Methods for patterning using shrink and angled ion beams

Abstract

Provided herein are methods of microfabrication comprising: forming a first patterned mask on a substrate comprising a cavity, the cavity having a first length / 1 along a first direction and a first width w1 along a second direction perpendicular to the first direction; forming a layer of a pattern treatment composition on the first patterned mask, wherein a modified cavity is formed having a second length / 2 along a first direction, less than the first length / 1, and a second width w2 along a second direction perpendicular to the first direction, less than the first width w1; performing an elongation patterning process, comprising directing angled ions to a sidewall of the modified cavity in a first exposure, wherein the sidewall of the modified cavity is etched, wherein after the first exposure, the modified cavity has a third length / 3 along the first direction, greater than the second length / 2, and a third width w3 along a second direction perpendicular to the first direction. These methods are useful for fabricating integrated circuits.

Description

[0001] Docket # PDH-025

[0002] METHODS FOR PATTERNING USING SHRINK AND ANGLED ION BEAMS CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] [1] This application claims the priority and benefit of U. S. Provisional Application No. 63 / 754,089, filed on February 5, 2025; which application is hereby incorporated herein by reference in its entirety.

[0004] FIELD OF THE DISCLOSURE

[0005] [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 patterns.

[0006] BACKGROUND

[0007] [3] This disclosure pertains to the fabrication of electronic devices, specifically methods for forming photolithographic patterns, it is particularly relevant to semiconductor manufacturing, where high- density lithographic patterning is essential for device fabrication.

[0008] [4] As semiconductor devices continue to scale, achieving precise patterning of small features becomes increasingly challenging. One significant hurdle is the lithographic printing of closely spaced cavities, with separations on the order of nanometers or tens of nanometers in current technology. For example, defining adjacent linear trenches or holes with the correct tip-to-tip spacing becomes progressively difficult as the overall pitch of device structures shrinks. A key limitation is the reliability of lithographic printing at such small pitches due to overlay issues. More specifically, achieving small separations for nanoscale cavities often requires multiple masks, where misalignment between masks can lead to overlapping cavities or excessive spacing between features.

[0009] [5] To overcome these limitations and enable the formation of high-resolution patterns using a single mask layer, one strategy involves lithographically defining a series of cavities and subsequently shrinking their dimensions. Various resist pattern shrink techniques have been developed to achieve this goal by effectively increasing the thickness of the resist sidewalls, thereby reducing the cavity size.

[0010] [6] Several known shrink processes include chemical vapor deposition (CVD) assist shrink, acid diffusion resist growth, and a polymer hydrogen acceptor approach. CVD assist shrink, as described by K. Oyama et al. (" The enhanced photoresist shrink process technique toward 22 nm node," Proc. SPIE 7972, Advances in Resist Materials and Processing Technology XXVIII, 79722Q, 2011), involves depositing a conformal CVD layer over a patterned photoresist, which effectively narrows the cavities. The acid diffusion resist growth process, commonly referred to as Resolution Enhancement Lithography Assisted by Chemical Shrink, or RELACS, as discussed by L. Peters (" Resists Join the Sub-X Revolution," Semiconductor International, 1999), employs an acid-catalyzed crosslinkable material applied over a resist pattern, where acid diffuses from the resist into the crosslinkable material, triggering crosslinking reactions that shrink cavity dimensions. The polymer hydrogen acceptor approach, as detailed in U. S. Patent 9,448,483, involves applying a shrink composition over a resist pattern, where the composition forms a polymer layer that reduces cavity size. Each of these methods presents a potential solution forDocket # PDH-025

[0011] sub-resolution patterning, allowing semiconductor manufacturers to push the limits of feature scaling while maintaining pattern fidelity and alignment accuracy.

[0012] [7] A challenge with these shrink approaches is shown in Fig. 1, which defines dimensions of interest in the cavity before and after shrink. The cavity has a first length along a first direction, / i, and a first width along a second direction perpendicular to the first direction, Wi. After shrink processing, the cavity has a second length along a first direction, and a second width along a second direction perpendicular to the first direction, 2. The difference in cavity dimension before and after shrink is defined in Equations 1-2:

[0013] A / = / i - 1 (1) A = I - 2 (2) Shrink methods of the prior art are undesirable because they result in, at best, equal cavity shrink along the length and width, where A / = Aw, or at worst, more shrink along the length of the cavity, such that A / > Aw.

[0014] [8] Accordingly, there is a continuing need in the art for improved photoresist pattern shrink methods which address one or more problems associated with the state of the art and which allow for the formation of fine patterns in electronic device fabrication.

[0015] SUMMARY

[0016] [9] This summary is provided to introduce a selection of concepts that are further described below in the detailed description. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.

[0017]

[0010] In a first aspect, embodiments disclosed herein relate to a method of microfabrication comprising: forming a first patterned mask on a substrate comprising a cavity, the cavity having a first length along a first direction and a first width i along a second direction perpendicular to the first direction; forming a layer of a pattern treatment composition on the first patterned mask, wherein a modified cavity is formed having a second length along the first direction, less than the first length / i, and a second width w2along the second direction, less than the first width i; performing an elongation patterning process, comprising directing angled ions to a sidewall of the cavity in a first exposure, wherein the sidewall of the cavity is etched, wherein after the first exposure, the cavity has a third length / ?, along the first direction, greater than the second length / 2, and a third width 3 along a second direction perpendicular to the first direction.

[0018]

[0011] Making reference to FIG. 3A-FIG. 3F, coated substrates are shown at respective points of the inventive method. The drawings show both cross-sectional (FIGS. 3A, 3C, and 3E, left) and top down (FIGS.

[0019] 3B, 3D, and 3F, right) illustrations. The cross-sections shown are taken from slicing vertically along the axes shown by the horizontal dotted lines denoted as " A - A" in the top down illustrations. In one example, a first patterned mask 303 is provided on one or more layers to be patterned 302 above the substrate 300, as shown in FIG. 3A and FIG. 3D. Cavities in the first patterned mask may be defined byDocket # PDH-025

[0020] dimensions along different directions, including length h along the Y-axis, height hi along the Z-axis, and width Wi along the X-axis of the Cartesian coordinate system shown in FIG. 3A and FIG. 3D. Next, as shown in FIG. 3B and Fig. 3E, a layer of a pattern treatment composition 304 is formed on the first patterned mask 303, thereby forming a second patterned mask having a second length / 2and second width w2and where / 22< wi. Then, as shown in FIG. 3C and Fig. 3F, an elongation patterning process is performed to increase the length of the cavity, forming a third patterned mask with a third length h where / a > / 2. The process enables cavities to shrink more in width than in length.

[0021]

[0012] In another embodiment of the first aspect, the third width is less than 150% of the second width.

[0022]

[0013] In another embodiment of the first aspect, the third width is less than 110% of the second width.

[0023]

[0014] In another embodiment of the first aspect, the third length is 90% - 150% of the first length.

[0024]

[0015] In another embodiment of the first aspect, the third length is 95% - 125% of the first length.

[0025]

[0016] In another embodiment of the first aspect, the first patterned mask comprises a photoresist.

[0026]

[0017] In another embodiment of the first aspect, the first patterned mask comprises a metal-containing photoresist.

[0027]

[0018] In another embodiment of the first aspect, the first patterned mask comprises an organic bottom anti-reflective coating, amorphous carbon, or spin-on carbon.

[0028]

[0019] In another embodiment of the first aspect, the first patterned mask comprises silicon oxide, silicon nitride, silicon oxynitride, tungsten, titanium, titanium nitride, titanium oxide, zirconium oxide, aluminum oxide, aluminum oxynitride, hafnium oxide, or a silicon bottom anti-reflective coating.

[0029]

[0020] In another embodiment of the first aspect, the layer of pattern treatment composition is formed by a CVD process.

[0030]

[0021] In another embodiment of the first aspect, the layer of pattern treatment composition is formed by an acid diffusion resist growth process.

[0031]

[0022] In another embodiment of the first aspect, the layer of pattern treatment composition is formed by a polymer blend self-assembly process.

[0032]

[0023] In another embodiment of the first aspect, the pattern treatment composition comprises a polymer comprising a reactive surface attachment group or reactive surface group precursor.

[0033]

[0024] In another embodiment of the first aspect, the pattern treatment composition is covalently bonded to the first patterned mask.

[0034]

[0025] In another embodiment of the first aspect, the pattern treatment composition is hydrogen bonded or ionic bonded to the first patterned mask.Docket # PDH-025

[0035]

[0026] In another embodiment of the first aspect, the pattern treatment composition comprises a polymer comprising silicon.

[0036]

[0027] In another embodiment of the first aspect, the pattern treatment composition comprises an organic polymer.

[0037]

[0028] In another embodiment of the first aspect, the pattern treatment composition comprises a polymer comprising a reactive surface attachment group chosen from one or more of hydroxyl, sulfhydryl, carboxyl, epoxide, amine, amide, imine, diazine, diazole, optionally substituted pyridine, pyridinium, and optionally substituted pyrrolidone groups.

[0038]

[0029] In another embodiment of the first aspect, the pattern treatment composition comprises a polymer comprising a reactive surface attachment group precursor comprising an acid-labile group 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.

[0039]

[0030] In another embodiment of the first aspect, the method further comprises: depositing a second sacrificial layer over the cavity in a second deposition procedure; and directing second angled ions to the cavity in a second exposure.

[0040]

[0031] In another embodiment of the first aspect, the method further comprises an elongation patterning process comprising: directing angled ions to the cavity in a first exposure, wherein the angled ions comprise a first angled ion beam having a first trajectory, directed to a first sidewall of the cavity; and a second angled ion beam having a second trajectory, directed to a second sidewall of the cavity, opposite the first sidewall.

[0041]

[0032] In another embodiment of the first aspect, forming a layer of a pattern treatment composition on the first patterned mask comprises: coating a pattern treatment composition over the first patterned mask; baking the substrate; and treating the substrate with a rinsing agent comprising a solvent.

[0042] BRIEF DESCRIPTION OF DRAWINGS

[0043]

[0033] FIG. 1 are schematic illustrations of cavities before and after shrink processing with defined dimensions, including first and second lengths / i and I2 and first and second widths wi and W2.

[0044]

[0034] Fig. 2 is a block-flow diagram of a method in accordance with one or more embodiments of the present disclosure.

[0045]

[0035] FIGS. 3A-F are schematic illustrations of coated substrates at respective points of the inventive method. The schematics show both top down (right) and cross-sectional (left) illustrations. Cross-sections shown on the left in FIGS. 3A, 3C, and 3E are taken from slicing vertically along the axes shown by the horizontal dotted lines denoted as " A — A" in the top down illustrations on the right in FIGS. 3B, 3D, and 3F.Docket # PDH-025

[0046]

[0036] FIGS. 4A-C are schematic illustrations of cavities before and after shrink processing and elongation with defined dimensions, including first, second, and third lengths / i, h, and h, and first, second, and third widths wi, wj, and w?,.

[0047] DESCRIPTION

[0048]

[0037] 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.

[0049]

[0038] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art. As used herein, the below terms have the following meanings unless specified otherwise. Any methods, devices and materials similar or equivalent to those described herein may also be used in the practice of the compositions and methods described herein. The following definitions are provided to facilitate understanding of certain terms used frequently herein and are not meant to limit the scope of the present disclosure. All references referred to herein are incorporated by reference in their entirety.

[0050]

[0039] The term "comprise" and variations thereof, such as, "comprises" and "comprising" are to be construed in an open, inclusive sense, that is, as "including, but not limited to." The term "consisting essentially of" is construed to mean that the composition / process (a) necessarily includes the listed ingredients / steps and (b) is open to unlisted ingredients / steps that do not materially affect the basic and novel properties of the composition / process. The term "consisting of" is closed-ended and excludes any element, step, or ingredient not specifically mentioned after that phrase. Further, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Thus, references to "the embodiment" includes a plurality of such embodiments.

[0051]

[0040] 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.

[0052]

[0041] 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."Docket # PDH-025

[0053]

[0042] " 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.

[0054]

[0043] 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.

[0055]

[0044] 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.

[0056]

[0045] " 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 (— NH2or — NR2), nitro (— NO2), acyl (— C(— O)R), alkylsulfonyl (— S(— O)2R), alkoxy (—OR), (C3-io)cycloalkyl, and like substituents, where R is a hydrocarbyl, aryl, Het, or like moieties, such as a monovalent alkyl or a divalent alkylene having from 1 to about 10 carbon atoms. For example, a hydroxy substituted alkyl, can be a 2-hydroxy substituted propylene of the formula — CH2— CH(OH)— CH2—, 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(NR2)— CH3.

[0057]

[0046] " Cycloalkyl" includes cyclic alkyls. " Substituted cycloalkyl" or "optionally substituted cycloalkyls" refers to a cycloalkyl substituent having from 1 to 4 optional substituents selected from, for example, alkyl, alkenyl, alkynyl, hydroxyl (—OH), halogen, amino (— NH2or — NR?), nitro (— NO2), acyl (— C(— O)R), alkylsulfonyl (— S(— O)2R), alkoxy (—OR), and like substituents.

[0058]

[0047] " Alkoxyl" 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.

[0059]

[0048] " Alkoxylcarbonyl" includes an alkyl group bound the base structure via an oxygen, with a carbonyl group adjacent the oxygen, -O-C(=0)-R, wherein R can include optionally substituted linear alkyls or branched alkyls as described above.

[0060]

[0049] " Carboxyl" means a moiety composed of carbon bonded to both an oxygen and a hydroxyl group, -C(=O)-O-H.

[0061]

[0050] " Hydroxyl" means an -O-H chemical moiety.

[0062]

[0051] " Cyano" means a -C=N chemical moiety.

[0063]

[0052] " Halogen" or "halo" includes fluoro (- F), chloro (—Cl), bromo (- Br), or iodo (-1) moieties.

[0064]

[0053] " 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.Docket # PDH-025

[0065]

[0054] " 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.

[0066] 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 tetramethylene diradical thereto.

[0067]

[0055] 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.

[0068]

[0056] 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 CH indicates a moiety of the integer "i" to the integer "j" carbon atoms, inclusive. Thus, for example, (Ci-Cg)alkyl or Cigalkyl refers to an alkyl of one to eight carbon atoms, inclusive, and hydrocarbyloxy such as (Ci-Cg)alkoxy or Ci.galkoxy refers to an alkoxy radical (—OR) having an alkyl group of one to eight carbon atoms, inclusive. Specifically, a Ci. alky I can be, for example, methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, 3-pentyl, hexyl, heptyl, or octyl; (C3 12)cycloalkyl can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, including bicyclic, tricyclic, or multi-cyclic substituents, and like substituents.

[0069]

[0057] A specific "hydrocarbyl" can be, for example, (Cio-2o)hydrocarbyl, including all intermediate chain lengths and values, and (Cg.^Jcyclohydrocarbyl including all intermediate values and ring sizes.

[0070]

[0058] Ci.galkoxy can be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, iso-butoxy, sec¬ butoxy, pentoxy, 3-pentoxy, hexyloxy, 1-methylhexyloxy, heptyloxy, octyloxy, and like substituents.

[0071]

[0059] A — C(— O)(C3-- / )a Ikyl- or — (C2-?)alkanoyl can be, for example, acetyl, propanoyl, butanoyl, pentanoyl, 4-methylpentanoyl, hexanoyl, or heptanoyl. Aryl (Ar) can be, for example, phenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, tetrahydronaphthyl, or indanyl. Het can be, for example, pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl, or heteroaryl. Heteroaryl can be, for example, furyl, imidazolyl, triazolyl, triazinyl, oxazoyl, isoxazoyl, thiazolyl, isothiazoyl, pyrazolyl, pyrrolyl, pyrazinyl, tetrazolyl, pyridyl, (or its N-oxide), thienyl, pyrimidinyl (or its N-oxide), indolyl, isoquinolyl (or its N-oxide) or quinolyl (or its N-oxide).

[0072]

[0060] Other conditions suitable for formation and modification of the compounds or like products of the disclosure, from a variety of starting materials or intermediates, as disclosed and illustrated herein are available. For example, see Feiser and Feiser, " Reagents for Organic Synthesis", Vol. 1, et seq., 1967; March, J. " Advanced Organic Chemistry," John Wiley & Sons, 4Supth / Suped. 1992; House, H. O., " Modem Synthetic Reactions," 2nned., W. A. Benjamin, New York, 1972; and Larock, R. C., " Comprehensive Organic Transformations," 2nded., 1999, Wiley-VCH Publishers, New York.Docket # PDH-025

[0073]

[0061] The term " Mn" used herein and in the appended claims in reference to a polymer of the present disclosure is the number average molecular weight of the polymer (in g / mol) determined according to the method used herein in the Examples. The term “Mw" used herein and in the appended claims in reference to a polymer of the present disclosure is the weight average molecular weight of the polymer (in g / mol) determined according to the method used herein in the Examples.

[0074]

[0062] The term " PDI" or " D" used herein and in the appended claims in reference to a polymer of the present disclosure is the polydispersity (also called polydispersity index or simply "dispersity") of the polymer determined according to the following equation:

[0075] PDI = Đ = Mw / Mn

[0076]

[0063] 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.

[0077]

[0064] The term "resin'' refers to a polymeric material, or a precursor thereof, that serves as a principal component of a composition, often acting as a binder, matrix, film-former, or structural component. The resin may comprise one or more monomers, oligomers, prepolymers, or polymers, and can exist as a blend or copolymer of different resin types.

[0078]

[0065] 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.

[0079]

[0066] The term "(meth)acrylate" or "(meth)acrylate monomer" refers to both acrylate and methacrylate species. For example, the term "methyl (meth)acrylate" refers to both methyl acrylate and methyl methacrylate. Similarly, the term "poly(meth)acrylate" refers to both acrylate and methacrylate polymer species. For example, the term "polymethyl (meth)acrylate" refers to both polymethyl acrylate and polymethyl methacrylate.

[0080]

[0067] 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.

[0081]

[0068] The present embodiments provide novel techniques and apparatus to pattern substrates and in particular novel techniques to form smaller cavities on a substrate. Some embodiments describe a method of forming a pattern of cavities on a substrate, applying a coating of a pattern treatment composition over the substrate, and then applying an elongation patterning process. Such processingDocket # PDH-025

[0082] may be deemed "shrink and elongation patterning", where a feature such as a via or trench may be formed having an initial shape and size, then shrunk to a smaller size, and finally elongated along the designed direction using a series of etch operations. The designed direction may correspond to a horizontal direction within a plane of the substrate. According to various embodiments, the elongation of the feature may take place along the designed direction (first direction) while the cavity is not enlarged or enlarged to a lesser extent along a perpendicular direction to the designed direction (second direction) within the plane of the substrate. In this manner, a cavity may be selectively elongated along just one direction, providing various concomitant advantages for patterning substrates, as disclosed herein.

[0083]

[0069] In particular embodiments, unidirectional cavity elongation within a given layer is accomplished using a novel set of deposition and etching operations. Unidirectional cavity elongation may refer to selective elongation of the dimensions of a cavity (or hole) along a select direction, such as along the Y- axis of a Cartesian coordinate system, where elongation does not take place along orthogonal directions, such as along the X-axis and along the Z-axis. In some embodiments, a cavity may be processed wherein the original thickness (along the Z-direction) of a layer containing the cavity may be preserved, while the cavity is etched within a plane of the layer along just one direction and not the other direction.

[0084]

[0070] In particular embodiments, a cavity is provided in a layer where the cavity has a first length along a first direction and a first width along a second direction perpendicular to the first direction. A first operation involves forming a coating of a pattern treatment composition over the cavity in a first deposition procedure, forming a smaller cavity with a second length and second width which are smaller than the first width and first length. A second operation then involves depositing a sacrificial layer over the cavity in a second deposition procedure, while a second operation involves directing angled ions to the cavity in a first exposure, wherein the cavity is etched. After the first exposure, the cavity may attain a third length or final length along the first direction, greater than the second length, wherein the cavity has a third width or final width along the second direction, which is no greater than the second width. In some instances, the final width is the same as the second width, and the final length is the same as the first length. In other instances, the final length is greater than the first length.

[0085]

[0071] An exemplary method for shrink and elongation patterning will now be described. A method, 200, for shrink and elongation patterning in accordance with one or more embodiments is shown in, and discussed with reference to, FIG. 2. Generally, method 200, includes a cavity shrink and elongation patterning process. Initially, at block 202, a first patterned mask comprising cavities is provided on the substrate via execution of an initial photolithography patterning step. The first patterned mask may be formed using a photolithographic process and may be made of a first resist, a hardmask, a metal, or other suitable compositions. Then, at block 204, a pattern treatment composition is coated on the first patterned mask. The coating may be applied over the substrate by spin coating, deposition, or other suitable process. Next, at block 206, the substrate is optionally baked. Then, at block 208, the substrate is optionally treated with a rinsing agent. Then, at block 210, the substrate is subjected to an elongation patterning process.Docket # PDH-025

[0086]

[0072] Schematic depictions of a coated substrate at various points during the method described above are shown in FIGS. 3A-3F. Herein "a coated substrate" refers to a substrate that is coated with one or more layers, such as a first resist layer and a pattern treatment composition. FIG. 3A and Fig. 3D show a substrate including a first patterned mask of cavities, showing both top down (right) and cross-sectional (left) illustrations. Cross-sections are taken from slicing vertically along the axis shown by the horizontal dotted line designated by the " A — A" in the top down illustration in Fig. 3A. FIG. 3B and Fig. 3E show a substrate including a first patterned mask treated with a pattern treatment composition. FIG. 3C and Fig. 3F show a substrate after application of an elongation patterning process. The method of FIG. 2 and coated substrates shown in FIGS. 3A-3F are discussed in detail below.

[0087]

[0073] At block 202 of method 200, a first patterned mask is provided. FIG. 3A and Fig. 3D show an example of a first patterned mask 303 on one or more layers to be patterned 302 above the substrate 300. The cavities in the first patterned mask may be defined by dimensions along different directions, including I-. along the Y-axis, h-, along the Z-axis, and wi along the X-axis of the Cartesian coordinate system shown in FIG. 3A and FIG. 3D.

[0088]

[0074] 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 I l-VI), 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.

[0089]

[0075] 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 oxycarbide, and porous silicon dioxide; high-k dielectrics such as hafniumDocket # PDH-025

[0090] 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 fluorinated 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-containing 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.

[0091]

[0076] 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. As shown in FIG. 3A and FIG. 3D, the first patterned mask may include isolated cavities where portions of the substrate are exposed. 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 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.

[0092]

[0077] Coatings of the photoresist can be achieved through various means known by those of ordinary skill in 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 patterned mask. 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.

[0093]

[0078] 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 withDocket # PDH-025

[0094] 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.

[0095]

[0079] 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 in 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 temperatures and times within the explicit ranges above are contemplated and are within the present disclosure.

[0096]

[0080] 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.

[0097]

[0081] 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.

[0098]

[0082] 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.

[0099]

[0083] 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.

[0100]

[0084] 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 treated to further condense the material and to further dehydrate, densify, or remove residual developer from the patterned mask. ThisDocket # PDH-025

[0101] is typically done by baking the substrate at 100 °C to 600 “C for at least one minute in air, vacuum, or an inert gas (like Ar or N2). Non-thermal methods, such as UV exposure or an O2plasma treatment, can also be used for similar purposes.

[0102]

[0085] 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.

[0103]

[0086] In some embodiments, a hardmask 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 1 to 50 nm, for example, from 5 to 20 nm.

[0104]

[0087] At block 204 of method 200, the first patterned mask 303 is coated with a pattern treatment composition. A coated substrate in accordance with block 204 is shown in FIG. 3B and Fig. 3E, where a pattern treatment composition layer 304 is formed on the first patterned mask 303 to form a second patterned mask. The pattern treatment composition is typically applied to the substrate by spin-coating or vapor-phase deposition. When applied by spin coating, the solids content of the coating solution can be adjusted to provide a desired film thickness based upon the specific coating equipment utilized, the viscosity of the solution, the speed of the coating tool and the amount of time allowed for spinning, with thicknesses of 200 to 1500 A being typical. Depending on the particular process, the composition can be applied so as to cover the first patterned mask entirely or to a height less than or equal to the thickness of the first patterned mask so as not to cover the pattern top surface, depending on the particular application.

[0105]

[0088] In some embodiments, at block 205 of method 200, the coated substrate is then optionally baked. The pattern treatment composition is optionally baked to remove solvent from the composition and to cause the composition to form the pattern treatment composition layer 304. A typical bake is conducted at a temperature of from about 70 to 300 °C, and a time of from about 30 to 120 seconds.

[0106]

[0089] In other embodiments, at block 208 of method 200, residual pattern treatment composition is removed from the substrate by rinsing with a first rinse agent, leaving behind layer 304 of the composition bound to the first patterned mask 303 as shown in FIG. 3B and FIG. 3E. Suitable rinsing materials include, for example, aqueous alkaline developers and organic solvents. The first rinsing agent is preferably an organic solvent, more preferably 2-heptanone or n-butylacetate, methyl isobutyl carbinol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and blends thereof. Optionally,Docket # PDH-025

[0107] the substrate can then be rinsed with a second rinse agent that is different from the second rinse agent. This rinse process is typically conducted using a spin-coater tool. The application of the second rinse agent and first rinse agent are typically conducted sequentially. Optionally, the first rinse agent can be gradiently changed to the composition of the second rinse agent in a continuous process. Optionally, a post-rinse bake can be conducted at a temperature of from about 70 to 150 °C and a time of from about 30 to 120 seconds. This bake can provide beneficial results, for example, in the form of improved pattern fidelity and roughness.

[0108]

[0090] After the shrink process, the cavities may be defined by dimensions along different directions, including l₂ along the Y-axis, h₂ along the Z-axis, and w₂ along the X-axis of the Cartesian coordinate system shown in FIG. 3B and FIG. 3E.

[0109]

[0091] In some embodiments, the pattern treatment composition layer is applied with a chemical vapor deposition, atomic layer deposition, or other deposition process. In other embodiments, the pattern treatment composition layer is formed by an acid diffusion resist growth process, also referred to as the RELACS process. In other embodiments, the pattern treatment composition layer is formed by a polymer blend self-assembly process.

[0110]

[0092] In one embodiment of the present disclosure, the pattern treatment composition layer 304 may be formed from a pattern treatment composition comprising one or more polymers having a reactive surface attachment group or reactive surface attachment group precursor, a solvent, and may include one or more additional optional components such as a catalyst.

[0111] Polymer having a reactive surface attachment group or reactive surface attachment group precursor

[0093] 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 bonding, ionic bonding, or covalent bonding of the polymer to the surface of the substrate.

[0112]

[0094] 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.

[0113]

[0095] 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.Docket # PDH-025

[0114]

[0096] 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.

[0115]

[0097] 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 polyarylsulfone, 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 polyoxadiazole, a polybenzothiazinophenothiazine, a polybenzothiazole, a polypyrazinoquinoxaline, a polypyromellitimide, a polyquinoxaline, a polybenzimidazole, a polyoxindole, a polyoxoisoindoline, a polydioxoisoindoline, a polytriazine, a polypyridazine, a polypiperazine, a polypyridine, 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-vinylpyridine such as poly(styrene-block-2-vinlpyridine), block copolymers of styrene and 4-vinylpyridine 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, C1-18 alkyl, C1-18 alkenyl (including norbornenyl), C1-18 alkoxyl, C2-18 alkenoxyl, C5-18 aryl, C5-18 aryloxyl, C6-18 alkylaryl, C6-18 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.

[0116]

[0098] 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-(trimethoxysilyl)propyl acrylate, 3-(triethoxysilyl)propyl acrylate, methacryloxypropyltri methoxysilane, methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane acrylate, tetraethylorthosilicate acrylate, silicone acrylates, polydimethylsiloxane-acrylate, hexamethyldisiloxane acrylate, octamethylcyclotetrasiloxane acrylate,Docket # PDH-025

[0117] trimethylsilylmethyl acrylate, dimethylsiloxypropyl acrylate, alkoxysilane acrylate derivatives, methoxyphenylsilyl 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.

[0118]

[0099] 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.

[0119]

[0100] In some embodiments, the polymer comprises the following Formula (1):

[0120] (1)

[0121]

[0122] 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 C6-30 aryl, or monocyclic or polycyclic C5-30 heteroaryl, each of which is substituted or unsubstituted, each optionally including as part of its structure one or more groups chosen from — O—, —6(0)—, —6(0) — O—, — CH₂O—, — NH—, — N(C1-C8 alkyl)—, or — S—; or a silicon containing moiety, including a linear 1-20 alkylsiloxane, branched 63-20 alkylsiloxane, or a monocyclic or polycyclic 63-20 cycloalkylsiloxane, each of which is substituted or unsubstituted, each optionally including as part of its structure one or more functional groups chosen from — O—, —6(0)—, — 6(0)— O—, — CH2O—, — NH—, — N(C1-C8alkyl)—, or — S—, and wherein the silicon can also be a part of a larger chain forming a siloxane backbone, such as a polysiloxane chain;

[0123] 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;

[0124] M is any one selected from the following substituents;Docket # PDH-025

[0125]

[0126] 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—, — CHzO—, — NH—, — N(Ci-Ca alkyl)—, or — S—. Where L1is absent, the bond connects directly to the silicon containing unit.

[0127]

[0101] 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 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.

[0128]

[0102] The polymer comprises a reactive surface attachment group for forming a bond, typically hydrogen bond, ionic bond, or a covalent bond, with the patterned mask. 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 patterned mask with which the reactive surface attachment group will depend on the material of the patterned mask. For example, in the case of an inorganic composition such as silicon oxide, silicon nitride or silicon oxynitride, the reactive surface attachment group can be suitable for reacting with silanol along exposed surfaces of the patterned mask 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-methylamine, N-ethyl amine, 1-aminopropane, 2-aminopropane and N-t-butylamine, secondary amines such as dimethylamine, methylethylamine and diethylamine, and tertiary amines such asDocket # PDH-025

[0129] 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.

[0130]

[0103] 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 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".

[0131]

[0104] The acid-labile group which, on decomposition, forms a carboxylic acid is preferably a tertiary ester group of the formula — C(O)OC(R1)3or an acetal group of the formula — C(O)OC(R2)2OR3, wherein: R1is each independently linear C1-20 alkyl, branched C3-20 alkyl, monocyclic or polycyclic C3-20 cycloalkyl, linear C2-20 alkenyl, branched C3-20 alkenyl, monocyclic or polycyclic C3-20 cycloalkenyl, monocyclic or polycyclic C5-20 aryl, or monocyclic or polycyclic C2-20 heteroaryl, preferably linear C1-5 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 R¹ groups 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 C5-20 aryl, or monocyclic or polycyclic C2-20 heteroaryl, preferably hydrogen, linear C1-5 alkyl, branched C3-5 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 C5-20 aryl, or monocyclic or polycyclic C2-20 heteroaryl, preferably linear C1-5 alkyl, branched C3-5 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 R optionally forming a ring. In other embodiments, the acid-labile group forms an alcohol group or a fluoroalcohol group decomposition.Docket # PDH-025

[0132] 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.

[0133]

[0105] 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. O2or N2 / H2plasma 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.

[0134]

[0106] 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 patterned mask) 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.

[0135]

[0107] 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.

[0136] Solvent

[0137]

[0108] 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 in the total composition, greater than 90 wt%, greater than 95 wt%, greater than 99 wt% or 100 wt% organic solvents, based on total solvents of the composition. Generally, the solvent may comprise one or more of a ketone-based solvent, an ester-based solvent, anDocket # PDH-025

[0138] alcohol-based solvent, an amide-based solvent, an ether-based solvent, a hydrocarbon-based solvent, or a combination thereof. The total solvent content (i.e., cumulative solvent content for all solvents) in the photoresist compositions is from 40 to 99 wt %, from 70 to 99 wt %, or from 85 to 99 wt %, based on total weight of the photoresist composition. The desired solvent content will depend, for example, on the desired thickness of the coated photoresist layer and coating conditions.

[0139] Optional components

[0140] Catalysts

[0141]

[0109] 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 10“6to 10 moles, preferably 10“5to 5 moles, more preferably 10“4to 1 mole, relative to 1 mole of reactive group on the functional polymer.

[0142]

[0110] 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; hydroxyalkanoic 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-l-sulfonic acid, 1-pentanesulfonic acid, 1-hexanesulfonic acid, and 1- heptanesulfonic acid.

[0143]

[0111] In some embodiments, the solubility shifting agent is an aromatic sulfonic acid. The aromatic sulfonic acid is of general Formula (2):

[0144] (SOgH)b

[0145] Ar1:

[0146]

[0147] 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, anthracenyl, pyrenyl or quinolinyl; or fused ring systems having both aromatic and non-aromatic rings such as 1, 2,3,4-Docket # PDH-025

[0148] tetrahydronaphthalene, 9,10-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 isfree 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.

[0149]

[0112] 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):

[0150]

[0151] 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, sulfonamide, ether, thioether, a substituted or unsubstituted alkylene group, or a combination thereof; Z1independently represents a group chosen from carboxyl, hydroxy, nitro, cyano, Ci to C5 alkoxy, formyl and sulfonic acid; c and d are independently an integer from 0 to 5; and c+d is 5 or less;

[0152]

[0153] Docket # PDH-025

[0154] 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, sulfonamido, ether, thioether, a substituted or unsubstituted alkylene group, or a combination thereof; Z2and Z3each independently represents a group chosen from carboxyl, hydroxy, nitro, cyano, Ci to C5 alkoxy, 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;

[0155]

[0156] 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, sulfonamide, ether, thioether, a substituted or unsubstituted alkylene group, or a combination thereof; Z4, Z5and Z6each independently represents a group chosen from carboxyl, hydroxy, nitro, cyano, Ci to C5 alkoxy, formyl and sulfonic acid; i and j are independently an integer from 0 to 4; i+j is 4 or less; k and I are independently an integer from 0 to 2; k+l is 2 or less; m and n are independently an integer from 0 to 3; and m+n is 3 or less;

[0157]

[0158] wherein: R11, R12and R13each 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; Z7, Z8and Z9each independently represents a group chosen from carboxyl, hydroxy, nitro, cyano, Ci to C5 alkoxy, 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;

[0159]

[0160] Docket # PDH-025

[0161] 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, sulfonamide, ether, thioether, a substituted or unsubstituted alkylene group, or a combination thereof; Z10and Z11each independently represents a group chosen from hydroxy, nitro, cyano, Ci to C5 alkoxy, 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

[0162]

[0163] 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 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, Ci to C5 alkoxy, 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.Docket # PDH-025

[0164]

[0113] Aromatic sulfonic acids include, without limitation, the following:

[0165]

[0166] Docket # PDH-025

[0167]

[0168]

[0114] 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, tris(pentafluorophenyl)borane), boron trifluoride, tetrafluorosilane (SiF4), and aluminum trihalides (for example, AlCl3).Docket # PDH-025

[0169]

[0115] 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)-l, 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.

[0170]

[0116] Preferably, the TAG is ionic with a reaction scheme for generation of a sulfonic acid as shown below:

[0171] heat

[0172] RSO3-X+→ RSO3H + X

[0173] wherein RSO3 " is the TAG anion and X* is the TAG cation, preferably an organic cation. In preferred embodiments, the TA is an ionic thermal acid generator represented by the Formula (9):

[0174] (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 (B H)+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, C1-20alkyl amines, and C3-30aryl 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.

[0175]

[0117] 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 boilingDocket # PDH-025

[0176] 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.

[0177]

[0118] Suitable nitrogen-containing cations (BH)+include NH4+, CF2HNH2+, CF3CH2NH3+, (CH3)3NH+, (C2H5)3NH+, (CH3)2(C2H5)NH+and the following:

[0178]

[0179] in which Y is alkyl, preferably, methyl or ethyl.

[0180]

[0119] 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.

[0181]

[0120] Examples of PAGs include a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imidosulfonate, an oxime sulfonate, a diazodisulfone, a disulfone an o-nitrobenzyl sulfonate, aDocket # PDH-025

[0182] cyclopentadienyl salt, and an indenyl salt. Suitable classes of PAGs generating sulfonic acids include, but are not limited to, sulfonium or iodonium salts, oximidosulfonates, bissulfonyldiazomethanes, and nitrobenzylsulfonate esters. The PAG may be in non-polymerized or polymeric form, for example, present in a polymerized repeating unit of the polymer matrix. In some embodiments, the PAG is a polymeric PAG, wherein the PAG is introduced into the main or side chain of the polymer.

[0183]

[0121] 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.

[0184]

[0122] Suitable cations for PAGs include onium cations, for example, sulfonium and iodonium cations, for example, those of the following general Formula (10):

[0185] +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 Cs.3o aryl, or a combination thereof, wherein when X is S, two of the R groups together optionally form a ring.

[0186]

[0123] Suitable iodonium cations include the following:Docket # PDH-025

[0187]

[0188] Docket # PDH-025

[0189]

[0124] Exemplary suitable sulfonium cations include the following:

[0190]

[0191] Docket # PDH-025

[0192]

[0125] 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-trimethylphenyldi phenylsulfonium perfluorobutanesulfonate, 2,4,6-trimethyl phenyldiphenylsulfonium benzenesulfonate, 2, 4, 6-trimethyl phenyldiphenylsulfonium 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- butylphenyljsulfonium benzenesulfonate, and phenylthiophenyldiphenylsulfonium perfluorooctanesulfonate.

[0193]

[0126] 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- butylphenyljiodonium benzenesulfonate, bis-(t-butylphenyl)iodonium 2,4,6- triisopropylbenzenesulfonate, and diphenyliodonium 4-methoxybenzensulfonate.

[0194]

[0127] 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.

[0195]

[0128] Further examples of suitable photoacid generators are bis(p-toluenesulfonyl)diazomethane, methylsulfonyl p-toluenesulfonyldiazomethane, l-cyclo-hexylsulfonyl-l-(l,l- dimethylethylsulfonyl)diazomethane, bis(l,l-dimethylethylsulfonyl)diazomethane, bis(l-methylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, 1-p-toluenesulfonyl-l- cyclohexylcarbonyldiazomethane, 2-methyl-2-(p-toluenesulfony I) 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-toluenesulfonyl) propane, 1- cyclohexylsulfonyl-lcyclohexylcarbonyldiazomethane, l-diazo-l-cyclohexylsulfonyl-3,3-dimethyl-2- butanone, l-diazo-l-(l,l-dimethylethylsulfonyl)-3,3-dimethyl-2-butanone, l-acetyl-l-(l-methylethylsulfonyljdiazomethane, l-diazo-l-(p-toluenesulfonyl)-3,3-dimethyl-2-butanone, 1-diazo-l-benzenesulfonyl-3,3-dimethyl-2-butanone, l-diazo-l-(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-trifluoromethyl benzenesulfonate.

[0196]

[0129] Additional PAG compounds include, for example: onium salts, for example, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-Docket # PDH-025

[0197] tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-t-butyphenyliodonium perfluorobutanesulfonate, and di-t-butyphenyliodonium 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-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, for example, 1,2,3-tris(methanesulfonyloxy) benzene, l,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 triazine 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. 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, 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.

[0198]

[0130] 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.

[0199]

[0131] 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.

[0200]

[0132] Suitable examples of organic amines include, but are not limited to, amine, 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.

[0201]

[0133] Specific examples of bases include ammonium carbonate, ammonium hydroxide, ammonium hydrogen phosphate, ammonium phosphate, tetramethylammonium carbonate, tetramethylammonium hydroxide, tetramethylammonium hydrogen phosphate, tetramethylammonium phosphate,Docket # PDH-025

[0202] tetraethylammonium carbonate, tetraethylammonium hydroxide, tetraethylammonium hydrogen phosphate, tetraethylammonium phosphate, and combinations thereof,

[0203]

[0134] 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).

[0204]

[0135] 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, triocylamine, tridodecylamine, 4-dimethylaminopyridine, 4,4'-diaminodiphenyl ether, 2,4,5-triphenylimidazole, l,4-diazabicyclo[4.3.0]non-5-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, l,8-diazabicyclo[5.4.0]undec-7-ene, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 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, l-(2-aminoethyl)pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-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.

[0205]

[0136] 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-hydroxyethylacetamide, n-methylacetamide, benzamide, pivalamide, and n-phenylacetamide. Examples of quaternary alkyl ammonium salts include tetrabutylammonium hydroxide or tetrabutylammonium lactate.

[0206]

[0137] 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, hydroxyethyl and hydroxybutyl groups. Specific examples of hydroxy amines include mono-, di- and tri-ethanolamine, 3-amino-l-propanol, 2-Docket # PDH-025

[0207] amino-2-methyl-l-propanol, 2-amino-2-ethyl-l,3-propanediol, tris(hydroxymethyl)ami nomethane, N-methylethanolamine, 2-diethylamino-2-methyl-l-propanol and triethanolamine.

[0208]

[0138] 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.

[0209]

[0139] 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.-(dimethylami no) propyl) aminocarbonyl]isophthalic acid, and combinations thereof.

[0210] Other optional components

[0211]

[0140] 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 in 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 pattern treatment composition.

[0212]

[0141] 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 in the photoresist compositions in an amount from 0.01 to 10 wt %, based on total solids of the photoresist composition.

[0213]

[0142] 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.

[0214] 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 metallicDocket # PDH-025

[0215] 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.

[0216]

[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 optionally treated to 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.

[0217]

[0144] In embodiments including a catalyst, the catalyst may be activated prior to thermal treatment by exposure to actinic radiation. Suitable radiation sources include extreme ultraviolet (EUV), ultraviolet (U V), 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 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 200 °C for 0.5 to 15 minutes depending on the specific materials utilized.

[0218]

[0145] After 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.

[0219]

[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.Docket # PDH-025

[0220] The thickness of the layer 304 is typically adjusted from about 2 to about 25 nm. For example, the thickness of the layer 304 may range from a lower limit of one of 2, 5, 10, 20, and 25 nm. In embodiments where actinic radiation is used to activate the optional catalyst, the coating layer thickness can be spatially tailored across the substrate surface.

[0221]

[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 composition comprises a poly(siloxane) that can be converted to a SiOx-like 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 O2).

[0222]

[0148] Next, at block 210 of method 200, a pattern elongation process is applied, and the resulting coated substrate with third patterned mask is shown in FIG. 3C and Fig. 3F, where the cavities have been elongated along their primary long axis. In some embodiments, the pattern elongation process can be carried out using a plasma-based tool. The process begins with plasma generation, which may produce depositing species responsible for forming a deposited polymer film in certain cases. However, in other embodiments, no deposited polymer film is deposited. Reactive gaseous species such as CH3F, CH4, or other known polymer-forming precursors may be introduced into the plasma, where they generate reactive depositing species. These species subsequently impinge on the substrate surface.

[0223]

[0149] As described earlier, the cavities are characterized by dimensions along different Cartesian coordinate directions, including 6 along the Y-axis, h-2 along the Z-axis, and W2 along the X-axis. The reactive depositing species may accumulate on the layer, including the cavity sidewalls. In some implementations, the substrate may be negatively biased relative to the plasma, with potential values such as -200 V, -100 V, -50 V, or -20 V, though the approach is not restricted to these values. As a result, a second polymeric layer may form on the substrate, acting as a sacrificial layer. Notably, the deposition process tends to produce a thicker polymer layer on the top horizontal surfaces compared to the vertical surfaces (sidewalls) or the cavity interior. This disparity arises from the greater solid angle available for the flux of radicals and neutral species originating from the plasma.

[0224]

[0150] Following the deposition of the sacrificial layer, a directional reactive ion etching (RIE) step is performed to elongate the cavity along the Y-axis, increasing its length ( / ) while preserving its width (w). The choice of etch chemistry depends on the composition of both the underlying layer and the deposited polymer film. During etching, a plasma is formed, and a reactive ion beam is directed at an oblique angle (0) relative to the substrate's surface normal. This plane may correspond to the upper surface of a wafer. The reactive species, present within the etching ambient, interact with the material in a manner consistent with established reactive ion beam etching techniques. In some embodiments, both the deposition and etching operations may be conducted within the same apparatus and chamber.

[0225]

[0151] The angle of incidence (0) for the reactive ion beam can range from approximately 15° to 75° in certain embodiments. This configuration allows both horizontal and vertical surfaces to be exposed to ionDocket # PDH-025

[0226] bombardment and subsequently etched. Because a deposited polymer film is present on the top surface, vertical material loss is reduced during pattern elongation. Additionally, formation of the deposited polymer film on the sidewalls contributes to a lower lateral etch rate, further controlling the pattern's final dimensions.

[0227]

[0152] Turning to FIG. 3C and FIG. 3F, the pattern treatment composition layer 304 and third patterned mask after the completion of the etch operation is shown on one or more layers to be patterned 302 above the substrate 300. The cavities have been elongated along the Y-axis to a length / 3, while the width of the cavity remains at the value of w3, and the thickness of the layer 304 remains at h2. More particularly, the cavity has been elongated by the angled reactive ion beam. Subsequently, at the completion of etching using angled reactive ion beam, a portion of deposited polymer film may remain, which remnant may be removed by an appropriate wet etch or dry etch, designed to preferentially etch a polymer material with respect to material of layer 304, for example. As such, after removal of the polymer layer, the corners of the cavity may exhibit less rounding than would otherwise occur without the use of the deposited polymer film.

[0228]

[0153] As shown in the above example, the present approach facilitates formation of a structure such as a cavity in a manner where the cavity is shrunk in only one direction. This is shown graphically in FIGS. 4A-C. The original cavity shown in FIG. 4A has a length h and width wi. After shrink, the cavity has a second length l2and width w2, as shown in FIG. 4B, where A is greater than / 3and wi is greater than W2. After elongation, as shown in FIG. 4C, the cavity has a third length / 3and width w3, where / 3is greater than l2and w3is approximately equivalent to w2. Accordingly, the cavity has shrunk only in width, not in length. The difference in cavity length, A / Sf£, and width, Aws+e, before and after shrink and elongation may be defined in Equations 3-4:

[0229] AU = / 1 - 13 (3) Aws+e= Wi - W (4) In some embodiments, Aws+eis greater than AU- In some embodiments, w3is less than 150% of w2, less than 125% of w2, less than 110% of w2, or equal to w2. In other embodiments, / 3is 85% - 200% of / >. In other embodiments, / 3is 90% - 150% of h. In other embodiments, I3 is 95% - 120% of h. In other embodiments, I3 is equal to.

[0230]

[0154] In certain embodiments, the pattern elongation process is performed using a processing apparatus designed for selective etching of substrate regions, such as extending cavity features. This apparatus may be a plasma-based system featuring a plasma chamber where plasma is generated through conventional methods. The plasma may be sustained by an RF power supply, for example. The system may include an extraction plate with an extraction aperture, enabling selective removal of material from the cavity sidewalls. A substrate, which may contain the described first patterned mask of cavities, is placed within the process chamber. In this coordinate system, the substrate plane is aligned with the X-Y plane, while the perpendicular to the substrate lies along the Z-axis.Docket # PDH-025

[0231]

[0155] During directional etching, an angled ion beam is extracted through the extraction aperture. In some implementations, this angled ion beam is a reactive ion beam, as described earlier. The ion beam is extracted when a voltage differential is applied between the plasma chamber and the substrate via a bias supply, consistent with established plasma processing methods. The bias supply can be connected to the process chamber such that the chamber and the substrate are maintained at the same potential. The angled ion beam may be continuous or pulsed, with the pulse characteristics— such as voltage amplitude, frequency, and duty cycle— adjustable independently.

[0232]

[0156] By scanning the substrate stage relative to the extraction aperture and the angled ion beam along a defined scan direction, selective etching of specific cavity surfaces is achieved. For example, the angled ion beam may be configured as a ribbon beam with its long axis extending along the X-direction. In this setup, one set of cavity sidewalls is preferentially exposed to the ion beam. Since the beam is incident at a nonzero angle relative to the Z-axis (normal to the substrate plane), it predominantly etches the sidewalls aligned in the X-Z plane while sparing the Y-Z sidewalls. This targeted etching results in selective elongation of the cavities. The angle of incidence can vary between approximately 10° and 75°, with typical values ranging from 20° to 60°.

[0233]

[0157] The composition of the angled ion beam can include inert gases, reactive gases, or a mixture thereof, and may be introduced alongside other reactive species. A gas source, such as a gas manifold, can supply multiple gases to the plasma chamber as needed. In specific embodiments, the angled ion beam and accompanying reactive species are provided in an etch recipe optimized for selectively removing material from the deposited polymer film and pattern treatment composition layer, while minimizing etching of the base substrate.

[0234]

[0158] In some implementations, the ribbon ion beam extends across the X-direction with a width sufficient to expose the entire substrate. Exemplary beam widths may range from 10 cm to 30 cm or more, while beam lengths along the Y-direction may range from 3 mm to 20 mm. The substrate is scanned in the X-Y plane, typically along the Y-direction, either in a bidirectional manner (180° sweeps) or unidirectionally (left-to-right or right-to-left). Because the ribbon beam extends along the X-direction, a complete scan ensures full exposure of the substrate.

[0235]

[0159] Alternative embodiments of the processing apparatus include additional features for angled ion treatment. For example, a beam blocker adjacent to the extraction aperture may define multiple apertures, producing two angled ion beams. These beams can be configured to have equal but opposite angles of incidence, enabling simultaneous etching of opposing sidewalls of a semiconductor fin. When implemented as a ribbon beam, this configuration allows uniform exposure of cavities across the substrate, elongating them symmetrically along the Y-axis in a single scan.

[0236]

[0160] The system can also support the deposition of a deposited polymer film prior to etching. In this case, a precursor gas such as CH3F may be introduced into the plasma chamber to form a deposited polymer film on the substrate. Once deposition is complete, the gas chemistry can be switched to facilitate reactive angled ion beam etching.Docket # PDH-025

[0237]

[0161] In some configurations, deposition and etching occur at separate stations within a cluster tool. This modular approach allows sequential processing without breaking vacuum conditions, as the substrate is transported between dedicated chambers via a transfer system. The system may include: an angled ion beam etch station, where a plasma chamber and extraction plate generate a directed ion beam at a nonzero angle to the substrate surface; and a polymer deposition chamber, where a thin deposited polymer film is formed. By alternating between these stations, unidirectional etching can be achieved while continually replenishing the deposited polymer film. This prevents top-layer etching and minimizes corner rounding of the cavities. The ability to maintain polymer replenishment enhances pattern fidelity and enables anisotropic etching.

[0238]

[0162] This process offers several advantages over conventional lithographic and etching techniques. First, it provides the ability to selectively shrink cavities in one dimension. Cavities can be extended in a preferred direction while maintaining the reduced dimensions in the perpendicular direction. The method enables feature spacing below the resolution limits of traditional lithography, allowing for finer patterning. By reducing the number of masks required, alignment accuracy improves, reducing errors in pattern registration.

[0239]

[0163] The techniques and apparatuses described herein are not limited to specific implementations. Variations and modifications may be adopted based on specific process requirements or environmental constraints. While this disclosure has been framed in the context of semiconductor processing, its principles may be applied broadly to other patterning and etching applications.

Claims

1. Docket # PDH-025We claim:

1. A method of microfabrication comprising:forming a first patterned mask on a substrate comprising a cavity, the cavity having a first length / i along a first direction and a first width wi along a second direction perpendicular to the first direction;forming a layer of a pattern treatment composition on the first patterned mask, wherein a modified cavity is formed having a second length / ? along a first direction, less than the first length / i, and a second widthalong a second direction perpendicular to the first direction, less than the first width wi;performing an elongation patterning process, comprising directing angled ions to a sidewall of the modified cavity in a first exposure, wherein the sidewall of the modified cavity is etched, wherein after the first exposure, the modified cavity has a third length / 3along the first direction, greater than the second length / 2, and a third width w3along a second direction perpendicular to the first direction.

2. The method of claim 1, wherein the third width w3is less than 150% of the second width W2.

3. The method of claim 1, wherein the third width w3is less than 110% of the second width w2.

4. The method of claim 1, wherein the third length / 3is 90% - 150% of the first length / 1.

5. The method of claim 1, wherein the third length / 3is 95% - 125% of the first length h.

6. The method of claim 1, wherein the first patterned mask comprises a photoresist.

7. The method of claim 1, wherein the first patterned mask comprises a metal-containing photoresist.

8. The method of claim 1, wherein the first patterned mask comprises an organic bottom anti- reflective coating, amorphous carbon, or spin-on carbon.

9. The method of claim 1, wherein the first patterned mask comprises silicon oxide, silicon nitride, silicon oxynitride, tungsten, titanium, titanium nitride, titanium oxide, zirconium oxide, aluminum oxide, aluminum oxynitride, hafnium oxide, or a silicon bottom anti-reflective coating.

10. The method of Claim 1, wherein the layer of a pattern treatment composition is formed by a chemical vapor deposition (CVD) process.

11. The method of Claim 1, wherein the layer of a pattern treatment composition is formed by an acid diffusion resist growth process.

12. The method of Claim 1, wherein the layer of a pattern treatment composition is formed by a polymer blend self-assembly process.Docket # PDH-02513. The method of Claim 1, wherein the pattern treatment composition comprises a polymer comprising a reactive surface attachment group or a reactive surface group precursor.

14. The method of Claim 1, wherein the pattern treatment composition is covalently bonded to the first patterned mask.

15. The method of Claim 1, wherein the pattern treatment composition is hydrogen bonded or ionically bonded to the first patterned mask.

16. The method of Claim 1, wherein the pattern treatment composition comprises a polymer comprising silicon.

17. The method of Claim 1, wherein the pattern treatment composition comprises an organic polymer.

18. The method of claim 1, wherein the pattern treatment composition comprises a polymer comprising a reactive surface attachment group, wherein the reactive surface attachment group is selected from one or more of hydroxyl, sulfhydryl, carboxyl, epoxide, amine, amide, imine, diazine, diazole, optionally substituted pyridine, pyridinium and optionally substituted pyrrolidone groups.

19. The method of claim 1, wherein the pattern treatment composition comprises a polymer comprising a reactive surface attachment group precursor, wherein the reactive surface attachment group precursor comprises an acid-labile group 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.

20. The method of claim 1, further comprising:depositing a sacrificial layer over the modified cavity in a second deposition procedure; anddirecting second angled ions to the modified cavity in a second exposure.

21. The method of claim 1, wherein the elongation patterning process comprises:directing angled ions to the modified cavity in a first exposure, wherein the angled ions comprise:a first angled ion beam having a first trajectory, directed to a first sidewall of the modified cavity; anda second angled ion beam having a second trajectory, directed to a second sidewall of the modified cavity, opposite the first sidewall.Docket # PDH-02522. The method of claim 1, wherein forming a layer of a pattern treatment composition on the first patterned mask comprises:coating a pattern treatment composition over the first patterned mask;baking the substrate; andtreating the substrate with a rinsing agent comprising a solvent.

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