on carbon.

57. The method of Claim 53, wherein the first patterned mask comprises silicon oxide, silicon nitride, silicon oxynitride, or a silicon bottom anti-reflective coating.

58. The method of Claim 53, wherein the first patterned mask comprises tin, bismuth, tellurium, cesium, antimony, indium, molybdenum, hafnium, iodine, zirconium, titanium, iron, cobalt, nickel, copper, zinc, silver, platinum, or lead, or a combination thereof,59. The method of Claim 53, wherein the pattern treatment composition is covalently bonded to the first patterned mask.

60. The method of Claim 53, wherein the pattern treatment composition is ionic or hydrogen bonded to the first patterned mask.

61. The method of Claim 53, wherein the polymer is of the general Formula (1):(I)wherein X is 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 Ce-30 aryl, or monocyclic or polycyclic C6-30 heteroaryl, each of which is substituted or unsubstituted, each optionally including as part of its structure one or more groups chosen from — O —, — C(O) —, — C(O) — O —, — CH2O —, — NH —, — N(Ci-Cs alkyl) —, or — S —; or a silicon containing moiety, including a linear C1-20 alkylsiloxane, branched C3-20 alkylsiloxane, or a monocyclic or polycyclic C3-20 cycloalkylsiloxane, each of which is substituted or unsubstituted, each optionally including as part of its structure one or more functional groups chosen from — O—, — C(O)—, — C(O)— O—, — CH2O—, — NH—, — N(Ci-Cs alkyl)—, or — S —, and wherein the silicon can also be a part of a larger chain forming a siloxane backbone, such as a poly siloxane chain;PDH-014L is optionally present. Where L is present, it is a linking group selected from a linear or branched alkyl having 1 to about 8 carbon atoms that is optionally substituted. Where L is absent, the bond connects directly to M;M is any one selected from the following substituents;CH3where L1is optionally present. Where L1is present, it is a linking group selected from an alkyl having 1 to about 8 carbon atoms that is optionally substituted with one or more groups chosen from — O—, — C(O)—, — C(O)— O—, — CH2O—, — NH—, — N(Ci-Cs alkyl)—, or — S—. Where L1is absent, the bond connects directly to the silicon containing unit.

62. The method of Claim 53, wherein the polymer comprises a polystyrene, poly(alkylacrylate), poly(alkylmethacrylate), poly(vinylpyridine), poly( arylene oxide), polyethylene, polypropylene, hydrogenated polybutadiene, polycyclohexylethylene, alternating copolymer of styrene and maleic anhydride or maleimide, polynorbornene, or polysiloxane.

63. The method of Claim 53, wherein the polymer comprises silicon or a metal.

64. The method of Claim 53, wherein the reactive surface attachment group comprises a hydroxyl, sulfhydryl, carboxyl, epoxide, amine, amide, imine, diazine, diazole, optionally substituted pyridine, pyridinium, optionally substituted pyrrolidone, or combinations thereof.

65. The method of Claim 53, wherein the reactive surface attachment group precursor is selected from a tertiary alkyl ester group, a secondary or tertiary aiyl ester group, a secondary or tertiary ester group having a combination of alkyl and aryl groups, a tertiary alkoxy group, an acetal group, or a ketal group.

66. The method of Claim 53, wherein the polymer comprises a reactive surface attachment group at one chain end.

67. The method of Claim 53, wherein the catalyst is free of fluorine.

68. The method of Claim 53, wherein the catalyst is selected from an acid, thermal acid generator, or a photoacid generator.

69. The method of Claim 53, wherein the catalyst comprises an aromatic acid of the general Formula (2):(SO3H)b(2)i Ar1wherein Ar1represents a C5-C40 monocyclic or polycyclic aromatic aryl group; R4independently represents a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C20 aryl group or a combination thereof, optionally containing one or more group chosen from carbonyl, carbonyloxy, sulfonamido, ether, thioether, a substituted or unsubstituted alkylene group, or a combination thereof; and a is independently an integer from 0 to 5.

70. The method of Claim 53, wherein the catalyst comprises a thermal acid generator of the general Formula (9):(A’)(BH)+(9) in which A is the anion of an organic or inorganic acid having a pKa of not more than 3; and (BH)!is the monoprotonated form of a nitrogen-containing base B having a pKa between 0 and 5.0, and a boiling point less than 170 °C.

71. The method of Claim 53, wherein the catalyst comprises an aromatic acid of the general Formula (10):+X—(R17)aa (10)wherein X is S or I, wherein when X is 1 then aa is 2, and when X is S then aa is 3; R17is independently chosen from organic groups such as optionally substituted Ci-so alkyl, polycyclic or monocyclic C3-30 cycloalkyl, polycyclic or monocyclic Ce-30 aryl, or a combination thereof, wherein when X is S, two of the R groups together optionally form a ring.

72. The method of Claim 53, wherein the second composition comprises at least one of carbon, silicon, or a metal.

73. The method of Claim 53, wherein the second composition comprises a polysiloxane, silsesquioxanes, silicon-containing poly(meth)acrylate, silicon-containing polystyrene, or spin- on glass.

74. The method of Claim 53, wherein the second composition comprises an organic polymer, an anti -reflective coating composition, a spin-on carbon hard mask, or other carbon based materials.

75. The method of Claim 53, wherein the second composition comprises tin, bismuth, tellurium, cesium, antimony, indium, molybdenum, hafnium, iodine, zirconium, titanium, iron, cobalt, nickel, copper, zinc, silver, platinum, or lead, or a combination thereof.

76. The method of claim 28, further comprising transferring the resulting final patterned mask into one or more layers to be patterned.

77. The method of claim 76, wherein the transferring comprises an etch of the one or more layers.

78. The method of claim 76, wherein the transferring comprises an implant of dopant into the one or more layers.

79. A method of forming a pattern, comprising:providing a semiconductor substrate comprising a layer to be patterned;forming a layer of a photoresist on the layer to be patterned;exposing the photoresist layer with a single exposure using EUV radiation and a numerical aperture of 0.5 or less or X-ray radiation to generate a latent image m the photoresist layer; anddeveloping the photoresist layer to form a plurality of features, wherein the plurality of features comprise holes and / or pillars; andwherein said plurality of features has a pitch of 35 nanometers or less; andPDH-014wherein a critical dimension of said plurality of features has a 3-sigma uniformity of less than 15% of a nominal critical dimension; andwherein said plurality of features has a defect rate of less than 1 defect per million holes.

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